JP4597638B2 - Method for producing photocurable composition, color filter, and method for evaluating photocurable composition - Google Patents

Description

The present invention relates to a method for producing a photocurable composition suitable for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a color filter, and a method for evaluating the photocurable composition.

  In recent years, as the use of a liquid crystal display device (LCD) has expanded from a personal computer application to a TV application, demands for color filters have increased, and improvement in contrast and improvement in color purity have been desired. Further, in image sensor applications such as solid-state imaging devices, when the colorant is an organic pigment, further miniaturization of the dispersion unit of the pigment particles is required, and improvement in the image quality of the reproduced image is desired.

  On the other hand, in order to improve the contrast of the color filter, many methods for reducing the pigment dispersion unit in the color filter pixel have been conventionally proposed (see, for example, Patent Documents 1 to 6).

  Conventionally, as a general method for measuring the size of particles dispersed in a medium, for example, a light scattering method, a sedimentation method, an image analysis method, or the like has been used. However, in any of these methods, it is necessary to dilute the dispersion by several tens to several hundred times with an appropriate liquid dispersion medium. When the dispersion is diluted in this way, the dispersion state of the particles is greatly changed by a solvent shock or the like when the dispersion is diluted, and it is impossible to measure with a dispersion size that actually behaves in the dispersion to be measured. There is. For this reason, in the measurement method for diluting the dispersion such as the light scattering method described above, a specific correlation cannot be obtained between the particle size and the contrast, and the particle size distribution obtained by these methods is used. It has not been possible to control the performance when producing a color filter for a display device typified by an LCD or the roughness of an image reproduced through a color filter for an image input device such as an image sensor.

Japanese Patent Laid-Open No. 6-324211 JP-A-7-198933 JP-A-8-171014 JP-A-9-197118 JP-A-10-130547 JP 2003-177530 A

The present invention aims at providing a method of manufacturing a photocurable composition capable of producing a color filter having excellent contrast, and color filters obtained therefrom.
In addition, the present invention can evaluate the contrast of a display image when a color filter for a display device typified by an LCD is produced and the roughness of an image reproduced through a color filter for an image input device such as an image sensor. An object of the present invention is to provide a method for evaluating a photocurable composition.

The above problem is solved by the following means.
<1> A method for producing a photocurable composition comprising two or more pigments, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator,
A dispersion containing the pigment and at least a dispersant, a dispersion in a high viscosity state and / or a dry dispersion in which the pigment is dispersed so that the viscosity after dispersion of the dispersion is 50,000 mPa · s or more. A step of dispersing in combination with dispersion in a low viscosity state and / or wet dispersion in which the pigment is dispersed so that the viscosity after dispersion of the dispersion having undergone the dispersion is 1000 mPa · s or less,
And a step of dispersing the pigment under a high-pressure condition of 100 kg / m ³ or more,
It is a method for producing a photocurable composition, wherein the particle size distribution of the pigment measured by the ultrasonic attenuation method after the step satisfies all of the following (1) to (4).
(1) D ₈₄ is 1.0 μm or less (2) D ₅₀ is 0.5 μm or less (3) D ₁₆ is 0.3 μm or less (4) Maximum distribution peak is 0.5 μm or less <2> In the high viscosity state In dispersion and / or dry dispersion and dispersion and / or wet dispersion in the low viscosity state, the dispersion contains an alkali-soluble resin,
In the dispersion and / or wet dispersion in the low viscosity state, the pigment is dispersed using an alkali-soluble resin having a molecular weight lower than that of the alkali-soluble resin used in the dispersion and / or dry dispersion in the high viscosity state. <1> The method for producing a photocurable composition according to <1>.
<3> A method for producing a photocurable composition comprising two or more pigments, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator,
A dispersion containing the pigment, at least an alkali-soluble resin, and a dispersant is dispersed in a high-viscosity state in which the pigment is dispersed so that the viscosity after dispersion of the dispersion is 50,000 mPa · s or more. or a dry dispersion, the steps of the viscosity after dispersion of the dispersion has passed through the dispersion is dispersed by combining the dispersion and / or wet dispersion in a low viscosity state to disperse the pigment so that less 1000 mPa · s,
The dispersion in the low viscosity state and / or the wet dispersion is performed by dispersing the pigment using an alkali-soluble resin having a molecular weight lower than that of the alkali-soluble resin used in the dispersion and / or dry dispersion in the high viscosity state,
It is a method for producing a photocurable composition, wherein the particle size distribution of the pigment measured by the ultrasonic attenuation method after the step satisfies all of the following (1) to (4).
(1) D ₈₄ is 1.0μm or lower (2) D ₅₀ is 0.5μm or lower (3) D ₁₆ is 0.3μm or less 4 maximum distribution peak is 0.5μm or less <4> Furthermore, the pigment 100kg / m ³ including the step of dispersing at least a high pressure under the conditions of a manufacturing method of the photocurable composition of the <3>, wherein the.

<5> above <1> to <4> with a photocurable composition obtained by the manufacturing method of the photocurable composition is applied to a substrate to form a film, and patterning the coating film by photolithography It is a color filter characterized by being obtained.

< 6 > An ultrasonic attenuation spectrum of the pigment is measured by an ultrasonic attenuation method using a photocurable composition containing a pigment, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. A particle size distribution of the pigment is calculated from the ultrasonic attenuation spectrum, and at least one D _x and a maximum distribution peak value are obtained from the calculated particle size distribution. It is an evaluation method.

<7> the one or more D _x is the evaluation method of the photocurable composition of the <6>, characterized in that the D _84, D ₅₀ and D _16.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the photocurable composition which can produce the color filter excellent in the contrast of a display image, and the color filter obtained by using this can be provided. In addition, according to the present invention, evaluation of contrast of a display image when a color filter for a display device typified by an LCD is produced, roughness of an image reproduced through a color filter for an image input device such as an image sensor, and the like. It is possible to provide a method for evaluating a photocurable composition that can be used.

<< Photocurable composition >>
The photocurable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) contains a pigment, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator, The particle size distribution measured by the ultrasonic attenuation method of the pigment satisfies all of the following (1) to (4).
(1) D ₈₄ is 1.0 μm or less (2) D ₅₀ is 0.5 μm or less (3) D ₁₆ is 0.3 μm or less (4) Maximum distribution peak is 0.5 μm or less

  Since the composition of the present invention includes a pigment having a fine particle size that satisfies all the above conditions (1) to (4), a color filter having a high contrast of a display image can be produced. In the present invention, the particle size can be measured by an ultrasonic attenuation method described later.

Here, “ _D84 is 1.0 μm or less” in the above condition (1) means that the cumulative amount when the deposition amount (mass basis) is counted from particles with a small particle size in the composition is the total particle size. When 100%, it means that the particle diameter corresponding to 84% is 1.0 μm or less. The D ₈₄ of the pigment in the composition of the present invention is preferably 0.5 μm or less, and more preferably 0.3 μm or less. When the D ₈₄ exceeds 1.0 μm, the contrast of the display image on the LCD is lowered, or the roughness of the image reproduced by the image sensor is noticeable (the S / N ratio is lowered).
Similarly, in the present invention, “D ₅₀ is 0.5 μm or less” in the above condition (2) is the cumulative amount when the deposition amount (mass basis) is counted from particles having a small particle size in the composition. However, it means that the particle diameter of the particles corresponding to 50% is 0.5 μm or less when the whole particles are taken as 100%. The D ₅₀ of the pigment in the above condition (2) is preferably 0.3 μm or less, and more preferably 0.1 μm or less. When the D ₅₀ exceeds 0.5 μm, the contrast of the display image on the LCD is lowered, or the roughness of the image reproduced by the image sensor is noticeable (S / N ratio is lowered).
Similarly, in the present invention, “D ₁₆ is 0.3 μm or less” in the above condition (3) means that the accumulated amount when the deposition amount (mass basis) is counted from particles having a small particle size in the composition. However, it means that the particle diameter corresponding to 16% is 0.3 μm or less when the entire particle is taken as 100%. D ₁₆ of the pigment in the condition (3) is preferably 0.2 μm or less, and more preferably 0.01 μm or less. When the D ₁₆ exceeds 0.3 μm, the contrast of the display image on the LCD is lowered, or the roughness of the image reproduced by the image sensor is noticeable (the S / N ratio is lowered).

  Furthermore, the maximum distribution peak of the pigment in the condition (4) is 0.5 μm or less, preferably 0.45 μm or less, and more preferably 0.4 μm or less. When the maximum distribution peak exceeds 0.5 μm, the contrast of the display image on the LCD is lowered or the roughness of the image reproduced by the image sensor is noticeable (S / N ratio is lowered).

In the composition of the present invention, each of the above flat _Dx and the maximum distribution peak is obtained from a particle size distribution measured by an ultrasonic attenuation method.
Here, the “ultrasonic attenuation method” means the ultrasonic attenuation spectroscopy described in “Coloring material, 75 [11], 530-537 (2002) Eiichi Takeda, Okayama University”. The ultrasonic attenuation method is an optimum method for measuring the average particle diameter and distribution pattern of non-spherical particles. Examples of the particle size distribution measuring apparatus using the ultrasonic attenuation method include trade name DT-1200 manufactured by Dispersion Technology.

The ultrasonic attenuation method is carried out by pouring a measurement suspension from the upper part of the measurement chamber and basically circulating the slurry, and by changing or stopping the circulation speed as necessary. . The ultrasonic attenuation method irradiates the suspension in the chamber with ultrasonic waves of 3 to 100 MHz from a vibrator installed on one side, receives this with the vibrator installed on the other side, and the ultrasonic waves are suspended. This is a method of measuring the rate of attenuation (ultrasonic attenuation spectrum) while propagating through the suspension and calculating the particle size distribution from the measured value.
The specific measurement method of the ultrasonic attenuation method is described in the above-mentioned “Coloring Material, 75 [11], 530-537 (2002), Eiichi Takeda, Okayama University”.

  The “particle size distribution” can be calculated from the ultrasonic attenuation spectrum obtained by measuring the ultrasonic attenuation spectrum of the pigment by the method described above. Specifically, the particle size distribution can be calculated according to the following formula A.

Critical frequency (peak value of damping factor) W _CR ≒ 2 x dynamic viscosity / particle radius ... (Formula A)
Here, the critical frequency W _CR means the peak value of the attenuation factor. The ultrasonic attenuation spectrum is measured by first measuring a blank dispersion medium solution from which particles have been removed, taking necessary data, and then measuring the target measurement sample. From the measurement data, the blank data of the solution is measured. To determine the particle size distribution.

  Unlike the conventional particle size distribution measurement method such as the light scattering method, the ultrasonic attenuation method is used without diluting the dispersion containing the pigment to be measured or diluting at a volume ratio of 10 times or less. Can be measured. From the viewpoint of measurement accuracy, it is preferably 2 times or less (the content of dispersed particles in the dispersion is 50% by mass or less). That is, according to the above ultrasonic attenuation method, it is usually not necessary to dilute the measurement sample, so that the measurement value differs from the actual value due to aggregation of particles due to solvent shock accompanying dilution as in the conventional measurement method. There is no fear of becoming. When the composition having the particle size distribution of the present invention and having excellent contrast of the display image and the composition having poor contrast of the conventional display image are measured by the ultrasonic attenuation method, as shown in FIG. The maximum distribution peaks are different and the difference is markedly shown. On the other hand, when the composition having the particle size distribution of the present invention and having excellent display image contrast is measured by the light scattering method, and the composition having inferior contrast of the conventional display image, as shown in FIG. The difference in the maximum distribution peak is very small, and the difference in effect cannot be shown sufficiently. 1 and 2, composition A is the composition of the present invention, and composition B is a photocurable composition that does not meet the conditions of the present invention.

Moreover, the evaluation method of the photocurable composition of the present invention (hereinafter sometimes referred to as “the evaluation method of the present invention”) is an evaluation method using the ultrasonic attenuation method described above, and includes a pigment and an alkali-soluble resin. A polymerizable monomer and a photopolymerization initiator are measured by an ultrasonic attenuation method, an ultrasonic attenuation spectrum of the pigment is measured, and the obtained ultrasonic attenuation spectrum is obtained. The particle size distribution of the pigment is calculated from the calculated particle size distribution, and the _Dx and the maximum distribution peak value of at least one pigment are obtained from the calculated particle size distribution.

In the evaluation method of the present invention, using the _Dx and maximum distribution peak value of the obtained one or more pigments, the contrast of the display image of the obtained color filter for LCD and the roughness reproduced through the color filter for image sensor Thus, the suitability for use in liquid crystal display devices (suitability for LCD applications) and suitability for use in image sensors (suitability for IS applications) can be evaluated. In general, the smaller the D _x and the maximum distribution peak value, the better the contrast of the display image when a color filter for a display device typified by an LCD is produced, and through the color filter for an image input device such as an image sensor. The roughness of the reproduced image tends to be reduced.

In this case, the above-mentioned “D _x ” is equivalent to x% when the accumulated amount when the amount of deposition (mass basis) is counted from particles having a small particle size in the composition is 100%. The particle size to be used. That is, when the particle size distribution (mass basis) is indicated by a curve, and the mountain shape surrounded by the curve and the horizontal axis is 100%, the shape of the shape when cut in parallel with the vertical axis from the smaller particle size is shown. This means the particle size (value on the horizontal axis) where the area is x%. The above x can be arbitrarily selected from a range exceeding 0 and less than 100. Further, according to the evaluation method of the present invention, it is preferable to identify a plurality of D _x, for example, in the case of specifying three points the D _x is a point between D ₁₀ ~D _20, D ₄₀ and one point between to D _60, it is preferred to identify the one point between the D ₈₀ to D _90, the D _x, for example, in the case of the pigment, three points D _84, D ₅₀ and D ₁₆ Is preferably specified.

<Method for Preparing Composition of the Present Invention>
As described above, the composition of the present invention is a novel composition having a fine particle size distribution in which the pigment satisfies all of the above conditions (1) to (4). In the present invention, the method for dispersing the pigment to a particle size distribution satisfying all of the above conditions (1) to (4) is not particularly limited, but in order to adjust the particle size distribution of the pigment to the above range, The pigment dispersion method is particularly important. Examples of such a dispersion method include the following dispersion methods.

  The composition of the present invention is a pigment, an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and other additives used as necessary, mixed with a solvent, and described below using various mixers and dispersers. It can prepare by combining each dispersion method of these.

  First, as a dispersion method suitable for the above-described present invention, dispersion and / or dry dispersion (kneading dispersion treatment) in a high-viscosity state using a roll mill such as a kneader or two rolls, and using a three roll or bead mill, etc. Examples thereof include a dispersion method in which dispersion and / or wet dispersion (fine dispersion treatment) is combined in a relatively low viscosity state ((high viscosity / low viscosity) sequential combination dispersion). Moreover, as a dispersion method suitable for the above-mentioned present invention, a dispersion method (co-dispersion) in which two or more kinds of pigments are dispersed together is also exemplified. Furthermore, as a dispersion method suitable for the present invention described above, a preliminary process for preliminarily preparing a dispersion in which a pigment having an average particle diameter of 1 μm or less is dispersed in a dispersant and a solvent, and the preliminary process are obtained. And a high-pressure dispersion step in which the dispersion is subjected to a dispersion treatment under high pressure.

-(High viscosity / Low viscosity) Sequential combination dispersion-
First, the above (high viscosity / low viscosity) sequential combination dispersion will be described. As described above, the above (high viscosity / low viscosity) sequential combination dispersion is performed in a high viscosity state using a roll mill such as a kneader or two rolls, and / or dry dispersion (kneading dispersion treatment), three rolls or bead mill, etc. Is a dispersion method that combines dispersion and / or wet dispersion (fine dispersion treatment) in a relatively low viscosity state.
During the kneading and dispersing treatment, it is also preferable not to use a solvent or to reduce the amount used as much as possible or to use various dispersants.

  Furthermore, in the above (high viscosity / low viscosity) sequential combination dispersion, it is preferable to add the resin component separately during the kneading dispersion treatment and during the fine dispersion treatment (use in two divisions) in order to reduce the solvent shock. In addition, it is preferable to use a resin component having excellent solubility in order to prevent the pigment particles from reaggregating when shifting from the kneading and dispersing process to the fine dispersing process. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment. In addition, as the resin component, for example, an alkali-soluble resin described later can be used.

  In addition, when adding the alkali-soluble resin, it is preferable to use an alkali-soluble resin having a high molecular weight during the kneading and dispersing treatment, and to use an alkali-soluble resin having a low molecular weight during the fine dispersion treatment. The weight average molecular weight of the alkali-soluble resin used during the kneading and dispersing treatment is preferably 5,000 to 100,000, and more preferably 10,000 to 50,000. Moreover, as a weight average molecular weight of alkali-soluble resin used at the time of the said fine dispersion process, 5,000-50,000 are preferable and 5000-20,000 are more preferable.

  The above (high viscosity / low viscosity) sequential combination dispersion preferably comprises kneading dispersion followed by fine dispersion treatment, but the kneading dispersion can be omitted.

The above (high viscosity / low viscosity) sequential combination dispersion will be specifically described.
In the above (high viscosity / low viscosity) sequential combination dispersion, first, the viscosity after the kneading dispersion treatment is, for example, 50,000 mPa · s or more (preferably 50,000 to 100,000 mPa · s). In such a manner, an alkali-soluble resin is added to the pigment and kneaded and dispersed. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion.

  Then, if necessary, an alkali-soluble resin is additionally added to the dispersion after the kneading dispersion treatment, and the viscosity after the fine dispersion treatment is, for example, a relatively low viscosity of 1000 mPa · s or less (preferably 100 mPa · s or less). A fine dispersion process is performed so that The fine dispersion treatment may be low viscosity dispersion or wet dispersion.

  In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. Thus, when dispersion is performed without using much solvent, the surface of the pigment particles can be promoted to wet with the constituent components mainly composed of the resin component of the vehicle, and the interface formed by the pigment particle surface is The solid / gas interface between the pigment particles and air can be converted to a solid / solution interface between the pigment particles and the vehicle solution. When the interface formed by the surfaces of the pigment particles is converted from air to a solution and mixed and stirred, the pigment can be dispersed to a fine state close to the primary particles.

  Thus, in order to highly disperse the pigment, it is effective to convert the interface formed by the pigment particle surface from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the above kneading and dispersing treatment, it is preferable to use a kneading machine capable of exhibiting a strong shearing force and compressing force, and to use a material having a high viscosity as the material to be kneaded.

  For example, when a color filter is produced using the composition of the present invention, the kneading and dispersing treatment is performed by first kneading a pigment such as an organic pigment, a dispersing agent, a surface treating agent, and a minimum amount of solvent. As a kneading machine, a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder, etc. can be used, and they are dispersed while giving a strong shearing force. As the kneader, a two-roll mill is particularly preferable. Next, a solvent and, if necessary, an alkali-soluble resin are added, mainly using a vertical or horizontal sand grinder, ball mill, pin mill, slit mill, homogenizer, disper, ultrasonic disperser, etc. Disperse with beads made of glass or zirconia of particle size.

In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, since it is necessary to distribute the pigment particles uniformly and stably to a fine state, a disperser capable of applying impact force and shear force to the aggregated pigment particles is provided. It is preferable to use a low-viscosity material to be dispersed.
The details of the kneading dispersion treatment and the fine dispersion treatment are also described in TC Patton "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964) and the like.

-Covariance-
Next, the covariance will be described.
The co-dispersion is a method in which two or more pigments are dispersed together. In the above-mentioned co-dispersion, two or more types of pigments mean two or more types of pigments having different chemical structures, volumes, masses, primary particle sizes, etc., and in particular, two or more types of pigments having different chemical structures may be used. preferable.

  Preferred combinations of the two or more pigments include a combination of Pigment Red 254 and Pigment Yellow 139, a combination of Pigment Red 254 and Pigment Red 177, a combination of Pigment Red 177 and Pigment Yellow 139, and Pigment B: 6 A combination with Pigment Violet 23 and a combination with Pigment Green 36 and Pigment Yellow 150 are included, but are not limited thereto.

−High pressure dispersion treatment−
As described above, the high-pressure dispersion treatment includes, for example, a preliminary process for preliminarily preparing a dispersion in which a pigment having an average particle diameter of 1 μm or less is dispersed in a dispersant and a solvent, and the dispersion obtained in the preliminary process. And a high-pressure dispersion step of dispersing the liquid under high pressure.

  The preliminary step is a step of preliminarily mixing and dispersing the pigment, the dispersant, and the solvent. A known mixer or disperser can be used for the mixing and dispersing. Examples of the known mixers and dispersers include sand mill type dispersers or mixers, dissolvers, homomixers, ball mill types, kneaders and other high-speed stirrer type dispersers, and two-roll or three-roll type dispersers. A sand mill type disperser or mixer is preferable.

  In the preliminary step, the particles (pigments) in the dispersion are preferably 1 μm or less in average particle diameter, more preferably 0.05 μm to 0.7 μm, and 0.05 μm to 0.4 μm. It is particularly preferred. Further, the viscosity of the dispersion in the preliminary step is preferably 50000 mPa or less, more preferably 20000 mPa or less, and particularly preferably 10,000 mPa or less.

The high-pressure dispersion step is a step of dispersing the dispersion obtained above under high-pressure conditions. The pressure in the high-pressure dispersion step is preferably 100 kg / m ² or more, and more preferably 300 kg / m ² or more. In the high-pressure dispersion step, it is preferable to use a disperser that can perform liquid / liquid collision at high speed under the high-pressure conditions. As the disperser, for example, a high-pressure disperser such as a microfluidizer (manufactured by microfluidics), an optimizer (manufactured by Hosokawa Micron Corporation), or a TK nanomizer (manufactured by Tokushu Kika Kogyo Corporation) can be used.

  The high-pressure dispersion treatment is a dispersion method in which particles are finely dispersed by an impact force when the preliminary dispersion liquids usually pressurized at a high pressure are collided at high speed as described above. As a dispersion method further improving this dispersion method, a high-pressure dispersion method with a decompression mechanism having a decompression mechanism structure that depressurizes the liquid by colliding a pre-dispersed liquid pressurized to a high pressure with a specific structure is called “FRAGRANCE”. JOURNAL, Vol.31, No.7.44 (2003) ”. Moreover, as a disperser with a decompression mechanism used for the high pressure dispersion system, a high pressure disperser with a multistage decompression module is commercially available from Nippon Bee Co., Ltd.

The characteristics of the high-pressure dispersion system with a decompressor mechanism were found in conventional dispersers and high-pressure dispersers without a decompression mechanism, even if the dispersion of particles progressed or the dispersion unit of particles became finer. There is no increase in the viscosity of such a dispersion, but rather a tendency for the viscosity to decrease as the dispersion progresses.
Therefore, if a photocurable composition is produced using the above-described high-pressure disperser with a decompression mechanism, the contrast of the display image on the LCD can be increased, and the reproduced image of the image sensor has less roughness (S / N ratio). In addition to a high color filter, a viscoelastic property as a coating solution is improved, and a photocurable composition excellent in wide coating suitability such as slit coating is obtained. For this reason, the application | coating to a large sized substrate becomes easier, and the fall of the manufacturing cost of a color filter can be anticipated.

  In addition, when using the high-pressure disperser with a pressure reducing mechanism, as an alkali-soluble resin contained in the photocurable composition, for example, polyalkylene oxide in the side chain as disclosed in JP-A-2003-222997 If a resin having a chain is used, further improvement in coating suitability can be expected.

  Therefore, it is preferable to use a high pressure dispersion system with a pressure reducing mechanism as the dispersion system in the present invention. Specifically, for example, a high-pressure disperser “NANO-3000-10” manufactured by Nippon BEE Co., Ltd. can be suitably used.

  In the high-pressure dispersion step, the average particle size of the pigment in the dispersion is preferably 0.05 μm to 0.7 μm, and more preferably 0.05 μm to 0.4 μm. Further, the concentration of the dispersion in the high pressure dispersion step is preferably 50000 mPa or less, more preferably 20000 mPa or less, and particularly preferably 10,000 mPa or less.

Thus, when the above-mentioned high-pressure dispersion treatment is applied to the composition of the present invention, aggregation of the pigments can be suppressed and the dispersion stability of the pigment over a long period of time can be ensured.
The preliminary step can be replaced with the fine dispersion treatment in the above-described (high viscosity / low viscosity) sequential combination dispersion. That is, after the composition of the present invention is dispersed by the above-described (high viscosity / low viscosity) sequential combination dispersion, the high-pressure dispersion step is performed, so that the effect of the (high viscosity / low viscosity) sequential combination dispersion and the above-described high pressure are achieved. Both the distributed processing effect can be obtained.

In order to obtain the composition of the present invention, it is preferable to apply at least two of the above (high viscosity / low viscosity) sequential combination dispersion, co-dispersion, and high-pressure dispersion treatment, and more preferably to apply all three types. In addition, it is particularly preferable to use alkali-soluble resins having different molecular weights as described above in the kneading dispersion treatment and fine dispersion treatment in the above (high viscosity / low viscosity) sequential combination dispersion.
Further, in the present invention, a method using a pigment in which pigment particles are made fine and the particle size distribution is sharp is suitable. Specifically, a method using a pigment constituted by including 75% by mass or more of pigment particles having an average particle size of about 0.01 μm and a particle size in the range of 0.01 ± 0.005 μm is preferable.

Further, in order to obtain the composition of the present invention, two or more kinds of pigments are dispersed in a high viscosity state of 50000 mPa · s or more (kneading dispersion treatment), and then further dispersed in a low viscosity state of 1000 mPa · s or less (slightly). (Dispersion treatment) is preferable.
In general, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder body. However, since water requires a large latent heat of vaporization for drying, it is preferable to apply a large amount of thermal energy to dry the powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

<Photocurable composition>
The composition of the present invention comprises a pigment, an alkali-soluble resin, a photopolymerization initiator, a polymerizable monomer as a photosensitive polymerization component, and a solvent as necessary. Hereinafter, the compounding component used for the composition of this invention and the usage method of this composition are demonstrated. In addition, the composition of this invention may contain surfactants, such as a fluorine-type organic compound, as needed.

(Pigment)
As the pigment that can be used in the present invention, various conventionally known pigments can be used singly or in combination.

  As the pigment that can be used in the composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having the smallest possible particle diameter. In consideration of handling properties, the average particle size of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As the organic pigment, for example,
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the polymerizable monomer and the pigment has an influence.

  Examples of pigments that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CIPigment Orange 36, 71,
CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CIPigment Violet 19, 23, 32,
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CIPigment Black 1,7;

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If the mass ratio is less than 100: 5, it may be difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

  The pigment content in the total solid content of the composition of the present invention is not particularly limited, but is preferably 30 to 60% by mass. If the amount of the pigment is too small, there is a tendency that an appropriate chromaticity as a color filter cannot be obtained. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, and the development latitude during alkali development tends to be narrow.

  In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. As these dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Zeneca), organosiloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), W001 (manufactured by Yusho), etc. Cationic surfactants of: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Fatty acid Nonionic surfactants such as Ru; Anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401 , EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other various Solsperse dispersants (manufactured by GENECA); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P 4, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co.) and Isonetto S-20 (manufactured by Sanyo Chemical Co.) and the like.

<Alkali-soluble resin>
The alkali-soluble resin is a linear organic high molecular polymer that is compatible with the monomer, and is organic solvent and alkali-soluble (preferably one that can be developed with a weak alkaline aqueous solution). As said alkali-soluble resin, the organic high molecular polymer which has a water-soluble atomic group in a part of side chain can be used. Examples of the alkali-soluble resin include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-sho 59-53836, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in JP-A-59-71048, There are partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also included.

  As the alkali-soluble resin, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Among these, specifically, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a benzyl (meth) acrylate / (meth) acrylic acid / multi-component copolymer with other monomers is preferable.

  The alkali-soluble resin includes at least (i) at least one acid component monomer selected from maleic anhydride (MA), acrylic acid (AA), methacrylic acid (MAA), and fumaric acid (FA); A copolymer comprising ii) alkylpolyoxyethylene (meth) acrylate and (iii) benzyl (meth) acrylate (hereinafter sometimes referred to as “copolymer A”) can be used.

The combinations of the above copolymers include (i) acid component monomer, (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (CH ₃ ) = CHR ) And (iii) the composition mass ratio of benzyl (meth) acrylate (BzMA) is preferably 10-25 / 5 to 25/50 to 85, more preferably 15 to 20/5 to 20/60 to 80. It is. The polystyrene-reduced mass average molecular weight (Mw) by GPC of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

When the composition mass ratio of the (i) acid component monomer is within the above range, the alkali solubility and the solubility in a solvent are unlikely to decrease. Further, when the composition mass ratio of (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (CH ₃ ) = CHR) is in the above range, the present invention Therefore, the present invention can be effectively achieved because the composition easily spreads on the substrate and the dispersibility of the colorant is hardly lowered.
When the composition mass ratio of (iii) benzyl (meth) acrylate (BzMA) is in the above range, the dispersion stability of the colorant, the solubility in the composition, and the alkali development suitability of the coating film are unlikely to decrease.

The number ( _n ) of polyoxyethylene (EO) _{n in} the above (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (CH ₃ ) = CHR) n Is preferably 2 to 15, more preferably 2 to 10, and particularly preferably 4 to 10. When the above repeating number n is within the above range, a development residue is less likely to occur after development with an alkali developer, the fluidity of the composition as a coating solution is improved, and uneven coating can be prevented from occurring, and the coating film It is possible to prevent the thickness uniformity and the liquid-saving property from decreasing.

As the alkali-soluble resin, a copolymer (i) (meth) acrylic acid and (ii) benzyl methacrylate (hereinafter sometimes referred to as “copolymer B1”) or (i) (meta ) A copolymer composed of acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate (hereinafter sometimes referred to as “copolymer B2”) can be used.
In the present invention, the copolymer B1 and the copolymer B2 are effective in the dispersion stability of the pigment. Further, when the composition in the present invention is produced, when dispersed by the above (high viscosity / low viscosity) sequential combination dispersion, the kneading dispersion treatment gives a strong shearing force to the aggregate of pigments to promote the dispersion. The dispersion stability of the pigment in the composition finally obtained through the subsequent fine dispersion treatment can be improved.

  10-50 mass% is preferable with respect to the total solid, and, as for the content rate of alkali-soluble resin in the composition of this invention, 10-40 mass% is more preferable.

<Polymerizable monomer>
Next, the polymerizable monomer used in the composition of the present invention will be described.
The polymerizable monomer is preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure. Compounds are more preferred.

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

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

Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are interposed via ethylene glycol or propylene glycol residues are preferred. These oligomer types are also used. These polymerizable monomers can be used singly or in combination of two or more.
The amount of these polymerizable monomers used is preferably 20 to 200% by mass, more preferably 50 to 120% by mass, based on the total solid content of the photocurable composition. If the amount of the polymerizable monomer used is less than the above range or too much, it is not preferable because curing is insufficient.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyloxadiazole described in JP-A-57-6096; halomethyl-s-- described in JP-B-59-1281 and JP-A-53-133428. Active halogen compounds such as triazines; aromatic carbonyl compounds such as ketals, acetals or benzoin alkyl ethers described in US Pat. No. 4,318791 and European Patent Publication EP-88050A; aromatics such as benzophenones described in US Pat. No. 4,1994,420 Group ketone compounds; (thio) xanthones or acridine compounds described in Fr-2456541; compounds such as coumarins or lophine dimers described in JP-A-10-62986; sulfoniums described in JP-A-8-015521 Organic boron complex etc. Can.

  In the present invention, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimer It is preferable to use a photopolymerization initiator such as a series or biimidazole.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl bezoate.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferable examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

  Other examples of the photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2, Examples include 4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalomethy disclosed in Japanese Patent Publication No. 51-48516 And ru-s-triazine compounds.
Moreover, these photoinitiators can also be used together.

  The usage-amount of the said photoinitiator is 0.1-10.0 mass% of the total solid of a photocurable composition, Preferably it is 0.5-5.0 mass%. When the amount of the photopolymerization initiator used is less than 0.1% by mass, the polymerization may not proceed easily, and when it exceeds 10.0% by mass, the film strength may be weakened.

<Solvent>
A solvent can be used in preparing the composition of the present invention. Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionate Ethyl acetate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xyles and the like.

Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention.
These solvents may be used alone or in combination of two or more.

<Fluorine organic compounds>
By including a fluorine-based organic compound having a fluorine content of 3 to 40% by mass in the composition of the present invention, the properties of the composition as a coating liquid can be further improved.
The fluorine content of the fluorinated organic compound is 3 to 40% by mass, preferably 5 to 30% by mass, and more preferably 7 to 25% by mass.
If the fluorine content of the fluorine-based organic compound is low, sufficient effects cannot be obtained in coating thickness uniformity and liquid-saving properties. Conversely, if the content is too large, the solubility in the composition is insufficient. There is a case.
By containing the fluorine-based organic compound in the composition of the present invention, the liquid properties as the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. In particular, the coating property to the substrate is improved, and a coating film having a uniform film thickness with no thickness unevenness can be obtained even with a small amount of liquid.

  Examples of the fluorine-based organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, manufactured by Dainippon Ink Co., Ltd.). ), FLORAD FC430, FC431, FC171 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.

  Moreover, the fluidity | liquidity as a coating liquid can be improved by containing the said fluorine-type organic compound. As a result, the interfacial tension between the substrate and the coating liquid can be reduced to improve the wettability to the substrate, and thus a coating film with small thickness unevenness can be obtained even for a thin film of about several μm. In particular, when the coating film is thin, good results are obtained for coating application, thickness unevenness, and slit coating that easily causes liquid breakage on the coating surface.

  The amount of the fluorinated organic compound added is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the entire coating solution.

<Other ingredients>
In the composition of the present invention, various additives, for example, fillers, polymer compounds other than the alkali-soluble resins, surfactants other than the above, adhesion promoters, antioxidants, ultraviolet absorbers, agglomerates, if necessary An inhibitor or the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Specifically, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, Cationic surfactants such as No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho); Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF) Nonionic surfactants such as L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; anionic surfactants such as W004, W005, W017 (manufactured by Yusho) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer Polymer dispersants such as 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94 , L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei);

UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone;
And an aggregation inhibitor such as sodium polyacrylate.

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

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl. Catechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful. .

<The usage method of the photocurable composition of this invention>
(Color filter manufacturing method)
The color filter of the present invention can be obtained by applying the composition of the present invention on a substrate to form a film, and patterning the film by a photolithography method. The color filter produced using the composition of the present invention is excellent in the contrast of the displayed image and the roughness of the reproduced image, and can be suitably used for LCD applications and image sensor applications.

  The above coating is first mixed with a pigment, an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and other additives used as necessary, and then used in various mixers and dispersers. The composition of the present invention can be prepared by combining and dispersing the above-described dispersion methods, and the resulting composition of the present invention can be applied on a substrate and dried. .

  More specifically, the obtained composition of the present invention is applied directly or via another layer to a substrate by a coating method such as spin coating, slit coating, cast coating, roll coating, etc. A radiation-sensitive composition layer) is formed, exposed through a predetermined mask pattern, and only the coating film portion irradiated with light is cured. In addition, as radiation used in the exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. The radiation referred to in the present invention is a broad concept including visible light, ultraviolet light, far ultraviolet light, X-rays and the like.

  Next, by developing the exposed colored resin film with a developer, a patterned film composed of pixels of each color (three colors or four colors) can be formed. The development is performed by performing an alkali development treatment, and the light non-irradiated part by the exposure can be eluted in an alkaline aqueous solution, and only the photocured part can be left. Any developer can be used as long as it dissolves the light-irradiated portion of the photosensitive layer but does not dissolve the light-irradiated portion.

As the developer, any developer can be used as long as it dissolves the composition of the present invention and does not dissolve the light irradiation part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass is used. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.

  Further, excess developer is washed away and dried, followed by heat treatment (post-bake) at a temperature of 50 to 240 ° C. Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, the color filter of the present invention can be obtained.

The post-baking is a post-development heating for complete curing, and usually a heating (hard baking) of about 200 ° C. to 220 ° C. is performed.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the coating film after development is in the above-mentioned condition. be able to.

  Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and those having a transparent conductive film attached thereto, photoelectric sensors used in solid-state imaging devices, and the like. Examples include a conversion element substrate, such as a silicon substrate. Furthermore, a plastic substrate is also possible. On these substrates, usually, black stripes for isolating each pixel are formed.

  The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  The coating film of the composition of the present invention applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.

  The thickness (after drying) of the film formed by applying the composition of the present invention is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, most preferably 1.0 to 2.5 μm.

  As the application of the composition of the present invention, the application mainly to the color filter has been mainly described, but it can also be applied to the black matrix provided between the pixels of the color filter. The black matrix is formed by photo-exposure and alkali development of a composition obtained by adding a black colorant such as carbon black or titanium black to the composition of the present invention, and then post-baking to promote film curing. Can be made.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by a following example. Unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.

[Example 1]
<< Preparation of photocurable composition >>
-Kneading and dispersing treatment-
Each component of the following composition A was kneaded for 30 minutes with a kneader. After kneading, a high viscosity dispersion treatment was further performed with two rolls. At this time, the viscosity of the dispersion was 70,000 mPa · s. In addition, the weight average molecular weight of alkali-soluble resin measured the molecular weight by GPC method for the resin solution, and calculated | required the weight average molecular weight of polystyrene conversion.

[Composition A]
Pigment Red 254 27 parts Pigment Yellow 139 4 parts Benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer propylene glycol monomethyl acetate solution 22 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 2 parts (Brand name: BY-161, manufactured by BYK)

-Fine dispersion processing-
Each component of the following composition B was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads. At this time, the viscosity of the mixed solution was 20 mPa · s.

[Composition B]
22 parts of propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30, Mw: 10000, solid content 50%)
・ 200 parts of propylene glycol monomethyl acetate

−High pressure dispersion treatment−
The obtained mixed solution was subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser with a pressure reducing mechanism (trade name: NANO-3000-10, manufactured by Nippon BEE Co., Ltd.). did. The high-pressure dispersion treatment was repeated 10 times to obtain a dispersion.

-Preparation of photocurable composition-
Each component of the following composition C was added to the obtained dispersion and mixed by stirring to prepare the photocurable composition of the present invention.

[Composition C]
・ Dipentaerythritol pentahexaacrylate 27 parts (photopolymerizable monomer)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 4 parts (photopolymerization initiator)
・ Propylene glycol monomethyl ether acetate 150 parts

<Ultrasonic attenuation method>
Without diluting the obtained photocurable composition with a solvent or the like, an attenuation spectrum is directly measured using an ultrasonic attenuation method particle size distribution analyzer (trade name: DT-1200, manufactured by DispersionTechnology), and a particle size distribution is obtained. Was calculated. The particle size distribution of the obtained pigment is shown in FIG. At this time, D ₈₆ was 0.266 μm, D ₅₀ was 0.069 μm, D ₁₆ was 0.020 μm, and the maximum distribution peak was 0.073 μm.

《Light scattering method》
Further, the obtained photocurable composition was diluted 500 times with propylene glycol monomethyl ether, and the particle size distribution was measured using a light scattering particle size distribution analyzer (trade name: Microtrac UPA, manufactured by Nikkiso Co., Ltd.). It was measured. The particle size distribution of the obtained pigment is shown in FIG. At this time, D ₈₆ was 0.091 μm, D ₅₀ was 0.0109 μm, D ₁₆ was 0.0241 μm, and the maximum distribution peak was 0.0107 μm.

<Liquid crystal display device characteristics>
The contrast of the colored resin film for a color filter obtained as described below was measured, and the characteristics for liquid crystal display device application were evaluated.

-Formation of colored resin film for color filter-
A photocurable composition obtained so as to have a film thickness of 2.0 μm was applied onto a 100 mm × 100 mm glass substrate (trade name: 1737, manufactured by Corning) and dried in a 90 ° C. oven for 120 seconds (prebaked) ) To form a photocurable coating film. Thereafter, the photocurable coating film is exposed in a pattern using a 2.5 kw ultra-high pressure mercury lamp. After the exposure, the entire surface of the photocurable coating film is exposed to an organic developer (trade name: CD, Fuji Film Arch). (Co., Ltd.) 10% aqueous solution and covered for 60 seconds.

  Thereafter, pure water was sprayed in the form of a shower to wash away the developer, and the coating film subjected to the photocuring treatment and the development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the colored resin film for color filters was formed on the glass substrate.

-Contrast measurement-
The colored resin film for color filter formed on the glass substrate was measured with a contrast measuring device (trade name: BM-7, manufactured by Topcon Corporation) to obtain the contrast of the colored resin film for color filter. The results are shown in Table 1 below.

<Image sensor characteristics>
The degree of roughness of the obtained colored resin film for a color filter was measured, and image sensor application characteristics were evaluated.
First, the obtained colored resin film for color filters is placed between the observation lens and the light source of the optical microscope, and the light is irradiated toward the observation lens, and the digital camera with a magnification of 1000 times installs the transmitted light state Was observed with an optical microscope. A digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format. The film surface was photographed on 20 arbitrarily selected areas.
In addition, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of RGB.

  Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged. In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.

For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A section having a difference of 5 or more from the average brightness of the adjacent section was recognized as a significant difference section, and the ratio of the average total number of significant difference sections in all the regions to the total number (39976) of each region was calculated. The results are shown in Table 1 below.
Note that the smaller the ratio of the average total number of significant difference sections in all the areas to the total number of sections in each area, the less the roughness of the reproduced image, which indicates that it is suitable for use as an image sensor.

[Example 2]
A photocurable composition of the present invention was prepared in the same manner as in Example 1 except that the high-pressure dispersion treatment in Example 1 was not performed, and the same evaluation as in Example 1 was performed. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Example 3]
A photocurable composition of the present invention was prepared in the same manner as in Example 1 except that the composition B added during the fine dispersion treatment in Example 1 was changed to the following composition D, and the same evaluation as in Example 1 was performed. went. The viscosity of the mixed solution when subjected to the fine dispersion treatment in Example 3 was 30 mPa · s. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Composition D]
22 parts of propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ 200 parts of propylene glycol monomethyl acetate

[Comparative Example 1]
Each component of the following composition E was kneaded with a kneader for 30 minutes. After kneading, dry dispersion treatment (kneading dispersion treatment) was further performed with two rolls. At this time, the viscosity of the dispersion was 70,000 mPa · s.
[Composition E]
-Pigment Red 254 80 parts-Pigment Yellow 139 20 parts-Benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer propylene glycol monomethyl acetate solution 25 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 30 parts (trade name: EDAPLAN472, manufactured by Enomoto Kasei Co., Ltd.)

-Fine dispersion processing-
To the obtained dispersion, 750 parts of propylene glycol monomethyl ethyl acetate as a solvent component was added, and the mixture was stirred for 30 minutes using a homogenizer at 2000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and then filtered with a 2.5 μm filter. A dispersion was obtained.

  Next, with respect to 200 parts of the obtained dispersion, the following composition F was uniformly mixed with a stirrer to obtain a photocurable composition for comparison.

[Composition F]
33 parts of propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ 36 parts of dipentaerythritol pentaacrylate (photopolymerizable monomer)
・ 110 parts of propylene glycol monomethyl ethyl acetate (solvent)
・ Ethyl-3-ethoxypropionate (solvent) 44 parts ・ Halomethyltriazine-based initiator 4 parts (photopolymerization initiator, trade name: TAZ107, manufactured by Midori Chemical Co., Ltd.)

  Evaluation similar to Example 1 was performed about the obtained photocurable composition. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Comparative Example 2]
In the kneading dispersion treatment in Example 3, a comparative photocurable composition was prepared in the same manner as in Example 3 except that the following composition G was used instead of the composition A, and the same evaluation as in Example 1 was performed. It was. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Composition G]
・ Pigment Red 254 31 parts ・ Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 22 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50% )
・ Dispersant 2 parts (Brand name: BY-161, manufactured by BYK)

[Comparative Example 3]
A comparative photocurable composition was prepared in the same manner as in Example 3 except that the following composition H was used instead of the composition B in the fine dispersion treatment without performing the kneading dispersion treatment in Example 3. The same evaluation as in Example 1 was performed. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Composition H]
Pigment Red 254 27 parts Pigment Yellow 139 4 parts Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 44 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ 200 parts of propylene glycol monomethyl acetate

[Comparative Example 4]
-Fine dispersion processing-
Each component of the following composition I was stirred with a homogenizer at 3000 rpm for 3 hours. After stirring and kneading, the obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

[Composition I]
・ Pigment Red 254 27 parts ・ Pigment Yellow 139 4 parts ・ Dispersant 2 parts (Brand name: BY-161, manufactured by BYK)
・ 200 parts of propylene glycol monomethyl acetate

−High pressure dispersion treatment−
The obtained mixed solution was subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser with a pressure reducing mechanism (trade name: NANO-3000-10, manufactured by Nippon BEE Co., Ltd.). did. The high-pressure dispersion treatment was repeated 10 times to obtain a dispersion.

-Preparation of photocurable composition-
Each component of the following composition J was added to the obtained dispersion and stirred and mixed to prepare a comparative photocurable composition. Evaluation similar to Example 1 was performed about the obtained photocurable composition. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.

[Composition J]
・ Dipentaerythritol pentahexaacrylate 27 parts (photopolymerizable monomer)
44 parts of propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30, Mw: 10000, solid content 50%)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 4 parts (photopolymerization initiator)
・ Propylene glycol monomethyl ether acetate 150 parts

[Example 4]
A photocurable composition of the present invention was prepared in the same manner as in Example 1 except that the composition A added during the kneading and dispersing treatment in Example 1 was changed to the following composition K, and the same evaluation as in Example 1 was performed. went. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.
[Composition K]
Pigment Red 254 21 parts Pigment Red 177 10 parts Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 22 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 2 parts (Brand name: BY-161, manufactured by BYK)

[Example 5]
A photocurable composition of the present invention was prepared in the same manner as in Example 1 except that the composition A added during the kneading dispersion treatment in Example 1 was changed to the following composition L, and the same evaluation as in Example 1 was performed. went. The results are shown in FIGS. 4 and 7 and Tables 1 and 2 below.
[Composition L]
Pigment Green 36 21 parts Pigment Yellow 150 10 parts Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 20 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 4 parts (Brand name: BY-161, manufactured by BYK)

[Example 6]
A photocurable composition of the present invention was prepared in the same manner as in Example 1 except that the composition A added during the kneading and dispersing treatment in Example 1 was changed to the following composition M, and the same evaluation as in Example 1 was performed. went. The results are shown in FIGS. 5 and 8 and Tables 1 and 2 below.
[Composition M]
Pigment Blue 15: 6 26 parts Pigment Violet 23 5 partsPropylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 20 parts (BzMA / MAA = 70/30, (Mw: 30000, solid content 50%)
・ Dispersant 4 parts (Brand name: BY-161, manufactured by BYK)

[Comparative Example 5]
A photocurable composition of the present invention was prepared in the same manner as in Comparative Example 2 except that the composition G added during the kneading dispersion treatment in Comparative Example 2 was changed to the following composition N and high-pressure dispersion was not performed. Evaluation similar to Example 2 was performed. The results are shown in FIGS. 3 and 6 and Tables 1 and 2 below.
[Composition N]
Pigment Red 254 21 parts Pigment Red 177 10 parts Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 22 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 2 parts (Brand name: BY-161, manufactured by BYK)

[Comparative Example 6]
The photocurable composition of the present invention was prepared in the same manner as in Comparative Example 2 except that the composition G added during the kneading dispersion treatment in Comparative Example 2 was changed to the following composition O and high-pressure dispersion was not performed. Evaluation similar to Example 2 was performed. The results are shown in FIGS. 4 and 7 and Tables 1 and 2 below.
[Composition O]
Pigment Green 36 21 parts Pigment Yellow 150 10 parts Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 20 parts (BzMA / MAA = 70/30, Mw: 30000, solid content 50%)
・ Dispersant 4 parts (Brand name: BY-161, manufactured by BYK)

[Comparative Example 7]
A photocurable composition of the present invention was prepared in the same manner as in Comparative Example 2 except that the composition G added during the kneading dispersion treatment in Comparative Example 2 was changed to the following composition Q and high-pressure dispersion was not performed. Evaluation similar to Example 2 was performed. The results are shown in FIGS. 5 and 8 and Tables 1 and 2 below.
[Composition Q]
Pigment Blue 15: 6 26 parts Pigment Violet 23 5 partsPropylene glycol monomethyl acetate solution of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA) copolymer 20 parts (BzMA / MAA = 70/30, (Mw: 30000, solid content 50%)
・ Dispersant 4 parts (Brand name: BY-161, manufactured by BYK)

From Table 1, the photocurable compositions of the examples had high contrast and reduced roughness, and could be suitably used for liquid crystal display (LCD) applications and image sensor (IS) applications. In particular, co-dispersion, (high viscosity / low viscosity) sequential combination dispersion, high pressure dispersion treatment, and (high viscosity / low viscosity) sequential combination dispersion of the alkali-soluble resin added during kneading dispersion treatment and fine dispersion treatment. Examples 1, 4, 5 and 6 having different molecular weights were excellent in improving contrast and suppressing the roughness.
In contrast, Comparative Example 1 in which the molecular weight of the alkali-soluble resin added during the kneading dispersion treatment and the fine dispersion treatment was the same and the high-pressure dispersion treatment was not performed, the molecular weight of the alkali-soluble resin added during the kneading dispersion treatment and the fine dispersion treatment Comparative Example 2 in which the same and no co-dispersion were performed, Comparative Example 3 in which (compared with high viscosity / low viscosity) sequential combination dispersion was used, and Comparative Example 4 in which only co-dispersion and high-pressure dispersion treatment were performed, kneading dispersion treatment Each of the photocurable compositions of Comparative Examples 5 to 7 in which the molecular weight of the alkali-soluble resin added at the time of the fine dispersion treatment was inferior in suitability for LCD and image IS.

  In addition, as can be seen from the comparison between FIGS. 3 to 5 and FIGS. 6 to 8, the particle size distribution obtained by the ultrasonic attenuation method shows the effect and correlation between the present embodiment. In the particle size distribution obtained by the method, it was difficult to find a correlation with the effect of this example.

It is a graph which shows the particle size distribution calculated | required by the ultrasonic attenuation method. It is a graph which shows the particle size distribution calculated | required by the light-scattering method. It is a graph which shows the particle size distribution calculated | required by the ultrasonic attenuation method about Examples 1-4 and Comparative Examples 1-5. It is a graph which shows the particle size distribution calculated | required by the ultrasonic attenuation method about Example 5 and Comparative Example 6. It is a graph which shows the particle size distribution calculated | required by the ultrasonic attenuation method about Example 6 and Comparative Example 7. It is a graph which shows the particle size distribution calculated | required by the light-scattering method about Examples 1-4 and Comparative Examples 1-5. It is a graph which shows the particle size distribution calculated | required by the light-scattering method about Example 5 and Comparative Example 6. It is a graph which shows the particle size distribution calculated | required by the light-scattering method about Example 6 and Comparative Example 7.

Claims (7)

A method for producing a photocurable composition containing two or more pigments, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator,
A dispersion containing the pigment and at least a dispersant, a dispersion in a high viscosity state and / or a dry dispersion in which the pigment is dispersed so that the viscosity after dispersion of the dispersion is 50,000 mPa · s or more. A step of dispersing in combination with dispersion in a low viscosity state and / or wet dispersion in which the pigment is dispersed so that the viscosity after dispersion of the dispersion having undergone the dispersion is 1000 mPa · s or less,
And a step of dispersing the pigment under a high-pressure condition of 100 kg / m ³ or more,
The method for producing a photocurable composition, wherein a particle size distribution of the pigment measured by an ultrasonic attenuation method after the step satisfies all of the following (1) to (4).
(1) D ₈₄ is 1.0 μm or less (2) D ₅₀ is 0.5 μm or less (3) D ₁₆ is 0.3 μm or less (4) Maximum distribution peak is 0.5 μm or less And dispersing and / or dry dispersion in said high viscosity state, the in the dispersion and / or wet dispersion in a low viscosity state, the dispersion comprises an alkali-soluble resin,
In the dispersion and / or wet dispersion in the low viscosity state, the pigment is dispersed using an alkali-soluble resin having a molecular weight lower than that of the alkali-soluble resin used in the dispersion and / or dry dispersion in the high viscosity state. The method for producing a photocurable composition according to claim 1. A method for producing a photocurable composition containing two or more pigments, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator,
A dispersion containing the pigment, at least an alkali-soluble resin, and a dispersant is dispersed in a high-viscosity state in which the pigment is dispersed so that the viscosity after dispersion of the dispersion is 50,000 mPa · s or more. Alternatively, a process of dispersing in combination with dry dispersion and dispersion in a low viscosity state and / or wet dispersion in which the pigment is dispersed so that the viscosity after dispersion of the dispersion after the dispersion is 1000 mPa · s or less,
The dispersion in the low viscosity state and / or the wet dispersion is performed by dispersing the pigment using an alkali-soluble resin having a molecular weight lower than that of the alkali-soluble resin used in the dispersion and / or dry dispersion in the high viscosity state,
The method for producing a photocurable composition, wherein a particle size distribution of the pigment measured by an ultrasonic attenuation method after the step satisfies all of the following (1) to (4).
(1) D ₈₄ is 1.0 μm or less (2) D ₅₀ is 0.5 μm or less (3) D ₁₆ is 0.3 μm or less (4) Maximum distribution peak is 0.5 μm or less The method for producing a photocurable composition according to claim 3, further comprising a step of dispersing the pigment under a high-pressure condition of 100 kg / m ³ or more.   The photocurable composition obtained by the manufacturing method of the photocurable composition of any one of Claims 1-4 is apply | coated on a board | substrate, a film is formed, and this film is patterned by the photolitho method A color filter obtained by An ultrasonic attenuation spectrum of the photocurable composition containing a pigment, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator is measured by an ultrasonic attenuation method,
Calculate the particle size distribution of the pigment from the ultrasonic attenuation spectrum obtained,
A method for evaluating a photocurable composition, comprising determining at least one _Dx and a maximum distribution peak value from the calculated particle size distribution. Said one or more D _x is the evaluation method of the photocurable composition according to claim 6, characterized in that the D _84, D ₅₀ and D _16.