TWI675889B - Pigment dispersion composition and method for producing the same, polymerizable composition,shielding film, and solid state image sensor - Google Patents

Abstract

The present invention provides a pigment dispersion composition suitable for producing a light-shielding film excellent in light-shielding properties, exhibiting low reflectivity, having low dependence on the coating environment, and further difficult to generate defects by a coating method, a method for producing the same, and a pigment containing the pigment. A polymerizable composition of a dispersed composition, a light-shielding film, and a solid-state imaging device. The method for producing a pigment dispersion composition of the present invention includes a step of producing a pigment dispersion composition by mixing a first pigment dispersion including a black pigment and a first dispersant and a second pigment dispersion including a black pigment and a second dispersant. The absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.0 MPa ^1/2 .

Description

Pigment dispersion composition, method for producing the same, polymerizable composition, Light-shielding film and solid-state imaging device

The present invention relates to a pigment dispersion composition, a method for producing the same, a polymerizable composition, a light-shielding film, and a solid-state imaging device.

A solid-state imaging device includes a solid-state imaging device such as a photographing lens, a charge coupled device (CCD) and a complementary metal oxide semiconductor (CMOS) disposed behind the photographing lens, and the solid-state imaging device is mounted on the solid-state imaging device. Circuit board of the imaging element. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, and a smart phone.

In a solid-state imaging device, noise may occur due to reflection of visible light. Therefore, in Patent Document 1, a predetermined light-shielding film is provided in the solid-state imaging device to suppress occurrence of noise. As a composition for forming a light-shielding film for a solid-state imaging device, a light-shielding composition containing a black pigment such as titanium black is used.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-169556

On the other hand, in recent years, various requirements have been placed on light-shielding films.

For example, with the reduction in size, thickness, and sensitivity of solid-state imaging devices, further reduction in reflection of light-shielding films is required. In particular, in terms of industry, it is preferable that the low-reflection light-shielding film can be formed by a coating method such as a spin coating method having excellent productivity.

In the case where the coating method is implemented, it is desirable that the properties of the obtained light-shielding film do not change depending on the coating environment. More specifically, from an industrial standpoint, it is desirable that the environment at the time of coating is always constant. However, depending on the weather or season, the humidity at the time of coating may be changed, or the exhaust amount of the solvent may be changed at the time of coating. It is desirable to obtain a light-shielding film that exhibits predetermined characteristics even when the coating environment such as humidity and exhaust volume is changed. That is, a light-shielding film having a small coating environment dependency is desirable. In addition, the coating environment dependency refers to how much the optical characteristics of the light-shielding film change due to the coating environment, and when the coating environment dependency is high, if the coating environment changes, The optical characteristics of the resulting light-shielding film will also change significantly.

Furthermore, in many cases, the light-shielding film is formed in a pattern on a predetermined member and is arranged in a solid-state imaging device. Furthermore, the components are arranged in the solid-state imaging device. Previously, in order to remove a foreign substance from a member, the member may be subjected to a cleaning treatment in which a cleaning solution is blown with a high pressure. In this cleaning process, it is also required that defects of the light-shielding film do not occur.

That is, it is desirable to produce a light-shielding film which is excellent in light-shielding properties, exhibits low reflectivity, has low dependency on the coating environment, and is less likely to cause defects by a coating method.

The inventors have used the polymerizable composition disclosed in Patent Document 1 to manufacture a light-shielding film by a coating method, and have studied the characteristics. As a result, they have found that a light-shielding film that satisfies all the characteristics cannot be obtained. Further improvements are needed.

This invention is made in view of the said situation, and an object is to provide the pigment dispersion composition suitable for manufacture of the light-shielding film which is excellent in light-shielding property by coating method, shows low reflectivity, has a small coating environment dependency, and is hard to generate a defect And its manufacturing method.

Another object of the present invention is to provide a polymerizable composition including the pigment dispersion composition, a light-shielding film, and a solid-state imaging device.

The present inventors conducted diligent research in order to achieve the above-mentioned problems, and as a result, they found that the above-mentioned problems can be solved by using a pigment dispersion composition obtained by using two kinds of dispersants having different Solubility Parameter (SP) values. This invention.

That is, the present inventors have found that the problems can be solved by the following configuration.

(1) A method for producing a pigment dispersion composition, comprising mixing a first pigment dispersion including a black pigment and a first dispersant and a second pigment dispersion including a black pigment and a second dispersant to produce a pigment dispersion composition The absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.0 MPa ^1/2 .

(2) The method for producing a pigment dispersion composition according to (1), wherein either of the first dispersant and the second dispersant is a polymer compound represented by the general formula (X) described later, and the first dispersant The other of the agent and the second dispersant is a polymer compound containing a structural unit having a graft chain.

(3) The method for producing a pigment dispersion composition according to (2), wherein the structural unit having a graft chain includes one or more structures selected from the structural units represented by formulas (1) to (4) described later unit.

(4) The method for producing a pigment dispersion composition according to any one of (1) to (3), wherein the black pigment is titanium black.

(5) The method for producing a pigment dispersion composition according to any one of (1) to (4), wherein an absolute value of a difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.5 MPa ^1/2 .

(6) A pigment dispersion composition comprising a black pigment, a first dispersant, and a second dispersant, and an absolute value of a difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.0 MPa ^{1 / 2} , one of the first dispersant and the second dispersant is a polymer compound represented by the general formula (X) described later, and the other of the first dispersant and the second dispersant contains a compound selected from the following formula (1) to a polymer compound of one or more structural units among the structural units represented by formula (4).

(7) The pigment dispersion composition according to (6), wherein the black pigment is titanium black.

(8) The pigment dispersion composition according to (6) or (7), wherein the absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.5 MPa ^1/2 .

(9) A polymerizable composition comprising the pigment dispersion composition according to any one of (6) to (8), a polymerizable compound, and a polymerization initiator.

(10) The polymerizable composition according to (9), further comprising a binder polymer having an SP value, the SP value, the SP value of the first dispersant, and the SP value of the second dispersant. The absolute value of the difference between the SP values was within 0.5 MPa ^1/2 .

(11) A light-shielding film formed using the polymerizable composition according to (9) or (10).

(12) A solid-state imaging device including the light-shielding film according to (11).

According to the present invention, it is possible to provide a pigment dispersion composition suitable for producing a light-shielding film excellent in light-shielding properties, exhibiting low reflectivity, having low dependence on the coating environment, and further less likely to cause defects, and a method for producing the same by a coating method.

Moreover, according to this invention, the polymerizable composition containing the said pigment dispersion composition, a light-shielding film, and a solid-state imaging device can also be provided.

2, 20, 30, 40‧‧‧ solid-state imaging device

3‧‧‧CMOS sensor

4‧‧‧circuit board

5‧‧‧ Holding substrate (ceramic substrate) for solid-state image sensor

5a‧‧‧ opening

6‧‧‧IR cut-off filter

6a‧‧‧ incident surface

7‧‧‧Photographic lens

8‧‧‧ lens holder

9‧‧‧ holding tube

11, 21, 31, 41, 102‧‧‧ light-shielding film (light-shielding layer)

100‧‧‧ substrate

102a‧‧‧Side Etching

104‧‧‧Fixing film

R1, R2, R3‧‧‧ reflected light

1 (A) to 1 (D) are cross-sectional views showing a procedure of a film repair step.

FIG. 2 is a perspective view showing the solid-state imaging device according to the first embodiment.

3 is an exploded perspective view of the solid-state imaging device according to the first embodiment.

FIG. 4 is a cross-sectional view showing the solid-state imaging device according to the first embodiment.

5 is a cross-sectional view showing a solid-state imaging device according to a second embodiment.

6 is a cross-sectional view showing a solid-state imaging device according to a third embodiment.

Fig. 7 is a sectional view showing a solid-state imaging device according to a fourth embodiment.

FIG. 8 is a schematic view of a patterned mask used in the embodiment.

FIG. 9 is a sectional photograph of a patterned light-shielding film.

10 is a cross-sectional photograph of a light-shielding film on which a repair film is formed.

11 (A) and 11 (B) are cross-sectional photographs of a light-shielding film after the etching process.

FIG. 12 is a diagram showing transmission and spectral characteristics of a light-shielding film before and after an etching process.

FIG. 13 is a graph showing the reflectance of the light-shielding film before and after the etching process.

Hereinafter, the preferable aspect of the pigment dispersion composition of this invention, its manufacturing method, a polymerizable composition, a light-shielding film, and a solid-state imaging device is described in detail.

In addition, in the description of the group (atomic group) in the present specification, the expressions that are not described as substituted and unsubstituted are expressions that include a group (atomic group) having no substituent and also include a group (atomic group) having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

In addition, "radiation" in this specification means including visible light, ultraviolet rays, Far ultraviolet, electron beam and X-ray.

The description of the constituent elements described below may be based on a representative embodiment of the present invention, and the present invention is not limited to such an embodiment. In addition, in this specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.

In addition, in this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic acid and methacrylic acid, and "(meth) acrylfluorenyl" means acrylic acid. And methacryl groups. In addition, in this specification, "single body" and "monomer" have the same meaning. The monomers in the present invention are different from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable group, and may be a singular body or a polymer. The polymerizable group refers to a group participating in a polymerization reaction.

As described above, as one of the characteristic points of the present invention, an aspect in which two kinds of dispersants having different SP values are used can be cited. The reason for obtaining the effects of the present invention is estimated below.

First, if two kinds of dispersants having different SP values are used, layer separation of the two kinds of dispersants is caused in a state of a light-shielding film formed by a coating method. If such layer separation occurs, a concave-convex structure is formed on the surface of the light-shielding film, and this structure reflects light and contributes to low reflection.

In addition, in the case where only one dispersant is used as described in Patent Document 1, when producing a light-shielding film, it is soluble in a binder (for example, alkali-soluble) other than the dispersant. Phase separation), it is easy to form a region containing a dispersant and a region not containing a dispersant, and a black pigment is biased to exist in a region containing a dispersant. Such a layer separation structure greatly changes due to a coating environment such as a humidity environment and an exhaust environment. For example, the size of a region that does not contain a black pigment may vary greatly depending on the coating environment. Therefore, the structure of the obtained light-shielding film changes depending on the coating environment, and its optical characteristics (especially reflectance) change. That is, the coating environment is highly dependent. In contrast, when the two dispersants with different SP values are used, although the phase separation occurs between the dispersants, the black pigment is included in the two regions. Therefore, if the entire light-shielding film is used, the black pigment is uniformly dispersed. . Therefore, it is difficult to generate a region not containing the black pigment as described above, and the coating environment dependency is small.

Furthermore, when the two kinds of dispersants having different SP values are used, it is difficult to generate undercuts during development to prevent defects during cleaning.

Hereinafter, the method for producing the pigment dispersion composition of the present invention will be described first, and then the pigment dispersion composition and the solid-state imaging device will be described in detail.

<< Manufacturing method of pigment dispersion composition >>

The method for producing a pigment dispersion composition of the present invention includes at least mixing a first pigment dispersion including a black pigment and a first dispersant with a second pigment dispersion including a black pigment and a second dispersant to produce a pigment dispersion composition. Step (hereinafter, also referred to as "step 3").

The first pigment dispersion and the second pigment dispersion used in Step 3 may be commercially available products or may be produced. Usually, before the mixing step, a step of preparing the first pigment dispersion (hereinafter, also referred to as "step 1") and a step of preparing the first pigment dispersion are performed. 2 pigment dispersion step (hereinafter, also referred to as "step 2"). In addition, steps 1 and 2 can be implemented in different orders. Step 2 can be performed after step 1 is performed, or step 1 can be performed after step 2. Alternatively, step 1 and step 2 may be performed simultaneously.

Hereinafter, the procedures of each step will be described in detail in the order of steps 1 to 3.

<Step 1>

Step 1 is a step of preparing a first pigment dispersion including a black pigment and a first dispersant. As described above, a commercially available product may be used as the first pigment dispersion, or a black pigment and a first dispersant may be mixed to produce the first pigment dispersion.

Hereinafter, the procedure of the step of mixing a black pigment and a first dispersant to produce a first pigment dispersion will be described in detail.

The state of the black pigment and the first dispersant used in this step will be described in detail later.

The mass ratio of the black pigment to the first dispersant (mass of the black pigment / mass of the first dispersant) is not particularly limited, and it is preferable in terms of better dispersibility of the black pigment and more excellent light-shielding film characteristics. It is 1 to 10, and more preferably 2.0 to 5.0.

Moreover, when manufacturing a 1st pigment dispersion, you may use other components other than a black pigment and a 1st dispersing agent together as needed. For example, as another component, the component (for example, a solvent, a polymerizable compound, a binder polymer) etc. which can be contained in the polymerizable composition mentioned later are mentioned.

When a solvent is included in the first pigment dispersion, the black pigment is more excellent in dispersibility and more excellent in the characteristics of the light-shielding film than the first pigment dispersion. The total mass of the pigment dispersion and the content of the solvent are preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 80% by mass.

The method of mixing a black pigment and a 1st dispersing agent is not specifically limited, A well-known method can be used. For example, a black pigment and a 1st dispersant can be mixed using well-known mixing apparatuses, such as a stirrer, a homogenizer, a high-pressure emulsifier, a wet grinder, and a wet disperser, and the 1st pigment dispersion can be prepared.

Specific examples of the mixing device include an Ultra Apex Mill manufactured by Shou Industry Co., Ltd., and a Dyno-Mill NPM series manufactured by Shinmaru Enterprises.

The temperature during the mixing treatment is not particularly limited, but from the viewpoint of dispersion stability, it is preferably 5 ° C to 70 ° C, and more preferably 20 ° C to 60 ° C.

The mixing treatment is preferably performed using beads. The composition or size (diameter) of the beads is not particularly limited, and a known composition or diameter can be applied. As the beads, for example, beads having a diameter of 0.01 mm to 0.30 mm are preferred.

The mixing treatment is preferably performed in the presence of a solvent. When a solvent is used, the mass ratio of the solvent to the black pigment [solvent / black pigment] is preferably 1.0 to 9.0, and more preferably 1.0 to 5.0 in terms of ease of dispersion.

<Step 2>

Step 2 is a step of preparing a second pigment dispersion including a black pigment and a second dispersant. As described above, the second pigment dispersion may be a commercially available product, or a second pigment dispersion may be produced by mixing a black pigment and a second dispersant.

As a procedure for producing the second pigment dispersion, the method described in Step 1 can be cited. The method is omitted here.

The state of the black pigment and the second dispersant used in this step will be described in detail later.

The mass ratio of the black pigment to the second dispersant (mass of the black pigment / mass of the second dispersant) is not particularly limited, and it is preferable in terms of better dispersibility of the black pigment and better characteristics of the light-shielding film. It is 1 to 10, and more preferably 2.0 to 5.0.

Moreover, when manufacturing a 2nd pigment dispersion, you may use other components other than a black pigment and a 2nd dispersing agent together as needed. For example, as another component, the component (for example, a solvent, a polymerizable compound, a binder polymer) etc. which can be contained in the polymerizable composition mentioned later are mentioned.

When a solvent is contained in the second pigment dispersion, the content of the solvent relative to the total mass of the second pigment dispersion is more excellent in the dispersibility of the black pigment and the characteristics of the light-shielding film. It is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 80% by mass.

The absolute value of the difference between the SP value of the first dispersant used in step 1 and the SP value of the second dispersant used in step 2 was more than 1.0 MPa ^1/2 . Among them, it is possible to obtain at least one of the following effects (hereinafter, also simply referred to as "effects of the present invention") in which at least one of the effects of lower reflectivity of the light-shielding film, difficulty in occurrence of defects of the light-shielding film, low dependence on the coating environment, and excellent pattern resolution is obtained. More excellent point "), the absolute value of the difference is preferably more than 1.5 MPa ^1/2 , and more preferably 2.5 MPa ^1/2 or more. Upper limit of the absolute value of the difference is not particularly limited, is usually most cases 5.0MPa ^1/2 or less, more cases of 4.0MPa ^1/2 or less.

The absolute value of the difference means a value represented by | SP value of the first dispersant-SP value of the second dispersant |.

The range of the SP value of the first dispersant and the SP value of the second dispersant is only required to satisfy the above-mentioned relationship. In terms of a more excellent effect of the present invention, it is preferably 16 MPa ^1/2 to 24 MPa ^1/2 . More preferably, it is 17 MPa ^1/2 to 22 MPa ^1/2 .

In addition, in terms of more excellent effects of the present invention, the SP value of one of the SP value of the first dispersant and the SP value of the second dispersant is preferably less than 18.5 MPa ^1/2 , and more preferably less than 18.0MPa ^1/2 .

When the SP value of one of the SP value of the first dispersant and the SP value of the second dispersant is less than 18.5 MPa ^1/2 , the SP value of the first dispersant and the SP value of the second dispersant are different. The SP value of one is preferably 19.5 MPa ^1/2 or more, and more preferably 20.0 MPa ^1/2 or more.

The SP value in the present invention refers to a solubility parameter, and represents a solubility parameter measured by the Otsutsu method. The Otsutsu method is described in detail in "Journal of the Japanese Academy of Adhesion" (Vol. 29, No. 5 (1993)). The SP value of a 1st dispersing agent and a 2nd dispersing agent is a value calculated | required as follows. First, the SP values of the monomers for forming the first dispersant and the second dispersant were determined by the Otsutsu method. Next, for each monomer, the product of the SP value of the monomer and the mass fraction of the monomer in the first dispersant and the second dispersant was determined. Next, the SP values of the first dispersant and the second dispersant are obtained by adding the products obtained for each monomer.

For example, a SP value of 15MPa ^1/2 of the monomer A (10 mass%), SP value 18MPa ^1/2 of the monomer B (20 mass%) SP value 20MPa ^1/2 and monomer C (70 The SP value of the resin a of the copolymer by mass%) was obtained by the following formula.

SP value of resin a (MPa ^1/2 ): 15 (MPa ^1/2 ) × (10/100) +18 (MPa ^1/2 ) × (20/100) +20 (MPa ^1/2 ) × (70 /100)=19.1(MPa ^1/2 )

<Step 3>

Step 3 is a step of mixing a first pigment dispersion and a second pigment dispersion to produce a pigment dispersion composition.

The mixing method in this step is not particularly limited, and examples thereof include a method using the mixing device described in the step 1.

Furthermore, for the purpose of reducing defects of the light-shielding film by removing foreign matter, it is preferable to perform a filtering process using a filter after the steps 1 to 3 as necessary.

The filter can be used without particular limitation as long as it is a filter that has been used for filtering purposes and the like since before. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (high density, including ultra-high molecular weight), etc. Filter. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is suitably about 0.1 μm to 7.0 μm, preferably about 0.2 μm to 2.5 μm, more preferably about 0.2 μm to 1.5 μm, and even more preferably 0.3 μm to 0.7 μm. By setting this range, the clogging of black pigment can be suppressed, and the black color can be reduced. Fine foreign matter such as impurities and aggregates contained in the color pigment is reliably removed.

When using filters, different filters can also be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. In the case where different filters are combined to perform two or more filtrations, it is preferable that the pore diameter of the second and subsequent filtrations is the same as or larger than the pore diameter of the first filtration. In addition, the first filters having different pore sizes may be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, Pall Co., Ltd., Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (Mykrolis Co., Ltd.) and Kitz Microfilter Co., Ltd.

As the second filter, a filter made of the same material as the first filter can be used. The pore diameter of the second filter is suitably about 0.2 μm to 10.0 μm, preferably about 0.2 μm to 7.0 μm, and more preferably about 0.3 μm to 6.0 μm.

<< Pigment dispersion composition (hereinafter, also simply referred to as "composition") >>

A pigment dispersion composition containing a black pigment, a first dispersant, and a second dispersant can be obtained by the production method. As described above, the first dispersant and the second dispersant satisfy a predetermined SP value relationship. Furthermore, as described above, since a concave-convex structure is formed on the surface of the light-shielding film by using two kinds of dispersants to achieve low reflection, a matting agent (not including a black pigment) is not necessary in the pigment dispersion composition of the present invention. The constituent elements are preferably not included, but can also be used without impairing the effects of the present invention. Use within range.

The content of the black pigment in the pigment-dispersed composition is not particularly limited, and in terms of the effect of the present invention, the total solid content (total solid content mass) of the composition is preferably 5% to 90% by mass. %, More preferably 20% to 80% by mass.

The content of the first dispersant in the pigment-dispersed composition is not particularly limited. In terms of the effect of the present invention, the total solid content (total solid content mass) of the composition is preferably 1% to 30% by mass Mass%, more preferably 5 mass% to 25 mass%.

The content of the second dispersant in the pigment-dispersed composition is not particularly limited. In terms of the effect of the present invention, the total solid content (total solid content mass) of the composition is preferably 1% by mass or more. 30 mass%, more preferably 5 mass% to 25 mass%.

The solid content refers to a component that can constitute a light-shielding film, and does not include a solvent.

In the pigment dispersion composition, the mass ratio of the first dispersant to the second dispersant (mass of the first dispersant / mass of the second dispersant) is not particularly limited, and the effect of the present invention is more excellent, It is preferably 0.1 to 9.0, and more preferably 0.2 to 3.0.

Hereinafter, each component contained in a pigment dispersion composition is demonstrated in detail.

<Black pigment>

As the black pigment, various known black pigments can be used. In particular, carbon black, titanium black, titanium oxide, and oxide are preferable from the viewpoint that a high optical concentration can be achieved in a small amount. Among them, iron, manganese oxide, graphite and the like are preferably at least one of carbon black and titanium black, and titanium black is particularly preferred.

More specifically, organic pigments such as C.I. Pigment Black 1 and inorganic pigments such as Pigment Black 7 can be used as commercially available products.

The black pigment preferably contains titanium black.

Titanium black refers to black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. For the purpose of improving dispersibility and suppressing cohesion, the surface of the titanium black particles may be modified as necessary. For example, titanium oxide particles can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconia, and a water-repellent substance shown in Japanese Patent Laid-Open No. 2007-302836 can also be used. For processing.

Titanium black is typically titanium black particles, and preferably particles having a small primary particle size and a small average primary particle size.

Specifically, particles having a range of 10 nm to 45 nm as the average primary particle diameter are preferred. The particle diameter in the present invention, that is, the particle diameter refers to the diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing in an electron microscope photograph and correcting the photographing magnification.

The specific surface area of titanium black is not particularly limited. In order to make the water repellency after surface treatment of the titanium black with a water-repellent agent a predetermined property, a value measured by the Brunauer-Emmett-Teller (BET) method typically 5m ² / g or more and 150m ² / g or less, and especially preferably 120m ² 20m ² / g or more / g or less.

Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (trade names: above, manufactured by Mitsubishi Materials (Stock)), Dila Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Furthermore, it is also preferable to contain titanium black in the form of a dispersion containing titanium black and Si atoms.

In this form, titanium black is contained in the composition in the form of a dispersion, and the content ratio (Si / Ti) of the Si atoms to the Ti atoms in the dispersion is preferably 0.05 or more in terms of mass conversion.

Here, the to-be-dispersed body includes both a state where titanium black is a primary particle and a state where titanium black is an aggregate (secondary particle).

In addition, regarding the content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion to be used in the present invention, when the dispersion ratio is 0.5 or less, the pigment dispersion in which the dispersion is used tends to be easily produced. The upper limit is preferably 0.5.

In addition, when patterning the light-shielding film using the dispersion by photolithography, etc., it is more preferable that the Si / Ti of the dispersion is 0.05 or more in terms of the difficulty that the residue remains in the removal portion and the light-shielding performance is excellent. 0.5 or less, more preferably 0.07 or more and 0.4 or less.

In order to change the Si / Ti of the dispersion (for example, 0.05 or more), the following method can be used.

First, a titanium oxide and silicon dioxide particles are dispersed using a disperser to obtain a mixture, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 ° C to 1000 ° C), thereby obtaining titanium black particles as a main component. Composition containing Si and Ti Scattered.

Here, a specific aspect of Si / Ti for changing the dispersion will be described.

The titanium black whose Si / Ti is adjusted to, for example, 0.05 or more can be produced by the methods described in paragraphs [0005] and [0016] to [0021] of Japanese Patent Laid-Open No. 2008-266045, for example.

In the present invention, by adjusting the content ratio of Si atoms to Ti atoms (Si / Ti) in a dispersion containing titanium black and Si atoms to a preferred range (for example, 0.05 or more), the dispersion containing the dispersion is used. When the light-shielding film is formed by the composition of the composition, residues derived from the composition outside the area where the light-shielding film is formed are reduced. The residue includes components derived from compositions such as titanium black particles and resin components.

The reason for the reduction of the residue is still unclear, and it is presumed that the dispersion as described above tends to have a small particle diameter (for example, the particle diameter is 30 nm or less), and further that the component containing the Si atom of the dispersion is increased, whereby The adhesion between the entire film and the substrate is reduced, and this case contributes to an improvement in the development removal property of the unhardened composition (especially titanium black) during the formation of the light-shielding film.

In addition, for light in a wide range of wavelengths from ultraviolet light to infrared light, titanium black has excellent light-shielding properties. Therefore, the above-mentioned dispersion containing titanium black and Si atoms (preferably Si / Ti to A light-shielding film having a mass conversion of 0.05 or more) exhibits excellent light-shielding properties.

The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion may be, for example, the method (1-1) or the method (1-) described in paragraph 0033 of Japanese Patent Laid-Open No. 2013-249417. 2) Perform the measurement.

In addition, regarding the dispersion to be contained in the light-shielding film obtained by curing the composition, in order to determine whether the content ratio (Si / Ti) of the Si atom to the Ti atom in the dispersion is 0.05 or more, Japanese Patent No. The method (2) described in paragraph 0035 of the 2013-249417 publication.

Among the dispersions containing titanium black and Si atoms, titanium black can be used as the titanium black.

In addition, in this dispersion, for the purpose of adjusting dispersibility and coloring, etc., a composite oxide containing cobalt, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, and aniline black may also be used. One or two or more of the black pigments are combined and used together with titanium black in the form of a dispersion.

In this case, the dispersion containing titanium black preferably accounts for 50% by mass or more of all the dispersions.

In addition, in this dispersion, for the purpose of adjusting light-shielding properties and the like, as long as the effects of the present invention are not impaired, other colorants (organic pigments, dyes, etc.) may be used together with titanium black as necessary.

Hereinafter, materials used when introducing Si atoms into a dispersion will be described. When introducing Si atoms into the dispersion, a substance containing Si, such as silicon dioxide, may be used.

Examples of the usable silicon dioxide include precipitated silica, fumed silica, colloidal silica, and synthetic silica, as long as these are appropriately selected and used.

Furthermore, when the light-shielding film is formed, if the particle diameter of the silicon dioxide is smaller than the film thickness, the light-shielding property is more excellent. Therefore, it is preferable to use fine-particle-type silicon dioxide as the For silicon dioxide particles. In addition, as an example of the fine particle type silicon dioxide, for example, the silicon dioxide described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2013-249417 can be cited, and these contents are incorporated in this specification.

The composition of the present invention may contain only one kind of titanium black, or may contain two or more kinds.

<Pigment other than black pigment>

In addition to the black pigment, the composition of the present invention may include an extender pigment, if necessary. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silicon dioxide, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in combination of two or more. The amount of the extender pigment used is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, with respect to 100 parts by mass of the black pigment. In the present invention, as for the black pigment and extender pigment, the surface of these polymers may be modified and used in some cases.

In addition, in addition to black pigments, colored organic pigments including red, blue, yellow, green, and purple may be included as needed. When a colored organic pigment is used in combination, it is preferable to use a red pigment in an amount of 1% to 40% by mass relative to a black pigment, and the red pigment is preferably pigment red 254.

<First dispersant and second dispersant>

The first dispersant and the second dispersant are compounds that function as a dispersant (pigment dispersant) for dispersing the black pigment. The type of the first dispersant and the second dispersant is not particularly limited as long as the SP value relationship is satisfied. In terms of a more excellent effect of the present invention, the first dispersant and the second dispersant are preferred. Any of One is a polymer compound represented by the general formula (X), and the other one of the first dispersant and the second dispersant is a polymer compound containing a structural unit having a graft chain. In addition, as the structural unit having a graft chain, one or more structural units selected from the structural units represented by the formulas (1) to (4) described below are preferably exemplified.

The SP value of the polymer compound represented by the general formula (X) is not particularly limited. In terms of the effect of the present invention, it is preferably 16 MPa ^1/2 or more, more preferably 17 MPa ^1/2 or more, good to 22MPa ^1/2 or less, more preferably 21MPa ^1/2 or less, and 19MPa ^1/2 or less is good, particularly preferably less than 18.5MPa ^1/2, most preferably less than 18.0MPa ^1/2.

A polymer compound comprising a structural unit having a graft chain of the SP value is not particularly limited, in terms of more excellent effect of the present aspect of the invention, preferably 18MPa ^1/2 or more, more preferably 19MPa ^1/2 or more, In addition to good 19.5MPa ^1/2 or more, particularly preferably 20.0MPa ^1/2 or more, preferably 24MPa ^1/2 or less, more preferably 22MPa ^1/2 or less.

Hereinafter, the polymer compound represented by the general formula (X) and the polymer compound including a structural unit having a graft chain will be described in detail.

(Polymer compound represented by general formula (X) (hereinafter, also referred to as polymer compound X))

Hereinafter, each group in the general formula (X) will be described in detail. In addition, the substituent A ^{1 in the} polymer compound X can interact with a black pigment. Therefore, the polymer compound X can have n (1 to 9) substituents A ¹ strongly interact with the black pigment. In addition, the m polymer chains P ¹ included in the polymer compound X can function as a steric repulsive group, and by having m, a good steric repulsive force can be exhibited to uniformly disperse the black pigment.

In the general formula (X), A ¹ represents, for example, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a cooperating oxygen atom, a phenol group, an alkyl group, and an aromatic group. Group, a group having an extended alkyloxy chain, amidino group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamido group, an alkoxysilyl group, an epoxy group, an isocyanate Functional groups that have the ability to adsorb black pigments, such as radicals, hydroxyl groups, and heterocyclic groups.

In addition, hereafter, the site | part (the said functional group) which has an adsorption ability with respect to a black pigment is suitably collectively called "adsorption site", and is demonstrated.

One A ¹ may include at least one adsorption site, and may include two or more sites.

Examples of the state where two or more adsorption sites are included in one A ¹ include, for example, two or more adsorption sites via a chain-like saturated hydrocarbon group (which may be linear or branched, and carbon number (carbon Atomic number) 1 to 10), cyclic saturated hydrocarbon group (preferably 3 to 10 carbon number), or aromatic group (preferably 5 to 10 carbon number, such as phenyl group) and other bonds to form a monovalent substitution The appearance of the radical A ¹ and so on. Among them, a state in which two or more adsorption sites are bonded through a chain-like saturated hydrocarbon group to form a monovalent substituent A ^{1 is} preferred.

When the adsorption site itself constitutes a monovalent substituent, the adsorption site itself may be a monovalent substituent represented by A ¹ .

First, the adsorption sites constituting A ¹ will be described below.

Examples of the "acid group" include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphate group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boric acid group. As a preferred example, a carboxylic acid group is more preferred An acid group, a sulfonic acid group, a monosulfate group, a phosphate group, a monophosphate group, a phosphonic acid group, and a phosphinic acid group, and more preferably a carboxylic acid group.

Examples of the "urea group" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ (here, R ¹⁵ , R ^16, and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aromatic group having 6 or more carbon atoms. Group or aralkyl group having 7 or more carbon atoms) as a preferred example, more preferably -NR ¹⁵ CONHR ¹⁷ (here, R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon Aryl having 6 or more or aralkyl having 7 or more carbons), and further preferably -NHCONHR ¹⁷ (here, R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbons, an aryl group having 6 or more carbons or Aralkyl with 7 or more carbon atoms).

Examples of the "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ^21, and -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² And R ²³ each independently represent 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 the like are preferred examples, and more preferably -NHCOOR ¹⁸ and -OCONHR ²¹ ( Here, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like, and more preferably -NHCOOR ¹⁸ and -OCONHR ²¹ (Here, R ¹⁸ and R ²¹ each independently represent 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) and the like.

Examples of the "group having a coordinating oxygen atom" include an acetoacetone group and a crown ether.

Examples of the "group having a basic nitrogen atom" include an amine group (-NH ₂ ) and a substituted imine group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ^9, and R ¹⁰ are respectively Independently represent 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 guanidino group represented by the following formula (a1), and a group represented by the following formula (a2) The fluorenyl group and the like are shown as preferred examples.

In formula (a1), R ¹¹ and R ¹² each independently represent 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 represent 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 ) and a substituted imine group (-NHR ⁸ , -NR ⁹ R ¹⁰ ) are more preferable, and R ⁸ , R ^9, and R ¹⁰ each independently represent a carbon number of 1 to 10 alkyl, phenyl, or benzyl), and a guanidino group represented by formula (a1) [In formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbons, phenyl, or benzyl Group], and a fluorenyl group represented by formula (a2) [in formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group, phenyl group, or benzyl group having 1 to 10 carbon atoms] and the like.

Particularly preferably, an amine group (-NH ₂ ) and a substituted imine group (-NHR ⁸ , -NR ⁹ R ^{10) are used} , where R ⁸ , R ⁹ and R ¹⁰ each independently represent a carbon number of 1 to 5 (Alkyl, phenyl, or benzyl), and a guanidino group represented by formula (a1) [in formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group, phenyl group, or benzyl group having 1 to 5 carbon atoms] And a fluorenyl group represented by the formula (a2) [In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group, a phenyl group, or a benzyl group having 1 to 5 carbon atoms] and the like.

The "alkyl" may be linear or branched. In addition, an alkyl group having 1 to 40 carbon atoms is preferred, an alkyl group having 4 to 30 carbon atoms is more preferred, and an alkyl group having 10 to 18 carbon atoms is more preferred.

The "aryl group" is preferably an aryl group having 6 to 10 carbon atoms.

As the "group having an alkyleneoxy chain", an alkyloxy group or a hydroxyl group is preferably formed at the terminal, and an alkyloxy group having 1 to 20 carbon atoms is more preferably formed. In addition, the alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, and preferably contains 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-.

As the alkyl portion in the "alkyloxycarbonyl group", an alkyl group having 1 to 20 carbon atoms is preferred.

As the alkyl portion in the "alkylaminocarbonyl group", an alkyl group having 1 to 20 carbon atoms is preferred.

Examples of the "carboxylate group" include a group containing an ammonium salt of a carboxylic acid.

As the "sulfonamido group", a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group), a fluorenyl group (such as an ethylfluorenyl group, a trifluoroethylfluorenyl group, or the like).

Examples of the "heterocyclic group" include thienyl, furyl, xanthenyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolyl, pyrazolyl, pyrazolinyl, and pyridine Oxazolyl, imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidyl, dioxanyl, morpholinyl, pyridazine Base, pyrimidinyl, piperazinyl, triazinyl, trithiaalkyl, isoindolinyl, isoindolinone, benzimidazolone, benzothiazolyl, hydantoinyl, indole Group, quinolinyl, carbazolyl, acridinyl, acridinone and anthraquinone.

Examples of the "fluorenimine group" include sulfonimine groups such as a succinimide group, a phthalimide group, and a naphthalenedimethylimide group.

Furthermore, the "heterocyclic group" and "fluorenimine" 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, and a hydroxyl group. Amino, carboxylic, sulfoamido, N-sulfoamido, and ethoxyl 1 to 6 carbon atoms such as fluorenyloxy, methoxy, ethoxy and other carbon numbers 1 to 20 Alkoxy, halogen atom, alkoxycarbonyl having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, and cyclohexyloxycarbonyl, carbonate groups such as cyano and tert-butyl carbonate, etc. .

The "alkoxysilyl group" may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, and is preferably a trialkoxysilyl group, and examples thereof include trimethoxy Silyl and triethoxy silyl.

As the "epoxy group", a substituted or unsubstituted oxepropyl group (cyclic Oxyethane).

In particular, A ^{1 is} preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, and more preferably a monovalent substituent having at least one functional group having a pKa of 5 to 14.

The "pKa" mentioned here refers to the definition described in "Chemical Fact Sheet (II)" (Revised 4th Edition, 1993, edited by the Japan Chemical Society, Maruzen Co., Ltd.).

Examples of the functional group having a pKa of 5 or more include a group having a cooperating 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, a group having an alkyleneoxy chain, a fluorenimine group, a carboxylate group, a sulfonamido group, a hydroxyl group, and a heterocyclic group.

Specific examples of the functional group having a pKa of 5 or more include a phenol group (pKa is about 8 to 10), an alkyl group (pKa is about 46 to 53), an aryl group (pKa is about 40 to 43), and urea. Group (pKa is about 12 to 14), carbamate group (pKa is about 11 to 13), -COCH ₂ CO- (coordinating pKa is about 8 to 10) as a cooperating oxygen atom, sulfonamide group (pKa is about 9 to 11), hydroxyl (pKa is about 15 to 17), heterocyclic group (pKa is about 12 to 30), and the like.

In the above, A ¹ preferably has at least one selected from the group consisting of 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, and a sulfonium group. A monovalent substituent of a group in a group consisting of an amine group, a fluorenimine group, and a group having a cooperating oxygen atom.

In the general formula (X), R ² represents a single bond or a divalent linking group. The n R ² may be the same or different.

The divalent linking group represented by R ² includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms. The group consisting of a sulfur atom may be unsubstituted or may further have a substituent.

As R ² , a single bond or a group consisting of 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 is preferable. A bivalent linking group of atoms.

R ^{2 is more} preferably selected from a chain saturated hydrocarbon group (which may be linear or branched, preferably having a carbon number of 1 to 20), a cyclic saturated hydrocarbon group (which is preferably a carbon number of 3 to 20), an aromatic A group (preferably 5 to 20 carbons, such as phenylene), a thioether bond, an ester bond, an amine bond, an ether bond, a nitrogen atom, and a carbonyl group, or a combination of these two More than one group combined, and further preferably a group selected 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 a amide bond, Or a group formed by combining two or more of these, particularly preferably a group selected from the group consisting of a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and a amide bond, or A combination of two or more of these.

In the above description, 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 amine. , Carboxylic acid group, sulfonylamino group, N-sulfonylfluorenylamino group, fluorenyloxy group having 1 to 6 carbon atoms such as ethoxyl, methoxyl, ethoxy group, etc. having 1 to 6 carbon atoms Halogen atoms such as alkoxy, chlorine, and bromine; alkoxycarbonyl groups having 2 to 7 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and cyclohexyloxycarbonyl; carbonic acids such as cyano and third butyl carbonate; Ester groups, etc.

In the general formula (X), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3 ~ 10.

The (m + n) -valent linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and The group consisting of 0 to 20 sulfur atoms 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 general formula, L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and T _{3 in} which there are three may be the same as or different from each other.

L ₄ represents a tetravalent basis. T ₄ represents a single bond or a divalent linking group, and four T _{4 in} existence may be the same as or different from each other.

L ₅ represents a pentavalent basis. T ₅ represents a single bond or a divalent linking group, and there are five T ₅ which may be the same as or different from each other.

L ₆ represents a hexavalent basis. T ₆ represents a single bond or a divalent linking group, and T _{6 in} which there are six may be the same as or different from each other.

Specific examples of the (m + n) -valent linking group represented by R ¹ [specific examples (1) to (17)] are shown below. However, the present invention is not limited to these specific examples.

In the specific examples, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, the best (m + n) -valent linking group is as follows (1), (2), (10), (11), (16), (17).

In the 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 particularly 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 particularly preferably 3 to 6.

In the general formula (X), P ¹ represents a polymer chain, and can be selected from known polymers and the like according to the purpose and the like. The m P ¹ may be the same or different.

Among polymers, in order to constitute a polymer chain, it is preferably selected from polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and amidine polymers. , Epoxy-based polymer, silicone-based polymer, and these modifications, or copolymers [for example, polymers containing polyether / polyurethane copolymers, polyether / vinyl monomers At least one of the group consisting of a copolymer, etc. (which may be any of a random copolymer, a block copolymer, and a graft copolymer)], more preferably a polymer or copolymer selected from a vinyl monomer , Ester polymer, ether polymer, amine At least one of the group consisting of a urethane-based polymer and these modifiers or copolymers is particularly preferably a polymer or copolymer of a vinyl monomer.

The polymer or copolymer, the ester-based polymer, and the ether-based polymer which are vinyl monomers that the polymer chain P ¹ may have, respectively, preferably have the following general formula (L), general formula (M), and general polymer. The structure represented by Formula (N).

In the general formula, X ¹ represents a hydrogen atom or a monovalent organic group. From a viewpoint of synthesis restriction, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is more preferable.

R ¹⁰ represents a hydrogen atom or a monovalent organic group, and is not particularly limited in terms of structure, and 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. The group is more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms. The general formula (L) may have two or more kinds of R ¹⁰ having different structures.

R ¹¹ and R ¹² represent branched or straight chain alkylene (carbon number is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6). Each formula may have two or more kinds of R ¹¹ or R ¹² having different structures.

k1, k2, and k3 each independently represent a number from 5 to 140.

The polymer chain P ¹ preferably contains at least one repeating unit.

From the viewpoint of exerting a steric repulsive force to improve dispersion stability, the number of repeating units k of at least one repeating unit in the polymer chain P ¹ is preferably 5 or more, and more preferably 7 or more.

In addition, from the viewpoint of suppressing an increase in the volume of the polymer compound X and allowing a black pigment to densely exist in the light-shielding film, the number of repeating units k of the at least one repeating unit is preferably 140 or less, more preferably 130 or less, It is more preferably 60 or less.

The polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is high, the affinity with a dispersion medium becomes strong, and it becomes easy to ensure a layer with sufficient dispersion stabilization.

The vinyl monomer is not particularly limited, and examples thereof include (meth) acrylates, butyrates, vinyl esters, vinyl monomers having acid groups, and maleic acid diesters. Type, fumaric acid diesters, itaconic acid diesters, (meth) acrylamide, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, and (Meth) acrylonitrile and the like are more preferably (meth) acrylates, butyrates, vinyl esters, and vinyl monomers having an acid group, and still more preferably (meth) acrylate , And butenoates.

As preferred examples of these vinyl monomers, paragraphs 0089 to 0094, paragraph 0096, and paragraphs of Japanese Patent Laid-Open No. 2007-277514 can be cited. The vinyl monomers described in 0097 (paragraph 0105 to paragraph 0117 and paragraph 0119 to paragraph 0120 in the corresponding US Patent Application Publication No. 2010/233595) are incorporated into the specification of the present application.

In addition to the compound, for example, a vinyl monomer having a functional group such as a urethane group, a urea group, a sulfonamido group, a phenol group, and a fluorenimine group can be used. Such a single body having a urethane group or a urea group can be suitably synthesized by, for example, an addition reaction of an isocyanate group and a hydroxyl group, or an isocyanate group and an amine group. Specifically, the addition reaction of an isocyanate-containing monomer with a compound containing one hydroxyl group or a compound containing one primary or secondary amine group, or a monomer containing a hydroxyl group or a primary amine group can be performed. Or it can synthesize | combine suitably by addition reaction of the monomer of a secondary amine group, and a monoisocyanate.

Among the polymer compounds represented by the general formula (X), polymer compounds represented by the following general formula (Y) are preferred.

In the general formula (Y), A ² has the same meaning as A ¹ in the general formula (X), and preferred embodiments are also the same.

In the general formula (Y), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ⁴ may be the same or different. The m R ⁵ may be the same or different.

As the divalent linking group represented by R ⁴ and R ⁵ , the same linking groups as those listed as the divalent linking group represented by R ^{2 of} the general formula (X) can be used, and preferred embodiments are also the same.

Among them, the divalent linking group represented by R ⁴ and R ⁵ is preferably selected from a chain saturated hydrocarbon group (which may be linear or branched, and preferably has a carbon number of 1 to 20), and cyclic saturation. A group consisting of a hydrocarbon group (preferably 3 to 20 carbons), an aromatic group (preferably 5 to 20 carbons, such as phenylene), an ester bond, an amido bond, an ether bond, a nitrogen atom, and a carbonyl group Or a combination of two or more of these is preferably selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, an ether bond, and an amidine bond. A group in a group, or a combination of two or more of these groups, further preferably a group selected from the group consisting of a chain saturated hydrocarbon group, an ester bond, an ether bond, and a amide bond, or A base obtained by combining two or more of these.

(M + n) -valent linking group represented by R ³ in the general formula (Y). m + n satisfies 3 ~ 10.

The (m + n) -valent linking group represented by R ³ may be unsubstituted or may further have a substituent, and a link to the (m + n) -valent link represented by R ¹ as the general formula (X) may be used. The same linking group as the linking group enumerated, and the preferred aspect is also the same.

In the general formula (Y), m and n have the same meanings as m and n in the general formula (X), respectively, and preferred embodiments are also the same.

In addition, P ² in the general formula (Y) has the same meaning as P ¹ in the general formula (X), and preferred embodiments are also the same. The m P ² may be the same or different.

Among the polymer compounds represented by the general formula (Y), it is most preferable to satisfy all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below.

R ³ : the specific example (1), specific example (2), specific example (10), specific example (11), specific example (16) or specific example (17)

R ⁴ : a single bond or a group selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, a amide bond, an ether bond, a nitrogen atom, and a carbonyl group, or A combination of two or more

R ⁵ : single bond, ethylidene, propylidene, 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, and modified products thereof

m: 1 ~ 3

n: 3 ~ 6

Among the polymer compounds represented by the general formula (X) and the general formula (Y), from the viewpoints of dispersion stability and coating surface, it is more preferable that they are represented by the following general formula (Z) Polymer compounds.

In the general formula (Z), R ⁶ represents a (m + n1 + n2) -valent linking group, and R ⁷ to R ⁹ each independently represent 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 . n1 A ³ and R ⁷ may be the same or different. The n2 A ⁴ and R ⁸ may be the same or different.

m has the same meaning as m in the general formula (X), and preferred embodiments are also the same.

n1 means 1 ~ 8, n2 means 1 ~ 8, m + n1 + n2 satisfies 3 ~ 10.

P ³ has the same meaning as P ² in the general formula (Y), and preferred embodiments are also the same. The m P ³ and R ⁹ may be the same or different.

As the linking group of (m + n1 + n2) valence related to R ⁶ , a linking of (m + n) valence represented by R ¹ as general formula (X) or R ³ as general formula (Y) can be used. The same linking group as the linking group enumerated, and the preferred aspect is also the same.

As the divalent linking group related to R ⁷ to R ⁹ , the same linking groups as those listed as the divalent linking groups represented by R ⁴ and R ^{5 in} the general formula (Y) can be used. The same.

Specific examples and preferable examples of the acid group that the substituent A ³ may have include the same as the specific examples and preferable examples described for the acid group in the general formula (X).

The substituent A ^{3 is} further preferably a monovalent substituent having at least one acid group having a pKa of less than 5, and more preferably at least one member selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphate group, a phosphonic acid group, and a phosphinic acid. The monovalent substituent of the group in the group consisting of groups is more preferably a carboxylic acid group.

Specific examples and preferred examples of the monovalent substituent A ⁴ different from A ³ include the same groups as the specific examples and preferred examples of A ¹ in the general formula (X) except for the acid group. By. Among them, the substituent A ^{4 is more} preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, and further preferably having at least one selected from a group having a cooperating oxygen atom and a basic nitrogen atom. Group, phenol group, ureido group, carbamate group, alkyl group, aryl group, alkyloxycarbonyl group, alkylaminocarbonyl group, group having extended alkyloxy chain, fluorenimine group, carboxylic acid A monovalent substituent of a group in a group consisting of a salt group, a sulfonamide group, a hydroxyl group, and a heterocyclic group. Particularly preferred are an alkyl group, an aryl group, a group having a cooperating oxygen atom, and a basic nitrogen atom. Group, urea group or urethane group.

As a combination of the substituent A ³ and the substituent A ⁴ , the substituent A ³ is preferably a monovalent substituent having at least one functional group having a pKa of less than 5 and the substituent A ⁴ is at least one having a pKa of 5 or more. A monovalent substituent of a functional group.

More preferably, the 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 phosphate group, a phosphonic acid group, and a phosphinic acid group, and the substituent A ⁴ is at least one selected from the group consisting of 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 alkane group. A monovalent substituent of a group in the group consisting of an aminoaminocarbonyl group, a group having an alkyleneoxy chain, an amidino group, a carboxylate group, a sulfonamido group, a hydroxyl group, and a heterocyclic group.

Further preferably, 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 cooperating oxygen atom, a group having a basic nitrogen atom, a urea group, or Carbamate.

From the viewpoint that the black pigment and the alkyl group of the substituent A ³ are well adsorbed, the substituent A ³ is particularly preferably a carboxylic acid group and the substituent A ⁴ is an alkyl group.

In terms of weight average molecular weight, the molecular weight of the polymer compound X is preferably 20,000 or less, more preferably 1,000 to 15,000, and even more preferably 3000 to 12,000. When the weight average molecular weight is within the range, the effect of the plurality of adsorption sites introduced to the ends of the polymer can be fully exerted, and the performance excellent in the adsorptivity to the surface of the black pigment can be exhibited.

As a method for measuring the weight-average molecular weight, HLC-8129 (manufactured by Tosoh Co., Ltd.) can be used, and TSKgel Multipore HXL-M (manufactured by Tosoh Co., Ltd.) can be used as a column, and Tetrahydrofuran (THF) was obtained as an eluent.

The acid value of the polymer compound X is preferably in a range of 0 mgKOH / g or more and 160 mgKOH / g or less, more preferably in a range of 10 mgKOH / g or more and 140 mgKOH / g or less, and further preferably in a range of 20 mgKOH / g or more and 120 mgKOH / g or less range.

The polymer compound represented by general formula (X) or general formula (Y) is not particularly Restrictions can be in accordance with paragraphs 0114 to 0140 and 0266 to 0348 of Japanese Patent Laid-Open No. 2007-277514 (corresponding to paragraph 0145 to paragraph 0173 and paragraph 0289 to the specification of U.S. Patent Application Publication No. 2010/233595). Synthetic method described in paragraph 0429).

(A polymer compound containing a structural unit having a graft chain (hereinafter, also referred to as a polymer compound G))

The polymer compound G includes a structural unit having a graft chain. In addition, in this specification, "structural unit" and "repeat unit" have the same meaning.

Such a polymer compound containing a structural unit having a graft chain has an affinity with a solvent due to the graft chain, and therefore, the black pigment has excellent dispersibility and dispersion stability over time. In addition, in the composition, the presence of the graft chain has affinity with a polymerizable compound or other binder polymer that can be used in combination, and therefore it is difficult to generate a residue during alkali development.

When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility increases. On the other hand, if the graft chain becomes too long, the adsorption force to the black pigment tends to decrease and the dispersibility tends to decrease. Therefore, the graft chain preferably has a range of 40 to 10,000 atoms other than hydrogen atoms, more preferably 50 to 2000 atoms other than hydrogen atoms, and even more preferably 60 to 60 atoms other than hydrogen atoms. 500.

Here, the graft chain means from the root of the main chain of the copolymer (atoms bonded to the main chain in the 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 acid structure). Structure), polyester structure, polyurethane structure, polyurea structure, polyfluorene structure, and polyether structure.

In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility, the graft chain is preferably selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure. At least one of the graft chains is more preferably a graft chain having at least one of a polyester structure and a polyether structure.

The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, and a macromonomer having a reactive double bond group is preferably used.

Corresponding to the structural unit having a graft chain contained in the polymer compound G, AA-6 (trade name, East Asia Synthesis ( Stock)), AA-10 (trade name, manufactured by Toa Kosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Kosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Kasei Corporation) -6 (commercial name, manufactured by Toa Kosei Co., Ltd.), AW-6 (trade name, manufactured by Toa Kosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Kosei Co., Ltd.), AY-707 (trade name , East Asia Synthetic (Stock), AY-714 (trade name, East Asia Synthetic (Stock)), AK-5 (trade name, East Asia Synthetic), AK-30 (trade name, East Asia Synthetic (Stock) )), AK-32 (trade name, manufactured by Toa Kosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PP-500 ( Trade name, made by Nippon Oil Co., Ltd., Blemmer PP-800 (trade name, made by Nippon Oil Co., Ltd.), Blemmer PP-1000 (trade name, Nippon Oil Co., Ltd.) (Manufactured), Blemmer 55-PET-800 (brand name, manufactured by Nippon Oil (Stock)), Blemmer PME-4000 (brand name, manufactured by Nippon Oil (Stock)), Branmer (Blemmer) PSE-400 (trade name, made by Nippon Oil & Gas Co., Ltd.), Blemmer PSE-1300 (trade name, made by Nippon Oil & Gas Co., Ltd.), and Blemmer 43PAPE-600B (product Name, made by Nippon Oil Co., Ltd.). Among them, it is preferable to use AA-6 (trade name, manufactured by Toa Kosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Kosei Co., Ltd.), and AB-6 (trade name, manufactured by Toa Kosei Co., Ltd.) , AS-6 (trade name, manufactured by Toa Kosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Kosei Co., Ltd.), and Blemmer PME-4000 (trade name, manufactured by Nippon Oil Co., Ltd.) )Wait.

The polymer compound G preferably contains a structural unit represented by any of the following formulae (1) to (4) as a structural unit having a graft chain, and more preferably contains the following formula (1A), the following A structural unit represented by any one of the following formula (2A), the following formula (3A), the following formula (3B), and the following formula (4).

[Chemical 11]

In 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 formulae (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. As X ¹ , X ² , X ³ , X ^4, and X ⁵ , from the viewpoint of constraints on synthesis, it is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably, they are independent of each other. Ground is a hydrogen atom or a methyl group, and particularly preferably each is independently a methyl group.

In the formulae (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the linking is not particularly limited in terms of structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B refer to the bonding sites with the left terminal group and the right terminal group in Formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable in terms of ease of synthesis.

[Chemical 12]

In the formulae (1) to (4), Z ¹ , Z ² , Z ^3, and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroaryl group. Thioether group and amine group. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , particularly from the viewpoint of improving dispersibility, a group having a stereorepulsive effect is preferred, and each is preferably independently Alkyl or alkoxy groups having 5 to 24 carbon atoms, of which particularly preferred are branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, or 5 to 24 carbon atoms, respectively. Alkoxy. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.

In formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoints of dispersion stability and developability, j and k in the formulae (1) and (2) are preferably integers of 4 to 6, and most preferably 5.

In the formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and 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 as or different from each other.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic is not particularly limited in terms of structure. R ^{4 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 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. The group is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In 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 as or different from each other.

In addition, the polymer compound G may include two or more kinds of structural units having graft chains having different structures. That is, the molecules of the polymer compound G may include structural units represented by formulas (1) to (4) having different structures from each other. In addition, regarding formulas (1) to (4), n, m, When p and q each represent an integer of 2 or more, in the formulae (1) and (2), a structure in which j and k are different from each other may be included in the side chain. In the formulae (3) and (4), A plurality of R ³ , R ⁴ and X ⁵ in the molecule may be the same as or different from each other.

From the viewpoint of dispersion stability and developability, the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A).

From the viewpoint of dispersion stability and developability, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A).

In the formula ^{(1A), X 1, Y} 1, Z 1 and n of formula X (1) is ^1, Y ^1, Z ¹ and n have the same meaning as the preferred range is also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and ^2, Y ² m of formula X (2) is, Z ² and m are the same meaning as the preferred range is also the same.

From the viewpoint of dispersion stability and developability, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B).

In formula (3A) or the formula ^{(3B), X 3, Y} 3, Z 3 and p of formula X (3) is ^3, Y ^3, Z ³ and p have the same meaning as the preferred range is also the same.

The polymer compound G more preferably contains a structural unit represented by the formula (1A) as a structural unit having a graft chain.

In the polymer compound G, it is preferable to include a structural unit having a graft chain in a range of 10% to 90% with respect to the total mass of the polymer compound G (for example, the above formula (1) to formula ( The structural unit represented by 4) is more preferably contained in a range of 30% to 70%. When the structural unit having a graft chain is included in this range, the dispersibility of the black pigment (especially titanium black particles) is high, and the developability when forming a light-shielding film is good.

The polymer compound G preferably contains a hydrophobic structural unit that is different from the structural unit having a graft chain (that is, does not correspond to the structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phenolic hydroxyl group, and the like).

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

The ClogP value is a value calculated by a program "CLOGP" available from Daylight Chemical Information System (Inc.). This program provides the value of "calculated logP" calculated by the fragment approach (refer to the following document) of Hansch and Leo. The fragment method divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and adds up the logP contribution values assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. The present invention uses a ClogP value calculated by the program CLOGP v4.82.

AJ Leo's "Comprehensive Medicinal Chemistry" Volume 4, C. Hansch, PGSammnens, JBaylor and CA Ram Edited by CARamsden, p. 295, Pergamon Press, 1990; C. Hansch and AJ Leo, "Relevant Analysis in Chemistry and Biology SUbstituent Constants For Correlation Analysis in Chemistry and Biology ", John Wiley &Sons; AJ Leo" Calculating logPoct from structure ", Chemistry Review (Chem. Rev.) 93, 1281-1306, 1993.

logP refers to the common logarithm of the partition coefficient P (Partition Coefficient). It is a quantitative value that represents the organic compound in oil (usually 1-octanol) and water. The physical property value of how the two phases are balanced 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 water phase.

If the value of logP increases to a positive number with 0 as the center, it means that the oil solubility increases. If the value of logP increases, the absolute value means that the water solubility increases, which means a negative correlation with the water solubility of organic compounds. It is widely used as a parameter to evaluate the hydrophobicity of organic compounds.

The polymer compound G preferably contains, as the hydrophobic structural unit, one or more structural units selected from the structural units derived from a single body represented by the following general formulae (i) to (iii).

[Chemical 15]

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkane having 1 to 6 carbon atoms. (For example, methyl, ethyl, propyl, etc.).

R ¹ , R ² and R ^{3 are more} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ^{3 are} particularly preferably a hydrogen atom.

X represents an oxygen atom (-O-) or an imine group (-NH-), and is preferably an oxygen atom.

L is 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 alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group) , Divalent aromatic group (e.g., arylene, substituted arylene), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imide group (-NH- ), A substituted imine group (-NR ^31- , where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. Aliphatic group The number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and is preferably a saturated aliphatic group. 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 even 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 ring or a 6-membered ring as a heterocyclic ring. It is also possible to condense other heterocycles, aliphatic rings or aromatic rings in the heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (= O), a thioketone group (= S), an imino group (= NH), and a substituted imino group (= NR ³² , where Where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

L 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. In addition, L may include a polyoxyalkylene structure which repeatedly contains 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-, and n is preferably an integer of 2 or more, more preferably an integer of 2-10.

Examples of Z include aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), and aromatic groups (for example, arylene group, substituted arylene group) , Heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ^31- , where R ³¹ is an aliphatic group , An aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group further includes a collective cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the collective cyclic hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include pinane, pinane, norbornane, norbornane, and bicyclooctane rings (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring Etc.) and other bicyclic hydrocarbon rings, tricyclic [5.2.1.0 ^3,8 ] decane (Homobrendane), adamantane, tricyclic [5.2.1.0 ^2,6 ] decane and tricyclic [4.3.1.1 ^2,5 ] Tricyclic hydrocarbon rings such as undecane ring, and tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] Dodecane and perhydro-1,4-methyl bridge-5,8-methyl bridge naphthalene ring And other tetracyclic hydrocarbon rings. In addition, cross-linked cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydrofluorene, perhydrofluorene, perhydroindene, and perhydrofluorene rings. A condensed ring formed by condensing a 5-membered cycloalkane ring to an 8-membered cycloalkane ring.

As for the unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 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. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. It is also possible to condense other heterocycles, aliphatic rings or aromatic rings in the heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (= O), a thioketone group (= S), an imino group (= NH), and a substituted imino group (= NR ³² , where Where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ^5, and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, methyl Group, ethyl, propyl, etc.), Z or -LZ. Here, L and Z have the same meaning as the above-mentioned L and Z. R ⁴ , R ⁵ and R ^{6 are} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the singular body represented by the general formula (i), R ¹ , R ² and R ³ are preferably a hydrogen atom or a methyl group, L is a single bond or an alkylene group or contains an oxyalkylene group. A compound having a divalent linking group of a basic structure, X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

In addition, as the unit weight represented by the general formula (ii), a compound in which 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. . In addition, as the unit weight represented by the general formula (iii), a compound in which 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 is preferred. .

Examples of the representative compounds represented by the formulae (i) to (iii) include radical polymerizable compounds selected from the group consisting of acrylates, methacrylates, and styrenes.

In addition, as examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of Japanese Patent Laid-Open No. 2013-249417 can be referred to, and these contents Incorporated into this specification.

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

The polymer compound G can introduce a functional group that can interact with a black pigment (especially titanium black). Here, the polymer compound G preferably further includes a structural unit having a functional group capable of interacting with a black pigment.

Examples of the functional group capable of interacting with the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.

When the polymer compound G contains an acid group, a basic group, a coordinating group, or a reactive functional group, it is preferable that the polymer compound G includes a structural unit having an acid group, a structural unit having a basic group, and A structural unit or a reactive structural unit.

In particular, when the polymer compound G further has an alkali-soluble group such as a carboxylic acid group as an acid group, it is possible to impart developability to the polymer compound G, which is used for pattern formation by alkali development.

That is, in the composition of the present invention, by introducing an alkali-soluble group into the polymer compound G, the polymer compound G, which is a dispersant that contributes to the dispersion of the black pigment, is made alkali-soluble. Exposure of a composition containing such a polymer compound G The light part has excellent light shielding properties, and the alkali developability of the unexposed part is improved.

In addition, since the polymer compound G includes a structural unit having an acid group, the polymer compound G is easily compatible with the solvent, and thus the coating property tends to be improved.

The reason is speculated that the acid groups in the structural unit having acid groups easily interact with the black pigment, the polymer compound G stably disperses the black pigment, and the viscosity of the polymer compound G which disperses the black pigment decreases, and the polymer Compound G itself is also easily and stably dispersed.

The structural unit having an alkali-soluble group as an acid group may be the same structural unit as the structural unit having a graft chain, or may be a different structural unit, but has a structural unit having an alkali-soluble group as an acid group Is a structural unit different from the hydrophobic structural unit (ie, does not correspond to the hydrophobic structural unit).

Examples of the acid group of the functional group that can interact with the black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and it is preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. In terms of good adsorption of the black pigment and high dispersibility of the black pigment, a particularly preferred one is a carboxylic acid group.

That is, the polymer compound G preferably further includes a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound G may contain one or two or more kinds of structural units having an acid group.

The polymer compound G may contain a structural unit having an acid group, or may not contain a structural unit having an acid group. When the polymer compound G is contained, the content of the structural unit having an acid group is converted to mass relative to the total mass of the polymer compound G. It is preferably 5% ~ 80% is more preferably 10% to 60% from the viewpoint of suppressing damage to the image intensity due to alkali development.

As a basic group of a functional group that can interact with a black pigment, there are, for example, a primary amine group, a secondary amine group, a tertiary amine group, a heterocyclic ring containing an N atom, and a sulfonylamine group. In terms of good strength and high dispersibility of the black pigment, a tertiary amine group is particularly preferred. The polymer compound G may have one or two or more of these basic groups.

The polymer compound G may contain a structural unit having a basic group, or may not contain a structural unit having a basic group. When it is contained, the content of the structural unit having a basic group is relative to the total mass of the polymer compound G. It is preferably 0.01% or more and 50% or less in terms of mass conversion, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing hindrance to developability.

Examples of the coordinating group and the reactive functional group of a functional group that can interact with a black pigment include ethanoylacetoxy, trialkoxysilyl, isocyanate, acid anhydride, and acid chloride.物 等。 And so on. In terms of good adsorption of the black pigment and high dispersibility of the black pigment, particularly preferred is acetamidoethoxy. The polymer compound G may have one or two or more of these groups.

The polymer compound G may contain a structural unit having a coordination group or a structural unit having a reactive functional group, or may not contain a structural unit having a coordination group or a structural unit having a reactive functional group. When it is contained, the content of these structural units is preferably 10% or more and 80% or less with respect to the total mass of the polymer compound G. From the viewpoint of suppressing the hindrance to the developability, In other words, it is more preferably 20% or more and 60% or less.

In the case where the polymer compound G in the present invention has a functional group capable of interacting with a black pigment other than the graft chain, as long as it contains a functional group capable of interacting with various black pigments as described above, the The manner in which these functional groups are introduced is not particularly limited, and the polymer compound G preferably contains one selected from the structural units derived from the basal body represented by the following general formula (iv) to general formula (vi) The above structural unit.

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 6 Alkyl (e.g., methyl, ethyl, propyl, etc.).

In the general formulae (iv) to (vi), R ¹¹ , R ^12, and R ^{13 are more} preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably each are independently a hydrogen atom or methyl. In the general formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (-O-) or an imine group (-NH-), and is preferably an oxygen atom.

In addition, Y in the general formula (v) represents a methine group or a nitrogen atom.

In addition, L ₁ in the general formulae (iv) to (v) 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 alkylene group, a substituted alkylene group, an alkylene group, and a substituted alkylene group) Group), divalent aromatic group (e.g., arylene and substituted arylene), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imide group (- NH-), substituted imine bond (-NR ^{31 '} -, where R ^31' is aliphatic, aromatic or heterocyclic group), carbonyl bond (-CO-) and combinations thereof .

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. As for the unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. 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 6-20, more preferably 6-15, and most preferably 6-10. 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 ring or a 6-membered ring as a heterocyclic ring. One or more of other heterocycles, aliphatic rings, or aromatic rings may be condensed in a heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (= O), a thioketone group (= S), an imino group (= NH), and a substituted imino group (= NR ³² , where Where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a 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 more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2-10.

In the general formulae (iv) to (vi), Z ₁ represents a functional group capable of interacting with a black pigment other than the graft chain, and is preferably a carboxylic acid group, a tertiary amine group, and more preferably a carboxylic acid group. .

In the general formula (vi), R ¹⁴ , R ^15, and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, etc.), - Z ₁ or -L ₁ -Z _1. Here, L ₁ and Z ₁ in the L ₁ and Z ₁ are the same meaning as the preferred embodiments are also the same. R ¹⁴ , R ^15, and R ¹⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom each independently.

In the present invention, as the singular body represented by the general formula (iv), it is preferable that R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or contains an oxyalkylene group. A compound having a structure of a divalent linking group, X ₁ is an oxygen atom or an imine group, and Z ₁ is a carboxylic acid group.

In addition, as the unit weight represented by the general formula (v), a compound in which 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 a methine group is preferable.

Furthermore, as the singular body represented by the general formula (vi), it is preferable that R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxyl group. Acid based compounds.

Representative examples of the singular body (compound) represented by the general formulae (iv) to (vi) are shown below.

Examples of the single body include methacrylic acid, butenoic acid, methacrylic acid, compounds having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate), and succinic anhydride. Reactant, reactant of compound having addition polymerizable double bond and hydroxyl group in molecule and phthalic anhydride, reactant of compound having addition polymerizable double bond and hydroxyl group in molecule and tetrahydroxyphthalic anhydride Reactants of compounds with addition polymerizable double bonds and hydroxyl groups in the molecule and trimellitic anhydride, Reactants of compounds with addition polymerizable double bonds and hydroxyl groups in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid Polymers, acrylic acid oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

From the viewpoints of interaction with a black pigment, dispersion stability, and permeability to a developing solution, the content of the structural unit having a functional group capable of interacting with the black pigment is smaller than the total mass of the polymer compound G. Preferably 0.05 quality % To 90% by mass, more preferably 1.0% to 80% by mass, and even more preferably 10% to 70% by mass.

Furthermore, for the purpose of improving properties such as image strength, as long as the effects of the present invention are not impaired, the polymer compound G may further include other structural units having various functions (for example, the The dispersion medium has structural units such as functional groups having affinity, and the other structural units are different from the structural unit having a graft chain, the hydrophobic structural unit, and the structural unit having a functional group capable of interacting with a black pigment.

Examples of such other structural units include a structural unit derived from a radical polymerizable compound selected from acrylonitrile and methacrylonitrile.

The polymer compound G may use one or two or more of these other structural units. The content of the other structural units relative to the total mass of the polymer compound G is preferably 0% or more and 80% or less in terms of mass conversion. It is preferably 10% or more and 60% or less. When the content is within the above range, sufficient pattern-formability can be maintained.

The acid value of the polymer compound G is preferably in a range of 0 mgKOH / g or more and 160 mgKOH / g or less, more preferably in a range of 10 mgKOH / g or more and 140 mgKOH / g or less, and still more preferably in a range of 20 mgKOH / g or more and 120 mgKOH / g or less. range.

When the acid value of the polymer compound G is 160 mgKOH / g or less, it is possible to more effectively suppress pattern peeling during development when a light-shielding film is formed. When the acid value of the polymer compound G is 10 mgKOH / g or more, alkali developability is more favorable. In addition, if the acid value of the polymer compound G is 20 mgKOH / g or more, it can be further suppressed. The sedimentation of a black pigment (especially titanium black) and a dispersion containing titanium black and Si atoms can further reduce the number of coarse particles, thereby further improving the stability of the composition over time.

The acid value of the polymer compound G can be calculated, for example, from the average content of acid groups in the polymer compound G. In addition, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group as a constituent component of the polymer compound G.

When forming a light-shielding layer, from the viewpoint of suppressing pattern peeling and developability during development, the weight average molecular weight of the polymer compound G is converted to polystyrene by GPC (Gel Permeation Chromatography) method The value is preferably 4,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, still more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less.

The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh Co., Ltd.), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Co., Ltd., 4.6mmID X 15 cm) as a column, and THF (tetrahydrofuran) was used as the eluent.

The polymer compound G can be synthesized based on a known method, and examples of solvents used in the synthesis of the polymer compound G include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, and propylene. Alcohol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1- Methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethane, toluene, ethyl acetate, methyl lactate, and Ethyl lactate and the like. These solvents can be used alone or in combination of two or more.

These polymer compounds G may be used alone or in combination of two or more kinds.

In addition, as examples of specific examples of the polymer compound G, the polymer compounds described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated into this specification.

<Other ingredients>

The pigment dispersion composition may contain components other than the black pigment, the first dispersant, and the second dispersant. For example, the component (for example, a polymerizable compound, a polymerization initiator, a binder polymer, a solvent, etc.) contained in the polymerizable composition mentioned later is mentioned.

<< Polymerizable composition >>

The polymerizable composition of the present invention includes the pigment dispersion composition, a polymerizable compound, and a polymerization initiator. The polymerizable composition contains a black pigment derived from a pigment dispersion composition, and is preferably used as a composition for forming a light-shielding film. That is, this polymerizable composition can be preferably used as a composition for forming a light-shielding film.

Hereinafter, each component contained in a polymerizable composition will be described in detail. In addition, the definition of a pigment dispersion composition is as mentioned above, and description is abbreviate | omitted.

In addition, the content of the black pigment in the polymerizable composition is not particularly limited, and in terms of the effect of the present invention being more excellent, it is preferably 5 masses with respect to the total solid content (total solid content mass) of the composition. % To 90% by mass, and more preferably 20% to 70% by mass.

The content of the first dispersant in the polymerizable composition is not particularly limited, and in terms of the effect of the present invention being more excellent, it is preferably 1% by mass relative to the total solid content (total solid content mass) of the composition. ~ 30 mass%, more preferably 5 mass% to 20 mass%.

The content of the second dispersant in the polymerizable composition is not particularly limited, and in terms of the effect of the present invention being more excellent, it is preferably 1% by mass relative to the total solid content (total solid content mass) of the composition. ~ 30 mass%, more preferably 5 mass% to 20 mass%.

The solid content refers to a component that can constitute a light-shielding film, and does not include solvents.

In the polymerizable composition, the mass ratio of the first dispersant to the second dispersant (mass of the first dispersant / mass of the second dispersant) is not particularly limited, and the effect of the present invention is more excellent, It is preferably 0.1 to 9.0, and more preferably 0.2 to 3.0.

<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 under normal pressure.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure include, for example, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (methyl) ) Monofunctional acrylates or methacrylates such as acrylates and phenoxyethyl (meth) acrylates; polyethylene glycol di (meth) acrylates, trimethylolethane tris (methyl) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris (propenyloxypropyl) ether, tris (propenyloxyethyl) isocyanurate (Meth) acrylic acid, glycerol, trimethylolethane, and the like, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol, and pentaerythritol or dipentaerythritol undergo poly (meth) acrylic acid Esterified compounds, urethane acrylates described in various publications of Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193. Japan Polyester acrylates described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490, react as epoxy resin with (meth) acrylic acid Multifunctional acrylates or methacrylates such as epoxy acrylates. Furthermore, the compounds described as "light-curable monomers and oligomers" in "Journal of the Japan Advocacy Association" Vol. 20, No. 7, pages 300 to 308 can also be used.

Moreover, you may use the polyfunctional alcohol which added ethylene oxide or propylene oxide to Japanese Patent Application Laid-Open No. 10-62986 as a general formula (1) and general formula (2), and describes it with the specific example. A compound obtained by (meth) acrylation.

Among them, a structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acrylfluorenyl groups are connected to dipentaerythritol through an ethylene glycol residue or a propylene glycol residue is preferable. These types of oligomers can also be used.

In addition, the urethanes described in the respective publications of Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Ester acrylates, Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication The urethane compounds having an ethylene oxide-based skeleton described in the publications of Nos. 62-39417 and Japanese Patent Publication No. Sho 62-39418 are also preferred. Furthermore, by using JP-A-63-277653, JP-A-63-260909, and JP-A-105238, each of the publications has an amine structure or a thioether in the molecule. The addition polymerizable compounds having a structure can obtain a photopolymerizable composition having a very excellent photosensitivity. Examples of commercially available products include urethane oligomers UAS-10 and UAB-140 (trade names, manufactured by Nippon Paper Chemical Co., Ltd.), UA-7200 (made by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, Kyoeisha Chemical Co., Ltd.) Manufacturing) etc.

In addition, ethylenically unsaturated compounds having an acid group are also preferable. As commercially available products, for example, TO-756, which is a trifunctional acrylate containing a carboxylic acid group, and a carboxylic acid containing, which are manufactured by Toa Synthesis Co., Ltd. Based pentafunctional acrylates such as TO-1382. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

The polymerizable compound may be used singly or in combination of two or more kinds.

When two or more kinds of polymerizable compounds are used in combination, the combination state can be appropriately set according to the physical properties required for the composition and the like. As one of the preferable combinations of polymerizable compounds, for example, a combination of two or more polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds may be mentioned. As an example, two Group of pentaerythritol hexaacrylate and pentaerythritol triacrylate Together.

The content of the polymerizable compound in the polymerizable composition is preferably 3% to 55% by mass, and more preferably 10% to 50% by mass based on the total solid content of the polymerizable composition.

<Polymerization initiator>

The polymerization initiator is not particularly limited, and may be appropriately selected from known polymerization initiators. For example, a polymerization initiator (a so-called photopolymerization initiator) having a sensitivity in the ultraviolet region to the visible region is preferred. Furthermore, it may be an active agent which generates an active radical by having a certain effect with a photo-excited sensitizer. Moreover, it may be an initiator which starts cationic polymerization according to the kind of monomer.

In addition, the polymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, hexaarylbiimidazole, and oxime derivatives Such as oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent Laid-Open No. 4225898 can also be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (trade names, manufactured by BASF).

As the aminoacetophenone-based initiator, commercially available products, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade name, BASF ( BASF).

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 can be used in which the absorption wavelength matches a long-wave light source such as 365 nm or 405 nm.

As the fluorenylphosphine-based initiator, commercially available IRGACURE-819 or DAROCUR-TPO (trade name, manufactured by BASF) can be used.

It is preferable to contain an oxime-based initiator (oxime compound) as a polymerization initiator.

Specific compound names of the oxime-based initiator include 2- (O-benzylideneoxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2 -(O-benzylideneoxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzylideneoxime) -1- [4- (Phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzylideneoxime) -1- [4- (phenylthio) phenyl] -1,2-heptanedione , 2- (O-benzylideneoxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzylideneoxime) -1- [ 4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzylideneoxime) -1- [4- (ethylphenylthio) phenyl] -1 , 2-butanedione, 2- (O-benzylideneoxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetamidine Oxime) -1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethanone, 1- (O-acetamidooxime) -1- [9-Methyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethanone, 1- (O-acetamido Oxime) -1- [9-propyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethanone, 1- (O-acetamidooxime) -1- [ 9-Ethyl-6- (2-ethylbenzylidene) -9H-carbazol-3-yl] ethanone and 1- (O-acetamidooxime) -1- [9-ethyl-6 -(2-butylbenzylidene) -9H-carbazol-3-yl] ethanone and the like.

As the oxime-based initiator, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) and other commercially available products. In addition, reference may be made to the description of the oxime-based initiators described in paragraphs 092 to 0096 of Japanese Patent Laid-Open No. 2012-113104, and these contents are incorporated into this specification. By using such an oxime-based initiator, it is possible to provide a composition having high curing sensitivity and good developability. The oxime initiator is a compound described in paragraph 0030 or later of Japanese Patent Laid-Open No. 2012-113104. As the general formula, it is represented by the general formula (I) described in claim 1 of Japanese Patent Laid-Open No. 2012-113104, and it is more preferably represented by the general formula (IA) described in claim 3, and these can be referred to. Document and incorporate these into this specification.

In addition, "JCSPerkin II" ((1979) 1653-1660), "JCSPerkin II" (( (1979) 156-162), "Journal of Photopolymer Science and Technology" ((1995) 202-232), compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open The compounds described in paragraphs 0218 to 0281 of Japanese Patent Publication No. 2000-80068 are described in paragraphs 0242 to 0251 of Japanese Patent Application Publication No. 2004-534797. IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylidene oxime)]) made by BASF Japan, IRGACURE OXE 02 (ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1- (O-ethyl Fluorenyl oxime)), 2- (ethylfluorenyloxyiminomethyl) thioxan-9-one, O-fluorenyl oxime-based compound (for example, Adeka Optomer N-1919 , Adeka Cruise (NCI-831), etc., which are incorporated into this specification.

Furthermore, cyclic oxime compounds described in paragraph 0003 of Japanese Patent Laid-Open No. 2007-231000 and paragraph 0039 of Japanese Patent Laid-Open No. 2007-322744, and paragraphs of Japanese Patent Laid-Open No. 2007-269779 can also be cited. The oxime compound having a specific substituent shown in 0060 to paragraph 062, the oxime compound having a thioaryl group shown in paragraph 0090 to paragraph 0106 of Japanese Patent Laid-Open No. 2009-191061, and the Japanese patent The compounds described in paragraphs 0375 to 0409 of the 2001-233842 publication are incorporated in this specification.

Alternatively, an oxime initiator having a fluorine atom may be used. Specific examples of such a starter include compounds described in Japanese Patent Laid-Open No. 2010-262028, and compounds 24 and 36 described in paragraph 0345 of Japanese Patent Laid-Open No. 2014-500852. Compound 40 and the compound (C-3) described in paragraph 0101 of Japanese Patent Laid-Open No. 2013-164471.

The content of the polymerization initiator in the polymerizable composition of the present invention is preferably 0.1% to 30% by mass relative to the total solid content of the polymerizable composition, and more preferably 1 mass% to 25 mass%, further preferably 1 mass% to 10 mass%.

<Other additives>

The polymerizable composition may include components other than the pigment dispersion composition, the polymerizable compound, and the polymerization initiator. An example is shown below.

<Solution>

The polymerizable composition of the present invention preferably contains a solvent. Examples of solvents include water and organic solvents.

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, and ethylene glycol. Dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, ethylene glycol Alcohol 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, dipropylene glycol dimethyl ether, 3-methoxypropyl acetate, N, N-dimethyl ether Methylformamide, dimethylmethylene sulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, ethyl lactate, and the like are not limited thereto.

Solvents can be used alone or in combination of two or more.

When two or more solvents are used in combination, it is particularly preferred that the solvent is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butyl Carbitol acetate, propylene glycol Two or more kinds of alcohol methyl ether and propylene glycol methyl ether acetate.

The amount of the solubilizer contained in the polymerizable composition is preferably 10% to 90% by mass, and more preferably 20% to 85% by mass relative to the total mass of the polymerizable composition.

<Binder polymer>

The polymerizable composition of the present invention may contain a binder polymer.

As the binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known linear organic polymer can be used arbitrarily. It is preferred to select a linear organic polymer that is soluble or swellable with respect to water or weakly alkaline water in order to enable development with water or weakly alkaline water.

The binder polymer is preferably an alkali-soluble resin, and more specifically, it can be appropriately selected from the following alkali-soluble resins: the alkali-soluble resins are linear organic high-molecular polymers, The copolymer and the styrene-based copolymer have at least one group which promotes alkali solubility among the molecules). From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferred, and from the viewpoint of controlling the developability Specifically, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include, for example, a carboxylic acid group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. It is preferably soluble in an organic solvent and weakly alkaline. A developer in an aqueous solution is more preferably a carboxylic acid group. As a repeating unit having such a carboxylic acid group, a repeating unit derived from (meth) acrylic acid is preferred. These acid groups may be only one kind, or two or more kinds.

As one of the preferable aspects of the binder polymer, a binder polymer having the following SP value is preferable, the SP value, the SP value of the first dispersant, and the SP value of the second dispersant. The absolute value of the difference between the SP values was within 2.0 MPa ^1/2 . When such a binder polymer is used, it is easy to be compatible with any of the first dispersant and the second dispersant, and the black pigment in the coating film obtained using the polymerizable composition is easily dispersed uniformly throughout the entire body. This makes it easy to obtain the desired effect.

In addition, in terms of a more excellent effect of the present invention, the absolute value of the difference is preferably within 1.5 MPa ^1/2 , and more preferably within 0.5 MPa ^1/2 . The lower limit is not particularly limited, and may be 0.

The absolute value of the difference is a value represented by | SP value of the first dispersant-SP value of the binder polymer | or | SP value of second dispersant-SP value of the binder polymer |

Examples of the binder polymer include a radical polymer having a carboxylic acid group on a side chain, such as Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Laid-Open No. 54-34327, and Japanese Patent Laid-Open No. 58-34327. It is described in various publications of Japanese Patent Publication No. 12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 59-53836, and Japanese Patent Publication No. 59-71048. Resins obtained by singly or copolymerizing a monomer having a carboxylic acid group, resins obtained by hydrolyzing or semi-esterifying or semi-aminating an acid anhydride unit obtained by separately or copolymerizing a monomer having an acid anhydride, and unsaturated Monocarboxylic acids and anhydrides are epoxy acrylates modified from epoxy resins. Examples of the monomer having a carboxylic acid group include acrylic acid and methacrylic acid. Acrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. Examples of the monomer having an acid anhydride include maleic anhydride and the like. Moreover, the acidic cellulose derivative which similarly has a carboxylic acid group in a side chain is mentioned as an example. Other than that, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

In addition, the film strength and development of an acetal-modified polyvinyl alcohol-based adhesive polymer having an acid group described in various publications such as European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463, and development The balance of properties is excellent, so it is better.

Furthermore, as other water-soluble linear organic polymers, polyvinylpyrrolidone, polyethylene oxide, and the like are useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon or polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin is also useful.

Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomers as needed] copolymers and [allyl (meth) acrylate / (methyl) ) Acrylic acid / other addition polymerizable vinyl monomers as needed] Copolymers are preferred because they have an excellent balance of film strength, sensitivity, and developability.

Examples of commercially available products include Acrybase FF-187 and FF-426 (manufactured by Fujikura Chemical Co., Ltd.), and Acrycure-RD-F8 (Japanese Catalysts Corporation) And Cyclomer P (ACA) 230AA manufactured by Daicel-Allnex.

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

The content of the binder polymer in the polymerizable composition of the present invention is preferably 0.1% to 30% by mass, and more preferably 0.3% to 25% by mass, relative to the total solid content of the polymerizable composition.

<Other additives>

For example, the polymerizable composition of the present invention may contain an adhesive. The adhesion of the light-shielding film to the substrate is improved by including an adhesive.

Examples of the adhesive include a silane-based coupling agent and a titanium coupling agent.

Examples of the silane-based coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), and N-β -Aminoethyl-γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethyl Oxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-903), γ-aminopropyl -Triethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), Glycidyloxyoctyltrimethoxysilane and the like.

The content of the adhesive is preferably 0.5% to 30% by mass, more preferably 0.7% to 20% by mass, and still more preferably 0.7% to 5% by mass, relative to the total solid content of the polymerizable composition.

The polymerizable composition of the present invention may contain an ultraviolet absorber. This makes it possible to produce a pattern having a more excellent (fine) shape.

As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorber can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 of Japanese Patent Laid-Open No. 2012-068418 (corresponding to columns of paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and these contents can be cited, and Into this manual.

In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical, trade name: UV-503) and the like can also be preferably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of Japanese Patent Laid-Open No. 2012-32556.

The polymerizable composition may or may not include an ultraviolet absorbent. When included, the content of the ultraviolet absorbent is preferably 0.001% to 15% by mass relative to the total solid content of the composition, and more preferably 0.01 mass% to 10 mass%, further preferably 0.1 mass% to 5 mass%.

From the viewpoint of further improving coatability, various surfactants may be added to the polymerizable composition. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the composition of the present invention further improves the solution characteristics (especially the fluidity) by containing a fluorine-based surfactant, so that it is possible to further improve the uniformity of the coating thickness or the liquid saving property.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Mega (Megafac) F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac (Megafac) F780, Megafac F781F (the above are manufactured by DIC), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above (Made for Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Sand Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon ) KH-40 (the above are manufactured by Asahi Glass).

Specific examples of the other surfactants include, for example, the surfactants described in paragraphs 0174 to 0177 of Japanese Patent Application Laid-Open No. 2013-249417, and the contents are incorporated into this specification.

The surfactant may be used alone or in combination of two or more.

With respect to the total mass of the polymerizable composition, the added amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass.

In addition to the above components, the following components may be further added to the composition. Examples include sensitizers, co-sensitizers, cross-linking agents, hardening accelerators, fillers, heat hardening accelerators, polymerization inhibitors, plasticizers, diluents, and lipophilic agents. If necessary, adhesion promoters and other additives (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, leveling agents, peeling accelerators, antioxidants, fragrances, and surface tension) Regulators, chain transfer agents, etc.) are known additives.

For these components, refer to, for example, paragraph number 0183 to paragraph number 0228 of Japanese Patent Laid-Open No. 2012-003225 (corresponding to [0237] to [0309] of the specification of US Patent Application Publication No. 2013/0034812), Japanese Patent Laid-Open Descriptions of paragraph numbers 0101 to 0102, paragraph number 0102, paragraph number 0103 to paragraph number 0104, paragraph number 0107 to paragraph number 0109, paragraph number 0159 to paragraph number 0184 of Japanese Patent Laid-Open Publication No. 2013-195480 These contents are incorporated into the specification of this application.

<Method for preparing polymerizable composition>

The polymerizable composition of the present invention can be prepared by mixing the various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser).

In addition, if necessary, it is carried out after the polymerizable composition is prepared during the production of the pigment-dispersed composition, and it is also possible to perform a filtration treatment with a filter.

<< Light-shielding film and its manufacturing method >>

By using the pigment dispersion composition or the polymerizable composition, a light-shielding film can be formed.

The method for producing the light-shielding film is not particularly limited, and examples thereof include a method of applying the pigment-dispersed composition or the polymerizable composition on a substrate to form a coating film, and The film is cured to produce a light-shielding film.

The method of the hardening treatment is not particularly limited, and examples include a light hardening treatment and a heat hardening treatment. In terms of easy pattern formation, a photohardening treatment (particularly, an ultraviolet irradiation treatment) is preferred.

In addition, the type of the substrate used is not particularly limited, and various members in the solid-state imaging device (for example, infrared cut-off filters) and the like are preferably listed.

As a preferable aspect when manufacturing a pattern-shaped light-shielding film, the aspect including the following steps: The process of apply | coating the polymerizable composition of this invention on a board | substrate, and forming a composition layer (henceforth simply referred to as "composition" Step of forming an object layer "), a step of exposing the composition layer through a mask (hereinafter referred to as" exposure step "as appropriate), and developing the exposed composition layer to form a light-shielding film (patterned light-shielding film ) (Hereinafter referred to as "development step" as appropriate).

Specifically, a patterned light-shielding film can be produced by coating the polymerizable composition of the present invention on a substrate directly or via another layer to form a composition layer (composition layer forming step), By exposing at predetermined mask patterns, only a portion of the coating film irradiated with light is hardened (exposure step), and development is performed with a developing solution (development step).

Hereinafter, each step in the said aspect is demonstrated.

[Composition layer forming step]

In the composition layer forming step, a polymerizable composition is applied on a substrate to form a composition layer.

Examples of the substrate include various members in a solid-state imaging device (for example, Infrared cut-off filter, outer periphery of solid-state imaging element, outer periphery of wafer-level lens, back side of solid-state imaging element, etc.).

As a method for applying a polymerizable composition to a substrate, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied.

The polymerizable composition applied on the substrate is usually dried under the conditions of 70 ° C. to 110 ° C., for 2 minutes to 4 minutes, to form a composition layer.

[Exposure steps]

In the exposing step, the composition layer formed in the composition layer forming step is exposed through a barrier mask, so that only the composition layer irradiated with light is partially hardened.

The exposure is preferably performed by irradiation with radiation. As the radiation that can be used during exposure, particularly ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used. The light source is preferably a high-pressure mercury lamp. The irradiation intensity is preferably ⁵ mJ / cm ² or more and 1500 mJ / cm ² or less, and more preferably 10 mJ / cm ² or more and 1000 mJ / cm ² or less.

[Developing steps]

After the exposure step, a development process (development step) is performed to dissolve the unirradiated portion of light in the exposure step into a developing solution (for example, an alkaline aqueous solution). As a result, only the portion subjected to photohardening remains.

As the developer, an organic alkaline developer is desirable. The developing temperature is usually 20 ° C or more and 30 ° C or less, and the developing time is 20 seconds or more and 90 seconds or less.

Examples of the alkaline aqueous solution include hydroxides which are inorganic developing solutions. Sodium, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate, ammonia as an organic alkaline developer, ethylamine, diethylamine, dimethylethanolamine, tetramethyl hydroxide Ammonium, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazobicyclo- [ An alkaline aqueous solution in which a basic compound such as 5,4,0] -undecene is dissolved in a concentration of 0.001% by mass to 10% by mass, preferably 0.005% by mass to 0.5% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the alkaline aqueous solution. When a developer containing such an alkaline aqueous solution is used, it is usually washed (washed) with pure water after development.

Furthermore, after performing the composition layer forming step, the exposure step, and the development step, a hardening step of hardening the formed light-shielding film by heating and / or exposure may be performed as necessary.

[Film repair steps]

After the developing step, the film repair step described below can also be performed as needed.

After the development step is performed, side etching may occur depending on the types of components constituting the light-shielding film. More specifically, as shown in FIG. 1 (A), at the end portion of the light-shielding film 102 disposed on the substrate 100 and subjected to the development treatment, a side etched portion 102a may be generated.

As described above, when removing foreign matter on the surface of a member on which a light-shielding film is formed, a method of cleaning the light-shielding film by blowing a cleaning solution under high pressure may be performed. At this time, if there is a side etched part, the cleaning liquid enters the side etched part, and the end of the light shielding film is caused by the pressure. Parts are prone to defects. As a method for further suppressing the occurrence of defects of such a light-shielding film, it is preferable to perform a film repair step.

As a procedure of the film repairing step, a composition for forming a repairing film (composition for forming a protective layer) is first coated on a light-shielding film, and a repairing film (protective layer) is formed on the light-shielding film. More specifically, as shown in FIG. 1 (B), a repair film 104 is formed on the light shielding film 102 by coating. The repair film 104 formed by coating is not only disposed on the surface of the light shielding film 102 on the side opposite to the substrate 100 side, but is also disposed so as to bury the side etched portions 102 a at the ends of the light shielding film 102.

Next, an etching process is performed to remove the repair film. More specifically, as shown in FIG. 1 (C), an etching process is performed on the self-repair film 104. By performing the etching process, as shown in FIG. 1 (D), the light-shielding film 102 functions as a so-called mask, and as a result, the repair film 104 remains to bury the side etched portion 102a. Therefore, defects at the end portions of the obtained light-shielding film are more difficult to occur.

That is, the film repair step includes a step (film formation step) of applying a composition for forming a repair film on a light-shielding film to form a repair film on the light-shielding film, and a step (etching step) of performing an etching process.

The materials used in these steps or their procedures are described in detail below.

(Film formation step)

This step is a step of applying the composition for forming a repair film on a light-shielding film, and forming a repair film on the light-shielding film.

As a material contained in the repair film forming composition used in this step, if it is a material (coating film forming material) that can form a coating film (repair film) on the light-shielding film, Although it does not specifically limit, A compound which has a polymerizable group is preferable. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group. The compound having a polymerizable group may be a low-molecular compound or a high-molecular compound. In terms of the formability of the coating film, a low-molecular compound is preferred.

The low-molecular compound herein refers to a compound having a molecular weight of less than 1,000, and the high-molecular compound refers to a compound having a molecular weight of 1,000 or more.

The type of the compound having a polymerizable group is not particularly limited, and a known compound can be used. In terms of transparency, a (meth) acrylic monomer (including an acrylic monomer and a methacrylic monomer) is preferably used. , Epoxy monomer.

Examples of the polymer compound having a polymerizable group (organic resin having a polymerizable group) include a side chain described in Japanese Patent Laid-Open No. 2000-187322 and Japanese Patent Laid-Open No. 2002-62698. Alkali-soluble resin with a double bond on it. Specific examples of the resin include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), and Photomer 6173 (polyurethane acrylic oligomer containing COOH) (Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.), Biscoat R-264, KS resist 106 (both Osaka Organic Chemical Industry Co., Ltd. (Manufactured by the company), Cyclomer P ACA230AA and other Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ai Ebecryl 3800 (manufactured by Daicel UCB).

In order to improve the coating property, a solvent (for example, water or an organic solvent) may be contained in the composition for repair film formation.

The repair film composition may include a polymerization initiator (for example, a photopolymerization initiator and a thermal polymerization initiator). Examples of the polymerization initiator include a polymerization initiator that can be contained in the polymerizable composition.

One of the preferable aspects of the composition for repair film formation includes a composition containing a compound having a polymerizable group, an organic resin, a polymerization initiator, and a solvent.

In addition, as the composition for forming a repair film, for example, a base agent composition for a color filter can be used, and those described in Japanese Patent Laid-Open No. 2010-77273 and Japanese Patent Laid-Open No. 2006-077098 can be mentioned.

The method for applying the composition for forming a repair film is not particularly limited, and a known method may be adopted, and the coating method described in the composition layer forming step may be mentioned.

Furthermore, after the composition for forming a repair film is applied, a drying process to remove the solvent may be performed as necessary. As a method of a drying process, heat processing (pre-baking process), air-drying process, etc. are mentioned.

(Etching step)

This step is a step of performing an etching process on the light-shielding film covered with the repair film produced in the step.

The method of the etching treatment is not particularly limited, and a known method can be adopted. Among them, a dry etching method using an etching gas (more specifically, a dry etching method using a plasma gas obtained by exciting the etching gas) is preferred.

The type of the etching gas is not particularly limited, and examples thereof include rare gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe), and include halogens such as a chlorine atom, a fluorine atom, and a bromine atom. Atomic halogen-based gases (for example, CCl ₄ , CClF ₃ , AlF ₃ , AlCl _3, etc.), H ₂ , N ₂ , O ₂ , CO, and CO _2, etc., may be used alone or in combination of two or more . Among them, the etching gas is preferably a gas selected from the group consisting of oxygen, a rare gas (especially argon), hydrogen, and nitrogen.

Conditions for the dry etching process vary depending on the material of the repair film. Generally, the total flow rate (total gas flow rate) of the gas is preferably 1500 mL / min (0 ° C, 1013 hPa) or less, and more preferably 500 mL / min (0 ° C, 1013hPa) ~ 1000mL / min (0 ℃, 1013hPa).

As the relationship between source power (radio frequency (RF) power) and bias, RF power / upper bias / electrode bias are preferably 600W ~ 1000W / 300W ~ 500W / 300W ~ 500W, more preferably RF The power / upper bias / electrode bias are 700W ~ 900W / 350W ~ 450W / 350W ~ 450W.

As the time of the dry etching process, the etching process is preferably performed within 10 minutes, and more preferably, the process is performed within 7 minutes.

The internal pressure of the chamber in the dry etching process is preferably 1.0 Pa to 5.0 Pa, and more preferably 2.0 Pa to 4.0 Pa.

The temperature of the stage (the stage on which the object to be subjected to the dry etching process is placed) during the dry etching process is preferably controlled to 30 ° C to 100 ° C.

In addition, when a compound having a polymerizable group is used as the coating film forming material, a hardening treatment may be performed after the film forming step and before the etching step or after the etching step, if necessary. Undercutting is performed by hardening The partially buried compound having a polymerizable group is polymerized and hardened, and the repair film is not easily peeled from the light-shielding film, thereby further suppressing the occurrence of defects in the light-shielding film.

The method of the hardening treatment is not particularly limited, and examples thereof include a heat hardening treatment (post-baking treatment) and a light hardening treatment. In addition, the heating conditions for the thermal hardening treatment are not particularly limited, and appropriate optimum conditions are selected according to the type of the repair film to be used. In terms of hardenability, it is preferably performed at 100 ° C for 1 hour or more. Heat treatment.

<< Solid-state imaging device >>

The light-shielding film can be preferably applied to a solid-state imaging device.

Hereinafter, a first embodiment of a solid-state imaging device including 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 sensor 3 as a solid-state imaging element, a circuit board 4 on which the CMOS sensor 3 is mounted, and ceramic ceramics holding the circuit board 4. Substrate 5. In addition, the solid-state imaging device 2 includes an IR cut filter 6 held by a ceramic substrate 5 and cutting infrared rays (IR) toward the CMOS sensor 3, a photographing lens 7, and an imaging lens 7. The held lens holder 8 and a holding tube 9 holding the lens holder 8 freely. In addition, a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3.

The ceramic substrate 5 is formed with an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds a side surface of the CMOS sensor 3. In this state, the circuit substrate 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy-based adhesive, the same applies hereinafter). Various circuit patterns are formed on the circuit substrate 4.

The IR cut filter 6 has a reflective film that reflects infrared light on a plate-shaped glass or blue glass, and the surface on which the reflective film is formed is an incident surface 6a. The IR cut filter 6 is formed to have a size larger than that of 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 (lower in FIGS. 3 and 4), and an IR cut filter 6 is disposed between the photographing lens 7 and the CMOS sensor 3. The light of the subject is incident on the light receiving surface of the CMOS sensor 3 through the imaging lens 7 and the IR cut filter 6. At this time, the infrared light is cut off 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 supplies power from the electronic device to the solid-state imaging device 2. The CMOS sensor 3 has a plurality of color pixels arranged two-dimensionally on a light-receiving surface, and each color pixel photoelectrically converts incident light and accumulates a generated signal charge.

As shown in FIGS. 3 and 4, the light-shielding film (light-shielding layer) 11 is arranged at the end of the incident surface 6 a of the IR-cut filter 6 over the entire circumference to form an infrared light-cut filter with a light-shielding film. sheet. A case where 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 repeatedly reflected or refracted in the device and is incident on the CMOS sensor 3, or When the reflected light R2 emitted from the photographing lens 7 and reflected by the inner wall surface of the lens holder 8 enters the CMOS sensor 3, it becomes a cause of flare in a photographed image. The light-shielding film 11 shields harmful light such as reflected light R1 and reflected light R2 toward the CMOS sensor 3. The light-shielding film 11 is applied by, for example, a spin coating method or a spray coating method. Furthermore, The thickness of the light shielding film 11 is exaggeratedly depicted in FIGS. 3 and 4.

FIG. 5 shows a solid-state imaging device 20 according to a second embodiment. In addition, the same components as those of the solid-state imaging device according to the first embodiment are denoted by the same reference numerals, and detailed descriptions thereof are 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 tube 9. The light-shielding film (light-shielding layer) 21 is formed on the side end surface 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 repeatedly reflected or refracted in the device and incident on the CMOS sensor 3, it becomes a cause of a flare in a photographed image. The light-shielding film 21 shields harmful light such as reflected light R3 toward the CMOS sensor 3.

FIG. 6 shows a solid-state imaging device 30 according to a third embodiment. In addition, the same components as those of the solid-state imaging device according to the first embodiment are denoted by the same reference numerals, and detailed descriptions thereof are 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 tube 9. The light-shielding film (light-shielding layer) 31 is formed on the end portion and the side end surface of the incident surface 6 a of the IR cut filter 6 over the entire circumference. That is, the solid-state imaging device is a combination of the first embodiment and the second embodiment. This embodiment has higher light-shielding performance than the first embodiment and the second embodiment, and therefore reliably suppresses the occurrence of light spots.

FIG. 7 shows a solid-state imaging device 40 according to a fourth embodiment. The same components as those of the solid-state imaging device according to the first embodiment are denoted by the same symbols. Number, and its detailed description is omitted.

The solid-state imaging device 40 includes a CMOS sensor 3, a circuit substrate 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding tube 9. The light-shielding film (light-shielding layer) 31 is formed on the end portion and the side end surface of the incident surface 6 a 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 the reflected light emitted from the photographing lens 7 and reflected by the inner wall surface of the ceramic substrate 5 through the IR cut filter 6 is incident on the CMOS sensor 3, it causes a flare in a photographed image. The light-shielding film 41 has higher light-shielding performance than the inner wall surface of the ceramic substrate 5, and therefore reliably suppresses the occurrence of light spots.

[Example]

Hereinafter, the present invention will be described more specifically. The present invention is not limited to the following examples as long as the present invention is not exceeded. In addition, unless otherwise specified, "part" and "%" are quality standards. The room temperature means 25 ° C.

In this example, DFA4201NXEY (0.45 μm nylon filter) manufactured by Japan Pall was used for filtration after the preparation of the dispersion described below and the preparation of the composition described below, respectively.

<< Example A >>

<Preparation of Titanium Black Dispersion>

-Production of Titanium Black A-1-

Weighing 120g BET specific surface area of 110m ² / g of titanium oxide TTO-51N (trade name, manufactured by Ishihara Sangyo), 25g BET specific surface area of 300m ² / g of silicon dioxide particles halloysite Hill (AEROSIL) 300 ( (Registered trademark) 300/30 (manufactured by Evonik) and 100 g of dispersant Disperbyk 190 (trade name, manufactured by BYK-Chemie), and added 71 g of ionized electrical Water was exchanged, and the mixture was treated with MAZERSTAR KK-400W manufactured by KURABO at 1360 rpm and 1047 rpm for 30 minutes to obtain a uniform aqueous solution. This aqueous solution was filled in a quartz container, and heated to 920 ° C in an oxygen environment using a small rotary kiln (manufactured by Motoyama Co., Ltd.). After that, the environment in the small-scale rotary furnace was replaced with nitrogen, and ammonia gas was allowed to flow in the small-scale rotary furnace at 100 mL / min at the same temperature for 5 hours, thereby performing a nitriding reduction treatment. The powder recovered after completion was pulverized in a mortar to obtain titanium black (A-1) [a dispersion containing titanium black particles and Si atoms] containing Si atoms and having a powder-like specific surface area of 85 m ² / g.

<Preparation of the first pigment dispersion>

Using a blender (Eurostar manufactured by IKA), the components shown in the following composition 1 were mixed for 15 minutes to obtain a dispersion a.

The polymer compound (G1) described below was synthesized by referring to the description in Japanese Patent Laid-Open No. 2013-249417. In the formula of the polymer compound (G1), x is 30% by mass, y is 20% by mass, and z is 50% by mass. The weight average molecular weight of the polymer compound (G1) was 30,000, the acid value was 60 mgKOH / g, and the number of atoms (excluding hydrogen atoms) of the graft chain was 117.

(Composition 1)

The obtained dispersion a was subjected to a dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. under the following conditions to obtain a first pigment dispersion.

(Dispersion conditions)

． Bead size: Φ0.05mm, made of zirconia

． Filling rate of beads: 65% by volume

． Grinding peripheral speed: 10m / sec

． Separator peripheral speed: 11m / s

． Dispersed mixed liquid: 15kg

． Circulation flow (pump supply): 60kg / hour

． Treatment liquid temperature: 19 ℃ ~ 21 ℃

． Cooling water: water

． Number of passes: 90 times

<Preparation of the second pigment dispersion (1)>

Except having used the following polymer compound (X1) instead of the polymer compound (G1), the 2nd pigment dispersion (1) was prepared according to the same procedure as the said <preparation of a 1st pigment dispersion>.

The polymer compound (X1) described below was synthesized by referring to the description in Japanese Patent Laid-Open No. 2014-177614. The weight average molecular weight of the polymer compound (X1) was 7000, and the acid value was 80 mgKOH / g.

<Preparation of the second pigment dispersion (2)>

Except that the following polymer compound (X2) was used instead of the polymer compound (G1), the procedure was the same as the procedure for <Preparation of the first pigment dispersion>. A second pigment dispersion (2) was prepared.

The polymer compound (X2) is synthesized by referring to the description in Japanese Patent Laid-Open No. 2014-177614. The weight average molecular weight of the polymer compound (X2) was 6,900, and the acid value was 82 mgKOH / g.

<Preparation of the second pigment dispersion (3)>

Except having used the following polymer compound (X3) instead of the polymer compound (G1), the 2nd pigment dispersion (3) was prepared according to the same procedure as the said <preparation of a 1st pigment dispersion>.

[Chemical 20]

The polymer compound (X3) is synthesized by referring to the description in Japanese Patent Laid-Open No. 2014-177614. The weight average molecular weight of the polymer compound (X3) was 7,300, and the acid value was 82 mgKOH / g.

<Preparation of the second pigment dispersion (4)>

Except having used the following polymer compound (X4) instead of the polymer compound (G1), the 2nd pigment dispersion (4) was prepared according to the same procedure as the said <preparation of a 1st pigment dispersion>.

[Chemical 21]

The polymer compound (X4) is synthesized by referring to the description in Japanese Patent Laid-Open No. 2014-177614. The weight average molecular weight of the polymer compound (X4) was 6,800, and the acid value was 81 mgKOH / g.

<Preparation of polymerizable composition (1)>

The first pigment dispersion and the second pigment dispersion (1) are mixed to produce a pigment dispersion composition, and various components such as a polymerizable compound are further added to produce a polymerizable composition (1) having the following composition. In addition, the following acrylic-RD-F8 is equivalent to a binder polymer, and SP value is 20 MPa ^1/2 .

Titanium black (A-1) 10 parts by mass

Polymer compound (G1) 4.2 parts by mass

Polymer compound (X1) 2.2 parts by mass

Acrycure-RD-F8 (Japanese Catalyst (stock), solid content 40%, solvent: propylene glycol monomethyl ether) 2.2 parts by mass

KAYARAD DPHA (Nippon Kayaku) 5.4 parts by mass

Irgacure OXE02 (BASF Japan) (Production) 1.5 parts by mass

Megafac F-781F (manufactured by DIC Corporation, fluoropolymer type surfactant) 0.03 parts by mass

0.003 parts by mass of p-methoxyphenol

Glycidyloxyoctyltrimethoxysilane 1.3 parts by mass

30.8 parts by mass of propylene glycol monomethyl ether acetate

11.8 parts by mass of butyl acetate

32.3 parts by mass of dipropylene glycol dimethyl ether

<Preparation of polymerizable composition (2)>

A polymerizable composition (2) was prepared in accordance with the same procedure as in the <Preparation of the polymerizable composition (1)> except that the second pigment dispersion (2) was used instead of the second pigment dispersion (1). .

The polymerizable composition (1) differs from the polymerizable composition (2) only in that the polymer compound (X2) is used instead of the polymer compound (X1), and the content ratios of the respective components are the same.

<Preparation of polymerizable composition (3)>

A polymerizable composition (3) was prepared according to the same procedure as in the <Preparation of the polymerizable composition (1)> except that the second pigment dispersion (3) was used instead of the second pigment dispersion (1). .

The polymerizable composition (1) differs from the polymerizable composition (3) only in that the polymer compound (X3) is used instead of the polymer compound (X1), and the content ratios of the respective components are the same.

<Preparation of polymerizable composition (4)>

A polymerizable composition (4) was prepared in accordance with the same procedure as in the <Preparation of the polymerizable composition (1)> except that the second pigment dispersion (4) was used instead of the second pigment dispersion (1). .

The polymerizable composition (1) differs from the polymerizable composition (4) only in that the polymer compound (X4) is used instead of the polymer compound (X1), and the content ratio of each component is the same.

<Fabrication of Light-shielding Film>

Use coating. A developer (coater.developer) ACT (manufactured by TEL) applied each of the produced polymerizable compositions to the incident surface of the IR cut filter by a spin coating method, and then performed a heating plate at 100 ° C. for 120 seconds. Heat treatment (pre-baking), thereby forming a coating film having a dry film thickness of 4.5 μm. The spin conditions for the spin coating at this time are set to the first stage: rotation at 300 rpm for 5 seconds, and the second stage: rotation at 50 rpm for 300 seconds. Next, an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon) was used to apply a 20m square island pattern mask to the coating film at an exposure of 200mJ / cm ² Make an exposure.

After that, for the IR cut filter on which the irradiated coating film was formed, coating was used. The developing machine ACT uses a 0.03% by mass aqueous solution of tetramethylammonium hydroxide as a developing solution, and performs spin development at 23 ° C. for 20 seconds. Next, the IR cut filter is rotated by a rotation device at a number of revolutions of 50 rpm, and pure water is continuously supplied from an ejection nozzle from above the center of rotation, and a leaching process is performed for 60 seconds. After washing, use clean baking Box (Clean Oven) CLH-21CD (III) (Koyo Thermo Systems), hardened at 150 ° C for 60 minutes at an oxygen concentration <50ppm, forming a light-shielding film on the incident surface of the IR cut filter .

In the same manner, a light-shielding film with a frame pattern of 7.0 mm × 5.0 mm and a width of 0.7 mm was formed on the IR cut filter to produce an IR cut filter with a frame pattern.

Furthermore, a glass substrate was used as the substrate, and a full exposure was performed without using a mask during exposure. A substrate for optical density (OD) and reflectance measurement was produced in the same manner as described above.

<Various evaluations>

(Light-shielding property: Evaluation of optical density (OD))

Using a light-shielding film produced on a glass substrate, the minimum value (ODmin) of the OD in a wavelength range of 400 nm to 800 nm was measured by a spectroscope UV4100 manufactured by Hitachi High-technologies, and evaluated based on the following criteria.

"1": When the minimum value of OD is 1.5 or less

"2": When the minimum value of OD exceeds 1.5 and is less than 2.5

"3": When the minimum value of OD exceeds 2.5 and is 3.0 or less

"4": When the minimum value of OD exceeds 3.0

(Reflectivity: Evaluation of reflectance)

The light is incident on the light-shielding film on the incident surface of the IR cut filter at an incident angle of 5 °, and the light in the wavelength range of 400 nm to 800 nm is measured by a spectroscope UV4100 manufactured by Hitachi High-technologies. Evaluation was performed based on the following criteria.

"1": When the maximum reflectance is 1% or less

"2": When the maximum reflectance exceeds 1% and is less than 2%

"3": When the maximum reflectance exceeds 2% and is less than 3%

"4": When the maximum reflectance exceeds 3% and is less than 4%

"5": When the maximum reflectance exceeds 4%

(Evaluation of surface roughness)

The atomic force microscope Dimension FastScan AFM (manufactured by Bruker) was used to measure the surface roughness of the light-shielding film on the incident surface of the IR cut filter.

(Analytical Evaluation 1)

Five 20 μm square samples with island-like patterns were prepared, and the size (length of one side) of each pattern was measured with a measuring-length scanning electron microscope S9260 (manufactured by Hitachi High-technologies), and the following were performed evaluation of.

"1": When the value of three times the standard deviation obtained from the measurement of five samples is 0.1 μm or less

"2": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 0.1 μm and is 0.5 μm or less

"3": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 0.5 μm and is 1.0 μm or less

"4": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 1.0 μm

"5": In the case of measurement of five samples, the analysis cannot be performed only once due to pattern peeling or the like.

(Analytical Evaluation 2)

Five samples of the light-shielding film with a frame pattern were prepared, and the width (0.7 mm) of one side of each frame pattern was measured by a micro line width measurement system MT-3600LW (FLOVEL), and the following Evaluation.

"1": When the value of three times the standard deviation obtained from the measurement of five samples is 0.50 μm or less

"2": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 0.50 μm and is 0.75 μm or less

"3": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 0.75 μm and is 1.00 μm or less

"4": When the value of three times the standard deviation obtained from the measurement of five samples exceeds 1.00 μm

"5": In the case of measurement of five samples, the analysis cannot be performed only once due to pattern peeling, pattern defects, or the like.

(Exhaust air volume dependence (reflectivity): Evaluation of exhaust air volume dependence of reflectance)

When coating each polymerizable composition on a glass substrate, adjust the coating. The exhaust damper of the developing machine ACT was measured by a hot wire anemometer DT-8880 (MK Scientific) to measure the wind speed at the center of the coater cup and at a height of 2 cm from the spin chuck. , Set the wind speed to 0.2m / s, 0.3m / s or 0.4 m / s, and a light-shielding film was produced by the procedure. For the light-shielding film produced at each wind speed, the maximum reflectance (% Rmax) was measured by a spectroscope UV4100 manufactured by Hitachi High-technologies at an incident angle of 5 ° in the region of 400nm to 800nm, and each wind speed was selected. The largest% Rmax and the smallest% Rmax of the% Rmax at (0.2 m / s, 0.3 m / s, or 0.4 m / s) were evaluated based on the following criteria. The temperature of the coater cup environment at the time of coating was 25 ° C, and the humidity was 60%. In practical terms, it is preferably "1" to "3".

"1": When the difference between the maximum% Rmax and the minimum% Rmax at each wind speed is 0.3% or less

"2": When the difference between the maximum% Rmax and the minimum% Rmax at each wind speed exceeds 0.3% and is less than 0.5%

"3": When the difference between the maximum% Rmax and the minimum% Rmax at each wind speed exceeds 0.5% and is less than 1.0%

"4": When the difference between the maximum% Rmax and the minimum% Rmax at each wind speed exceeds 1.0%

(Humidity dependence (reflectance): Evaluation of humidity dependence of reflectance)

When each polymerizable composition is coated on a glass substrate, a PAP10A1-K (trade name, manufactured by Orionkikai Co., Ltd.) duct is introduced to the suction side of the coating machine. The temperature and humidity are adjusted to air, and the humidity of the coater cup environment is set to 45%, 55%, 65%, or 75%, and a light-shielding film is produced by the procedure. The temperature was 23.5 ° C. The light-shielding film produced under each humidity was made by a spectroscope manufactured by Hitachi High-technologies UV4100 measures the maximum reflectance (% Rmax) in the 400nm ~ 800nm area at an incident angle of 5 °. Select the largest% Rmax and% Rmax of each humidity (45%, 55%, 65% or 75%). The minimum% Rmax is evaluated based on the following criteria. The temperature of the coater cup environment at the time of coating was 25 ° C, and the wind speed at the position of the center of the coater cup and a height of 2 cm from the spin chuck was 0.3 m / s. In practical terms, it is preferably "1" to "3".

"1": When the difference between the maximum% Rmax and the minimum% Rmax at each humidity is 0.3% or less

"2": When the difference between the maximum% Rmax and the minimum% Rmax at each humidity exceeds 0.3% and is less than 0.5%

"3": When the difference between the maximum% Rmax and the minimum% Rmax at each humidity exceeds 0.5% and is less than 1.0%

"4": When the difference between the maximum% Rmax and the minimum% Rmax in each humidity exceeds 1.0%

(Defect evaluation in the dicing step)

The obtained IR cut filter with a frame pattern was singulated using a dicer (DFD6240, manufactured by DISCO). After cutting with a blade, cleaning was performed using a cleaning mechanism attached to the cutting machine in order to remove debris generated in the cutting step. The dried pattern was observed with an optical microscope at a magnification of 50 times. The pattern (250) on the cut filter was counted, and the number of pattern defects was counted, and evaluated based on the following criteria.

"1": The number of defects is less than 5

"2": The number of defects is 5 or more and less than 10

"3": The number of defects is 10 or more and less than 50

"4": The number of defects is 50 or more and less than 100

"5": 100 or more defects

In addition, as Comparative Example 2, a light-shielding film was produced using the polymerizable composition used in the Example column of Patent Document 1, and various evaluations were performed.

As shown in Table 1, when the polymerizable composition containing the pigment dispersion composition of the present invention was used, a desired effect was obtained.

In particular, it was confirmed that when the absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.5 MPa ^1/2 , defects are unlikely to occur.

On the other hand, in Comparative Examples 1 and 2 that did not satisfy the predetermined relationship, the desired effect was not obtained.

<< Example B >>

[Patternization of polymerizable composition]

The obtained polymerizable composition (1) was spin-coated on a glass wafer using a spin coater ACT-8 manufactured by Tokyo Electron at 300 rpm for 3 minutes, and then heated at 100 ° C. on a hot plate. After 2 minutes and then cooling for 1 minute, a coating film having a thickness of 5.0 μm was formed.

Next, using a mask with a pattern as shown in FIG. 8, the area corresponding to the white portion was coated with an i-ray stepper (manufactured by Canon (FPA3000i5 +)) at 300 mJ / cm ² . The film is subjected to step and repeat exposure.

Then, the coating film subjected to the exposure treatment was subjected to liquid-cover development with a 0.16% by mass aqueous solution of tetramethylammonium hydroxide for 30 seconds. Thereafter, the coating film was rinsed with pure water at 200 rpm for 20 seconds using a straight nozzle. Thereafter, spin drying was performed to obtain a matrix of a pattern of 3000 μm (internally excavated 2000 μm).

Then, a clean oven CLH-21CD (III) (Koyo Thermo Systems) was used for post-baking treatment to form a patterned light-shielding film. As a condition of the post-baking treatment, the temperature was raised from an initial temperature of 23 ° C. to 150 ° C. (about 13 minutes) at a rate of 10 ° C./min. After being held at 150 ° C. for 1 hour, it was naturally cooled to 40 ° C. (processing time (A total of about 3 hours and 30 minutes).

[Confirmation of pattern shape]

The cross-sectional shape of the obtained patterned light-shielding film was confirmed using a scanning microscope (S4800 Hitachi High-technologies Corporation, observation magnification: 30.0K, acceleration voltage: 2.0 keV).

As shown in FIG. 9, the side etch enters about 5 μm from the end face of the pattern.

[Formation of repair film]

Using a spin coater (ACT-8 manufactured by Tokyo Electron), the following repair film forming composition 1 was spin-coated on a glass wafer having a patterned light-shielding film at 600 rpm for 1 minute, and thereafter A heating film was preheated at 100 ° C. for 2 minutes (pre-baking treatment), and a repair film (thickness: 0.80 μm) was formed so as to bury the periphery of the patterned light-shielding film.

(Composition 1 for repairing film formation)

Organic resin: Cyclomer P (ACA) 230AA (resin manufactured by Daicel Co., Ltd.) 10.96wt%

Surfactant: Megafac F-781F (fluoropolymer surfactant) 0.01wt%

Solvent: PGMEA 89.03wt%

[Confirmation of pattern shape]

A scanning microscope (manufactured by Hitachi High-technologies S4800, observation magnification: 30.0K, acceleration voltage: 2.0keV) was used to confirm the cross-sectional shape of the light-shielding film on which the repaired film was formed.

As shown in FIG. 10, the side etch of the pattern end face is buried by the repair film.

[Etching]

Then, a dry etching apparatus (manufactured by Hitachi High-technologies, U621) was used to perform dry etching treatment under the following conditions to remove the repair film.

After the etching is performed, a post-baking treatment is performed using a clean oven CLH-21CD (III) (Koyo Thermo Systems) in order to harden the repair film. As a condition of the post-baking treatment, the temperature was raised from an initial temperature of 23 ° C to 150 ° C (about 13 minutes) at a heating rate of 10 ° C / min, and after being held at 150 ° C for 1 hour, it was naturally cooled to 40 ° C (the total processing time was about 3 Hours and 30 minutes).

(Dry etching conditions)

Device used: Dry etching chamber using U-621 (chip-on-chip dry etching, ashing device) manufactured by Hitachi High-technologies

Processing parameters

Pressure: 2.0Pa

Gas used: Ar / O ₂ = 500/20 (mL / min)

Processing temperature: 50 ℃

Source power: 800W

Upper bias / electrode bias: 400/400 (W)

Processing time: 300sec

[Confirmation of pattern shape]

A scanning microscope (manufactured by Hitachi High-technologies S4800, observation magnification: 30.0K, acceleration voltage: 2.0 keV) was used to confirm the cross-sectional shape of the light-shielding film after the etching process.

As shown in FIGS. 11 (A) to 11 (B), it was confirmed that the side etch of the pattern end surface disappeared, the light-shielding film became a mask, and the repair film was etched in a vertical shape. In addition, the area to be etched is free from residues, which is good.

[Spectral transmittance measurement, reflectance measurement]

Whether or not the light-shielding film is etched by the etching process is determined based on the transmission spectral characteristics (OD). In addition, the measurement of transmittance is performed using a spectroscope UV4100 (measurement range: 400 nm to 1200 nm) manufactured by Hitachi High-technologies. As shown in FIG. 12, it was confirmed that the transmission and spectral characteristics of the light-shielding film before and after the etching process did not change much, and the hue of the light-shielding film was maintained after the etching process. More specifically, the OD of the light-shielding film before the etching process at a wavelength of 450 nm is 3.0, and the OD of the light-shielding film after the etching process at a wavelength of 450 nm is 3.0.

The reflectance of the light-shielding film before and after the etching process is shown in FIG. 13. The reflectance was measured using a spectroscope UV4100 (measurement angle of incidence: 5 degrees, measurement range: 400 nm to 1200 nm) manufactured by Hitachi High-technologies. Compared with before the etching treatment, the reflection after the etching treatment is further reduced. It is presumed that the organic component in the uppermost layer of the light-shielding film is removed to promote surface roughness. More specifically, the reflectance of the light-shielding film before the etching treatment at a wavelength of 750 nm is 1.4%, and the reflectance of the light-shielding film after the etching treatment at a wavelength of 750 nm is 0.8%.

As described above, it is possible to form a patterned light-shielding film that satisfies OD ≦ 3.0 and reflectivity ≦ 2.0% in a region of 400 nm to 1200 nm.

[Reliability of the pattern]

After obtaining a patterned light-shielding film by the above operations, a reliability test of the patterned light-shielding film is performed. As a result, it turned out that it is a pattern which does not have a problem in terms of reliability.

The reliability test is as follows.

First, as an evaluation of the solvent resistance, the patterned light-shielding film was immersed in a PGMEA solution for 10 minutes. At this time, there was no peeling of the light-shielding film and no deformation of the pattern.

As an evaluation of alkali resistance, the patterned light-shielding film was immersed in an aqueous solution containing 2.38% by mass of tetramethyl ammonium hydroxide (TMAH) for 10 minutes. At this time, there was no peeling of the patterned light-shielding film and no deformation of the pattern.

In addition, as an evaluation of heat resistance, the patterned light-shielding film was subjected to a heat treatment at 260 ° C. for 10 minutes on a hot plate. At this time, there was no change in the patterned light-shielding film.

In addition, as an evaluation of light resistance, 500,000 Lx. h exposure. At this time, the spectral transmittance of the patterned light-shielding film did not change.

In addition, as an evaluation of the cleaning resistance, the patterned light-shielding film was subjected to spin cleaning for 10 minutes (pressure of 50 Pa, nozzle distance of 10 mm, and nozzles were driven at 10 mm / s from one edge to the other edge-edge). At this time, the patterned light-shielding film was not peeled.

In addition, as an evaluation of the abrasion resistance, the patterned light-shielding film was subjected to a rubbing treatment using Bemcot. At this time, no powder was attached to Bemcot, and the patterned light-shielding film was also free of defects.

Claims (12)

A method for producing a pigment dispersion composition, comprising a step of producing a pigment dispersion composition by mixing a first pigment dispersion including a black pigment and a first dispersant and a second pigment dispersion including a black pigment and a second dispersant. And the absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.0 MPa ^1/2 , the SP value represents a solubility parameter measured by the Otsutsu method, wherein The first dispersant and the second dispersant are polymer compounds. The method for producing a pigment dispersion composition according to item 1 of the scope of patent application, wherein any one of the first dispersant and the second dispersant is a polymer compound represented by the general formula (X), The other of the first dispersant and the second dispersant is a polymer compound containing a structural unit having a graft chain, In the general formula (X), R ¹ represents a (m + n) valent linking group; R ² represents a single bond or a linear or branched chain saturated hydrocarbon group having 1 to 20 carbon atoms, and a carbon number of 3 A cyclic saturated hydrocarbon group of ~ 20, an aromatic group having 5 to 20 carbon atoms, a thioether bond, an ester bond, an amine bond, an ether bond, a nitrogen atom and a carbonyl group, or a group of these A combination of two or more groups; A ¹ has at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a cooperating oxygen atom, a group having a basic nitrogen atom, and a phenol group. , Alkyl, aryl, group having an extended alkyloxy chain, fluorenimine, alkyloxycarbonyl, alkylaminocarbonyl, carboxylate, sulfonamido, heterocyclic, alkoxy A monovalent substituent of a group consisting of a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group; n A ¹ and R ² may be the same or different; m represents a positive number of 8 or less, and n represents 1 to 9, m + n satisfies 3 to 10; P ¹ represents a polymer chain; m P ¹ may be the same or different. The method for producing a pigment dispersion composition according to item 2 of the scope of patent application, wherein the structural unit having a graft chain includes one selected from the structural units represented by the following formulae (1) to (4) The above structural unit, In Formulas (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH; X ¹ , X ² , X ³ , X ^4, and X ⁵ each independently represent hydrogen Atomic or C1-C12 alkyl groups; Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent the following (Y-1) to (Y-21) linking group, wherein the structure shown below In the formula, A and B refer to the bonding sites with the left terminal group and the right terminal group in formulas (1) to (4), respectively. ; Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl group Sulfide or amine group; R ³ represents a branched or straight chain alkylene group, R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; n, m, p, and q each independently represent 1 to 500 Integers; j and k each independently represent an integer from 2 to 8; in formula (3), when p is 2 to 500, multiple R ^3s may be the same or different from each other; in formula (4), when When q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same as or different from each other. The method for manufacturing a pigment dispersion composition according to any one of claims 1 to 3, wherein the black pigment is titanium black. The method for producing a pigment dispersion composition according to any one of claims 1 to 3, wherein the absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant is The value exceeds 1.5 MPa ^1/2 . A pigment dispersion composition comprising a black pigment, a first dispersant, and a second dispersant, and an absolute value of a difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.0 MPa ^{1 / 2} , where the SP value represents a solubility parameter measured by the Otsutsu method, and either of the first dispersant and the second dispersant is a polymer compound represented by the general formula (X), and The other of the first dispersant and the second dispersant is a polymer compound containing one or more structural units selected from the structural units represented by the following formulae (1) to (4), In the general formula (X), R ¹ represents a (m + n) valent linking group; R ² represents a single bond or a linear or branched chain saturated hydrocarbon group having 1 to 20 carbon atoms, and a carbon number of 3 A cyclic saturated hydrocarbon group of ~ 20, an aromatic group having 5 to 20 carbon atoms, a thioether bond, an ester bond, an amine bond, an ether bond, a nitrogen atom and a carbonyl group, or a group of these A combination of two or more groups; A ¹ has at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a cooperating oxygen atom, a group having a basic nitrogen atom, and a phenol group. , Alkyl, aryl, group having an extended alkyloxy chain, fluorenimine, alkyloxycarbonyl, alkylaminocarbonyl, carboxylate, sulfonamido, heterocyclic, alkoxy A monovalent substituent of a group consisting of a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group; n A ¹ and R ² may be the same or different; m represents a positive number of 8 or less, and n represents 1 ~ 9, m + n satisfies 3 ~ 10; P ¹ represents a polymer chain; m P ¹ may be the same or different; In Formulas (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH; X ¹ , X ² , X ³ , X ^4, and X ⁵ each independently represent hydrogen Atomic or C1-C12 alkyl groups; Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent the following (Y-1) to (Y-21) linking group, wherein the structure shown below In the formula, A and B refer to the bonding sites with the left terminal group and the right terminal group in formulas (1) to (4), respectively. ; Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl group Sulfide or amine group; R ³ represents a branched or straight chain alkylene group, R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; n, m, p, and q each independently represent 1 to 500 Integers; j and k each independently represent an integer from 2 to 8; in formula (3), when p is 2 to 500, multiple R ^3s may be the same or different from each other; in formula (4), when When q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same as or different from each other. The pigment dispersion composition according to item 6 of the patent application scope, wherein the black pigment is titanium black. The pigment dispersion composition according to claim 6 or claim 7, wherein the absolute value of the difference between the SP value of the first dispersant and the SP value of the second dispersant exceeds 1.5 MPa ^1/2 . A polymerizable composition comprising the pigment dispersion composition according to any one of claims 6 to 8 of the scope of patent application, a polymerizable compound, and a polymerization initiator. The polymerizable composition according to item 9 of the scope of patent application, further comprising a binder polymer having an SP value, the SP value, the SP value of the first dispersant, and the second dispersant. The absolute value of the difference between the SP values of any of the SP values was within 0.5 MPa ^1/2 . A light-shielding film formed by using a polymerizable composition as described in claim 9 or 10 of the scope of patent application. A solid-state imaging device includes the light-shielding film according to item 11 of the scope of patent application.