WO2016129381A1

WO2016129381A1 - Light-shielding film, light-shielding film-equipped infrared cut-off filter, and solid-state imaging device

Info

Publication number: WO2016129381A1
Application number: PCT/JP2016/052087
Authority: WO
Inventors: 啓之山本; 薫青柳; 嶋田　和人
Original assignee: 富士フイルム株式会社
Priority date: 2015-02-09
Filing date: 2016-01-26
Publication date: 2016-08-18
Also published as: JP6476211B2; TW201629538A; JPWO2016129381A1; KR101971891B1; KR20170070202A; TWI700519B

Abstract

The present invention provides: a light-shielding film exhibiting excellent shielding of visible light, and capable of suppressing flaring when positioned in a solid-state imaging device; a light-shielding film-equipped infrared cut-off filter; and a solid-state imaging device. A light-shielding film according to the present invention and containing at least a black-colored layer, wherein the black pigment content contained in the black-colored layer constitutes 20-60 mass% relative to the total mass of the black-colored layer, the reflectance of light of at least one wavelength selected from within the wavelength range of 800-1,000nm is 3.0% or less, and the transmittance at a wavelength of 400-750nm is 50% or less.

Description

Light shielding film, infrared light cut filter with light shielding film, and solid-state imaging device

The present invention relates to a light shielding film, an infrared light cut filter with a light shielding film, and a solid-state imaging device.

A solid-state imaging device includes a photographing lens, a solid-state imaging device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographing lens, and a circuit on which the solid-state imaging device is mounted. A substrate. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smartphone, and the like.
In a solid-state imaging device, a phenomenon called flare is induced by incident light from an oblique direction and / or incident light that has been irregularly reflected.
Therefore, in Patent Document 1, flare generation is suppressed by providing a light shielding film in the solid-state imaging device. In addition, the light shielding film used is formed from the black coloring photosensitive composition containing carbon black.

JP 2011-107588 A

On the other hand, in recent years, with the demand for improvement in the performance of solid-state imaging devices, further improvement has been demanded regarding the performance of the light shielding film used. More specifically, there is a demand not only for further improving the light-shielding property of visible light but also for further suppressing flare generation when a light-shielding film is disposed in the solid-state imaging device.
The present inventors have examined the performance of a light-shielding film formed from a composition containing carbon black specifically described in Patent Document 1, and have sufficiently possessed the characteristics required recently. It was found that further improvement is necessary.

In view of the above circumstances, it is an object of the present invention to provide a light-shielding film that has excellent light-shielding properties for visible light and that can further suppress the occurrence of flare when placed in a solid-state imaging device.
Another object of the present invention is to provide an infrared light cut filter with a light-shielding film and a solid-state imaging device having the light-shielding film.

As a result of earnest research to achieve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved by using a light-shielding film exhibiting predetermined optical characteristics, and has completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) including at least a black layer,
The content of the black pigment contained in the black layer is 20 to 60% by mass with respect to the total mass of the black layer,
The reflectance in light of at least one wavelength selected in the wavelength range of 800 to 1000 nm is 3.0% or less,
A light-shielding film having a transmittance of 50% or less at a wavelength of 400 to 750 nm.
(2) The light shielding film according to (1), further including a low refractive index layer having a refractive index of 1.50 or less, which is disposed on the black layer.
(3) The light shielding film according to (2), wherein the low refractive index layer has a refractive index of 1.30 or less.
(4) The light-shielding film according to (2) or (3), wherein the average thickness of the low refractive index layer is 50 to 300 nm.
(5) The light-shielding film according to any one of (2) to (4), wherein the low refractive index layer contains a particle aggregate in which a plurality of silica particles are chain-connected.
(6) A red with a light-shielding film, comprising: an infrared light cut filter; and the light-shielding film according to any one of (1) to (5) disposed on at least a part of the surface of the infrared light cut filter Outside light cut filter.
(7) A solid-state imaging device comprising the light shielding film according to any one of (1) to (5).

According to the present invention, it is possible to provide a light-shielding film that has excellent light-shielding properties for visible light and that can further suppress the occurrence of flare when placed in a solid-state imaging device.
Moreover, according to this invention, the infrared-light cut filter with a light shielding film and solid-state imaging device which have the said light shielding film can be provided.

1 is a cross-sectional view of a preferred embodiment of a light-shielding film of the present invention. It is a perspective view which shows the solid-state imaging device of 1st Embodiment. It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.

Below, the suitable aspect of the light shielding film of this invention is explained in full detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

The light-shielding film of the present invention includes at least a black layer, and the content of the black pigment contained in the black layer is 20 to 60% by mass with respect to the total mass of the black layer, and is selected in the wavelength range of 800 to 1000 nm. The reflectance of the light having at least one wavelength is 3.0% or less, and the transmittance at a wavelength of 400 to 750 nm is 50% or less.
The light shielding film may include at least a black layer containing a predetermined amount of a black pigment, and may include other layers as long as the entire light shielding film exhibits a predetermined reflectance and transmittance.
The reason why a desired effect can be obtained by the light-shielding film of the present invention is that, since the black layer contains a large amount of black pigment and exhibits a predetermined transmittance, the light-shielding property for visible light is excellent. Further, the present inventors have found that the flare generated in the prior art is derived from infrared light, and in the light of at least one wavelength selected in the wavelength range of 800 to 1000 nm. It has been found that the occurrence of flare is further suppressed by setting the reflectance to a predetermined value or less.

The content of the black pigment contained in the black layer is 20 to 60% by mass with respect to the total mass of the black layer, and the light shielding property of the light shielding film is more excellent, and the occurrence of flare is further suppressed. 22.5 to 57.5% by mass is preferable and 27.5 to 52.5% by mass is more preferable in that at least one of them is satisfied (hereinafter, also simply referred to as “the point where the effect of the present invention is more excellent”).
The average thickness of the black layer is not particularly limited, and it is sufficient that the entire light shielding film exhibits a predetermined reflectance and transmittance. Among these, 0.5 to 8.0 μm is preferable and 1.0 to 4.0 μm is more preferable in that the effect of the present invention is more excellent.
The average thickness is obtained by measuring the thickness of any 10 or more points of the black layer and arithmetically averaging them.
Various components contained in the black layer will be described in detail later.

The reflectance of light of at least one wavelength selected in the wavelength range of 800 to 1000 nm of the light-shielding film is 3.0% or less, and 2.0% or less is preferable in terms of further suppressing the occurrence of flare. 1.0% or less is more preferable. Although a minimum in particular is not restrict | limited, 0% is mentioned.
As a method for measuring the reflectance, light of at least one wavelength selected in a wavelength range of 800 to 1000 nm is incident on a light shielding film as an object to be measured at an incident angle of 5 °, and the reflectance is measured by Hitachi High. Measured with a spectroscope UV4100 (trade name) manufactured by Technologies.
The wavelength used for the measurement is preferably measured using at least one light of 850 nm and 940 nm, and the measurement is performed using both light of 850 nm and 940 nm, and the respective reflectances are in the above range. It is more preferable that

The transmittance of the light-shielding film at a wavelength of 400 to 750 nm is 50% or less, and 10.0% or less is preferable and 2.0% or less is more preferable in that the light-shielding property of the light-shielding film is more excellent. Although a minimum in particular is not restrict | limited, 0% is mentioned.
As a method for measuring the transmittance, a light-shielding film is formed on a glass substrate, and transmittance at a wavelength of 400 to 750 nm is measured at an incident angle of 0 ° using a spectroscope UV4100 manufactured by Hitachi High-Technologies.

The light shielding film has the black layer and the structure thereof is not particularly limited as long as it exhibits predetermined optical characteristics. And a low refractive index layer having a refractive index of 1.50 or less. In this aspect, the light reflected at the surface of the low refractive index layer and the light reflected at the interface between the low refractive index layer and the black layer are canceled out by interference, thereby realizing low reflectivity.
Specifically, as shown in FIG. 1, a light shielding film 50 having a black layer 52 and a low refractive index layer 54 is exemplified.

A low refractive index layer is a layer arrange | positioned on the black layer mentioned above.
The low refractive index layer is a layer having a refractive index of 1.50 or less, and the refractive index is preferably 1.45 or less, more preferably 1.4 or less, and 1.3 or less in that the effect of the present invention is more excellent. Further preferred. The lower limit is not particularly limited, but is usually 1.1 or more in many cases.
The refractive index is measured by placing a low refractive index layer having an average thickness of about 0.1 μm on a silicon substrate (silicon wafer) and using an ellipsometer (VASE) manufactured by JA Woollam Japan Co., Ltd., with a wavelength of 800 Measure the refractive index for light of at least one wavelength selected in the range of ~ 1000 nm.
The wavelength used for the measurement is preferably measured using at least one light of 850 nm and 940 nm, and the refractive index is measured using both light of 850 nm and 940 nm. It is more preferable that

The average thickness (average physical film thickness) of the low refractive index layer is not particularly limited, but is preferably from 50 to 300 nm, more preferably from 100 to 250 nm, and even more preferably from 150 to 200 nm from the viewpoint that the effects of the present invention are more excellent.
The average thickness is obtained by measuring the thickness of any 10 or more points of the low refractive index layer and arithmetically averaging them.
The material constituting the low refractive index layer will be described in detail later.

The optical film thickness of the low refractive index layer is not particularly limited, but is preferably from 50 to 540 nm, more preferably from 100 to 450 nm, and even more preferably from 150 to 360 nm from the viewpoint that the effects of the present invention are more excellent.
The optical film thickness is a value represented by the product of the average thickness (average physical film thickness) of the low refractive index layer and the refractive index.

Hereinafter, the black layer and the low refractive index layer described above will be described in detail.

<< Black layer >>
A black layer is a layer containing a black pigment, and as described above, the content of the black pigment is not particularly limited as long as the content of the black pigment is within the above range.
Among these, a black layer-forming composition containing a black pigment, a dispersant, and a solvent (hereinafter, also simply referred to as “composition” or “composition of the present invention”) from the viewpoint of easy production of a black layer. It is preferable that it is a black layer formed using. Moreover, the other component (For example, a polymeric compound, a binder polymer, or a polymerization initiator) may be contained in the composition.
Hereinafter, each component contained in the composition for black layer formation used for formation of a black layer is explained in full detail.

<Black pigment>
Various known black pigments can be used as the black pigment. In particular, from the viewpoint of realizing a high optical density with a small amount, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite and the like are preferable, and among them, at least one of carbon black and titanium black is preferable. It is preferable to include seeds, and titanium black is particularly preferable.
More specifically, C.I. I. Organic pigments such as Pigment Black 1 and inorganic pigments such as Pigment Black 7 can also be used.

The black pigment preferably contains titanium black.
Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. For example, it is possible to coat titanium black particles with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and repellent properties as disclosed in JP-A-2007-302836. Treatment with an aqueous material is also possible.
The titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm. In the present invention, the particle diameter, that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. Therefore, the value measured by the BET method is usually 5 m ² / g or more. It is about 150 m ² / g or less, preferably 20 m ² / g or more and 100 m ² / g or less.
Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si (silicon) atoms.
In this form, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti (titanium) atoms in the dispersion is 0 in terms of mass. .05 or more is preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In addition, since the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention is 0.5 or less, it tends to be easy to produce a pigment dispersion using the dispersion. The upper limit is preferably 0.5.
Further, when the black layer using the object to be dispersed is patterned by photolithography or the like, Si / Ti of the object to be dispersed is 0.05 or more and 0.0. It is more preferably 5 or less, and further preferably 0.07 or more and 0.4 or less.
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a mixture is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to thereby mainly contain titanium black particles. Thus, a dispersion containing Si and Ti can be obtained.
Here, the specific aspect for changing Si / Ti of a to-be-dispersed body is demonstrated.
Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is prepared by the method described in paragraphs [0005] and [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. Can do.

In the present invention, by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved. When a black layer is formed using a composition containing a dispersion, a residue derived from the composition outside the black layer formation region is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle and / or a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less). By increasing the amount of components contained, the adsorptivity of the entire film with the underlying layer is reduced, and this is presumed to contribute to the improvement of development removal of uncured compositions (particularly titanium black) in the formation of black layers. Yes.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is in terms of mass) And a black layer formed using a material having a thickness of 0.05 or more exhibits excellent light shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the black layer obtained by curing the composition Is determined by using the method (2) described in paragraph 0035 of JP2013-249417A.

In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Moreover, in this to-be-dispersed body, in addition to titanium black, for the purpose of adjusting dispersibility and coloring properties, complex oxides such as Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide, carbon black Further, a black pigment composed of aniline black or the like may be used in combination as a dispersion to be used alone or in combination of two or more.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In addition, in this dispersion, for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Furthermore, when the particle size of the silica particles is smaller than the film thickness when the black layer is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
The composition of the present invention may contain only one type of titanium black, or may contain two or more types.

The composition of the present invention may contain extender pigments as necessary in addition to black pigments. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the black pigment. In the present invention, the black pigment and extender pigment can be used after the surface thereof is modified with a polymer in some cases.
Moreover, in addition to a black pigment, you may contain colored organic pigments, such as red, blue, yellow, green, and purple, as needed. When the colored organic pigment is used in combination, it is preferable to use 1 to 40% by mass of the red pigment with respect to the black pigment, and it is preferable to use Pigment Red 254 as the red pigment.

<Dispersant>
The composition of the present invention preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the black pigment such as titanium black described above.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [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, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

The polymer compound is adsorbed on the surface of a dispersion such as a black pigment and a pigment to be used together if desired, and acts to prevent re-aggregation thereof. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures.
On the other hand, by adsorbing the surface of titanium black or the above-described dispersion to be dispersed containing titanium black and Si atoms, it is possible to promote the adsorptivity of the polymer compound to these.

The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of the black pigment and dispersion stability after aging because it has an affinity for a solvent by the graft chain. In addition, since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
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 the black pigment is lowered and the dispersibility tends to be lowered. Therefore, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

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

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

Corresponding to the structural unit having a graft chain of the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Gosei Co., Ltd.), AA-10 ( Product name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product) Name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer PP-500 ( Product name, NOF Corporation), BLEMMER PP-800 (trade name, NOF Corporation), BLEMMER PP-1000 (trade name, NOF Corporation), BLEMMER 55-PET-800 (product) Name, manufactured by NOF Corporation), BREMMER PME-4000 (trade name, manufactured by NOF Corporation), BREMMER PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, NOF Corporation) and BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) are used. Of 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.) 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 polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).

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

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. . In the structures shown below, A and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively. 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 each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

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

In formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other.
In the formula (4), R 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 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

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

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

The structural unit represented by the formula (3) is 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 are as defined ^X ^3, Y 3, ^{Z 3} and p in formula (3), and preferred ranges are also the same.

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

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

Further, the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (for example, a carboxylic acid group (carboxyl group), a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group).

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

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

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

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

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

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

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

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

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

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is 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—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, arylene group, substituted arylene group), heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, wherein R ³¹ is an aliphatic group, aromatic group or heterocyclic group), carbonyl And a group (—CO—) and combinations thereof.

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

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

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

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

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

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

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

A functional group capable of forming an interaction with a black pigment (particularly titanium black) can be introduced into the polymer compound. Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the black pigment.
Examples of the functional group capable of forming an interaction with the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. It is preferable to have a structural unit having or a structural unit having reactivity.
In particular, since the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, the polymer compound can be provided with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of the black pigment has alkali solubility in the composition of the present invention. A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
This is because the acid group in the structural unit having an acid group is likely to interact with the black pigment, the polymer compound stably disperses the black pigment, and the viscosity of the polymer compound that disperses the black pigment is low. This is presumably because the polymer compound itself is easily dispersed stably.

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

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

The polymer compound may have one or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is calculated in terms of mass with respect to the total mass of the polymer compound. The content is preferably 5 to 95%, and more preferably 10 to 90% from the viewpoint of suppressing damage to the image strength due to alkali development.

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

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

When the polymer compound in the present invention has a functional group capable of interacting with a black pigment in addition to the graft chain, it contains a functional group capable of interacting with various black pigments as described above. There is no particular limitation on how these functional groups are introduced, but polymer compounds are structural units derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to have one or more structural units selected from

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

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

In the general formulas (iv) to (v), L ₁ represents a single bond or a divalent linking group. 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, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

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

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

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

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is 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—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with the black pigment in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group. A carboxylic acid group is more preferable.

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

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

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

The content of the structural unit having a functional group capable of forming an interaction with the black pigment is based on the total mass of the polymer compound from the viewpoint of the interaction with the black pigment, the dispersion stability, and the permeability to the developer. 0.05 to 90 mass% is preferable, 1.0 to 80 mass% is more preferable, and 10 to 70 mass% is still more preferable.

Furthermore, for the purpose of improving various properties such as image strength, the polymer compound forms an interaction with the structural unit having a graft chain, the hydrophobic structural unit, and the black pigment as long as the effects of the present invention are not impaired. And further having other structural units having various functions (for example, structural units having functional groups having affinity with the dispersion medium used in the dispersion). May be.
Examples of such other structural units include structural units derived from radical polymerizable compounds selected from acrylonitriles and methacrylonitriles.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. More preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g. The range is as follows.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming the black layer is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Moreover, if the acid value of the polymer compound is 20 mgKOH / g or more, the precipitation of the black pigment (particularly titanium black) and the dispersion containing the titanium black and Si atoms can be further suppressed, and the number of coarse particles can be further increased. It can be reduced, and the stability with time of the composition can be further improved.

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

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene converted value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition and developability during development when forming a black layer. It is preferably 300 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

The polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include “Disperbyk-161, 162, 163, 164, 165, 166, 170, 190 (trade name, polymer copolymer)” manufactured by BYK Chemie, and Examples thereof include “EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane type), EFKA 4330, 4340 (trade name, block copolymer)” manufactured by EFKA.
These polymer compounds may be used alone or in combination of two or more.

As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

As the dispersant, in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

The content of the dispersant in the composition of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the composition.

<Solvent>
The composition of the present invention preferably contains a solvent.
Examples of the solvent include water and organic solvents.
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, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Nomethyl 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, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.

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

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable composition.
The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.
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, and 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 (acryloyloxypropiate) ) Polyether of pentaerythritol or dipentaerythritol after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane (Meth) acrylates, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-43191 and JP-B 52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid Can be mentioned Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.
Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 as general formula (1) and general formula (2) together with specific examples thereof and then (meth) acrylated Can also be used.
Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via an ethylene glycol residue or a propylene glycol residue. Is preferred. These oligomer types can also be used.
Further, 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 oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxylic acid group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxylic acid group-containing pentafunctional group. Examples thereof include TO-1382 which is an acrylate. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When using in combination of 2 or more types of polymeric compounds, the combination aspect can be suitably set according to the physical property etc. which are requested | required of a composition. As one suitable combination mode of the polymerizable compound, for example, a mode in which two or more polymerizable compounds selected from the polyfunctional acrylate compounds described above are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
The content of the polymerizable compound in the composition of the present invention is preferably 3% by mass to 55% by mass, and more preferably 10% by mass to 50% by mass with respect to the total solid content of the composition.

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity with respect to a visible ray from an ultraviolet region (what is called a photoinitiator). Preferably, it may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of monomer.
The polymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, oximes such as hexaarylbiimidazole and oxime derivatives. Examples thereof include compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by Ciba Japan) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Ciba Japan Co., Ltd.) can be used.
As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by Ciba Japan) can be used.

It is preferable to contain an oxime initiator (oxime compound) as a polymerization initiator.
Specific compound names of the oxime initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [ 4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O -Benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenyl) E) Phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyl) Oxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone and 1- (O-acetyloxime) -1- [9-ethyl- - (2-butyl benzoyl) -9H- carbazol-3-yl] ethanone, and the like.

Examples of oxime initiators include TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD). Commercial products can be used. In addition, the description of oxime initiators described in paragraphs 0092 to 0096 of JP2012-113104A can be referred to, and the contents thereof are incorporated in the present specification. By using such an oxime initiator, a composition having high curing sensitivity and good developability can be provided. The oxime-based initiator is a compound described in paragraphs 0030 and later of JP2012-113104A. The general formula is represented by the general formula (I) described in claim 1 of JP2012-113104A, and more preferably expressed by the general formula (IA) described in claim 3. Yes, these descriptions can be referred to, and the contents thereof are incorporated in the present specification.
In addition, J.H. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Paragraphs 0218-0281 of Japanese Patent Application Laid-Open No. 2000-80068, Special Table 2004 Compounds described in paragraphs 0242 to 0251 of No. 534797, IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE manufactured by BASF Japan OXE 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) thioxa Ten-9-one, O- acyl oxime compounds (e.g., ADEKAOPTOMER N-1919, ADEKA cruise NCI-831) or the like may be mentioned, the contents of which are incorporated herein.
Further, the cyclic oxime compounds described in paragraph 0031 of JP 2007-231000 A and paragraph 0039 of JP 2007-322744 A and specific substitutions shown in paragraphs 0060 to 0062 of JP 2007-26979 A Oxime compounds having a group, oxime compounds having a thioaryl group shown in paragraphs 0090 to 0106 of JP-A-2009-191061, and compounds described in paragraphs 0375 to 0409 of JP-A-2001-233842, etc. These contents are incorporated herein.
It is also possible to use an oxime initiator having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP And compound (C-3) described in paragraph 0101 of JP2013-164471A.

The content of the polymerization initiator in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content of the composition. More preferably, it is ˜10% by mass.

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

Examples of the binder polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, ie, resins obtained by homopolymerizing or copolymerizing monomers having a carboxylic acid group; Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated by homo- or copolymerization of monomers having products, epoxy acrylates in which epoxy resins are modified with unsaturated monocarboxylic acids and acid anhydrides, etc. Is mentioned. Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples of monomers having an acid anhydride include And maleic anhydride. 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.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has film strength and developability. It is excellent in balance and is suitable.
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 which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin is 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.
Commercially available products include, for example, Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Co., Ltd. 230AA etc. are mentioned.

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

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

<Other ingredients>
The composition of the present invention may contain components other than those described above.
For example, the composition of the present invention may contain an adhesive. By including the adhesive, the adhesion of the black layer to the base material is improved.
Examples of the adhesion agent include a silane coupling agent and a titanium coupling agent.
Examples of silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy. Silane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503) and the like.
The content of the adhesion agent is preferably 0.5% by mass to 30% by mass, more preferably 0.7% by mass to 20% by mass, based on the total solid content of the composition. More preferably, it is 7% by mass to 5% by mass.

The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 of JP2012-068418A (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and the contents thereof can be incorporated and incorporated in the present specification. It is.
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The composition may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition. The content is more preferably from 01 to 10% by mass, and further preferably from 0.1 to 5% by mass.

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

In addition to the above components, the following components may be further added to the composition. Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, sensitizers, and the like. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) These known additives may be added as necessary.
These components are described in, for example, paragraphs 0183 to 0228 of JP2012-003225A (corresponding [0237] to [0309] of US Patent Application Publication No. 2013/0034812) and JP2008-250074A. Paragraphs 0101 to 0102, paragraphs 0103 to 0104, paragraphs 0107 to 0109, paragraph numbers 0159 to 0184 of JP 2013-195480 A, and the like, which are incorporated herein by reference.

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

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. Can do.
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, more preferably about 0.3 to 6.0 μm. By setting it as this range, the foreign material mixed in the liquid mixture can be removed while the component particles contained in the liquid mixture remain.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

<Black layer production method>
A black layer can be formed by using the composition for forming a black layer described above.
Although the manufacturing method in particular of a black layer is not restrict | limited, The method of apply | coating the composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a black layer is mentioned.
The method for the curing treatment is not particularly limited, and examples thereof include a photocuring treatment and a thermosetting treatment, and a photocuring treatment (particularly, an ultraviolet irradiation treatment) is preferable because pattern formation is easy.
In addition, the kind of board | substrate used in particular is not restrict | limited, The various members (for example, infrared-light cut filter) in a solid-state imaging device etc. are mentioned preferably.

As a preferred embodiment in the case of producing a patterned black layer, a step of forming a composition layer by applying the composition of the present invention on a substrate (hereinafter, abbreviated as “composition layer formation step” as appropriate). ), A step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing the exposed composition layer to form a black layer (patterned black layer). And a step (hereinafter abbreviated as “development step” as appropriate).
Specifically, the composition of the present invention is applied on a substrate directly or via another layer to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern. By curing only the light-irradiated coating film portion (exposure step) and developing with a developer (development step), a patterned black layer can be produced.
Hereinafter, each process in the said aspect is demonstrated.

[Composition layer forming step]
In the composition layer forming step, a composition layer is formed by applying the composition of the present invention on a substrate.
Examples of the substrate include various members in the solid-state imaging device (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of a wafer level lens, and a back surface of the solid-state imaging device).
As a coating method of the composition of the present invention on the 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 composition coated on the substrate is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a composition layer.

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

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

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

<< Low refractive index layer >>
The material constituting the low-refractive index layer is not particularly limited, and may satisfy the above-described refractive index. Among them, a transparent resin such as a siloxane resin and a fluororesin is preferable because the refractive index can be easily controlled. It is preferable. Moreover, as will be described later, the low refractive index layer may contain hollow particles, non-hollow particles, or a surfactant. The low refractive index layer is preferably formed using a coating solution containing the transparent resin and other components.
Hereinafter, the material constituting the low refractive index layer will be described in detail.

<Siloxane resin>
A siloxane resin can be obtained through an hydrolysis reaction and a condensation reaction using an alkoxysilane compound. More specifically, for example, a part or all of alkoxy groups of alkyltrialkoxysilane are hydrolyzed to be converted into silanol groups, and at least a part of the generated silanol groups is condensed to form Si—O—Si bonds. What was formed is mentioned. The siloxane resin may be a siloxane resin having any silsesquioxane structure such as a cage type, a ladder type, and a random type. The “cage type”, “ladder type”, and “random type” can refer to, for example, the structures described in the chemistry and application development of silsesquioxane materials (CMC Publishing).

The siloxane resin of this embodiment preferably has a silsesquioxane structure represented by the following formula (1).
-(R ¹ SiO _3/2 ) _n -Formula (1)
(In the above formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom (preferably a fluorine atom), preferably 1 to 6 carbon atoms, 3 is more preferable, and n is an integer of 10 to 10,000, preferably an integer of 20 to 1,000.)
The alkyl group represented by R ¹ is not particularly limited as long as the carbon number is within the above range, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. R ¹ may have a substituent T described later, and examples of the optional substituent include a glycidyloxy group and a fluoroalkyl group having a fluorine atom.

In the present invention, unless otherwise specified, a silicon-containing polymer whose main chain is composed of siloxane bonds is called a polysiloxane or a siloxane resin. Since silicon has four bonds, the basic structural unit of polysiloxane is classified according to the number of organic groups typified by methyl and phenyl groups per silicon atom. It can be divided into two. In the following formula, R is an organic group.

In the present invention, silsesquioxane means a general term for polysiloxanes whose basic structural units are T units unless otherwise specified. Since silicon in silsesquioxane is bonded to three oxygens and oxygen is bonded to two silicons, the theoretical composition is RSiO _3/2 (the Latin word for three-half is "Sesquix (SESQUI) "). In the present embodiment, it is preferable that R in the formula of the T unit is R ¹ and that this silsesquioxane structure site is contained at a specific content described later.

The siloxane resin of the present embodiment preferably has a silsesquioxane structure in which 50% by mass or more and 100% by mass or less is represented by the above formula (1). This ratio is more preferably 80% by mass or more and 100% by mass or less, further preferably 95% by mass or more and 100% by mass or less, and particularly preferably 100% by mass (however, 100% by mass). %, Other components such as inevitable impurities may be contained within a range that does not impair the desired effect.) In addition, the siloxane resin of this embodiment may contain the specific polysilsesquioxane structure individually by 1 type, or may contain 2 or more types.

The siloxane resin of this embodiment is preferably a hydrolysis condensate obtained by hydrolytic condensation of alkyltrialkoxysilane. In order to produce the hydrolysis condensate in this embodiment, an alkoxysilane compound containing an alkyltrialkoxysilane can be used as a starting material. In addition, an alkoxysilane compound intends the starting material comprised from alkoxysilane (silicon compound which has an alkoxy group).
The alkyltrialkoxysilane is an organosilicon compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (2).
Formula (2): R ² Si (OR ³ ) ₃
(R ² is a halogen atom (preferably, an alkyl group having fluorine atoms) and having 1 carbon atoms which may 12 have, preferably from 1 to 6 carbon atoms, more preferably .R ³ is 1 to 3 carbon atoms Represents an alkyl group.)
The alkyl group (R ² in the formula (2)) of the alkyltrialkoxysilane is not particularly limited as long as it has a carbon number of 1 to 12, but is preferably a methyl group or an ethyl group, more preferably a methyl group. R ² may have a substituent T, and examples of the optional substituent include a glycidyloxy group and a fluoroalkyl group having a fluorine atom.
In addition, the compound represented by Formula (3) is mentioned as one of the suitable aspects of the organosilicon compound represented by Formula (2).
CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR ¹⁰ ) ₃ Formula (3)
(Wherein R ¹⁰ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 8)

The alkoxy group of the alkyltrialkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ³ in the formula (2) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R ³ in the formula (2) is an ethyl group is preferable because the hydrolysis rate can be easily controlled. R ³ may have a substituent T.

Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane and trifluoropropyltrimethoxysilane. Of these, methyltriethoxysilane and ethyltriethoxysilane are preferably used, and methyltriethoxysilane is more preferably used. In addition, as alkyl trialkoxysilane, only 1 type may be used and 2 or more types may be used together.

65% by mass or more of the alkoxysilane compound is preferably alkyltrialkoxysilane, more preferably 80% by mass or more and 100% by mass or less, and further preferably 95% by mass or more and 100% by mass or less.

In addition to the trialkoxysilane, other alkoxysilanes can be used as the alkoxysilane compound, and tetraalkoxysilane is particularly preferable.
Tetraalkoxysilane is an organosilicon compound in which four alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (4).
Formula (4): Si (OR ⁴ ) ₄
(R ⁴ each independently represents an alkyl group.)
The alkoxy group of tetraalkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ⁴ in formula (4) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R ⁴ in the formula (4) is an ethyl group is preferable because the hydrolysis rate can be easily controlled. R ⁴ may have a substituent T.
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-tert-butoxysilane. Can be mentioned. Of these, tetramethoxysilane and tetraethoxysilane are preferably used.
In addition, as tetraalkoxysilane, only 1 type may be used and 2 or more types may be used together.

The content of tetraalkoxysilane in the alkoxysilane compound is not particularly limited, but is preferably 35% by mass or less, and more preferably 20% by mass or less. Although there is no particular lower limit, in order to obtain the effect of adding tetraalkoxysilane, the content is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.
In addition, in the present invention, as a resin contained in the low refractive index layer, a hydrolyzate with a predetermined silicon compound described in paragraphs 0016 to 0024 of JP2013-253145A, and JP2012-0214772A The compounds described in paragraph Nos. 0030 to 0043 can be referred to, and the contents thereof are incorporated in the present specification.

In addition, in this specification, it uses for the meaning containing the salt and / or its ion other than the said compound itself about the display of a compound (For example, when attaching | subjecting and attaching | subjecting to a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
As described above, in the present specification, a substituent that does not clearly indicate substitution or non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also the same for compounds that do not specify substitution and non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentyl group, heptyl group, 1-ethylpentyl group, benzyl group, 2-ethoxyethyl group) And 1-carboxymethyl group), alkenyl group (preferably alkenyl group having 2 to 20 carbon atoms such as vinyl group, allyl group and oleyl group), alkynyl group (preferably 2 to 20 carbon atoms). Alkynyl groups such as ethynyl group, butadiynyl group and phenylethynyl group, etc., cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and 4-methylcyclohexyl group, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, An phenyl group, a 1-naphthyl group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-methylphenyl group, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably at least 1 A 5- or 6-membered heterocyclic group having two oxygen atoms, sulfur atoms, and nitrogen atoms is preferable. For example, a 2-pyridyl group, a 4-pyridyl group, a 2-imidazolyl group, a 2-benzimidazolyl group, a 2-thiazolyl group, And 2-oxazolyl groups), alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropyloxy group, and benzyloxy group), aryloxy groups (preferably carbon Aryloxy groups of 6 to 26, for example, phenoxy group, 1-naphthyloxy group, 3-methylphenoxy group, and 4- A toxiphenoxy group, etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as an ethoxycarbonyl group and a 2-ethylhexyloxycarbonyl group), an aryloxycarbonyl group (preferably having 6 to 6 carbon atoms). 26 aryloxycarbonyl groups such as phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 3-methylphenoxycarbonyl group, 4-methoxyphenoxycarbonyl group, etc., amino groups (preferably amino acids having 0 to 20 carbon atoms) Group, alkylamino group, arylamino group, such as amino group, N, N-dimethylamino group, N, N-diethylamino group, N-ethylamino group, and anilino group), sulfamoyl group (preferably C 0-20 sulfamoyl groups, eg For example, an N, N-dimethylsulfamoyl group and an N-phenylsulfamoyl group), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as an acetyl group, a propionyl group, and a butyryl group) An aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms such as a benzoyl group), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as an acetyloxy group), an aryloyloxy group (Preferably an aryloyloxy group having 7 to 23 carbon atoms, such as a benzoyloxy group), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as an N, N-dimethylcarbamoyl group, and an N— A phenylcarbamoyl group), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetyl An amino group, a benzoylamino group, etc.), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, such as a methylthio group, an ethylthio group, an isopropylthio group, and a benzylthio group), an arylthio group (preferably a carbon An arylthio group having a number of 6 to 26, such as a phenylthio group, a 1-naphthylthio group, a 3-methylphenylthio group and a 4-methoxyphenylthio group, an alkylsulfonyl group (preferably an alkylsulfonyl having 1 to 20 carbon atoms) A group such as a methylsulfonyl group and an ethylsulfonyl group, an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl), an alkylsilyl group (preferably having a carbon number of 1 to 20). An alkylsilyl group of, for example, a monomethylsilyl group A dimethylsilyl group, a trimethylsilyl group, and a triethylsilyl group), an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, such as a triphenylsilyl group), and a phosphoryl group (preferably having 0 to 20 carbon atoms). Phosphate groups such as —OP (═O) (R ^P ) ₂ ), phosphonyl groups (preferably phosphonyl groups having 0 to 20 carbon atoms such as —P (═O) (R ^P ) ₂ ), phosphinyl group (preferably phosphinyl group having 0 to 20 carbon atoms, for example, ^-P (R _P) 2), (meth) acryloyl group, (meth) acryloyloxy group, a hydroxyl group, a cyano group, and a halogen atom (e.g., fluorine atom , Chlorine atom, bromine atom, iodine atom, etc.).
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.
When a compound or a substituent, a linking group or the like includes an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group or the like, these groups may be cyclic or chain-like. Alternatively, when these groups are chain-like, they may be linear or branched. Further, these groups may be substituted as described above or unsubstituted.
Each substituent may be substituted via the following linking group Lx as long as the effects of the present invention are achieved. For example, an alkyl group, an alkylene group, an alkenyl group, and an alkenylene group may further have the following hetero-linking group interposed in the structure.
Examples of the linking group Lx include a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably Has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), an alkynylene group having 2 to 10 carbon atoms (more preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), 6 to 22 carbon atoms Arylene groups (more preferably 6 to 10 carbon atoms)], hetero-linking groups [carbonyl group (—CO—), thiocarbonyl group (—CS—), ether group (—O—), thioether group (—S—) ), An imino group (—NR ^N —), an imine linking group (R ^N —N═C <, —N═C (R ^N ) —)], or a linking group obtained by combining these. In addition, when condensing and forming a ring, the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect. The ring formed is preferably a 5-membered ring or a 6-membered ring. As the 5-membered ring, a nitrogen-containing 5-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, and These derivatives are exemplified. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Further, when an aryl group, a heterocyclic group or the like is included, they may be monocyclic or condensed, and may be similarly substituted or unsubstituted.
^RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (2 carbon atoms). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyl group (preferably 2 to 24, preferably 2 to 12). More preferably, 2 to 6 carbon atoms are more preferable, and 2 to 3 carbon atoms are particularly preferable), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and even more preferably 7 to 10 carbon atoms). ), An aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, and still more preferably having 6 to 10 carbon atoms).
^RP is a hydrogen atom, a hydroxyl group, or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (2 carbon atoms). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyl group (preferably 2 to 24, preferably 2 to 12). More preferably, 2 to 6 carbon atoms are more preferable, and 2 to 3 carbon atoms are particularly preferable), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and even more preferably 7 to 10 carbon atoms). ), An aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, preferably having 1 to 12 carbon atoms) Preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and an alkenyloxy group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and further preferably 2 to 6 carbon atoms). An alkynyloxy group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms). An aralkyloxy group (preferably having 7 to 22 carbon atoms, more preferably having 7 to 14 carbon atoms, and further preferably having 7 to 10 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, and having 6 to 14 carbon atoms) More preferred are those having 6 to 10 carbon atoms).
The number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and particularly preferably 1 to 6. The number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH ₂ —C (═O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
Specific examples of combinations of linking groups include the following. Oxycarbonyl group (OCO), carbonate group (OCOO), amide group (CONH), urethane group (NHCOO), urea group (NHCONH), (poly) alkyleneoxy group (-(Lr-O) x-), carbonyl ( Poly) oxyalkylene group (—CO— (O—Lr) x—, carbonyl (poly) alkyleneoxy group (—CO— (Lr—O) x—), carbonyloxy (poly) alkyleneoxy group (—COO— ( Lr-O) x-), (poly) alkyleneimino group (-(Lr-NR ^N ) x), alkylene (poly) iminoalkylene group (-Lr- (NR ^N -Lr) x-), carbonyl (poly) iminoalkylene group ^{(-CO- (NR N -Lr) x-} ), carbonyl (poly) alkyleneimino group ^{(-CO- (Lr-NR N)} x -), ( poly) S. Group (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-(O-Lr-CO) x-,-(Lr-CO-O) x-,-(Lr -O-CO) x-), (poly) amide group (-(CO-NR ^N -Lr) x-,-(NR ^N -CO-Lr) x-,-(NR ^N -Lr-CO) x- ,-(Lr-CO-NR ^N ) x-, and-(Lr-NR ^N -CO) x-), etc. x is an integer of 1 or more, preferably 1 to 100, and preferably 1 to 20 More preferred.
Lr is preferably an alkylene group, an alkenylene group or an alkynylene group. The carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. A plurality of Lr, R ^N , R ^P , and x need not be the same. The direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.

The siloxane resin can be obtained through the hydrolysis reaction and the condensation reaction using the above-described alkoxysilane compound.
As the hydrolysis reaction and the condensation reaction, known methods can be used, and a catalyst such as an acid or a base may be used as necessary. The catalyst is not particularly limited as long as it changes the pH. Specifically, examples of the acid (organic acid, inorganic acid) include nitric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid. . Examples of the alkali include ammonia, triethylamine, and ethylenediamine. The amount to be used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.

If necessary, a solvent may be added to the reaction system of the hydrolysis reaction and condensation reaction. The solvent is not particularly limited as long as the hydrolysis reaction and the condensation reaction can be performed. For example, water, alcohols such as methanol, ethanol, and propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether And ethers such as methyl acetate, ethyl acetate, butyl acetate, and esters such as propylene glycol monomethyl ether acetate, and ketones such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.

The conditions for the hydrolysis reaction and condensation reaction (temperature, time, amount of solvent) are appropriately selected according to the type of material used.

The weight average molecular weight of the siloxane resin used in the present embodiment is preferably 1,000 or more, more preferably 2,000 or more, further preferably 2,500 or more, and particularly preferably 3,000 or more. The upper limit is preferably 50,000 or less, more preferably 45,000 or less, and particularly preferably 25,000 or less.
In the present invention, the molecular weight of the polymer means a weight average molecular weight unless otherwise specified, and is measured in terms of standard polystyrene by gel permeation chromatography (GPC). The measuring apparatus and conditions are basically based on the following condition 1 and are allowed to be set to condition 2 depending on the solubility of the sample. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for it may be selected and used.
(Condition 1)
Column: TOSOH TSKgel Super HZM-H, TOSOH
TSKgel Super HZ4000, TOSOH TSKgel
A column connected with Super HZ2000 is used Carrier: Tetrahydrofuran Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (Condition 2)
Column: Two TOSOH TSKgel Super AWM-Hs are connected Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

<Fluorine resin>
A fluororesin is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl. Examples thereof include vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluoride, and vinylidene fluoride / ethylene copolymers. For example, fluorine siloxane polymers described in JP-A No. 2004-21036 are also exemplified.

Of these, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are preferable, and polytetrafluoroethylene is more preferable. A polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferably used.
Amorphous fluororesins are also preferably used, and examples of commercially available products include CYTOP (manufactured by Asahi Glass). The molecular weight of fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, which is particularly effective for extrusion moldability and flame retardancy. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800 and the like are commercially available.

Further, as the fluororesin, an amorphous fluororesin, a copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, a fluorocoating agent, a fluorosurfactant, an electron beam or a fluorocarbon surface treatment containing an ultraviolet curing component A fluorine-based surface treatment agent containing an agent and a thermosetting component is also preferable. As another copolymerization component of the copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, alkyl acrylate or alkyl methacrylate is preferable.

A specific example is shown below. Examples of the amorphous fluororesin include Lumiflon manufactured by Asahi Glass Co., Ltd. and CYTOP. Copolymer oligomers containing perfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate as main components include Nippon Oil & Fats Modiper F Series, Daikin Industries Unidyne, Dainippon Ink & Chemicals Examples thereof include F470 series, F480 series, and F110 series, and the copolymerization is more preferably block copolymerization. As a fluorine-type coating agent, Sumitomo 3M EGC1700 is mentioned. Examples of the fluorosurfactant include Megafac F114, F410 series, 440 series, 450, and 490 series manufactured by Dainippon Ink and Chemicals, Inc. Examples of the fluorine-based surface treatment agent containing an electron beam or an ultraviolet ray curable component include Polyfox PF-3320 manufactured by Omniva Solutions, Cheminox FAMAC-8 manufactured by Unimatec, and EGC1720 manufactured by Sumitomo 3M. Examples of the fluorine-based surface treating agent containing a thermosetting component include EGC1720 manufactured by Sumitomo 3M, NH-10 manufactured by Dainippon Ink and Chemicals, and NH-15.

<Solvent>
The solvent used in preparing the coating liquid containing the transparent resin (siloxane resin or fluororesin) (hereinafter also simply referred to as “transparent resin coating liquid”) is not limited, but the reaction used in the hydrolysis reaction. Examples of the solvent or organic solvent are given. Of these, alcohol compounds, ether compounds, and ester compounds are preferable, and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, and ethyl lactate are more preferable.
The solid content concentration in the coating solution of the transparent resin is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. As an upper limit, 50 mass% or less is preferable, 25 mass% or less is more preferable, and 10 mass% or less is further more preferable.

<Surfactant>
The coating solution containing the transparent resin may contain a surfactant from the viewpoint of further improving the coating property. Especially, it is preferable that the surfactant which has a polyoxyalkylene structure is contained in the coating liquid containing transparent resin. The polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are adjacent to each other, and specifically includes an ethylene oxide (EO) structure, a propylene oxide (PO) structure, and the like. Can be mentioned. As the surfactant having a polyoxyalkylene structure, as long as it has the polyoxyalkylene structure, a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant, etc. Various surfactants can be used. Among these, nonionic surfactants, anionic surfactants, and silicone surfactants are preferable, nonionic surfactants and anionic surfactants are more preferable, and anionic surfactants are more preferable.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, F781F (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, S-141, S- 145, SC-101, SC-103, SC-104, SC-105, SC-106, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), EFtop EF301, EF303, EF351, EF352 (above, manufactured by Gemco), PF636, PF65 , PF6320, PF6520, PF7002 (OMNOVA Co., Ltd.), and the like.
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane ethoxylate and propoxylate (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether (Emulgen 404 manufactured by Kao Corporation), polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, ELEBASE manufactured by Aoki Oil & Fat Co., Ltd. Examples include BUB-3.
Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), EMULSOGEN COL-020, EMULSOGEN COA-070, EMULSOGEN COL-080, manufactured by Clariant Japan Co., Ltd., Daiichi Kogyo Examples include Prisurf A208B manufactured by Pharmaceutical Co., Ltd., ETC-3 manufactured by Nippon Chemicals Co., Ltd.
Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 ", manufactured by Big Chemie," DBE-22 "manufactured by GELEST ", Such as" DBE-621 ", and the like.
Only one type of surfactant may be used, or two or more types may be combined.

Moreover, as a surfactant having a preferred polyoxyalkylene structure of the present embodiment, a surfactant represented by the following formula (5) can be mentioned.
Equation ^{^{(5): R 5 O (}} R 6 O) m R 7
(In the above formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. R ⁶ represents an alkylene group having 1 to 4 carbon atoms. R ⁷ represents a hydrogen atom, a carboxylic acid group, or —PO ₃ H ₂ . M represents an integer of 1 to 8.)
R ⁵ may be a linear or branched alkyl group. Of these, 5 to 20 carbon atoms are preferable, and 12 to 18 carbon atoms are more preferable.
R ⁶ may be a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among these, an ethylene group and an isopropylene group (a group forming an adjacent O atom and an ethylene oxide structure or a propylene oxide structure) are preferable.
R ⁷ is preferably a hydrogen atom or a carboxylic acid group, and more preferably a carboxylic acid group.

Other surfactants may be used, and among them, a silicone surfactant is preferably used. Preferred silicone surfactants include polysiloxane surfactants in which an organic group is introduced into a side chain or a terminal, or a side chain and a terminal. As a side chain group, an amino group, an epoxy group, a carbinol group, a mercapto group, a carboxylic acid group, a hydrogen group, a polyether group, an aralkyl group, a fluoroalkyl group, and a phenyl group, as a terminal group, an amino group, Examples thereof include an epoxy group, a carbinol group, a methacryl group, a polyether group, a mercapto group, a carboxylic acid group, a phenol group, a silanol group, and a diol group.

Alternatively, it is also preferable to contain an alkylalkoxysilane compound having a specific carbon number (hereinafter referred to as “alkoxysilane compound α”). You may use together 3 types of surfactant of surfactant which has said polyoxyalkylene structure, silicone type surfactant, and alkoxysilane compound (alpha). As the alkoxysilane compound α, an alkoxysilane compound having an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms) is preferably used. When this is represented by a general formula, it is preferably a compound represented by the following formula (6).
Formula (6): Si (OR ⁵¹ ) _n-4 (R ⁵² ) _n
Here, R ⁵¹ is the same group as R ⁴ described above. R ⁵² is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms. n is an integer of 1 to 3.

The addition amount of the surfactant is not particularly limited, but the lower limit is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, based on 100 parts by mass of the transparent resin. More preferably 5 parts by mass or more. Although an upper limit is not specifically limited, 30 mass parts or less are preferable and 15 mass parts or less are more preferable.

<Hollow particles and non-hollow particles>
The coating liquid or low refractive index layer containing a transparent resin preferably contains hollow particles and / or non-hollow particles. As the particles, porous fine particles may be used. The hollow particle has a structure having a cavity inside, and refers to a particle having a cavity surrounded by an outer shell. The porous particle refers to a porous particle having a large number of cavities. Hereinafter, the hollow particles and / or the non-hollow particles are appropriately referred to as “specific particles”. The specific particles may be organic particles or inorganic particles.

The porosity of the specific particles is preferably 10 to 80%, more preferably 20 to 60%, and still more preferably 30 to 60%. The porosity of the specific particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
Among the specific particles, hollow particles are more preferable from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = 1.6).

As a method for producing hollow particles, for example, the method described in JP-A-2001-233611 can be applied. Further, as a method for producing porous particles, for example, methods described in JP-A-2003-327424, 2003-335515, 2003-226516, and 2003-238140 can be applied. .

The specific particles preferably have an average primary particle size of 1 nm or more, and more preferably 10 nm or more. The upper limit is preferably 200 nm or less, and more preferably 100 nm or less.
The average primary particle size of the specific particles here can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, and the average primary particle size is obtained. In the present specification, the average primary particle diameter is obtained by measuring the projected area of 300 or more particles, obtaining the equivalent circle diameter, and calculating the number average diameter.
The refractive index of the specific particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and still more preferably 1.15 to 1.30.

The specific particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride or silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The crystal system of the inorganic particles may be either crystalline or amorphous. The inorganic particles may be monodispersed particles or aggregated particles as long as a predetermined particle diameter is satisfied. The shape of the inorganic particles may be a spherical shape, a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape, and a spherical shape is more preferable.
The specific surface area of the inorganic particles is preferably 10 m ² / g to 2000 m ² / g, more preferably 20 m ² / g to 1800 m ² / g, and 50 m ² / g to 1500 m ² / g. Is more preferable.

Specific examples of specific particles include IPA-ST having a number average particle size of 12 nm using isopropanol as a dispersant, MIBK-ST having a number average particle size of 12 nm using methyl isobutyl ketone as a dispersant, and number average using isopropanol as a dispersant. IPA-ST-L with a particle size of 45 nm, IPA-ST-ZL with a number average particle size of 100 nm using isopropanol as a dispersant, PGM-ST with a number average particle size of 15 nm using propylene glycol monomethyl ether as a dispersant (product names above) (Manufactured by Nissan Chemical Industries, Ltd.), “Oscar (registered trademark)” 101 having a number average particle diameter of 12 nm using γ-butyrolactone as a dispersant, and “Oscar” having a number average particle diameter of 60 nm using γ-butyrolactone as a dispersant. 105, “Oscar” 10 having a number average particle size of 120 nm using diacetone alcohol as a dispersant 6. Number average particle diameter of 5 to 80 nm “Cataloid (registered trademark)”-S (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl ether as a dispersant. “Quartron” PL-2L-PGME with a particle size of 16 nm, “Quartron” PL-1-PGME with a number average particle size of 12 nm, and “Quartron” PL with a number average particle size of 17 nm using γ-butyrolactone as a dispersant. -L-BL, “Quatron” PL-1-BL with a number average particle size of 13 nm, “Quatron” PL-2L-DAA with a number average particle size of 17 nm using diacetone alcohol as a dispersant, “Quatron” with a number average particle size of 13 nm "Quartron" PL-1-DAA, "Quortron" PL-2L, GP with a number average particle size of 18 to 20 nm, whose dispersion is water 2L, the number-average particle size 13 ~ 15 nm "Quartron" PL-1 (trade name, manufactured by Fuso Chemical Co.), silica number average particle diameter of _{100nm (SiO 2) SG-SO100} ( trade name, Kyoritsu Material Co., Ltd.), “Leosil (registered trademark)” (manufactured by Tokuyama Co., Ltd.) having a number average particle size of 5 to 50 nm, and the like. Specific examples of the hollow silica particles include those commercially available, such as those disclosed in Japanese Patent Application Laid-Open No. 2001-233611 and Japanese Patent No. 3272111. Moreover, you may contain 2 or more types of these silica particles and hollow silica particles.

Specific particles used in the present invention include silica fine particles having a porous and / or hollow inside, and silica fine particles having a non-porous inside and having no hollow. Among these silica fine particles, silica fine particles having a porous and / or hollow interior are preferable for lowering the refractive index of the low refractive index layer. Silica fine particles that are not porous inside and do not have a hollow have a refractive index of 1.45 to 1.5, so that the expected effect of lowering the refractive index is small. On the other hand, silica fine particles having a porous and / or hollow interior have a large refractive index reducing effect because the refractive index of the particles themselves is 1.2 to 1.4. That is, silica fine particles having a porous and / or hollow interior are preferably used in that they can impart excellent hardness and low refractive index properties.

In this specification, the refractive index of specific particles can be measured by the following method. A mixed resin sample of a matrix resin and a specific particle having a solid content concentration of 10%, which are prepared so that the content of the specific particle is 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass is prepared. Each is coated on a silicon wafer by using a spin coater so as to have a thickness of 0.3 to 1.0 μm. Next, the obtained silicon wafer is heated on a hot plate at 200 ° C. for 5 minutes and then dried to obtain a coating film. Next, for example, the refractive index of the coating film at a wavelength of 633 nm (25 ° C.) is obtained using an ellipsometer (VUV-base [trade name] manufactured by JA Woollam), and the value of 100% by mass of silica fine particles is extrapolated. Can be sought.

Introducing silica fine particles having a porous and / or hollow interior into the coating material not only can optimize the refractive index of the film obtained from the coating material, but also increase the hardness of the film. preferable.

Silica fine particles that are not porous inside and have no hollow are, for example, IPA-ST in which isopropanol having a particle size of 12 nm is used as a dispersant, MIBK-ST in which methyl isobutyl ketone having a particle size of 12 nm is used as a dispersant, particles IPA-ST-L using isopropanol having a diameter of 45 nm as a dispersant, IPA-STZL using isopropanol having a particle diameter of 100 nm as a dispersant (trade name, manufactured by Nissan Chemical Industries, Ltd.), γ-butyrolactone having a particle diameter of 12 nm Oscar 101 using γ-butyrolactone as a dispersant, Oscar 105 using γ-butyrolactone with a particle size of 60 nm, Oscar 106 using diacetone alcohol with a particle size of 120 nm as a dispersant (trade name, JGC Catalysts & Chemicals Co., Ltd.) Manufactured). In addition, the presence or absence of a hollow can be confirmed by a particle cross-sectional image by a TEM (transmission electron microscope) photograph.

Examples of commercially available silica fine particles include organosilica sol “OSCAL” (manufactured by JGC Catalysts & Chemicals Co., Ltd.), colloidal silica “Snowtex”, organosilica sol (manufactured by Nissan Chemical Industries, Ltd.), and high purity colloidal. Silica, high-purity organosol “Quartron” (Fuso Chemical Co., Ltd.) and the like can be mentioned.

In order to stabilize dispersion or to increase the affinity or binding property with the binder component, the specific particles may be subjected to physical surface treatments such as plasma discharge treatment and corona discharge treatment, or surfactants and cups. Chemical surface treatment with a ring agent or the like may be performed. Of these, the use of a coupling agent is preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the specific particles are silica particles and the coupling agent is a silane compound, organosilyl groups (monoorganosilyl, diorganosilyl, triorganosilyl groups) are converted into silica particles by the reaction of the silane compound and the silanol group. It binds to the surface. Examples of the organic group on the surface of the surface-treated silica particles include a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms and a halogenated hydrocarbon group having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for specific particles in advance for surface treatment prior to the preparation of the coating solution for the low refractive index layer, or may be added as an additive during the preparation of the coating solution.
The specific particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Commercially available particles can be preferably used as the specific particles made of silica.
For example, Julia Catalysts Co., Ltd. through rear series (hollow particles, isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc., such as through rear 2320), OSCAL series, Nissan Chemical Co., Ltd. Snowtex series (porous particles, IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate) Dispersion, xylene-n-butanol dispersion, toluene dispersion, etc. For example, MIBK-SD-L, MIBK-ST, etc.), Sirenax (porous particles) manufactured by Nittetsu Mining Co., Ltd., PL manufactured by Fuso Chemical Industry Co., Ltd. series Porous particles, IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc., such as PL-1-IPA, PL-2L-PGME, etc., Aerosil series manufactured by EVONIK (porous particles, propylene glycol acetate dispersion) Silica particles such as ethylene glycol dispersion and MIBK dispersion) can be used.

In the present invention, it is also preferable to use a particle aggregate (also referred to as beaded silica) in which a plurality of silica particles are linked in a chain as the specific particle, and more specifically, the beaded colloidal silica particles are contained in a liquid medium. It is also more preferable to use a sol dispersed in the above. Generally, as the silica particles contained in the silica sol, in addition to the bead shape, spherical, needle-like or plate-like ones are widely known, but in this embodiment, the silica sol in which the bead-like colloidal silica particles are dispersed is used. It is preferable to use it. This is because the presence of these beaded colloidal silica particles facilitates formation of pores in the formed film, and a film having a very low refractive index can be formed. Further, the particle size is small, and the haze of the film can be reduced.

The beaded colloidal silica particles are preferably those in which a plurality of spherical colloidal silica particles having an average particle diameter of 5 to 50 nm are joined by a metal oxide-containing silica. If the average particle diameter is less than the lower limit, the refractive index of the film after formation does not sufficiently decrease. On the other hand, if the average particle diameter exceeds the upper limit, the haze of the film may increase due to irregularities on the film surface. The average particle diameter of the spherical colloidal silica particles is preferably in the range of 5 to 30 nm. In addition, the average particle diameter of the said spherical colloidal silica particle means the average particle diameter measured by BET method.

The beaded colloidal silica particles have a number average particle diameter (D1 nm) measured by the dynamic light scattering method of the spherical colloidal silica particles and a specific surface area Sm ² measured by the nitrogen adsorption method of the spherical colloidal silica particles. The ratio D1 / D2 with respect to the average particle diameter (D2 nm) obtained by the formula of D2 = 2720 / S from / g is 3 or more, the D1 is 30 to 300 nm, and the spherical colloidal silica particles are in one plane. It is preferable that it is connected only to. If D1 / D2 is less than 3, the haze of the film after formation may increase. D1 / D2 is preferably 3 to 20. If it is less than the lower limit, the particles tend to aggregate and form a precipitate. On the other hand, if the upper limit is exceeded, the haze of the formed film may increase. D1 is preferably 35 to 150 nm. Moreover, as a metal oxide containing silica which joins a spherical colloidal silica particle, an amorphous silica, an amorphous alumina, etc. are illustrated, for example. Examples of the liquid medium in which the beaded colloidal silica particles are dispersed include methanol, ethanol, IPA, ethylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
The silica sol used preferably has a SiO ₂ concentration of 5 to 40% by mass. If the SiO ₂ concentration of the silica sol to be used is too low, the refractive index of the film after formation may not be sufficiently lowered. On the other hand, if it is too high, the SiO ₂ in the silica sol tends to aggregate and the liquid may become unstable. . As such a silica sol in which beaded colloidal silica particles are dispersed, for example, a silica sol described in Japanese Patent No. 4328935 or JP2013-253145A can be used.

The content of the specific particles in the dispersion is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and further preferably 15% by mass to 30% by mass.

The content of the specific particles with respect to the total solid content in the coating solution of the transparent resin is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass. More preferably, it is mass%.
When a transparent resin film is formed, the coating amount of the specific particles is preferably 1 mg / m ² to 100 mg / m ² , more preferably 5 mg / m ² to 80 mg / m ² , still more preferably 10 mg / m ² to 60 mg / m ² . By being 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be surely obtained, and by being 100 mg / m ² or less, the low refractive index layer (cured film) It is possible to suppress the deterioration of the integrated reflectance due to the formation of fine irregularities on the surface of the substrate.
In this specification, the total solid component or the total solid content refers to a component that does not volatilize or evaporate when dried at 100 ° C. Typically, it refers to components other than solvents and dispersion media.

<Curing agent>
The transparent resin coating solution may further contain a curing agent. As a hardening | curing agent, the hardening | curing agent containing Al, Mg, Mn, Ti, Cu, Co, Zn, Hf, and Zr is preferable, and these can also be used together.

These curing agents can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

Preferable specific examples of the metal group chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tris Aluminum chelate compounds such as (acetylacetonate), ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, magnesium chelate compounds such as magnesium bis (acetylacetonate), zirconium tetra Acetylacetonate, zirconium tributoxyacetylacetonate, di Benzalkonium acetylacetonate bis (ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, and, and titanium oxy acetylacetonate. Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering availability, aluminum tris (acetylacetonate) and aluminum tris (ethyl acetoacetate) are particularly preferable.

The total content of the curing agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total content of the transparent resin. More preferably, it is 0.01 parts by mass to 0.5 parts by mass.

<Viscosity>
The viscosity of the transparent resin coating solution is preferably adjusted from the viewpoint of forming a thick and permeable film. The specific viscosity range is not particularly limited, but is preferably 1 to 20 mPa · s, more preferably 1.2 to 15 mPa · s, and particularly preferably 1.5 to 6 mPa · s. . Unless otherwise indicated, the viscosity value in this specification shall be based on the following measuring method.
Measurement method Measured at room temperature (about 25 ° C.) using an E-type viscometer “TV-20 type viscometer / corn plate type TVE-20L” (manufactured by Toki Sangyo). Sampling is the average of the values measured for viscosity 5 times every 100 seconds.

The method for producing the low refractive index layer is not particularly limited, but the low refractive index is obtained by applying a coating solution containing the above-described transparent resin such as siloxane resin or fluorine resin on the black layer, and performing heat treatment as necessary. The method of forming a layer is mentioned.
As an application mode, a spin coating method, a dip coating method, a roller blade method, a spray method, or the like can be applied.
The conditions for the heat treatment are not particularly limited, but are preferably 50 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher. As an upper limit, it is preferable that it is 200 degrees C or less, It is more preferable that it is 150 degrees C or less, It is further more preferable that it is 120 degrees C or less. Although the said heating time is not specifically limited, It is preferable that it is 0.5 to 60 minutes, and it is more preferable that it is 1 to 10 minutes.
The method for the heat treatment is not particularly limited, and it can be heated by a hot plate, an oven, a furnace, or the like.
There is no particular limitation on the atmosphere in the heat treatment, and an inert atmosphere, an oxidizing atmosphere, or the like can be used. The inert atmosphere can be realized by an inert gas such as nitrogen, helium and argon. The oxidizing atmosphere can be realized by a mixed gas of these inert gas and oxidizing gas, or air may be used. Examples of the oxidizing gas include oxygen, carbon monoxide, and oxygen dinitride. The heating step can be carried out under pressure, normal pressure, reduced pressure, or vacuum.

<Method of forming light shielding film in pattern>
When the light shielding film of the present invention is formed in a pattern, the above-described method for producing the black layer in a pattern and the method for forming the low refractive index layer in a pattern can be appropriately combined.
As a specific example, a black layer forming composition and a low refractive index layer forming composition are both made into a photocurable composition containing a photopolymerization initiator and a polymerizable compound. The method of patterning simultaneously is mentioned. In addition, a black layer is formed in a pattern, a low refractive index layer is formed on the black layer so as to cover the patterned black layer, and a resist film is further disposed on the low refractive index layer for pattern exposure. And developing to form a resist pattern on the low refractive index layer, and then dry etching using the resist pattern as a mask so that the low refractive index layer remains on the patterned black layer. There is also a method of removing the resist pattern after etching. As a method for forming a pattern by dry etching, for example, methods described in JP2013-64993A and JP2010-134352A can be referred to.

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

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

As shown in FIGS. 3 and 4, the light shielding film (light shielding layer) 11 described above is arranged over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided. A cut filter is formed. The reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 3 and 4) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the device, When the reflected light R2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image. The light shielding film 11 shields harmful light such as reflected light R <b> 1 and R <b> 2 toward the CMOS sensor 3. The light shielding film 11 is applied by, for example, spin coating or spray coating. 3 and 4, the thickness of the light shielding film 11 is exaggerated.

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

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

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

Note that the above-described light-shielding film (light-shielding layer) can also be disposed in a part of the CMOS sensor 3 shown in FIG. 3, and this is preferable because the occurrence of flare is suppressed in such applications.

Hereinafter, the present invention will be described more specifically. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. Unless otherwise specified, “part” and “%” are based on mass. Room temperature refers to 25 ° C.
In addition, about the present Example, it filtered all using DFA4201NXEY (0.45 micrometer nylon filter) made from a Japanese pole about each after adjusting the dispersion mentioned later and preparing the composition mentioned later.

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

<Preparation of titanium black dispersion (TB dispersion 1)>
According to the production method of paragraphs 0338 to 0340 of JP 2010-106268 A, a specific resin 2 represented by the following formula was obtained. The weight average molecular weight of the specific resin 2 was 40000, the acid value was 100 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

Specified resin 2

Components shown in the following composition I were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a mixture a.
(Composition I)
-Titanium black (A-1) obtained as described above-25 parts by mass-30% by mass solution of propylene glycol monomethyl ether acetate in specific resin 2-25 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA ) (Solvent): 23 parts by mass / Butyl acetate (Solvent): 27 parts by mass

The obtained dispersion a was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd., and a titanium black dispersion (hereinafter referred to as TB dispersion 1). Got.

(Distribution condition)
・ Bead diameter: φ0.05mm, made of zirconia ・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 11m / s
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 60 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Number of passes: 90 passes

<Preparation of black layer forming composition 1>
A black layer forming composition 1 was prepared by mixing the following components.
TB dispersion 1 43.4 parts by mass Cyclomer P (ACA) 230AA (binder polymer; solid content 54%) manufactured by Daicel Chemical Industries, Ltd. 13.2 parts by mass KAYARAD DPHA (polymerizable compound) manufactured by Nippon Kayaku Co., Ltd. 7.1 parts by mass KAYARAD RP-1040 (polymerizable compound) manufactured by Nippon Kayaku Co., Ltd. 7.1 parts by mass IRGACURE OXE02 (polymerization initiator) manufactured by Chibake Specialty Chemical 2.1 parts by mass 4-methoxyphenol (polymerization inhibitor) 0.007 parts by mass Megafac F781F (fluorine-containing polymer surfactant) manufactured by DIC Corporation 0.02 parts by mass Propylene glycol monomethyl ether acetate (solvent) 22.7 parts by mass butyl acetate (solvent) 1.14 parts by mass Part compound 1 (adhesive) 1.14 parts by mass

<Preparation of low refractive dispersion B-1>
According to the description in paragraphs 0032 to 0034 and paragraph 0042 (Example 1-1) of JP2013-253145A, a low refractive dispersion B-1 was obtained.

<Preparation of composition 1 for forming a low refractive index layer>
The composition 1 for forming a low refractive index layer was prepared by mixing the following components. In addition, the composition 1 for forming a low refractive index layer contained a particle aggregate (beaded colloidal silica) in which a plurality of silica particles continued in a chain.
・ Low refractive dispersion B-1 75.3 parts by mass ・ Surfactant 1: 0.1 part by mass of 10 mass% PGMEA solution of F-781F (fluorinated polymer type surfactant) manufactured by DIC Corporation ・ Organic solvent 1 : Ethyl lactate 24.6 parts by mass

<Preparation of low refractive resin B-2>
Hydrolysis and condensation reactions of methyltriethoxysilane were carried out using ethanol as a solvent and hydrochloric acid as a catalyst to obtain a hydrolysis-condensation product having a weight average molecular weight of about 10,000. The weight average molecular weight was confirmed by GPC according to the procedure described above.

<Preparation of composition 2 for forming a low refractive index layer>
A composition 2 for forming a low refractive index layer was prepared by mixing the following components.
-Low refractive resin B-2 6.3 parts by mass-Surfactant 2: EMUL-020: Emulsogen COL-020
(Anionic surfactant, manufactured by Clariant Co., Ltd.) 0.5 parts by mass Organic solvent 3: 93.2 parts by mass of 2-heptanone

<Preparation of low refractive dispersion B-3>
In the low refractive dispersion B-1, the beaded colloidal silica contained in the low refractive dispersion B-1 was changed to hollow particles, and the others were performed in the same manner. Specifically, the hydrolyzate of silicon alkoxide (A) and silicon alkoxide (B) and the silica of the hollow particles are used in such a ratio that the hollow particles become 200 parts by mass with respect to 100 parts by mass of SiO ₂ in the hydrolyzate. The composition was obtained by stirring and mixing.

<Preparation of composition 3 for forming a low refractive index layer>
The composition 3 for forming a low refractive index layer was prepared by mixing the following components.
-Low refractive dispersion B-3 75.3 parts by mass-Surfactant 1: 0.1 part by mass of 10 mass% PGMEA solution of F-781F (fluorinated polymer type surfactant) manufactured by DIC Corporation-Organic solvent 2 : Propylene glycol monomethyl ether acetate 24.6 parts by mass

<Examples 1 to 3: Production of light shielding film (part 1)>
After apply | coating the composition 1 for black layer formation produced above to the glass substrate by the spin coat method, it heat-processed (prebaked) for 120 second using a 100 degreeC hotplate with respect to the obtained coating film. . Next, the coating film was exposed at an exposure amount of 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Then, the black layer with a film thickness of 3.5 micrometers was formed by performing heat processing (post-baking) for 300 second using a 200 degreeC hotplate.
Next, the low refractive index layer-forming compositions 1 to 3 were applied onto the obtained black layer using a spin coater so as to obtain an average film thickness of the low refractive index layer shown in Table 1 described later. Then, the low refractive index layer was formed by implementing a drying process at 100 degreeC / 120sec with a hotplate, and the light shielding film was manufactured.

In Comparative Example 1 described later, a black layer was formed using the black layer forming composition 1 according to the same procedure as in Examples 1 to 3 described above, and a low refractive index layer was disposed. Absent.

<Evaluation>
(Evaluation of reflectance)
Light of 400 to 1300 nm was incident on the produced light-shielding film at an incident angle of 5 °, and the reflectance was measured with a spectrometer UV4100 manufactured by Hitachi High-Technologies.

(Evaluation of transmittance)
Light of 400 to 750 nm was incident on the prepared light shielding film at an incident angle of 0 °, and the transmittance was measured with a spectrometer UV4100 manufactured by Hitachi High-Technologies. Table 1 shows the maximum value of the transmittance of the above light of 400 to 750 nm.

(Measurement of refractive index of low refractive index layer)
The refractive index of the low refractive index layer obtained from the low refractive index layer forming compositions 1 to 3 was measured as follows.
The low refractive index layer-forming compositions 1 to 3 were each applied to an 8-inch silicon wafer by spin coating, and then the coating film was heated on a hot plate at 100 ° C. for 2 minutes. Furthermore, the coating film was heated on a hot plate at 230 ° C. for 10 minutes to obtain a low refractive index layer (film thickness: 0.1 μm).
The refractive index of the low refractive index layer with respect to light having a wavelength of 850 nm and 940 nm was measured on the silicon wafer with a low refractive index layer obtained above using ellipsometry manufactured by JA Woollam Japan.

<Preparation of light shielding film (part 2)>
The black layer-forming composition 1 prepared above is applied to the incident surface of the IR cut filter by a coater / developer ACT (made by TEL) by spin coating, and then heat-treated for 120 seconds using a 100 ° C. hot plate. By performing (pre-baking), a coating film was formed. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the coating film was subjected to pattern exposure in a frame shape with an exposure amount of 200 mJ / cm ² through a mask.
Then, using the coater / developer ACT and the organic alkaline developer CD-2060 (manufactured by FUJIFILM Electronics Materials) as the developer for the IR cut filter on which the irradiated coating film is formed. Paddle development was performed for 60 seconds at room temperature. After development, the coating film is rinsed with pure water for 20 seconds in a spin shower, and further washed with pure water with respect to the coating film, and then heated for 300 seconds using a 200 ° C. hot plate ( By performing post-baking, a black layer having a frame pattern of 7.0 mm × 5.0 mm and a width of 0.7 mm was formed on the IR cut filter to produce an IR cut filter with a frame pattern.
Next, on the black layer from which the low refractive index layer-forming composition 1, 2, or 3 was obtained using a spin coater so as to obtain an average film thickness of the low refractive index layer shown in Table 1 described later. It was applied and dried on a hot plate at 100 ° C. for 120 seconds, and then heat-treated (post-baked) for 600 seconds using a 230 ° C. hot plate to form a low refractive index layer.
Next, a resist pattern was formed on the low-refractive index layer, and then dry etching was performed, and the resist pattern was peeled off to produce a light-shielding film so that the low-refractive index layer remained only on the black layer. Specifically, pattern formation was performed according to the following procedure.
On the low refractive index layer, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied with a spin coater, and heat treatment is performed at 100 ° C. for 2 minutes, and the film thickness is 1.0 μm. A photoresist layer was formed to a thickness. Next, pattern exposure of 250 mJ / cm ² was performed on the photoresist layer with an i-line stepper (manufactured by Canon Inc., FPA3000i5 +), followed by heat treatment at 110 ° C. for 1 minute. . Then, after developing the pattern-exposed photoresist layer with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, post-baking at 100 ° C. for 1 minute is performed. The photoresist layer on the low refractive index layer region not formed on the black layer was removed to form a resist pattern. Next, the low refractive index layer that was not formed on the black layer was removed under the following dry etching conditions. Thereafter, the resist pattern was removed under the following removal conditions.

<Dry etching conditions: removal of low refractive index layer>
Equipment used: Dry etching chamber use treatment parameters of U-621 (Single wafer dry etching, ashing equipment) manufactured by Hitachi High-Technologies Corporation Pressure: 2.0 Pa
Gas used: Ar / C ₄ F ₆ / O ₂ = 1000 mL / min / 20 mL / min / 50 mL / min
Processing temperature: 20 ° C
Source power: 500W
Upper bias / electrode bias = 500 W / 1000 W
Processing time: 220 sec

<Removal condition: removal of photoresist>
Equipment used: U-621 ashing chamber use treatment parameters manufactured by Hitachi High-Technologies Corporation Pressure: 2 Pa
Gas used: O ₂ / Ar = 50/1000 (mL / min 60 sec)
Temperature: 20 ° C
Source power: 1000W
Processing time: 60 sec

(Flare evaluation)
A solid-state imaging device in which the light-shielding film produced as described above is arranged in the state of FIG. 2 of the attached drawing is placed in a dark room and irradiated with an infrared LED (SMD) light (model number TIR-LN90S) manufactured by 3D Corporation Was imaged. The results were judged as follows.
Similar results were obtained even when the irradiated light was changed to a 3D infrared LED (SMD) light (model number TIR-LN80S).
A: Overexposure does not occur in the entire image B: Overexposure occurs slightly, but the image can be recognized C: Overexposure occurs, and the image cannot be recognized

In Table 1, the “black pigment content” column represents the content (mass%) of the black pigment relative to the total mass of the black layer.

As shown in Table 1 above, it was confirmed that when the light-shielding film of the present invention was used, the visible light transmittance was low and flare was suppressed.
In particular, in Examples 1 and 3 in which the reflectance is 1.0% or less (the refractive index of the low refractive index layer is 1.30 or less), flare is further suppressed.
On the other hand, in Comparative Example 1 where the reflectance is outside the predetermined range, the desired effect was not obtained.
A similar flare suppression effect was also observed for the frame pattern produced around the CMOS sensor.

2, 20, 30, 40 Solid-state imaging device 3 CMOS sensor 4 Circuit board 5 Ceramic substrate 5a Opening 5b Inner wall surface 6 IR cut filter 7 Shooting lens 8 Lens holder 9 Holding cylinder 11, 21, 31, 41, 50 layer)
52 Black layer 54 Low refractive index layer

Claims

Including at least a black layer,
The content of the black pigment contained in the black layer is 20 to 60% by mass with respect to the total mass of the black layer,
The reflectance in light of at least one wavelength selected in the wavelength range of 800 to 1000 nm is 3.0% or less,
A light-shielding film having a transmittance of 50% or less at a wavelength of 400 to 750 nm.
Furthermore, the light shielding film of Claim 1 containing the low-refractive-index layer of refractive index 1.50 or less arrange | positioned on the said black layer.
The light-shielding film according to claim 2, wherein a refractive index of the low refractive index layer is 1.30 or less.
The light-shielding film according to claim 2 or 3, wherein the average thickness of the low refractive index layer is 50 to 300 nm.
The light-shielding film according to any one of claims 2 to 4, wherein the low refractive index layer includes a particle aggregate in which a plurality of silica particles are chain-connected.
An infrared light with a light shielding film, comprising: an infrared light cut filter; and the light shielding film according to any one of claims 1 to 5 disposed on at least a part of a surface of the infrared light cut filter. Cut filter.
A solid-state imaging device comprising the light-shielding film according to any one of claims 1 to 5.