WO2017057222A1

WO2017057222A1 - Method for producing pigment dispersion, method for producing curable composition, method for producing cured film, method for producing solid-state imaging element equipped with cured film, method for producing color filter equipped with cured film, and method for producing image display device equipped with cured film

Info

Publication number: WO2017057222A1
Application number: PCT/JP2016/078165
Authority: WO
Inventors: 久保田　誠
Original assignee: 富士フイルム株式会社
Priority date: 2015-09-30
Filing date: 2016-09-26
Publication date: 2017-04-06
Also published as: JP6644803B2; CN108026402A; JPWO2017057222A1

Abstract

The present invention provides: a method for producing a pigment dispersion, which method achieves a quick treatment time and is capable of producing a pigment dispersion having excellent storage stability; a method for producing a curable composition; a method for producing a cured film; a method for producing a solid-state imaging element equipped with a cured film; a method for producing a color filter equipped with a cured film; and a method for producing an image display device equipped with a cured film. The method for producing a pigment dispersion according to the present invention has a step 1 for preheating a precursor composition containing a pigment, a dispersing agent, and an organic solvent and having a viscosity of 3-20 mPa·s at 25°C, and a step 2 for subjecting the preheated precursor composition to a dispersion treatment using a bead mill while keeping the liquid temperature of the preheated precursor composition at 40°C or higher but lower less than 60°C.

Description

Manufacturing method of pigment dispersion, manufacturing method of curable composition, manufacturing method of cured film, manufacturing method of solid-state imaging device including cured film, manufacturing method of color filter including cured film, and cured film Of manufacturing image display device

The present invention relates to a method for producing a pigment dispersion, a method for producing a curable composition, a method for producing a cured film, a method for producing a solid-state imaging device comprising a cured film, a method for producing a color filter comprising a cured film, and The present invention relates to a method for manufacturing an image display device having a cured film.

The pigment is preferably used as a colorant from the viewpoint of excellent fastness such as light resistance. In the case of using a pigment, since the pigment is usually present as an aggregate, a predetermined dispersion treatment is performed to dissolve the aggregate, and a pigment dispersion in which the pigment is finely dispersed is prepared and used.
For example, Patent Document 1 discloses a method of obtaining a pigment dispersion by subjecting a composition containing a pigment and a polymer (dispersant) to a dispersion treatment using beads.

JP 2006-182885 A

In recent years, a pigment dispersion having a higher pigment concentration has been demanded. In order to obtain such a pigment dispersion, it is necessary to increase the concentration of the pigment contained in the precursor composition subjected to the dispersion treatment. is there. On the other hand, when trying to increase the pigment concentration in the precursor composition, the viscosity of the precursor composition increases.
When the present inventors prepared a precursor composition having a high viscosity and applied a dispersion treatment (so-called bead mill) using beads as described in Patent Document 1, the pigment composition is sufficient. It has been found that if fine dispersion is not achieved or if sufficient dispersion of the pigment is to be achieved, the processing time becomes long and the productivity is poor.
It is also found that when the obtained pigment dispersion is stored for a predetermined time, the viscosity of the pigment dispersion increases and / or the pigment settles, and further improvement is necessary in terms of so-called storage stability. is doing.

An object of this invention is to provide the manufacturing method of a pigment dispersion which can manufacture the pigment dispersion which is short in processing time and excellent in storage stability in view of the said situation.
Moreover, this invention comprises the manufacturing method of a curable composition, the manufacturing method of a cured film, the manufacturing method of the solid-state image sensor which comprises a cured film, the manufacturing method of the color filter which comprises a cured film, and a cured film. It is another object of the present invention to provide a method for manufacturing an image display device.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by providing a step of preheating a precursor composition containing a predetermined component, and have completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) Step 1 of preheating a precursor composition containing a pigment, a dispersant, and an organic solvent and having a viscosity of 3 to 20 mPa · s at 25 ° C .;
And a step 2 of subjecting the precursor composition to a dispersion treatment by a bead mill while keeping the liquid temperature of the preheated precursor composition at 40 ° C. or more and less than 60 ° C.
(2) The method for producing a pigment dispersion according to (1), wherein the primary particle diameter of the pigment is less than 55 nm.
(3) The method for producing a pigment dispersion according to (1) or (2), wherein the acid value of the dispersant is from 30 to 100 mgKOH / g.
(4) The method for producing a pigment dispersion according to any one of (1) to (3), wherein beads having a diameter of 0.05 mm or less are used in a bead mill.
(5) The process for producing a pigment dispersion according to any one of (1) to (4), wherein in step 1, the liquid temperature of the precursor composition is preheated to 40 to 60 ° C.
(6) The method for producing a pigment dispersion according to any one of (1) to (5), wherein the liquid temperature of the precursor composition in Step 2 is maintained at more than 40 ° C. and less than 57 ° C.
(7) A step of obtaining a pigment dispersion by the production method according to any one of (1) to (6);
A method for producing a curable composition, comprising: mixing a pigment dispersion obtained in the step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition.
(8) A step of obtaining a pigment dispersion by the production method according to any one of (1) to (6);
Mixing the pigment dispersion obtained in the step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
Curing the curable composition obtained in the step to obtain a cured film.
(9) A step of obtaining a pigment dispersion by the production method according to any one of (1) to (6);
Mixing the pigment dispersion obtained in the step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
A method for producing a solid-state imaging device, comprising: a step of curing the curable composition obtained in the step to obtain a cured film.
(10) A step of obtaining a pigment dispersion by the production method according to any one of (1) to (6);
Mixing the pigment dispersion obtained in the step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
A method for producing a color filter comprising a cured film comprising: curing the curable composition obtained in the step to obtain a cured film.
(11) A step of obtaining a pigment dispersion by the production method according to any one of (1) to (6);
Mixing the pigment dispersion obtained in the step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
And a step of curing the curable composition obtained in the step to obtain a cured film.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a pigment dispersion which can manufacture the pigment dispersion which is short in processing time and excellent in storage stability can be provided.
Further, according to the present invention, there is provided a method for producing a curable composition, a method for producing a cured film, a method for producing a solid-state imaging device comprising a cured film, a method for producing a color filter comprising a cured film, and a cured film. It is also possible to provide a method for manufacturing the image display device provided.

It is the schematic which shows one embodiment for enforcing the manufacturing method of this invention typically It is a perspective view which shows the solid-state imaging device of 1st Embodiment. It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
The pigment in the present invention means, for example, an insoluble coloring compound that does not dissolve in a solvent. Here, the solvent includes the solvent exemplified in the solvent column described later. Therefore, the coloring compound which does not melt | dissolve in these solvents corresponds to the pigment in this invention.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.
In the present specification, “structural unit” is synonymous with “repeating unit”.

One of the features of the present invention is that, first, a precursor composition containing a predetermined component is subjected to a preheating treatment prior to a dispersion treatment using a bead mill. In the first place, when the viscosity of the precursor composition is high, even if the dispersion treatment by the bead mill is performed, the dispersion force to the precursor composition is hardly transmitted, and the fine dispersion of the pigment is difficult. In Patent Document 1, the dispersion treatment is carried out while heating the precursor composition to a predetermined temperature. However, as a result of investigation by the present inventor, such treatment has not always obtained a sufficient effect. Therefore, after preheating (preheating) the precursor composition to sufficiently reduce its viscosity, it is found that a desired effect can be obtained by carrying out a dispersion treatment with a bead mill while maintaining a predetermined temperature. Yes.
Further, as a preferred embodiment of the present invention, it has also been found that it is preferable to use a pigment having a size less than a predetermined size and a dispersant having a predetermined acid value for the components used. In particular, when such a component is used, when the precursor composition is adjusted to a predetermined temperature, the adsorptivity of the dispersant to the pigment is improved, and as a result, a pigment dispersion having better storage stability is obtained. It is estimated that.

The method for producing a pigment dispersion of the present invention has at least the following two steps.
Step 1: Preheating a precursor composition containing a pigment, a dispersant, and an organic solvent and having a viscosity of 3 to 20 mPa · s at 25 ° C. Step 2: Liquid temperature of the preheated precursor composition The process which performs the dispersion process by a bead mill with respect to a precursor composition, keeping 40 degreeC or more and less than 60 degreeC Hereinafter, each process is explained in full detail. The details of the materials used in this production method will be described in detail later.

<Process 1 (preheating process)>
Step 1 is a step of preheating a precursor composition containing a pigment, a dispersant, and an organic solvent and having a viscosity at 25 ° C. of 3 to 20 mPa · s. By sufficiently preheating the precursor composition before the dispersion treatment described below, the dispersion force in the dispersion treatment is sufficiently transmitted, shortening the treatment time and improving the storage stability of the resulting pigment dispersion. To do.

The precursor composition used in this step includes at least a pigment, a dispersant, and an organic solvent. Each component contained in the precursor composition will be described in detail later.
The viscosity at 25 ° C. of the precursor composition used in this step is 3 to 20 mPa · s, the processing time of the dispersion treatment is further shortened, and the storage stability of the pigment dispersion is more excellent 3 to 17 mPa · s is preferable, and 3 to 15 mPa · s is more preferable in that at least one of the above is satisfied (hereinafter also referred to simply as “the point where the effect of the present invention is more excellent”).
The viscosity is measured using a viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.) after adjusting the precursor composition to 25 ° C.

In this step, the precursor composition is preheated (heated). By preheating the precursor composition, wetting of the organic solvent to the pigment surface is improved, and the dissolution of the dispersant and the homogenization of the dispersion medium proceed. In addition, since the adsorption of the dispersant to the pigment occurs efficiently, the treatment time is shortened and the storage stability of the pigment dispersion is excellent.
Furthermore, since the adsorption of the dispersant to the pigment proceeds efficiently from the initial stage of the dispersion treatment, the amount of the unadsorbed dispersant is reduced, so that foreign matter (pigment particles, unadsorbed dispersant, etc.) It was found that the generation of aggregates was suppressed. In particular, when a black pigment is used, the effect is remarkable.
In addition, it is expected that the viscosity of the precursor composition is lowered by preheating, the shearing force due to the beads described later in detail is easily transmitted, and the progress of dispersion is thought to be accelerated.
From the viewpoint of remarkably obtaining the above effect, it is preferable to preheat the liquid temperature of the precursor composition to 40 ° C. or higher. Among these, the temperature of the liquid is preferably preheated to 40 to 60 ° C, more preferably preheated to more than 40 ° C and less than 57 ° C, and preheated to 42 to 50 ° C in terms of more excellent effects of the present invention. Is more preferable.
From the viewpoint of remarkably obtaining the above effect, it is preferable to preheat the liquid temperature of the precursor composition to 40 ° C. or higher. Among these, the temperature of the liquid is preferably preheated to 40 to 60 ° C, more preferably preheated to more than 40 ° C and less than 57 ° C, and preheated to 42 to 50 ° C in terms of more excellent effects of the present invention. Is more preferable.
The preheating time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 2 hours, and further preferably 15 minutes to 1.5 hours. Within the above range, the adsorption of the dispersing agent to the pigment proceeds efficiently from the initial stage of the dispersion treatment, the above effects can be obtained remarkably, overheating can be prevented, and there is no problem in the working time.
The method for preheating the precursor composition is not particularly limited, and a known method can be adopted.
In addition, this process of preheating a precursor composition is a process different from the process 2 (dispersion process process) mentioned later. As will be described in detail later, in step 2, a bead mill disperser for performing bead milling is used, but step 1 is a process performed before the precursor composition is supplied into the grinding chamber of the bead mill disperser. is there. That is, it is a process of preheating the precursor composition before being supplied into the grinding chamber of the bead mill disperser.
The crushing chamber is a rotor (rotary rotor) arranged and filled with beads. The beads are agitated by the rotation of the rotor, and shearing force is applied to the pigment in the precursor composition by the agitated beads. It is a room.

<Process 2 (dispersion process)>
Step 2 is a step of subjecting the precursor composition to a dispersion treatment by a bead mill while keeping the liquid temperature of the preheated precursor composition at 40 ° C. or more and less than 60 ° C. By carrying out this step, the pigment is dissolved and a pigment dispersion having high pigment dispersion stability can be obtained.

In step 2, a dispersion treatment described later is performed while keeping the liquid temperature of the precursor composition preheated in step 1 at 40 ° C. or higher and lower than 60 ° C. That is, the dispersion treatment is performed on the precursor composition whose liquid temperature is adjusted to 40 ° C. or more and less than 60 ° C. Among these, the temperature of the precursor composition is preferably maintained at more than 40 ° C. and less than 57 ° C., more preferably from 42 to 50 ° C., in that the effect of the present invention is more excellent.
By treating under the above temperature conditions, the adsorption of the dispersant to the pigment occurs efficiently, so the treatment time is shortened and the storage stability of the pigment dispersion is excellent.
Also, by maintaining or raising the temperature from the pre-heat treatment (step 1), the adsorption of the dispersant to the pigment proceeds efficiently from the beginning of the dispersion treatment, so the amount of the unadsorbed dispersant can be reduced. It has been found that the reduction reduces the generation of foreign matter (aggregates such as pigment particles and unadsorbed dispersant) over time. In particular, when black pigments and white pigments are used, the pigment surface tends to agglomerate because the activity of the pigment surface is higher than that of chromatic pigments, and the effect is remarkable.

As will be described in detail later, the dispersion treatment in step 2 is performed using a known bead mill disperser. The method for supplying the precursor composition preheated in step 1 into the grinding chamber of the bead mill disperser is not particularly limited. For example, as shown in FIG. 200, and can be continuously supplied from the tank 200 to the grinding chamber of the bead mill disperser 500 through the pipe 300 using a pump (not shown). The pipe 300 itself may be heated to a predetermined temperature so that the temperature of the precursor composition W does not change.
FIG. 1 shows an embodiment in which the precursor composition W preheated to a predetermined temperature is continuously supplied to the pulverization chamber of the bead mill pulverizer. However, the present invention is not limited to this embodiment. After the preheated precursor composition is supplied to the bead mill and processed, the precursor composition is circulated so that the further processed precursor composition is supplied to the bead mill again. You may perform a dispersion process, making it.

The supply amount (treatment liquid amount) when the preheated precursor composition is supplied to the bead mill disperser (grinding chamber in the bead mill disperser) is not particularly limited, but from the viewpoint of productivity, 3 to 500 kg / Min is preferred, and 10 to 100 kg / min is more preferred.

In step 2, a dispersion process using a bead mill is performed by using a known bead mill disperser.
Examples of the bead mill disperser include an ultra visco mill, an agitator mill, a super apex mill, an ultra apex mill, a dyno mill, a fine mill, an annular gap type mill, an MSC mill, and the like, and can be preferably used.
In addition, the bead separation method includes a centrifugal separation method, a screen method, and a slit method. When using beads of 0.1 mm or less, the centrifugal separation method is preferable.
In addition, as will be described in detail later, when using finer beads, the rotor for moving the beads and the separator (centrifugation mechanism) must be driven separately from the viewpoint of bead separation. preferable. As such a device, screenless devices such as NPM-Pilot manufactured by Shinmaru Enterprises, Eco-Mill manufactured by Asada Tekko, and dual apex mill manufactured by Kotobuki Kogyo are preferred because they can avoid clogging.

In the bead mill disperser, a crushing chamber is provided. As described above, a rotor is usually provided in the grinding chamber. The rotor has, for example, a disk shape, a rod shape, or a blade shape, and is connected to a rotation shaft that is rotationally driven by a driving device. For this reason, the rotor is provided so as to be rotatable in the circumferential direction along with the rotation of the rotation shaft. Furthermore, a protrusion may be formed near the end of the rotor so that the beads can be efficiently stirred by the rotation of the rotor.

The grinding chamber is filled with beads.
The kind of bead is not particularly limited, and examples thereof include glass beads, alumina beads, zirconia silicate beads, and zirconia beads.
The diameter of the bead is not particularly limited, but is usually 3 mm or less, and is preferably 1 mm or less, more preferably 0.3 mm or less, and even more preferably 0.05 mm or less from the viewpoint that the effects of the present invention are more excellent. The lower limit is not particularly limited, but is usually 0.01 mm or more in many cases.
The diameter of the beads is an average value. Specifically, it is a value obtained by measuring the diameters of arbitrary 100 beads and arithmetically averaging them. In addition, when a bead is not perfect circle shape, it measures by making a major axis into a diameter.

The filling rate of beads in the grinding chamber is not particularly limited, but is preferably 40% by volume or more, more preferably 50% by volume or more, and still more preferably 60% by volume or more. As an upper limit, 98 volume% or less is preferable, 95 volume% or less is more preferable, and 90 volume% or less is still more preferable. By making the filling rate equal to or more than the above lower limit value, the pigment can be efficiently dispersed. In addition, by setting it to the upper limit value or less, it is possible to secure a sufficient space for the beads to move around in the grinding chamber. Here, the filling rate of the beads is obtained by calculating the filling volume of the beads by dividing the weight of the beads by the bulk density of the beads and dividing the filling volume by the volume of the grinding chamber.

In the grinding chamber, the pigment is dispersed by the rotor and beads. That is, the beads are agitated by the rotation of the rotor. The stirred beads give a shearing force to the pigment. By this shearing force, the secondary particles of the pigment are solved and become primary particles. Further, since these pigments are stirred by beads, they are uniformly dispersed in a solvent such as an organic solvent.

The peripheral speed of the rotor during rotation of the rotor is not particularly limited, and is usually preferably 0.1 m / second or more, more preferably 1 m / second or more, and further preferably 5 m / second or more. The upper limit is not particularly limited, but is often 15 m / second or less. Here, the circumferential speed of the rotor refers to the speed of the outer edge of the rotor.
In addition, as described above, depending on the type of the bead mill disperser, the rotor and the separator (separation unit, in particular, the centrifuge unit) that separates the dissolved pigment and beads are driven by separate drive systems. There is. In such an apparatus, the separator is also rotated in the same manner as the rotor to separate the pigment and the beads. In this case, the peripheral speed of the separator is not particularly limited, and is usually preferably 0.1 m / second or more, more preferably 1 m / second or more, and further preferably 5 m / second or more. The upper limit is not particularly limited, but is often 15 m / second or less. Here, the peripheral speed of the separator refers to the speed of the outer edge portion of the separator.

The treatment time of the dispersion treatment is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, 1 to 10 hours are preferable and 5 to 9.0 hours are more preferable when the amount of the treatment liquid charged is 15 kg. Although the length of the treatment time is not strict, it is preferable to increase the treatment time in proportion to the liquid amount.

Furthermore, when the rotor is rotated, heat may be generated due to the friction of the beads. Therefore, the liquid temperature of the precursor composition in the grinding chamber can be adjusted by arranging piping around the grinding chamber and flowing the refrigerant in the piping.

The pigment dissolved in the grinding chamber is separated from the beads by a filter and collected. In addition, as above-mentioned, when a separator rotates, a pigment and a bead are isolate | separated by centrifugation.

The average particle size (that is, the average particle size of the pigment in the pigment dispersion) of the pigment (fine powder pigment) that has been subjected to the above-described dispersion treatment is not particularly limited, and varies depending on the primary particle size of the pigment used. From the viewpoint of more excellent effects of the present invention, it is preferably in the range of (primary particle diameter of pigment) or more (primary particle diameter of pigment × 10 times) or less, (primary particle diameter of pigment) or more (primary particle diameter of pigment). (Particle diameter × 6 times) or less is more preferable.
As a method for measuring the average particle diameter of the pigment in the pigment dispersion, a dynamic light scattering method (FFT (Fast Fourier Transform) power spectrum method) is known. More specifically, D90 calculated by Microtrac EX-150 (manufactured by Nikkiso) is defined as the average particle diameter of the pigment.

Hereinafter, various materials used in this production method will be described in detail.

<Pigment>
Various conventionally known inorganic pigments or organic pigments can be used as the pigment.
The primary particle diameter of the pigment used in the present invention is preferably less than 55 nm. In the initial stage of the dispersion treatment, the surface area of the pigment particles involved in the adsorption / desorption of the dispersant is increased, and the effect of the present invention is more excellent. Furthermore, 50 nm or less is more preferable, and 40 nm or less is still more preferable. The lower limit is not particularly limited, but is often 5 nm or more.
The primary particle diameter of the pigment is an average value, and the primary particle diameters of arbitrary 400 pigments are measured with an electron microscope, and they are arithmetically averaged. In addition, when a pigment is not a perfect circle shape, a circle equivalent diameter is used. The equivalent circle diameter means the diameter of a circle corresponding to the same area as the area (projected area) of the observed two-dimensional image of the pigment.

Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include the following.
C. I.

Pigment YELLOW

1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I.

Pigment Red

1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase the color purity.

Of these, a black pigment is preferably used as the pigment.
Various known black pigments can be used as the black pigment. In particular, from the viewpoint of realizing high optical density in a small amount, tungsten oxide compounds such as carbon black, titanium black, titanium oxide, tungsten oxide, and cesium tungsten oxide, metal borides, iron oxide, manganese oxide, graphite, titanium carbide Zirconium carbide, zirconium boride, boron carbide, and silicon boride are preferable, carbon black or titanium black is more preferable, and titanium black is still more preferable.

Titanium black is black particles containing titanium atoms. Preferred is low-order titanium oxide or titanium oxynitride. The surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, the surface of titanium black can be treated with a water-repellent substance as disclosed in JP-A-2007-302836.
Titanium black is typically particulate and preferably has a small primary particle size for each particle.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET method is usually about 5 m ² / g to 150 m ² / g, and preferably 20 m ² / g to 120 m ² / g.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), and T For example, Rack D (trade name: manufactured by Ako Kasei Co., Ltd.).

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. It is preferable that
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
The content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.5 or less, which makes it easier to produce a pigment dispersion using the dispersion. Is preferably 0.5.
Further, when the light shielding film using the object to be dispersed is patterned by photolithography or the like, the residue has less residue and the light shielding ability is excellent. It is more preferably 5 or less, and further preferably 0.07 or more and 0.4 or less.
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a mixture is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to thereby mainly contain titanium black particles. Thus, a dispersion containing Si and Ti can be obtained.
Here, the specific aspect for changing Si / Ti of a to-be-dispersed body is demonstrated.
Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045. it can.

Hereinafter, when Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Titanium black may use only 1 type and may use 2 or more types.

Although the content of the pigment in the precursor composition is not particularly limited, it is preferably 5 to 50% by mass and preferably 10 to 40% by mass with respect to the total mass of the precursor composition in terms of more excellent effects of the present invention. More preferred is 15 to 35% by mass.

<Dispersant>
A dispersing agent contributes to the dispersibility improvement of the pigment mentioned above.
The acid value of the dispersant is preferably from 30 to 100 mgKOH / g, and more preferably from 30 to 90 mgKOH / g from the viewpoint that the effect of the present invention is more excellent. When the amount is within the above range, the amount of the unadsorbed dispersant can be further reduced, and the effects of the present invention can be advantageously obtained, and the effects of preheating (step 1) and heat treatment during dispersion (step 2) can be obtained. Together, foreign matter (aggregates such as pigment particles and unadsorbed dispersant) is less likely to occur over time.
As a method for calculating the acid value of the dispersant, a potentiometric titration method may be mentioned. That is, the dispersant is dissolved in a titration solvent (for example, 9: 1 mixed solvent of propylene glycol monomethyl ether and water), titrated with a 0.1 mol / L potassium hydroxide aqueous solution, and until the inflection point on the titration curve. The acid value can be calculated from the titration amount.
The acid value of the dispersant can be calculated from, for example, the average content of acid groups in the dispersant.

The weight average molecular weight of the dispersant is not particularly limited, but it is preferably 4,000 or more and 300,000 or less, and 5,000 or more and 200,000 or less as a polystyrene conversion value by GPC (gel permeation chromatography). More preferably, it is 6,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

As the dispersant, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamines or salts thereof, polycarboxylic acids or salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine and the like.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

The high molecular compound is adsorbed on the surface of the object to be dispersed such as a pigment and acts to prevent reaggregation of these. Therefore, the polymer compound is preferably a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface.
On the other hand, by modifying the surface of the pigment, the adsorptivity of the polymer compound to these can be promoted.

The polymer compound preferably has a structural unit having a graft chain.
The polymer compound having a structural unit having such a graft chain is excellent in the dispersibility of the pigment and the dispersion stability after the lapse of time because the affinity with the solvent is improved by the graft chain.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment is improved. However, when the graft chain is too long, the adsorptive power of the polymer compound to the pigment is lowered and the dispersibility of the pigment tends to be lowered. Therefore, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
In order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the pigment, the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. A graft chain having a seed is preferable, and a graft chain having at least one of a polyester structure and a polyether structure is more preferable.

The macromonomer having such a polymer structure as a graft chain is not particularly limited, but a macromonomer having a reactive double bond group is preferable.

Corresponding to the structural unit having a graft chain of the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Gosei Co., Ltd.), AA-10 ( Product name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product) Name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer PP-500 ( Product name, NOF Corporation), BLEMMER PP-800 (trade name, NOF Corporation), BLEMMER PP-1000 (trade name, NOF Corporation), BLEMMER 55-PET-800 (product) Name, manufactured by NOF Corporation), BREMMER PME-4000 (trade name, manufactured by NOF Corporation), BREMMER PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, NOF Corp.) and BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corp.). Among them, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (Trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), or Bremer PME-4000 (trade name, manufactured by NOF Corporation) is preferred.

(Preferred embodiment 1)
The polymer compound (dispersant) preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain. More preferably, it includes a structural unit represented by any one of (2A), the following formula (3A), the following formula (3B), and the following (4).

In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. In the structures shown below, A and B mean binding sites with the left end group and the right end group in formulas (1) to (4), respectively. Of the structures shown below, a linking group of (Y-2) or (Y-13) is preferred from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The type of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving the dispersibility of the pigment, and each independently has 5 carbon atoms. To 24 alkyl groups or alkoxy groups are preferable, and branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, or alkoxy groups having 5 to 24 carbon atoms are more preferable. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of dispersion stability of the pigment.

In formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other.
In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the type of the monovalent organic group is not particularly limited. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

In addition, the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R ³ , R ⁴ and X ⁵ present in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability of the pigment.
Moreover, as a structural unit represented by Formula (2), the structural unit represented by following formula (2A) is preferable from a viewpoint of the dispersion stability of a pigment.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^X ^1, Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^X ^2, Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

The structural unit represented by the formula (3) is preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of dispersion stability of the pigment.

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and p are as defined ^X ^3, Y 3, ^{Z 3} and p in formula (3), and preferred ranges are also the same.

More preferably, the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.

In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90 relative to the total mass of the polymer compound in terms of mass. % Is preferably included, and more preferably in the range of 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersibility of the pigment (particularly titanium black) is high.

Further, the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group).

The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.

ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

The polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.

In the general formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or An alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.) is represented.
R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, Here, R ³¹ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), or a combination thereof.

The divalent aliphatic group may be branched or cyclic. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , where R ³² is an aliphatic group, Aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.

L is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group and a substituted aryl group), or The group which combined these is mentioned. Each of the above groups includes a heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, wherein R ³¹ represents Represents an aliphatic group, an aromatic group or a heterocyclic group), or may contain a carbonyl group (—CO—).

The aliphatic group may be branched or cyclic. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4- Examples thereof include a cyclohexylphenyl group. The bridged cyclic hydrocarbon ring includes two rings such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) A tricyclic hydrocarbon ring such as a formula hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring, And tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , where R ³² is an aliphatic group, Aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.

Representative compounds represented by the general formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As typical compounds represented by the general formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in this specification. Incorporated.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.

The polymer compound may have a functional group that can form an interaction with a pigment (particularly titanium black). Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the pigment.
Examples of the functional group capable of forming an interaction with the pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. It is preferable to have a structural unit having or a structural unit having reactivity.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
This is because the acid group in the structural unit having an acid group easily interacts with the pigment, the polymer compound stably disperses the pigment, and the viscosity of the polymer compound that disperses the pigment is low. It is presumed that the compound itself is also easily dispersed stably.

However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).

Examples of the acid group that is a functional group capable of forming an interaction with the pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group, and At least one of phosphoric acid groups is preferable, and a carboxylic acid group is more preferable in terms of good adsorbing power to the pigment and high dispersibility of the pigment.
That is, the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is calculated in terms of mass with respect to the total mass of the polymer compound. 5 to 80% is preferable, and 10 to 60% is more preferable from the viewpoint of suppressing damage of image strength due to alkali development.

Examples of the basic group that is a functional group capable of forming an interaction with the pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Tertiary amino groups are preferred because they have good adsorption power to the pigment and high dispersibility of the pigment. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, 0.01 to 50% is preferable, and 0.01 to 30% is more preferable from the viewpoint of inhibiting the development inhibition.

Examples of the coordinating group, which is a functional group capable of forming an interaction with the pigment, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acid chloride Etc. Of these, an acetylacetoxy group is preferred because it has a good adsorptive power to the pigment and has a high dispersibility of the pigment. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10 to 80% or less with respect to the total mass of the polymer compound, and more preferably 20 to 60% from the viewpoint of inhibiting developability inhibition.

When the polymer compound has a functional group capable of forming an interaction with the pigment in addition to the graft chain, the polymer compound was selected from structural units derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to have one or more structural units.

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or An alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
In general formula (iv) to general formula (vi), R ¹¹ , R ¹² and R ¹³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or A methyl group is more preferred. In general formula (iv), R ¹² and R ¹³ are each more preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.

In the general formulas (iv) to (v), L ₁ represents a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ³¹ ′ —) Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

The divalent aliphatic group may be branched or cyclic. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , where R ³² is an aliphatic group, Aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.

L ₁ is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is preferably an oxyethylene structure or an oxypropylene structure. L ₁ may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group capable of forming an interaction with the pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group. More preferably, it is a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - represents a _{Z 1,} or _-L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the general formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is a divalent alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or imino group and Z is a carboxylic acid group is preferred as a linking group.
Further, as the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as a monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid group is preferred.

The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxy Phenyl methacrylamide.

The content of the structural unit having a functional group capable of forming an interaction with the pigment is preferably 0.05 to 90% by mass with respect to the total mass of the polymer compound from the viewpoint of dispersion stability of the pigment. 0 to 80% by mass is more preferable, and 10 to 70% by mass is still more preferable.

Furthermore, for the purpose of improving various performances, the polymer compound has a structural unit having a graft chain, a hydrophobic structural unit, and a functional group capable of interacting with a pigment, as long as the effects of the present invention are not impaired. You may further have other structural units (for example, a structural unit which has a functional group etc. which have affinity with the dispersion medium used for a dispersion) different from the structural unit which has various functions.
Examples of such other structural units include structural units derived from radical polymerizable compounds selected from acrylonitriles and methacrylonitriles.
The polymer compound may contain one or more of these other structural units, and its content is preferably 0 to 80% based on the total mass of the polymer compound in terms of mass, 10 to 60% is more preferable.

(Preferred embodiment 2)
As another suitable aspect of a dispersing agent, the high molecular compound X represented by general formula (X) is mentioned.
Hereinafter, each group in the general formula (X) will be described in detail.
Since the substituent A ¹ of the polymer compound X can interact with the pigment, the polymer compound X can strongly interact with the pigment by having n (1 to 9) substituents A ^1. . In addition, m polymer chains P ¹ of the polymer compound X function as steric repulsion groups, and by having m, the polymer can exhibit uniform steric repulsive force and uniformly disperse the pigment.

In the general formula (X), A ¹ is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a phenol group, an alkyl group, an aryl group, or an alkyleneoxy chain. Adsorption ability for pigments such as imide groups, imide groups, alkyloxycarbonyl groups, alkylaminocarbonyl groups, carboxylate groups, sulfonamido groups, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups, or heterocyclic groups Represents a functional group possessed.
Hereinafter, the site having the ability to adsorb to the pigment (the above functional group) will be described as an “adsorption site” as appropriate.

As long as at least one adsorption site is included in one A ¹ , two or more adsorption sites may be included.
As an embodiment in which two or more adsorption sites are included in one A ¹ , for example, a chain saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 10 carbon atoms) A monovalent substitution wherein two or more adsorption sites are bonded via a cyclic saturated hydrocarbon group (preferably having 3 to 10 carbon atoms), an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group), etc. Examples include an embodiment in which the group A ¹ is formed, and an embodiment in which two or more adsorption sites are bonded via a chain saturated hydrocarbon group to form a monovalent substituent A ¹ is preferable.
In the case where adsorption sites themselves constitute a monovalent substituent, adsorption sites themselves may also be a monovalent substituent represented by A ^1.

First, the adsorption site constituting A ¹ will be described below.
As the “acid group”, for example, a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, or a boric acid group is preferable. A sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, or a phosphinic acid group is more preferable, and a carboxylic acid group is still more preferable.
Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 or more carbon atoms). Or an aralkyl group having 7 or more carbon atoms is preferred, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, An aryl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms is more preferable, and —NHCONHR ¹⁷ (where R ¹⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms). The above aryl group or an aralkyl group having 7 or more carbon atoms is more preferred.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , and —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently an alkyl group having 6 or more aryl group having a carbon number of 1 to 20 carbon atoms, or represents the number 7 or aralkyl group having a carbon.) are preferred, -NHCOOR ^18, or, -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and is more preferably —NHCOOR ¹⁸ , or, -OCONHR ²¹ ^(wherein each R ^{18, R 21} are independently an alkyl group having 6 or more aryl carbons of 1 to 10 carbon atoms , Or represents the number 7 or aralkyl group having a carbon.) It is more preferred.

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.
Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each Independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), or the following formula: The amidinyl group represented by (a2) is preferable.

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently alkyl having 1 to 10 carbon atoms. Group, a phenyl group or a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, Represents a phenyl group or a benzyl group. Or an amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, A phenyl group or a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group; Or represents a benzyl group. Or an amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.

The “alkyl group” may be linear or branched and is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms. An alkyl group having 10 to 18 carbon atoms is more preferable.
The “aryl group” is preferably an aryl group having 6 to 10 carbon atoms.
As the “group having an alkyleneoxy chain”, the terminal preferably forms an alkyloxy group or a hydroxyl group, and more preferably an alkyloxy group having 1 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but preferably comprises an alkyleneoxy group having 1 to 6 carbon atoms. Examples of the alkyleneoxy group include —CH ₂ CH ₂ O— and —CH ₂ CH ₂ CH ₂ O—.
The alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
The alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the “carboxylic acid group” include a group consisting of an ammonium salt of a carboxylic acid.
In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).

Examples of the “heterocyclic group” include thiophene group, furan group, xanthene group, pyrrole group, pyrroline group, pyrrolidine group, dioxolane group, pyrazole group, pyrazoline group, pyrazolidine group, imidazole group, oxazole group, thiazole group, oxalate group. Diazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benz Examples include imidazolone group, benzothiazole group, hydantoin group, indole group, quinoline group, carbazole group, acridine group, acridone group, and anthraquinone group.
Examples of the “imide group” include imide groups such as a succinimide group, a phthalimide group, and a naphthalimide group.

The “heterocyclic group” and the “imide group” may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, Hydroxyl group, amino group, carboxylic acid group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy group, C1-C20 alkoxy group, halogen atom, methoxycarbonyl group, ethoxycarbonyl And a C2-C7 alkoxycarbonyl group such as a cyclohexyloxycarbonyl group, a cyano group, and a carbonate group such as t-butyl carbonate.

The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group and trialkoxysilyl group, but trialkoxysilyl group is preferable, for example, trimethoxysilyl group and triethoxysilyl group Etc.
Examples of the “epoxy group” include a substituted or unsubstituted oxiranyl group (ethylene oxide group).

In particular, A ¹ is preferably a monovalent substituent having at least one functional group of pKa5 or higher, and more preferably a monovalent substituent having at least one functional group of pKa5 to 14.
Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The functional group having a pKa of 5 or more includes a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, and an alkylaminocarbonyl group. A group having an alkyleneoxy chain, an imide group, a carboxylate group, a sulfonamide group, a hydroxyl group, and a heterocyclic group.
Specific examples of functional groups having a pKa of 5 or more include, for example, a phenol group (about pKa 8 to 10), an alkyl group (about pKa 46 to 53), an aryl group (about pKa 40 to 43), a urea group (pKa 12 to 14). Degree), urethane group (about pKa 11 to 13), —COCH ₂ CO— (about pKa 8 to 10) as a coordinating oxygen atom, sulfonamide group (about pKa 9 to 11), hydroxyl group (pKa 15 to 17) Degree) and heterocyclic groups (pKa of about 12 to 30).
In the above, A ¹ has an acid group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, a hydroxyl group, a urea group, a urethane group, a sulfonamide group, an imide group, and a coordinating oxygen atom. A monovalent substituent having at least one group selected from the group consisting of groups is preferred.

In general formula (X), R ² represents a single bond or a divalent linking group. n R ² may be the same or different.
Examples of the divalent linking group represented by R ² include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 A group consisting of a single sulfur atom is included, and it may be unsubstituted or may further have a substituent.

R ² is a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. A divalent linking group consisting of
R ² includes a chain saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 20 carbon atoms), or a cyclic saturated hydrocarbon group (having 3 to 20 carbon atoms). Selected from the group consisting of an aromatic group (preferably having 5 to 20 carbon atoms, such as a phenylene group), a thioether bond, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a carbonyl group. More preferably a group or a combination of two or more of these, from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, a thioether bond, an ester bond, an ether bond, and an amide bond. A group selected or a combination of two or more of these is more preferable, and a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and an amide A group selected from the group consisting of a bond, or a group obtained by combining two or more of these is particularly preferable.

Among the above, when the divalent linking group represented by R ² has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyl group, and an amino group. Groups, carboxylic acid groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and other acyloxy groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine atoms, methoxycarbonyl Groups, an ethoxycarbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a cyclohexyloxycarbonyl group, a cyano group, and a carbonate group such as t-butyl carbonate.

In general formula (X), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and A group consisting of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

The (m + n) -valent linking group represented by R ¹ is preferably a group represented by any one of the following general formulas.

In the above general formula,
L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T _{3 s} may be the same or different from each other.
L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and the four T _{4 s} may be the same or different from each other.
L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five T _{5 s} may be the same or different from each other.
L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and six T _{6 s} may be the same or different from each other.
Specific examples (specific examples (1) to (17)) of the (m + n) -valent linking group represented by R ¹ are shown below. However, it is not limited to these.

Among the above specific examples, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, the following (1), (2), (10 ), (11), (16) or (17) are preferred.

In general formula (X), m represents a positive number of 8 or less. m is preferably 0.5 to 5, more preferably 1 to 4, and still more preferably 1 to 3.
In the general formula (X), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and still more preferably 3 to 6.

In the general formula (X), P ¹ represents a polymer chain and can be selected from known polymers according to the purpose. The m P ¹ may be the same or different.
Among the polymers, polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products thereof, or the copolymer of these Copolymer [For example, a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, etc. (any of a random copolymer, a block copolymer, and a graft copolymer may be used. )including. More preferably at least one selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof, and vinyl monomers. More preferred are polymers or copolymers.
The polymer or copolymer of vinyl monomers, the ester polymer, and the ether polymer that the polymer chain P ¹ may have are each represented by the following general formula (L), (M), or (N). It is preferable to have a structure.

In the above general formula,
X ¹ represents a hydrogen atom or a monovalent organic group. X ¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group, from the viewpoint of synthesis constraints.
R ¹⁰ represents a hydrogen atom or a monovalent organic group. R ¹⁰ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ¹⁰ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. The polymer chain may have two or more types of repeating units in which R ¹⁰ in the general formula (L) is different.
R ¹¹ and R ¹² represent a linear or branched alkylene group (the carbon number is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 6). The polymer chain may have two or more kinds of repeating units in which R ¹¹ or R ¹² in each general formula is different.
k1, k2, and k3 each independently represents a number of 5 to 140.

The polymer chain P ¹ preferably contains at least one repeating unit.
The number k of the repeating units of at least one repeating unit in the polymer chain P ¹ is preferably 5 or more, more preferably 7 or more, from the viewpoint of exhibiting steric repulsion and improving dispersion stability. .
Further, from the viewpoint of suppressing the bulk of the polymer compound X and allowing the pigment to be densely present in the film, the number k of repeating units of at least one repeating unit is preferably 140 or less, and 130 Or less, more preferably 60 or less.

The polymer is preferably soluble in an organic solvent. When the affinity with the organic solvent is high, the affinity with the dispersion medium becomes strong.
Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, vinyl monomers having an acid group, maleic acid diesters, fumaric acid diesters, itaconic acid diesters , (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, or (meth) acrylonitrile, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, or The vinyl monomer having an acid group is more preferable, and (meth) acrylic acid esters or crotonic acid esters are still more preferable.
Preferable examples of the vinyl monomer include paragraphs 0089 to 0094, 0096 and 0097 of JP-A-2007-277514 (paragraphs 0105 to 0117 and 0119 to 0120 in the corresponding US 2010/233595). And their contents are incorporated herein by reference.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. As such a monomer having a urethane group or a urea group, for example, it can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, it can be synthesized by an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group.

Among the polymer compounds represented by the general formula (X), the polymer compound represented by the following general formula (Y) is preferable.

In the general formula (Y), ^{A 2} has the same meaning as ^{A 1} in the general formula (X), preferable embodiments thereof are also the same.
In the general formula (Y), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent linking group represented by R ⁴ or R ⁵ , the same divalent linking groups as those represented by R ² in the general formula (X) can be used, and preferred embodiments are also described. It is the same.
Among them, as the divalent linking group represented by R ⁴ or R ⁵ , a chain saturated hydrocarbon group (which may be linear or branched and preferably has 1 to 20 carbon atoms) A cyclic saturated hydrocarbon group (preferably having 3 to 20 carbon atoms), an aromatic group (preferably having 5 to 20 carbon atoms, such as a phenylene group), an ester bond, an amide bond, an ether bond, a nitrogen An atom, a carbonyl group, or a group in which two or more of these are combined is preferable, and a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, an ether bond, an amide bond, or these two A group in which two or more are combined is more preferable, and a chain saturated hydrocarbon group, an ester bond, an ether bond, an amide bond, or a group in which two or more of these are combined is more preferable.

In the general formula (Y), R ³ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
The (m + n) -valent linking group represented by R ³ may further have a substituent, and is exemplified as the (m + n) -valent linking group represented by R ¹ in the general formula (X). The same thing as a thing is used, and a preferable aspect is also the same.
In general formula (Y), m and n are synonymous with m and n in general formula (X), respectively, and a preferable aspect is also the same.
Further, ^{P 2} in formula (Y) has the same meaning as ^{P 1} in the general formula (X), preferable embodiments thereof are also the same. the m P ² can be the same or different.

Among the polymer compounds represented by the general formula (Y), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific example (1), (2), (10), (11), (16), or (17) above
R ⁴ : a single bond, a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, an amide bond, an ether bond, a nitrogen atom, a carbonyl group, or a group in which two or more of these are combined R ⁵ : Single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, or modified products thereof m: 1 to 3
n: 3-6

Among the polymer compounds represented by the general formula (X) or (Y), the polymer compound represented by the following general formula (Z) is preferable from the viewpoint of the dispersion stability of the pigment.

In the general formula (Z),
R ⁶ represents a (m + n1 + n2) -valent linking group, and R ⁷ to R ⁹ each independently represents a single bond or a divalent linking group.
A ³ represents a monovalent substituent having at least one acid group. A ⁴ represents a monovalent substituent different from A ³ . The n1 A ³ and R ⁷ may be the same or different from each other. The n2 A ⁴ and R ⁸ may be the same or different from each other.
m is synonymous with m in the general formula (X), and preferred embodiments are also the same.
n1 represents 1 to 8, n2 represents 1 to 8, and m + n1 + n2 satisfies 3 to 10.
P ³ has the same meaning as ^{P 2} in formula (Y), preferable embodiments thereof are also the same. The m P ³ and R ⁹ may be the same or different.
The (m + n1 + n2) -valent linking group for R ⁶ is the same as the (m + n) -valent linking group represented by R ^{1 in the} general formula (X) or R ³ in the general formula (Y). The preferred embodiment is the same.
As the divalent linking group for R ⁷ to R ⁹ , the same divalent linking groups as those represented by R ⁴ and R ⁵ in formula (Y) can be used, and preferred embodiments Is the same.
Specific examples and preferred examples of the acid group that the substituent A ³ may have include those similar to the specific examples and preferred examples described above for the acid group in formula (X).
The substituent A ³ is preferably a monovalent substituent having at least one acid group having a pKa smaller than 5 and is composed of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group. A monovalent substituent having at least one group selected from the group is more preferable, and a carboxylic acid group is still more preferable.
Specific examples and preferred examples of the monovalent substituent A ⁴ different from A ³ include those similar to the groups other than the acid group in the specific examples and preferred examples described above for A ¹ in the general formula (X). Can be mentioned. Among these, the substituent A ⁴ is more preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and a phenol group. , Urea group, urethane group, alkyl group, aryl group, alkyloxycarbonyl group, alkylaminocarbonyl group, group having an alkyleneoxy chain, imide group, carboxylate group, sulfonamide group, hydroxyl group and heterocyclic group It is preferably a monovalent substituent having at least one selected group, and is an alkyl group, an aryl group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a urea group or a urethane group It is more preferable.

As a combination of the substituent A ³ and the substituent A ⁴ , the substituent A ³ is a monovalent substituent having at least one functional group having a pKa of less than 5, and the substituent A ⁴ has a functionality of pKa 5 or more. A monovalent substituent having at least one group is preferable.
Substituent A ³ is a monovalent substituent having at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group, and A ⁴ has a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, or an alkyleneoxy chain. It is more preferably a monovalent substituent having at least one group selected from the group consisting of a group, an imide group, a carboxylate group, a sulfonamide group, a hydroxyl group and a heterocyclic group.
The substituent A ³ is a monovalent substituent having a carboxylic acid group, and the substituent A ⁴ is an alkyl group, an aryl group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, More preferably, it is a urea group or a urethane group.
And pigments, from the viewpoint that the adsorption of alkyl group substituents A ³ is good, the substituent A ³ is a carboxylic acid group, and the substituent A ⁴ is particularly preferably an alkyl group.

Specific examples of the dispersant include, for example, “Disperbyk-161, 162, 163, 164, 165, 166, 170, 190 (trade name, polymer copolymer)” manufactured by BYK Chemie, and “manufactured by EFKA” EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane type), EFKA 4330, 4340 (trade name, block copolymer) ”and the like.
As specific examples of the dispersant, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A, the contents of which are incorporated herein.
Further, as the dispersant, the graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to columns 0075 to 0133 in US2011 / 0124824) can be used, and the contents thereof can be used. Embedded in the book.
In addition to the above, it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
A dispersing agent may be used independently and may be used in combination of 2 or more type.

The content of the dispersant in the precursor composition is not particularly limited, but is preferably 1 to 30% by mass, and preferably 1 to 20% by mass, based on the total solid content of the composition, in that the effect of the present invention is more excellent. Is more preferable, and 1 to 15% by mass is still more preferable.

Further, the ratio (D / P ratio) between the mass of the dispersant (D) and the mass of the pigment (P) in the precursor composition is excellent in the viscosity with time and solid content stability of the dispersion, and at the same time, the coating film In view of improving the in-plane uniformity of the film thickness, it is preferably 0.1 to 0.45, more preferably 0.12 to 0.4, and still more preferably 0.14 to 0.35.

<Organic solvent>
The precursor composition contains an organic solvent.
Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, and ethyl lactate, but are not limited thereto.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more organic solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone A mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.

The content of the organic solvent in the precursor composition is not particularly limited, but is preferably 10 to 95% by mass, more preferably 50 to 95% by mass with respect to the total mass of the composition in terms of more excellent effects of the present invention. Preferably, 55 to 90% by mass is more preferable.

(Other additives)
The precursor composition may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives such as foaming agents, viscosity modifiers, rust inhibitors, chelating agents, antioxidants, adhesion aids, surfactants, resin coating agents, and pigment derivatives can be used.

<Pigment dispersion>
The pigment dispersion produced by the above procedure includes a pigment, a dispersant, and an organic solvent. The preferable range of the average particle diameter of the pigment in the pigment dispersion is as described above.
Each of the main components such as a polymerization initiator, a polymerizable compound, and an alkali-soluble resin may be added to the obtained pigment dispersion to form a curable composition.
As a curable composition, it can apply to various uses, for example, when a black pigment is used as a pigment, it can apply to a light shielding film formation use.
Moreover, the cured film formed from the said curable composition can be applied to various uses, for example, a color filter etc. are mentioned.
Moreover, the said cured film can be applied to various apparatuses, for example, a solid-state image sensor, an image display apparatus, etc. are mentioned.

Details of forming a curable composition (hereinafter also referred to as “composition”) using the pigment dispersion of the present invention will be described below.

(Polymerization initiator)
The composition of the present invention may contain a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer. Moreover, the initiator which starts cationic polymerization according to the kind of monomer may be sufficient.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and US Pat. No. 4,221,976. Compounds described in the specification, and the like.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable.

Among these, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, trihalomethyltriazine compounds, α -More preferred are aminoketone compounds, oxime compounds, triallylimidazole dimers or benzophenone compounds.

In particular, when a curable composition is used for the production of a light-shielding film for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It's important to. From such a viewpoint, an oxime compound is preferable as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, considering these points, it is preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are also preferable. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine initiators described in Japanese Patent No. 4225898 are also included.
Examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF).
Examples of aminoacetophenone-based initiators include commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF). Examples of the aminoacetophenone-based initiator include compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm.
Examples of the acylphosphine initiator include IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF), which are commercially available products.

As the photopolymerization initiator, an oxime compound (oxime initiator) is preferable. Oxime compounds are preferred because they are highly sensitive, have high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
Specific examples of the oxime compound include a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, and a compound described in JP-A No. 2006-342166.
Preferred embodiments of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3 -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166. It is done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N position, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety A compound described in JP 2010-15025 A and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same Examples thereof include compounds described in US Pat. No. 7,556,910 contained in the molecule, and compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source.
As the oxime compound, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Examples thereof include compound (C-3). This content is incorporated herein.

As the photopolymerization initiator, a compound represented by the following general formula (1) or (2) can also be used.

In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^R ^1, R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5} ^is -R 6, -OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , —CSOR ⁶ , —CN, halogen R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but are not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is more preferable.
The molar extinction coefficient of the compound can be measured by a known method. For example, the molar extinction coefficient is measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrphotometer manufactured by Varian) using an ethyl acetate solvent. It is preferable.
You may use a polymerization initiator in combination of 2 or more type as needed.

The content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass with respect to the total solid content of the curable composition. Within this range, better sensitivity and pattern formability can be obtained. The curable composition of the present invention may contain only one type of polymerization initiator or two or more types of polymerization initiators. When two or more types are included, the total amount is preferably within the above range.

(B) Polymerizable compound The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or higher at normal pressure. In particular, the polymerizable compound preferably contains 2 to 10 ethylenically unsaturated groups, and is preferably a so-called polyfunctional polymerizable compound.
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, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylate or methacrylate such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) A polyfunctional alcohol such as ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, after addition of ethylene oxide or propylene oxide and (meth) acrylate, pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, 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, are described in JP-A-43191 and JP-B-52-30490. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.
Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 as general formula (1) and general formula (2) together with specific examples thereof and then (meth) acrylated Can also be used.
Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and structures in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.
Also, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, or JP-B-58 Urethane compounds having an ethylene oxide skeleton described in JP-B Nos. -49860, 56-17654, 62-39417, and 62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are also suitable. It is.
Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxylic acid group-containing trifunctional acrylate manufactured by Toa Gosei Co., Ltd., and a carboxylic acid group-containing pentafunctional group. Examples thereof include TO-1382 which is an acrylate. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound. Examples of the tetrafunctional or higher acrylate compound include KAYARD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.).

A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more polymerizable compounds are used in combination, the combination mode can be appropriately set according to the physical properties required for the composition. As one suitable combination mode of the polymerizable compound, for example, a mode in which two or more polymerizable compounds selected from the polyfunctional acrylate compounds described above are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
The content of the polymerizable compound is preferably 3 to 55% by mass, more preferably 10 to 50% by mass, based on the total solid content in the curable composition.

〔Silane coupling agent〕
The composition of the present invention may contain a silane coupling agent.
A silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the cured film, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded). Silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms are It is desirable not to include.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si- (R _Z1 ) ₃
In the formula (Z), R _Z1 represents a hydrolyzable group, and the definition thereof is as described above.

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.

The molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.

One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula (W) R _Z2 -Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR ^{_{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.

As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503) and glycidoxyoctyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-4803) and the like.

As another preferred embodiment of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided. Can be mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms or substituents. The bondable atom or substituent includes a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an amino group that can be substituted with an aryl group, silyl Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group or a salt thereof, and a sulfo group or a salt thereof.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxylic acid group or salt thereof, and sulfo group.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described nitrogen atom and substituents that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to take an embodiment having two or more curable functional groups, sensitivity and stability. From this point, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and still more preferably 6 to 10.

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).

The content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the composition. More preferably, it is 0 to 6% by mass.

The composition of the present invention may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

(Alkali-soluble resin)
The composition of the present invention may contain an alkali-soluble resin.
It is preferable to use a linear organic polymer as the alkali-soluble resin. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is used to enable water development or weak alkaline water development.
The alkali-soluble resin is a linear organic polymer having at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Alkali-soluble resins are preferred.
From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin is preferable, and from the viewpoint of developing property control, an acrylic resin, Acrylamide resins or acrylic / acrylamide copolymer resins are preferred.
Examples of groups that promote alkali solubility (hereinafter also referred to as acid groups) include carboxylic acid groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups, but are soluble in organic solvents and weakly alkaline. Those that can be developed with an aqueous solution are preferred, and carboxylic acid groups are more preferred. These acid groups may be used alone or in combination of two or more.

Examples of the alkali-soluble resin include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxylic acid group Examples include a resin obtained by hydrolyzing, half-esterifying or half-amidating an acid anhydride unit, or an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. . Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene. Examples of the monomer having an acid anhydride include anhydrous Maleic acid is mentioned. Similarly, acidic cellulose derivatives having a carboxylic acid group in the side chain are also included. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
In addition, polyvinyl pyrrolidone or polyethylene oxide is useful as the water-soluble linear organic polymer.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
Commercially available products include, for example, Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Corporation. 230AA etc. are mentioned.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions Can also be determined.

Moreover, it is also preferable to use a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the alkali-soluble resin.
The definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable. Carboxylic acid groups are more preferred.

The structural unit having an acid group is preferably at least one structural unit selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).

In the general formulas (vii) to (ix), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number 1 to 6 alkyl groups (for example, methyl group, ethyl group, propyl group, etc.) are represented.
In general formula (vii) to general formula (ix), R ²¹ , R ²² , and R ²³ are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (vii), R ²¹ and R ²³ are each particularly preferably a hydrogen atom.

X ₂ in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (viii) represents a methine group or a nitrogen atom.

In the general formulas (vii) to (ix), L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), and a divalent aromatic group (for example, arylene). Group, substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ⁴¹ ′ —, here R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ⁴² , where R ⁴² is an aliphatic group, Aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₂ is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formulas (vii) to (ix), Z ₂ is an acid group, preferably a carboxylic acid group.

In the general formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - represents a _{Z 2,} or _-L 2 -Z _2. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. R ²⁴ , R ²⁵ and R ²⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the general formula (vii), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ is a divalent alkylene group or an oxyalkylene structure. A compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

The alkali-soluble resin can be synthesized by a known method.

The alkali-soluble resin may have one or more structural units having an acid group.
The content of the structural unit having an acid group is preferably 5 to 95% in terms of mass with respect to the total mass of the alkali-soluble resin, and is 10 to 90% from the viewpoint of suppressing image strength damage due to alkali development. More preferred.

The content of the alkali-soluble resin in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition. .

〔solvent〕
The composition of the present invention may contain a solvent.
Examples of the solvent include water or an organic solvent.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples include butyl acetate, methyl lactate, and ethyl lactate.

A solvent may be used individually by 1 type and may be used in combination of 2 or more type.
When two or more solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, It is preferably composed of two or more selected from the group consisting of cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The amount of the solvent contained in the composition of the present invention is preferably 10 to 90% by mass, and more preferably 20 to 85% by mass with respect to the total mass of the composition.

[Others]
The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. As specific examples of these, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
Other examples include diethylamino-phenylsulfonyl ultraviolet absorbers (manufactured by Daito Chemical Co., Ltd., trade name: UV-503).
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition. 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is still more preferable.

The composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the composition of the present invention can further improve the uniformity of coating thickness or the liquid-saving property because the liquid property (particularly fluidity) is further improved by containing a fluorine-based surfactant.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781F (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
Specific examples of other surfactants include, for example, surfactants described in paragraphs 0174 to 0177 of JP2013-249417A, the contents of which are incorporated herein.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001 to 2.0% by mass and more preferably 0.005 to 1.0% by mass with respect to the total mass of the composition.

In addition to the above components, the composition of the present invention may further contain the following components. For example, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, sensitizers, adhesion promoters, and other auxiliaries Well-known additives such as conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents, etc. .
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A. Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .

The solid content concentration of the composition of the present invention is preferably 5 to 50% by mass, and more preferably 15 to 40% by mass from the viewpoint of the balance between the thickness of the formed colored layer and the light shielding property.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the various components described above by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. The filter is not particularly limited as long as it has been conventionally used for filtration. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used. Among these materials, polypropylene (including high density polypropylene) or nylon is preferable.
The pore size of the filter is suitably about 0.1 to 7.0 μm, preferably 0.2 to 2.5 μm, more preferably 0.2 to 1.5 μm, and still more preferably 0.3 to 0.7 μm. If it is the said range, it will become possible to remove fine foreign materials, such as the impurity contained in a pigment, or an aggregate, reliably, suppressing the filtration clogging of a pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can select from the various filters which Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Japan Microlith Co., Ltd.), KITZ micro filter, etc. provide, for example.
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably 0.2 to 7.0 μm, and more preferably 0.3 to 6.0 μm.

<Hardened film and manufacturing method thereof>
A cured film can be formed by using the composition described above.
The thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 μm, more preferably 1.0 to 10 μm, from the viewpoint that the effect of the present invention is more excellent.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.

Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating the curable composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned. .
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
The type of substrate used is not particularly limited. In particular, when a cured film is disposed in the solid-state imaging device, various members in the solid-state imaging device (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of a wafer level lens, and The back surface of the solid-state imaging device is preferable.

A preferred embodiment in the case of producing a patterned cured film is a step of applying a composition of the present invention on a substrate by spin coating to form a composition layer (hereinafter referred to as “composition layer forming step” as appropriate). Abbreviated), a step of exposing the composition layer by irradiation with actinic rays or radiation (hereinafter abbreviated as “exposure step” as appropriate), and a cured film obtained by alkali development of the exposed composition layer. And a step of forming (hereinafter abbreviated as “development step” where appropriate).
Specifically, the composition of the present invention is applied onto a substrate directly or via another layer by spin coating to form a composition layer (composition layer forming step), and through a predetermined mask pattern. It is possible to produce a pattern-like cured film by exposing it to irradiation with actinic rays or radiation, curing only the coating film portion irradiated with light (exposure process), and developing with an alkaline developer (development process). .
Hereinafter, each process in the said aspect is demonstrated.

[Composition layer forming step]
In the composition layer forming step, a composition layer is formed by applying the composition of the present invention on a substrate.
The type of the substrate is not particularly limited, but when a cured film is disposed in the solid-state imaging device, for example, various members in the solid-state imaging device (for example, infrared light cut filter, outer peripheral portion of the solid-state imaging device, wafer level lens) And the like, and the like.
As a coating method of the composition of the present invention on the substrate, various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing method are applied. Although spin coating is possible, spin coating is preferred.
The composition coated on the substrate is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a composition layer.

[Exposure process]
In the exposure step, the composition layer formed in the composition layer forming step is exposed by irradiating actinic rays or radiation through a mask, and only the coating film portion irradiated with the light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferable, and a high-pressure mercury lamp is preferable as a light source. The irradiation intensity is preferably 5 ~ 1500mJ / cm ^2, more preferably 10 ~ 1000mJ / cm ^2.

[Development process]
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
As the developer, it is desirable to use an organic alkali developer. The development temperature is usually 20 to 30 ° C., and the development time is usually 20 to 90 seconds.
Examples of the alkaline aqueous solution include an inorganic developer containing an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, and sodium metaoxalate, and aqueous ammonia, ethylamine, Diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [ And an organic alkali developer containing an alkaline compound such as 5,4,0] -7-undecene.
The concentration of the alkaline compound is preferably 0.001 to 10% by mass, and more preferably 0.005 to 0.5% by mass.
An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, or a surfactant can also be added to the alkaline aqueous solution. In the case of using a developer composed of such an alkaline aqueous solution, it is generally washed (rinsed) with pure water after development.

In addition, after performing a composition layer formation process, an exposure process, and a image development process, you may implement the hardening process which hardens | cures the formed pattern-shaped light shielding film by heating and / or exposure as needed.

<Infrared light cut filter with light shielding film, solid-state imaging device>
When a black pigment is used as the colorant, the above-described cured film can be suitably applied as a so-called light shielding film. Such a light shielding film can be suitably applied to a solid-state imaging device.
In the following, a first embodiment of a solid-state imaging device having a light shielding film of the present invention will be described in detail.
As shown in FIGS. 2 and 3, the solid-state imaging device 2 includes a CMOS (complementary metal oxide semiconductor) sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a circuit board 4. And a ceramic substrate 5 made of ceramic. The solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) toward the CMOS sensor 3, a photographing lens 7, and a lens holder 8 that holds the photographing lens 7. And a holding cylinder 9 that holds the lens holder 8 movably. Further, instead of the CMOS sensor 3, a CCD (charge coupled device) sensor or an organic CMOS sensor may be provided.
The ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds the side surface of the CMOS sensor 3. In this state, the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy adhesive, the same applies hereinafter). Various circuit patterns are formed on the circuit board 4.

In the IR cut filter 6, a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a. The IR cut filter 6 is formed in a size slightly larger than the opening 5a, and is fixed to the ceramic substrate 5 with an adhesive so as to cover the opening 5a.
A CMOS sensor 3 is disposed behind the photographing lens 7 (downward in FIGS. 3 and 4), and an IR cut filter 6 is disposed between the photographing lens 7 and the CMOS sensor 3. The subject light enters the light receiving surface of the CMOS sensor 3 through the photographing lens 7 and the IR cut filter 6. At this time, the infrared light is cut by the IR cut filter 6.
The circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2. In the CMOS sensor 3, a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.

As shown in FIGS. 3 and 4, the light shielding film (light shielding layer) 11 described above is arranged over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided. A cut filter is formed. The reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 3 and 4) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected or refracted in the device, and photographing. When the reflected light R <b> 2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image. The light shielding film 11 shields harmful light such as reflected light R <b> 1 and R <b> 2 toward the CMOS sensor 3. The light shielding film 11 is applied by, for example, a spin coating method and a spray coating method. 3 and 4, the thickness of the light shielding film 11 is exaggerated.

FIG. 5 shows a solid-state imaging device 20 according to the second embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The above-described light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference. When the reflected light R3 emitted from the photographing lens 7 and reflected by the front surface of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus, it causes flare in the photographed image. . The light shielding film 21 shields harmful light such as reflected light R <b> 3 directed toward the CMOS sensor 3.

FIG. 6 shows a solid-state imaging device 30 according to the third embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare is reliably suppressed.

FIG. 7 shows a solid-state imaging device 40 according to the fourth embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
A light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5. When reflected light that is emitted from the photographing lens 7, passes through the IR cut filter 6, and is reflected by the inner wall surface of the ceramic substrate 5 enters the CMOS sensor 3, flare of the photographed image occurs. Since the light shielding film 41 has a light shielding performance higher than that of the inner wall surface of the ceramic substrate 5, the occurrence of flare is reliably suppressed.

<Color filter>
Moreover, the cured film of this invention is applicable also to a color filter. That is, it can be used as a color filter having the cured film of the present invention.
The color filter can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. For example, the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

Moreover, the color filter can be preferably used for an organic electroluminescence (organic EL) element. As the organic EL element, a white organic EL element is preferable. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, JP 2003-45676 A, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate. The lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region. The organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked. For example, the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer. The organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light. In that case, the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, a spectrum excellent in color reproducibility can be obtained, and a clearer image or image can be displayed.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.
The size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.

<Image display device>
The cured film (color filter, light-shielding film, etc.) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.

For the definition of the display device or details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., issued in 1990)”, “Display Device (Junsho Ibuki, Industrial Book Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a super-twist neutral (STN). TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of low dielectric constant, a resin film may be provided on the color filter.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

The liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), 25-30 pages (Takaaki Yagi), etc. It is described in.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation of precursor composition>
Precursor compositions were prepared by mixing predetermined amounts of pigments, dispersants, and solvents described in Table 1 described below.
In Table 1, “D / P” represents the mass of the dispersant / the mass of the pigment.
In Table 1, “viscosity (25 ° C.) (mPas)” in the “precursor composition” column intends the viscosity of the precursor composition at 25 ° C.
In Table 1, “Step 1 solution temperature” in the “Processing conditions” column intends the liquid temperature of the precursor composition in Step 1 (liquid temperature of the preheated precursor composition).
In Table 1, “Step 2 liquid temperature” in the “Processing conditions” column intends the liquid temperature of the precursor composition in Step 2 (liquid temperature of the precursor composition to which the dispersion treatment is applied).

Hereinafter, each component shown in Table 1 will be described in detail.

(Preparation of Pigment 1)
120 g of titanium oxide TTO-51N (trade name: manufactured by Ishihara Sangyo) with a BET specific surface area of 110 m ² / g, 25 g of silica particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Evonik) with a BET surface area of 300 m ² / g, and Dispersant Disperbyk190 (trade name: manufactured by Big Chemie) was weighed in an amount of 100 g. 71 g of ion exchange water was added to the mixture of these. Then, using a MURASTAR KK-400W manufactured by KURABO, the mixture was processed at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm for 30 minutes to obtain a uniform mixture aqueous solution. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was carried out by flowing. After the completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (pigment 1) [pigment 1] containing titanium atoms and Si atoms, and containing Si atoms and a specific surface area of 85 m ² / g.

Pigment 2: TTO-51 (C) (titanium oxide) manufactured by Ishihara Sangyo
Pigment 3: Mitsubishi Materials 13M-T (Titanium Black)
Pigment 4: Mitsubishi Materials 12S (Titanium Black)

(Synthesis of dispersants 1-2 and 4-7)
Dispersants 1-2 and 4-7 described below were synthesized with reference to the description of JP2013-249417A.
Dispersant 1 is a compound (acid value: 75 mgKOH / g) in which x / y / z (mol%) in formula (D1) is 43/8/49, and dispersant 4 is in formula (D1). X / y / z (mol%) of the compound is 63/8/29 (acid value: 110 mg KOH / g), and dispersant 5 has x / y / z (mol%) in formula (D1) 69/8/23 (acid value: 120 mgKOH / g), and dispersant 6 is a compound (acid value) in which x / y / z (mol%) in formula (D1) is 14/8/78 The dispersant 7 is a compound (acid value: 20 mgKOH / g) in which x / y / z (mol%) in the formula (D1) is 11/8/81.

(Synthesis of Dispersant 3)
The dispersant 3 described below was synthesized with reference to the description in JP-A No. 2014-62221. In addition, the number in following structural formula represents the mol% of each repeating unit.

PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

<Step 1 and Step 2>
Precursor compositions of each Example and Comparative Example were preheated to the liquid temperatures shown in Table 1 (Step 1 liquid temperature), and the precursor composition preheated to a predetermined temperature was subjected to a bead mill disperser (NPM). -Pilot (manufactured by Shinmaru Enterprises Co., Ltd.) was subjected to dispersion treatment with a bead mill to produce a pigment dispersion. The conditions of the bead mill are as follows.
Bead type: zirconia beads, diameter 0.05 mm (YSZ, manufactured by Nikkato)
Body peripheral speed: 12m / s
Separator peripheral speed: 13m / s
Bead filling rate: 65% by volume
Supply amount: 90 kg / min Treatment liquid amount: 15 kg
Refrigerant type: Nybrine Z-1 type (Tokyo Science Instruments Co., Ltd.)
In Comparative Examples 1 to 3, the precursor composition was cooled so as to have the liquid temperature shown in Table 1, and in Comparative Example 7, the precursor composition was not preheated.

Further, during the treatment with the bead mill, the dispersion treatment was carried out while adjusting the liquid temperature of the precursor composition to the temperature shown in (Step 2 liquid temperature) shown in Table 1.
The end of the dispersion process was performed according to the following criteria. The processing time in each example and comparative example is summarized in Table 1.
In addition, the completion | finish time of the dispersion | distribution process of each Example and a comparative example was determined as follows.
During the dispersion treatment, 0.063 mL of the processing solution was sampled every 10 minutes, and the sampled sample was mixed with 10 g of propylene glycol monomethyl ether acetate to prepare a measurement sample. Microtrack EX-150 The average particle diameter (D90) of the pigment is measured by (Nikkiso Co., Ltd.). The end point of the dispersion treatment was determined when the state in which the change in the average particle diameter (D90) of the sample sampled every 10 minutes was 10 nm or less continued four times continuously.

<Evaluation of primary particle size of pigment>
Each of the pigment dispersions was diluted 500 times with propylene glycol monomethyl ether acetate, and the diluted pigment dispersion was dropped on a carbon thin film and dried to obtain a TEM (transmission electron microscope) (Hitachi High-Technologies Corporation). Manufactured) was taken to observe the morphology of the pigment particles (dispersed material) contained in each pigment dispersion. From the obtained photograph, the projected area of the outer surface of 400 pigment particles was determined, the diameter of the circle corresponding to this area was calculated, and the primary particle diameter of the pigment was determined as the average value.

<Measurement of viscosity of precursor composition>
Using a viscometer RE-85 (manufactured by Toki Sangyo Co., Ltd.), the viscosity (25 ° C.) of the precursor compositions of each Example and Comparative Example was measured.

<Measurement of average particle diameter of pigment in pigment dispersion>
The pigment dispersion was diluted 500 times with propylene glycol monomethyl ether acetate, and the average particle size (D90) was measured with Microtrac EX-150 (manufactured by Nikkiso).

<Measurement of viscosity of pigment dispersion>
The pigment dispersions obtained in each Example and Comparative Example were stored at a predetermined temperature for a predetermined time, and the viscosity increase rate was measured.
Specifically, the viscosity of the pigment dispersion before aging (before storage) and the viscosity of the pigment dispersion after aging (after storage for a predetermined time) were measured, and the thickening rate was determined according to the following formula.
In addition, as storage conditions, the aspect which stored for one month at 23 degreeC and the aspect stored for one month at 7 degreeC were examined.
Thickening rate = (viscosity of pigment dispersion after aging−viscosity of pigment dispersion before lapse) / (viscosity of pigment dispersion before lapse) × 100

<Evaluation (sedimentation test)>
In the sedimentation test, the solid content concentration of the pigment dispersion after the predetermined time with respect to the solid content concentration of the pigment dispersion before the predetermined time was determined, and the sedimentation property of the particles was evaluated using this as an index.
Specifically, the solid content concentration was measured by weighing 1 g of the pigment dispersion, heating it in an oven at 165 ° C. for 60 minutes, measuring the amount of the dispersion after heating, and solid content [mass%] = dispersion after heating Quantity / dispersion quantity before heating × 100 was calculated. At this time, in order to measure the solid content concentration after the lapse of time, the dispersion was put in a glass container having an inner diameter of 5 cm and a capacity of 1 L, and left standing in an environment of 23 ° C. for 9 months. 5 g of the supernatant liquid up to the depth of was collected, and the solid content [% by mass] was measured.
Next, the sedimentation rate was calculated according to the following formula.
Sedimentation rate = (solid content after aging [mass%] − solid content before aging [mass%]) / (solid content before aging [mass%]) × 100

As shown in Table 1, according to the production method of the present invention, it was confirmed that the treatment time for producing the pigment dispersion was shortened and the storage stability of the obtained pigment dispersion was more excellent. In particular, when the liquid temperature of the precursor composition in step 2 is higher than 40 ° C. and lower than 50 ° C., it was confirmed that the effect is more excellent.
Further, from comparison between Example 2 and Examples 10 to 13, it was confirmed that the effect was more excellent when the acid value of the dispersant was 30 to 100 mgKOH / g.
Further, from comparison between Example 2 and Examples 14 to 15, it was confirmed that the effect was more excellent when the primary particle diameter of the pigment was less than 55 nm.
On the other hand, in Comparative Examples 1 to 7 in which the temperature in Step 1 was not within the predetermined range, the desired effect was not obtained.

(Example 16)
A pigment dispersion was obtained in the same manner as in Example 5, except that the pigment was changed to carbon black (trade name: Color Black S170, average primary particle diameter: 17 nm, manufactured by Degussa). When the same evaluation as in Example 5 was performed, the same result as in Example 5 was obtained. From this result, it was confirmed that the effects of the present application can be obtained with respect to the other pigments described above.

(Example 17)
A pigment dispersion was obtained in the same manner as in Example 5, except that the pigment was changed to Pigment Red 254 (manufactured by Ciba Specialty Chemicals, trade name BK-CF average primary particle size 30 nm). When the same evaluation as in Example 5 was performed, the same result as in Example 5 was obtained. From this result, it was confirmed that the effects of the present application can be obtained with respect to the other pigments described above.

(Example 18)
A pigment dispersion was obtained in the same manner as in Example 5 except that the dispersant was changed to Disperbyk110 (trade name, manufactured by Big Chemie Japan, acid value 53 mgKOH / g). When the same evaluation as in Example 5 was performed, the same result as in Example 5 was obtained. From this result, it was confirmed that the effects of the present application can be obtained with respect to other dispersants.

(Example 19)
In Example 1, the solid content concentration was increased to adjust the viscosity (25 ° C.) of the precursor composition to 17 mPa · s, and the dispersion treatment was performed. Although the dispersion processing time was longer than that in Example 1, substantially the same evaluation results were obtained.

(Example 20)
The dispersion treatment was performed in the same manner as in Example 1 except that zirconia beads having a diameter of 0.1 mm were used in the dispersion treatment. In addition to the time required for dispersion in Example 1, the yield of the pigment dispersion decreased. As a result of various evaluations, the same evaluation results as in Example 1 were obtained except that the amount of solid content sedimentation after 9 months was 3.0% as compared with Example 1.

(Comparative Example 8)
In Example 1, the solid content concentration was increased to adjust the viscosity (25 ° C.) of the precursor composition to 23 mPa · s, and the dispersion treatment was performed. The solid content sedimentation amount after 9 months was 11.2%, and it was found that the storage stability was inferior.

(Comparative Example 9)
In Example 1, the solid content concentration was reduced, the viscosity (25 ° C.) of the precursor composition was adjusted to 2 mPas, and the dispersion treatment was performed. Processing time exceeded 20 hours, and dispersion took time.

(Preparation of binder solution 1)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. A solution prepared by adding 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) to 159 g of 1-methoxy-2-propanol was added dropwise over 2 hours. did. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours.
Subsequently, the heating was stopped to obtain a solution containing a copolymer of benzyl methacrylate / methacrylic acid (30/70 mol ratio).
Next, 120.0 g of the obtained copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 3.0 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 184 g of 1-methoxy-2-propanol was added to the reaction solution to prepare a binder solution 1 having a weight average molecular weight of 12,000 (polystyrene conversion value determined by GPC method), an acid value of 35 mgKOH / g, and a solid content of 30% by mass. .

(Preparation of curable composition A)
Components of the following composition were mixed with a stirrer and filtered through a filter to prepare curable composition A. In addition, the following "part" intends a mass part.
(composition)
(A) 50 parts of the pigment dispersion of Example 1 (F-1) Alkali-soluble resin: 17.0 parts of binder solution 1 (B) Polymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
5.0 parts (C) Polymerization initiator: IRGACURE-OXE02 (manufactured by BASF)
2.5 parts · (F-4) polymerization inhibitor: p-methoxyphenol 0.003 parts · (F-6) surfactant: MegaFac F781 (fluorine type surfactant,
Dainippon Ink & Chemicals, Inc.) 0.01 parts Organic solvent: 10 parts propylene glycol monomethyl ether acetate Organic solvent: 10 parts cyclohexanone

The curable composition A immediately after preparation was put in a solution cup of a spray coating apparatus, applied to a glass substrate under the following application and heating conditions, and further subjected to a curing treatment to form a cured film 1.
Spray coating device: PS-268 made by GSI Creos
Spray application air pressure condition: 3000 cc / min Application amount: 0.2 cc / min Nozzle diameter: 0.4 mm
The spray outlet and the glass substrate coating surface are installed vertically.
Distance between spray outlet and glass substrate: 3cm
Spray spray angle *: 90 degrees (* An angle from the spray outlet to the glass substrate from the normal to both sides)
Spray coating was performed until the average film thickness of the coated portion was 2.5 μm, and after coating, the coating was heated on a hot plate at 120 ° C. for 2 minutes.

(Evaluation of clogging of spray application)
About the curable composition A, spray coating was performed on the following conditions, and clogging was evaluated.
Spray coating device: PS-268 made by GSI Creos
The curable composition A to be evaluated is put in a solution cup of a spray coating apparatus, and after being allowed to stand at 25 ° C. for 96 hours, coating is performed under the following conditions with the spray coating apparatus, and evaluation is made on whether clogging occurs. It was possible to apply without clogging.
Spray application air pressure condition: 3000 cc / min Application amount: 0.2 cc / min Nozzle diameter: 0.4 mm

(Measurement of surface reflectance)
The cured film 1 obtained above was measured for surface reflectance at a wavelength of 450 nm (incident angle of 5 degrees) with a spectrophotometer manufactured by Hitachi High Technology, U-4100, and the reflectance was measured in%.
In particular, in the case of a solid-state imaging device application, it is judged that there is practicality if the surface reflectance is 4% or less. The results obtained are as follows.
Surface reflectance: 0.38%

(Light shielding)
The cured film 1 obtained above was measured for transmittance at a wavelength of 550 nm with a spectrophotometer manufactured by Hitachi High-Technology Co., Ltd. U-4100, and used as an indicator of light shielding rate. In particular, in the case of a solid-state imaging device application, it is determined that there is practicality if the transmittance is 1% or less. The results obtained are as follows.
Transmittance: 0.004%

From these results, it was found that the cured film of the present invention has good spray application suitability, and excellent light shielding properties and antireflection performance.
Further, from this result, the cured film produced using the pigment dispersion of the present application is excellent in light shielding properties and antireflection performance, so that a solid-state imaging device having a light shielding layer, a color filter, a black matrix, and further It can be used suitably for manufacture of the image display apparatus which comprised.

2, 20, 30, 40 Solid-state imaging device 3 CMOS sensor 4 Circuit board 5 Ceramic substrate 5a Opening 5b Inner wall surface 6 IR cut filter 7 Shooting lens 8 Lens holder 9

Holding cylinder

10, 11, 21, 31, 41 Light shielding film (light shielding layer)
12 Black layer 14 Coating layer 100 Substrate 200 Tank 300 Piping 500 Bead mill disperser

Claims

Step 1 of preheating a precursor composition containing a pigment, a dispersant, and an organic solvent and having a viscosity of 3 to 20 mPa · s at 25 ° C .;
And a step 2 of subjecting the precursor composition to a dispersion treatment by a bead mill while keeping the liquid temperature of the preheated precursor composition at 40 ° C. or more and less than 60 ° C.
The method for producing a pigment dispersion according to claim 1, wherein the primary particle diameter of the pigment is less than 55 nm.
The method for producing a pigment dispersion according to claim 1 or 2, wherein the acid value of the dispersant is from 30 to 100 mgKOH / g.
The method for producing a pigment dispersion according to any one of claims 1 to 3, wherein beads having a diameter of 0.05 mm or less are used in the bead mill.
The method for producing a pigment dispersion according to any one of claims 1 to 4, wherein in the step 1, the liquid temperature of the precursor composition is preheated to 40 to 60 ° C.
The method for producing a pigment dispersion according to any one of claims 1 to 5, wherein the liquid temperature of the precursor composition in the step 2 is maintained at more than 40 ° C and less than 57 ° C.
Obtaining a pigment dispersion by the production method according to any one of claims 1 to 6,
A method of producing a curable composition comprising: a step of mixing the pigment dispersion obtained in the above step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition.
Obtaining a pigment dispersion by the production method according to any one of claims 1 to 6,
Mixing the pigment dispersion obtained in the above step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
Curing the curable composition obtained in the step to obtain a cured film.
Obtaining a pigment dispersion by the production method according to any one of claims 1 to 6,
Mixing the pigment dispersion obtained in the above step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
A method for producing a solid-state imaging device, comprising: a step of curing the curable composition obtained in the step to obtain a cured film.
Obtaining a pigment dispersion by the production method according to any one of claims 1 to 6,
Mixing the pigment dispersion obtained in the above step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
A method for producing a color filter comprising a cured film comprising: a step of curing the curable composition obtained in the step to obtain a cured film.
Obtaining a pigment dispersion by the production method according to any one of claims 1 to 6,
Mixing the pigment dispersion obtained in the above step, a polymerization initiator, a polymerizable compound, and an alkali-soluble resin to obtain a curable composition;
And a step of curing the curable composition obtained in the step to obtain a cured film.