JP2010146012A - Radiation sensitive color filter composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive color filter composition which has excellent coatability, wide latitude for development and excellent process allowability and avoids failure in coating, such as a mark of a chuck. <P>SOLUTION: The radiation sensitive color filter composition contains a radiation-sensitive component, a binder resin, a nonionic surfactant selected from the group consisting of compounds represented by general formula (G), (H) or (J), a pigment and a solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for a radiation-sensitive color filter suitable for producing a color filter used in a liquid crystal display device or a solid-state imaging device. From another viewpoint, the present invention has excellent coating properties and wide development latitude. The present invention relates to a radiation-sensitive color filter composition having excellent properties.

  Color filters are indispensable components for liquid crystal panels. Compared to CRT as a display device, it is compact and has the same or better performance, and is replacing CRT as a display device for TV screens, personal computer screens, and others. However, liquid crystal display devices are expensive, and in order to overcome the competition with CRTs, it is essential to make them inexpensive.

  In order to reduce the price of the liquid crystal display device, in addition to reducing the price of each component such as a color filter and a glass substrate, an improvement in yield without causing defective products is required. In the case of a color filter, it is indispensable to further reduce the amount of color resist coating solution. In addition, improving the yield of color filter manufacturing can be one means of reducing the price. In order to improve the yield, it is necessary to manufacture more color filters in one process. Specifically, a large color filter is manufactured by applying a color resist on a larger substrate. Then, it can be performed by cutting into a desired size. However, if the amount of the coating liquid is reduced as it is or coating is performed on a large substrate, coating unevenness occurs. Most of the coating unevenness is thickness unevenness, and in order to overcome this, it is necessary to improve the fluidity of the liquid and make it difficult for the coating unevenness to occur even with a small amount of liquid. As a means for improving the fluidity of the coating solution, the viscosity of the coating solution is generally lowered by lowering the molecular weight of the polymer or increasing the solubility in a solvent. However, simply lowering the viscosity is a problem in that uneven thickness tends to occur at the center and the periphery of the coated substrate.

  In this way, in order to reduce the amount of color resist coating solution and improve yield, even if the amount of coating solution is small or even when applied to a large substrate, it can be applied uniformly on the substrate without thickness unevenness. Is required.

  Further, color resists are generally required to have a wide range of appropriate development time in development performed after exposure, that is, wide development latitude and excellent process tolerance. However, as the area to be processed at the same time or the display panel becomes larger as described above, the time difference immersed in the developer at the top and the end of the substrate increases, and the development time varies. For this reason, since the development unevenness is enlarged and the pattern size is different, a color resist having a wider development latitude is demanded.

  An object of the present invention is to provide a composition for a radiation-sensitive color filter which is excellent in coating properties and has a wide development latitude and excellent process tolerance. In addition, when applying spinner to a glass substrate, in order to resist the centrifugal force of securing / rotating the flatness of the glass substrate, vacuum suction is applied to the coating stage through a slit or ring-shaped hole (chuck) on the coating stage. It is necessary to fix them. However, suction marks may remain on the dried substrate. This is the chuck mark. A further object of the present invention is to provide a composition for a radiation sensitive color filter which is excellent in coating property, has a wide development latitude, is excellent in process tolerance, and does not cause coating failure such as chuck marks.

According to the present invention, a radiation-sensitive color filter composition having the following constitution is provided to achieve the above object.
(1) (a) a radiation sensitive component, (b) a binder resin, (c ′) at least one selected from the group of compounds represented by the following general formulas (G), (H) and (J) A radiation-sensitive color filter composition comprising a nonionic surfactant, (d) a pigment, and (e) a solvent.

In the formula: Styryl represents ph-CH = CH-. Here, ph is a phenyl group. benzyl is, ph-CH ₂ - represents a. Here, ph is a phenyl group. PO represents propylene oxide. EO represents ethylene oxide. p represents 2 or 3, r represents 5 to 25, s represents 8 to 30, and t represents an integer of 3 to 20, respectively. (PO / EO) q is the coexistence of the above PO and EO, and the presence ratio (molar ratio) of PO and EO is in the range of 0/10 to 10/1, and q represents the total number of PO and EO. , Represents an integer of 5-20. R ₁ or R ₂ each independently represents a hydrocarbon group having 1 to 19 carbon atoms.
(2) (c ′) The radiation-sensitive color as described in (1) above, wherein the nonionic surfactant is at least one selected from the compounds represented by the following (i) to (iii): Filter composition.
(I) In the general formula (G), p is 3, an integer of 7 to 15, and (PO / EO) q is an abundance ratio (molar ratio) of PO and EO of 1/5 to 1/1. The compound which exists in a range and q represents the integer of 6-15.
(Ii) A compound in which p is 3 and s is an integer of 10 to 20 in the general formula (H).
(Iii) A compound in which t is an integer of 3 to 15 in the general formula (J).
(3) The radiation-sensitive color as described in (1) or (2) above, wherein the content of the nonionic surfactant is 0.05 to 2% by mass with respect to the total mass of the composition. Filter composition.
(4) (d) The pigment content is 25% by mass or more based on the solid material content, and the total solid content is 20% by mass or more based on the total mass of the composition. The composition for a radiation sensitive color filter according to any one of (1) to (3).
(5) (b) The binder resin is an acrylic copolymer having an acid value in the range of 20 to 100 and a hydroxyl value in the range of 30 to 100. (4) The composition for radiation sensitive color filters according to any one of (4).

The radiation-sensitive color filter composition of the present invention is excellent in coating property even at high pigment concentration and high solid content concentration, has wide development latitude and excellent process tolerance, and can also prevent chuck marks. In addition, the entire surface of the substrate can be applied with a small amount of coating liquid. Therefore, from the composition of the present invention, a color filter used for a liquid crystal display device or a solid-state imaging device can be produced with high process quality and low cost with little process difficulty.

Hereinafter, the compounding component used for the composition for radiation sensitive color filters of this invention and the usage method of this composition are demonstrated.
The radiation-sensitive color filter composition of the present invention for forming a color filter comprises (a) a radiation-sensitive component, (b) a binder resin, (c ′) a nonionic surfactant having a specific structure, (d ) A pigment, and (e) a solvent.

[I] (a) Radiation-sensitive component Examples of the radiation-sensitive component used in the composition of the present invention include the following (A), (B) and (C).
(A) A compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure, having at least one addition-polymerizable ethylene group.
(B) at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, and a 3-aryl-substituted coumarin compound. (C) At least one lophine dimer. Here, (b) and (c) are photopolymerization initiators and have a function of polymerizing a polymerization component of a radiation sensitive component by light irradiation. Accordingly, (a) the radiation-sensitive component preferably contains at least one of (b) and (c).

  Examples of the compound (b) having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) A , Tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B-49-43191 and JP-B-52-30490 I can list them. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can be used as component (a).

If the radiation-sensitive color filter composition of the present invention is capable of forming a coating film having adhesiveness upon irradiation with radiation, these radiation-polymerizable monomers or oligomers are within a range that does not impair the purpose and effect of the present invention. Can be used in any proportion. The amount used is 5 to 90% by mass, preferably 10 to 50% by mass, based on the total solid content of the radiation-sensitive color filter composition. Here, the total solid content refers to the remaining components obtained by removing the solvent from all the components constituting the composition.

Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine (b), the halomethyloxadiazole compound is represented by the following general formula IV described in JP-B-57-6096. -Halomethyl-5-vinyl-1,3,4-oxadiazole compounds.

  In general formula IV: W represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom, an alkyl group or an aryl group. Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents an integer of 1 to 3. Specific compounds of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4- Examples include oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole. As a photopolymerization initiator of the halomethyl-s-triazine compound, a vinyl-halomethyl-s-triazine compound represented by the following general formula V described in JP-B-59-1281, JP-A-53-133428, is disclosed. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VI and 4- (p-aminophenyl) -2 represented by the following general formula VII , 6-di-halomethyl-s-triazine compound.

In general formula V: Q represents Br or Cl. P is, -CQ ₃ (Q is as defined _{above), - NH 2, -NHR,} -N (R) 2, or -OR (wherein, R represents a phenyl or alkyl group). W represents an aromatic group which may be substituted, a heterocyclic group which may be substituted, or a monovalent group represented by the following general formula VA.

  In the general formula VA, Z is —O— or —S—, and R is as defined above.

  In general formula VI: X represents Br or Cl. m and n are integers of 0-3. R ′ represents a group represented by the following general formula VIA.

(In the general formula VIA, R ₁ represents a hydrogen atom or ORc (Rc represents an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group.)

In the general formula VII: R ₁ and R ₂ are the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by the following general formula VIIA or VIIB. R ₃ and R ₄ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y are the same or different and each represents Cl or Br. m and n are the same or different and represent 0, 1 or 2.

In the general formulas VIIA and VIIB, R ₅ , R ₆ and R _{7 each} represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of substituents in substituted alkyl groups and substituted aryl groups include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, etc. Is mentioned.

In the general formula VII, R ₁ and R ₂ may form a heterocycle consisting of a nonmetallic atom together with the nitrogen atom bonded thereto, and in this case, examples of the heterocycle include those shown below. It is done.

  Specific examples of general formula V include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl). And aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

  Specific examples of general formula VI include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-to Azine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy- Naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. Can be mentioned.

  Specific examples of the general formula VII include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p -N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p- N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Riazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N -Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) Aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro- p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m Chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p- N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -S-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-to Azine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, and the like.

  The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, benzothiazole compounds of benzanthrone like and Sho 51-48516 JP thereof.

  The 3-aryl-substituted coumarin compound in (b) is a compound represented by the following general formula VIII.

R ₈ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group), and R ₉ represents a hydrogen atom or a carbon atom. An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIIIA (preferably a methyl group, an ethyl group, a propyl group, a butyl group, a group represented by the general formula VIIIA, particularly preferably Represents a group represented by the general formula VIIIA). R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), or a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, Fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), C6-C10 aryl group (for example, phenyl group) which may be substituted, amino Represents a group, —N (R ₁₆ ) (R ₁₇ ), a halogen atom (eg Cl, Br, F). Preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, —N (R ₁₆ ) (R ₁₇ ), and Cl. R ₁₂ represents an optionally substituted aryl group having 6 to 16 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, cumyl group). Examples of the substituent include an amino group, —N (R ₁₆ ) (R ₁₇ ), an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), and 1 to 8 carbon atoms. Haloalkyl group (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, halogen atom (for example, Cl, Br, F). R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group). R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are bonded to each other to form a heterocyclic ring (for example, a piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.) together with a nitrogen atom. Also good. R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group). Group), an optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an amino group, N (R ₁₆ ) (R ₁₇ ), and a halogen atom (for example, Cl, Br, F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably, = O, = S, = C (CN) ₂ , and particularly preferably = O. R ₁₈ and R ₁₉ are the same or different and each represents a cyano group, —COOR ₂₀ , or —COR ₂₁ . R ₂₀ and R ₂₁ are each an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, A trifluoromethyl group and the like, and an optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group).

  Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.

  (C) Lophine dimer means 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.

  Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxy). Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

  In the present invention, other known compounds can be used in addition to the above initiators. Vicinal polykettle aldonyl compounds disclosed in US Pat. No. 2,367,660, α-disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatic acyloin substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallylimidazole dimers disclosed in US Pat. No. 3,549,367 / P-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / trihalomethyl- s-triazine compounds.

  The usage-amount of an initiator is 0.01 mass%-10 mass% of the total solid of the composition for radiation sensitive color filters, Preferably they are 1 mass%-8 mass%. When the amount of the initiator used is less than 0.01% by mass, the polymerization is difficult to proceed, and when it exceeds 10% by mass, the polymerization rate increases, but the molecular weight decreases and the film strength decreases.

(A) The radiation-sensitive component is preferably blended in the composition for a radiation-sensitive color filter in a proportion of 10 to 80% by mass, particularly 20 to 70% by mass, based on the total solid content of the composition.

[II] (b) Binder Resin As the binder resin, an acrylic copolymer as a binder resin having an acid value in the range of 20 to 100 and a hydroxyl value in the range of 30 to 100 is preferable. In the radiation-sensitive color filter composition of the present invention, as a preferred binder resin, the acid value is in the range of 20 to 100, preferably 25 to 70 (KOHmg / g polymer), and the hydroxyl value is 30 to 100, Preferably, an acrylic copolymer (hereinafter also referred to as “(b) acrylic binder resin”) in the range of 40 to 80 (KOH mg / g polymer) is used. By using an acrylic binder resin in combination with a (c ′) nonionic surfactant having a specific structure, which will be described in detail later, the radiation-sensitive color filter composition of the present invention has excellent coatability and is suitable for development. (Development latitude) has a synergistic effect of widening.When chuck marks are generated, (c ′) nonionic surfactant can be used to further prevent the generation of chuck marks. There is a result.

(B) The acrylic binder resin is an acrylic copolymer that satisfies the above acid value and hydroxyl value, dissolves in the solvent (e) described later, and forms a film and functions as a binder resin. It can be used without any particular limitation.

  As a structural unit of the preferred (b) acrylic binder resin, a copolymer of (meth) acrylic acid, a hydroxy group-containing (meth) acrylate, and another monomer copolymerizable with these monomers is used. Can be mentioned. Preferred hydroxy group-containing (meth) acrylates include hydroxyalkyl acrylates and hydroxyaryl acrylates. The alkyl group of the hydroxyalkyl acrylate preferably has 2 to 12 carbon atoms. The alkyl group may be linear, branched or cyclic, and the hydrogen atom may be substituted with a substituent. Examples of the substituent include an aryl group, a halogen group, a phenyl group, and an alkoxyl group. Specific examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexyl group, and a benzyl group. The aryl group of hydroxyaryl acrylate preferably has 6 to 12 carbon atoms. In the aryl group, the hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen group, a phenyl group, and an alkoxyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group, and a benzyl group. Particularly preferred hydroxy group-containing (meth) acrylates are hydroxyethyl (meth) acrylate, hydroxy n-propyl (meth) acrylate, and hydroxy n-butyl (meth) acrylate. The said hydroxy group containing (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.

  Examples of other monomers copolymerizable with (meth) acrylic acid and hydroxy group-containing (meth) acrylates include alkyl (meth) acrylates, aryl (meth) acrylates and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent. Examples of the substituent include the alkyl group and aryl group substituents described for hydroxyalkyl acrylate and hydroxyaryl acrylate. Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. it can. Other particularly preferred copolymerizable monomers are phenyl (meth) acrylate, benzyl acrylate, and styrene. These other copolymerizable monomers can be used singly or in combination of two or more.

  Particularly preferred (b) acrylic binder resin is at least one selected from (meth) acrylic acid and hydroxyethyl (meth) acrylate, hydroxy n-propyl (meth) acrylate, and hydroxy n-butyl (meth) acrylate. It is a copolymer of a monomer of a kind and at least one monomer selected from phenyl (meth) acrylate, benzyl acrylate, and styrene.

(B) The acrylic binder resin has an acid value in the range of 20 to 100 and 30 to 30 as described above.
It has a hydroxyl value in the range of 100. When at least one of the acid value and the hydroxyl value exceeds 100, (b) the acrylic binder resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, when it is too small, such as less than 20 or 30, the solubility in alkali is small and it takes too much time for development, which is not preferable. In addition, (b) the weight average molecular weight (polystyrene equivalent value measured by GPC method) of the acrylic binder resin is used to achieve a viscosity range that is easy to use in the process of applying a color resist, and the film strength is In order to ensure, it is preferable that it is 5,000-100,000, More preferably, it is 8,000-50,000.

(B) In order to make the acid value and hydroxyl value of the acrylic binder resin within the ranges specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer. Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized. (B) The acrylic binder resin can be produced, for example, by a known radical polymerization method. Those skilled in the art can easily set polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when producing (a) an acrylic binder resin by radical polymerization. You can also know the conditions experimentally.

  The amount of the (b) binder resin in the composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. (B) When the amount of the binder resin is less than 5% by mass, the film strength is lowered, and when it is more than 90% by mass, the acid content increases, so that it becomes difficult to control the solubility, and the pigment is relatively pigmented. Therefore, a sufficient image density cannot be obtained.

[III] (c ′) Nonionic surfactant The radiation-sensitive color filter composition of the present invention contains at least one nonionic surfactant selected from the group of compounds represented by the general formulas G to J. An agent is contained. As a result, the coating property of the color resist is improved, and coating unevenness and chuck traces are eliminated. The cause of the chuck trace is presumed to be that the temperature difference between the contact part and the non-contact part of the stage differs between the liquid and the substrate during the drying, resulting in uneven drying. One way to prevent this would be to prevent the liquid from leveling during drying. On the other hand, in order to prevent thickness unevenness, it is preferable that the liquid has good fluidity and smoothness when the liquid is spin or the like. That is, when large shear is applied to the liquid (when spinning), the fluidity is good, and when the shear is small (such as when stationary or dry), the fluidity is required to be small. For this reason, focusing on the selection of the binder resin and the surfactant as important factors, the present invention has been achieved.

  In addition, by adding a nonionic surfactant (c ′) having such a specific structure to the color resist, it plays a role of lowering the frictional force inside the liquid when shearing is applied. Improves film thickness uniformity by increasing fluidity. In addition, the surface tension of the liquid is lowered and the spreadability of the liquid on the substrate is improved.

    Hereinafter, the general formulas G to J will be further described.

(1) In the general formulas G, H and J; p is 2 or 3, preferably 3. r is an integer of 5 to 25, preferably 8 to 15. (PO / EO) q is such that the above-mentioned PO and EO coexist, and the existing ratio (molar ratio) of PO and EO is in the range of 0/10 to 10/1, preferably 2/8 to 5/5. q represents the total number of PO and EO, and represents an integer of 5 to 20, preferably 5 to 15. s is an integer of 8 to 30, preferably an integer of 15 to 25. t represents an integer of 3 to 20. R ₁ or R ₂ each independently represents a hydrocarbon group having 1 to 19 carbon atoms, preferably an alkyl group having 5 to 20 carbon atoms in total of R ₁ and R ₂ , and more preferably R ₁ and R _2. Each has 3 to 8 carbon atoms, and their total carbon number is 6 to 18.

In the general formulas (G) to (J), EO means ethylene oxide, PO means propylene oxide, and this propylene is — (CH ₂ ) ₃ —, —CH ₂ CH (CH ₃ ) —. Any of these are included.

In the above (c ′) nonionic surfactant, a preferable surfactant is the following compound (G1), (H1) or (J1).
(G1): In the general formula (G), p is an integer of 3 and r is an integer of 7 to 15, and (PO / EO) q is an abundance ratio (molar ratio) of PO and EO of 1/5 to 1/1. In which q represents an integer from 6 to 15.
(H1): A compound in which p is 3 and s is an integer of 10 to 25 in general formula (H).
(J1): A compound in which t is an integer of 3 to 15 in the general formula (J).

Further preferred (c ′) nonionic surfactants are the following compounds (G2), (H2) and (J2).
(G2): In general formula (G), p is 3, r is an integer of 7 to 15, and (PO / EO) q is a ratio of PO and EO (molar ratio) of 1/4 to 1/2. And q represents an integer of 10 to 15.
(H2): A compound in which p is 3 and s is an integer of 15 to 25 in the general formula (H).
(J2): A compound in which in formula (J), R ₁ and R ₂ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, and t is an integer of 5 to 15.

  These surfactants (c ′) can be used singly or in combination of two or more.

(C ′) The nonionic surfactant is preferably contained in the composition of the present invention in an amount of 0.01 to 1% by mass, more preferably 0.1 to 0.8% by mass with respect to the total mass of the composition. %.

[IV] (d) Pigment As the pigment that can be used in the present invention, various conventionally known inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals. Examples of organic pigments include those shown below by color index (CI) number, and carbon black.
CI Pigment Yellow: 11, 20, 24, 31, 53, 83, 86, 93, 99, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 151, 153 CI Pigment Orange: 36, 38, 43, 51, 55, 59, 61 CI Pigment Red: 9, 97, 105, 122, 123, 149, 150, 155, 154, 166, 168, 167, 185 C.I. 168, 171, 175, 176, 177, 180, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 254 C.I. Pigment Violet: 19, 23, 29, 30, 32, 37, 39, 40, 50 C.I.Pigment Blue: 1 2, 15, 15: 3, 15: 6, 16, 22, 60, 64, 66, CI Pigment Green: 7, 36, 37 C.I. Pigment Brown: 23, 25, 26, 28 C.I. Pigment Black: 1, 7

  Particularly preferable examples of these pigments can be listed below, but are not limited thereto.

  These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below. A red pigment and a yellow pigment or two or more red pigments may be mixed, and one or more yellow pigments may be further mixed and used. The general ratio of the mixing ratio is 100: 20 to 100: 60, but this range may be exceeded.

  A preferred ratio of the green pigment to the yellow pigment is 100: 20 to 100: 80, but a green pigment and a yellow pigment or two or more kinds of green pigments and two or more kinds of yellow pigments are used in combination. A general ratio of the mixing ratio is 100: 20 to 100: 60 for green: yellow, but it is possible to exceed this range.

  As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 was good. The mass ratio of the blue pigment to the purple pigment was 100: 50 better than 100: 5. If it is 100: 4 or less, the light transmittance from 400 nm to 420 nm cannot be suppressed, and the color purity cannot be increased. When the ratio is 100: 51 or more, the dominant wavelength becomes longer and the deviation from the NTSC target hue becomes large. In particular, the range of 100: 5 to 100: 20 is optimal.

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. Can be obtained. As the black matrix pigment, carbon, titanium carbon, iron oxide alone, or a mixture thereof is used, and carbon and titanium carbon are preferable.

  Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

  It is not easy to disperse pigments forming such aggregates in fine particles. Therefore, it is preferable to treat the pigment with various resins in advance. Examples of these resins include the above-described binder resins. As a processing method, there are a flushing process, a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, and the like. Among these, a flushing process or a kneading method using two or three roll mills is suitable for fine particle formation.

  The flushing treatment is usually a method in which an aqueous dispersion of a pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. According to this method, since the pigment is not dried, the aggregation of the pigment can be prevented and the dispersion becomes easy. In kneading with a two or three roll mill, the pigment and resin or resin solution are mixed, and then the pigment and resin are kneaded while applying a high shear (shearing force), thereby coating the pigment surface with the resin. , A method for treating pigments. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.

  In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be used conveniently. In the present invention, the processed pigment treated with the above-mentioned various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed. Further, a non-uniform lump in which the resin is gelled is not preferable. The colored dispersion thus obtained is mixed with a radiation-sensitive component and used for a radiation-sensitive color filter composition.

  The pigment concentration in the radiation-sensitive color filter composition of the present invention is preferably 25% by mass or more, more preferably 30 to 50% by mass, and particularly preferably 35 to 45% by mass with respect to the total mass of the solid. . The present invention is effective even when the pigment concentration is outside this range. The effect of the present invention is further exhibited when the total solid concentration of the composition of the present invention is 20% by mass or more, preferably 22 to 30% by mass with respect to the total mass of the composition. In the case of such a high pigment concentration and a high solid content concentration, the coating solution has a high viscosity and it has been difficult to perform uniform coating, but the composition of the present invention enables uniform coating.

[V] (e) Solvent Examples of the solvent used in preparing the radiation-sensitive color filter composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate , Methyl ethoxyacetate, ethyl ethoxyacetate,

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid ethyl,

  Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,

  Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xyle .

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

  These solvents may be used alone or in combination of two or more.

[VI] Other components The composition for a radiation-sensitive color filter of the present invention includes various additives as required, for example, a filler, a binder resin other than the above-mentioned (b) acrylic binder resin, and the above nonionic one. Surfactants other than surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended.

  In the composition of the present invention, the binder resin other than the above-mentioned (b) acrylic binder resin is usually 30 masses with respect to 100 mass parts of the acrylic binder resin as long as the achievement of the object of the present invention is not impaired. Part or less can be blended. As binder resins that can be blended, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, acid anhydrides to polymers having hydroxyl groups , Poly 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, alcohol-soluble nylon, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and epichlorohydrin Examples include polyether (phenoxy resin).

Further, in the composition of the present invention, a surfactant other than the nonionic surfactant is usually equal to or less than 100 parts by mass of the nonionic surfactant within a range that does not impair the achievement of the object of the present invention. Can be blended. As the surfactant that can be blended, many kinds of compounds can be used. For example, phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) , (Meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.),
Cationic surfactants such as W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, Nonionic surfactants such as polyethylene glycol distearate and sorbitan fatty acid ester; EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), MegaFuck F171, F172, F173 (Dainippon Ink), Florard FC430, FC431 ( Manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 Fluorosurfactants such as Asahi Glass; anionic surfactants such as W004, W005 and W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersants such as EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Geneca Corporation); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77 P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) and Isonetto S-20 (manufactured by Sanyo Chemical Industries, Ltd.) and the like. These compounds are often used as pigment dispersants.

  Specific examples of other additives include fillers such as glass and alumina; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Agent; 2, 2 Antioxidants such as thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol: 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro UV absorbers such as benzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

  In addition, when promoting the alkali solubility in the unirradiated part and further improving the developability of the composition of the present invention, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above, a thermal polymerization inhibitor is preferably added to the radiation-sensitive color filter composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol. Pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzo Imidazole and the like are useful.

[VII] Method of using the composition of the present invention The radiation-sensitive color filter composition of the present invention is prepared by mixing the above main components, and other optional components used as necessary, with a solvent, various mixers, dispersing It can be prepared by mixing and dispersing using a machine.

  The composition for radiation-sensitive color filter of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, roll coating, and the like to form a radiation-sensitive layer, and is exposed through a predetermined mask pattern. Then, a colored pattern is formed by developing with a developer. As the radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  As the substrate, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, and a photoelectric conversion element substrate used for a solid-state imaging device, for example, A silicon substrate etc. are mentioned. These substrates are generally formed with black stripes that isolate pixels.

  Any developer can be used as long as it dissolves the radiation-sensitive layer in the non-irradiated part, but does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.

  Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, An alkaline aqueous solution in which an alkaline compound such as pyrrole or piperidine is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

The acrylic binder resin component and surfactant component used in the following examples and comparative examples are as follows.
<Acrylic binder resin component>
Resin 1: Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 69/13/18), acid value 47, hydroxyl value 65, mass average molecular weight 20,000
Resin 2 (comparison): benzyl methacrylate / acrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 65/32/3), acid value 127, hydroxyl value 12, mass average molecular weight 30000
Resin 3: benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 55/13/32), acid value 49, hydroxyl value 120, mass average molecular weight 20000
Resin 4: Styrene / methacrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 80/10/10), acid value 53, hydroxyl value 53, mass average molecular weight 20000
Resin 6 (comparison): benzyl methacrylate / acrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 67.5 / 30 / 2.5), acid value 120, hydroxyl value 10, mass average molecular weight 50,000
Resin 7 (comparison): benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 54.5 / 13.5 / 32), acid value 50, hydroxyl value 120, mass average molecular weight 30,000
Resin 8: Styrene / methacrylic acid / hydroxyethyl methacrylate copolymer resin (molar ratio: 81.5 / 9.5 / 9), acid value 50, hydroxyl value 50, mass average molecular weight 30,000

<Surfactant component>
Surfactant E: Asahi Denka Co., Ltd., Pluronic TR702
Surfactant G: Polyethylene glycol, polymerization degree 300
Surfactant W1: Compound of general formula G, p = 3, (PO / EO) q: PO = 2, EO = 6, r = 10 (Takemoto Yushi Co., Ltd., trade name: D6112W)
Surfactant W2: Compound of general formula H, p is 3, and s is 10 (manufactured by Takemoto Yushi Co., Ltd., trade name: D6310)
Surfactant W3: Compound of general formula J, R ₁ is methyl group, R ₂ is —C ₈ H ₁₇ , t is 10 (product name: D1109S, manufactured by Takemoto Yushi Co., Ltd.)
Surfactant W4: Compound of general formula G, p = 1, (PO / EO) q: PO = 4, EO = 20, r = 4 (synthesized by conventional methods)
Surfactant W6: Compound of general formula H, p is 3 and s is 20 (manufactured by Takemoto Yushi Co., Ltd., trade name: D6320)

Reference example 1
・ Propylene glycol monomethyl ether acetate solution of the above resin (solid content 50%)
58 parts by mass I. Pigment Red 254 20 parts by mass, C.I. I. Pigment Yellow 139 8 parts by mass. Propylene glycol monomethyl ether acetate (solvent) 150 parts by mass was dispersed with a sand mill all day and night. Next, the following radiation-sensitive component, thermal polymerization inhibitor, and solvent were added.
Acrylate monomer (consisting of (1) below) 23 parts by mass (1) Hexaacrylate obtained by adding six ethylene oxides to dipentaerythritol. 4- [o-bromo-pN, N-di ( Ethoxycarbonyl) aminophenyl]
2,6-di (trichloromethyl) -S-triazine (photopolymerization initiator) 3 parts by mass, hydroquinone monomethyl ether (polymerization inhibitor) 0.01 part by mass, 3-ethoxyethylpropylene glycol acetate (solvent) 70 parts by mass After mixing each of the above components, 0.3% by mass of the surfactant E is added to these mixtures with respect to the total mass of the composition, and the mixture is filtered with a filter having a pore size of 5 μm. For the radiation-sensitive color filter of the present invention A composition (coating solution) was obtained.

Examples 10 to 14 and Comparative Example 3
In the above Reference Example 1, for the radiation-sensitive color filters of Examples 10 to 14 and Comparative Example 3, in the same manner as in Reference Example 1, except that the binder resin and the surfactant are respectively replaced with those shown in Table 1 below. A composition (coating solution) was prepared and evaluated for developability, coating property, and amount of coating solution used as follows. Furthermore, the following chuck marks were also evaluated. The results are shown in Table 1 below.

The resulting composition was evaluated for developability, coatability, and amount of coating solution used by the following methods.
(I) Developability: The coating solution was spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying was 1.5 μm, prebaked at 90 ° C. for 60 seconds, and then 200 mj with a mask having a line width of 20 μm. / cm ² exposure (illuminance is 20 mW / cm ² ), and development was performed at 30 ° C. with a 10% diluted solution of an alkali developer CD (manufactured by Fujifilm Orin). The development time was 10 seconds to 10 to 100 seconds. It was described in the table as the number of development seconds in which the line width remained stable.
(Ii) Coating property: 30 g of coating solution was dropped on the center of a glass substrate of 550 mm × 650 mm and spin-coated at 800 rpm. The coating unevenness was observed with a sodium lamp and the coating state of the edge of the glass substrate was visually observed, and the following two-stage evaluation was performed.
◯: No coating unevenness was observed.
X: The dripping trace was observed.
(Iii) Coating liquid usage: When a 25 to 40 g coating liquid was dropped onto a glass substrate of 550 mm × 650 mm in the center and spin-coated at 800 rpm, the determination was made based on the minimum liquid volume at which a part of the outermost edge was not applied.
(Iv) 30 g of each coating solution was dropped onto a glass substrate having a chuck mark of 550 mm × 650 mm in the center and spin-coated at 800 rpm. The applicator was a model SF-700G manufactured by Dainippon Screen Co., Ltd., and chucked at standard vacuum pressure. The chuck marks were visually observed with a sodium lamp and compared and evaluated according to the following criteria.
○: No chuck marks were seen.
X: A trace was visible on some chucks.
XX: Traces were visible on all chuck parts.

  The radiation-sensitive color filter composition of the present invention was excellent in any of developability, coatability, coating liquid usage, and further chuck trace.

Claims (5)

(A) radiation sensitive component, (b) binder resin, (c ′) at least one nonionic interface selected from the group of compounds represented by the following general formulas (G), (H) and (J) A radiation-sensitive color filter composition comprising an activator, (d) a pigment, and (e) a solvent.

In the formula: Styryl represents ph-CH = CH-. Here, ph is a phenyl group. benzyl is, ph-CH ₂ - represents a. Here, ph is a phenyl group. PO represents propylene oxide. EO represents ethylene oxide. p represents 2 or 3, r represents 5 to 25, s represents 8 to 30, and t represents an integer of 3 to 20, respectively. (PO / EO) q is the coexistence of the above PO and EO, and the presence ratio (molar ratio) of PO and EO is in the range of 0/10 to 10/1, and q represents the total number of PO and EO. , Represents an integer of 5-20. R ₁ or R ₂ each independently represents a hydrocarbon group having 1 to 19 carbon atoms. (C ′) The nonionic surfactant is at least one selected from the compounds represented by the following (i) to (iii): The composition for radiation-sensitive color filter according to claim 1 .
(I) In the general formula (G), p is 3, an integer of 7 to 15, and (PO / EO) q is an abundance ratio (molar ratio) of PO and EO of 1/5 to 1/1. The compound which exists in a range and q represents the integer of 6-15.
(Ii) A compound in which p is 3 and s is an integer of 10 to 25 in the general formula (H).
(Iii) A compound in which t is an integer of 3 to 15 in the general formula (J).   3. The composition for a radiation-sensitive color filter according to claim 1, wherein the content of the nonionic surfactant is 0.05 to 2% by mass with respect to the total mass of the composition.   (D) The pigment content is 25% by mass or more with respect to the solid substance amount, and the total solid content is 20% by mass or more with respect to the total mass of the composition. 4. The radiation-sensitive color filter composition according to any one of 3 above.   (B) The binder resin is an acrylic copolymer having an acid value in the range of 20 to 100 and a hydroxyl value in the range of 30 to 100. The composition for a radiation sensitive color filter as described in 2.