TW201504372A - Light-shielding composition, light-shielding film and method for producing same - Google Patents

Abstract

A purpose of the invention is to provide a light-shielding composition which may easily form a light-shielding film showing low reflectivity, and a light-shielding film and a method for producing same. The light-shielding composition of the invention at least contains: (A) any one of light-shielding particles and a light-shielding dye; and (B) a filler wherein a particle diameter ranges from 100 nm to 3000 nm. And a content of the filler (B) ranges from 3 mass% to 30 mass% relative to all solid constituents in the light-shielding composition.

Description

Light-shielding composition, light-shielding film and manufacturing method thereof

The present invention relates to a light-shielding composition, a light-shielding film, and a method of producing the same.

In solid-state imaging devices such as Charge Coupled Device (CCD) image sensors or Complementary Metal-Oxide Semiconductor (CMOS) image sensors, noise prevention and image quality are improved. A light shielding film is provided for the purpose.

A light-shielding composition containing a black color material such as carbon black or titanium black is known as a composition for forming a light-shielding film for a solid-state image sensor (Patent Document 1).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-237952

Patent Document 1 discloses that if the disclosed light-shielding composition is used, It can form coating uniformity, good step followability and high temperature. High light fastness and good light shielding film.

On the other hand, as the solid-state imaging device is reduced in size, thickness, and sensitivity, it is required to reduce the reflection of the light-shielding film. In particular, it is industrially preferable as long as the low-reflection light-shielding film as described above can be formed by a spin coating method excellent in productivity.

The present inventors have studied the reflection characteristics of the light-shielding composition specifically disclosed in Patent Document 1, and as a result, it has been found that although the level required by the prior art is satisfied, it does not satisfy the higher level required recently, and further research is required. Improvement.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a light-shielding composition which can easily form a light-shielding film which exhibits low reflectivity.

Another object of the present invention is to provide a light-shielding film formed using the light-shielding composition and a method for producing the same.

The inventors of the present invention conducted active research to achieve the above problems, and as a result, have found that the above problems can be solved by using a composition containing a predetermined component, and the present invention has been completed.

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

(1) A light-shielding composition containing at least one of (A) a light-shielding particle and a light-shielding dye, and (B) a filler having a particle diameter of 100 nm to 3000 nm, and having a light-shielding composition The content of the filler (B) in all the solid components in the product is from 3% by mass to 30% by mass.

(2) The light-shielding composition according to (1), wherein the content of the filler (B) is from 4% by mass to 16% by mass based on the total solid content of the light-shielding composition.

(3) The light-shielding composition according to (1) or (2), further comprising a binder polymer having an acid value of 50 mgKOH/g or less and a weight average molecular weight of 8,000 to 50,000.

(4) The light-shielding composition according to (3), wherein the binder polymer has an acid value of 20 mgKOH/g to 50 mgKOH/g and a weight average molecular weight of 8,000 to 30,000.

(5) A method of producing a light-shielding film, comprising the step of spin-coating the light-shielding composition according to any one of (1) to (4) to form a light-shielding film.

(6) A light-shielding film comprising at least one of (A) one of light-shielding particles and a light-shielding dye, and (B) a filler having a particle diameter of from 100 nm to 3,000 nm, and the content of the filler (B) is at least 3% by mass to 30% by mass.

(7) The light-shielding film according to (6), wherein the reflectance at a wavelength of from 400 nm to 700 nm is 4% or less.

(8) The light-shielding film according to (6) or (7), wherein the surface roughness is from 0.07 μm to 1.55 μm.

(9) A light-shielding composition containing at least one of (A) light-shielding particles and a light-shielding dye, and (C) a binder having an acid value of 50 mgKOH/g or less and a weight average molecular weight of 8,000 to 50,000. Polymer, and with respect to all solid components in the light-shielding composition, the binder polymer The amount is 4% by mass to 30% by mass.

(10) The light-shielding composition according to (9), wherein the content of the binder polymer is from 7 to 30% by mass based on the total solid content of the light-shielding composition.

According to the present invention, it is possible to provide a light-shielding composition which can easily form a light-shielding film which exhibits low reflectivity by a method such as a spin coating method.

Further, according to the present invention, a light shielding film formed using the light-shielding composition and a method for producing the same can be provided.

2, 20, 30, 40‧‧‧ solid camera

3‧‧‧CMOS sensor

4‧‧‧ circuit board

5‧‧‧Ceramic substrate

5a‧‧‧ openings

5b‧‧‧ inner wall

6‧‧‧IR cut filter

6a‧‧‧Incoming surface

7‧‧‧Photographic lens

8‧‧‧ lens holder

9‧‧‧ Keeping the cylinder

11, 21, 31, 41‧‧ ‧ shading film (shading layer)

R1, R2, R3‧‧‧ reflected light

Fig. 1 is a perspective view showing a solid-state imaging device according to a first embodiment.

Fig. 2 is an exploded perspective view of the solid-state imaging device according to the first embodiment.

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

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

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

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

Hereinafter, preferred aspects of the light-shielding composition of the present invention will be described in detail.

First, the feature points of the present invention which are compared with the prior art will be described in detail.

As described above, one of the feature points of the present invention can be exemplified by a predetermined amount of a filler of a predetermined size. By including a filler having a predetermined size, it is easy to form irregularities on the surface of the light-shielding film by a simpler method such as a spin coating method, and a light-shielding film having desired reflection characteristics can be obtained.

Further, other features of the present invention include aspects in which a binder polymer exhibiting a predetermined acid value and a weight average molecular weight is used. When the binder polymer is used, layer separation is likely to occur between the light-shielding particles and the light-shielding dye, and as a result, a light-shielding film having excellent reflection properties is obtained.

In the following, a first embodiment of a solid-state imaging device having a light-shielding film produced by using the light-shielding composition (light-shielding film-forming composition) of the present invention will be described in detail.

As shown in FIGS. 1 and 2, the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state image sensor, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic ceramic substrate 5 on which the circuit board 4 is held. . Further, the solid-state imaging device 2 includes an IR cut filter 6 that is held on the ceramic substrate 5 and cuts off infrared light (IR) toward the CMOS sensor 3, a photographic lens 7, and a lens holder 8 that holds the photographic lens 7. And holding the holding cylinder 9 of the lens holder 8 in a freely movable manner. 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 5a into which the CMOS sensor 3 is inserted, and is formed in a frame shape to surround the side surface of the CMOS sensor 3. In this state, the circuit board 4 on which the CMOS sensor 3 is mounted is fixed by an adhesive (for example, an epoxy-based adhesive, the same below). It is set on the ceramic substrate 5. Various circuit patterns are formed on the circuit board 4.

The IR cut filter 6 forms a reflection film that reflects infrared light on a sheet glass or a blue glass, and the surface on which the reflection film is formed serves as an incident surface 6a. The IR cut filter 6 is formed to have a larger size than the opening 5a, and is fixed to the ceramic substrate 5 by an adhesive so as to cover the opening 5a.

A CMOS sensor 3 is disposed behind the photographic lens 7 (below in FIGS. 2 and 3), and an IR cut filter 6 is disposed between the photographic lens 7 and the CMOS sensor 3. The subject light is incident on the light receiving surface of the CMOS sensor 3 through the photographic lens 7 and the IR cut filter 6. At this time, the infrared light is turned off by the IR cut filter 6.

The circuit board 4 is connected to a control unit provided on an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and electric power is supplied to the solid-state imaging device 2 by the electronic device. The CMOS sensor 3 two-dimensionally arranges a plurality of color pixels on the light-receiving surface, and each color pixel photoelectrically converts the incident light to accumulate the generated signal charges.

As shown in FIGS. 2 and 3, a light shielding film (light shielding layer) 11 for shielding visible light is formed around the entrance surface 6a of the IR cut filter 6 over the periphery. The reflected light (visible light) R1 emitted from the photographic lens 7 and reflected on the front surface (the upper surface in FIGS. 2 and 3) of the ceramic substrate 5 is reflected or refracted in the apparatus and then incident on the CMOS sensor 3 In the case where the reflected light (visible light) R2 emitted from the imaging lens 7 and reflected on the inner wall surface of the lens holder 8 is incident on the CMOS sensor 3, glare or ghosting is caused in the captured image. The light shielding film 11 shields the harmful light such as the reflected light R1 and the reflected light R2 of the CMOS sensor 3. The light shielding film 11 is applied by, for example, a spin coating method or a spray coating method. In addition, in Figures 2 and 3, exaggeration The thickness of the light shielding film 11 is drawn.

Further, the above-described aspect of the solid-state imaging device including the light shielding film of the present invention may be other aspects.

<Light-shielding composition>

Hereinafter, each component which can be contained in the light-shielding composition (hereinafter, simply referred to as "composition") used when forming the light-shielding film 11 will be described in detail.

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

In addition, the term "radiation" as used herein means radiation including visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to the embodiment. In addition, the numerical range represented by "~" in this specification is a range which contains the numerical value of the before and after the "~" as a lower limit and an upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means acrylonitrile group. And methacryl oxime. In addition, in this specification, "single quantity" and "monomer" have the same meaning. The single substance in the present invention is distinguished from the oligomer and the polymer, and the mass average molecular weight is 2,000 or less compounds. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a single amount or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

The first aspect of the light-shielding composition contains at least (A) light-shielding particles and Any one of the light-shielding dyes and (B) a filler having a particle diameter in the range of 100 nm to 3000 nm.

Hereinafter, the components will be described in detail.

((A) Light-shielding particles and light-shielding dyes)

The light-shielding particles and the light-shielding dye (hereinafter collectively referred to as "light-shielding material") used in the present invention preferably have absorption mainly at 800 nm to 1200 nm, and have good light permeability for use in exposure.

In addition, the light-shielding particles and the light-shielding dye in the present invention can be used for any of light-shielding particles and light-shielding dyes having absorption at 800 nm to 1200 nm, but from the viewpoint of heat resistance, light-shielding particles are preferred. . The light-shielding particles are preferably fine particles, and the particle diameter showing the maximum value in the particle size distribution is preferably in the range of 5 nm to 100 nm, more preferably in the range of 5 nm to 50 nm, and still more preferably in the range of 5 nm to 30 nm. When the particle diameter is in the above range, the occurrence of sedimentation of the light-blocking particles decreases with the passage of time, and the composition of the present invention has better stability over time.

The total content of the light-shielding material in the composition is not particularly limited, but in terms of the more excellent reflection property of the light-shielding film, the total content is preferably 30% by mass to 70% based on the total solid content in the composition. The mass% is more preferably 40% by mass to 60% by mass, and particularly preferably 45% by mass to 55% by mass.

In addition, the total solid content is a total mass of a component (for example, a light-shielding material, a binder polymer, and a polymerizable compound) which can constitute a light-shielding film, and does not include a component which does not constitute a film, such as a solvent.

Examples of the dye which can be used as the light-shielding dye include cyanine dye, phthalocyanine dye, naphthalocyanine dye, immonium dye, aminium pigment, and quinoline. A metal complex dye such as a quinolium pigment, a pyrylium pigment, or a Ni complex dye.

Further, from the viewpoint of heat resistance, the light-shielding particles are preferably selected from the group consisting of organic pigments and inorganic pigments, and particularly preferably inorganic pigments.

Examples of the inorganic pigment which can be used as the light-shielding particles include carbon black, titanium black, tungsten compound, zinc oxide, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, and heavy Barytes, minium, iron oxide red, chrome yellow, zinc yellow (zinc yellow, zinc yellow), ultramarine blue ), Prussian blue (potassium ferric ferrocyanide), zircon gray, praseodym yellow, chrome titan yellow, chrome green ), peacock, Victoria green, deep blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, manganese red (manganese pink) ), orange pink, etc., further, a black pigment can be used: comprising selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag One or two or more metal oxides of metal elements, metal nitrides, or a mixture thereof, among the constituent groups.

Among these inorganic pigments, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite, etc. are preferable from the viewpoint of infrared light shielding properties, and among them, at least carbon black and titanium black are preferably contained. 1 kind, especially good for titanium black.

The carbon black may be a carbon black disclosed in Paragraph No. [0020] to Paragraph No. [0024] of JP-A-2006-301101.

The titanium black refers to black particles having a titanium atom. It is preferably a black particle such as a low-valent titanium oxide or a titanium oxynitride. For the purpose of improving dispersibility and suppressing cohesiveness, titanium black may need to be modified on the surface. The coating may be carried out using cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or zirconium oxide, or may be treated with a water-repellent substance as shown in Japanese Laid-Open Patent Publication No. 2007-302836.

The method for producing titanium black includes a method in which a mixture of titanium oxide and titanium metal is heated and reduced in a reducing gas atmosphere (Japanese Patent Laid-Open Publication No. SHO 49-5432); and high temperature hydrolysis by titanium tetrachloride is used. A method for reducing the obtained ultrafine titanium dioxide in a reducing gas atmosphere containing hydrogen (Japanese Patent Laid-Open Publication No. SHO 57-205322); a method of performing high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent Laid-Open) Japanese Laid-Open Patent Publication No. SHO 61-201610, Japanese Patent Application Laid-Open No. 61-201610, and a method of performing high-temperature reduction in the presence of ammonia by attaching a vanadium compound to titanium dioxide or titanium hydroxide (Japanese Patent Laid-Open No. 61-201610) Bulletin, etc.; but is not limited to these methods.

Typically, titanium black is titanium black particles, preferably the primary particle size of each particle is And particles having a small average particle size. Specifically, it is preferably in the range of 10 nm to 45 nm in terms of the average primary particle diameter, and more preferably in the range of 12 nm to 20 nm. Further, the particle diameter in the present invention, that is, the particle diameter, means a 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 is obtained by measuring the area obtained by photographing in an electron microscope photograph and correcting the photographing magnification.

The specific surface area of the titanium black is not particularly limited. However, in order to achieve a predetermined performance of the water repellency after the surface treatment of the titanium black by the water repellent, it is preferable to use Brunauer Emmet and Teller (BET). value is usually measured ^{5m 2 / g ~ 150m 2 /} g, in particular, more preferably ^{20m 2 / g ~ 100m 2 /} g.

Examples of the commercially available product of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name; manufactured by Mitsubishi Materials Co., Ltd.), and Tilack. ) D (trade name; Ako-Sui Chemicals Co., Ltd.) and the like.

For the purpose of improving dispersibility and suppressing cohesiveness, titanium black may need to be modified on the surface of the particles. The modification of the surface of the particles can be carried out by, for example, cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like, and can also be used as shown in Japanese Laid-Open Patent Publication No. 2007-302836. Water-repellent substances are treated.

Further, the composition of the present invention preferably contains titanium black as a dispersion containing titanium black and Si atoms. In this embodiment, titanium black is contained as a dispersion in the composition, and it is preferable that the content ratio of Si atoms to Ti atoms in the dispersion (Si/Ti) is 0.05 to 0.5 in terms of mass, more preferably 0.07~0.4. Here, the said is dispersed The body includes both titanium black as a state of primary particles and titanium black as a state of aggregates (secondary particles).

In addition, when the Si/Ti of the dispersion is too small, when the light-shielding film using the dispersion is patterned by photolithography or the like, it is easy to leave a residue in the removal portion, and if the Si/Ti of the dispersion is excessively large, There is a tendency for the shading ability to decrease.

In order to change the Si/Ti of the dispersion (for example, 0.05 or more), the method as described below can be used. First, a dispersion is obtained by dispersing titanium oxide and cerium oxide particles by using a disperser, and the mixture is subjected to a reduction treatment at a high temperature (for example, 850 ° C to 1000 ° C), whereby titanium black particles can be obtained as a main component. The component contains a dispersion of Si and Ti. The Si/Ti-adjusted titanium black can be produced, for example, by the method described in paragraph number [0005] (6) of JP-A-2008-266045, and paragraph number [0016] to paragraph number [0021] of the above-mentioned publication. .

In the present invention, by adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to an appropriate range (for example, 0.05 or more), the inclusion of the dispersed body is used. When the light-shielding film is formed in the composition of the present invention, the residue derived from the composition outside the formation region of the light-shielding film is reduced. Further, the residue contains a component derived from a composition such as titanium black or a resin component.

In addition, since titanium black is excellent in light-shielding property of light in a wide range of wavelength regions from ultraviolet to infrared, the light-shielding film formed using the dispersion containing titanium black and Si atoms exhibits excellent light-shielding properties.

Further, the content ratio (Si/Ti) of the Si atom to the Ti atom in the dispersion can be, for example, the method described in paragraphs 0054 to 0056 of WO2011/049090. (2-1) or method (2-3) to measure.

Among the dispersions containing titanium black and Si atoms, titanium black can be used. Further, in the dispersion, a composite oxide containing Cu, Fe, Mn, V, Ni or the like, cobalt oxide, iron oxide, carbon black, aniline black may be used for the purpose of adjusting dispersibility, coloring property and the like. One type of the black pigment is used in combination with titanium black or two or more types are combined with titanium black to be used as a dispersion. In this case, it is preferred that the dispersion containing titanium black accounts for 50% by mass or more of the total dispersion.

Further, in the dispersion, for the purpose of adjusting the light blocking property and the like, other coloring agents (organic pigments, dyes, and the like) may be used in combination with the black coloring agent as needed, as long as the effects of the present invention are not impaired.

((B) filler)

The particle size of the filler contained in the composition is from 100 nm to 3,000 nm, and is preferably from 100 nm to 1000 nm, more preferably from 100 nm to 800 nm, even more preferably from 100 nm to 600 nm, in terms of more excellent reflection properties of the light-shielding film.

In the present specification, the particle diameter means an average particle diameter (D50). The particle diameter (average particle diameter (D50)) is defined by the particle size of 50% of the cumulative value when expressed in cumulative (accumulated) volume percentage. More specifically, in the graph (volume-based particle size distribution) in which the horizontal axis represents the particle diameter and the vertical axis represents the cumulative frequency from the small-diameter side, the cumulative value (100%) of all the particles is self-small. The cumulative value of the volume % of the side is 50% and the particle diameter corresponds to D50. A method of measuring the particle size (average particle diameter (D50)) can be performed by using a dynamic light scattering photometer (trade name: DLS7000, manufactured by Otsuka Electronics Co., Ltd.), and the measurement principle is a dynamic light scattering method, and the size distribution analysis method is used as a cumulative amount. law (cumulant method) and / or histogram method to determine.

The content of the filler in the composition is from 3% by mass to 30% by mass based on the total solid content in the composition, and is preferably from 4% by mass to 16% in terms of the more excellent reflection property of the light-shielding film. %, more preferably 7 mass% to 16 mass%. When the content of the filler is less than 3% by mass, the reflection property of the light-shielding film is inferior, and when it exceeds 30% by mass, the light-shielding property of the light-shielding film is inferior.

In addition, the total solid content refers to the total mass of the components constituting the light shielding film described later, and does not include a solvent or the like.

Further, the filler and the light-shielding particles are made of different materials.

The filler may be any of an organic filler, an inorganic filler, and an inorganic-organic composite filler, and these fillers may be used in combination of two or more kinds.

Examples of the organic filler include synthetic resin particles and natural polymer particles, and are preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, and polyamine. Resin particles such as carbamate, polyurea, polyester, polyamine, polyimine, carboxymethylcellulose, gelatin, starch, chitin, chitosan More preferably, it is a resin particle, such as an acrylic resin, polyethylene, a polypropylene, and polystyrene.

Commercially available fillers suitable as organic fillers include, in particular, Chemipearl W100, W200, W300, W308, W310, W400, W401, W4005, W410, W500, WF640, W700, W800 manufactured by Mitsui Chemicals. , W900, W950, WP100, MX-150, MX-180, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-2G, MR-7G, MR-10G, MR-20G, MR-5C, MR-7GC, SX-130H, SX-350H, SX- 500H, SGP-50C, SGP-70C, MBX-5, MBX-8, MBX-12, MBX-15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X- manufactured by Sekisui Chemicals Industrial Co., Ltd. 20, SBX-6, SBX-8, SBX-12, SBX-17 and so on.

Examples of the inorganic filler include metals and metal compounds such as oxides. A composite oxide, a hydroxide, a carbonate, a sulfate, a citrate, a phosphate, a nitride, a carbide, a sulfide, and a composite of at least two or more of these compounds, and specific examples thereof include, for example, Cerium oxide, mica compound, glass, zinc oxide, aluminum oxide, zirconium oxide, tin oxide, potassium titanate, barium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium citrate, magnesium citrate, calcium phosphate, tantalum nitride, titanium nitride, aluminum nitride, tantalum carbide, titanium carbide, Zinc sulfide and a composite of at least two or more of these compounds.

Preferably, it is cerium oxide, mica compound, glass, alumina, potassium titanate, barium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium phosphate, sulfuric acid. Calcium, etc.

Among these inorganic fillers, cerium oxide is preferred. Specific examples of the inorganic filler include cerium oxide filler (manufactured by Admatechs Co., Ltd., SO-C1) (having a particle diameter of 250 nm), cerium oxide filler (manufactured by Yadoma Technology Co., Ltd., SO- C2) (particle size 500nm), cerium oxide filler (made by Yadoma Technology Co., Ltd., SO-C3) (particle size 900nm), cerium oxide filler (made by Yadoma Technology Co., Ltd., SO-C5) (particle size is 1600 nm) and the like.

Examples of the shape of the filler include a fiber shape, a needle shape, a plate shape, a spherical shape, a tetrapod shape, and a balloon shape. Among these shapes, it is preferably spherical.

(other ingredients)

The first aspect of the light-shielding composition may include the light-shielding material and other components other than the filler, and examples thereof include a binder polymer, a dispersant, a solvent, a polymerizable compound, a polymerization initiator, and a sensitization. Agent, polymerization inhibitor, adhesion promoter, surfactant, and the like.

Hereinafter, the arbitrary components will be described in detail.

((C) binder polymer)

In the composition of the present invention, a binder polymer may be further included as needed for the purpose of improving film properties and the like.

The acid value of the binder polymer to be used is preferably 50 mgKOH/g or less, more preferably 20 mgKOH/g to 50 mgKOH/g, and particularly preferably 20 mgKOH/g to 40 mgKOH/g. When it is the said range, the reflection characteristic of a light-shielding film is more excellent. Further, the lower limit of the acid value is not particularly limited, and is preferably 20 mgKOH/g or more from the viewpoint of lithographic performance. Further, as long as the effects of the present invention are not impaired, a binder polymer having an acid value of more than 50 mgKOH/g can be used as the binder polymer. Further, the acid value of the binder polymer is also preferably 30 mgKOH/g or less.

The acid value (unit: mgKOH/g) of the binder polymer in the present invention is the amount (mg) of potassium hydroxide (KOH) required for neutralizing 1 g of the binder polymer. The acid value of the present invention is measured by the method of item 11.1 of JIS K 5407 (1990). The value is fixed.

The weight average molecular weight of the binder polymer is preferably from 8,000 to 50,000, more preferably from 8,000 to 30,000. When it is the said range, the reflection characteristic of a light-shielding film is more excellent. Further, the weight average molecular weight of the binder polymer is also preferably 20,000 or less, and more preferably 15,000 or less.

The method for determining the weight average molecular weight of the binder polymer is carried out by, for example, HPC-8220GPC (manufactured by Tosoh), protective column: TSKguardcolumn Super HZ-L, column: TSKgel SuperHZM- M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, TSKgel SuperHZ2000 are directly connected, and 10 μl of a tetrahydrofuran solution having a column temperature of 40 ° C and a sample concentration of 0.1% by mass is injected, and tetrahydrofuran is used as a dissolution solvent to flow at a flow rate of 0.35 ml per minute. A Refractive Index (RI) detection device detects the peak value of the sample. Further, the weight average molecular weight was calculated using a standard curve prepared using standard polystyrene.

Further, the binder polymer may have a polymerizable group (for example, (meth)acryl fluorenyl group, vinyl group) or the like.

The binder polymer is preferably a linear organic polymer. A well-known polymer can be used arbitrarily for such a "linear organic polymer". It is preferred to select a linear organic polymer which is soluble or swellable to water or alkaline water in order to perform water development or development of alkaline water (preferably weak alkaline water). The linear organic polymer is not only used as a film forming agent, but is also selected for use according to a developing solution (developer) containing water, alkaline water, or an organic solvent. For example, if a water-soluble organic polymer is used, it can be carried out. Water development.

Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho-58- a compound described in Japanese Patent Laid-Open No. Sho 54-95723, Japanese Patent Laid-Open No. Hei. a resin obtained by homopolymerizing or copolymerizing a monomer of a carboxyl group, a homopolymerized or copolymerized monomer having an acid anhydride, and a resin obtained by hydrolyzing or semi-esterifying or semi-esterifying an acid anhydride unit, using an unsaturated monocarboxylic acid and An epoxy acrylate obtained by modifying an epoxy resin with an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like, and examples of the monomer having an acid anhydride Maleic anhydride or the like can be mentioned. Further, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition to this, a compound obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.

In addition, Japanese Patent Laid-Open No. 7-12004, Japanese Patent Special Publication No. 7-120041, Japanese Patent Special Publication No. 7-120042, Japanese Patent Special Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent The acid group-containing urethane-based adhesive polymer described in Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. It is advantageous in terms of low exposure adaptability.

Further, an acetal modification having an acid group described in each of the publications such as European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463 The polyvinyl alcohol-based binder polymer is preferred because it has excellent balance between film strength and developability. Further, in addition to the above, as the water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin or the like is also useful.

In particular, among these compounds, [(meth)acrylic acid benzyl ester / (meth)acrylic acid / optionally other addition polymerizable vinyl monomer] copolymer, and [(meth)acrylic acid allyl ester / ( The methyl methacrylate/other addition polymerizable vinyl monomer as needed is excellent in the balance of film strength, sensitivity, and developability.

The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.

The binder polymer can be synthesized by a conventionally known method. The solvent used in the synthesis may, for example, be tetrahydrofuran, dichloroethane or cyclohexanone. These solvents may be used singly or in combination of two or more. In addition, examples of the radical polymerization initiator used in the synthesis of the binder polymer include known compounds such as an azo initiator and a peroxide initiator.

In the present invention, by using an alkali-soluble resin having a double bond in a side chain as a binder polymer, in particular, both the curability of the exposed portion and the alkali developability of the unexposed portion can be improved. The alkali-soluble resin having a double bond in the side chain has properties such as an acid group for making the resin alkali-soluble and at least one unsaturated double bond in the structure, thereby improving properties such as non-image-removing property. The resin having such a structure is described in detail in Japanese Laid-Open Patent Publication No. 2003-262958, and the resin described therein can be used as a paste. Mixture polymer.

Further, a cardo resin may be used as the binder polymer, preferably selected from the group consisting of epoxy resins, polyester resins, polycarbonate resins, acrylic resins, polyether resins, polyamide resins, and polyurea resins. And a cardo resin having an anthracene skeleton in a group consisting of a polyimide resin. Here, the "cardo resin" refers to a resin having a cardo structure in the molecule (a skeleton structure in which two cyclic structures are bonded to a 4-stage carbon atom constituting a cyclic structure). More specifically, the compound described in paragraph [0046] to paragraph [0057] of JP-A-2011-170334 can be used.

Further, one of the preferable aspects of the binder polymer may be Cyclomer P (ACA) 230AA, 200M, Z250, Z251, Z300, Z320 manufactured by Daicel Chemical Industry Co., Ltd.

In the case where the binder polymer is contained in the composition, the content of the binder polymer in the composition is preferably 4 in terms of the total reflection property of the light-shielding film. The mass % to 30% by mass, more preferably 7 mass% to 30 mass%, and particularly preferably 15 mass% to 25% by mass.

((D) dispersant)

In order to improve the dispersion stability of the light-shielding material (particularly, the light-shielding particles) and the filler (hereinafter collectively referred to as "dispersion"), the composition may contain a dispersant.

The dispersing agent is preferably a dispersing agent of a polymer compound, and more preferably a polymer compound including a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having a graft chain.

Examples of the dispersant include polymer dispersants [for example, polyamidoamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified Poly(meth)acrylate, (meth)acrylic copolymer, fumarate naphthalenesulfonate condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and pigment derivative Wait.

Further, the polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure thereof.

The dispersant acts by being adsorbed on the surface of the dispersoid to prevent re-agglomeration. Therefore, a terminal modified type polymer having a anchor portion of the surface, a graft type polymer, and a block type polymer are preferable.

On the other hand, the adsorption property of the dispersant on the surfaces may be promoted by modifying the surface of the titanium black or the dispersion containing the titanium black and the Si atoms.

The dispersant preferably comprises a structural unit having a graft chain as described above. In addition, in this specification, "structural unit" has the same meaning as "repeating unit". Such a dispersing agent including a structural unit having a graft chain has affinity with a solvent by a graft chain, and thus is excellent in dispersibility of a dispersoid and dispersion stability after passage. Further, since the composition has affinity with a polymerizable compound or other reusable resin or the like by the presence of a graft chain, it is difficult to cause residue in alkali development.

When the graft chain is elongated, the steric repellency effect is improved and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorption force to the dispersoid is lowered, and the dispersibility tends to be lowered. Therefore, the graft chain is preferably a graft chain having a number of atoms other than a hydrogen atom in the range of 40 to 10,000, more preferably a hydrogen atom. The graft chain having an atomic number of 50 to 2000 is particularly preferably a graft chain having a number of atoms other than a hydrogen atom of 60 to 500. Here, the term "graft chain" means the end of the group from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched in the autonomous chain) up to the branch branching on the autonomous chain.

The graft chain preferably has a polymer structure, and examples of such a polymer structure include a polyacrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, a polyurethane structure, and a polyurea structure. , polyamine structure, and polyether structure.

In order to improve the interaction between the graft site and the solvent, thereby improving the dispersibility, the graft chain preferably has at least one selected from the group consisting of a polyester structure, a polyether structure, and a polyacrylate structure. The graft chain 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 as long as it has a substituent reactive with the polymer main chain portion, and it is preferred to use a reactive double bond group. Giant monomer.

Corresponding to the structural unit having a graft chain included in the dispersant, a commercially available macromonomer suitable for use in synthesizing a dispersant can be used: AA-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AA-10 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AB-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AS-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AN-6 (trade name, East Asia) Synthetic (manufactured by the company), AW-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AA-714 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AY-707 (trade name, manufactured by East Asia Synthetic Co., Ltd.) ), AY-714 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AK-5 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AK-30 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AK-32 (trade name, manufactured by East Asia Synthetic Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nippon Oil Co., Ltd.), Bly Blemmer PP-500 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PP-800 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PP-1000 ( Trade name, manufactured by Nippon Oil Co., Ltd., Blemmer 55-PET-800 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PME-4000 (trade name, Nippon Oil ( () manufacturing), Blemmer PSE-400 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PSE-1300 (trade name, manufactured by Nippon Oil Co., Ltd.), Bremer (Blemmer) 43PAPE-600B (trade name, manufactured by Nippon Oil Co., Ltd.). Among them, it is preferred to use: AA-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AA-10 (trade name, East Asian Synthetic Co., Ltd.), AB-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.) , AS-6 (trade name, East Asia Synthetic (Share)), AN-6 (trade name, East Asia Synthetic (Stock) manufacturing), Blemmer PME-4000 (trade name, Nippon Oil Co., Ltd.) Wait.

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

[Chemical 1]

In the formulae (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. From the viewpoint of the restriction on the synthesis, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably independently A hydrogen atom or a methyl group is particularly preferably 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 group is not particularly limited in structure. Specifically, examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups and the like. In the structures shown below, A and B refer to the bonding sites of the left end group and the right end group in the formulas (1) to (4), respectively. Among the structures shown below, it is more preferably (Y-2) or (Y-13) in terms of ease of synthesis.

[Chemical 2]

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, and specific examples thereof include 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. a thioether group, an amine group, and the like. Among these groups, in particular, in view of improving dispersibility, the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably groups having a steric repulsion effect, preferably independently of each other. The alkyl group having 5 to 24 carbon atoms is particularly preferably a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms, respectively.

In the formulas (1) to (4), n, m, p, and q are 1 to 500, respectively. Integer. Further, in the 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 an integer 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, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ^3s may be the same or different.

In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ^{4 is} preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and particularly 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 base is more preferably a linear alkyl group having 1 to 20 carbon atoms, particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In the formula (4), when q is from 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same or different.

The dispersant is preferably in terms of mass, relative to the total mass of the dispersant The amount of the structural unit represented by the formula (1) to the formula (4) is in the range of 10% to 90%, and more preferably in the range of 30% to 70%, including the formula (1) to the formula (4). Structural units. If the structural unit represented by the formula (1) to the formula (4) is included in the range, then The dispersibility of the dispersoid is high, and the developability at the time of forming a light-shielding film is favorable.

Further, the dispersant may include two or more structural units having a graft chain having different structures. In other words, the molecules of the dispersant may include structural units represented by the formulae (1) to (4) having different structures, and n, m, p, and q in the formulas (1) to (4), respectively. In the case of an integer of 2 or more, in the formulas (1) and (2), a structure in which j and k are different from each other may be included in the side chain, and in the formulas (3) and (4), a plurality of molecules exist in the formula. R ³ , R ⁴ and X ⁵ may be the same or different from each other.

From the viewpoint of dispersion stability and developability, represented by the formula (1) The structural unit is more preferably a structural unit represented by the following formula (1A). In addition, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of the dispersion stability and the developability.

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, 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, the preferred range is also the same.

Further, from the viewpoint of dispersion stability and developability, the formula (3) The structural unit represented 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, the preferred range is also the same.

More preferably, the dispersant includes a structural unit represented by the formula (1A) as a structural unit having a graft chain.

The dispersant is preferably in terms of mass, relative to the total mass of the dispersant The amount includes a structural unit having a graft chain in a range of 10% to 90%, and more preferably a structural unit having a graft chain in a range of 30% to 70%. When a structural unit having a graft chain is contained in the range, the dispersibility of the dispersoid is high, and when the light-shielding film is formed Good developability.

Further, the dispersing agent is preferably as described above, and includes a hydrophobic structural unit which is different from the structural unit having a graft chain (that is, does not correspond to a structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, or the like).

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

The dispersing agent preferably comprises, as a hydrophobic structural unit, one or more structural units selected from the structural units derived from the unitary bodies represented by the following general formulae (i) to (iii).

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

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 imido group (-NH-), preferably an oxygen atom.

L is a single bond or a divalent linking group. The divalent linking group may be exemplified by a divalent aliphatic group (for example, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynylene group, a substituted alkynyl group), 2 a valent aromatic group (for example, an aryl group, a substituted aryl group), a divalent heterocyclic group, and the group and an oxygen atom (-O-), a sulfur atom (-S-), an imine group (-NH-), a substituted imido group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group) or a combination of a carbonyl group (-CO-).

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 particularly preferably from 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The number of carbon atoms of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, most preferably from 6 to 10. Further, 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. Other heterocyclic rings, aliphatic rings or aromatic rings may also be condensed on the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thio group (=S), an imido group (=NH), a substituted imido group (=NR ³² , 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 divalent linking group containing a single bond, an alkylene group or an oxygen alkyl group structure. The oxygen-extended alkyl structure is more preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L may comprise a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. The polyoxyalkylene structure is preferably a polyoxyalkylene structure or a polyoxyalkylene structure. The polyoxyalkylene 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 to 10.

Z may be exemplified by an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an extended aryl group, a substituted extended aryl group). a heterocyclic group and the same with an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), a substituted imido group (-NR ³¹ -, here R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group) or a combination of a carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and particularly preferably from 1 to 10. Further, it includes a cyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group (a group including a crosslinked cyclic hydrocarbon ring), and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group, a biphenyl group, a 4-cyclohexylphenyl group, and the like. . Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring. a bicyclic hydrocarbon ring such as a bicyclo [3.2.1] octane ring; and a tricyclic ring [5.2.1.0 ^3,8 ] homobrendane, adamantane, and a tricyclic ring [5.2.1.0 ^{2, 6} ] 3 ring hydrocarbon ring such as decane, tricyclo[4.3.1.1 ^2,5 ] undecane ring; tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, all hydrogen-1, A 4-ring hydrocarbon ring such as a 4-hydrogen-1,4-methano-5 (8-methanonaphthalene ring) or the like. In addition, the cross-linked cyclic hydrocarbon ring also contains a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, and perhydroanthracene. (Perhydroacenaphthene), perhydrofluorene, perhydroindene, perhydrophenalene ring, etc., a condensed ring obtained by condensing a plurality of 5 to 8 membered cycloalkane rings.

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

The number of carbon atoms of the aromatic group is preferably from 6 to 20, particularly preferably from 6 to 15, most Good for 6~10. Further, 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. Among them, 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. Other heterocyclic rings, aliphatic rings or aromatic rings may also be condensed in the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thio group (=S), an imido group (=NH), a substituted imido group (=NR ³² , here R ³² It is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group. Among them, 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 (e.g., fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms, 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, more preferably a hydrogen atom.

In the present invention, the monomeric body represented by the formula (i) is preferably: R ¹ , R ² and R ³ are a hydrogen atom or a methyl group, and L is an alkylene group or an oxygen-containing alkyl group structure. A compound having a valent linking group, wherein X is an oxygen atom or an imido group, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

Further, the unitary body represented by the formula (ii) is preferably: R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group or an aromatic group, and Y A compound that is a methine group. Further, the monomer of the formula (iii) is preferably a compound wherein 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. .

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

Further, specific examples of the radically polymerizable compound include those described in paragraph 0069 to paragraph 0071 of the Japanese Patent Laid-Open Publication No. 2010-106268 (paragraph 0113 to paragraph 0114 of the specification of the corresponding US Patent Application Publication No. 2011-0124824). Definitions, such contents are incorporated in this specification.

Among these radical polymerizable compounds, methacrylate is suitably used. Classes, styrenes, particularly suitable for use: benzyl methacrylate, butyl methacrylate, 4-tert-butyl phenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanoacrylate Phenyl phenyl ester, cyclohexyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, isopropyl methacrylate, methyl methacrylate, methacrylic acid 3,5-dimethyladamantyl ester, 2-naphthyl methacrylate, neopentyl methacrylate, phenyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, styrene , methyl styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxylate Methylstyrene, ethoxylated methylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorobenzene Ethylene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4- Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene.

Further, among the monomeric substances corresponding to the hydrophobic structural unit, the compound having a heterocyclic group may, for example, be a compound shown below.

[Chemical 6]

[Chemistry 7]

The dispersant is preferably in terms of mass, relative to the total mass of the dispersant The amount includes a hydrophobic structural unit in a range of 10% to 90%, and more preferably a hydrophobic structural unit in a range of 20% to 80%.

The dispersant is capable of introducing a functional group that can form an interaction with the dispersoid. Here, the dispersing agent preferably further comprises a knot having a functional group capable of forming an interaction with the dispersing substance. Construction unit. Examples of the functional group capable of forming an interaction with the dispersoid include an acid group, a basic group, a coordinating group, and a reactive functional group.

In the case where the dispersing agent has an acid group, a basic group, a coordinating group, or a reactive functional group, it preferably includes a structural unit having an acid group, a structural unit having a basic group, and a compounding unit. A structural unit of a position or a structural unit having reactivity. In particular, the dispersing agent can impart developability for pattern formation by alkali development to the dispersing agent by using an alkali-soluble group such as a carboxylic acid group as an acid group. That is, the dispersing agent has an alkali solubility by introducing an alkali-soluble group into the dispersing agent. The polymerizable composition containing such a composition is a composition excellent in light blocking properties of the exposed portion, and the alkali developability of the unexposed portion is improved.

In addition, the dispersing agent includes a structural unit having an acid group, and the present component The powder tends to be easily dissolved in the solvent, and the coating property tends to be improved. This is because the acid group in the structural unit having an acid group easily interacts with the dispersing substance, and the dispersing agent stably disperses the dispersing substance.

Wherein, 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 of an alkali-soluble group as an acid group. It is a structural unit different from the hydrophobic structural unit (ie, does not correspond to the hydrophobic structural unit).

As the acid group which can form a functional group which interacts with a dispersoid, for example The carboxylic acid group, the sulfonic acid group, the phosphoric acid group, the phenolic hydroxyl group or the like is preferably at least one of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group, and particularly preferably has a good adsorption force for a dispersoid and a dispersibility thereof. High carboxylic acid group.

That is, the dispersant 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 dispersing agent may include one or more structural units having an acid group. The dispersing agent may contain a structural unit having an acid group or may not contain the structural unit having an acid group, and in the case of containing the structural unit having an acid group, it has an acid in terms of mass, relative to the total mass of the dispersing agent. The content of the structural unit of the group is preferably from 5% to 80%, and more preferably from 10% to 60% from the viewpoint of suppressing damage of image strength due to alkali development.

As a basic group which can form a functional group which interacts with a dispersoid, for example There are a 1-stage amine group, a 2-stage amine group, a 3-stage amine group, a hetero ring containing a N atom, a guanamine group, etc., and a 3-stage amine group which is excellent in the adsorption power to titanium black and has high dispersibility is particularly preferable. The dispersing agent may have one or more of these basic groups.

The dispersing agent may contain a structural unit having a basic group or may not contain the The structural unit having a basic group, in the case of containing the structural unit having a basic group, the content of the structural unit having a basic group is preferably 0.01% to 50 in terms of mass, relative to the total mass of the dispersing agent. % is more preferably 0.01% to 30% from the viewpoint of suppressing the hindrance of the developability.

a coordinating group as a functional group capable of forming an interaction with a dispersoid, Examples of the reactive functional group include an ethenethyloxycarbonyl group, a trialkoxyalkylene group, an isocyanate group, an acid anhydride, and an anthracene chloride. Particularly preferred is an ethyl fluorenyl ethoxy group having a good adsorptivity to a dispersoid and a high dispersibility. The dispersing agent may have one or more of these groups.

The dispersing agent may contain a structural unit having a coordinating group or contain The structural unit of the reactive functional group may not contain the structural unit, and in the case of containing the structural unit, the content of the structural unit is preferably 10 in terms of mass, relative to the total mass of the dispersing agent. % to 80% is more preferably 20% to 60% from the viewpoint of suppressing the hindrance of the developability.

The dispersant of the present invention has a graftable chain in addition to a graft chain. In the case where the bulk forms an interacting functional group, there is no particular limitation on how to introduce the functional groups, and the dispersing agent preferably has a single selected from the following formulas (iv) to (vi). One or more structural units in the structural unit of the volume.

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 or a bromine atom), or a carbon atom of 1~. 6 alkyl.

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and are preferably independently represented by each other. A hydrogen atom or a methyl group. In the formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

X ₁ in the formula (iv) represents an oxygen atom (-O-) or an imido group (-NH-), preferably an oxygen atom. Further, Y in the formula (v) represents a methine group or a nitrogen atom.

Further, L ₁ in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkyne group). a divalent aromatic group (for example, an extended aryl group, and a substituted aryl group), a divalent heterocyclic group, and the group and an oxygen atom (-O-), a sulfur atom (-S-) , an imido group (-NH-), a substituted imine bond (-NR ³¹ '-, where R ³¹ 'is an aliphatic group, an aromatic group or a heterocyclic group) or a carbonyl bond (-CO-) One or more combinations or the like.

Further, the definitions of the divalent aliphatic group, the divalent aromatic group, and the divalent heterocyclic group have the same meanings as the definition of each group represented by the above L.

In addition, the preferred aspect of L _{1 has} the same meaning as the preferred aspect of L.

In the general formulae (iv) to (vi), Z ₁ represents a functional group which can form an interaction with a dispersoid other than the graft site, and is preferably a carboxylic acid group, a tertiary amino group, and more preferably a carboxylic acid group. .

In the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms, -Z ₁ , or -L ₁ -Z ₁ . Here, L ₁ and Z ₁ have the same meanings as the above-mentioned L ₁ and Z ₁ , and preferred examples are also the same. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the present invention, the unitary body represented by the formula (iv) is preferably such 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 an oxygen-containing alkyl group structure. A divalent linking group, wherein X is an oxygen atom or an imine group, and Z is a compound of a carboxylic acid group.

Further, the monomer of the formula (v) is preferably a compound wherein 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.

Further, the unitary body represented by the formula (vi) is preferably such that R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z is a carboxylic acid group. compound of.

Hereinafter, the single-quantity represented by the general formula (iv) to the general formula (vi) is shown. A representative example of the compound). Examples of the monolith are methacrylic acid, crotonic acid, methacrylic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in a molecule and a phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, and tetrahydroxyphthalic anhydride; a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride Reaction product, reaction of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, anti Butenedioic acid, 4-vinylbenzoic acid, vinyl phenol, 4-hydroxyphenylmethacrylamide, and the like.

Interaction with dispersoids, dispersion stability, and developer From the viewpoint of permeability, the content of the functional group capable of forming an interaction with the dispersant is preferably from 0.05% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, based on the total mass of the dispersing agent. Good is 10% by mass to 70% by mass.

Further, for the purpose of improving performance such as image strength, as long as it does not damage According to the effects of the present invention, the dispersant may further include other structural units having various functions different from the structural unit having a graft chain, the hydrophobic structural unit, and the structural unit having a functional group capable of forming an interaction with the dispersed substance ( For example, a structural unit containing a functional group having affinity with a dispersion medium used in the dispersion).

Examples of such other structural units include structural units derived from a radically polymerizable compound selected from the group consisting of acrylonitriles and methacrylonitriles.

The dispersing agent may be used alone or in combination of two or more kinds of the other structural units, and the content of the other structural units is preferably from 0% to 80%, particularly preferably 10, based on the total mass of the dispersing agent. %~60%. When the content is within the above range, sufficient pattern formability is maintained.

The acid value of the dispersant is preferably from 0 mgKOH/g to 160 mgKOH/g. The range is more preferably in the range of 10 mgKOH/g to 140 mgKOH/g, and particularly preferably in the range of 20 mgKOH/g to 120 mgKOH/g. The acid value of the dispersant is also preferably more than 30 mgKOH/g.

When the acid value of the dispersant is 160 mgKOH/g or less, pattern peeling at the time of development at the time of forming a light-shielding film can be more effectively suppressed. In addition, when the acid value of the dispersant is 10 mgKOH/g or more, the alkali developability is further improved. In addition, when the acid value of the dispersant is 20 mgKOH/g or more, sedimentation of titanium black or a dispersion containing titanium black and Si atoms can be further suppressed, and the number of coarse particles can be further reduced, and the composition can be further improved. Time stability.

The acid value of the dispersant can be calculated, for example, from the average content of the acid groups in the dispersant. Further, by changing the content of the acid group-containing structural unit in the dispersant, a resin having a desired acid value can be obtained.

When a light-shielding film is formed, pattern peeling and developability at the time of development are suppressed The weight average molecular weight of the dispersant is preferably 4,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000, in terms of polystyrene equivalent value by a gel permeation chromatography (GPC) method. In the following, it is particularly preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less. The weight average molecular weight of the dispersant is also preferably more than 15,000, and more preferably more than 20,000.

The GPC method is based on the following method: using HLC-8020GPC (manufactured by Tosoh Corporation), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as a column, and using tetrahydrofuran (tetrahydrofuran, THF) as a solution.

Specific examples of the dispersing agent are shown below, but the present invention is not limited to these. Specific examples. In addition, among the following exemplified compounds, the numerical value (the numerical value collectively described in the main chain repeating unit) which is described in each structural unit is the content of the structural unit [described as mass %: (wt%)]. The numerical value described in the repeated portion of the side chain together indicates the number of repetitions of the repeated portion.

[Chemistry 9]

[化10]

[11]

In addition to the above, specific examples of the dispersing agent can also be cited: BYK Chemical "Disperbyk-161, 162, 163, 164, 165, 166, 170 (trade name, polymer copolymer)", manufactured by BYK Chemie, EFKA EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane), EFKA 4330, 4340 (trade name, block copolymer), etc. . These dispersing agents may be used singly or in combination of two or more.

When the dispersant is contained in the composition, the content of the dispersant in the composition is preferably 1% by mass based on the total solid content of the composition in terms of the dispersion stability of the dispersoid or the like. ~90% by mass, more preferably 3% by mass to 70% by mass.

((E) solvent)

The composition of the present invention may also contain a solvent.

The kind of the solvent is not particularly limited, and is preferably an organic solvent.

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether , ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl azine, Γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate or the like, but is not limited to these compounds.

The solvent may be used singly or in combination of two or more. In the case where two or more solvents are used in combination, it is particularly preferred to include a 3-ethoxy group selected from the group consisting of Methyl propyl propionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate Two or more of 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

When the solvent is contained in the composition, the content of the solvent contained in the composition is not particularly limited, and is preferably 10% by mass to 80% by mass, and more preferably 20% by mass based on the total mass of the composition. 70% by mass, particularly preferably 30% by mass to 65% by mass.

((F) polymerizable compound)

The composition of the present invention may contain a 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 more at normal pressure.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at normal pressure include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(methyl). Monofunctional acrylate or methacrylate such as acrylate or phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate , neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate Addition of an epoxy resin to a polyfunctional alcohol, such as trimethylolpropane tris(propylene methoxypropyl)ether, tris(propylene methoxyethyl) isocyanurate, glycerin or trimethylolethane a compound obtained by (meth)acrylation after ethane or propylene oxide, pentaerythritol or dipentaerythritol is subjected to poly(meth) propylene The urethane amides described in each of the publications of Japanese Patent Publication No. Sho-48-41708, Japanese Patent Publication No. Sho-50-6034, and Japanese Patent Laid-Open Publication No. SHO-51-37193, Japanese Patent No. Polyester acrylates described in each of the publications of Japanese Patent Publication No. Sho-49-43191, Japanese Patent Publication No. SHO-52-30490, and the reaction product of an epoxy resin and (meth)acrylic acid A multifunctional acrylate or methacrylate such as an epoxy acrylate. Further, a compound which is described as a photocurable monomer and an oligomer in "Japan Next Society Association", Vol. 20, No. 7, page 300 to page 308 can also be used.

Further, a compound described in the general formula (1) and the general formula (2) together with a specific example thereof, which is an ethylene oxide added to a polyfunctional alcohol, may be used in JP-A-10-62986. Or propylene oxide is obtained by (meth)acrylation.

Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which an acryl fluorenyl group of these compounds is bonded to dipentaerythritol via an ethylene glycol or a propylene glycol residue are preferable. Oligomer types of these compounds can also be used.

Among the above-mentioned polymerizable compounds, NK ester (NK Ester) A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd., Light Acrylate DCP-A manufactured by Kyoei Chemical Co., Ltd., 3-functional As a tetrafunctional mixture, Aronix M-305 and M-510 manufactured by Toagosei Co., Ltd., and a 4-functional compound can be exemplified by KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd. NK Ester A-TMMT manufactured by Nakamura Chemical Co., Ltd., 5 A mixture of a functional group and a hexafunctional compound is exemplified by KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., and the 6-member functional group is KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. NK Ester A-DPH-12E manufactured by the company.

In addition, as disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open The urethane urethanes described in each of the publications of Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. A urethane compound having an ethylene oxide skeleton described in each of the publications of Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also suitable. In addition, an amine-based structure or a thioether structure is described in each of the molecules described in each of the publications of JP-A-63-277653, JP-A-63-260909, and JP-A-10-1-5238. As the addition polymerizable compound, a photopolymerizable composition having a very excellent photospeed can be obtained. Commercially available products include: urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemical Co., Ltd.), UA-7200 (trade name, manufactured 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) and so on.

In addition, ethylenically unsaturated compounds having an acid group are also suitable, and are commercially available. Examples of the product include a carboxyl group-containing trifunctional acrylate TO-756 manufactured by Toagosei Co., Ltd., and a carboxyl group-containing 5-functional acrylate TO-1382.

The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate. Compound.

One type of the polymerizable compound may be used alone or two or more types may be used in combination. When two or more types of polymerizable compounds are used in combination, the combined form can be appropriately set depending on the physical properties required for the polymerizable composition and the like. One of the preferable combinations of the polymerizable compounds is, for example, a combination of two or more kinds of polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds, and another example thereof is dipentaerythritol hexaacrylate. A combination of pentaerythritol triacrylate.

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

((G) polymerization initiator)

The composition of the present invention may contain a polymerization initiator (preferably a photopolymerization initiator).

The polymerization initiator is a compound which is decomposed by light or heat to initiate and accelerate the polymerization of the polymerizable compound, and is preferably a compound which absorbs light in a region having a wavelength of 300 nm to 500 nm.

Specific examples of the polymerization initiator include an organic halogenated compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an organic peroxidation compound, an azo compound, a coumarin compound, an azide compound, and a metallocene compound. An organoboric acid compound, a disulfonic acid compound, an anthraquinone compound (particularly an oxime ester compound), an onium salt compound, and a mercaptophosphine (oxide) compound. More specific examples include the polymerization start described in paragraph number [0081] to paragraph number [0100], paragraph number [0101] to paragraph number [0139] of JP-A-2006-78749. Agent. Among the polymerization initiators, from the viewpoint of improving the shape of the obtained pattern, a ruthenium compound (particularly an oxime ester compound) is more preferable. The hydrazine compound is preferably IRGACURE OXE01 and OXE02 manufactured by BASF. OXE01 and OXE02 achieve the same effect.

When the polymerization initiator is contained in the composition, the content of the polymerization initiator in the composition is preferably from 0.1% by mass to 30% by mass, more preferably 1% by mass based on the total solid content of the composition. ~25% by mass, particularly preferably 2% by mass to 20% by mass.

((H) sensitizer)

The composition of the present invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength.

The sensitizer is preferably a compound which sensitizes the polymerization initiator used by an electron transfer mechanism or an energy transfer mechanism. Preferable examples of the sensitizer include the compounds described in Paragraph No. [0085] to Paragraph No. [0098] of JP-A-2008-214395.

When the sensitizer is contained in the composition, the content of the sensitizer is preferably from 0.1% by mass to 30% by mass based on the total solid content of the composition from the viewpoint of sensitivity and storage stability. It is 1% by mass to 20% by mass, and particularly preferably 2% by mass to 15% by mass.

((I) polymerization inhibitor)

In order to prevent unwanted thermal polymerization of the polymerizable compound during or during storage of the composition of the present invention, the composition of the present invention preferably contains a small amount of a polymerization inhibitor.

As the polymerization inhibitor, a known thermal polymerization inhibitor can be used, and specific examples thereof include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, and pyrogallol. , t-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'- Methylene bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine sulfonium salt, and the like.

The content of the polymerization inhibitor is preferably from about 0.01% by mass to about 5% by mass based on the total solid content of the composition.

Further, in order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or decyl behenate may be added, and higher fatty acid derivatives may be biased in the drying process after coating. The surface of the coated film. The amount of the higher fatty acid derivative added is preferably from about 0.5% by mass to about 10% by mass based on the total composition.

((J) Adhesion Promoter)

In order to improve the adhesion to a hard surface such as a support, the composition of the present invention may contain an adhesion promoter. Examples of the adhesion promoter include a decane coupling agent, a titanium coupling agent, and the like.

The decane coupling agent is preferably: γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-acryloxypropyltrimethoxy. Decane, γ-acryloxypropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, phenyltrimethoxydecane, more preferably γ- Methyl propylene methoxy propyl trimethoxy decane.

In the case where the adhesion promoter is included in the composition, relative to the composition The content of all the solid components and the adhesion promoter is preferably from 0.5% by mass to 30% by mass, more preferably from 0.7% by mass to 20% by mass.

((K) surfactant)

In the composition of the present invention, various surfactants can be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, since the composition of the present invention contains a fluorine-based surfactant, the liquid characteristics (particularly fluidity) when the coating liquid is prepared are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved. In other words, when a film is formed using a coating liquid using a composition containing a fluorine-based surfactant, the interface tension between the surface to be coated and the coating liquid is lowered to improve the surface to be coated. Wettability improves the coating property on the surface to be coated. Therefore, it is effective in the case where a film having a thickness of about several μm is formed in a small amount of liquid, and a film having a uniform thickness having a small thickness unevenness can be more suitably formed.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass. % is more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. Meijia Method (Megafac) F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Meijiafa (Megafac) F482, Megafac F554, Megafac F780, Megafac F781 (above by Di Aisheng (DIC)), Fluorad FC430, Vlad (Fluorad) FC431, Fluorad FC171 (above Sumitomo 3M (share)), Surflon S-382, Surflon SC-101, Surflon SC -103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383 , Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass).

Specific examples of the nonionic surfactant include glycerin and trimethylol Propane, trimethylolethane and their ethoxylates and propoxylates (eg glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic, 304, 701, 704, 901, 904, 150R1, Sol, manufactured by BASF Solsperse 20000 (made by Lubrizol, Japan) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name; EFKA-745, manufactured by Morishita Industries Co., Ltd.), and polymerization of an organic siloxane. KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.) , W001 (Yu Shang (share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusei Co., Ltd.).

Examples of the fluorenone-based surfactants include: Toray Silicone DC3PA, Toray Silicone SH7PA, and Toray Silicone DC11PA. "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF" manufactured by Momentive Performance Materials -4452" "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemical Co., Ltd., etc.

The surfactant may be used alone or in combination of two or more. When the surfactant is contained in the composition, the content 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 based on the total mass of the composition.

The preparation aspect of the composition of the present invention is not particularly limited, and for example, Preparing the light-shielding material, the filler, and the solvent by using a mixer, a homogenizer, a high-pressure emulsion device, a wet pulverizer, or a wet disperser, etc., However, it is not limited to this method. The dispersion treatment can also be carried out by two or more dispersion treatments (multistage dispersion).

In the above, the first aspect of the composition of the present invention has been described. In the second aspect of the composition of the present invention, the light-shielding composition comprising at least one of (A) the light-shielding particles and the light-shielding dye, and (C) the acid value of 50 mgKOH/ a binder polymer having a weight average molecular weight of 8,000 to 50,000 and a binder polymer of 4% by mass to 30% by mass (preferably 7 mass%) based on the total solid content of the light-shielding composition. ~30% by mass). In the case of this composition, a light-shielding film excellent in reflection characteristics is obtained.

<shading film>

The light shielding film of the present invention is formed using the composition. That is, the light-shielding composition is used to form a light-shielding film.

The film thickness of the light-shielding film is not particularly limited, but it is preferably 0.2 μm to 50 μm, more preferably 0.5 μm to 30 μm, in terms of the film thickness after drying, in terms of the light-reflecting film. It is 0.7 μm to 20 μm.

In the case where the light-shielding film is in the form of a pattern, the size (the length of one side) is preferably from 0.001 mm to 5 mm, more preferably from 0.05 mm to 4 mm, in terms of obtaining the effect of the present invention more effectively. It is 0.1mm~3.5mm.

The reflectance of the light-shielding film is not particularly limited, and is preferably 4% or less, and more preferably 2% or less in terms of the effects of the present invention. The lower limit is not particularly limited and may be 0%.

Further, the method of measuring the reflectance of the light-shielding film is to block the light as the object to be measured. The film was irradiated with light having a wavelength of 400 nm to 700 nm at an incident angle of 5°, and the reflectance was measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

The surface roughness (Ra) of the light-shielding film is not particularly limited, and is preferably from 0.07 μm to 1.55 μm, more preferably from 0.08 μm to 1.3 μm, from the viewpoint of further excellent reflection properties of the light-shielding film.

Further, the surface roughness of the light-shielding film was measured using a stylus type film thickness meter DEKTAK150 (manufactured by VEECO).

<Method of Manufacturing Light-Shielding Film>

Next, a method of producing the light-shielding film of the present invention will be described.

The method for producing the light-shielding film of the present invention is not particularly limited, and preferably includes the step of applying the composition onto a predetermined support and, if necessary, performing a curing treatment to form a light-shielding film.

The method of applying the composition is not particularly limited, and various applications such as spin coating, spray coating, slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing, and the like can be applied. The coating method is preferably a spin coating method (spin coating) in terms of excellent productivity.

The method of the hardening treatment is not particularly limited, and a light irradiation treatment or a heat treatment is usually performed.

Further, as a method of manufacturing the light shielding film 11 described in FIG. 1, it is preferred. In the case where the polymerizable compound is contained in the composition, a method comprising the steps of applying the composition of the present invention to the incident surface 6a of the IR cut filter 6 to form a composition layer may be mentioned. (hereinafter referred to as "the composition layer" a forming step "), a step of exposing the composition layer via a mask (hereinafter, simply referred to as "exposure step"), and a step of developing the exposed composition layer to form a colored pattern (hereinafter suitably Referred to as "development step").

More specifically, the composition layer of the present invention can be applied to the incident surface 6a of the IR cut filter 6 directly or via another layer to form a composition layer (component layer forming step), which is predetermined The mask pattern is exposed, and only the portion of the coating film irradiated with light is cured (exposure step), and development is carried out by a developing solution (development step) to form a pattern-like light-shielding film.

Hereinafter, each step of the preferred embodiment will be described.

[Composition layer formation step]

In the composition layer forming step, the composition of the present invention is applied onto the incident surface 6a of the IR cut filter 6 to form a light-shielding film 11 as a polymerizable composition layer.

On the incident surface 6a of the IR cut filter 6, an undercoat layer may be provided in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or flatten the surface of the substrate, as needed.

The method of applying the composition of the present invention to the incident surface 6a of the IR cut filter 6 can be exemplified.

The composition applied to the incident surface 6a of the IR cut filter 6 is preferably dried at 70 ° C to 110 ° C for 2 minutes to 4 minutes to form a composition layer.

[Exposure step]

In the exposure step, the composition layer formed in the composition layer forming step is exposed through a mask, and only the portion of the coating film irradiated with light is cured. The exposure is preferably performed by irradiation of radiation, and radiation which can be used for exposure is particularly preferably an ultraviolet ray such as g-ray, h-ray or i-ray, and more preferably a high-pressure mercury lamp. The irradiation intensity is preferably ⁵ mJ/cm ² to 1500 mJ/cm ² , more preferably 10 mJ/cm ² to 1000 mJ/cm ² , and most preferably 10 mJ/cm ² to 800 mJ/cm ² .

[Development Step]

After the exposure step, an alkali development treatment (development step) is performed to dissolve the unexposed portion of the light in the exposure step in the alkaline aqueous solution. Thereby, only the photohardened portion remains. The developer is preferably an organic alkali developer. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, and sodium metasilicate, which are inorganic developing solutions, and ammonia as an organic alkali developing solution. Amine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]- An alkaline aqueous solution obtained by dissolving a basic compound such as 7-undecene so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution. Further, in the case of using a developer containing such an aqueous alkaline solution, it is usually washed (rinsed) with pure water after development.

Further, in the method of manufacturing the light-shielding film 11 of the present invention, after the composition layer forming step, the exposing step, and the developing step, the formed light-shielding film may be optionally included by heating and/or exposure. A hardening step of hardening is performed. When it is hardened by heating, it is washed with pure water and then heated. The plate was subjected to a hardening treatment at 200 ° C for 5 minutes.

As described above, the solid-state imaging device including the light-shielding film of the present invention is not limited to the aspect of FIG.

FIG. 4 shows a solid-state imaging device 20 according to the second embodiment. 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 description thereof will be 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 photographic lens 7, a lens holder 8, and a holding cylinder 9. A light shielding film (light shielding layer) 21 is formed on the side end surface of the IR cut filter 6 over the periphery. When the reflected light R3 emitted from the photographic lens 7 and reflected on the front surface of the ceramic substrate 5 is reflected or refracted repeatedly in the apparatus and is incident on the CMOS sensor 3, glare is generated in the photographic image. The light shielding film 21 shields harmful light such as the reflected light R3 toward the COMS sensor 3.

FIG. 5 shows a solid-state imaging device 30 according to the third embodiment. 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 description thereof will be 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 photographic lens 7, a lens holder 8, and a holding cylinder 9. A light shielding film (light shielding layer) 31 is formed on the end portion and the side end surface of the incident surface 6a of the IR cut filter 6 over the periphery. In other words, the first embodiment and the second embodiment are combined. In the first embodiment and the second embodiment, since the light-shielding performance is improved, the production of glare or ghost is surely suppressed. Health.

Fig. 6 shows a solid-state imaging device 40 according to a fourth embodiment. In addition, right 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 description thereof will be omitted.

The solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographic lens 7, a lens holder 8, and a holding cylinder 9. A light shielding film (light shielding layer) 31 is formed on the end portion and the side end surface of the incident surface 6a of the IR cut filter 6 over the periphery.

Further, a light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5. When the reflected light reflected from the imaging lens 7 and reflected by the IR cut filter 6 on the inner wall surface of the ceramic substrate 5 is incident on the CMOS sensor 3, the photographic image is caused to emit glare. Since the light shielding film 41 is improved in light shielding performance from the inner wall surface of the ceramic substrate 5, the generation of glare is surely suppressed.

[Examples]

Hereinafter, the present invention will be specifically described, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In addition, "part" "%" is a quality standard unless otherwise specified. In addition, room temperature means 25 °C.

<Synthesis of Specific Resin 1>

Using the same method as in the paragraph 0349 of JP-A-2012-237952, 200 g of a solid precursor M1 [structure described below] was obtained. By ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear Magnetic Resonance,} 1 H-NMR), IR, mass spectrometry identified as M1. Further, in the following formula, n is 20.

Precursor M1 (50.0g), NK ester (NK Ester) CB-1 (2- Methyl propylene methoxyethyl phthalate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (30.0 g), benzyl methacrylate (20.0 g), dodecyl mercaptan (2.3 g), and propylene glycol Methyl ether acetate (233.3 g) was introduced into a three-necked flask which was replaced with nitrogen, and stirred with a stirrer (New East Science Co., Ltd.: Three-One Motor), and nitrogen gas was poured into the flask. The temperature was raised to 75 ° C while heating. 0.2 g of 2,2-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred under heating at 75 ° C for 2 hours. After 2 hours, 0.2 g of V-65 was further added, and after heating and stirring for 3 hours, a 30% solution of the specific resin 1 was obtained.

The composition ratio of the specific resin 1 below is X = 20, Y = 30, Z = 50, the number of atoms of the graft chain other than the hydrogen atom = 257, the acid value = 40 mgKOH/g, and the weight average molecular weight is 30,000.

[Chemical 13] Specific Resin 1

<Preparation of titanium black dispersion> -Manufacture of titanium black A-1 -

Titanium oxide MT-150A (trade name; manufactured by Tayca Co., Ltd.) having a particle size of 15 nm and a particle size of 300 m ² /g of erbium dioxide particles AEROPERL (registered trademark) 300/30 (manufactured by Evonik) 25 g, and dispersing agent Disperbyk 190 (trade name; manufactured by BYK Chemical Co., Ltd.) 100 g, and ion-exchanged water 71 g, using KURABO The manufactured MAZERSTAR KK-400W was treated at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm for 20 minutes, thereby obtaining a uniform aqueous mixture solution. The aqueous solution was filled in a quartz vessel, and heated to 920 ° C in an oxygen atmosphere using a rotary kiln (manufactured by Motoyama Co., Ltd.), and the ambient gas was replaced with nitrogen gas at the temperature. Ammonia gas was passed through at 100 mL/min for 5 hours, thereby performing a nitrogen reduction treatment. The powder recovered after completion was pulverized in a mortar to obtain Titanium Black A-1 (dispersion containing titanium black particles and Si atoms) having a silicon atom and having a specific surface area of 73 m ² /g.

<Preparation of titanium black dispersion>

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

(composition 1)

. Titanium black (A-1)...25 parts obtained in the manner described

. Specific resin 1 propylene glycol monomethyl ether acetate 30% by mass solution...25 parts

. Propylene glycol monomethyl ether acetate (PGMEA) (solvent)...50 parts

The obtained dispersion a was subjected to dispersion treatment under the following conditions using a superabrasive machine (Ultra Apex Mill) UAM015 manufactured by Shou Industrial Co., Ltd. to obtain Titanium Black Dispersion 1.

(dispersion condition)

. Bead diameter: Φ0.05mm

. Bead filling rate: 75% by volume

. Grinding machine peripheral speed: 8m/sec

. The amount of the mixture to be dispersed: 500 g

. Circulating flow (pump supply): 13kg / hour

. Treatment liquid temperature: 25 ° C ~ 30 ° C

. Cooling water: tap water

. Bead grinding machine annular passage internal volume: 0.15L

. Passes: 90 times

<Preparation of cerium oxide particle dispersion 2a>

31 parts by mass of cerium oxide filler (manufactured by Yadoma Technology Co., Ltd., SO-C1) (particle size: 250 nm), Cyclomer P (ACA) 230AA (large Daicel Cytec (shares), solid content 54%, acid value (mgKOH/g): 21.0, weight average molecular weight: 14000) 58 parts by mass and hexamethoxymethyl melamine 11 parts by mass after premixing A cerium oxide particle dispersion was prepared by using a motor mill M-50 (manufactured by Eiger Co., Ltd.) using zirconia beads having a diameter of 1.0 mm and dispersing at a peripheral speed of 9 m/s for 1.5 hours. 2a.

<Preparation of cerium oxide particle dispersion 2b>

In the preparation of the cerium oxide particle dispersion 2a, in addition to the cerium oxide filler (manufactured by Yadoma Technology Co., Ltd., SO-C1) (particle size: 250 nm) is replaced with cerium oxide filler (Adamma Technology Co., Ltd.) The cerium oxide particle dispersion 2b was obtained in the same manner as in the preparation of the cerium oxide particle dispersion 2a except for the production of SO-C2) (having a particle diameter of 500 nm).

<Preparation of cerium oxide particle dispersion 2c>

In the preparation of the cerium oxide particle dispersion 2a, in addition to the cerium oxide filler (manufactured by Yadoma Technology Co., Ltd., SO-C1) (particle size: 250 nm) is replaced with cerium oxide filler (Adamma Technology Co., Ltd.) The cerium oxide particle dispersion 2c was obtained in the same manner as in the preparation of the cerium oxide particle dispersion 2a except for the production of SO-C3) (particle diameter: 900 nm).

<Preparation of cerium oxide particle dispersion 2d>

In the preparation of the cerium oxide particle dispersion 2a, in addition to the cerium oxide filler (manufactured by Yadoma Technology Co., Ltd., SO-C1) (particle size: 250 nm) is replaced with cerium oxide filler (Adamma Technology Co., Ltd.) In addition to the production of SO-C5) (particle diameter: 1600 nm), cerium oxide particles were obtained in the same manner as in the preparation of cerium oxide particle dispersion 2a. Dispersion 2d.

<Comparative Example 1>

Comparative composition 1 was prepared by mixing the following components using a stirrer. Further, the comparative composition 1 did not contain a predetermined filler and a binder polymer having an acid value of 50 mgKOH/g or less.

(solid content: 40% propylene glycol monomethyl ether acetate solution, composition ratio: benzyl methacrylate / acrylic acid copolymer = 80 / 20 (% by mass), acid value (mgKOH / g): 112.8, weight average molecular weight: 30000, binder polymer)

<Example 1>

The light-shielding composition 1 was prepared by mixing the following components with a stirrer.

(solid content: 40% propylene glycol monomethyl ether acetate solution, composition ratio: benzyl methacrylate / acrylic acid copolymer = 80 / 20 (% by mass), acid value (mgKOH / g): 112.8, weight average molecular weight: 30000, binder polymer)

<Example 2>

The light-shielding composition 2 was prepared by mixing the following components with a stirrer.

<Example 3>

3.4 parts by mass of Cyclomer P (ACA) 230AA (adhesive polymer; solid content 54%) manufactured by Daicel Chemical Industries Co., Ltd. was further added to the light-shielding composition 2. A light-shielding composition 3 was prepared.

<Comparative Example 2>

Comparative composition 2 was prepared by mixing the following components with a stirrer. Further, the comparative composition 2 did not contain a predetermined filler and a binder polymer having an acid value of 50 mgKOH/g or less.

(solid content: 40% propylene glycol monomethyl ether acetate solution, composition ratio: benzyl methacrylate / acrylic acid copolymer = 80 / 20 (% by mass), acid value (mg KOH / g): 112.8, weight average molecular weight: 30000, binder polymer)

<Example 4>

The light-shielding composition 4 was prepared by adding 5.6 parts by mass of the cerium oxide particle dispersion 2a to the comparative composition 2.

<Example 5>

The light-shielding composition 5 was prepared by adding 11.3 parts by mass of the cerium oxide particle dispersion 2a to the comparative composition 2.

<Example 6>

The light-shielding composition 6 was prepared by adding 19.2 parts by mass of the cerium oxide particle dispersion 2a to the comparative composition 2.

<Example 7>

The light-shielding composition 7 was prepared by adding 29.6 parts by mass of the cerium oxide particle dispersion 2a to the comparative composition 2.

<Example 8>

The light-shielding composition 8 was prepared by adding 29.6 parts by mass of the cerium oxide particle dispersion 2b to the comparative composition 2.

<Example 9>

The light-shielding composition 9 was prepared by adding 29.6 parts by mass of the cerium oxide particle dispersion 2c to the comparative composition 2.

<Example 10>

The light-shielding composition 10 was prepared by adding 29.6 parts by mass of the cerium oxide particle dispersion 2d to the comparative composition 2.

<Production of shading film>

Any one of the light-shielding composition 1 to the light-shielding composition 10 or the comparative composition 1 to the comparative composition 2 produced by the spin coating method is applied to the incident of the IR cut filter 6 shown in FIG. 2 . On the surface 6a, heat treatment (prebaking) was then performed for 120 seconds using a hot plate at 100 ° C, thereby forming a coating film having a dry film thickness of 1.5 μm. The rotation conditions of the spin coating at this time were set as follows: First step: rotation at 300 rpm for 5 seconds, and second step: rotation at 1000 rpm 20 times. Then, using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon), an island pattern mask having a pattern of 2 μm square was used at a wavelength of 365 nm at 1000 mJ/cm ² . The exposure is exposed.

Then, the IR cut filter 6 formed with the irradiated coating film is placed on the rotation. On a horizontal rotating table of a shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), a 0.3% aqueous solution of tetramethylammonium hydroxide was used, and a liquid-repellent development was carried out at 23 ° C for 90 seconds.

Then, the IR cut filter 6 on which the coating film was formed was fixed to the horizontal rotary table by a vacuum chuck, and the IR cut filter 6 was rotated at a rotation speed of 50 rpm by a rotating device, and self-discharged from above the center of rotation thereof. The nozzle is supplied with pure water in a shower form to perform rinsing treatment, and further washed with pure water, and then hardened at 200 ° C for 5 minutes on a hot plate to form a light-shielding film on the incident surface 6 a of the IR cut filter 6 . 11.

<Evaluation of reflectance>

On the incident surface 6a of the IR cut filter 6, light of 400 nm to 700 nm is incident on the light-shielding film 11 at an incident angle of 5°, and the reflectance is measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Co., Ltd. based on the following criteria. Conduct an evaluation.

"1": The case where the reflectance is 1% or less

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

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

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

"5": When the reflectance exceeds 4%

<Evaluation of Surface Roughness>

The surface roughness of the light-shielding film 11 was measured using the stylus type film thickness meter DEKTAK150 (manufactured by Veeco Co., Ltd.) on the incident surface 6a of the IR cut filter 6.

The "particle size" in Table 1 means the size of the filler.

The content of the binder polymer and the filler in Table 1 corresponds to the content (% by mass) relative to the total solid content in the light-shielding composition. Further, these contents are the same as those in the light-shielding film.

As shown in Table 1, when the light-shielding composition of the present invention was used, the obtained light-shielding film showed low reflectance.

On the other hand, in Comparative Example 1 and Comparative Example 2 which do not contain a predetermined component, the reflection characteristics of the light-shielding film were inferior.

2‧‧‧Solid camera

3‧‧‧CMOS sensor

4‧‧‧ circuit board

5‧‧‧Ceramic substrate

6‧‧‧IR cut filter

6a‧‧‧Incoming surface

7‧‧‧Photographic lens

8‧‧‧ lens holder

9‧‧‧ Keeping the cylinder

11‧‧‧Shade film (shading layer)

R1, R2‧‧‧ reflected light

Claims (10)

A light-shielding composition containing at least one of (A) a light-shielding particle and a light-shielding dye, and (B) a filler having a particle diameter of 100 nm to 3000 nm, and the light-shielding composition The content of the filler (B) in all the solid components is from 3% by mass to 30% by mass. The light-shielding composition according to the first aspect of the invention, wherein the content of the filler (B) is from 4% by mass to 16% by mass based on the total solid content of the light-shielding composition. The light-shielding composition according to claim 1 or 2, further comprising a binder polymer having an acid value of 50 mgKOH/g or less and a weight average molecular weight of 8,000 to 50,000. The light-shielding composition according to claim 3, wherein the binder polymer has an acid value of 20 mgKOH/g to 50 mgKOH/g and a weight average molecular weight of 8,000 to 30,000. A method for producing a light-shielding film, comprising the step of spin-coating a light-shielding composition according to any one of claims 1 to 4 to form a light-shielding film. A light-shielding film containing at least one of (A) one of light-shielding particles and a light-shielding dye, and (B) a filler having a particle diameter of from 100 nm to 3,000 nm, and the content of the filler (B) is three Mass%~30% by mass. The light-shielding film according to claim 6, wherein the reflectance at a wavelength of 400 nm to 700 nm is 4% or less. The light-shielding film according to Item 6 or Item 7 of the patent application has a surface roughness of 0.07 μm to 1.55 μm. A light-shielding composition containing at least one of (A) light-shielding particles and a light-shielding dye, and (C) a binder polymer having an acid value of 50 mgKOH/g or less and a weight average molecular weight of 8,000 to 50,000. Further, the content of the binder polymer is from 4% by mass to 30% by mass based on the total solid content of the light-shielding composition. The light-shielding composition according to claim 9, wherein the content of the binder polymer is from 7 to 30% by mass based on the total solid content of the light-shielding composition.