JP2014215326A - Color filter, photosensitive resin composition for color filter, liquid crystal display device and organic light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter capable of preventing a cavity between a light-shielding layer and a pigmented layer even with a thinner line width of the light-shielding layer and capable of realizing high definition and high color purity, a photosensitive resin composition for a color filter capable of manufacturing the color filter, and a liquid crystal display device and an organic light-emitting display device capable of realizing high definition and high color purity using the color filter.SOLUTION: A color filter 10 at least includes: a transparent substrate 1; and a light-shielding layer 2 and pigmented layers 3 (3R, 3B, 3G) formed on the transparent substrate 1. Each of the pigmented layers 3 includes: a cured product of a polyfunctional copolymer having a constitutional unit containing a coloring material adsorptive functional group and a constitutional unit containing an ethylenically unsaturated bond-containing group, with an acid value of 5-200 mgKOH/g and a weight average molecular weight of 5000-1000000; and a coloring material. A pigmented layer 3 includes 1 wt.% or less of a component other than the cured product of the polyfunctional copolymer, the coloring material, a photoinitiator or a decomposition product thereof.

Description

  The present invention relates to a color filter, a photosensitive resin composition for a color filter, a liquid crystal display device, and an organic light emitting display device.

In recent years, display devices such as liquid crystal display devices and organic electroluminescence display devices have been required to have higher optical performance such as higher definition and higher color purity, especially mobile displays (cell phones, smartphones, tablets). In PC), improvement of optical performance is a big problem. In order to perform color display, the display device usually includes a color filter having a colored layer. Even in such a color filter, further improvement in optical performance is required.
In order to improve the optical performance of the color filter, for example, the brightness is improved by widening the opening by narrowing the line width of the light shielding layer (black matrix), or the color layer is thinned to increase the definition. Studies have been made on increasing the color purity of a color filter by increasing the colorant content in the colored layer.

  FIG. 5 is a schematic view showing an example of a conventional color filter manufacturing method. When forming a colored layer using the photosensitive resin composition, first, the photosensitive resin composition is applied onto the transparent substrate 1 on which the light shielding layer 2 is formed as shown in FIG. A coating film 14 is formed. Next, after exposure 11 through a mask 13 having a predetermined pattern, development with a developer is performed to form a cured coating film 15. The cured coating film 15 is subjected to a heat treatment after the development process to form a sufficiently cured colored layer 16. When the colored layer is exposed from above, the upper side of the colored layer undergoes more curing reaction, and the lower side is less likely to proceed with the curing reaction, so the lower side is easily dissolved during development. It tends to be in reverse taper shape

  Patent Document 1 discloses a copolymer having a molecular structure in which a structural unit having a specific cyclic imide group, a structural unit having an acidic functional group, and a structural unit having a photocurable functional group are linked. It is shown that the colored layer was formed using the photosensitive resin composition containing. However, in Patent Document 1, a copolymer having a molecular structure in which a structural unit having a specific cyclic imide group, a structural unit having an acidic functional group, and a structural unit having a photocurable functional group are linked, It is used as a dispersion assisting polymer and contains a dispersant for dispersing the pigment and a photocurable monomer separately.

JP 2004-285281 A

FIG. 6 is a schematic diagram illustrating an example of a method for manufacturing a color filter when the opening is widened by narrowing the line width of the light shielding layer 2. As shown in the example of FIG. 6, when the opening is widened by narrowing the line width of the light shielding layer 2, it is difficult for exposure light to reach near the base of the light shielding layer 2, and the curing reaction of the coating film does not proceed easily. In addition, since the overlap between the light shielding layer and the coating film pattern is small, the developer may enter the opening during development to dissolve the coating film, resulting in the formation of cavities 17. If such a cavity 18 remains even after heat curing, it causes panel unevenness such as glare of the display device.
Further, when trying to increase the content of the color material in the colored layer in order to achieve high color purity, such a cavity 18 was particularly likely to occur. This is because when the concentration of the color material in the photosensitive resin composition is increased, the concentration of the dispersant is usually increased, so that the curing component is relatively reduced and the lower side of the coating film is difficult to cure. . In addition, when the coating film is thickened in order to increase the colorant content in the colored layer, it is difficult for exposure light to reach and harden the lower side of the coating film. For example, even if the photosensitive resin composition disclosed in Patent Document 1 is used, if the colorant content in the colored layer is increased for high color purity, the film thickness becomes thicker, so the upper side is sufficiently cured. However, when the line width of the light shielding layer is reduced, a cavity is generated between the light shielding layer and the colored layer.

  The present invention has been made in view of the above problems, and even if the line width of the light shielding layer is reduced, a cavity is not generated between the light shielding layer and the colored layer, and a color capable of realizing high definition and high color purity. It is an object to provide a filter, a photosensitive resin composition for a color filter capable of producing the color filter, a liquid crystal display device and an organic light emitting display device capable of realizing high definition and high color purity using the color filter. .

  The color filter according to the present invention is a color filter including at least a transparent substrate, a light-shielding layer and a colored layer provided on the transparent substrate, and each of the colored layers has a colorant-adsorbing functional group. A cured product of a multifunctional copolymer having a unit and a structural unit having an ethylenically unsaturated bond-containing group, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5,000 to 1,000,000; A colored layer containing only 1% by weight or less of a component different from the cured product of the multifunctional copolymer, the colored material, and the photopolymerization initiator or decomposition product thereof. It is characterized by being.

  In the color filter according to the present invention, the weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the colored layer is 0.55 or more. This is preferable from the viewpoint of realizing color purification.

  In the color filter according to the present invention, the line width of the light shielding layer is preferably 5 μm or less from the viewpoint of realizing high definition.

  The photosensitive resin composition for a color filter according to the present invention has a structural unit having a colorant-adsorbing functional group and a structural unit having an ethylenically unsaturated bond-containing group, and an acid value of 5 to 200 mgKOH / g. And a multifunctional copolymer having a weight average molecular weight of 5,000 to 1,000,000, a colorant, and a photopolymerization initiator, and the multifunctional copolymer, the colorant, And the component different from the said photoinitiator is 1 weight% or less, It is characterized by the above-mentioned.

  In the photosensitive resin composition for color filters according to the present invention, the weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the total solid content is 0.55 or more. It is preferable from the viewpoint of realizing high color purity of the obtained color filter.

The liquid crystal display device according to the present invention includes the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
The organic light emitting display device according to the present invention includes the color filter according to the present invention and an organic light emitter.

  According to the present invention, even if the line width of the light-shielding layer is reduced, no cavity is formed between the light-shielding layer and the colored layer, and the color filter capable of realizing high definition and high color purity and the color filter can be manufactured. A photosensitive resin composition for a color filter, a liquid crystal display device and an organic light emitting display device capable of realizing high definition and high color purity using the color filter can be provided.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the manufacturing method of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. It is the schematic which shows an example of the organic light emitting display apparatus of this invention. It is the schematic which shows an example of the manufacturing method of the conventional color filter. It is the schematic which shows an example at the time of expanding the opening part by narrowing the line | wire width of a light shielding layer in the manufacturing method of the conventional color filter.

Hereinafter, a color filter, a photosensitive resin composition for a color filter, a liquid crystal display device, and an organic light emitting display device according to the present invention will be described.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.

[Color filter]
The color filter according to the present invention is a color filter including at least a transparent substrate, a light-shielding layer and a colored layer provided on the transparent substrate, and each of the colored layers has a colorant-adsorbing functional group. A cured product of a multifunctional copolymer having a unit and a structural unit having an ethylenically unsaturated bond-containing group, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5,000 to 1,000,000; A colored layer containing only 1% by weight or less of a component different from the cured product of the multifunctional copolymer, the colored material, and the photopolymerization initiator or decomposition product thereof. It is characterized by being.
Moreover, the photosensitive resin composition for color filters which concerns on this invention has a structural unit which has a coloring material adsorptive functional group, and a structural unit which has an ethylenically unsaturated bond containing group, and an acid value is 5-200 mgKOH. / G and a weight average molecular weight of 5,000 to 1,000,000, a multifunctional copolymer, a colorant, and a photopolymerization initiator, and the multifunctional copolymer, the color It is characterized by containing only 1% by weight or less of a material and a component different from the photopolymerization initiator.
In addition, in the said multifunctional copolymer, multifunctionality means having colorant dispersibility, photocurability, and alkali developability.
Moreover, solid content shall mean components other than the solvent component contained in the photosensitive resin composition.

The color filter according to the present invention will be described below with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has at least a transparent substrate 1, a light shielding layer 2, and colored layers 3R, 3B, and 3G. It may be similar to known ones (not shown).
FIG. 2 shows a schematic diagram of an example of a method for producing a color filter of the present invention. In the color filter of the present invention, for example, a photosensitive resin composition for a color filter is coated on the transparent substrate 1 to form a coating film 14, exposed 11 through a mask 13 having a predetermined pattern, and then developed with a developer. It can manufacture by developing and forming the cured coating film 15, baking the obtained cured coating film 15, and forming the colored layer 3 fully hardened | cured.

Conventionally, in a colored layer of a color filter using a photolithographic method, a colorant and a colorant dispersing agent for uniformly dispersing the colorant and light having an ethylenically unsaturated group for imparting photocurability are used. Generally, a cured product of a composition of a curable monomer and an alkali-soluble resin is included.
On the other hand, in the color filter according to the present invention, each of the colored layers 3 includes a cured product of the specific multifunctional copolymer and a coloring material, and the multifunctional copolymer is cured in the colored layer. Since it contains only 1% by weight or less of components different from those of the product, the coloring material, and the photopolymerization initiator or its decomposition product, even if the line width of the light shielding layer is narrowed, there is a cavity between the light shielding layer 2 and the colored layer 3 Therefore, the color filter can achieve high definition and high color purity. The action of the color filter according to the present invention exerting the above-described effects is estimated as follows although it is not yet elucidated.
The multifunctional copolymer contained in the colored layer 3 of the color filter according to the present invention has a color material dispersibility by having a structural unit having a color material adsorbing functional group, and further has an ethylenically unsaturated bond. It has photocurability by having a structural unit having a containing group, and has alkali developability by having the acid value specified above. Therefore, the colored layer 3 can be substantially free of a colorant dispersant for improving the dispersibility of the colorant and a photocurable monomer for improving the curability. As a result of substantially not containing the color material dispersant and the photocurable monomer, the color material content in the composition for forming the colored layer 3 can be increased. Therefore, the coating film to be the colored layer 3 is a thin film. High color purity can be achieved. When the coating film to be the colored layer 3 is a thin film, the exposure light reaches the lower side of the coating film and cures when cured, so that the lower side is not easily dissolved during development of the cured coating film. 3 is less likely to have an inversely tapered shape, and cavities are less likely to occur between the light shielding layer 2 and the colored layer 3. In addition, when the coating film has a small number of double bonds that cause a curing reaction as compared with the case of containing a conventional photocurable monomer, only the upper side is not cured early when the coating film is exposed. The curing reaction proceeds slowly and the fluidity continues to be high. As described above, in the present invention, since the colored layer 3 is formed by slowly and uniformly curing to the lower side while the coating film flows until after firing, the colored layer 3 is unlikely to have a reverse taper shape, and is light-shielded. A cavity is not easily generated between the layer 2 and the colored layer 3.

In order to produce a high-purity and high-definition color filter, if the colored layer is conventionally a thick colored layer, the colored layer 3 tends to have an inversely tapered shape, and the width of the tapered portion where the film thickness is relatively thin. Was getting bigger. A tapered portion having a relatively thin film thickness causes color unevenness. When the width of the colored layer is large, the ratio of the width of the tapered portion having a relatively thin film thickness with respect to the width of the colored layer is small, so that the color unevenness is not noticeable and does not cause a problem. However, when reducing the width of the light-shielding layer and the colored layer in order to obtain a high-definition color filter, the ratio of the width of the tapered portion having a relatively thin film thickness to the width of the colored layer is increased. The ratio of color unevenness becomes large and becomes a problem. On the other hand, in the present invention, since the colored layer 3 is a thin film and hardly forms an inversely tapered shape, the width of the light shielding layer and the colored layer is reduced when manufacturing a highly purified and high-definition color filter. Even color unevenness is not a problem.
Further, in the color filter of the present invention, since the multifunctional copolymer having photocurability itself has alkali developability and does not substantially contain a photocurable monomer, the alkali development derived from the monomer is performed. Subsequent residue is unlikely to occur. Conventionally, when the line width of the light shielding layer is reduced, there is a problem that a part of adjacent pixels is mixed with the residue after alkali development or the linearity of the pattern of the colored layer is inferior. However, since the color filter of the present invention has little residue after alkali development, even if the line width of the light-shielding layer is reduced, a color layer having excellent linearity can be obtained without mixing a part of adjacent pixels. Since it can be formed, high definition can be coped with.

(Colored layer)
Each of the colored layers included in the color filter according to the present invention includes a structural unit having a colorant-adsorbing functional group and a structural unit having an ethylenically unsaturated bond-containing group, and an acid value of 5 to 200 mgKOH / g. A cured product of a multifunctional copolymer having a weight average molecular weight of 5,000 to 1,000,000, and a coloring material, and the cured product of the multifunctional copolymer, the coloring material, and light in the colored layer What is necessary is just to contain the component different from a polymerization initiator or its decomposition product only 1 weight% or less, and it adjusts and uses it suitably. The colored layer can be formed using, for example, the photosensitive resin composition for a color filter according to the present invention.
Hereinafter, the coloring layer with which the color filter which concerns on this invention is equipped, and the component contained in the photosensitive resin composition for color filters which concerns on the said this invention are demonstrated in order.

<Multifunctional copolymer>
The multifunctional copolymer has a structural unit having a colorant-adsorbing functional group, a structural unit having an ethylenically unsaturated bond-containing group, an acid value of 5 to 200 mgKOH / g, and a weight. The average molecular weight is 5,000 to 1,000,000. The acid value of the multifunctional copolymer is within the above range by using an acidic functional group as the colorant-adsorbing functional group, or by having a structural unit having an acidic functional group in addition to the above structural unit. be able to.
Further, the main chain structure of the multifunctional copolymer is not particularly limited, but a main chain structure obtained by polymerizing an ethylenically unsaturated bond is preferably used, and the multifunctional copolymer is A copolymer of monomers having an ethylenically unsaturated bond is preferably used.

1. Constituent unit having a colorant-adsorbing functional group The constituent unit having a colorant-adsorptive functional group has good dispersibility and dispersion stability of the colorant, and can uniformly disperse the colorant in the colored layer. it can.
As the structural unit having the colorant-adsorbing functional group, for example, a structural unit represented by the following general formula (I) having the following Q as the colorant-adsorbing functional group is preferable.

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, Q is a group having an organic dye structure or a heterocyclic structure, an acidic functional group, a basic group. It is either a group having a nitrogen atom or an ionic functional group.)

  In the multifunctional copolymer, the colorant-adsorbing functional group Q of the structural unit represented by the general formula (I) is adsorbed on the surface of the colorant, and the entire polymer forms steric hindrance and In order to avoid agglomeration, it is possible to disperse the color material.

  A in the general formula (I) is a direct bond or a divalent linking group. The direct bond means that Q is directly bonded to a carbon atom without a linking group as in the following general formula (I-1).

(In general formula (I-1), R ¹ and Q are the same as in general formula (I).)

  Examples of the divalent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R'-OR "- : R ′ and R ″ each independently represents an alkylene group) and combinations thereof. Especially, it is preferable that A is a bivalent coupling group containing a direct bond, -CONH- group, or -COO- group from the heat resistant point of the obtained polymer.

For example, examples of the divalent linking group containing a —CONH— group or a —COO— group include a —CONH—R ² — or —COO—R ² — group in addition to a —CONH— group or a —COO— group. . Here, R ² is an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁵ ) —CH (R ⁶ ) —O] _x —CH (R ⁵ ) —CH (R ⁶ ) — or — [( _{CH 2) y -O] z -} (CH 2) y - in and, ^{R 5} and ^{R 6} are each independently a hydrogen atom or a methyl group. x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18.
The alkylene group having 1 to 8 carbon atoms in R ² may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, And various hexylene groups and various octylene groups.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.
R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R ² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.

Q in the general formula (I) is any one of a group having an organic dye structure or a heterocyclic structure, an acidic functional group, a group having a basic nitrogen atom, and an ionic functional group. In the multifunctional copolymer, the structural unit having a colorant-adsorbing functional group may be one type or two or more types, and Q in the general formula (I) is appropriately selected according to the type of colorant One type may be used alone, or two or more types may be used in combination.
The structural unit represented by the general formula (I) is an ethylenically unsaturated bond with any of a group having an organic dye structure or a heterocyclic structure, an acidic functional group, a group having a basic nitrogen atom, and an ionic functional group. Can be introduced by using a compound containing as a monomer for copolymerization. Alternatively, after copolymerizing using an ethylenically unsaturated bond and a compound containing a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bondable group as a monomer, these A compound having any one of a functional group capable of reacting with the above-described substituent and a group having an organic dye structure or a heterocyclic structure, an acidic functional group, a group having a basic nitrogen atom, or an ionic functional group, and a copolymer A structural unit having any one of a group having an organic dye structure or a heterocyclic structure, an acidic functional group, a group having a basic nitrogen atom, and an ionic functional group by reacting with the substituent contained in You may do it.

Examples of the compound containing an organic dye structure or a heterocyclic structure and an ethylenically unsaturated bond include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthra. Pigment structures such as pyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, etc .; thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, pyrrolidone, dioxolane, pyrazole, pyrazoline, pyrazolidine , Imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithia , Isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, and vinyl groups and (meth) acryloyloxy And compounds containing an ethylenically unsaturated bond-containing group such as a group. Examples thereof include N-vinyl-2-pyrrolidone and N-vinylcarbazole, but are not limited thereto.
In addition, when it corresponds also to the group which has a basic nitrogen atom among the groups which have the above-mentioned heterocyclic structure, it shall be contained in the group which has the below-mentioned basic nitrogen atom.

In the compound containing an acidic functional group and an ethylenically unsaturated bond, examples of the acidic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
Compounds containing a carboxyl group and an ethylenically unsaturated bond include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, ω-carboxy-poly Examples thereof include caprolactone mono (meth) acrylate. As a compound containing a carboxyl group and an ethylenically unsaturated bond, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride The addition reaction product may be used.
Examples of the compound containing a sulfonic acid group and an ethylenically unsaturated bond include 2-acrylamido-2-methylpropanesulfonic acid, and the compound containing a phosphoric acid group and an ethylenically unsaturated bond include, for example, phosphorus. Examples include acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester).
In addition, as a structural unit having an acidic functional group, a copolymer is formed using a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and then maleic anhydride, phthalic anhydride, cyclohexane is added to the hydroxyl group. What formed the addition reaction product with cyclic anhydrides, such as dicarboxylic acid anhydride, may be used. Furthermore, as a structural unit having an acidic functional group, after forming a copolymer using a monomer having a carboxyl group, it has a hydroxyl group by addition reaction of an epoxy group-containing monomer to the carboxyl group, Further, it may be obtained by introducing an ethylenically unsaturated bond site into the side chain and further adding a polybasic acid anhydride to the hydroxyl group.

  Among the compounds containing a basic nitrogen atom and an ethylenically unsaturated bond, examples of the monomer having a heterocyclic ring include vinylpyridine, vinylimidazole, and vinyltriazole. (Meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and 1- (N, N-(meth) acrylic acid. (Dimethylamino) -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, ( N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, (meth ) 1-pyrrolidinoethyl acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate and (meth) acrylic Acid and N, N- methylphenylamino ethyl. Further, (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′- Diethylaminoethyl) acrylamide, N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N , N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) ) Acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) Examples include hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, and styrenes include N, N-dimethylaminostyrene, N, N -Dimethylaminomethylstyrene etc. are mentioned.

Examples of the ionic functional group include an anionic functional group and a cationic functional group. Examples of the anionic functional group include alkali metal salts of the acidic functional groups and salts with organic amines (for example, tertiary amines such as triethylamine and dimethylaminoethanol). In addition, as the cationic functional group, the basic nitrogen atom, an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); halogenation such as benzyl chloride, benzyl bromide, etc. Benzyl; alkyl sulfonic acid ester such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkyl ester such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1-18); dialkyl sulfate (alkyl group: C1) -4) and the like, dialkyl diallylammonium salts, salts with acidic phosphates, and the like.
The introduction of the ionic functional group may be carried out using a compound containing the ionic functional group and an ethylenically unsaturated bond, but the compound containing the acidic functional group and the ethylenically unsaturated bond or the base It is preferable to form a salt by forming a salt after copolymerization using a compound containing an ionic nitrogen atom and an ethylenically unsaturated bond.

  Q in the general formula (I) is preferably a group having an organic dye structure or a heterocyclic structure, and a cyclic imide group represented by the following general formula (II) is preferably used. In the general formula (I), when Q is a cyclic imide group of the general formula (II), the dispersibility and dispersion stability of the coloring material are improved. In addition, since the cyclic imide group of the general formula (II) itself reacts as a photocurable functional group, the multifunctional copolymer is obtained by changing the Q to the cyclic imide group of the general formula (II). The sensitivity of the curing reaction is improved.

(In General Formula (II), R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or , Each group forming a carbocyclic ring.)

  Examples of the cyclic imide group represented by the general formula (II) include those represented by the following formulas (IIa), (IIb) and (IIc), respectively.

In the general formula (I), for example, when Q is a group represented by the general formula (II), as the A, the —COO—R ² — group is preferably used.

  The structural unit represented by the general formula (I) is introduced into the copolymer molecule as a pendant structure containing Q which is a colorant-adsorbing functional group. The pendant structure containing Q is smaller in size than the so-called graft structure, and the polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “polystyrene”) measured by GPC (gel permeation chromatography) of the monomer for introducing the pendant structure. Simply referred to as “weight average molecular weight” or “Mw”) is 1000 or less. In the present invention, the weight average molecular weight refers to a polyethylene conversion value using gel permeation chromatography. The weight average molecular weight is determined, for example, by gel permeation chromatography (for example, high performance liquid chromatography CCP series (CCPE, CO-8010, RI-8010, SD-8000) using tetrahydrofuran containing 20 mmol / liter of citric acid as a developing solution. ), Manufactured by Tosoh Corporation).

2. Structural unit having an ethylenically unsaturated bond-containing group An ethylenically unsaturated bond-containing group is a functional group that is cured by photoradical polymerization because it has an ethylenically unsaturated bond. As the ethylenically unsaturated bond-containing group, a vinyl group, a (meth) acryloyl group, an allyl group, or the like is preferably used.

  Note that when a multifunctional copolymer is synthesized using a monomer having two or more ethylenically unsaturated bond-containing groups, side reactions are likely to occur, and therefore the ethylenically unsaturated bond-containing group is the main component of the copolymer. After forming the chain linkage, it is preferably introduced via a suitable functional group.

  For example, after copolymerization using an ethylenically unsaturated bond and a compound containing a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bondable group as a monomer, A copolymer having an ethylenically unsaturated bond-containing group by reacting a compound having a functional group capable of reacting with the above-described substituent and an ethylenically unsaturated bond-containing group with the substituent contained in the copolymer. It is preferable to introduce into. For example, glycidyl (meth) acrylate is reacted with a copolymer having a carboxyl group, hydroxyalkyl (meth) acrylate is reacted with a copolymer having an isocyanate group, or (meth) acryloyl is added to a copolymer having a hydroxyl group. An ethylenically unsaturated bond-containing group can be introduced into the copolymer, for example, by reacting with an oxyalkyl isocyanate.

  As the structural unit having an ethylenically unsaturated bond-containing group, those represented by the following formula (III) are preferable.

(In formula (III), R ^{1 ′} represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group.)

R ^{1 ′} contained in the formula (III) and other formulas described later is hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. Monomers used for introducing the structural unit of the formula (III) include acrylic acid, methacrylic acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, and 2-carboxy-1-hexene. , 2-carboxy-1-heptene and the like.
In order to introduce the structural unit of the formula (III) into the multifunctional copolymer, first, at least one monomer including a carboxyl group such as (meth) acrylic acid is polymerized to be multifunctional. After forming the main chain portion of the copolymer, glycidyl (meth) acrylate may be reacted with the carboxyl group derived from (meth) acrylic acid or the like. However, if the number of carboxyl groups derived from (meth) acrylic acid or the like is too small, alkali solubility is insufficient, so the amount of glycidyl (meth) acrylate must be adjusted appropriately.

  In addition, a copolymer having an isocyanate group is allowed to react with a hydroxyalkyl (meth) acrylate, or a copolymer having a hydroxyl group copolymerized using hydroxyalkyl (meth) acrylate or the like is added with (meth) acryloyloxyalkyl isocyanate. When the ethylenically unsaturated bond-containing group is introduced into the copolymer, for example, by reaction, the hydroxyalkyl (meth) acrylate includes 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2 -Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like are exemplified. Moreover, as (meth) acryloyloxyalkyl isocyanate, it is preferable to use what (meth) acryloyloxy group couple | bonded with isocyanate group (-NCO) through the C2-C6 alkylene group, specifically, Examples thereof include 2-acryloyloxyethyl isocyanate and 2-methacryloylethyl isocyanate.

  Moreover, as a standard of photocuring property which a multifunctional copolymer has, it is preferable that a double bond equivalent is 100-2000. More preferably, it is 150-1500, More preferably, it is 150-1000. By setting it as the said range, it can anticipate satisfy | filling favorable plate-making characteristics, such as alkali developability, color material dispersibility, and a sensitivity and a pattern shape. The double bond equivalent is a weight average molecular weight per polymer double bond (ethylenically unsaturated bond).

3. Structural unit having acidic functional group The multifunctional copolymer has an acidic functional group separately so that the acid value is 5 to 200 mgKOH / g when the colorant-adsorbing functional group is not an acidic functional group. Having structural units.
The structural unit having the acidic functional group is a component that contributes to alkali solubility, and the content ratio thereof is adjusted by the degree of alkali solubility required for the photosensitive resin composition. As the monomer used for introducing the structural unit having an acidic functional group into the main chain of the multifunctional copolymer, a compound containing an acidic functional group and an ethylenically unsaturated bond can be used. . Specific examples of the compound containing an acidic functional group and an ethylenically unsaturated bond may be the same as those described in the section of the structural unit having a colorant-adsorbing functional group. The acidic functional group only needs to be capable of alkali development, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. A carboxyl group is preferable from the viewpoint of alkali developability and handling properties of the resin composition. .
Among them, as the structural unit having an acidic functional group, a polybasic acid anhydride is added to the hydroxyl group described in the structural unit derived from (meth) acrylic acid or the structural unit having a colorant-adsorbing functional group. A structural unit having an acidic functional group obtained in this manner can be suitably used.
In the case where the multifunctional copolymer has the colorant-adsorbing functional group other than the acidic functional group, the structural unit having the acidic functional group is usually introduced for the purpose of adjusting the acid value. Is done.

4). Other structural units The multifunctional copolymer may contain other structural units. For example, it is preferable to include a constitutional unit that contributes to solvent affinity from the viewpoint of improving solvent affinity and improving dispersibility and dispersion stability of the coloring material. As other structural units, those represented by the following formula (IV) are preferable.

(In Formula (IV), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrocarbon group, a cyano group, — [CH (R ¹² ) —CH (R ¹³ ) —O] _x —R ^14. , — [(CH ₂ ) _y —O] _z —R ¹⁴ , — [CO— (CH ₂ ) _y —O] _z —R ¹⁴ , —CO—O—R ¹⁵ or —O—CO—R ¹⁶ . R ¹² and R ¹³ each independently represents a hydrogen atom or a methyl group.
R ¹⁴ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO or —CH ₂ COOR ¹⁷ , and R ¹⁵ is a hydrocarbon group, a cyano group, — [CH (R _{^{12) -CH (R 13) -O}} ] x -R 14, - [(CH 2) y -O] z -R 14, - represented by _{[CO- (CH 2) y -O} ] z -R 14 It is a monovalent group. R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms, and R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Each of the hydrocarbon groups may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

The hydrocarbon group for R ¹¹ , R ¹⁴ , and R ¹⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, cyclopentyl group. Cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include a nitro group and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

  x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

  Other structural units include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methyl Those having a structural unit containing at least one of a ring structure and an ester group, such as a structural unit derived from styrene, vinylcyclohexane and the like, are preferred, methyl methacrylate, benzyl (meth) acrylate, Eniru (meth) acrylate, cyclohexyl (meth) acrylate, more preferably has a constitutional unit derived from isobornyl (meth) acrylate. However, it is not limited to these. Among them, benzyl (meth) acrylate is preferable from the viewpoint of adjusting the colorant dispersibility.

As the monomer for introducing each constituent unit into the main chain of the multifunctional copolymer, one exemplified for each constituent unit may be used alone, or two or more kinds may be mixed. May be used.
The multifunctional copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

  Specific examples of the multifunctional copolymer include a random copolymer or a block copolymer represented by the following formula (V), and a random copolymer is particularly preferable. In addition, the main chain of the copolymer may include other main chain constituent units as necessary.

(In Formula (V), R ¹ , R ^{1 ′} , R ² , R ³ , R ⁴ , and R ⁷ are the same as above, and R ¹ may be the same or different. , N is an integer.)

  Specific examples of the multifunctional copolymer include, for example, a polymer in which a structural unit having an ethylenically unsaturated bond is introduced into an alkali-soluble graft polymer described in JP-A-2003-241374, and JP-A-2004 Although the polymer etc. which are obtained by Example I-2 of -217735 gazette are also mentioned, it is not limited to these specific examples.

The content ratio of each structural unit in the multifunctional copolymer is adjusted in consideration of the degree of color material dispersibility required depending on the color material used and other physical properties.
If the content ratio of the structural unit having the colorant-adsorptive functional group is too small, the dispersibility of the colorant becomes insufficient, and if it is too much, the adsorption point to the colorant increases too much, causing cross-linking between the colorants, On the contrary, the dispersibility may decrease. The content ratio of the structural unit having the colorant-adsorptive functional group is adjusted within a range in which such a problem does not occur, and is preferably 5 mol% to 80 mol% in terms of the charged amount as a monomer, particularly 10 A mol% to 60 mol% is preferable. When the multifunctional copolymer has a colorant-adsorbing functional group other than the acidic functional group, the structural unit having the acidic functional group is included in the content ratio of the structural unit having the colorant-adsorbing functional group. Is not included.

If the content ratio of the structural unit having an ethylenically unsaturated bond-containing group is too small, the photocurability becomes insufficient, and if it is too large, there is a problem that the substrate adhesion is deteriorated. The range is used as a guide, and it is adjusted as appropriate within the range where no problem occurs.
If the content ratio of the structural unit having the acidic functional group is too small, the alkali solubility becomes insufficient, and if it is too large, there is a problem that the solvent solubility decreases, so the acid value becomes 5 to 200 mgKOH / g, Adjustments are made as appropriate within a range where such problems do not occur.

  When a structural unit containing at least one of a ring structure and an ester group is included, the molar ratio of the content ratio of the structural unit having a colorant-adsorbing functional group and the structural unit containing at least one of the ring structure and the ester group Is preferably 90:10 to 10:90, and more preferably 80:20 to 20:80, and is preferably adjusted as appropriate depending on the type of the color material to be dispersed.

  Specifically, for example, in the case of the copolymer of the formula (V), the structural unit having a cyclic imide group is converted into an acidic functional group in an amount of about 5 to 80 mol% in terms of the amount charged as a monomer. About 20 mol% to 70 mol% of (meth) acrylic acid as a pendant linking site of a structural unit having an ethylenic unsaturated bond, and glycidyl acid (meth) as a pendant introducing unit of an ethylenically unsaturated bond The acrylate is about 5 mol% to 60 mol%. Furthermore, for example, when the structural unit containing at least one of a ring structure and an ester group is contained as the other structural unit, it is preferably contained in an amount of about 5 mol% to 70 mol%.

  The multifunctional copolymer has a weight average molecular weight of 5,000 to 1,000,000. The weight average molecular weight is preferably adjusted to a range of 5,000 to 500,000. If the weight average molecular weight is less than 5,000, sufficient steric hindrance cannot be formed, and the distance between the color materials becomes close, so that the number of adsorption points to the color material in one molecule becomes too small and the color material is adsorbed. There is a problem that the dispersibility is lowered due to a problem such as difficulty. On the other hand, if the weight average molecular weight is larger than 1,000,000, the adsorption point to the color material in one molecule increases too much, causing cross-linking between the color materials, resulting in problems such as a decrease in dispersibility and developability.

  The acid value of the multifunctional copolymer is 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g. The acid value is related to color material dispersibility and alkali solubility, and if the acid value is too low, there are problems such as poor color material dispersibility and developability. On the other hand, if the acid value is too high, the solubility in the solvent is lowered and the dispersibility is poor, and the alkali solubility is too large to control the pattern shape during pattern exposure, or the adhesion to the substrate is poor, etc. There's a problem. Here, the acid value indicates the acid value per gram of solid content, and can be determined by potentiometric titration according to JIS K 0070.

  Furthermore, the hydroxyl value of the multifunctional copolymer is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, from the viewpoint of colorant dispersibility. Here, the hydroxyl value indicates the hydroxyl value per gram of solid content, and can be determined by potentiometric titration according to JIS K 0070.

  The multifunctional copolymer can be synthesized according to a known method, for example, a method according to the procedure and conditions described in JP-A-2000-105456. First, a functional group capable of introducing a pendant structure having a structural unit having a colorant-adsorbing functional group represented by formula (I), a structural unit having an acidic functional group, and an ethylenically unsaturated bond-containing group later. And a polymer having a main chain containing a constituent unit and, if necessary, other constituent units (raw polymer), and then producing another functional group together with the ethylenically unsaturated bond-containing group in the raw polymer. A pendant structure of an ethylenically unsaturated bond-containing group may be introduced by reacting a compound having a group.

In the colored layer of the present invention, the multifunctional copolymer may be used alone or as a mixture of two or more multifunctional copolymers as appropriate. Property and photocurability can be adjusted.
Since the colored layer of the present invention undergoes a curing reaction through a light irradiation step as will be described later, at least a part of the ethylenically unsaturated bonds of the multifunctional copolymer undergoes a curing reaction, and thus the multifunctional copolymer. A cured product of the polymer is included.

  In this invention, it is preferable that the content rate of the multifunctional copolymer in a colored layer shall be a ratio which can achieve P / V ratio mentioned later. The content ratio of the multifunctional copolymer is preferably 45 to 64 parts by weight, and preferably 50 to 60 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition of the present invention. More preferred. In addition, it is preferable that the sum total content of the said multifunctional copolymer and a photoinitiator is 64.5 weight part or less with respect to 100 weight part of total solid of the said photosensitive resin composition.

<Color material>
In the present invention, the color material is not particularly limited as long as it can produce a desired color, and for example, conventionally known organic pigments, dyes, lake pigments, and the like are used alone or in admixture of two or more. Among them, it is preferable to use an organic pigment from the viewpoint of color developability and heat resistance. From the viewpoint of improving the brightness, a lake pigment in which a water-soluble dye is precipitated with a lake agent (precipitant) to make it insoluble is also preferably used.
Specific examples of the organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).
Specifically, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 176,177,179,180,181,182,185,187,188,193,194,199,213,214; C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; C. I. Pigment Green 7, 10, 36, 37, 58; I. The Cl substituents of Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. 80; C.I. I. Pigment violet 1, 19, 23, 27, 32, 37, 42; C.I. I. Pigment brown 25, 28; C.I. I. And CI pigment black 1 and 7.

  Among these, conventionally, C.I. I. Pigment Green 58 (PG58) and C.I. I. In order to achieve green target chromaticity with high color density using Pigment Green 7 (PG7), it is necessary to make the green colored layer thicker than before or to increase the color material density. However, in the present invention, even when such a green color material is used, a high-definition color filter can be obtained without generating a cavity.

  Specific examples of the lake pigment include C.I. I. Pigment Blue 1, 1: 2, 2, 3, 8, 9, 10, 11, 12, 14, 17: 1, 18, 19, 24, 24: 1, 53, 56, 61, 62, 63, 78 C. I. Pigment Violet 1, 2, 2: 2, 3, 3: 1, 3: 3, 3: 4, 4, 5, 5: 1, 6: 1, 7: 1, 9, 12, 20, 26, 27, 39; C.I. I. Pigment Green 1, 2, 3, 4, 8, 9, 10, 12, 45; I. Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 49: 1, 49: 2, 49: 3, 50, 50: 1, 51, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 58, 58: 1, 58: 2, 58: 3, 58: 4, 60: 1, 63, 63: 1, 63: 2, 63: 3, 64: 1, 68, 81, 81: 1, 81: 2, 81: 3, 81: 4, 82, 83, 84, 90, 90: 1, 151, 169, 172, 173, 174, 191, 193, 200, 237, 239, 247; I. Pigment orange 17, 18, 19, 46; I. Pigment yellow 18, 61, 61: 1, 62, 100, 104, 115, 133, 168, 169, 183, 191, 209, 209: 1, 212, and the like.

In the present invention, the content ratio of the color material may be appropriately adjusted so as to achieve the target color purity.
Since the photosensitive resin composition of the present invention uses the multifunctional copolymer and does not substantially use a dispersant or other photocurable resin, it is possible to increase the content ratio of the coloring material. It becomes. The content ratio of the coloring material can be 35.5 parts by weight or more with respect to 100 parts by weight of the total solid content of the photosensitive resin composition, and in a more preferable aspect, 37.5 parts by weight or more. be able to. Thereby, the color purity of a colored layer can be improved more. Further, from the viewpoint of curability of the colored layer and the prevention of the generation of voids, the content of the coloring material with respect to 100 parts by weight of the total solid content of the photosensitive resin composition is preferably 44.4 parts by weight or less. 42.8 parts by weight or less, more preferably 41.2 parts by weight or less.

<Photopolymerization initiator>
In the present invention, as the photopolymerization initiator, an agent that generates an appropriate active species is appropriately selected and used in accordance with the reaction mode of the photocurable functional group of the multifunctional copolymer. Examples of the photopolymerization initiator include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, ketals. Compound, azo compound, peroxide, 2,3-dialkyldione compound, disulfide compound, thiuram compound, fluoroamine compound and the like are used.
Among them, 2-benzyl-2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one, 1-hydroxy-cyclohexyl- is one which starts and accelerates a polymerization reaction by irradiation with ionizing radiation in a small amount. Phenyl-ketone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferably used.
Any one of these may be used alone or in combination.

In the present invention, the content ratio of the photopolymerization initiator is not particularly limited, but is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition, and 5 to 15 parts by weight. More preferably, it is a part.
In addition, although the said photoinitiator usually hardly remains in the colored layer after hardening, the colored layer with which the color filter which concerns on this invention is equipped may contain the said photoinitiator or its decomposition product. It may be good, and it may contain more than 1% by weight in the colored layer.

<Solvent>
The photosensitive resin composition according to the present invention may contain a solvent in order to disperse the coloring material. The solvent used in the photosensitive resin composition is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive resin composition and can dissolve or disperse them. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl Ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Le acetate, dipropylene glycol, can be used diethylene glycol monobutyl ether acetate and the like.
What is necessary is just to set content of the said solvent suitably. For example, it is usually preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the resin composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

<Other ingredients>
The colored layer of the present invention is a colored layer containing only 1% by weight or less of a component different from the cured product of the multifunctional copolymer, the colorant, and the photopolymerization initiator or a decomposition product thereof.
In addition, the photosensitive resin composition for a color filter according to the present invention contains only 1% by weight or less of a component different from the multifunctional copolymer, the color material, and the photopolymerization initiator in the total solid content. There is nothing.
The cured product of the multifunctional copolymer in the colored layer, the coloring material, a component different from the photopolymerization initiator or its decomposition product, and the multifunctional copolymer in the resin composition, the coloring material And a component different from the photopolymerization initiator may be contained in the colored layer and the resin composition in a total solid content of 1% by weight or less, respectively. Preferably, it does not contain a colorant dispersant different from the polymer, preferably does not contain a curable resin different from the multifunctional copolymer, and contains an alkali-soluble resin different from the multifunctional copolymer. It is preferably not included.
Examples of the component different from the multifunctional copolymer or its cured product and the coloring material and the photopolymerization initiator or the decomposition product thereof include, for example, a dispersant, an alkali-soluble resin different from the multifunctional copolymer, In addition to the curable resin, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, and the like can be given.

  In addition, the weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the colored layer is 0.55 or more from the viewpoint that high color purity can be achieved. It is preferable that it is 0.60 or more. From the viewpoint of film physical properties in the colored layer, the weight ratio (P / V) of the color material (P) to the weight of all components (V) is preferably 0.8 or less.

<Method for forming colored layer>
The colored layer is usually formed in an opening of a light shielding layer on a transparent substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily. In the present invention, since the colored layer can cope with high definition as described above, even when the width of the colored layer is 20 to 40 μm and a fine line, variation in the width is suppressed and linearity is increased, which is preferably used. It is done.

The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive resin composition, but is usually preferably in the range of 1 to 5 μm.
In the present invention, since the weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the colored layer can be increased, the film thickness is 1.5 μm. A colored layer with high color purity can be achieved with the following colored layers.

  For example, in order to achieve a color space having a wide color gamut, in particular, the green pixel of the color filter has a high color density of green chromaticity (x = 0.20 to 0.30, y = 0.60. However, the chromaticity can be realized with a film thickness of 1.6 μm or less.

The colored layer can be formed, for example, by the following method.
First, the above-described photosensitive resin composition for a color filter of the present invention is applied on a transparent substrate to be described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Then, a wet coating film is formed.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, and the multifunctional copolymer is subjected to a photopolymerization reaction to be exposed to light. The coating film of the conductive resin composition. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the photosensitive resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Light shielding layer)
The light shielding layer in the color filter of the present invention is formed in a pattern on a transparent substrate to be described later, and can be the same as that used as a light shielding layer in a general color filter.
The pattern shape of the light shielding layer is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light shielding layer include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. This metal thin film may be a laminate of a CrOx film (x is an arbitrary number) and a Cr film, or a CrOx film (x is an arbitrary number) with a reduced reflectance, CrNy A film (y is an arbitrary number) and three layers of Cr films may be laminated.

  In the present invention, since it is difficult to form a cavity between the colored layer and the light shielding layer, the line width of the light shielding layer can be 5 μm or less, and is preferably 4 to 5 μm. By setting the line width of the light shielding layer to 5 μm or less, a high-luminance color filter having a large opening can be obtained.

  The thickness of the light shielding layer is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

In the transparent substrate provided with the light shielding layer, the light shielding layer is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding layer in a general color filter.
When using a printing method or an inkjet method as a method for forming the light shielding layer, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, Examples thereof include a polyvinyl chloride resin, a melamine resin, a phenol resin, an alkyd resin, an epoxy resin, a polyurethane resin, a polyester resin, a maleic acid resin, and a polyamide resin.

  In the above case, when a photolithography method is used as a method for forming the light shielding layer, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the photosensitive resin composition for the light-shielding layer containing the black colorant and the photosensitive resin, and further, if necessary, a sensitizer, a coating property improver, A development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be added.

  On the other hand, when the light-shielding layer is a metal thin film, the light-shielding layer can be formed by any method that can pattern the light-shielding layer, and is not particularly limited. For example, photolithography and vapor deposition using a mask. Method, printing method and the like.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.

(Overcoat layer)
The color filter of the present invention preferably further has an overcoat layer. By having an overcoat layer, the colored layer can be more firmly fixed and further protected.
The overcoat layer is required to have a wide range of properties such as transparency, surface smoothness, adhesion to upper and lower adjacent layers, light resistance, heat resistance, and chemical resistance. For example, a high electric resistance light or thermosetting acrylic resin, urethane resin, polyglycidyl methacrylate resin, epoxy resin and the like can be used. The overcoat layer can be formed by a conventionally known method.

  Furthermore, the color filter of the present invention has a conventionally known configuration such as a transparent electrode layer, an alignment film, and a columnar spacer in addition to the transparent substrate, the light shielding layer, the colored layer, and the overcoat layer. May be.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 3, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 3, and can generally have a known configuration as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 4 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 4, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 4, and can generally have a known configuration as an organic light emitting display device using a color filter.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of multifunctional copolymer 1)
In the polymerization tank, 40 parts by weight of 3,4,5,6-tetrahydrophthalimidoethyl acrylate (THPI-AA), 19 parts by weight of benzyl methacrylate (BzMA), 19 parts by weight of acrylic acid (AA), propylene glycol monomethyl ether Acetate (PGMEA) was added in an amount twice the weight of the monomer, stirred and dissolved, and then 2,2′-azobis (2-methylbutyronitrile) (AMBN) was added in an amount of 10% by weight based on the weight of the monomer. % Was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. Further, 22 parts by weight of glycidyl methacrylate (GMA), 10% by weight of triethylamine (TEA) with respect to parts by weight of GMA, 1% by weight of hydroquinone (HQ) with respect to the weight of GMA, and a monomer charged into the obtained solution And PGMEA were added so that the combined weight of GMA and GMA would be 35% by weight, and the mixture was stirred at 100 ° C. for 5 hours to obtain the desired multifunctional copolymer 1 solution (solid content concentration 31.3% by weight). It was.
The copolymer obtained had an acid value of 67 mgKOH / g, a hydroxyl value of 86 mgKOH / g, and a polystyrene-reduced weight average molecular weight Mw of 9200 by gel permeation chromatography.
The obtained copolymer solution was adjusted to a solid content concentration of 30% by weight with PGMEA and then used for the preparation of a colorant dispersion and the like.

(Synthesis Example 2: Synthesis of Multifunctional Copolymer 2)
The raw material initially charged in the reactor was changed as shown in Table 1, and the multifunctional co-polymer was prepared in the same manner as in Synthesis Example 1 except that diethylene glycol dimethyl ether was used as a polymerization solvent in an amount twice as much as the weight part of the monomer. A polymer 2 solution was obtained. In addition, THPI-MA in Table 1 represents 3,4,5,6-tetrahydrophthalimidoethyl methacrylate.

(Production Example 1-1: Preparation of colorant dispersion)
50 parts by weight of the multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight), C.I. I. 30 parts by weight of Pigment Red 254 (PR254) and 220 parts by weight of PGMEA were mixed, 500 parts by weight of zirconia beads having a diameter of 0.3 mm were added, and dispersed for 4 hours using a paint shaker (manufactured by Asada Steel Corporation). 1 color material dispersion (solid content 15% by weight) was prepared.

(Production Examples 1-2 to 1-8: Preparation of colorant dispersion)
Except having used what was shown in Table 2 instead of PR254 as a color material, it carried out similarly to manufacture example 1-1, and obtained the color material dispersion liquid of manufacture example 1-2 to 1-8.

(Production Examples 2-1 to 2-8: Preparation of colorant dispersion)
Instead of the multifunctional copolymer 1 solution (solid content: 30% by weight), the multifunctional copolymer 2 solution (solid content: 30% by weight) obtained in Synthesis Example 2 above was used, and Table 2 was used as a coloring material. Except having used what is shown to manufacture the coloring material dispersion liquid of manufacture example 2-1 to 2-8 like manufacture example 1-1.

(Comparative Production Example 1: Preparation of colorant dispersion)
50 parts by weight of the multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight), C.I. I. 30 parts by weight of Pigment Red 254 (PR254), 15 parts by weight of a dispersant (Ajisper PB821, manufactured by Ajinomoto Co., Inc., solid content: 40% by weight, solvent: PGMEA) and 245 parts by weight of PGMEA were mixed, and zirconia beads having a diameter of 0.3 mm were mixed. 500 parts by weight was added and dispersed for 4 hours using a paint shaker (manufactured by Asada Steel Corporation) to prepare a colorant dispersion (solid content 15% by weight) of Comparative Production Example 1.

(Comparative Production Examples 2 to 8: Preparation of colorant dispersion)
Instead of PR254, instead of PR254, PR177 is used in Comparative Production Example 2, PY139 is used in Comparative Production Example 2, PG58 is used in Comparative Production Example 4, PY138 is used in Comparative Production Example 5, and Comparative Production Example 6 is used. In the same manner as Comparative Production Example 1 except that PY150 was used, PB15: 6 was used in Comparative Production Example 7, and PV23 was used in Comparative Production Example 8, the colorant dispersions of Comparative Production Examples 2 to 8 were obtained. It was.

Example 1
The color filter of Example 1 was produced according to the following procedure.
(1) Formation of light shielding layer
First, 500 parts by weight of zirconia beads having a diameter of 0.3 mm were added to the following components, and dispersed for 4 hours using a paint shaker (manufactured by Asada Steel Corporation) to prepare a black pigment dispersion.

<Composition of black pigment dispersion>
-Titanium black pigment: 30 parts by weight-Dispersant (Azisper PB821, Ajinomoto Co., Inc., solid content: 40% by weight, solvent: PGMEA): 15 parts by weight-Multifunctional copolymer 1 solution obtained in Synthesis Example 1 (Solid content 30% by weight): 50 parts by weight PGMEA: 205 parts by weight

Next, the following components were sufficiently mixed to obtain a photosensitive shading composition.
<Composition of photosensitive shading composition>
-Black pigment dispersion liquid: 72 parts by weight-Dipentaerythritol pentaacrylate: 5.87 parts by weight-2-Benzyl-2-dimethylamino-1- (4'-morpholinophenyl) butan-1-one: 3 .31 parts by weight PGMEA: 120 parts by weight

The photosensitive shading composition is applied onto a glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 55 cm × 65 cm using a spin coater, and prebaked on a hot plate at 90 ° C. for 3 minutes. A 1.2 μm coating film was formed. Next, after cooling the substrate to room temperature, the coating film was irradiated with ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 50 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was developed with a swing type developing machine using a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with pure water for 1 minute, and dried. Thereafter, the substrate was post-baked in a clean oven at 230 ° C. for 30 minutes to form a 5 μm line-and-space light-shielding layer in the region where the light-shielding layer was to be formed on the substrate.

(2) Preparation of red pixel The photosensitive red resin composition 1 was obtained by stirring and mixing each component mix | blended with the following composition at room temperature.
<Composition of photosensitive red resin composition 1>
-PR254 color material dispersion of Production Example 1-1 (solid content 15 wt%): 30 parts by weight-PR177 color material dispersion of Production Example 1-2 (solid content 15 wt%): 110 parts by weight-Production Example 1 -3 PY139 colorant dispersion (solid content 15% by weight): 30 parts by weight. Multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight): 55 parts by weight. 2-Benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 3.3 parts by weight PGMEA: 70 parts by weight P / V ratio: 0.60

The photosensitive red resin composition 1 was applied onto a substrate on which a light-shielding layer was formed with a spin coater, and pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film. Next, after cooling the substrate to room temperature, the coating film was irradiated with ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 50 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was developed with a swing type developing machine using a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with pure water for 1 minute, and dried. Thereafter, the substrate was post-baked in a clean oven at 230 ° C. for 30 minutes to produce a pixel array in which red pixel patterns having a final film thickness of 1.41 μm were arranged on the substrate.

(3) Preparation of green pixel The photosensitive green resin composition 1 was obtained by stirring and mixing each component mix | blended with the following composition at room temperature.
<Composition of photosensitive green resin composition 1>
-PG58 color material dispersion of Production Example 1-4 (solid content 15 wt%): 180 parts by weight-PY138 color material dispersion of Production Example 1-5 (solid content 15 wt%): 20 parts by weight-Production Example 1 -6 PY150 colorant dispersion (solid content 15% by weight): 40 parts by weight. Multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight): 70 parts by weight. 2-Benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 5.0 parts by weight PGMEA: 30 parts by weight P / V ratio: 0.63

A pixel array in which a green pixel pattern having a final film thickness of 1.53 μm is arranged in the same manner as the red pixel pattern except that the photosensitive green resin composition 1 is used instead of the photosensitive red resin composition 1. Produced.

(4) Production of blue pixel The photosensitive blue resin composition 1 was obtained by stirring and mixing each component mix | blended with the following composition at room temperature.
<Composition of photosensitive blue resin composition 1>
-PB15 of Production Example 1-7: 6 color material dispersion (solid content 15 wt%): 180 parts by weight-PV23 color material dispersion of Production Example 1-8 (solid content 15 wt%): 5 parts by weight-Synthesis 1. Multifunctional copolymer 1 solution of Example 1 (solid content 30% by weight): 60 parts by weight 2-benzyl-2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 2. 9 parts by weight PGMEA: 75 parts by weight P / V ratio: 0.61

  A pixel array in which blue pixel patterns having a final film thickness of 1.38 μm are arranged in the same manner as the red pixel pattern except that the photosensitive blue resin composition 1 is used instead of the photosensitive red resin composition 1. Produced.

(Example 2)
The photosensitive red resin composition 2 having the following composition is used in place of the photosensitive red resin composition 1 used for producing the red pixel, and the following composition is used instead of the photosensitive blue resin composition 1 used for producing the blue pixel. Except that the photosensitive blue resin composition 2 was used and the photosensitive green resin composition 2 having the following composition was used in place of the photosensitive green resin composition 1 used for producing the green pixel, the same procedure as in Example 1 was performed. Thus, a color filter of Example 2 was produced. In the color filter of Example 2, the final film thickness of the red pixel pattern was 1.39 μm, the final film thickness of the blue pixel pattern was 1.37 μm, and the final film thickness of the green pixel pattern was 1.51 μm. .

<Composition of photosensitive red resin composition 2>
-PR254 color material dispersion of Production Example 2-1 (solid content 15 wt%): 100 parts by weight-PR177 color material dispersion of Production Example 2-2 (solid content 15 wt%): 30 parts by weight-Production Example 2 -3 PY139 colorant dispersion (solid content 15% by weight): 20 parts by weight. Multifunctional copolymer 2 solution of Synthesis Example 2 (solid content 30% by weight): 44 parts by weight. 2-Benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 3.1 parts by weight PGMEA: 65 parts by weight P / V ratio: 0.63

<Composition of photosensitive green resin composition 2>
-PG58 color material dispersion of Production Example 2-4 (solid content 15 wt%): 150 parts by weight-PY138 color material dispersion of Production Example 2-5 (solid content 15 wt%): 10 parts by weight-Production Example 2 -6 PY150 colorant dispersion (solid content 15% by weight): 15 parts by weight. Multifunctional copolymer 2 solution of Synthesis Example 2 (solid content 30% by weight): 60 parts by weight. 2-Benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 4.8 parts by weight PGMEA: 68 parts by weight P / V ratio: 0.62

<Composition of photosensitive blue resin composition 2>
-PB15 of Production Example 2-7: 6 color material dispersion (solid content 15 wt%): 150 parts by weight-PV23 color material dispersion of Production Example 2-8 (solid content 15 wt%): 0 parts by weight-Synthesis Multifunctional copolymer 2 solution of Example 2 (solid content 30% by weight): 45 parts by weight 2-benzyl-2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 2. 8 parts by weight PGMEA: 80 parts by weight P / V ratio: 0.63

(Comparative Example 1)
The comparative photosensitive red resin composition 1 having the following composition is used in place of the photosensitive red resin composition 1 used for producing the red pixel, and the following composition is used in place of the photosensitive blue resin composition 1 used for producing the blue pixel. Example 1 except that the comparative photosensitive green resin composition 1 was used and the comparative photosensitive green resin composition 1 having the following composition was used in place of the photosensitive green resin composition 1 used for the production of a green pixel. In the same manner, a color filter of Comparative Example 1 was produced. When the chromaticity is matched with Example 1, the color filter of Comparative Example 1 has a red pixel pattern with a final film thickness of 2.8 μm, a blue pixel pattern with a final film thickness of 2.7 μm, and a green pixel pattern. The final film thickness was 3.3 μm.

<Composition of Comparative Photosensitive Red Resin Composition 1>
-PR254 color material dispersion of Comparative Production Example 1 (solid content 15 wt%): 30 parts by weight-PR177 color material dispersion of Comparative Production Example 2 (solid content 15 wt%): 110 parts by weight-Comparative Production Example 3 PY139 colorant dispersion (solid content 15% by weight): 30 parts by weight. Multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight): 60 parts by weight. Photocurable monomer (TO-1382, Toa Gosei Co., Ltd.): 4 parts by weight 2-benzyl-2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 4 parts by weight PGMEA: 85 parts by weight P / V Ratio: 0.41

<Composition of Comparative Photosensitive Green Resin Composition 1>
-PG58 color material dispersion of Comparative Production Example 4 (solid content 15 wt%): 180 parts by weight-PY138 color material dispersion of Comparative Production Example 5 (solid content 15 wt%): 20 parts by weight-of Comparative Production Example 6 PY150 colorant dispersion (solid content 15% by weight): 40 parts by weight. Multifunctional copolymer 1 solution of Synthesis Example 1 (solid content 30% by weight): 60 parts by weight. Photocurable monomer ((TO-1382 Toa Gosei Co., Ltd.): 15 parts by weight 2-Benzyl-2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 5.8 parts by weight PGMEA: 35 parts by weight P / V ratio: 0.40

<Composition of Comparative Photosensitive Blue Resin Composition 1>
-Comparative production example 7 PB15: 6 color material dispersion (solid content 15 wt%): 180 parts by weight-PV23 color material dispersion liquid of comparative production example 8 (solid content 15 wt%): 5 parts by weight-Synthesis example 1 Multifunctional copolymer 1 solution (solid content 30% by weight): 50 parts by weight. Photocurable monomer (TO-1382, manufactured by Toagosei Co., Ltd.): 8 parts by weight. 2-Benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one: 3.1 parts by weight PGMEA: 90 parts by weight P / V ratio: 0.44

(Evaluation)
(1) Measurement of xy chromaticity coordinates The xy chromaticity coordinates in the XYZ color system of CIE were measured for the spectrum of each pixel pattern obtained in Examples 1-2 and Comparative Example 1 using a C light source. The results are shown in Table 3.

(2) Evaluation of presence / absence of voids For the color filters obtained in Examples 1 and 2 and Comparative Example 1, the glass substrate was cut vertically with respect to the line & space of the pixel pattern, and a cross-sectional photograph from right side and diagonally above Was photographed with a scanning electron microscope, and the presence or absence of a cavity between the light shielding layer and the colored layer was confirmed. The image was taken at a magnification of 10,000 times straight and 5,000 times diagonally above. Table 3 shows the presence or absence of cavities.

(Summary of results)
In the color filters obtained in Examples 1 and 2, the colored layers each include a cured product of a specific multifunctional copolymer and a coloring material, and are separately provided as components different from these and a photopolymerization initiator or a decomposition product thereof. Since a dispersant and a photocurable resin are not included, no void was generated between the light shielding layer and the colored layer even when the line width of the light shielding layer was as thin as 5 μm. In addition, a high-quality color filter corresponding to high definition could be obtained with little residue after alkali development, excellent linearity of the colored layer, and high definition. In the color filters obtained in Examples 1 and 2, the thickness of each colored layer was thin, and the color density was large and the color reproduction range was wide while corresponding to thinning.
On the other hand, the colored layer of the color filter obtained in Comparative Example 1 corresponds to the example of Patent Document 1, and the dispersant and photocurability are further added to the colored layer of the color filter obtained in Example 1. It contains a resin. If the target chromaticity is the same, the final film thickness of each pixel pattern formed in Comparative Example 1 becomes thicker than that in Example 1, and in each pixel pattern, between the light shielding layer and the colored layer. There was a cavity.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding layer 3 (3R, 3B, 3G) Colored layer 10 Color filter 11 Exposure light 13 Photomask 14 Coating film of photosensitive resin composition 15 Cured coating film 16 Colored layer 17 Cavity generated by development 18 Cavity 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (7)

  A color filter comprising at least a transparent substrate, a light-shielding layer and a colored layer provided on the transparent substrate, each of the colored layers having a colorant-adsorbing functional group, and an ethylenically unsaturated bond A cured product of a multifunctional copolymer having a structural unit having a containing group, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5000 to 1000000, and a coloring material, A colored layer comprising a colored layer containing only 1% by weight or less of a component different from the cured product of the multifunctional copolymer, the coloring material, and the photopolymerization initiator or a decomposition product thereof, filter.   2. The color according to claim 1, wherein a weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the colored layer is 0.55 or more. filter.   The color filter according to claim 1, wherein a line width of the light shielding layer is 5 μm or less.   A structural unit having a colorant-adsorbing functional group and a structural unit having an ethylenically unsaturated bond-containing group, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5000 to 1000000 1% by weight of a component different from the multifunctional copolymer, the colorant, and the photopolymerization initiator in the total solid content, including a functional copolymer, a colorant, and a photopolymerization initiator A photosensitive resin composition for a color filter containing only the following.   The color according to claim 4, wherein the weight ratio (P / V) of the color material (P) to the weight of all components (V) other than the color material in the total solid content is 0.55 or more. Photosensitive resin composition for filters.   A liquid crystal display device comprising: the color filter according to claim 1; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   An organic light emitting display device comprising the color filter according to claim 1 and an organic light emitter.