JP2016212347A - Manufacturing method of photosensitive composition for forming color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-soluble photosensitive composition that has good sensitivity, adhesion to a substrate, and resolution, has high contrast and excellent color reproducibility, and can be suitably used for forming a black matrix and a color filter of a liquid crystal display or the like.SOLUTION: There is provided a manufacturing method of an alkali-soluble photosensitive composition for forming a color filter containing a colorant (A), a radical polymerizable substance (B), and a radical initiator (C), the method including the steps of: performing cubical expansion of a mixture (X) of the colorant (A), radical polymerizable substance (B), and compressible fluid (F) to obtain a dispersing element (Y); and mixing the dispersing element (Y) with the radical initiator (C), wherein the content of a polymer (BP) in the radical polymerizable substance (B) is 5 wt.% or less based on the total weight of the radical polymerizable substance.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a photosensitive composition for forming a color filter used in a liquid crystal panel such as a liquid crystal display device, and the photosensitive composition. Specifically, the present invention relates to a method for producing an alkali-soluble photosensitive composition having good substrate adhesion and resolution, high contrast and excellent color reproducibility.

The color filter is an indispensable part for colorization of the liquid crystal display device. In the color filter, colored pixels of red (R), green (G), and blue (B) are arranged on a transparent substrate such as glass. Furthermore, a black shielding part (black matrix) is generally provided between the colored pixels in order to improve contrast and prevent malfunction caused by light of TFT elements provided on the counter substrate in the liquid crystal display device. It is.

As a method for forming the colored pixels (R, G, B) and the black matrix, a photolithography method that is excellent in terms of quality is generally used. Specifically, after a composition in which a colorant such as an organic pigment, a dye or a black pigment is uniformly dispersed or dissolved in a photosensitive resin component is applied on a substrate and dried, a predetermined pattern different for each color is applied. Exposure is performed through a photomask having Next, a pixel pattern is obtained by developing and heat-treating this with an alkali developer or the like. By repeating this process for the black matrix, R, G, and B, a color filter is formed.

  Conventionally, a metal chromium thin film having excellent dimensional accuracy and reliability has been used for the black matrix of the color filter. However, in recent years, a resin black matrix in which a black colorant is dispersed in a resin has been used from the viewpoint of environmental problems, low reflection, and low cost. Carbon black is most commonly used as the black colorant for these resin black matrices, but it has a problem of low light-shielding properties compared to metallic chromium.

  In order to improve the color reproducibility of the color filter and the light-shielding property of the black matrix, there is a method of increasing the content of the colorant in the resin, but in this case, it becomes difficult to disperse the colorant, and the pattern formability That is, there has been a problem that the resolution deteriorates (for example, Patent Document 1). For this reason, a material having good dispersibility and dispersion stability of the colorant and high resolution has been desired.

JP 2013-218347 A

    The present invention has been made in view of the problems as described above, and the object of the present invention is to provide good sensitivity, substrate adhesion and resolution, high contrast and excellent color reproducibility, liquid crystal display devices, and the like. An object is to provide an alkali-soluble photosensitive composition that can be suitably used for forming a black matrix or a color filter.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a method for producing a photosensitive composition containing a colorant (A), a radical polymerizable substance (B) and a radical initiator (C), and the colorant (A) and the radical polymerizable substance (B ) And the compressible fluid (F) are subjected to volumetric expansion to obtain a dispersion (Y), and a step of mixing the dispersion (Y) and the radical initiator (C). The alkali-soluble photosensitive composition for forming a color filter, wherein the content of the polymer (BP) of the reactive substance (B) is 5% by weight or less based on the total weight of the radical polymerizable substance (B) A photosensitive resin composition for forming a color filter, characterized by being obtained by this production method.

  The method for producing a photosensitive composition of the present invention has an effect that a color filter and a black matrix can be formed which have good sensitivity, adhesion to a substrate and resolution, high contrast and excellent color reproducibility.

FIG. 1 is a flowchart of an experimental apparatus used for producing a dispersion in the mixing method by line blending in the present invention.

The method for producing a photosensitive composition for forming a color filter of the present invention contains a colorant (A), a radical polymerizable substance (B), and a radical initiator (C) as essential components, and comprises the following steps (1) and (2).
Step (1): A step of obtaining a dispersion (Y) by volume expansion of a mixture (X) of a colorant (A), a radical polymerizable substance (B) and a compressive fluid (F),
Step (2): A step of mixing and homogenizing the dispersion (Y), the radical initiator (C), and if necessary, the radical polymerizable substance (B).

Hereinafter, specific embodiments of methods (1) and (2) in the method for producing a photosensitive composition for forming a color filter of the present invention will be described in detail.

The step (1) in the present invention is a step of obtaining a dispersion (Y) by volume expansion of a mixture (X) of a colorant (A), a radical polymerizable substance (B) and a compressible fluid (F). is there.

The compressible fluid (F) used in the present invention may be methane, ethylene, chlorofluorocarbon alternative, etc., but is preferably carbon dioxide from the viewpoint of safety and ease of handling, and more preferably liquid carbon dioxide, Subcritical carbon dioxide or supercritical carbon dioxide is preferred. In addition, a compressive fluid means the fluid compressed by the pressure more than normal pressure at normal temperature.

In the present invention, the mixture (X) is composed of at least a colorant (A), a radical polymerizable substance (B), and a compressible fluid (F). In the mixture (X), the colorant (A) exists as a solid, and the compressive fluid (F) is infiltrated into the solid, and the compressive fluid is volume-expanded inside the colorant. As a result of pulverizing and crushing A), a dispersion (Y) in which the fine colorant (A) is uniformly dispersed is produced.

In addition, the pressure when mixing the mixture with the compressive fluid (F) such as supercritical carbon dioxide, subcritical carbon dioxide, liquid carbon dioxide, etc., is sufficient to disperse the colorant (A) in the compressive fluid. The pressure is preferably 2 MPa or more, more preferably 4 MPa or more, still more preferably 6 MPa or more, and particularly preferably 8 MPa or more. From the viewpoint of equipment cost and operation cost, it is preferably 40 MPa or less. More preferably, it is 4-35 MPa, More preferably, it is 8-30 MPa, Most preferably, it is 8.5-25 MPa.

If the colorant (A) is present as a solid in the mixture, other media such as additives such as dispersants and solvents may be used in combination. When carbon dioxide is used as the compressive fluid (F), it is desirable that the purity of carbon dioxide in the compressive fluid (F) is high, but a part of the gas may be mixed.

The weight fraction of the compressible fluid (F) in the mixture (X) composed of the compressible fluid and other substances may be any ratio as long as the mixture (X) is at the target temperature and pressure. .
At this time, the proportion of the compressive fluid (F) is 1 to 99% by weight based on the weight of the mixture (X), preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 15%. ~ 70 wt%.

The volume ratio of the colorant (A) and the compressive fluid (F) in the mixture (X) is not particularly limited as long as the mixture (X) is at a target temperature and pressure.
The volume ratio (F) / (X) of the compressive fluid (F) and the mixture (X) is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more and 0.8 or less, particularly preferably. Is 0.4 or more and 0.7 or less.

In the present invention, liquid carbon dioxide refers to a triple point of carbon dioxide (temperature = −57 ° C., pressure 0.5 MPa) and a critical point of carbon dioxide (temperature = −57 ° C.) on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Supercritical carbon dioxide, which represents carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the gas-liquid boundary line passing through (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line Represents carbon dioxide which is a temperature / pressure condition above the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components). From the viewpoints of solubility, inertness and diffusibility of the medium, for example, supercritical carbon dioxide, subcritical carbon dioxide, liquid carbon dioxide and the like can be mentioned.

The solvent that can be used in the mixture is not particularly limited, but is a liquid at normal temperature and pressure, such as a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an ether solvent (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, cyclic ether, etc.), ester solvent (acetic acid ester, pyruvate ester, 2-hydroxyisobutyric acid ester, lactic acid ester etc.), amide solvent (dimethylformamide etc.), alcohol solvent (Methanol, ethanol, isopropanol, fluorine-containing alcohol, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), and aliphatic hydrocarbon solvents (octane, decane, etc.), water, Beauty mixtures thereof, as well as low-molecular compound solution, and include polymeric compound solution or the like.

After the volume expansion of the mixture, the solvent may be removed by any method such as by reducing the pressure with an evaporator, or may be used while containing the solvent.

Examples of gases that can be mixed include inert gases such as nitrogen, helium, argon, and air. The weight fraction of carbon dioxide in the total of carbon dioxide and gas is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

  The pressure after volume expansion of the mixture is not particularly limited as long as it does not cause vaporization of the colorant (A) and the radical polymerizable substance (B), and solidification of a compressible fluid, but before the volume expansion of the mixture. The pressure difference after volume expansion is preferably 2 to 100 MPa, and the pressure difference is more preferably 5 to 30 MPa, and particularly preferably 7 to 25 MPa.

The mixture (X) can be produced by a batch mixing method, a continuous mixing method, or the like. The batch type mixing method includes a method in a pressure vessel, and the continuous mixing method includes a line blend (in-line mixing) method. It is preferable from the viewpoints of improvement in quality, constant quality, and reduction in manufacturing space.

  A specific example of the apparatus used for the batch type mixing method is a mixer such as a pressure vessel. In the case of the batch type mixing method, as a preparation procedure of the mixture, a solid raw material is charged into the pressure vessel and heated as necessary. A compressive fluid is introduced into the kettle by a pressurizing means such as a pump provided in the pressure kettle until a desired pressure is reached. Thereafter, mixing is performed by stirring or the like for a predetermined time, and particles are produced by ejecting the mixture from a high pressure state to a predetermined pressure or the atmosphere at once. There are no limitations on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the working pressure.

As described above, it is preferable to provide a nozzle for taking out the mixture at the outlet of the apparatus used for the batch type mixing method. There is no particular limitation as long as it can withstand the working pressure, and it is preferable to be able to eject the mixture from a high pressure state to a predetermined pressure or the atmosphere.

In the case of the line blend method, the mixture (X) and the compressible fluid (F) mixed with the solid raw material and the medium as necessary are transported through the line using a pump, and the mixture is pressurized from the nozzle for taking out the mixture. Particles are produced by jetting from a state to a predetermined pressure or atmosphere. There are no limitations on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the working pressure.

The residence time in the apparatus is not particularly limited as long as mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.

Specific examples of equipment used in the line blend system include static inline mixers such as static mixers, inline mixers, lamond super mixers, and sulzer mixers, and agitation type inline mixers such as vibrator mixers and turbo mixers. It is done. There is no limitation on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the target pressure.

The outlet of the apparatus used for the line blending method is preferably provided with a nozzle for removing the slurry, similar to the pressure vessel.

An apparatus used for such a line blending method will be described with reference to the drawings.
FIG. 1 is a flowchart of an experimental apparatus used for producing a dispersion in the mixing method by line blending in the present invention.

As a method for mixing the mixture (X) and carbon dioxide in a liquid or supercritical state as a compressive fluid, first, the compressive fluid is subjected to line blending from the carbon dioxide cylinder B1 through the carbon dioxide pump P2 (static mixer). M1), the pressure and temperature at which carbon dioxide becomes liquid or supercritical is adjusted, and then the mixture (X) is introduced from the dissolution tank T1 into liquid or supercritical carbon dioxide through the solution pump P1. The method is preferred.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.
Next, by opening the valve V1 leading to the pressure receiving tank T2, the mixture (X) after line blending is decompressed and expanded to atmospheric pressure, and the compressive fluid is vaporized and removed, whereby the particles are dispersed in the dispersion medium. A dispersion is obtained.

In the above-described two systems, when the mixture (X) is volume-expanded, it is preferable to reduce the pressure to a target pressure at once in order to efficiently obtain pulverization and pulverization power. Therefore, when the mixture (X) is prepared and the compressive fluid (F) is removed to obtain the dispersion liquid (L), an exhaust pressure valve capable of reducing the mixture to the target pressure at once is required. In addition, when the mixture (X) is prepared in a pressure vessel or in a line and then the mixture (X) is transferred to another receiving container prepared at a target pressure, the nozzle having a diameter that can transfer the mixture (X) And a regulator that keeps the receiving vessel at the same pressure. However, in the latter case, a regulator is not required if the pressure in the receiving container is atmospheric pressure.

  When an additive such as a dispersing agent or a solvent is used, these may be mixed at the same time when the colorant (A) and the compressive fluid (F) are mixed, and the colorant (A) or compressive fluid ( It may be mixed with F). Furthermore, after mixing the solid material and the compressive fluid, pressure may be introduced and mixed in the process up to volume expansion.

From the viewpoint of the physical properties of the photosensitive composition for forming a color filter, the content of the polymer (BP) of the radical polymerizable monomer (B) in the photosensitive composition is 5% based on the total weight of the radical polymerizable monomer. % Or less, preferably 2% by weight or less, more preferably 1% by weight or less.
When it exceeds 5 weight%, the base-material adhesiveness or resolution of a photosensitive composition falls. Conventional sand grinders, sand mills, and the like that use physical shearing tend to produce a polymer (BP), and therefore, a method of dispersing using the volume expansion of a compressive fluid is optimal.

The content of the polymer is a value determined by the following calculation formulas (1) to (3).
The method is as follows: the integral value (r1) of the signal derived from the radical polymerizable group in the composition in which the colorant is dispersed and the integral value of the signal derived from the structure other than the radical polymerizable group detected using the ¹ H-NMR method. The ratio (r1 / s1) of (s1) and the integral value (r2) of the signal derived from the radical polymerizable group in the reference composition for NMR measurement blended in the same composition as the above composition without dispersing the colorant; Using the ratio (r2 / s2) of the integral value (s2) of the signal derived from the structure other than the radical polymerizable group (r2 / s2), the ratio (polymerization rate) of the radical polymerizable group that has been polymerized by dispersing the colorant First, it is obtained by the calculation formula (1).
Next, the weight of the polymer can be obtained from the calculation formula (2) by calculating the product of the determined polymerization rate and the total weight of the blended radical polymerizable monomer.
Furthermore, the content of the polymer is obtained from the calculation formula (3).

This will be described below using a specific example.
<Measurement conditions for ¹ H-NMR>
Measuring device: AVANCE300 (manufactured by Nippon Bruker Co., Ltd.)
Frequency: 300MHz
Deuterated solvent: Deuterated dimethyl sulfoxide The deuterated solvent here is deuterated dimethyl sulfoxide, deuterated chloroform, deuterated toluene, deuterated dimethylformamide, etc. It can be selected as appropriate.

<Method of calculating weight of polymer>
Here, styrene will be described as an example of the polymerizable substance.
When ¹ H-NMR measurement of styrene after dispersing the colorant is performed, a signal (r1) derived from a radical polymerizable group (vinyl group) is observed around 6.7 ppm, and a structure other than the radical polymerizable group (aromatic ring) is derived. The derived signal (s1) is observed around 7.3 to 7.4 ppm.
Similarly, ¹ H-NMR measurement was performed on styrene in which no colorant was dispersed, and a signal derived from a radical polymerizable group (vinyl group) (r2) and a signal derived from a structure other than the radical polymerizable group (aromatic ring) (s2) Is observed, the polymerization rate is calculated by the following equation [1].
Polymerization rate (%) = {1- (r1 / s1) / (r2 / s2)} × 100 [1]

However,
r1: Integral value of a signal derived from a vinyl group near 6.7 ppm before dispersion processing s1: Integral value of a signal derived from an aromatic group near 7.3 to 7.4 ppm before dispersion processing r2: 6. Integral value s2 of a signal derived from a vinyl group in the vicinity of 7 ppm: an integrated value of a signal derived from an aromatic in the vicinity of 7.3 to 7.4 ppm after the dispersion treatment.

Next, the weight of the polymer is calculated by the following formula [2].
Weight of polymer = total weight of the radically polymerizable material blended x polymerization rate (%) / 100 [2]

Finally, the content (% by weight) of the polymer is calculated by the following formula [3].
Polymer content (% by weight) = weight of polymer / total weight of radically polymerizable substance [3]

By using the dispersion in the present invention, the content of the polymer in the photosensitive composition for forming a color filter can also be reduced, and active energy ray curing for hard coats that achieves both resolution and high contrast and color reproducibility. Resin composition can be obtained.

In the step (2) in the present invention, the dispersion (Y) obtained in the step (1), the radical initiator (C) and, if necessary, other components such as a radical polymerizable substance (B) are mixed. It is a process of equalizing.

The homogenization can be performed using various dispersing devices such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a dissolver, a high speed mixer, a homomixer, and an attritor. The mixing temperature is usually 10 ° C to 40 ° C, preferably 15 ° C to 30 ° C.

Next, the colorant (A), the radical polymerizable substance (B) and the radical initiator (C), which are components used in the production method of the present invention, will be described in order.

As the colorant (A) in the present invention, pigments such as organic pigments and inorganic pigments, and dyes can be used.

Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as cinderdinone-based, quinacridone-based, dioxazine-based, perinone-based, and perylene-based compounds. For example, a color index (CI; published by The Society of Dyersand Colorists) Compounds that are classified into placement (Pigment), specifically, there may be mentioned those color index (C.I.) numbers are assigned as follows.

  C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180 and C.I. I. Pigment yellow 185;

  C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71 and C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36 and C.I. I. Pigment violet 38;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1 and C.I. I. Pigment red 97,

  C. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264 and C.I. I. Pigment red 265;

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60; C.I. I. Pigment green 7, C.I. I. Pigment green 36; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1 and C.I. I. Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

Examples of the inorganic pigment include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, or titanium black.

  Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or open-chain active methylene compounds as coupling components, open-chain activity as coupling components Examples thereof include azomethine dyes having a methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes having, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of coupling components include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

Since the photosensitive composition for forming a color filter obtained by the production method of the present invention has high sensitivity, it is particularly suitable for forming a black matrix. That is, a black pigment can be preferably used as the colorant (A), and carbon black is particularly preferable.

Examples of the carbon black include known carbon blacks such as channel black, furnace black, thermal black, and lamp black. Of these, channel black is preferable from the viewpoint of shielding properties.

  The volume average particle diameter of the colorant (A) is preferably 1 nm to 1 μm, and more preferably 1 nm to 400 nm, from the viewpoint of color reproducibility and shielding properties of the cured film.

  The content of the colorant (A) is preferably 10 to 99% by weight, more preferably 20 to 98% by weight, based on the solid content weight of the color filter forming photosensitive composition. When the content is less than 10% by weight, the color reproducibility and shielding properties of the obtained color filter are insufficient. Moreover, when there is more content than 99 weight%, the dispersion stability of a coloring agent will worsen.

The radical polymerizable substance (B) in the present invention includes a polymerizable resin (B1) having an ethylenic double bond and a carboxyl group in the molecule and a weight average molecular weight of 1,500 to 200,000, and a carboxyl group. However, known compounds such as a radically polymerizable resin (B2) having an ethylenic double bond and a polymerizable monomer (B3) having a weight average molecular weight of less than 1,500 can be used.
As the radically polymerizable substance (B), from the viewpoint of alkali developability and film strength, a polymerizable resin having an ethylenic double bond and a carboxyl group in the molecule and a weight average molecular weight of 1,500 to 200,000 ( B1) is preferred, and a polymerizable monomer (B3) having a weight average molecular weight of less than 1,500 is preferred from the viewpoint of curability and resolution.

The polymerizable resin (B1) that can be suitably used in the present invention has an ethylenic double bond and a carboxyl group in the molecule, and its weight average molecular weight is 1,500 to 200,000. The ethylenic double bond contained in the molecule is preferably a (meth) acryloyl group, a vinyl group or an allyl group, more preferably a (meth) acryloyl group, from the viewpoint of photocurability.

Specific examples of the polymerizable resin (B1) having an ethylenic double bond and a carboxyl group and having a weight average molecular weight of 1,500 to 200,000 include an epoxy resin having an ethylenic double bond and a carboxyl group ( B11) and (meth) acrylic resin (B12) having an ethylenic double bond and a carboxyl group.
In this specification, the term “(meth) acryl” means “acryl or methacryl”.

The epoxy resin (B11) having an ethylenic double bond and a carboxyl group of the present invention is synthesized by reacting a commercially available epoxy resin with a compound having an ethylenic double bond and further reacting with a compound having a carboxyl group. can do.
For example, there is a method in which (meth) acrylic acid is reacted with a novolak type epoxy resin having an epoxy group in the molecule, and further a polyvalent carboxylic acid such as phthalic acid or phthalic anhydride or a polyvalent carboxylic acid anhydride is reacted. It is done.

As the above-mentioned commercially available epoxy resins, in addition to the novolak type, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester Known compounds such as aliphatic or cycloaliphatic epoxy resins, amine epoxy resins, dihydroxybenzene type epoxy resins can be used.

  The (meth) acrylic resin (B12) having an ethylenic double bond and a carboxyl group according to the present invention is obtained by, for example, polymerizing a (meth) acrylic acid derivative by an existing method and further reacting a compound having an ethylenic double bond. Can be obtained.

  As a method for producing the (meth) acrylic resin (B12) having a carboxyl group, radical polymerization is preferable, and a solution polymerization method is preferable because the molecular weight is easily adjusted.

  As a monomer which comprises the (meth) acrylic resin (B12) which has a carboxyl group, (meth) acrylic acid (b121) and (meth) acrylic acid ester (b122) are mentioned.

Examples of (b112) include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, and preferably ( (Meth) methyl acrylate.

  As a monomer constituting the (meth) acrylic resin (B12) having a carboxyl group, an aromatic ring-containing vinyl compound (b123) is used in combination with (b121) and (b122) from the viewpoint of heat resistance and film strength of the cured product. May be. Examples of such (b123) include styrene.

In the (meth) acrylic resin (B12) having a carboxyl group, it is preferable to introduce a (meth) acryloyl group into a side chain or a terminal as necessary from the viewpoint of sensitivity during exposure and film strength of the cured product.
In the present specification, the term “(meth) acryloyl” means “acryloyl or methacryloyl”.

  Examples of the method for introducing a (meth) acryloyl group into the side chain include the following methods (1) and (2).

(1) A polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (b121) or (b122); A method of reacting a compound [(meth) acryloyloxyethyl isocyanate etc.] having a (meth) acryloyl group and an isocyanate group.

(2) Using at least a part of (b121) or (b122) a monomer having a functional group capable of reacting with an epoxy group (such as a hydroxyl group, a carboxyl group, or a primary or secondary amino group) A method of producing and then reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl (meth) acrylate).

The weight average molecular weight of the polymerizable resin (B1) having an ethylenic double bond and a carboxyl group of the present invention is preferably 1,500 to 200,000, more preferably 1,600 to 50,000. By setting the weight average molecular weight of the resin (B1) to 2,000 or more, the heat resistance and film strength of the cured product can be improved. Moreover, sufficient solubility with respect to an alkali developing solution can be acquired by setting it as 200,000 or less.

The acid value of the polymerizable resin (B1) having an ethylenic double bond and a carboxyl group of the present invention is preferably 40 to 150, more preferably 60 to 150, and particularly preferably 60 to 140. When it is 40 or more, developability is further improved when developing, and when it is 150 or less, the water resistance of the cured product is further improved.

Examples of the polymerizable resin (B1) having an ethylenic double bond and a carboxyl group of the present invention include a fluorene skeleton described in Japanese Patent No. 5618118, Japanese Patent No. 5293120, Japanese Patent No. 4364216, etc. It is also possible to use a cardo resin, a compound having two or more functional ethylenic double bonds. When a cardo resin is used, the heat resistance and chemical resistance of the cured product are further improved.

  The content of the polymerizable resin (B1) having an ethylenic double bond and a carboxyl group of the present invention is preferably 3 to 70% by weight with respect to the solid content weight of the photosensitive composition from the viewpoint of developability, Preferably it is 3 to 60% by weight.

Examples of the radical polymerizable resin (B2) having no carboxyl group and having an ethylenic double bond include a carboxyl group having a weight average molecular weight of 1,500 or more, such as epoxy (meth) acrylate and urethane (meth) acrylate. A known polymerizable resin having no can be used.

Examples of the radical polymerizable monomer (B3) having a weight average molecular weight of less than 1,500 that can be suitably used in the present invention include (meth) acrylate (B31), (meth) acrylamide compound (B32), and aromatic vinyl compound (B33). , A known compound containing an ethylenic double bond such as a vinyl ether compound (B34) can be used. Among these, from the viewpoint of curability, it is particularly preferable to contain (meth) acrylate (B31) having a (meth) acrylate group.

  Examples of the (meth) acrylate (B31) include monofunctional (meth) acrylate (B311), bifunctional (meth) acrylate (B312), trifunctional (meth) acrylate (B313), and 4-6 functional (meth) acrylate ( B314) and 7 to 10 functional (meth) acrylate (B315). These may be used alone or in combination of two or more.

  As monofunctional (meth) acrylate (B311), ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclo Hexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate Rate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (Meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2- Butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate , Phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate , Glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, diethylene glycol monovinyl ether mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate , Polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl Ether (meth) acrylate, dipropylene glycol (meth) a Relate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2 -Hydroxypropylphthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) ) (1-40 mol, the same applies hereinafter) Addition phenol (meth) acrylate, EO addition cresol (meth) acrylate, EO addition nonylphenol (meth) acrylate DOO, propylene oxide (hereinafter, PO hereinafter) (1 to 40 mol, hereinafter the same) added nonylphenol (meth) acrylate and EO adduct of 2-ethylhexyl alcohol (meth) acrylate.

  Examples of the bifunctional (meth) acrylate (B312) include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) ) Acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2- Echi -2-butyl-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate, EO-added bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate , Oligopropylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, and the like.

    As trifunctional (meth) acrylate (B313), trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, alkylene oxide of trimethylolpropane (EO and PO, etc., and the following alkylene oxides are also the same) (1 to 40 mol, the same applies hereinafter) Adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, Isocyanuric acid alkylene oxide adduct tri (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypival Aldehyde modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate.

Examples of the tetra- to hexa-functional (meth) acrylate (B314) include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; dipentaerythritol ethylene oxide addition Tetra (meth) acrylate of a product, penta (meth) acrylate of an ethylene oxide adduct of dipentaerythritol, penta (meth) acrylate of a propylene oxide adduct of dipentaerythritol, and the like.

  Examples of 7 to 10 functional (meth) acrylate compounds include a compound obtained by reaction of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate, and the like by reaction of a diisocyanate compound with a hydroxyl group-containing polyfunctional (meth) acrylate compound. Can be obtained.

Among these, trifunctional (meth) acrylate (B313) and 4-6 functional (meth) acrylate (B314) are particularly preferable from the viewpoint of curability and the strength of the cured film.

  Examples of the (meth) acrylamide compound (B32) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-butyl (meth). Acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide and (meth) acryloylmorpholine.

  As the aromatic vinyl compound (B33), vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, Bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3 -Hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenyls Ren, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

Examples of the vinyl ether compound (B34) include the following monofunctional or polyfunctional vinyl ethers.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

The content of the radically polymerizable substance (B) of the present invention is from 3 to 95% by weight, preferably from 5 to 90% by weight, based on the solid content weight of the photosensitive composition, from the viewpoint of achieving both sensitivity and color reproducibility. %.

In this invention, a radical initiator (C) means the compound which generate | occur | produces a radical by at least 1 sort (s) of actinic light, an acid, and a base.
Examples of the radical initiator (C) include a photoradical initiator (C1) that generates radicals by active light, a radical initiator (C2) that generates radicals by acid or base, and a radical that is generated by active light, acid or base. It is possible to use a known compound such as an initiator (C12) that can be used.
As an example below, the initiator (C12) capable of generating radicals by actinic rays, acids, or bases will be described in the photoradical initiator (C1) in the above classification.

Examples of the photoradical initiator (C1) include a radical initiator (C12) that generates radicals by actinic rays, acids, or bases, for example, acylphosphine oxide derivative polymerization initiator (C121), α-aminoacetophenone derivative. System polymerization initiator (C122), benzyl ketal derivative polymerization initiator (C123), α-hydroxyacetophenone derivative polymerization initiator (C124), benzoin derivative polymerization initiator (C125), oxime ester derivative polymerization initiator ( C126) and titanocene derivative polymerization initiators (C127).
As the photo radical initiator (C1), radical initiators (C121) to (C127) exemplified below can be preferably used.

  As the acylphosphine oxide derivative polymerization initiator (C121), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF Japan (LUCIRIN TPO)] and bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide [manufactured by BASF Japan Ltd. (IRGACURE 819)] and the like.

  As the α-aminoacetophenone derivative-based polymerization initiator (C122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907)], 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan Ltd. (IRGACURE 379)] and the like.

  Examples of the benzyl ketal derivative polymerization initiator (C123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (C124), 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd. (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [BASF Japan (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [BASF Japan (IRGACURE) 2959)] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF Japan Ltd. (IRGACURE 127 )] And the like.

  Examples of the benzoin derivative-based polymerization initiator (C125) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (C126), 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF Japan Ltd. (IRGACURE OXE 01)] and Etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF Japan Ltd. (IRGACURE OXE 02)] and the like. .

  As titanocene derivative polymerization initiator (C127), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Examples thereof include titanium [manufactured by BASF Japan (IRGACURE 784)].

Examples of the benzophenone derivative polymerization initiator (C128) include benzophenone, 4,4-bis (dimethylamino) benzophenone [manufactured by SHUANG-BANG (SB-PI 701)], 4-benzoyl-4′-methyldiphenyl sulfide [SHUANG]. -BANG Co. (SB-PI 705)] and the like.

  Examples of the thioxanthone derivative (C129) include isopropylthioxanthone [Nippon Kayaku Co., Ltd. (Kayacure ITX)], 2,4-diethylthioxanthone [Nippon Kayaku Co., Ltd. (Kayacure DETX-S)], 2- Examples include chlorothioxanthone [manufactured by Nippon Kayaku Co., Ltd. (Kayacure CTX)].

Examples of the radical initiator (C2) that generates radicals by acid or base include organic peroxide polymerization initiators (C21), azo compound polymerization initiators (C22), and other radical initiators (C23). Can be mentioned.

  Examples of the organic peroxide polymerization initiator (C21) include benzoyl peroxide (BPO), tert-butyl peroxyacetate, 2,2-di- (tert-butylperoxy) butane, tert-butyl peroxybenzoate, n-butyl 4,4-di- (tert-butylperoxy) valerate, di- (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5,- Dimethyl-2,5, -di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3 , 3-Tetramethylbutylhydro Chromatography, cumene hydroperoxide, tert- butyl hydroperoxide and tert- butyl trimethylsilyl peroxide.

  As the azo compound-based polymerization initiator (C22), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of other polymerization initiator (C23) include 2,3-dimethyl-2,3-diphenylbutane.

  Among these radical initiators (C), from the viewpoint of storage stability, the radical initiator (C1) that generates radicals with actinic rays is preferred, and further, radical initiators that generate radicals with actinic rays, acids, or bases. (C12) is preferred.

Of the photoradical initiator (C1), the acyl phosphine oxide derivative polymerization initiator (C121), the α-aminoacetophenone derivative polymerization initiator (C122), and the benzyl ketal derivative polymerization are preferable from the viewpoint of photocurability. An initiator (C123), an α-hydroxyacetophenone derivative polymerization initiator (C124) and an oxime ester derivative polymerization initiator (C126), more preferably an acylphosphine oxide derivative polymerization initiator (C121) and α -Aminoacetophenone derivative polymerization initiator (C122).

The content of the radical initiator (C) in the photosensitive composition for forming a color filter of the present invention is based on the solid content weight of the photosensitive composition for forming a color filter, from the viewpoint of curability and coloring of the cured product. Preferably it is 0.5-30 weight%, More preferably, it is 1-25 weight%.

In the manufacturing method of the photosensitive composition for color filter formation of this invention, it is preferable to use an acid generator (D) or a base generator (E) further from a viewpoint of a sensitivity and base-material adhesiveness.

In the present invention, the acid generator (D) means a compound that generates an acid by at least one of actinic rays, radicals, acids and bases.
Examples of the acid generator (D) include known compounds such as a photoacid generator (D1) that generates an acid by actinic rays and an acid generator (D2) that generates an acid by a radical, acid, or base.
In addition, among acid generators, there is an acid generator (D12) that can generate acid by either actinic rays or radicals. For example, photoacid generation is performed according to the above classification. It demonstrates in an agent (D1).
(D) may be used alone or in combination of two or more.

Examples of the photoacid generator (D1) that generates an acid by actinic rays include an acid generator (D12) that can generate an acid by either actinic rays or radicals, for example, a sulfonium salt derivative (D121). ), An iodonium salt derivative (D122), and the like.
These (D121) and (D122) can generate an acid also by a radical, and can be applied not only as a photoacid generator (D1) but also as an acid generator (D2).

Examples of the acid generator (D2) that generates an acid by a radical, an acid, or a base include a sulfonic acid ester derivative (D21), an acetic acid ester derivative (D22), and a phosphonic acid ester (D23).
In addition, (D) may be used independently and may use 2 or more types together.

  Among these acid generators (D), the acid generator (D1) that generates an acid by actinic rays including (D12) is preferable.

  Specific examples of the aforementioned sulfonium salt derivative (D121) include compounds represented by the following general formula (1) or the following general formula (2).

In General Formula (1) or (2), A ¹ is a divalent or trivalent group represented by any of the following General Formulas (3) to (10), and Ar ^{1 to} Ar ⁷ are each independently Having at least one benzene ring skeleton, halogen atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, carbon At least one atom or substitution selected from the group consisting of an alkylsilyl group, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group An aromatic hydrocarbon group or a heterocyclic group which may be substituted with a group, Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is a divalent group, and (X ¹ )-And (X ²⁾ - represents an anion, a is an integer of 0 to 2, b is an integer from 1 to 3, and a + b is an integer equal the valence of ^{A 1} in 2 or 3.

R ^{1 to} R ⁷ in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R ¹ And R ² , R ⁴ and R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

As A ¹ in the general formula (2), groups represented by the general formula (5) and the general formulas (7) to (11) are preferable from the viewpoint of acid generation efficiency. The groups represented by 8) to (11) are more preferable.

Ar ^{1 to} Ar ⁷ in the general formula (1) and the general formula (2) are groups in which the compound represented by the general formula (1) or the general formula (2) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{1 to} Ar ⁷ is preferably 1 to 5, and more preferably 1 to 4.

As an example in the case of having one benzene ring skeleton, a residue obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline, coumarin, and the like can be given.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
As an example in the case of having three benzene ring skeletons, for example, one or two hydrogen atoms are removed from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
As an example in the case of having four benzene ring skeletons, for example, a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

As the atoms or substituents substituted by Ar ^{1 to} Ar ⁷ , preferred from the viewpoint of acid generation efficiency are halogen atoms, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, phenylthio groups, alkyl groups having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, They are an alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2, 4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.

Ar ⁵ is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and 2- or 3-chloro, from the viewpoint of acid generation efficiency. A phenylene group.

Examples of the anion represented by (X ¹ )-or (X ² )-in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, a carbonate anion, a hydrogen carbonate anion, Inorganic anions such as hexafluoroantimonate anion (SbF _6- ), phosphorus hexafluoride anion (PF _6- ); aliphatic alkyl fragrance optionally substituted with a C 1-4 dialkyldithiocarbamate anion and halogen Organic anions such as aliphatic carboxy anions, aliphatic or aromatic sulfoxy anions optionally substituted with halogen, and organic boron anions.

Specific examples of the aliphatic or aromatic carboxy anion include benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion and the like; aliphatic or aromatic sulfoxy optionally substituted with halogen Anion as trifluoromethanesulfonate anion, etc .; Triphosphoric tris (perfluoroethyl) phosphorus anion (PF ₃ (C ₂ F ₅ ) ₃ —) etc. as organophosphorus anion]; Tetraphenylborate as organoboron anion, Examples include tetrakis (perfluorophenyl) borate and butyltriphenylborate anion.

From the viewpoint of acid generation efficiency, a phosphine anion, an aliphatic sulfoxy anion substituted with a halogen, and a borate anion are preferred.
More preferred are hexafluorophosphate anion, trifluoro [tris (perfluoroethyl)] phosphate anion and tetrakis (perfluorophenyl) borate anion, and particularly preferred is trifluoro [tris (perfluoroethyl)] phosphate anion and Tetrakis (perfluorophenyl) borate anion.

  As the sulfonium salt derivative (D121), compounds having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton are preferable from the viewpoint of acid generation efficiency, and Compounds represented by the following general formulas (12) to (16) are preferable, and compounds represented by the following general formulas (12) to (16) are more preferable.

Formula (12) to the ^{(16) (X 3) -~} (X 7) - represents an anion, specifically, the general formula (1) or in (2) ^{(X 1)} - or ^(X 2) The thing similar to what was illustrated as-is mentioned, A preferable thing is also the same.

  Specific examples of the aforementioned iodonium salt derivative (D122) include compounds represented by the following general formula (17) or the following general formula (18).

In the formula, A ² is a divalent or trivalent group represented by any one of the chemical formulas (3) to (4), the general formulas (5) to (8), and the chemical formulas (9) to (11). , Ar ^{8 to} Ar ¹² each independently have at least one benzene ring skeleton, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group. An aromatic hydrocarbon group or a heterocyclic group which may be substituted with at least one kind of substituent selected from: Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, and Ar ¹¹ is a divalent group. in it, ^{(X 7} - and ^{(X 8)} - represents an anion, c is an integer of 0 to 2, d is an integer from 1 to 3, and c + d is an integer equal the valence of ^{A 2} in 2 or 3.

    As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

As A ² in the general formula (18), a group represented by the general formula (5) and the general formulas (7) to (11) is preferable from the viewpoint of the efficiency of generating an acid. And groups represented by (8) to (11) are more preferable.

Ar ^{8 to} Ar ¹² in the general formula (17) or the general formula (18) are groups in which the compound represented by the general formula (17) or the general formula (18) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{8 to} Ar ¹² is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar ^{8 to} Ar ¹² include general formula (1) or general formula (2). The thing similar to what was illustrated as Ar < ¹ > -Ar < ⁷ > of these is mentioned, A preferable thing is also the same.

Examples of (X ⁸ )-and (X ⁹ )-include those exemplified as (X ¹ )-or (X ² )-in general formula (1) or (2), and preferable ones are also included. It is the same.

  As the iodonium salt derivative (D122), (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4-t-butylphenyl)] iodonium is preferable from the viewpoint of acid generation efficiency. Cation, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation and [bis (4-methoxyphenyl)] iodonium cation as cation skeleton, and the following other general compounds Compounds represented by formulas (19) to (22) are preferred, and compounds represented by the following general formulas (19) to (22) (including exemplified compounds) are more preferable.

In General Formulas (19) to (22), R ^{8 to} R ¹³ are a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An atom or substitution selected from the group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group And (X ¹⁰ )-to (X ¹³ )-represent an anion.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

R ^{8 to} R ¹³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, A phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms. An alkoxy group and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Formula (19) to (22) in the ^{(X 10) -~ (X 13} ) - As the general formula (1) or in (2) ^{(X 1)} - or ^{(X 2)} - similar to those exemplified for The preferable thing is also the same.

  In general, a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) is colored by the initiator itself because it absorbs visible light, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (18), an adverse effect on the hue of the cured film can be suppressed.

  Examples of the acid generator (D2) that generates an acid with an acid include a sulfonic acid ester derivative (D21), an acetic acid ester derivative (D22), and a phosphonic acid ester (D23).

Specific examples of the sulfonic acid ester derivative (D21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-t-butyl ester, p-toluenesulfonic acid cyclohexyl ester, naphthalenesulfonic acid cyclohexyl ester, and the like. Is mentioned.

  Specific examples of the acetic acid ester derivative (D22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.

  Specific examples of the phosphonic acid ester (D23) include triphenylphosphonic acid cyclohexyl ester.

  In addition, as a radical acid generator which generate | occur | produces an acid by a radical, what was illustrated by the acid generator (D12) which can generate | occur | produce an acid by either actinic light or a radical corresponds also to this.

In the present invention, the base generator (E) means a compound that generates a base by at least one of actinic rays, radicals, acids or bases.
Known compounds such as a base generator (E1) that generates a base by actinic rays and a base generator (E2) that generates a base by a radical, an acid, or a base can be used.
Among base generators, there is also a base generator (E12) capable of generating bases by either actinic rays or radicals. For example, photobase generation is performed according to the above classification. It demonstrates in an agent (E1).
In addition, (E) may be used independently and may use 2 or more types together.

Examples of the base generator (E1) that generates a base by actinic rays include a base generator (E12) that can generate a base by either actinic rays or radicals, for example, an oxime derivative (E121), A quaternary ammonium salt derivative (E122), a quaternary amidine salt derivative (E123), etc. are mentioned.
These (E121), (E122), and (E123) can generate a base by actinic rays or radicals, and can be applied not only as a photobase generator (E1) but also as a base generator (E2).

The carbamate derivative (E21) can generate a base with a base, and can be applied as a base generator (E2) that generates a base with a radical, an acid, or a base.
(E) may be used alone or in combination of two or more.
Among these base generators (E), the base generator (E1) that generates a base by actinic rays including (E12) is preferable.

  Examples of the photobase generator (E1) include a base generator (E12) capable of generating a base by either actinic rays or radicals, for example, an oxime derivative (E121), a quaternary ammonium salt derivative ( E122) and quaternary amidine salt derivatives (E123), and (E121), (E122) and (E123) can be preferably used as the photobase generator (E1).

Specific examples of the aforementioned oxime derivative (E121) include O-acyloxime.

Specific examples of the quaternary ammonium salt derivative (E122) and the quaternary amidine salt derivative (E123) include compounds represented by any of the following general formulas (23) to (25).

R ^{14 to} R ⁴¹ in the general formulas (23) to (25) are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , An alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, represented by the general formula (26) An atom or a substituent selected from the group consisting of a substituent represented by formula (27) and a substituent represented by formula (27), wherein any one of R ^{14 to} R ²³ is represented by formula (26) or formula ( 27), any one of R ^{24 to} R ³¹ is a substituent represented by the general formula (26) or the general formula (27), and any one of R ^{32 to} R ⁴¹ One is general formula (26) or general (27) is a substituent represented by.

R < ⁴² > -R < ⁴⁵ > in General formula (26) and (27) is a hydrogen atom or a C1-C20 alkyl group, R < ⁴⁶ > -R < ⁴⁸ > is C1-C20 which may be substituted by the hydroxyl group. alkyl group, ^{(X 14) -} and ^{(X 15) -} represents an anion, e is an integer of 2 to 4.

  In general formulas (23) to (25), a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon Examples of the alkylsilyl group having 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).

The compound represented by the general formula (23) is an anthracene skeleton, the compound represented by the general formula (24) is a thioxanthone skeleton, and the compound represented by the general formula (25) is a compound having a benzophenone skeleton, and each has an i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity. R ^{14 to} R ²³ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity and decomposability, and are a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkyl silyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, naphthyl group The atom or substituent selected from the group consisting of is modified according to the purpose. However, any one of R < ¹⁴ > -R < ²³ > is a substituent represented by General formula (26) or General formula (27).

R ^{14 to} R ²³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, A phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms. An alkoxy group and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Specific examples of R ^{14 to} R ²³ include the compounds described in the description of R ^{8 to} R ^{13 in} the general formulas (19) to (21).

The substituent represented by the general formula (26) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4. Examples of the substituent include a substituent having a cationized structure of 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4, and 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R ⁴² and R ⁴³ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. It is.

The general formula (27) has a quaternary ammonium structure, R ⁴⁴ and R ⁴⁵ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, More preferably, they are a hydrogen atom or a C1-C5 alkyl group. R ^{46 to} R ⁴⁸ represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R ^{46 to} R ⁴⁸ are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

(X ¹⁴ ) ⁻ and (X ¹⁵ ) ⁻ in the general formulas (26) and (27) represent anions, specifically, (X ¹ ) ⁻ or (X ^{2 in the} general formula (1) or (2). ) ^- it includes the same as those exemplified as. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

The compound represented by the general formula (26) generates a basic compound having an amidine skeleton by cleaving the bond between carbon and nitrogen to which R ⁴² and R ⁴³ are bonded by irradiation with actinic rays. In the compound represented by 27), upon irradiation with actinic rays, the bond between carbon and nitrogen to which R ⁴⁴ and R ⁴⁵ are bonded is cleaved to produce a tertiary amine.

Examples of the base generator (E2) that generates a base by a radical, acid, or base include a carbamate derivative (E21). Examples of the carbamate derivative (E21) include 1-Fmoc-4-piperidone, o-nitrobenzoyl carbamate, and 1-Z-4-piperidone.
In addition to the carbamate derivative (E21), the oxime derivative (E121) and the quaternary ammonium salt derivative (E122) described above can be used as the base generator (E2) that generates a base by a radical, acid, or base. A quaternary amidine salt derivative (E123) is also included.

  In addition, as a radical base generator (E3) which generate | occur | produces a base by a radical, what was illustrated by the base generator (E12) which can generate a base by any of actinic light or a radical corresponds also to this. .

By including any of the acid generator (D) and the base generator (E), high sensitivity can be obtained, and good curability can be obtained even when a large amount of the colorant (A) that shields light is contained. In addition, since the macroscopic reaction rate distribution is suppressed, defects are less likely to occur, and a cured product having excellent homogeneity can be obtained. As a result, it is estimated that the resolution and the substrate adhesion are also improved.
The above effect can be obtained by using any of the acid generator (D) and the base generator (E), but from the viewpoint of photocurability, it is preferable to use the acid generator (D).

In the photosensitive composition for forming a color filter of the present invention, at least one of the radical initiator (C), the acid generator (D) and the base generator (E) is activated by irradiation with actinic rays (H). This active species (H) reacts with the radical initiator (C), the acid generator (D) or the base generator (E) to produce a new active species (I). The polymerization reaction of the radically polymerizable substance (B) of the present invention by the generated active species (I) preferably proceeds.
Here, examples of the active species (H) and (I) include radicals, acids and bases. In the above reaction, either the active species (H) or the active species (I) is a base or Preferably there is. Curing is further promoted by the diffusion of the active species (H). Moreover, the adhesiveness to the base material of the hardened | cured material obtained improves. In order for the active species (H) to diffuse easily, it is preferable to use the radical polymerizable substance (B) of the present invention that does not react with the active species (H).

In the present invention, (C1), (C2), (D1), (D2), (E1), or (E2) may be contained in any combination of the following (1) to (3) preferable.
(1) Contains (C1) and (D2) and / or (E2).
(2) Contains (D1) and (C2).
(3) Contains (E1) and (C2).
In addition to the above (1) to (3), two or more of these may be combined.

In (1) above, radicals are generated as active species (H) upon irradiation with actinic rays, and acids and / or bases are generated as active species (I).
In (2) above, an acid is generated as the active species (H) by irradiation with actinic rays, and a radical is generated as the active species (I).
In (3) above, a base is generated as an active species (H) by irradiation with actinic rays, and a radical and an acid are generated as necessary as an active species (I).
Among these combinations, more preferred are those containing (C1) and (D2) in (1), and acids capable of generating an acid by any of the actinic rays or radicals in (2). Those containing a generator (D12) and those containing a base generator (E12) capable of generating a base by any of actinic rays or radicals among (3), particularly preferred are: Those containing (C1) and (D2), and those containing (E1) and (C12).

The photosensitive composition for forming a color filter of the present invention does not need to contain both the acid generator (D) and the base generator (E) at the same time. Therefore, the content of (D) in the case of only (D), the content of (E) in the case of only (E), or the total content when (D) and (E) are used together is photosensitivity. Preferably it is 0.005 to 10 weight% with respect to the solid content weight of a composition, More preferably, it is 0.01 to 5 weight%.
By adjusting the content of the acid generator (D) and / or the base generator (E) to the above range, the solubility of the unexposed area in the alkaline developer and the sensitivity of the exposed area are appropriately controlled. , Developability and curability can be compatible.
Further, since the substrate adhesion is improved as compared with the case where (D) and / or (E) is not used, sufficient substrate adhesion can be obtained even when the content of the radical polymerizable substance (B) is relatively small. It can be secured.
That is, since the content of the colorant (A) in the photosensitive resin for forming a color filter can be increased, in the case of R, G, and B applications, both color reproducibility and substrate adhesion can be achieved. In the case of a black matrix application, both high shielding properties and substrate adhesion can be achieved.

The photosensitive composition concerning this invention can contain a polymerization inhibitor, a sensitizer, etc. as needed.

  Examples of the polymerization inhibitor include 2,6-di-tert-butylcresol, butylated hydroxyanisole, 2,6-ditert-butyl-4-ethylphenol, stearyl β- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate and 2,2-methylenebis (4-methyl-6-tert-butylphenol).

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene.

The photosensitive composition according to the present invention further includes an adhesion-imparting agent (such as a coupling agent), a tackifier, a dispersant, an antifoaming agent, a leveling agent, a thixotropy-imparting agent, a slip according to the purpose of use. Agents, flame retardants, antistatic agents, antioxidants, ultraviolet absorbers and the like.

Examples of the coupling agent include 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-amino Propylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3 -Mekakuri Silane coupling agents such as loxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyltriisostearoyl titanate, titaniumdi (dioctyl) Pyrophosphate) Titanium coupling agents such as oxyacetate, tetraisopropyldi (dioctylphosphite) titanate, neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr -Methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoylzirconate, neoalkoxytris (dodecanoyl) benzenesulfonylzil , Neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, zirconium such as ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, or aluminum coupling agents Of these, silicon-based coupling agents are preferred. The amount used is preferably 0.01 to 10% by weight, preferably 0.02 to 5% by weight, based on the solid content weight of the photosensitive composition.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1 [Production of polymerizable resin (B1-1)]
A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen introduction tube was charged with 90 parts of styrene, 10 parts of methyl methacrylate, 30 parts of methacrylic acid, and 85 parts of propylene glycol monomethyl ether acetate as a solvent. . After replacing the gas phase part in the system with nitrogen, 38 parts of a solution prepared by dissolving 8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 20 parts of propylene glycol monomethyl ether acetate was added, And further reacted at the same temperature for 4 hours.
Further, 15 parts of glycidyl methacrylate and 1 part of triethylamine were added to the obtained solution and reacted at 90 ° C. for 6 hours. As an acrylic resin having a (meth) acryloyl group and a carboxyl group, a 60% solution of acrylic resin (B1- 1) was obtained.
The acid value in terms of solid content of this acrylic resin was 96.1. The number average molecular weight by GPC was 4,500.
This polymerizable resin (B1-1) is blended in dispersions (Y-1) to (Y-5) of Production Examples 2 to 6.

Comparative Production Example 1 [Production of non-polymerizable resin (G-1)]
A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction tube was charged with 50 parts of styrene, 50 parts of methyl methacrylate, 30 parts of methacrylic acid and 72 parts of diethylene glycol dimethyl ether as a solvent. After replacing the gas phase part in the system with nitrogen, 38 parts of a solution prepared by dissolving 8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 20 parts of diethylene glycol dimethyl ether were added and heated to 90 ° C. Further, the mixture was reacted at the same temperature for 4 hours to obtain a 60% acrylic resin solution (G-1) as a non-polymerizable resin having a carboxyl group. This non-polymerizable resin (G-1) is blended in the dispersion (Y-6) of Production Example 7.

<Production of Dispersions (Y-1) to (Y-5)>
Production Example 2 [Production of Dispersion (Y-1)]
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 30 parts of carbon black “MA-77” (A-1) (manufactured by Mitsubishi Chemical Corporation) and 70 parts of a polymerizable resin (B1-1) were placed in the reaction vessel. The mixture was charged to 40% of the volume, sealed and heated with stirring, and the system temperature was raised to 40 ° C.
After raising the temperature, carbon dioxide is supplied to 10 MPa and stirred for 15 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, A dispersion (Y-1) in which carbon black was dispersed was obtained.
The dispersed particle diameter of carbon black in the dispersion (Y-1) was 100 nm as measured with a transmission electron microscope (TEM).

Production Example 3 [Production of Dispersion (Y-2)]
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 30 parts of carbon black “MA-77” (A-1) (manufactured by Mitsubishi Chemical Corporation), 50 parts of polymerizable resin (B1-1), diethylene glycol dimethyl ether 20 The portion was charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, and the system temperature was raised to 40 ° C.
After raising the temperature, carbon dioxide is supplied to 10 MPa and stirred for 15 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, A dispersion (Y-2) in which carbon black was dispersed was obtained.
The dispersed particle diameter of carbon black in the dispersion (Y-2) was 81 nm as measured with a transmission electron microscope (TEM).

Production Examples 4 to 6 [Production of Dispersions (Y-3) to (Y-5)]
Dispersions (Y-3) to (Y-5) were carried out in the same manner as in Production Example 3 except that the carbon black of Production Example 3 was changed to the colorants (A-2) to (A-4) shown in Table 1. )

Production Example 7 [Production of Dispersion (Y-6)]
A dispersion (Y-6) was obtained in the same manner as in Production Example 3 except that the polymerizable resin (B1-1) in Production Example 3 was changed to a non-polymerizable resin (G-1).

In addition, each symbol in Table 1 is the following commercially available colorant.
Red pigment (A-2): “PR254” Product name: Irgaphor Red B-CF, manufactured by BASF Japan Ltd. Green pigment (A-3): “PG36” Product name: Lionol Green 6YK, manufactured by Toyochem Co., Ltd. Blue pigment (A-4): “PB15: 6” Product name: Lionol Blue ES, manufactured by Toyochem Co., Ltd.

Comparative Production Example 2 [Production of Dispersion (RY-1)]
In a mixing vessel equipped with a stir bar and a thermometer, 25 parts of carbon black (A-1) and 75 parts of polymerizable resin (B1-1) were charged and stirred to obtain a mixture. The obtained mixture was subjected to a sand mill to obtain a comparative dispersion (RY-1) in which carbon black was dispersed.
The dispersion particle diameter of the spherical alumina in the dispersion (RY-1) was 500 nm as measured by TEM.

<Production of acid generator (D)>
Production Example 8 [Synthesis of Compound Represented by Acid Generator (D-1) Chemical Formula (28)]

(1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (D-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) yielded 3.1 parts of intermediate (D-1-1) (yellow solid).

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (D-1-2)]:
While stirring 11.2 parts of intermediate (D-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide was gradually added dropwise thereto. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (D-1-2) (yellow solid).

(3) Synthesis of sulfonium salt derivative (D-1):
While stirring 4.3 parts of the intermediate (D-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise to the mixture. After reacting at 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. did. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, poured into 65 parts of 10% potassium {trifluoro [tris (perfluoroethyl)] phosphate} aqueous solution, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing three times with water by a liquid separation operation, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of an acid generator (D-1) (yellow solid) as a sulfonium salt derivative.

<Manufacture of base generator (E)>
Production Example 9 [Synthesis of base generator (E-1) {compound represented by chemical formula (29)}]

  2.0 parts of 9-chloromethylanthracene was dissolved in chloroform, and 3.1 parts of trioctylamine was added little by little (a slight exotherm was observed after the addition), and the temperature was kept at room temperature (about 25 ° C.). The reaction solution was obtained by stirring for 1 hour. The reaction solution is dropped little by little into an aqueous solution consisting of 4.0 parts of sodium tetraphenylborate salt and 40 parts of water, and the mixture is further stirred for 1 hour at room temperature (about 25 ° C.). The layer was washed 3 times with water. The organic solvent was distilled off under reduced pressure to obtain 7.1 parts of a white solid. This white solid was recrystallized from acetonitrile to obtain 6.2 parts of a base generator (E-1) (white solid).

<Production of photosensitive composition for forming color filter>
Examples 1 to 13 and Comparative Example 1
According to the number of parts in Table 2, the dispersion (Y), radical polymerizable substance (B), radical initiator (C), acid generator (D), base generator (E), silane coupling are made in a glass container. An agent and a solvent (propylene glycol monomethyl ether acetate) were added and stirred until uniform, and color filter-forming photosensitive compositions (Q-1) to (Q-13) of the present invention and a composition for comparison (RQ-1) was produced.

Comparative Example 2
According to the number of parts in Table 2, a dispersion (RY-1) for comparison, a radical polymerizable substance (B), a radical initiator (C), an acid generator (D), a base generator (in a glass container) E), a silane coupling agent and a solvent (propylene glycol monomethyl ether acetate) were charged and stirred until uniform to prepare a composition (RQ-2) for comparison.

The compounds indicated by the symbols in Table 2 are as follows.
Neomer DA-600 (B3-1): Dipentaerythritol pentaacrylate [manufactured by Sanyo Chemical Industries, Ltd.]
Light acrylate PE-3A (B32-2): Pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd.]
IRGACURE907 (C-1): 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan Ltd.]
KR-513: Silicone alkoxy oligomer [manufactured by Shin-Etsu Chemical Co., Ltd.]

  The performance evaluation method will be described below.

[Measurement of average dispersed particle size (nm) of colorant in photosensitive resin]
The photosensitive compositions obtained in Examples 1 to 13 and Comparative Examples 1 and 2 were applied onto a glass plate by a spin coater and dried to form a coating film having a dry film thickness of 20 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes to remove the solvent. Next, the cured film was obtained by irradiating light of an ultrahigh pressure mercury lamp at 100 mJ / cm ² .
The obtained cured film was subjected to TEM measurement. The volume average particle diameter of the metal oxide was measured from the obtained TEM image.
The smaller this value, the better the resolution and color reproducibility, and it is generally preferred that the value is 100 nm or less.

[Evaluation of dispersion stability of colorant in photosensitive resin]
The viscosity (p) at 25 ° C. of the photosensitive compositions of Examples 1 to 13 and Comparative Examples 1 and 2 and the viscosity (q) after storage in a thermostatic bath at 25 ° C. for 2 weeks were measured using an E-type viscometer [TOKI SANGYO Measured using a TVE-22L viscometer manufactured by Co., Ltd. The viscosity change rate was calculated from the following formula.
Viscosity change rate (%) = {(q / p) -1} × 100
Next, the dispersion stability was determined according to the following criteria.
A: Viscosity change rate of less than 1% B: Viscosity change rate of 1% or more and less than 3% Δ: Viscosity change rate of 3% or more and less than 5% ×: Viscosity change rate of 5% or more

[Evaluation of sensitivity]
The photosensitive compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were applied onto a 10 cm × 10 cm square glass plate by a spin coater and dried to form a coating film having a dry film thickness of 1 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes to remove the solvent.
Line width / space width of the obtained coating film is 5/5, 6/6, 7/7, 8/8, 9/9, 10/10, 11/11, 12/12, 20/20 μm, respectively. The light of the ultra high pressure mercury lamp was irradiated through the photomask on which the line pattern was formed. In addition, the exposure (exposure gap) between the mask and the substrate was 100 μm.
Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes. Next, the line width of the pattern formed in the part having a line / space width of 20 μm was measured with an optical microscope.
Irradiation exposure went increased stepwise by 10 mJ / cm ² increments from 30 mJ / cm ^2, and the sensitivity of the resist with minimum exposure amount becomes the same line width as that of the photomask (mJ / cm ^2). The smaller this value, the higher the sensitivity, and it is preferably 60 mJ / cm ² or less.

[Resolution Evaluation]
The photosensitive compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were applied onto a 10 cm × 10 cm square glass plate by a spin coater and dried to form a coating film having a dry film thickness of 1 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
The obtained coating film was irradiated with light of an ultrahigh pressure mercury lamp at 60 mJ / cm ² through a photomask having a line pattern of line width / space width = 5 / 5-20 / 20 μm. The exposure gap was 100 μm.
Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes, and the resulting cured film was observed with an optical microscope.
The unexposed part was removed without residue, and the minimum value of the line width / space width of the line pattern formed without the meandering and chipping of the exposed part was observed with a microscope to evaluate the resolution.
The smaller this minimum value is, the higher the resolution is, and it is desirable that it be 10 μm or less.

[Evaluation of substrate adhesion]
The photosensitive compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were applied on a 10 cm × 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 1 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
The obtained coating film was irradiated with 60 mJ / cm ² of light from an ultrahigh pressure mercury lamp. Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a protective film having a thickness of 1 μm.
About the obtained protective film, the adhesiveness of the protective film was evaluated by the adhesiveness (cross-cut method) of JIS K5600-5-6. The measurement result is expressed as “number of squares remaining on base film after test / 100”. The larger this value, the higher the substrate adhesion, and it is desirable that it is 95/100 or more.

[Evaluation of optical density (OD value)]
The black photosensitive compositions of Examples 1, 2, and 6 to 13 and Comparative Examples 1 and 2 were applied on a 10 cm × 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 1 μm. . This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
The obtained coating film was irradiated with 60 mJ / cm ² of light from an ultrahigh pressure mercury lamp. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a protective film having a thickness of 1 μm.
This substrate was measured using a microspectrophotometer (“MSV-5100” manufactured by JASCO Corporation), and the optical density (OD value) at a film thickness of 1.0 μm was determined from the following formula.
OD value = log ₁₀ (I ₀ / I)
Here, I _{0 is} incident light intensity, and I is transmitted light intensity.
The larger this value, the higher the shielding property and the less light leakage of the backlight when the liquid crystal panel is formed. When used in a black matrix application, the OD value is preferably 3.5 or more.

  Table 2 shows the results of evaluating the dispersed particle diameter of the colorant, the dispersion stability of the colorant, the sensitivity, the resolution, the substrate adhesion, and the optical density for Examples 1 to 13 and Comparative Examples 1 and 2.

The photosensitive composition for forming a color filter according to Examples 1 to 13 of the present invention or the cured film of each color using the same is obtained by dispersing the colorant dispersion particle size, the colorant dispersion stability, sensitivity, resolution, and substrate adhesion. Excellent results were obtained for all evaluation items of optical density. In addition, in an Example, when mix | blending a radically polymerizable substance (B) with a dispersion (Y) previously, when mix | blending later, it may mix | blend both.
On the other hand, in Comparative Example 1 in which the radical initiator (C) was not used, the resin was not sufficiently cured, and performance evaluation of sensitivity, resolution, substrate adhesion, and optical density could not be performed. Moreover, the comparative example 2 using the dispersion (RY-1) disperse | distributed with the sand mill had a large dispersion | distribution particle size of the coloring agent in a photosensitive composition, and its dispersion stability was bad. For this reason, the resolution, substrate adhesion and optical density of the cured film were also insufficient.

T1: Mixing tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T2: Dispersion tank B1: Carbon dioxide cylinder P1: Solution pump P2: Carbon dioxide pump M1: Static mixer V1: Valve

Since the photosensitive composition for forming a color filter of the present invention is excellent in curability, resolution, substrate adhesion and shielding properties, it can be suitably used for forming color filters and black matrixes for liquid crystal display devices.

Claims (7)

In the method for producing a photosensitive composition containing a colorant (A), a radical polymerizable substance (B) and a radical initiator (C), the colorant (A), the radical polymerizable substance (B) and a compressive fluid ( A step of volume-expanding the mixture (X) with F) to obtain a dispersion (Y), and a step of mixing the dispersion (Y) and the radical initiator (C). A method for producing an alkali-soluble photosensitive composition for forming a color filter, wherein the content of the polymer (BP) is 5% by weight or less based on the total weight of the radical polymerizable substance (B).   The color filter according to claim 1, wherein the radical polymerizable substance (B) contains a polymerizable resin (B1) having an ethylenic double bond and a carboxyl group in the molecule and having a weight average molecular weight of 1,500 to 200,000. Manufacturing method of photosensitive composition for formation.   The method for producing a photosensitive composition for forming a color filter according to claim 1 or 2, wherein the radical polymerizable substance (B) contains a polymerizable monomer (B3) having a weight average molecular weight of less than 1,500. The method for producing a photosensitive composition for forming a color filter according to any one of claims 1 to 3, wherein the volume average particle diameter of the colorant in the photosensitive composition is 1 nm to 400 nm. Furthermore, the manufacturing method of the photosensitive composition for color filter formation in any one of Claims 1-4 containing an acid generator (D) or a base generator (E).   The method for producing a photosensitive composition for forming a color filter according to any one of claims 1 to 5, wherein the colorant (A) is a black pigment. The color filter using the hardened | cured material of the photosensitive resin composition for color filter formation obtained with the manufacturing method in any one of Claims 1-6.