JP5689691B2 - Titanium black dispersion, photosensitive resin composition, light shielding film, method for producing the same, and solid-state imaging device - Google Patents

Description

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

  A solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor is provided with a light shielding film for the purpose of preventing noise generation and improving image quality.

As a composition for forming a light-shielding film for a solid-state imaging device, a photosensitive resin composition containing a black color material such as carbon black or titanium black is known.
Specifically, for the purpose of improving optical density or the like, a photosensitive resin composition containing titanium black having a specific X-ray diffraction peak intensity ratio (for example, see Patent Documents 1 and 2), a specific nitrogen concentration, A photosensitive resin composition containing titanium black having a specific crystallite size (for example, see Patent Documents 3 to 5) has been studied.

  In addition, a composition for forming a light-shielding film containing titanium black and a resin component has been disclosed for the purpose of obtaining high light-shielding properties with a thin film (see, for example, Patent Document 6).

Japanese Patent No. 3724269 International Publication No. 2005/037926 Pamphlet JP 2006-182627 A JP 2006-206871 A JP 2006-209102 A JP 2007-115921 A

In recent years, with the downsizing, thinning, and high sensitivity of solid-state imaging devices, there is a demand for shielding infrared light incident on the silicon substrate from the other surface side of the silicon substrate having the imaging device portion on one surface. It is getting stronger.
The reason is that the silicon substrate, which is the base of the solid-state image sensor, exhibits a high transmittance for infrared light. Furthermore, the image sensor provided in the solid-state image sensor is not only for visible light but also for infrared light. This is because the sensitivity is also shown.

Under such circumstances, a light-shielding film using carbon black has high infrared light transmittance, so it is difficult to say that the above requirement is satisfied. In contrast, a light-shielding film using titanium black is suitable as a light-shielding film that satisfies the above requirements because it has a low infrared light transmittance and an excellent infrared light-shielding ability.
However, when the light-shielding film is formed using a dispersion or photosensitive resin composition containing titanium black, the residue derived from the photosensitive resin composition outside the region where the light-shielding film is formed remains. It became clear that it was easy.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a photosensitive resin composition capable of forming a light-shielding film having excellent infrared light-shielding ability and reducing residues outside the formation region of the light-shielding film when the light-shielding film is formed. And providing a titanium black dispersion used in the photosensitive resin composition.
Another object of the present invention is to provide a light-shielding film excellent in infrared light-shielding ability, and to form a light-shielding film excellent in infrared light-shielding ability. It is an object of the present invention to provide a method for manufacturing a light-shielding film that can reduce residue outside the region.
Another object of the present invention is to provide a solid-state imaging device in which noise due to infrared light is reduced and noise due to residue is reduced.

Means for solving the above-mentioned problems are as follows.
<1> containing (A) titanium black particles, (B) a dispersant, and (C) an organic solvent,
90% or more of the dispersion of (A) titanium black particles has a particle size of 30 nm or less,
On the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes have a image sensor portion to one surface to the other surface, patterned such that at least a portion of the metal electrode is exposed A titanium black dispersion used for forming a light-shielding film that is provided and shields infrared light.
<2> The titanium black dispersion according to <1>, wherein 95% or more of the (A) titanium black particles to be dispersed have a particle size of 30 nm or less.
<3> The titanium black dispersion according to <1> or <2>, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound.
< 4 > The titanium black according to any one of <1> to <3>, wherein the dispersant is a graft copolymer having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. Dispersion.

< 5 > The titanium black dispersion according to < 4 >, wherein the graft copolymer includes at least a structural unit represented by any of the following formulas (1) to (4).

In [Equation (1) to ^{(4), W 1, W} 2, W 3, and ^{W 4} each independently represent an oxygen atom or ^{NH, X 1, X 2,} X 3, X 4, and ^{X 5} Each independently represents a hydrogen atom or a monovalent organic group, Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a monovalent organic group. R ³ represents a branched or straight chain alkylene group. R ⁴ represents a hydrogen atom or a monovalent organic group, the R ⁴ may be mixed different structures R ⁴ in the copolymer. n, m, p, and q are each an integer of 1 to 500. j and k each independently represents an integer of 2 to 8. ]

< 6 > The structural unit represented by any one of the formulas (1) to (4) is 10% to 90% in terms of mass with respect to the total mass of the graft copolymer. The titanium black dispersion according to < 5 >, which is contained in the range of
< 7 > The titanium black dispersion according to any one of <1> to < 6 >, (D) a photopolymerizable compound, and (E) a photopolymerization initiator,
On the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes have a image sensor portion to one surface to the other surface, patterned such that at least a portion of the metal electrode is exposed A photosensitive resin composition used for forming a light-shielding film that is provided and shields infrared light.
<8> The photosensitive resin composition according to <7>, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound.
<9> on the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes into a closed and the other surface of the image pickup device unit on one surface, a photosensitive resin composition according to <7> A light-shielding film formed by using an object and patterned so that at least a part of the metal electrode is exposed .
<10> The light shielding film according to <9>, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound.
<11> according to <7> The photosensitive resin composition, the other silicon substrate having the image pickup device unit and electrically connected to the metal electrodes have a image sensor portion to one surface to the other surface A step of coating the surface to form a photosensitive layer, a step of exposing the photosensitive layer in a pattern, and a pattern in which at least a part of the metal electrode is exposed by developing the photosensitive layer after exposure. Forming the light shielding film.
<12> The method for producing a light-shielding film according to <11>, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound.
<13> The method for producing a light shielding film according to <11>, wherein the metal electrode is made of Cu or a Cu compound.

< 14 > a silicon substrate having an image sensor portion on one surface;
A metal electrode provided on the other surface of the silicon substrate and electrically connected to the imaging element unit;
The light shielding film according to < 9 >, provided on the surface of the silicon substrate on which the metal electrode is provided, and patterned so that at least a part of the metal electrode is exposed;
Solid-state image pickup device that have a.
<15> The solid-state imaging device according to <14>, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound.
<16> The solid-state imaging device according to <14>, wherein the metal electrode is made of Cu or a Cu compound.

According to the present invention, it is possible to provide a photosensitive resin composition that can form a light-shielding film having excellent infrared light-shielding ability, and that can reduce residues outside the formation region of the light-shielding film when the light-shielding film is formed. And the titanium black dispersion used for this photosensitive resin composition can be provided.
In addition, according to the present invention, it is possible to provide a light shielding film excellent in infrared light shielding ability, and to form a light shielding film excellent in infrared light shielding ability. It is possible to provide a method for manufacturing a light-shielding film that can reduce residue outside the region.
In addition, according to the present invention, it is possible to provide a solid-state imaging device in which noise due to infrared light is reduced and noise due to residue is reduced.

It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor which concerns on an example of this invention. It is a schematic sectional drawing of the solid-state image sensor which concerns on an example of this invention. It is a schematic sectional drawing of the board | substrate A used in Example 2 and Comparative Example 2. FIG. 2 is a schematic cross-sectional view showing a state where a light shielding film is formed on a substrate A. FIG. 6 is a schematic cross-sectional view of a substrate B used in Example 3 and Comparative Example 3. FIG. 4 is a schematic cross-sectional view showing a state where a light shielding film is formed on a substrate B. FIG.

≪Titanium black dispersion and photosensitive resin composition≫
The titanium black dispersion of the present invention contains (A) titanium black particles, (B) a dispersant, and (C) an organic solvent, and 90% or more of the dispersion made of the (A) titanium black particles is 30 nm. This titanium black dispersion has the following particle size and is used for forming a light-shielding film that is provided on the other surface of a silicon substrate having an image sensor portion on one surface and shields infrared light.
Moreover, the photosensitive resin composition of the present invention contains the titanium black dispersion of the present invention, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, and has an image pickup element portion on one surface. It is a photosensitive resin composition used for forming a light shielding film that is provided on the other surface of a silicon substrate and shields infrared light.

In recent years, with the downsizing, thinning, and high sensitivity of solid-state imaging devices, the other surface of the silicon substrate having the imaging device portion on one surface (hereinafter also referred to as “first main surface” or “front surface”) is provided. There is an increasing demand for shielding infrared light incident on the silicon substrate from the side of the surface (hereinafter also referred to as “second main surface” or “back surface”). A light-shielding film using titanium black is suitable as a light-shielding film that satisfies the above requirements because of its excellent infrared shielding ability.
However, as a result of the study by the present inventors, when a light shielding film is formed using a dispersion or a photosensitive resin composition containing titanium black, a residue derived from the photosensitive resin composition outside the formation region of the light shielding film is present. It became clear that it was easy to remain. The reason why the residue is likely to remain is not clear, but it is presumed that the titanium black particles have a property of being easily settled with time and the titanium black particles have a property of being easily coarsened.
Therefore, as a result of further studies, the present inventor forms a light-shielding film using a titanium black dispersion or a photosensitive resin composition in which 90% or more of the dispersions made of titanium black particles have a particle size of 30 nm or less. Thus, the present inventors have found that this residue can be reduced while maintaining the infrared shielding ability of titanium black, and completed the present invention.

Therefore, according to the titanium black dispersion and the photosensitive resin composition of the present invention, it is possible to form a light-shielding film having excellent infrared light-shielding ability, and in the formation of the light-shielding film, residues outside the light-shielding film formation region Can be reduced.
Here, “infrared” refers to a wavelength region of 700 nm to 1200 nm.
Further, “shielding infrared light” refers to a state where the transmittance is 10% or less over the entire wavelength region of 700 nm to 1200 nm.
Furthermore, according to the titanium black dispersion and the photosensitive resin composition of the present invention, the curability (pattern formability) of the light shielding film is also improved when the light shielding film is formed.
The reason why the curability is improved is not clear, but 90% or more of the dispersion made of titanium black particles has a particle size of 30 nm or less, so that the ultraviolet light used for curing in the formed light shielding film. This is presumed to be because the ultraviolet light can be easily propagated in the film thickness direction. However, the present invention is not limited by this assumption.

Further, in this specification, the imaging element unit refers to a region where a plurality of imaging elements (CCD, CMOS, etc.) are arranged (for example, in a matrix).
In the present specification, a silicon substrate provided with an image sensor section is sometimes referred to as a “solid-state image sensor” or a “solid-state image sensor substrate”. In the solid-state imaging device, other elements (color filter, microlens, etc.) may be further formed.

  Hereinafter, each component contained in the titanium black dispersion or the photosensitive resin composition of the present invention will be sequentially described.

(A) Titanium black particles The titanium black dispersion and photosensitive resin composition of the present invention contain titanium black particles.
The titanium black particles are contained as a dispersion in the dispersion. In the present invention, 90% or more of the dispersion made of titanium black particles needs to have a particle size of 30 nm or less.
In the present invention, the particle size of the dispersed material means the particle diameter of the dispersed material, and the particle diameter is the diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.

  Here, the “dispersed body composed of titanium black particles” in the present invention includes both those in which the titanium black particles are in the state of primary particles and those in the state of the aggregates (secondary particles).

  The photosensitive resin composition of this invention contains the to-be-dispersed body which consists of a titanium black particle originating in the titanium black dispersion of this invention. 90% or more of the photosensitive resin composition and a dispersion made of titanium black particles contained in a cured film (light-shielding film) obtained by curing the photosensitive resin composition have a particle size of 30 nm or less. It is.

In the present invention, 90% or more of the dispersion of titanium black particles has a particle size of 30 nm or less, so that when the light shielding film is formed using the photosensitive resin composition of the present invention, Residues derived from the photosensitive resin composition outside the formation region are reduced. The residue includes components derived from the photosensitive resin composition such as titanium black particles and resin components.
The reason why the residue is reduced is not yet clear, but the dispersed material having a small particle size contributes to the improvement of the removability of the uncured photosensitive resin composition (particularly titanium black particles) in the formation of the light shielding film. I guess because.

  Titanium black particles have excellent light blocking properties for light in a wide wavelength range from ultraviolet to infrared. In particular, the titanium black particles have excellent light blocking properties for infrared light (infrared light blocking properties). The light-shielding film formed using the product or the photosensitive resin composition exhibits excellent infrared light-shielding properties.

  In order to determine whether 90% of the dispersion to be contained in the titanium black dispersion or photosensitive resin composition of the present invention has a particle size of 30 nm or less, the following method (1) is used. Use.

  In addition, about 90% of the dispersion to be contained in the cured film (light-shielding film) obtained by curing the photosensitive resin composition of the present invention, it is judged whether or not it has a particle size of 30 nm or less. Uses the method (2) shown below.

<Method (1)>
A titanium black dispersion or a photosensitive resin composition is diluted 500 times with propylene glycol monomethyl ether acetate (hereinafter also abbreviated as PGMEA), dropped onto a carbon thin film and dried to form using a dropping electron microscope. Take an observation picture. From the obtained photograph, the projected area of the outer surface is obtained for 400 particles, the diameter of the circle corresponding to this area is calculated, and the frequency distribution is evaluated.

<Method (2)>
Using a scanning electron microscope (S-3400N (trade name) manufactured by Hitachi High-Technologies Corporation) and an energy dispersive X-ray analyzer (Genesis (trade name) manufactured by EDAX) A morphological observation photograph and an element map of Ti and Si are taken. From the obtained photograph, the projected area of the outer surface is obtained for 400 particles in which Ti element is detected, the diameter of a circle corresponding to this area is calculated, and the frequency distribution is evaluated.

Hereinafter, the titanium black particles will be described in more detail.
In the present invention, the titanium black particles are black particles having titanium atoms, and preferably black particles such as low-order titanium oxide and titanium oxynitride.

  The titanium black particles can be modified on the particle surface as necessary for the purpose of improving dispersibility and suppressing aggregation. As the modification of the particle surface, for example, coating treatment with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like is possible. Treatment with an aqueous material is also possible.

  Examples of commercially available titanium black particles include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Examples include Tilac D (trade name: manufactured by Ako Kasei Co., Ltd.).

As a method for producing titanium black particles, a mixture of titanium dioxide and metal titanium is heated in a reducing atmosphere for reduction (a method described in JP-A-49-5432), or obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing the obtained ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (a method described in JP-A-57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (JP-A No. 57-305322) (Methods described in JP-A-60-65069 and JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (JP-A 61-201610). However, the method is not limited to these.
The titanium black particles applied to the present invention preferably have a small primary particle size.

  The titanium black dispersion and the photosensitive resin composition of the present invention may contain only one type of (A) titanium black particles, or may contain two or more types.

  Further, as long as the effects of the present invention are not impaired, the composite oxide such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, You may use together as a to-be-dispersed body, combining the black pigment which consists of carbon black, aniline black, etc. 1 type, or 2 or more types. In this case, it is preferable that 50% by mass or more of the dispersion is occupied by the dispersion made of titanium black particles.

  Further, as will be described later, other colorants (such as organic pigments and dyes) may be used in combination with the titanium black particles, if desired, for the purpose of adjusting the light shielding property and the like, as long as the effects of the present invention are not impaired. .

The content of (A) titanium black particles in the titanium black dispersion is preferably 5% by mass to 60% by mass and more preferably 10% by mass to 50% by mass with respect to the total mass of the dispersion. preferable.
Moreover, it is preferable that content of (A) titanium black particle in the photosensitive resin composition is 2.5 mass%-30 mass% with respect to the total mass of a dispersion, and 5 mass%-20 mass%. More preferably

(B) Dispersant The titanium black dispersion and the photosensitive resin composition of the present invention contain a dispersant.
The dispersant in the present invention includes a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meta ) Acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The dispersant in the present invention can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to its structure.

The dispersant in the present invention acts to adsorb on the surface of a dispersion such as titanium black particles and a pigment used in combination, if desired, and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the dispersant in the present invention has an effect of promoting the adsorption of the dispersed resin by modifying the surface of the dispersion.

Specific examples of the dispersant that can be used in the present invention include “Disperbyk-101 (trade name, polyamidoamine phosphate), 107 (trade name, carboxylic acid ester), 110 (trade name, containing acid group) manufactured by BYK Chemie. Copolymer)), 130 (trade name, polyamide), 161, 162, 163, 164, 165, 166, 170, 180 (trade name, polymer copolymer) "," BYK-P104, P105 (trade name, High molecular weight unsaturated polycarboxylic acid), “EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane), EFKA 4330, 4340 (trade name, block copolymer), 4400, 4402 (trade name, modified) manufactured by EFKA Polyacrylate), 5010 (trade name, polyester amide), 5765 (trade name, high molecular weight polycal) Bonate), 6220 (trade name, fatty acid polyester), 6745 (trade name, phthalocyanine derivative), 6750 (trade name, azo pigment derivative) "," Ajisper PB821, PB822 (trade name) manufactured by Ajinomoto Fine Techno Co., Ltd. " “Kyoeisha Chemical Co., Ltd.” “Floren TG-710 (trade name, urethane oligomer)”, “Polyflow No. 50E, No. 300 (trade name, acrylic copolymer)”, “Enomoto Kasei Co., Ltd.” Disparon KS-860, 873SN, 874, # 2150 (trade name, aliphatic polycarboxylic acid), # 7004 (trade name, polyether ester), DA-703-50, DA-705, DA-725 (trade name) ) ”,“ Demol RN, N (trade name, naphthalenesulfonic acid formalin polycondensate) ”manufactured by Kao Corporation, MS, C, SN− (Trade name, aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (trade name, polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (trade name, polyoxyethylene nonylphenyl) Ether) ”,“ acetamine 86 (trade name, stearylamine acetate) ”,“ Solsperse 5000 (trade name, phthalocyanine derivative) ”, 22000 (trade name, azo pigment derivative), 13240 (trade name, polyesteramine) manufactured by Lubrizol. 3000, 17000, 27000 (trade name, polymer having a functional part at the end), 24000, 28000, 32000, 38500 (trade name, graft type polymer) ", Nikko Chemical's" Nikkor T106 (trade name, Polyoxyethylene sorbitan monooleate), MY -IEX (trade name, polyoxyethylene monostearate) ", and the like. Also included are amphoteric dispersants such as Hinoact T-8000E (trade name) manufactured by Kawaken Fine Chemicals.
These dispersants may be used alone or in combination of two or more.

The acid value of the dispersant is preferably in the range of 5.0 mgKOH / g to 200 mgKOH / g, more preferably in the range of 10 mgKOH / g to 150 mgKOH / g, still more preferably in the range of 60 mgKOH / g to 150 mgKOH / g. Range.
When the acid value of the dispersant is 200 mgKOH / g or less, pattern peeling during development when forming the light-shielding film is more effectively suppressed. Moreover, if the acid value of a dispersing agent is 5.0 mgKOH / g or more, alkali developability will become more favorable. Further, if the acid value of the dispersant is 60 mgKOH / g or more, the precipitation of titanium black particles can be further suppressed, the number of coarse particles can be reduced, and the time stability of the titanium black dispersion or the photosensitive resin composition can be reduced. Can be improved.

  In the present invention, the acid value of the dispersant can be calculated from, for example, the average content of acid groups in the dispersant. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which is a structural component of a dispersing agent.

  The weight average molecular weight of the dispersant in the present invention is preferably 10,000 or more and 300,000 or less, and preferably 15,000 or more, from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. It is more preferably 200,000 or less, further preferably 20,000 or more and 100,000 or less, and particularly preferably 25,000 or more and 50,000 or less. In addition, the weight average molecular weight of a dispersing agent can be measured by GPC, for example.

(Graft copolymer)
In the present invention, it is also preferable to use a graft copolymer (hereinafter also referred to as “specific resin”) as a dispersant. Dispersibility and storage stability can be further improved by using a graft copolymer as a dispersant.

As the graft copolymer, those having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 are preferable. The graft chain in this case refers to a portion from the base of the main chain of the copolymer to the end of the group branched from the main chain.
This specific resin is a dispersion resin capable of imparting dispersibility to the titanium black particles, and has excellent dispersibility and affinity with the solvent due to the graft chain. Excellent dispersion stability. Moreover, when it is set as the photosensitive resin composition, since it has affinity with a polymerizable compound or other resins that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.

Further, by introducing an alkali-soluble partial structure such as a carboxylic acid group into this specific resin, a function as a resin imparting developability can be imparted for pattern formation by alkali development.
Therefore, by introducing an alkali-soluble partial structure into the graft copolymer, the dispersion resin itself essential for the dispersion of titanium black particles in the titanium black dispersion of the present invention has alkali solubility. The photosensitive resin composition containing such a titanium black dispersion has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.

  When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to titanium black is lowered and the dispersibility is lowered. For this reason, as the graft copolymer used in the present invention, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, and the hydrogen atoms per graft chain are excluded. The number of atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms per graft chain is more preferably 60 to 500.

  Examples of the polymer structure of the graft chain include poly (meth) acryl, polyester, polyurethane, polyurea, polyamide, polyether and the like. The graft chain is preferably a graft chain having poly (meth) acryl, polyester, or polyether in order to improve the interaction between the graft site and the solvent and thereby increase dispersibility. A graft chain having a polyether is more preferable.

  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 capable of reacting with the polymer main chain portion and satisfies the requirements of the present invention. A macromonomer having a reactive double bond group can be preferably used.

  As a commercially available macromonomer suitably used for the synthesis of the specific resin, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 ( Product name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.) AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (trade name, manufactured by Toa Gosei Co., Ltd.), BLEMMER PP-100 (Trade name, manufactured by NOF Corporation), BLEMMER PP-500 (trade name, manufactured by NOF Corporation), BLEMMER PP-800 (trade name, manufactured by NOF Corporation), BLEMMER PP-1 00 (trade name, manufactured by NOF Corporation), BREMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BREMMER PME-4000 (trade name, manufactured by NOF Corporation), Blemmer PSE- 400 (trade name, manufactured by NOF Corporation), BLEMMER PSE-1300 (trade name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation), and the like are used. Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) are preferable. ), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is done.

  The graft site in the specific resin preferably includes at least a structural unit represented by any of the following formulas (1) to (4), and at least includes the following formula (1A), the following formula (2A), and the following formula It is more preferable that the structural unit represented by either (3A), the following formula (3B), or the following (4) is included.

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

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

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and are represented by Z ^{1 to} Z ^3. As the organic group, an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms is preferable, and among them, an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms is particularly preferable. An alkoxy group having a cyclic alkyl group having 5 to 24 carbon atoms is preferred. The organic group represented by Z ⁴ each preferably an alkyl group having 5 to 24 carbon atoms independently, among them, each independently of 5 to 24 carbon atoms branched alkyl group or cyclic carbon atoms 5-24 Alkyl groups are preferred.

In Formula (1)-Formula (4), n, m, p, and q are integers of 1-500, respectively.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

R ³ in the formula (3) represents a branched or straight chain alkylene group. R ³ in Formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
R ⁴ in the formula (4) represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ in formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ in Formula (4) is an alkyl group, the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a carbon number having 5 to 20 carbon atoms. Are preferable, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. Further, as R ⁴ in the formula (4), two or more types of R ⁴ having different structures may be mixed and used in the specific resin.

  In the specific resin, the structural units represented by the formulas (1) to (4) are preferably contained in a range of 10% to 90%, in terms of mass, with respect to the total mass of the specific resin, 30% to 70%. It is more preferable that it is contained in the range of%. When the structural units represented by the formulas (1) to (4) are included within this range, the dispersibility of the titanium black particles is high and the developability when forming the light-shielding film is good.

  Further, the specific resin can contain two or more types of graft copolymers having different structures.

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

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n, the equation (1) is ^{X 1,} Y 1, synonymous with ^{Z 1} and n in, and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m is the formula (2) have the same meanings as ^{X 2,} Y 2, ^{Z 2} and m in the preferred range is also the same.

  The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoints of dispersion stability and developability.

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

  The specific resin is more preferably one having a structural unit represented by the formula (1A).

A functional group capable of forming an interaction with the titanium black particles can be introduced into the specific resin in addition to the graft site.
Examples of functional groups capable of forming an interaction with the titanium black particles include, for example, acid groups, basic groups, coordinating groups, reactive functional groups, and the like. Introduced using a structural unit having a basic group, a structural unit having a basic group, a structural unit having a coordinating group, or a structural unit having reactivity.

Examples of acid groups that are functional groups capable of interacting with titanium black particles include, for example, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, and the like. This is a carboxylic acid group having a good adsorbing power and high dispersibility. The specific resin can use one or more of these acid groups.
Such introduction of an acid group also has an advantage of improving the alkali developability of the specific resin.

  When introduced into the specific resin as a copolymerization component, the preferred content of the structural unit having an acid group is 0.1 mol% or more and 50 mol% or less, particularly preferably, with respect to all the structural units in the specific resin. From the viewpoint of suppressing damage to the image strength due to alkali development, it is 1 mol% or more and 30 mol% or less.

Examples of basic groups that are functional groups capable of interacting with titanium black particles include, for example, primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, amides Particularly preferred are tertiary amino groups that have good adsorptive power to pigments and high dispersibility. One or more of these basic groups can be introduced into the specific resin.
When introduced into the specific resin as a copolymerization component, the preferred content of the structural unit having a basic group is 0.01 mol% or more and 50 mol% or less, particularly preferably based on all structural units in the specific resin. Is from 0.01 mol% to 30 mol% from the viewpoint of inhibiting developability inhibition.

Examples of the coordinating group, which is a functional group capable of forming an interaction with the titanium black particle, and the reactive group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride and the like. Is mentioned. Particularly preferred is an acetylacetoxy group which has a good adsorptive power to the pigment and a high dispersibility. The specific resin may have one or more of these groups.
A suitable content of the structural unit having a basic group or a reactive structural unit that can be introduced as the specific resin copolymerization component is 0.5 mol% or more and 50 mol% or less with respect to all the structural units in the specific resin. Yes, and particularly preferably from 1 mol% to 30 mol% from the standpoint of inhibiting developability inhibition.

  When the specific resin in the present invention has a functional group capable of interacting with titanium black particles in addition to the graft site, it contains a functional group capable of interacting with various titanium black particles as described above. However, there is no particular limitation on how these functional groups are introduced, but structural units obtained from monomers represented by any one of the following general formulas (i) to (iii) It is preferable to introduce at least one kind.

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

L in the formulas (i) to (ii) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group ( For example, an arylene group and a substituted arylene group), a divalent heterocyclic group and an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR) ^31- , wherein R ³¹ is a combination with one or more of an aliphatic group, an aromatic group or a heterocyclic group) or a carbonyl group (—CO—).

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of the said aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of the said bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

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

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

  In the formulas (i) to (iii), Z represents a functional group capable of forming an interaction with titanium black separately from the graft site, preferably a carboxylic acid or a tertiary amino group, and preferably a carboxylic acid. Is more preferable. Y represents a methine group or a nitrogen atom.

In formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, etc.), -Z, or -LZ. Here, L and Z are synonymous with L and Z in the above, and a preferable example is also the same.
R ⁴ , R ⁵ , and R ⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are each independently a hydrogen atom or a methyl group, and L is an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid is preferable.

Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is a carboxylic acid, and Y is a methine group. Compounds are preferred. Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid is preferred.

Below, the typical example of the monomer (compound) represented by Formula (i)-(iii) is shown.
Examples of the monomer include a reaction product of methacrylic acid, crotonic acid, isocrotonic 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 the 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 a tetrahydroxyphthalic anhydride, a molecule A reaction product of a compound having an addition polymerizable double bond and hydroxyl group and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic Acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenyl methacrylate And the like.

  The content of a functional group capable of forming an interaction with titanium black such as a monomer having an acidic group in a specific resin is from the viewpoint of interaction with titanium black, dispersion stability, and permeability to a developer. 0.05 mass%-90 mass% is preferable with respect to specific resin, 1.0 mass%-80 mass% is more preferable, 10 mass%-70 mass% is still more preferable.

  Furthermore, the specific resin contained in the dispersion composition of titanium black according to the present invention is not limited to the structural unit having the graft site and titanium as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. In addition to the functional group capable of forming an interaction with black, another structural unit having various functions, for example, a functional unit having an affinity for the dispersion medium used in the dispersion is shared. It can be included as a polymerization component.

  Examples of the copolymerizable component that can be copolymerized with the specific resin include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes, acrylonitriles, methacrylonitriles, and the like.

  These can be used singly or in combination of two or more. The content of these copolymerization components in the specific resin is preferably 0 mol% or more and 90 mol% or less, particularly preferably 0 mol% or more. 60 mol% or less. When the content is in the above range, sufficient pattern formation can be obtained.

  Examples of the solvent used when synthesizing the specific resin include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1 Examples include -methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

  Specific examples of such a specific resin include the following exemplary compounds 1 to 54. In addition, the suffix of each structural unit (main chain part) is mass%.

The content of the dispersant in the titanium black dispersion of the present invention is 1% by mass to 90% with respect to the total solid content mass of the dispersion (including the dispersion made of titanium black particles and other colorants). % By mass is preferable, and 3% by mass to 70% by mass is more preferable.
Moreover, as content of the dispersing agent in the photosensitive resin composition of this invention, it is 1 mass with respect to the total solid content mass of a to-be-dispersed body (a to-be-dispersed body consisting of a titanium black particle and another coloring agent). % To 90% by mass is preferable, and 3% to 70% by mass is more preferable.

(C) Organic solvent The titanium black dispersion and photosensitive resin composition of the present invention contain an organic solvent.
Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, ethyl lactate and the like, but are not limited thereto.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more organic solvents are used in combination, particularly preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -A mixed solution composed of two or more selected from heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The amount of the organic solvent contained in the titanium black dispersion is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass with respect to the total amount of the dispersion, 30 It is still more preferable that it is mass%-65 mass%.
The amount of the organic solvent contained in the photosensitive resin composition is preferably 10% by mass to 90% by mass and more preferably 20% by mass to 80% by mass with respect to the total amount of the composition. Preferably, it is 25 mass%-75 mass%.

(D) Photopolymerizable compound The photosensitive resin composition of the present invention contains a photopolymerizable compound.
The photopolymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.

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

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

  Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and structures in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.

  Also, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the situation, a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained. Commercially available products include urethane oligomer UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 ”(trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (trade name) , Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

A photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more kinds of photopolymerizable compounds are used in combination, the combination mode can be appropriately set according to physical properties required for the photosensitive resin composition. As one suitable combination aspect of a photopolymerizable compound, the aspect which combines 2 or more types of polymeric compounds selected from the polyfunctional acrylate compound mentioned above is mentioned, for example, As an example, dipentaerythritol hexa A combination of acrylate and pentaerythritol triacrylate may be mentioned.
As content in the photosensitive resin composition of a photopolymerizable compound, 3 parts-55 parts are preferable with respect to 100 parts of total solid content, More preferably, they are 10 parts-50 parts.

(E) Photopolymerization initiator The photosensitive resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator is a compound that is decomposed by light or heat and starts and accelerates the polymerization of the above-described photopolymerizable compound, and preferably has absorption with respect to light having a wavelength of 300 to 500 nm. .

Specific examples of the photopolymerization initiator include, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples thereof include organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
More specific examples include polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749.
As the photopolymerization initiator, an oxime ester compound is particularly preferable.

  The content of the polymerization initiator in the photosensitive resin composition of the present invention is preferably 0.1% by mass to 30% by mass in the total solid content of the photosensitive resin composition, and 1% by mass to 25% by mass. Is more preferable, and 2 mass%-20 mass% is still more preferable.

(F) Other additives The photosensitive resin composition of the present invention contains various additives depending on the purpose in addition to the titanium black dispersion, the photopolymerizable compound, and the photopolymerization initiator of the present invention. Can do.

(F-1) Binder polymer In the photosensitive resin composition, a binder polymer can be further used as needed for the purpose of improving film properties.
As the binder polymer, a linear organic polymer is preferably used. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer.

For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. No. 25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. Is mentioned. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and examples of monomers having an acid anhydride include maleic anhydride. An acid etc. are mentioned.
Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and are advantageous in terms of suitability for low exposure.

  In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in each of publications such as European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance of film strength and developability. It is preferable. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.

  The weight average molecular weight of the binder polymer used in the photosensitive resin composition of the present invention is preferably 1,000 to 300,000 from the viewpoint of pattern peeling inhibition during development and developability, and preferably 1,500 to 250,000 is more preferable, 2,000 to 200,000 is still more preferable, and 2,500 to 100,000 is particularly preferable. About the number average molecular weight of a binder polymer, Preferably it is 1000 or more, More preferably, it is the range of 1500-250,000. The polydispersity (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 1 or more, more preferably 1.1 to 10.

  These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used for synthesizing the binder polymer include known compounds such as an azo initiator and a peroxide initiator.

Among various binder polymers, by including an alkali-soluble resin having a double bond in the side chain, both the curability of the exposed area and the alkali developability of the unexposed area can be improved.
The alkali-soluble binder polymer having a double bond in the side chain has a non-image area removability by having an acid group for making the resin alkali-soluble in the structure and at least one unsaturated double bond. Improve various performances. The binder resin having such a partial structure is described in detail in JP-A No. 2003-262958, and the compounds described herein can be used in the present invention.

  In addition, the weight average molecular weight of a binder polymer can be measured by GPC, for example.

  The content of the binder polymer in the photosensitive resin composition of the present invention is preferably 0.1% by mass to 7.0% by mass with respect to the total solid content of the composition, and can prevent peeling of the light shielding film. From the viewpoint of coexistence of development residue suppression, it is more preferably 0.3% by mass to 6.0% by mass, and further preferably 1.0% to 5.0% by mass.

(F-2) Colorant In the present invention, it is possible to use a colorant other than inorganic pigments such as known organic pigments and dyes in order to develop desired light-shielding properties.

  Examples of the colorant that can be used in combination include organic pigments such as pigments described in paragraph numbers [0030] to [0044] of JP-A-2008-224982, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the Cl substituent is changed to OH, and the like. Among these, pigments that can be preferably used include the following. However, the colorant applicable to the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 38, 62, 64,
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255
C. I. Pigment Violet 19, 23, 29, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1

  There is no restriction | limiting in particular as an example of the dye which can be used as a coloring agent, A well-known dye can be selected suitably and can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 Examples thereof include dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure of the dye includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole Examples thereof include dyes having chemical structures such as azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene.

  As a colorant in the photosensitive resin composition of the present invention, an orange pigment, a red pigment, from the viewpoint of achieving both curability and light-shielding properties when combined with titanium black particles that the composition essentially contains, One or more organic pigments selected from the group consisting of violet pigments are preferred, and most preferred are combinations with red pigments.

  Examples of the orange pigment, red pigment, and violet pigment used in combination with the titanium black particles in the present invention include “CI Pigment Orange”, “CI Pigment Red”, and “C.I. What is necessary is just to select suitably from the various pigments which belong to "I. Pigment Violet" according to the target light-shielding property. From the viewpoint of improving the light shielding property, C.I. I. Pigment Violet 29, C.I. I. Pigment Orange 36, 38, 62, 64, C.I. I. Pigment Red 177, 254, 255 and the like are preferable.

(F-3) Sensitizer The photosensitive resin composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength.
As a sensitizer, what sensitizes the polymerization initiator used by an electron transfer mechanism or an energy transfer mechanism is preferable.
Preferable examples of the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and 1 to 20% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and storage stability. Is more preferable, and it is still more preferable that it exists in the range of 2-15 mass%.

(F-4) Polymerization inhibitor The photosensitive resin composition of the present invention contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. It is desirable to do. As the polymerization inhibitor, known thermal polymerization inhibitors can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The content of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive resin composition.

  If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be included to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The content of the higher fatty acid derivative is preferably about 0.5 to about 10% by mass of the total composition.

(F-5) Adhesion improver The photosensitive resin composition of the present invention may contain an adhesion improver in order to improve adhesion to a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

  Examples of silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyl. Trimethoxysilane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is preferable.

  The content of the adhesion improver is preferably 0.5% by mass to 30% by mass and more preferably 0.7% by mass to 20% by mass in the total solid content of the photosensitive resin composition.

(F-6) Surfactant The photosensitive resin composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the photosensitive resin composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, in the case of forming a film using a coating liquid to which a photosensitive resin composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coating surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the photosensitive resin composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), and the like.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

  Examples of silicone surfactants include Toray Dow Corning (Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Tore Silicone SH29PA. ”,“ Tore Silicone SH30PA ”,“ Tore Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF-4442 ”manufactured by Momentive Performance Materials, Inc. ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the photosensitive resin composition of the present invention. %.

(F-7) Other Additives Further, the photosensitive resin composition further improves the sensitivity of the sensitizing dye and initiator to active radiation, or suppresses polymerization inhibition of the photopolymerizable compound by oxygen. And may contain a co-sensitizer. Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as a diluent, a plasticizer, a fat-sensitizing agent, as needed.

-Preparation of titanium black dispersion-
The preparation mode of the titanium black dispersion of the present invention is not particularly limited. For example, the titanium black particles, the dispersant, and the organic solvent are mixed using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, and the like. Although it can prepare by performing a dispersion process, the method is not limited to these.
The dispersion process may be performed by two or more dispersion processes (multistage dispersion).

-Preparation of photosensitive resin composition-
The preparation mode of the photosensitive resin composition of the present invention is not particularly limited. For example, the titanium black dispersion of the present invention, a polymerization initiator, a polymerizable compound, and various additives used in combination as desired are mixed. Can be prepared.

The titanium black dispersion and the photosensitive resin composition of the present invention described above are light-shielding films provided on the back surface of a silicon substrate having an imaging element portion on the front surface, and shield the infrared light. Can be used without any particular limitation in applications (that is, applications for forming a light shielding film for shielding infrared light incident from the back side of a silicon substrate that is a base of a solid-state imaging device).
Among the solid-state imaging devices, the structure of the solid-state imaging device according to the structure K, which will be described later, has a strong need to block infrared light incident from the back side and to reduce development residue on the metal electrode. It is a structure.
For this reason, the titanium black dispersion and photosensitive resin composition of the present invention having the effects of improving the infrared light shielding ability and reducing the residue are particularly suitable for forming a light shielding film of a solid-state imaging device according to the structure K described later. .

≪Shading film≫
The light-shielding film of the present invention is formed using the photosensitive resin composition of the present invention.
For this reason, the light shielding film of this invention is excellent in infrared light shielding ability.
Further, residue is reduced in the vicinity of the light shielding film of the present invention (region where the light shielding film is not formed on the silicon substrate).

  The thickness of the light-shielding film is not particularly limited, and is preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5.0 μm, and more preferably 0.5 μm to 3 from the viewpoint of obtaining the effect of the present invention more effectively. 0.0 μm is particularly preferable. Further, the pattern size of the light shielding film is not particularly limited, and is preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 300 μm or less from the viewpoint of obtaining the effect of the present invention more effectively. About a minimum, 1 micrometer is desirable.

The spectral characteristics of the light-shielding film of the present invention are not particularly limited, but from the viewpoint of further improving the infrared light shielding ability, the balance of the light shielding ability between the visible region and the infrared region, and the like, the optical density at a wavelength of 1200 nm ( OD ₁₂₀₀₎ and the ratio _[OD 1200 _{/ OD 365]} of the optical density _{(OD 365)} at a wavelength of 365 nm, is preferably 0.5 to 3.
The optical density (OD) is obtained by measuring the transmittance of the obtained film using UV-3600 manufactured by Shimadzu Corporation, and converting the obtained transmittance (% T) by the following formula B to obtain an OD value. .
OD value = −Log (% T / 100) Formula B

In the present invention, the optical density at the wavelength _λ nm is represented by “OD _λ ”.
From the viewpoint of the balance between the light shielding ability in the visible region and the infrared region, and from the viewpoint of obtaining the effect of the present invention more effectively, the following conditions are suitable as the optical density of the light shielding film. That is,
[OD ₁₂₀₀ / OD ₃₆₅ ] is more preferably 1.0 or more and 2.5 or less, and particularly preferably 1.3 or more and 2.0 or less.
The optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm of the light shielding film is preferably 1.5 to 10, and more preferably 2 to 10.
The optical density (OD ₃₆₅ ) at a wavelength of 365 nm of the light shielding film is preferably 1 to 7, and more preferably 2 to 6.
The optical density of the light-shielding film in the wavelength region of 900 nm to 1300 nm is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, and particularly preferably 2 or more and 8 or less.
The ratio of the light shielding film [OD ₉₀₀ / OD ₃₆₅ ] is preferably 1.0 or more and 2.5 or less, and more preferably 1.1 or more and 2.5 or less.
The ratio [OD ₁₁₀₀ / OD ₃₆₅ ] of the light shielding film is preferably 0.6 or more and 2.5 or less, and more preferably 0.7 or more and 2.5 or less.
The ratio [OD ₁₃₀₀ / OD ₃₆₅ ] of the light-shielding film is preferably 0.4 or more and 2.3 or less, and more preferably 0.5 or more and 2.0 or less.

  Specific examples of the light-shielding film of the present invention described above include the light-shielding films described as applications of the titanium black dispersion and the photosensitive resin composition of the present invention.

≪Method of manufacturing light shielding film≫
The method for producing a light-shielding film of the present invention includes a step of forming a photosensitive layer by applying the above-described photosensitive resin composition of the present invention to the other surface of a silicon substrate having an image pickup element portion on one surface (hereinafter referred to as “photosensitive layer”). , Also referred to as “photosensitive layer forming step”), a step of exposing the photosensitive layer in a pattern (hereinafter also referred to as “exposure step”), and developing the photosensitive layer after exposure to form a pattern. (Hereinafter, also referred to as “development process”).
According to the method for producing a light-shielding film of the present invention, a light-shielding film having excellent infrared light-shielding ability can be formed. When the light-shielding film is formed, a residue (hereinafter referred to as “development residue”) outside the light-shielding film formation region. (Also called).
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

-Photosensitive layer forming step-
In the photosensitive layer forming step, the photosensitive resin composition of the present invention is applied on a silicon substrate to form a photosensitive layer.

As a coating method of the photosensitive resin composition of the present invention on a silicon substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied. .
The coating film thickness (dry film thickness) of the photosensitive resin composition is preferably 0.35 μm to 3.0 μm and more preferably 0.50 μm to 2.5 μm from the viewpoint of resolution and developability. preferable.

  The photosensitive resin composition applied on the silicon substrate is usually dried at 70 ° C. to 130 ° C. for about 2 minutes to 4 minutes to form a photosensitive layer.

-Exposure process-
In the exposure step, the photosensitive layer formed in the photosensitive layer forming step is exposed and cured in a pattern, for example, through a mask (in the case of exposure through a mask, a light-irradiated coating film Only the part is cured).

  The exposure is preferably performed by irradiation with radiation. Examples of radiation that can be used for exposure include ultraviolet rays such as g-line, h-line, and i-line, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 3000 mJ, more preferably 10 mJ to 2000 mJ, and most preferably 10 mJ to 1000 mJ.

-Development process-
Subsequent to the exposure step, the exposed photosensitive layer is developed by, for example, an alkali development process to form a pattern. In the development step, the non-irradiated portion of the photosensitive layer in the exposure step is eluted in an alkaline aqueous solution or the like, leaving only the light irradiated portion.

  The developer is preferably an organic alkali developer in that it does not damage the underlying circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is usually 20 seconds to 240 seconds.

  Examples of the developer include an alkaline aqueous solution in which an organic alkali compound is diluted with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Examples of organic alkali compounds that can be used include, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like. In addition, when alkaline aqueous solution is used as a developing solution, generally washing | cleaning (rinsing) with a pure water is performed after image development.

  In the method for producing a light-shielding film of the present invention, in addition to the photosensitive layer forming step, the exposure step, and the development step, the method may further include a curing step for curing the developed pattern by heating and / or exposure, if necessary. Good.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention is configured to have the light shielding film of the present invention.
That is, since the solid-state imaging device of the present invention includes a light-shielding film formed using the photosensitive resin composition of the present invention, a silicon substrate (solid-state imaging device) is formed from the surface opposite to the surface on which the imaging device unit is provided. Noise due to infrared light incident on the substrate) and noise due to residue are reduced.
The structure of the solid-state image pickup device of the present invention is provided with an image pickup device portion (specifically, an image pickup device portion configured by arranging a plurality of image pickup devices in a matrix, for example) on one surface of a silicon substrate. There is no particular limitation as long as the light shielding film of the present invention is provided on the other surface.
Further, the image sensor may be a CCD or a CMOS.

In particular, a mounting substrate (hereinafter referred to as a “circuit board”) is provided on the surface opposite to the surface on which the image sensor portion is formed, as described in Japanese Unexamined Patent Application Publication Nos. 2009-99951 and 2009-158863. The structure of the solid-state imaging device having a metal electrode for connection to the solid-state imaging device is suitable as the structure of the solid-state imaging device of the present invention.
That is, a preferred structure of the solid-state imaging device of the present invention (also referred to as structure K in the present specification) is a silicon substrate having an imaging device portion on one surface (hereinafter also referred to as “first main surface”). A metal electrode that is provided on the other surface of the silicon substrate (hereinafter also referred to as “second main surface”) and is electrically connected to the imaging element unit, and the metal electrode of the silicon substrate is provided. And a light-shielding film according to the present invention patterned so that at least a part of the metal electrode is exposed.

First, as a comparison with the structure K, a conventional solid-state imaging device that employs a wire bonding method will be described.
Conventionally, solid-state image sensors have been connected to circuit boards by wire bonding. More specifically, a solid-state image sensor is disposed on a circuit board, and the connection electrodes provided on the surface of the silicon substrate on the image sensor section side are connected to the connection electrodes on the circuit board by wires. It was. The structure employing this wire bonding method is a structure in which the area of the bonding area is large and it is difficult to reduce the size of the camera module.

On the other hand, the solid-state imaging device having the structure K is connected to a mounting board (hereinafter also referred to as a circuit board) via a connecting material such as a solder ball instead of a wire.
The solid-state imaging device having the structure K and the circuit board are connected by arranging the solid-state imaging device and the circuit board in a direction in which the metal electrode and the connection electrode on the circuit board face each other. This is performed by connecting the metal electrode and the connection electrode (for example, see FIGS. 1 and 2 described later).
By using a solid-state imaging device connected to a circuit board by a metal electrode on the back side (without using a wire) like the solid-state imaging device having the above-described structure K, the wire bonding space can be omitted. Miniaturization becomes possible (for example, “Toshiba News Release“ Reinforcement of CMOS Image Sensor Business by In-House CMOS Camera Module Production ””, [online], October 1, 2007, [Heisei Search on November 12, 2009], Internet <URL: http://www.toshiba.co.jp/about/press/2007_10/pr_j0102.htm>).

However, when a solid-state imaging device connected to the circuit board by the metal electrode on the back side is used, the solid-state imaging device and the circuit board are caused by the thickness of the metal electrode and the size of the connection material (for example, solder ball 60). A gap (for example, a gap S in FIG. 1) is likely to occur between the two and the infrared light easily enters the silicon substrate from this gap.
Further, for example, in the case of the camera module 200 described later, although the light shielding / electromagnetic shield 44 is provided, due to the influence of volume variation of the solder ball 60 and the like, between the light shielding / electromagnetic shield 44 and the circuit board 70 due to the influence of the volume variation of the solder ball 60 and the like. It is extremely difficult to completely eliminate the gap S.

For the reasons described above, the structure of the solid-state imaging device connected to the circuit board by the metal electrode on the back surface side is a structure that is particularly required to shield infrared light incident from the back surface side of the silicon substrate.
Therefore, in such a structure, the effects of the present invention (improvement of infrared light shielding ability and noise reduction effect by infrared light) are more effectively achieved.

Furthermore, a solid-state imaging device having a metal electrode on the back surface has a structure that requires connectivity between the metal electrode and a connection material for connection to a circuit board.
Therefore, in such a structure, the effects of the present invention (the effect of reducing the residue and the effect of reducing the noise due to the residue) are more effectively achieved.

The structure K further includes a protective insulating layer such as a solder resist layer on the lower layer side (side closer to the silicon substrate) of the light shielding film and on the upper layer side (side away from the silicon substrate) of the metal electrode. It may be.
That is, the structure K includes a protective insulating layer that is provided on the second main surface on which the metal electrode is formed and is patterned so as to expose at least a part of the metal electrode. Further, the protective insulating layer may be provided so as to cover and patterned so as to expose at least a part of the metal electrode.

  Note that “electrically connected” in the structure K is not limited to the form of being directly connected, but also includes a state of being indirectly connected via a peripheral circuit or the like.

Hereinafter, specific examples of the structure K will be described with reference to FIGS. 1 and 2, but the present invention is not limited to the following specific examples.
Throughout FIGS. 1 and 2, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” refer to the side closer to the silicon substrate 10. Point to.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state imaging device according to a specific example of the structure K.
A camera module 200 shown in FIG. 1 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 includes a solid-state image sensor substrate 100 having an image sensor section on a first main surface of a silicon substrate, and a glass substrate disposed above the first main surface side of the solid-state image sensor substrate 100. 30 (light transmissive substrate), an infrared cut filter 42 disposed above the glass substrate 30, a lens holder 50 disposed above the glass substrate 30 and the infrared cut filter 42 and having the imaging lens 40 in the internal space, The solid-state image pickup device substrate 100 and the glass substrate 30 are configured to include a light shielding / electromagnetic shield 44 disposed so as to surround the periphery. Each member is bonded by adhesives 20, 41, 43, 45.
In the camera module 200, incident light hν from outside passes through the imaging lens 40, the infrared cut filter 42, and the glass substrate 30 in order, and then reaches the imaging element portion of the solid-state imaging element substrate 100.
The camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in FIG.
The solid-state image sensor substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a color filter 15R, a color filter 15G, a color filter 15B, an overcoat 16, a microlens 17, and a light shielding film 18. , An insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and an element surface electrode 27.
However, the solder resist layer 24 may be omitted.

First, the configuration on the first main surface side of the solid-state imaging device substrate 100 will be mainly described.
As shown in FIG. 2, an imaging element unit in which a plurality of imaging elements 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of the silicon substrate 10 that is a base of the solid-state imaging element substrate 100. ing.
An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13. Furthermore, on the base layer 14, a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) Are arranged.
A light shielding film (not shown) may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit. This light shielding film can be produced using, for example, a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).

In addition, a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit. Has been.
Furthermore, an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
A base layer 14 is formed on the element surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.

The above is the configuration on the first main surface side of the solid-state imaging device substrate 100.
On the first main surface side of the solid-state image sensor substrate 100, an adhesive 20 is provided around the image sensor section, and the solid-state image sensor substrate 100 and the glass substrate 30 are bonded via the adhesive 20.

  The silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole. The imaging element portion and the circuit board 70 are electrically connected by the through electrode.

Next, the configuration on the second main surface side of the solid-state imaging device substrate 100 will be mainly described.
On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
On the insulating film 22, a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the image pickup element portion in the solid-state image pickup element substrate 100 and the circuit board 70.
The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective layer) that covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a part of the metal electrode 23 on the second main surface side. Insulating film).
Further, on the second main surface side, a light shielding film 18 is provided that covers the second main surface on which the solder resist layer 24 is formed and has an opening that exposes a portion on the metal electrode 23. It has been.
As the light shielding film 18, the above-described light shielding film of the present invention is used.
Thereby, the infrared light which injects into the silicon substrate 10 from the 2nd main surface side (back surface side) can be light-shielded. Further, development residues are suppressed at the opening of the light shielding film 18 (the portion where the metal electrode 23 is exposed). For this reason, the connectivity between the metal electrode 23 and the solder ball 60, and the connectivity between the image pickup device portion constituted by the image pickup device 12 and the circuit board 70 is also maintained well.
In FIG. 2, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24).
The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

  A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode (not shown) of the circuit board 70 are connected via the solder ball 60. , Are electrically connected.

Although the configuration of the solid-state image sensor substrate 100 has been described above, each part of the solid-state image sensor substrate 100 other than the light-shielding film 18 is the method described in paragraphs 0033 to 0068 of JP 2009-158863 A or JP 2009. It can be formed by a known method such as the method described in paragraphs 0036 to 0065 of JP-A-99591.
The light shielding film 18 can be formed by the above-described manufacturing method of the light shielding film of the present invention.
The interlayer insulating film 13 is formed as a SiO ₂ film or a SiN film by, for example, sputtering or CVD (Chemical Vapor Deposition).
The color filter 15 (15R, 15G, 15B) is formed by photolithography using a known color resist, for example.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
The microlens 17 is formed by using styrene resin or the like, for example, by photolithography.
The solder resist layer 24 is formed by photolithography using a known solder resist including, for example, a phenol resin, a polyimide resin, or an amine resin.
The solder ball 60 is formed using, for example, Sn—Ag, Sn—Cu, Sn—Ag—Cu as Sn—Pb (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder. . The solder ball 60 is formed in a spherical shape having a diameter of 100 μm to 1000 μm (preferably a diameter of 150 μm to 700 μm), for example.
The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example. The metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers.
The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm).
The silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used. Although the thickness of the substrate is not limited, for example, a silicon wafer having a thickness of 20 to 200 μm (preferably 30 to 150 μm) is used.
The through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).

  As described above, the solid-state imaging device substrate 100 which is a specific example of the structure K has been described with reference to FIGS. 1 and 2. However, the structure K is not limited to the embodiment of FIGS. The configuration is not particularly limited as long as it has a light shielding film.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass. “Room temperature” refers to 25 ° C.

<Preparation of substrate A and substrate B>
(Preparation of substrate A)
A substrate A was prepared as follows for verification of development residue in the solid-state imaging device having the structure K (a form having no solder resist layer on the back surface).
That is, a Ti plating seed layer is formed on a silicon substrate by a microfabrication (photolithography) technique and a sputtering method, and a circular metal electrode made of copper (Cu) having a thickness of 5 μm and a diameter of 10 μm is formed using an electrolytic plating method. Obtained.
As described above, a substrate A having a configuration having a plurality of circular metal electrodes 310 on a silicon substrate 300 as shown in the schematic cross-sectional view of FIG. 3 was obtained.

(Preparation of substrate B)
A substrate B was prepared as follows for verification of development residue in the solid-state imaging device having the structure K (a form having a solder resist layer on the back surface).
A patterned solder resist layer was formed on the circular metal electrode forming surface side of the substrate A by photolithography using a commercially available solder resist.
The pattern of the solder resist layer was a pattern having an opening that exposes a part of the metal electrode, as shown in FIG.
As described above, a substrate B having a configuration in which a plurality of circular metal electrodes 310 and solder resist layers 330 are provided on the silicon substrate 300 as shown in the schematic cross-sectional view of FIG. 5 was obtained.

<Synthesis of Dispersant 1>
Into a 500 mL three-necked flask, 600.0 g of ε-caprolactone and 22.8 g of 2-ethyl-1-hexanol were introduced and dissolved with stirring while blowing nitrogen. To the flask was added 0.1 g of monobutyltin oxide and the contents of the flask were heated to 100 ° C. After 8 hours, the disappearance of the raw materials was confirmed by gas chromatography, and then the contents of the flask were cooled to 80 ° C. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 27.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, the disappearance of the raw material was confirmed by ¹ H-NMR, and then cooled to room temperature to obtain 200 g of a solid precursor M1 [the following structure]. It was confirmed by ¹ H-NMR, IR, and mass spectrometry that the obtained substance was M1.

  30.0 g of the precursor M1, 70.0 g of NK ester CB-1 (2-methacryloyloxyethylphthalic acid, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2.3 g of dodecyl mercaptan, and propylene glycol monomethyl 233.3 g of ether acetate was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C. . To this, 0.2 g of 2,2-azobis (2-methylpropionic acid) dimethyl (“V-601” (trade name) manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 75 ° C. for 2 hours. I did it. Two hours later, 0.2 g of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of Dispersant 1 below.

The composition ratio, acid value, and weight average molecular weight (Mw) of the dispersant 1 are as follows.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. Measurement by GPC was performed using HLC-8020GPC (manufactured by Tosoh Corporation) and using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation) as columns.
Composition ratio: x = 35 (mass%), y = 65 (mass%)
・ Acid value: 80 mgKOH / g
・ Mw: 30,000

[Example 1, Comparative Example 1]
<Preparation of titanium black dispersions A and B>
The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.

(Composition 1)
-Titanium black (titanium black with an average particle size of 30 nm or less)-25 parts-30% solution of dispersant 1-25 parts-Propylene glycol monomethyl ether acetate (PGMEA) (solvent)
... 50 copies

The “titanium black having an average particle size of 30 nm or less” was obtained as follows.
100 g of Teica titanium oxide MT-150A (trade name) with a particle size of 15 nm, 25 g of Evonik silica particles AEROPELL (registered trademark) 300/30 with a BET surface area of 300 m ² / g, and Disperbyk 190 (trade name) manufactured by BYK Chemie. Weigh 100g, add 71g of ion-exchange water, and use KURABO MAZERSTAR KK-400W (trade name) for 20 minutes at a revolution speed of 1360rpm and a rotation speed of 1047rpm to obtain a uniform aqueous mixture solution. It was. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln manufactured by Motoyama Co., Ltd., then the atmosphere is replaced with nitrogen, and ammonia gas is allowed to flow at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was carried out. After completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black having an average particle size of 30 nm or less.

The obtained dispersion a was subjected to dispersion treatment under the following conditions using Ultra Apex Mill UAM015 (trade name) manufactured by Kotobuki Industries Co., Ltd.
<Distribution conditions>
・ Bead diameter: 0.05mm in diameter
・ Bead filling rate: 75% by volume
・ Mill peripheral speed: 8m / sec
・ Amount of liquid mixture to be dispersed: 500 g
・ Circulation flow rate (pump supply amount): 13 kg / hour
-Treatment liquid temperature: 25 ° C to 30 ° C
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Number of passes: 90 passes

  Thus, a titanium black dispersion A of Example 1 was obtained.

  A dispersion b having the same composition as the dispersion a in Example 1 was prepared except that the titanium black used in Example 1 was changed to “13M-T” (trade name) manufactured by Mitsubishi Materials Corporation. The titanium black dispersion B of Comparative Example 1 was obtained by performing the same dispersion treatment as in Example 1.

<Evaluation of titanium black dispersions A and B>
Each of the obtained titanium black dispersions A and B was diluted 500 times with propylene glycol monomethyl ether acetate, dropped onto a carbon thin film and dried, and each of them was obtained by TEM (manufactured by Hitachi High-Technologies Corporation). Morphological observation photographs of particles (dispersed material) contained in the dispersion were taken. From the obtained photograph, the projected area of the outer surface was obtained for 400 particles, the diameter of the circle corresponding to this area was calculated, and the frequency distribution was evaluated.
Moreover, about the average particle diameter of the titanium black particle (to-be-dispersed body) contained in each dispersion liquid, 400 particle images are sampled from a TEM photograph, the projected area of an outer surface is calculated | required, and the circle | round | yen equivalent to this area The diameter was calculated, and the average value was obtained.

As a result, in the titanium black dispersion A of Example 1, the average particle diameter of the titanium black particles contained was 19 nm, and 95% of all titanium black particles had a particle diameter of 30 nm or less. .
Moreover, in the titanium black dispersion B of Comparative Example 1, the average particle size of the titanium black particles contained was 50 nm, and among all the titanium black particles, the particle size of 30 nm or less was 6%.
These results are shown in Tables 1 to 3.

[Example 2, Comparative Example 2]
<Preparation of black curable composition (photosensitive resin composition)>
The component of the following composition 2 was mixed with the stirrer, and the black curable composition A of Example 2 was prepared.

(Composition 2)
・ Benzyl methacrylate / methyl methacrylate / hydroxyethyl methacrylate / acrylic acid copolymer (50/15/5/30 [molar ratio]) [binder polymer]
1.6 parts dipentaerythritol hexaacrylate [polymerizable compound] 2.0 parts pentaerythritol triacrylate [polymerizable compound] 1.0 part polymerization initiator with the following structure Photopolymerization initiator] 0.3 parts

Titanium black dispersion A: 24 parts Propylene glycol monomethyl ether acetate (PGMEA): 10 parts Ethyl-3-ethoxypropionate (EEP): 8 parts

  Moreover, except having changed the titanium black dispersion A into the titanium black dispersion B among the components of the composition 2, the black curable composition B of Comparative Example 2 was changed in the same manner as the black curable composition A. Prepared.

<Production of light shielding film>
The black curable composition A or B obtained above is applied to the surface of the substrate A on which the metal electrode is formed by a spin coating method, and then heated at 120 ° C. for 2 minutes on a hot plate to give a black color. A curable composition coating layer was obtained.
Then, the resultant coating layer, an i-line stepper ^and pattern exposure at ^{100mJ / cm 2, 200mJ / cm} 2, 300mJ / cm 2, 400mJ / cm 2, the exposure amount of 500 mJ / cm ^2.
Next, paddle development was performed on the coated layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds. Thereafter, the coated layer after development was rinsed with a spin shower and washed with pure water to obtain a patterned light-shielding film.
Here, as shown in FIG. 4, the light shielding film is a pattern having an opening that exposes part of the metal electrode 310 (light shielding film 320 in FIG. 4).

[Example 3, Comparative Example 3]
In Example 2 and Comparative Example 2, a patterned light-shielding film was formed in the same manner as in Example 2 and Comparative Example 2 except that the substrate B was used instead of the substrate A.
Here, as shown in FIG. 6, the light shielding film is a pattern having an opening that exposes a part of the metal electrode 310 provided on the silicon substrate 300 (more specifically, a solder resist layer when viewed from the normal direction of the substrate). The light-shielding film 340 in FIG.

<Evaluation>
In the formation of each of the patterned light-shielding films obtained in Examples 2 and 3 and Comparative Examples 2 and 3, the exposure amount at which peeling did not occur was determined using an optical microscope. The smaller the exposure amount, the more effective the adhesion between the light shielding film and the substrate.

The particle size (nm) of the dispersion in each of the patterned light shielding films (cured films) obtained in Examples 2 and 3 and Comparative Examples 2 and 3 was measured as follows.
Observe the cross-section of the film-formed substrate with a scanning electron microscope (S-3400N (trade name) manufactured by Hitachi High-Technologies Corporation) and an energy dispersive X-ray analyzer (Genesis (trade name) manufactured by EDAX). Thus, a morphology observation photograph and an element map of Ti and Si were obtained. From the obtained photograph, the projected area of the outer surface was obtained for 400 particles in which Ti element was detected, the diameter of a circle corresponding to this area was calculated, and the frequency distribution was evaluated.
As a result, in each of the light shielding films formed in Examples 2 and 3, the ratio of those having a particle size of 30 nm or less among the dispersions included in the light shielding film was 95%.
Further, in each of the light shielding films formed in Comparative Examples 2 and 3, the proportion of the dispersions contained in the light shielding film having a particle size of 30 nm or less was 6%.

Moreover, about the developing part (exposed metal electrode surface) of each pattern-shaped light shielding film (exposure amount is described in Tables 1 and 2) obtained in Examples 2 and 3 and Comparative Examples 2 and 3. Observation was made with a scanning electron microscope (S-4800 (trade name) manufactured by Hitachi High-Technologies Corporation), and the presence or absence of a development residue on the substrate A or the substrate B was evaluated.
The fact that a development residue of 10 nm or more is not observed on the circular metal electrode of the substrate A or the substrate B indicates that the light shielding film is good.
Tables 1 and 2 show the evaluation results of the development residue.

In Tables 1 and 2, “not observed” indicates that a development residue of 10 nm or more is not observed on the circular metal electrode.
“With residue” indicates that a development residue of 10 nm or more was observed on the circular metal electrode.
“Pattern cannot be formed” indicates that the curability is insufficient and peeling of the pattern occurs.

  As shown in Table 1 and Table 2, the black curable composition A of the example is excellent in curability at any exposure amount in comparison with the black curable composition B of the comparative example, and In the formation of the light shielding film using this, no development residue was observed in the case of using either the substrate A or the substrate B.

  From the evaluation results of Examples 2 and 3, when forming the light shielding film on the back side of the solid-state imaging device having the structure K, it is possible to reduce the development residue derived from the photosensitive resin composition for forming the light shielding film. I understood.

[Example 4, Comparative Example 4]
<Evaluation of infrared shading ability>
In Example 2 and Comparative Example 2, a glass substrate (1737 manufactured by Corning) was used instead of the substrate A, and the entire surface was exposed instead of pattern exposure to form a solid light-shielding film (film thickness 2 μm) on the glass substrate. The light shielding films of Example 4 and Comparative Example 4 were obtained.
About the obtained light shielding film, the transmittance | permeability in each wavelength range was measured using Shimadzu UV3600 (brand name). From the measurement results, the maximum transmittance (%) in the wavelength region of 700 nm to 1200 nm was obtained.

  As shown in Table 3, in Example 4 and Comparative Example 4, the maximum transmittance in the infrared region is low, and the black curable composition A maintains the excellent infrared shading ability of titanium black, while reducing the development residue. It was confirmed to have an effect of improving curability.

[Examples 5 and 6, Comparative Examples 5 and 6]
First, the black curable composition A was prepared.
Next, black curable compositions C, D, E, and F having “average particle diameter” and “ratio of dispersed materials having a particle diameter of 30 nm or less” shown in Table 4 below were prepared.
In the black curable compositions C, D, E, and F, the adjustment of the “average particle diameter” and the “ratio of the object to be dispersed having a particle diameter of 30 nm or less” is adjusted to the black curable composition A (titanium black dispersion A). A part of the used “25 parts of titanium black having an average particle size of 30 nm or less” was replaced with commercially available titanium black (12S (trade name) manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.).

<Evaluation of development residue>
About the developing part (exposed metal electrode surface) of the light shielding film of Examples 5 and 6 and Comparative Examples 5 and 6 by the same process as above, a scanning electron microscope (S-3400N manufactured by Hitachi High-Technologies Corporation) (product) Name)) and an energy dispersive X-ray analyzer (Genesis (trade name) manufactured by EDAX), a morphological observation photograph and an element map of 10 μm × 10 μm size of Ti and Si were taken. From the obtained photographs, the number of particulate substances having a diameter of 10 nm or more in which Ti element was detected was evaluated, and the frequency distribution was evaluated.

From the obtained results, the development residue was evaluated according to the following criteria. The evaluation results are shown in Table 4.
-Evaluation criteria-
A The number was less than 10.
The number of B was 10 or more and less than 50, which was practically acceptable.
C The number was 50 or more and less than 100.
D The number was 100 or more.

<Evaluation of infrared shading ability>
In Examples 2, 5, and 6 and Comparative Examples 5 and 6, a glass substrate (1737 manufactured by Corning) was used instead of the substrates A and B, and the entire surface was exposed instead of pattern exposure, and a solid light-shielding film (on the glass substrate) A film thickness of 2 μm) was formed.
About the obtained light shielding film, the transmittance | permeability in each wavelength range was measured using Shimadzu UV3600 (brand name). From the measurement results, the maximum transmittance (%) in the wavelength region of 700 nm to 1200 nm was obtained.

From the obtained results, the infrared shielding ability was evaluated according to the following criteria. The evaluation results are shown in Table 4.
-Evaluation criteria-
A: The maximum transmittance was less than 7%.
B: The maximum transmittance was 7% or more and less than 10%, which was practically acceptable.
C: The maximum transmittance was 10% or more and less than 15%.
D: The maximum transmittance was 15% or more.

  As shown in Table 4, it was confirmed that when the proportion of the dispersion having a particle size of 30 nm or less is 90% or more, an extremely excellent development residue reduction effect can be obtained.

DESCRIPTION OF SYMBOLS 10 Silicon substrate 12 Image pick-up element 13 Interlayer insulating film 14 Base layer 15R Red color filter 15G Green color filter 15B Blue color filter 16 Overcoat 17 Microlens 18 Light shielding film 22 Insulating film 23 Metal electrode 24 Solder resist layer 26 Internal electrode 27 Element surface electrode 30 Glass substrate 40 Imaging lens 42 Infrared cut filter 44 Light shielding / electromagnetic shield 50 Lens holder 60 Solder ball 70 Circuit board 100 Solid-state imaging device substrate 200 Camera module hν Incident light S Gap

Claims (16)

(A) titanium black particles, (B) a dispersant, and (C) an organic solvent,
90% or more of the dispersion of (A) titanium black particles has a particle size of 30 nm or less,
On the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes have a image sensor portion to one surface to the other surface, patterned such that at least a portion of the metal electrode is exposed A titanium black dispersion used for forming a light-shielding film that is provided and shields infrared light. The titanium black dispersion according to claim 1, wherein 95% or more of the dispersion (A) made of titanium black particles has a particle size of 30 nm or less. The titanium black dispersion according to claim 1 or 2, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound. The titanium black dispersion according to any one of claims 1 to 3, wherein the dispersant is a graft copolymer having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. The titanium black dispersion according to claim 4 , wherein the graft copolymer includes at least a structural unit represented by any one of the following formulas (1) to (4).

In [Equation (1) to ^{(4), W 1, W} 2, W 3, and ^{W 4} each independently represent an oxygen atom or ^{NH, X 1, X 2,} X 3, X 4, and ^{X 5} Each independently represents a hydrogen atom or a monovalent organic group, Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a monovalent organic group. R ³ represents a branched or straight chain alkylene group. R ⁴ represents a hydrogen atom or a monovalent organic group, the R ⁴ may be mixed different structures R ⁴ in the copolymer. n, m, p, and q are each independently an integer of 1 to 500. j and k each independently represent an integer of 2 to 8. ] In the graft copolymer, the structural unit represented by any one of the formulas (1) to (4) is in a range of 10% to 90% in terms of mass with respect to the total mass of the graft copolymer. The titanium black dispersion according to claim 5 . The titanium black dispersion according to any one of claims 1 to 6 , (D) a photopolymerizable compound, and (E) a photopolymerization initiator,
On the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes have a image sensor portion to one surface to the other surface, patterned such that at least a portion of the metal electrode is exposed A photosensitive resin composition used for forming a light-shielding film that is provided and shields infrared light. The photosensitive resin composition according to claim 7, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound. On the other surface of the silicon substrate having one possess an imaging device unit on the surface the image pickup device unit and electrically connected to the metal electrodes on the other surface, using a photosensitive resin composition according to claim 7 A light-shielding film formed by patterning so that at least a part of the metal electrode is exposed . The light shielding film according to claim 9, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound. Applying a photosensitive resin composition according to claim 7, on the other surface of the silicon substrate having the image pickup device unit and electrically connected to the metal electrodes on the surface of the have a image sensor portion on one side the other Forming a photosensitive layer, exposing the photosensitive layer in a pattern, and developing the exposed photosensitive layer to form a pattern in which at least a part of the metal electrode is exposed. And a method for producing a light shielding film. The method for producing a light-shielding film according to claim 11, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound. The method for producing a light-shielding film according to claim 11, wherein the metal electrode is made of Cu or a Cu compound. A silicon substrate having an image sensor portion on one surface;
A metal electrode provided on the other surface of the silicon substrate and electrically connected to the imaging element unit;
The light-shielding film according to claim 9 , wherein the light-shielding film is provided on a surface of the silicon substrate on which the metal electrode is provided, and is patterned so that at least a part of the metal electrode is exposed
Solid-state image pickup device that have a. The solid-state imaging device according to claim 14, wherein the metal electrode is made of Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound. The solid-state imaging device according to claim 14, wherein the metal electrode is made of Cu or a Cu compound.