KR20200028028A - Structure, partition wall forming composition, solid-state imaging element, and image display device - Google Patents

Abstract

A structure having a partition wall having a small refractive index and excellent smoothness is provided. In addition, a composition for forming a barrier rib used in the structure, a solid-state imaging device including the structure, and an image display device are provided. The structure 100 has a support 1, a partition 2 provided on the support 1, and a pixel 4 provided in a region partitioned by the partition, and the partition 2 is a cage-type siloxane compound. It is a partition wall formed using the composition. It is preferable that the cage-type siloxane compound has a partial structure represented by "(* -SiO _1.5 ) _n ". In the formula, * represents a connecting hand, and n represents an integer from 6 to 16.

Description

Structure, partition wall forming composition, solid-state imaging element, and image display device

The present invention relates to a structure in which a pixel is provided in a region partitioned by a partition wall on a support. Moreover, it is related with the composition for partition formation, a solid-state imaging element, and an image display device.

2. Description of the Related Art Recently, with the spread of digital cameras, mobile phones equipped with cameras, and the like, demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has grown significantly. Color filters are used as key devices for displays and optical elements.

As one form of the solid-state imaging element, a solid-state imaging element or the like having a structure in which a colored layer is provided in a region partitioned by a partition on a support is known.

For example, Patent Document 1 includes a color filter array having a semiconductor substrate, a separation wall separating a color filter layer of two or more colors, and a color filter layer of at least two colors, and a semiconductor filter and a color filter array. A solid-state imaging device having a condensing means disposed therebetween is described.

On the other hand, Patent Literatures 2 and 3 describe inventions related to a composition containing a cage-type siloxane compound. Patent Document 2 describes that an insulating film is formed using a composition containing a cage-type siloxane compound. In addition, Patent Document 3 describes that an antireflection film is formed using a composition containing a cage-type siloxane compound.

Patent Document 1: Japanese Patent Application Publication No. 2009-111225 Patent Document 2: Japanese Patent Application Publication No. 2007-254506 Patent Document 3: Japanese Patent Application Publication No. 2008-214455

In a structure in which a pixel is provided in a region partitioned by a partition on a support, it is considered to use a material having a low refractive index as a material for the partition. For example, in paragraph 0046 of Patent Document 1, it is described that a low-refractive material such as glass, a porous layer of an SiO ₂ film, a fluorine-based polymer, or a siloxane polymer is used as the material of the partition wall.

For example, by making the refractive index of the partition wall relatively smaller than the refractive index of the pixel, the light collection rate of light passing through the pixel can be increased or light leakage to other adjacent pixels can be prevented. Can increase. For this reason, in recent years, it is desired to further reduce the refractive index of the partition wall.

On the other hand, when the inventor proceeded to examine the partition wall using the low refractive material described in Patent Document 1, it was found that there is room for further improvement in the refractive index of the partition wall.

In addition, although the partition wall is generally formed by forming a partition material layer on a support and patterning the partition material layer by a dry etching method or the like, it is understood that the smoothness of the partition wall side surface may be insufficient. Could. When the smoothness of the side surface of the partition wall is insufficient, scattering of light passing through the pixel or the like may occur, and the light collection rate of the light may not be sufficiently increased. For this reason, it is preferable that the smoothness of the side surface of the partition wall is high.

Accordingly, an object of the present invention is to provide a structure having a partition wall having a small refractive index and excellent smoothness. Moreover, it is providing the composition for partition formation used for the structure mentioned above, the solid-state imaging element containing the structure, and an image display apparatus.

According to the examination of the inventors of the present invention, it has been found that a structure having a partition wall having a small refractive index and excellent smoothness can be produced by forming a partition wall using a composition containing a cage-type siloxane compound and a solvent. I came to Hagi. Therefore, the present invention provides the following.

<1> a support,

The partition wall provided on the support,

A pixel provided in an area partitioned by a partition,

A structure in which the partition wall is a partition wall formed using a composition containing a cage-type siloxane compound.

<2> The structure according to <1>, wherein the cage-type siloxane compound contains a cage-type siloxane compound having an O / Si ratio of 1.3 to 1.7, which is a ratio between the number of oxygen atoms and the number of silicon atoms.

<3> The structure according to <1> or <2>, wherein the cage-type siloxane compound contains a partial structure represented by the following formula (S1);

(* -SiO _1.5 ) _n … (S1)

In the formula, * represents a connecting hand, and n represents an integer from 6 to 16.

<4> The structure according to any one of <1> to <3>, wherein the cage-type siloxane compound contains at least one selected from a compound represented by the following formula (S2) and a polymer obtained by polymerizing the compound;

(R ^S1 -SiO _1.5 ) _n … (S2)

Wherein, R ^S1 is an alkyl group or polymerizable group, n is an integer of 6 ~ 16, n of 2 or more R R ^S1 of ^S1 is a polymerizable group.

The <5> cage-type siloxane compound is a structure according to any one of <1> to <4>, which has a partial structure represented by the following formula (S1-1);

Formula (S1-1)

[Formula 1]

The broken line in the above formula represents a bonding hand.

<6> The structure according to any one of <1> to <5>, wherein the cage-type siloxane compound contains a polymer having a weight average molecular weight of 50,000 to 300,000.

The structure according to any one of <1> to <6>, wherein the <7> pixel contains at least one pixel selected from a colored pixel, a transparent pixel, and a pixel of the infrared transmission layer.

<8> A composition for forming a barrier rib used for forming a barrier rib of a structure having a support, a partition provided on the support, and a pixel provided in a region partitioned by the partition, for forming a partition comprising a cage-type siloxane compound and a solvent. Composition.

<9> A solid-state imaging device having the structure according to any one of <1> to <7>.

<10> An image display device having the structure according to any one of <1> to <7>.

According to the present invention, it is possible to provide a structure having a partition having a small refractive index and excellent smoothness. Further, it is possible to provide a composition for forming a barrier rib used in the above-described structure, a solid-state imaging device including the structure, and an image display device.

1 is a side cross-sectional view showing an embodiment of the structure of the present invention.
It is a top view seen from the direction just above the support body in the same structure.

Hereinafter, the content of the present invention will be described in detail.

In the description of the group (atomic group) in the present specification, the notation that does not describe substitution and unsubstitution includes those that do not have a substituent and have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In the present specification, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Moreover, as a light used for exposure, active light rays or radiations, such as bright spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams, are generally mentioned.

In the present specification, the numerical range indicated by using "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of components from which the solvent has been removed from all components of the composition.

In the present specification, "(meth) acrylate" represents both or both of acrylate and methacrylate, and "(meth) acrylic" represents both of acrylic and methacryl, or either, "(Meth) allyl" represents both or both of allyl and metalyl, and "(meth) acryloyl" represents both or both of acryloyl and methacryloyl.

In the present specification, the term "process" is included in this term when the desired action of the process is achieved, even if it is not clearly distinguishable from other processes as well as independent processes.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Structure>

The structure of the present invention will be described with reference to the drawings. 1 is a side cross-sectional view showing an embodiment of the structure of the present invention, and FIG. 2 is a plan view seen from the direction directly above the support in the structure.

1 and 2, the structure 100 of the present invention includes a support 1, a partition 2 provided on the support 1, and a pixel 4 provided in a region partitioned by the partition 2 ). Then, in the structure 100 of the present invention, the partition wall 2 is characterized in that it is a partition wall formed using a composition containing a cage-type siloxane compound.

Since the partition wall in the structure of the present invention is formed using a composition containing a cage-type siloxane compound, the refractive index is small and excellent in smoothness. Since the cage-type siloxane compound has a structure having a relatively large pore in the molecular structure, the refractive index of the barrier can be further reduced by forming the partition wall using a composition containing the cage-type siloxane compound. Moreover, by forming a partition wall using a cage-type siloxane, it is possible to suppress roughness or the like of the obtained partition wall, and a partition wall having excellent smoothness can be formed. For this reason, according to the structure of the present invention, a structure having a partition wall having a small refractive index and excellent smoothness can be obtained. In addition, since the structure of the present invention has a small refractive index of the partition wall and excellent smoothness, it is possible to further increase the light condensation rate of light passing through the pixel. For this reason, by introducing and using the structure of the present invention as a solid-state imaging element or an image display device, the sensitivity of imaging and sensing can be further increased.

Moreover, the structure of the present invention is also excellent in adhesion between the partition wall and the pixel. Since the cage-type siloxane compound has a structure in which a functional group such as an organic group is bonded to a siloxane skeleton, the affinity with the pixel is improved by this functional group, or it becomes easy to interact with the pixel, resulting in excellent adhesion. I guess I was able to get it.

The structure of the present invention can be suitably used for solid-state imaging elements, image display devices, and the like. More specifically, it can be suitably used for an imaging device mounted on a digital still camera, digital video camera, surveillance camera, in-vehicle camera, or the like. Hereinafter, the structure of the present invention will be described in detail.

In the structure of the present invention, the material of the support 1 is not particularly limited. It can be appropriately selected depending on the application. For example, substrates made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, or substrates (silicon wafers, silicon carbide wafers) used in various electronic devices such as solid-state imaging devices , Silicon nitride wafer, sapphire wafer, glass wafer, etc.) can be used. Further, a charge bonding element (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. Moreover, a black matrix made of a light-shielding material such as tungsten may be formed on the support. Moreover, the base layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate, if necessary.

A partition 2 is formed on the support 1. In this embodiment, as shown in Fig. 2, the partition wall 2 is formed in a lattice shape in a plan view seen from the direction directly above the support 1. In this embodiment, the shape of the region partitioned by the partition 2 on the support 1 (hereinafter also referred to as the shape of the opening of the partition) has a square shape, but the shape of the opening of the partition is , It is not particularly limited, and may be, for example, a rectangular shape, a circular shape, an elliptical shape, or a polygonal shape.

The partition 2 is formed using a composition containing a cage-type siloxane compound. Here, the cage-type siloxane compound is a compound having a cage-type siloxane structure. It is preferable that the partition wall 2 has a cage-like siloxane structure. The cage-type siloxane structure may be a fully cage-type siloxane structure or an incomplete cage-type siloxane structure, but may be formed of a fully caged type because it is easier to form a partition having a smaller refractive index and more smoothness. It is preferably a siloxane structure. Here, the full-cage siloxane structure means a siloxane structure of a polyhedral structure including a closed space formed by siloxane linkage, and an incomplete-cage siloxane structure is a full-cage siloxane structure. It means the siloxane structure of the structure partially opened by.

It is preferable that the cage-type siloxane compound contains a cage-type siloxane compound having O / Si of 1.3 to 1.7, which is a ratio between the number of oxygen atoms and the number of silicon atoms.

Moreover, it is preferable that a cage-type siloxane compound is a compound containing the partial structure represented by following formula (S1).

(* -SiO _1.5 ) _n … (S1)

In the formula, * represents a connecting hand, and n represents an integer from 6 to 16.

n is preferably 8, 10, 12, 14, or 16, more preferably 8, 10, or 12, and more preferably 8.

As a specific example of the partial structure represented by Formula (S1), the structures represented by Formulas (S1-1) to (S1-7) are listed below, and those having a partial structure represented by Formula (S1-1) have refractive index and smoothness It is preferred in terms of. In addition, the broken line in Formula (S1-1)-(S1-7) represents a bonding hand, respectively.

Formula (S1-1)

[Formula 2]

[Formula 3]

The form of the cage-type siloxane compound may be either a monomer or a polymer, but it is preferable to include at least a polymer from the viewpoints of refractive index and smoothness of the partition walls to be obtained. The content of the polymer in the total mass of the cage-type siloxane compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

The molecular weight of the monomer (monomer type cage type siloxane compound) is preferably 400 to 2,000.

It is preferable that the weight average molecular weight of a polymer (polymer type cage type siloxane compound) is 50,000-300,000. The upper limit is more preferably 280,000 or less, more preferably 250,000 or less, and even more preferably 240,000 or less from the viewpoint of the filterability of the composition containing this polymer. The lower limit is more preferably 70,000 or more, more preferably 90,000 or more, and even more preferably 100,000 or more from the viewpoint of refractive index. Moreover, as for the dispersion degree (weight average molecular weight / number average molecular weight) of a polymer, 2-4 are preferable, 2-3.5 are more preferable, and 2.5-3.5 are more preferable.

Moreover, it is preferable that the polymer mentioned above is a polymer which has a partial structure represented by said Formula (S1-1).

The cage-type siloxane compound preferably contains at least one selected from the compound represented by the following formula (S2) and the polymer obtained by polymerizing the compound, and more preferably contains the above-described polymer.

(R ^S1 -SiO _1.5 ) _n … (S2)

Wherein, R ^S1 is an alkyl group or polymerizable group, n is an integer of 6 ~ 16, n of 2 or more R R ^S1 of ^S1 is a polymerizable group.

As for carbon number of the alkyl group represented by R ^S1 , 1-10 are preferable, 1-8 are more preferable, 1-5 are more preferable, and 1-3 are especially preferable. The alkyl group may be either linear, branched or cyclic, preferably linear or cyclic, more preferably linear. As a specific example of an alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-butyl group, cyclobutyl group, pentyl group, 2- A pentyl group, 3-pentyl group, isoamyl group, cyclopentyl group, hexyl group, 2-hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclooctyl group, preferably , Methyl group or ethyl group, and more preferably methyl group.

As the polymerizable group represented by R ^S1 , a group containing a carbon-carbon double bond or a carbon-carbon triple bond is preferable. As a group containing a carbon-carbon double bond or a carbon-carbon triple bond, for example, a vinyl group, an allyl group, 1-propenyl group, 1-butenyl group, 2-buten-1-yl group, 1-butene-4 -Yl group, 1-hexene-6-yl group, ethanine group, propargyl group, 2-butyn-1-yl group. These groups may have a substituent. Preferably, a vinyl group, a vinyl group which has a substituent, an ethynyl group, or an ethynyl group which has a substituent is mentioned. Examples of the substituent in the above include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and the like.

The polymerizable group represented by R ^S1 may be composed of only a group containing a carbon-carbon double bond or a carbon-carbon triple bond, and a contribution consisting of a group containing a carbon-carbon double bond or a carbon-carbon triple bond and a divalent linking group do. In this case, a group containing a carbon-carbon double bond or a carbon-carbon triple bond is bonded to the silicon atom through a divalent linking group.

As said divalent coupling group,

-[C (R ¹¹ ) (R ¹² )] _k- , -CO-, -O-, -N (R ¹³ )-, -S-, -O-Si (R ¹⁴ ) (R ¹⁵ )-, and And a divalent linking group capable of combining them arbitrarily. (R ¹¹ to R ¹⁵ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and k represents an integer of 1 to 6.) Among them,-[C (R ¹¹ ) (R ¹² )] _k -, -O-, -O-Si (R ¹⁴ ) (R ¹⁵ )-or a divalent linking group capable of arbitrarily combining them is preferred.

The polymerizable group represented by R ^S1 is preferably a vinyl group and an ethynyl group, and more preferably a vinyl group.

The polymer obtained by polymerizing the compound represented by formula (S2) can be obtained by a radical polymerization or hydrosilylation reaction of the compound represented by formula (S2).

Examples of the initiator used for radical polymerization include organic peroxides and organic azo compounds, and organic peroxides are preferred. For details of the organic peroxide and the organic azo-based compound, compounds described in paragraphs 0041 to 0042 of JP 2007-254506 A can be cited, the contents of which are incorporated herein by reference.

It is preferable to perform the polymerization by the hydrosilylation reaction of the compound represented by Formula (S2) with the compound represented by Formula (S2) and a silane compound in the presence of a radical generator or a transition metal catalyst. Examples of the radical generator include organic peroxides and organic azo-based compounds. Examples of the transition metal catalyst include platinum catalyst, rhodium catalyst, nickel catalyst, cobalt catalyst, rhenium catalyst, manganese catalyst, chromium catalyst, and iridium catalyst, and platinum catalyst is preferred. For details of the transition metal catalyst, reference may be made to the description of paragraph No. 0048 of JP 2007-254506 A, which is incorporated herein by reference. Moreover, when performing polymerization by a hydrosilylation reaction, it is preferable to use a crosslinking agent. As the crosslinking agent, a compound having a plurality of SiH bonds is preferable, and tetramethylcyclotetrasiloxane, hydro-T8-silsesquioxane, and the like can be preferably used.

In the present invention, the cage-type siloxane compound preferably contains at least one selected from the compound represented by the formula (S2-1) and the polymer obtained by polymerizing the compound, and more preferably contains the above-described polymer. desirable.

Expression (S2-1)

[Formula 4]

In the above formula, R ^S11 to R ^S18 each independently represent an alkyl group or a polymerizable group, and 2 to 4 of R ^S11 to R ^S18 represent a polymerizable group.

About the alkyl group and polymerizable group represented by R ^S11 -R ^{S18, it} is synonymous with the alkyl group and polymerizable group represented by R ^S1 of Formula (S2), and a preferable range is also the same.

Specific examples of the compound represented by the formula (S2) include compounds described in paragraphs 0023 to 0039 of JP 2007-254506, and compounds described in paragraphs 0021 to 0024 of JP 2008-214455 A, and The content is incorporated herein. Moreover, as a polymer of the compound represented by Formula (S2), the polymer which has a structure represented by following formula (S2-1-1)-Formula (S2-1-3) is mentioned.

[Formula 5]

The composition used for the formation of the partition 2 can further contain other components such as a solvent in addition to the cage-type siloxane compound. The composition (composition for partition formation) used for formation of the partition 2 will be described later.

It is preferable that the width W1 of the partition 2 is 20 to 500 nm. The lower limit is more preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The upper limit is more preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.

The height H1 of the partition 2 is preferably 200 to 1000 nm, and more preferably 300 to 700 nm. Further, the height H1 of the partition 2 is preferably less than or equal to 200% of the thickness of the pixel 4, more preferably less than or equal to 150% of the thickness of the pixel 4, and substantially equal to the thickness of the pixel 4 It is more preferable to say the same.

The ratio (height (H1) / width (W1)) of the height H1 and the width W1 of the partition 2 is preferably 1 to 100 from the viewpoint of formability of the partition, and more preferably 5 to 50 And more preferably 5 to 30.

The pitch P1 of the partition 2 is not particularly limited. It can be appropriately selected depending on the application. For example, in the use of a high-pixel solid-state imaging device, it is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, and even more preferably 500 to 1000 nm.

The refractive index of the light having a wavelength of 550 nm of the partition wall 2 is preferably 1.10 to 1.40, more preferably 1.15 to 1.37, and even more preferably 1.20 to 1.35.

The pixel 4 is formed in the region (opening of the partition wall) on the support 1 and partitioned by the partition wall 2. The type of the pixel is not particularly limited. And colored pixels such as red, blue, green, magenta, and cyan, and pixels of the infrared transmission layer and transparent pixels. Although the type and arrangement of pixels can be arbitrarily selected, it is preferable that the pixel 4 includes at least one pixel selected from a colored pixel and a pixel of the infrared transmission layer.

As a transparent pixel, it is preferable that the minimum value of the transmittance | permeability in the range of wavelength 400-600 nm is 80% or more, it is more preferable that it is 90% or more, and it is more preferable that it is 95% or more.

As a pixel of the infrared transmission layer, for example, it is preferably a pixel of a filter layer having a spectral characteristic that transmits at least a portion of light in a wavelength range of 700 to 2500 nm, and a spectral characteristic that transmits at least a portion of light in a wavelength range of 700 to 2000 nm. It is more preferable that it is a pixel of the filter layer having a, and it is more preferable that it is a pixel of the filter layer having a spectral characteristic that transmits at least a portion of light in the wavelength range of 700-1500 nm, It is more preferable that it is a pixel of the filter layer having spectral characteristics, and it is particularly preferable that it is a pixel of the filter layer having spectral characteristics that transmits at least a part of light in the wavelength range of 700 to 1000 nm. Moreover, the infrared ray transmitting layer may be composed of a single layer film (single layer film) or a laminate (multilayer film) of two or more layers. In addition, when the infrared transmission layer is composed of a multi-layer film, it is sufficient to have the above-described spectral properties as a whole of the multi-layer film, and it is not necessary to have the above-described spectral properties for the film itself of each layer.

Preferred examples of the pixels of the infrared transmission layer include, for example, pixels of the filter layer having any one of the following (1) to (4) spectral characteristics.

(1): The maximum value in the range of the wavelength of 400 to 640 nm of the transmittance of light in the thickness direction is 20% or less (preferably 15% or less, more preferably 10% or less), and in the thickness direction The pixel of the filter layer whose light transmittance has a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the range of 800 to 1300 nm in wavelength. According to this pixel, light in the range of 400 to 640 nm in wavelength can be shielded and light of wavelength 720 nm or more can be transmitted.

(2): The maximum value in the range of the wavelength 400 to 750 nm of the light transmittance in the thickness direction is 20% or less (preferably 15% or less, more preferably 10% or less), and in the thickness direction The pixel of the filter layer whose light transmittance has a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the range of wavelength 900 to 1300 nm. According to this pixel, light in a wavelength range of 400 to 750 nm can be shielded, and light having a wavelength of 850 nm or more can be transmitted.

(3): The maximum value in the range of the wavelength of 400 to 850 nm of the transmittance of light in the thickness direction is 20% or less (preferably 15% or less, more preferably 10% or less), and in the thickness direction The pixel of the filter layer whose light transmittance has a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in a wavelength range of 1000 to 1300 nm. According to this pixel, light in a range of 400 to 850 nm in wavelength can be shielded and light of wavelength 940 nm or more can be transmitted.

(4): The maximum value in the range of the wavelength of 400 to 950 nm of the transmittance of light in the thickness direction is 20% or less (preferably 15% or less, more preferably 10% or less), and in the thickness direction The pixel of the filter layer whose light transmittance has a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in a wavelength range of 1100 to 1300 nm. According to this pixel, light in a range of 400 to 950 nm in wavelength can be shielded and light of wavelength 1040 nm or more can be transmitted.

The height H2 of the pixel 4 can be appropriately selected depending on the application. For example, in the use of a solid-state imaging device, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, and even more preferably 300 to 600 nm. Further, the height H2 of the pixel 4 is preferably 50 to 150% of the height H1 of the partition 2, more preferably 70 to 130%, and more preferably 90 to 110%. Do.

The pixel 4 can be formed using various composition for pixel formation. The composition for pixel formation will be described later.

In the structure of the present invention, an organic material layer may be provided between the partition 2 and the pixel 4. According to this aspect, the adhesion between the partition 2 and the pixel 4 can be further improved. As an organic material layer, it can form using a composition containing a resin, a curable compound, or the like. As a resin, (meth) acrylic resin, epoxy resin, polyester resin, etc. are mentioned, for example. Examples of the curable compound include materials described later.

In the structure of the present invention, a condenser lens or the like may be provided on the pixel 4. Further, the condenser lens may be provided on the surface of the pixel, or an intermediate layer may be further provided between the pixel 4 and the condenser lens. Examples of the intermediate layer include the above-described organic material layer, low-refractive layer, and the like. The low-refractive layer may be a film formed using the composition for forming a partition wall of the present invention.

<Composition for bulkhead formation>

Next, the composition (composition for partition formation) used for formation of the partition wall in the structure of the present invention is further described in detail.

(Cage-type siloxane compound)

The composition for forming a partition wall contains a cage-type siloxane compound. The above-mentioned thing is mentioned about cage type siloxane compound.

The content of the cage-type siloxane compound in the composition for partition formation is preferably 1% by mass or more, and more preferably 5% by mass or more.

The content of the cage-type siloxane compound in the total solid content of the composition for forming a partition is preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more. The larger the content of the cage-like siloxane compound in the total solid content of the composition for forming a partition, the lower the refractive index and the easier the formation of the partition with excellent smoothness.

The content of the polymer type cage-type siloxane compound in the total solid content of the composition for forming a partition is preferably 45% by mass or more, more preferably 65% by mass or more, and even more preferably 85% by mass or more.

Moreover, the content of the polymer type cage-type siloxane compound in the total mass of the cage-type siloxane compound contained in the composition for forming a partition is preferably 50% by mass or more, more preferably 70% by mass or more, and 90 It is more preferable that it is at least mass%. It is also preferable that the cage-type siloxane compound is substantially only a polymer-type cage-type siloxane compound. In addition, when the cage-type siloxane compound contained in the composition for forming a partition wall is substantially only a polymer-type cage-type siloxane compound, a polymer-type cage-type siloxane compound in the total mass of the cage-type siloxane compound It means that the content of is 99% by mass or more, more preferably 99.5% by mass or more, and more preferably only a polymer type cage-type siloxane compound.

Moreover, as a cage type siloxane compound, a polymer type cage type siloxane compound and a monomer type cage type siloxane compound can also be used together. The curability of the composition for partition formation can be improved by using both together. In addition, it is possible to increase the adhesion to the pixel. When both are used together, it is preferable that the monomer type cage-type siloxane compound is 0.01 to 10 parts by mass, and more preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the polymer-type cage-type siloxane compound.

(Other low-refractive materials)

The composition for forming a partition wall of the present invention may contain other low-refractive materials other than cage-type siloxane compounds. Other low-refractive materials include siloxane resins, fluorine resins, colloidal silica particles, and the like other than cage-type siloxane compounds.

As a siloxane resin, the resin obtained through a hydrolysis reaction and a condensation reaction using an alkoxysilane raw material is mentioned. The siloxane resin may be a siloxane resin having a cage-type silsesquioxane structure.

Examples of the fluorine resin include resins containing fluorine in the molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer Coalescence, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, and the like. Moreover, amorphous fluorine resin is preferably used, and CYTOP (made by Asahi Glass) etc. is mentioned as a commercial item. The weight average molecular weight of fluororesins such as polytetrafluoroethylene is preferably in the range of 100,000 to 10 million, more preferably 100,000 to 1 million. As commercially available products of polytetrafluoroethylene, Teflon (registered trademark) 6-J, Teflon (registered trademark) 6C-J, Teflon (registered trademark) 62-J, Asahi ICI Fluoro manufactured by Mitsui Dupont Fluoro Chemical Co., Ltd. Fluone CD1 or CD076 manufactured by Low Polymers Co., Ltd. is mentioned. Moreover, as a commercial item of a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer, it is commercially available from Mitsubishi Rayon Co., Ltd. as a "meta-blen (registered trademark)" A series, and "meta-blen ( "Registered trademark" A-3000, "metablen (registered trademark)" A-3800, etc. are commercially available. In addition, in this specification, about the resin containing a siloxane bond and a fluorine atom in a molecule | numerator, it shall be set as the siloxane resin.

The following 1st-3rd aspect is mentioned as a preferable aspect of a colloidal silica particle.

1st aspect: The average particle diameter D ₁ measured by the dynamic light scattering method is 25-1000 nm, and also the average particle diameter D ₁ and the average particle diameter calculated from the specific surface area S of colloidal silica particles measured by the nitrogen adsorption method D ₂ ratio D ₁ / D ₂ is 3 or more aspects with.

Second aspect: An aspect in which a plurality of spherical silica particles are planarly connected.

Third aspect: An aspect in which a plurality of spherical silica particles are connected in a columnar shape.

The colloidal silica particles of the first aspect may further satisfy the requirements of the colloidal silica particles of the second aspect or the third aspect. Further, the colloidal silica particles of the second aspect may further satisfy the requirements of the first aspect. In addition, the colloidal silica particles of the third aspect may further satisfy the requirements of the colloidal silica particles of the first aspect.

In addition, in this specification, "spherical" should just be substantially spherical, and is the meaning which may be modified in the range which shows the effect of this invention. For example, it is meant to include a shape having irregularities on the surface or a flat shape having a long axis in a predetermined direction.

In addition, "a plurality of spherical silica particles are connected in a columnar shape" means a structure in which a plurality of spherical silica particles are connected in a linear and / or branched form. For example, a structure in which a plurality of spherical silica particles are connected at a junction having a smaller outer diameter is mentioned. In addition, in the present invention, the structure in which "a plurality of spherical silica particles are connected in a columnar shape" includes not only a structure having a ring-shaped structure, but also a structure having a chain shape having a terminal.

In addition, "a plurality of spherical silica particles are planarly connected" means a structure in which a plurality of spherical silica particles are connected on substantially the same plane. In addition, "approximately coplanar" means not only the case of the same plane, but also may be shifted up and down in the same plane. For example, it may be shifted up and down within a range of 50% or less of the particle diameter of the silica particles.

The colloidal silica particles used in the present invention preferably have a ratio D ₁ / D ₂ of the average particle diameter D ₁ and the average particle diameter D ₂ measured by dynamic light scattering method of 3 or more. The upper limit of D ₁ / D ₂ is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. By setting D ₁ / D ₂ in such a range, good optical properties can be expressed, and furthermore, aggregation during drying can be effectively suppressed. In addition, the value of D ₁ / D _{2 in} the colloidal silica particles is also an index of the degree of connection of the spherical silica particles.

The average particle diameter D ₂ of the colloidal silica particles, can be regarded as the average particle diameter approximating the primary particles of spherical silica. The average particle diameter D ₂ is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and particularly preferably 7 nm or more. The upper limit is preferably 100 nm or less, more preferably 80 nm or less, more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less.

The average particle diameter D ₂ can be substituted for the diameter (D0) per circle in the projected image of the spherical portion measured by a transmission electron microscope (TEM). The average particle diameter by diameter per circle is evaluated by the number average of 50 or more particles, unless otherwise specified.

The average particle diameter D ₁ of the colloidal silica particles can be regarded as a number average particle diameter of secondary particles in which a plurality of spherical silica particles are collected. Therefore, normally, the relationship of D ₁ > D ₂ is established. The average particle diameter D ₁ is preferably 25 nm or more, more preferably 30 nm or more, and particularly preferably 35 nm or more. The upper limit is preferably 1000 nm or less, more preferably 700 nm or less, more preferably 500 nm or less, and particularly preferably 300 nm or less.

The average particle diameter D ₁ of the colloidal silica particles is measured using a dynamic light scattering type particle size distribution measuring device (Nano Track Nanotrac Wave-EX150 (trade name) manufactured by Nikkiso Co., Ltd.) unless otherwise specified. The procedure is as follows. The dispersion of colloidal silica particles is aliquoted into a 20 ml sample bottle, and diluted with toluene to adjust the solid content concentration to 0.2 mass%. The sample solution after dilution is irradiated with 40 kHz ultrasonic waves for 1 minute, and is used for the test immediately thereafter. Data was fetched 10 times using a 2 ml measuring quartz cell at a temperature of 25 ° C, and the obtained "number average" was taken as the average particle diameter. For other detailed conditions and the like, refer to the description of JISZ8828: 2013 "Particle size analysis-dynamic light scattering method". Five samples are produced per level, and the average value is adopted.

It is preferable that a plurality of colloidal silica particles have spherical silica particles having an average particle diameter of 1 to 80 nm connected through a connecting material. The upper limit of the average particle diameter of the spherical silica particles is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less. Moreover, as a lower limit of the average particle diameter of a spherical silica particle, it is preferable that it is 3 nm or more, it is more preferable that it is 5 nm or more, and it is more preferable that it is 7 nm or more. In addition, in this invention, the value of the average particle diameter of the spherical silica particle uses the value of the average particle diameter calculated from the diameter per circle in the projection image of the spherical part measured by the transmission electron microscope (TEM).

Metal oxide-containing silica is mentioned as a connecting material which connects spherical silica particles. Examples of the metal oxides include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti. Examples of the metal oxide-containing silica include reactants and mixtures of these metal oxides and silica (SiO ₂ ). As for the connecting material, description of International Publication No. WO2000 / 015552 can be referred to, and the content is incorporated herein.

As the number of spherical silica particles connected, three or more are preferable, and five or more are more preferable. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. The number of connections of spherical silica particles can be measured by TEM.

The colloidal silica particles may be used in a particle liquid (sol) state. For example, silica sol or the like described in Japanese Patent Publication No. 4428935 can be used. As a medium for dispersing colloidal silica particles, alcohols (eg, methanol, ethanol, isopropanol (IPA)), ethylene glycol, and glycol ethers (eg, propylene glycol monomethyl ether) ), Glycol ether acetate (for example, propylene glycol monomethyl ether acetate) and the like. Moreover, the solvent A1, solvent A2, etc. mentioned later can also be used. In the particle solution (sol), the SiO ₂ concentration is preferably 5 to 40% by mass. Commercially available products can also be used for the particle liquid (sol). For example, "Snowtex OUP", "Snowtex UP", "IPA-ST-UP", "Snowtex PS-M", "Snowtex PS-MO", "Snowtex PS" made by Nissan Chemical Industries, Ltd. -S "," Snowtex PS-SO "," Fine Cataloid F-120 "manufactured by Shokubai Kasei High School Co., Ltd.," Quartron PL "manufactured by Fuso Kagaku High School Co., Ltd., and the like.

The content of the other low refractive material is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the cage-type siloxane compound.

Moreover, it is also preferable that the composition for partition formation does not substantially contain other low-refractive materials. When the content of another low-refractive material is substantially free of other low-refractive materials, it is preferably 1 part by mass or less, more preferably 0.1 part by mass or less, with respect to 100 parts by mass of the cage-type siloxane compound It is more preferable not to contain a low refractive index material.

(solvent)

The composition for forming a partition wall contains a solvent. Examples of the solvent include an organic solvent (aliphatic compound, halogenated hydrocarbon compound, alcohol compound, ether compound, ester compound, ketone compound, nitrile group compound, amide compound, sulfoxide compound, aromatic compound) or water. Each example is listed below.

· Aliphatic compounds

Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc.

· Halogenated hydrocarbon compounds

Methylene chloride, chloroform, dichloromethane, dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, HCFC, methyl monochloroacetate, Ethyl monochloroacetate, monochloroacetic acid, trichloroacetic acid, methyl bromide, tri (tetra) chloroethylene, and the like.

・ Alcohol compound

Methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol , Xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol and the like.

Ether compounds (including hydroxyl group-containing ether compounds)

Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, ethylene glycol monomethyl ether, Ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dibutyl ether, Triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monophenyl ether, di Ethylene glycol monohexyl Grounds, diethylene glycol monobenzyl the emitter, tri-propylene glycol mono methyl emitter, the emitter of polyethylene glycol monomethylether, and the emitter of polyethylene glycol dimethyl.

· Ester compounds

Ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol monomethyl ether acetate, 3-ethoxypropionic acid ethyl, propylene carbonate, 1,3-butylene glycol diacetate, and the like.

· Ketone compounds

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and the like.

· Nitrile group compounds

Acetonitrile groups and the like.

· Amide compounds

N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, Formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphorictriamide, 3-methoxy-N, N- Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and the like.

· Sulfoxide compounds

Dimethyl sulfoxide and the like.

· Aromatic compounds

Benzene, toluene, etc.

In the composition for partition formation, the content of the solvent is preferably 70 to 99% by mass relative to the total amount of the composition for partition formation. The upper limit is more preferably 97% by mass or less, more preferably 95% by mass or less, and even more preferably 93% by mass or less. The lower limit is more preferably 75% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.

(Surfactants)

The composition for partition formation may contain a surfactant. As the surfactant, any one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant may be used. In the nonionic surfactant, a fluorine-based surfactant is preferable. In particular, fluorine-based surfactants, anionic surfactants, and cationic surfactants are preferred, and fluorine-based surfactants are more preferred.

In the present invention, it is preferable to contain a surfactant having a polyoxyalkylene structure. The polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are adjacent to each other, specifically, an ethylene oxide (EO) structure, a propylene oxide (PO) structure, and the like. The polyoxyalkylene structure may constitute a graft chain of an acrylic polymer.

When the surfactant is a polymer compound, the weight average molecular weight is preferably 1500 or more, more preferably 2500 or more, more preferably 5000 or more, and particularly preferably 10000 or more. As an upper limit, it is preferable that it is 50000 or less, it is more preferable that it is 25000 or less, and it is especially preferable that it is 17500 or less.

The fluorine-based surfactant is preferably a polymer (polymer) surfactant having a polyethylene main chain. Among them, a polymer (polymer) surfactant having a poly (meth) acrylate structure is preferable. Especially, in this invention, the copolymer of the (meth) acrylate structural unit which has the said polyoxyalkylene structure and the fluorinated alkylacrylate structural unit is preferable.

Further, as the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group (preferably 1 to 24 carbon atoms, and more preferably 2 to 12 carbon atoms) at any one site can be suitably used. Preferably, a polymer compound having the above fluoroalkyl group or fluoroalkylene group in the side chain can be used. The fluorine-based surfactant further preferably has the above-mentioned polyoxyalkylene structure, and more preferably has a polyoxyalkylene structure in the side chain. For compounds having a fluoroalkyl group or a fluoroalkylene group, reference can be made to paragraphs 0034 to 0040 of International Publication No. WO2015 / 190374, the contents of which are incorporated herein.

As the fluorine-based surfactant, for example, Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F559, F780, F781F (above, DIC Corporation) Manufactured), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M Co., Ltd.), SUPRON S-382, S-141, S-145, SC-101, SC-103, Copper SC-104, SC- 105, SC1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Garas Co., Ltd.), F-top EF301, EF303, EF351, EF352 (above, manufactured by Gemco Corporation), And PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA).

Moreover, a block polymer can also be used for a fluorochemical surfactant. For example, the compound described in JP 2011-089090 A can be cited. The fluorine-based surfactant (meth) having a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). ) A fluorinated polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 6]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. Among the above compounds,% representing the proportion of repeating units is mol%.

For nonionic surfactants, anionic surfactants, and cationic surfactants other than fluorine-based surfactants, reference can be made to paragraphs 0042 to 0045 of International Publication WO2015 / 190374, the contents of which are incorporated herein by reference.

When the composition for forming a partition wall contains a surfactant, the surfactant content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, in the total solid content of the composition for forming a partition. Do. As an upper limit, 1 mass% or less is preferable, 0.75 mass% or less is more preferable, and 0.5 mass% or less is especially preferable. As for surfactant, only 1 type may be sufficient and 2 or more types may be included. When 2 or more types are included, it is preferable that their total is the said range.

Moreover, it is also preferable that the composition for partition formation does not contain a surfactant substantially. When the composition for partition formation does not substantially contain a surfactant, it is easy to further improve adhesion to a pixel. In addition, when it does not contain a surfactant substantially, the content of surfactant means that it is 0.005 mass% or less in all solid content of the composition for partition formation, it is preferable that it is 0.001 mass% or less, and it does not contain surfactant. It is more preferable.

(Curable compound)

The composition for partition formation may further contain a curable compound as a component other than the cage-type siloxane compound. As a curable compound, the compound which has an ethylenically unsaturated bond group, the compound which has an epoxy group, etc. are mentioned, for example. Examples of the ethylenically unsaturated bond group include a vinyl group, (meth) allyl group, and (meth) acryloyl group. The compound having an ethylenically unsaturated bond group is preferably a polymerizable compound, and more preferably a radically polymerizable compound.

As the compound having an ethylenically unsaturated bond group used as a curable compound, any of chemical forms such as a monomer, a prepolymer and an oligomer may be used, but a monomer is preferred. The molecular weight of the compound having an ethylenically unsaturated bond group is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

The compound having an ethylenically unsaturated bond group is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and 3 to 3 ethylenically unsaturated bond groups. It is more preferable that it is a compound containing six. Moreover, it is preferable that the compound which has an ethylenically unsaturated bond group is a 3-15 functional (meth) acrylate compound, and it is more preferable that it is a 3-6 functional (meth) acrylate compound. Specific examples of the compound having an ethylenically unsaturated bond group include paragraphs 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, and paragraphs 0254 to 0257 of JP 2008-292970 A. The compound described is mentioned, and these content is incorporated in this specification.

As a compound having an epoxy group used as a curable compound (hereinafter also referred to as an epoxy compound), it is preferable that it is a compound having 1 to 100 epoxy groups in one molecule. The lower limit of the epoxy group is more preferably two or more. The upper limit of the epoxy group may be, for example, 10 or less, or 5 or less.

The epoxy compound has an epoxy equivalent (= molecular weight of epoxy compound / number of epoxy groups) of preferably 500 g / equivalent or less, more preferably 100-400 g / equivalent, more preferably 100-300 g / equivalent.

The epoxy compound may be a low-molecular compound (for example, a molecular weight less than 1000), or a high-molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight-average molecular weight of 1000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50000. The upper limit of the weight average molecular weight is more preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of JP 2013-011869, JP 2014-043556 A 0147 to 0156, and JP 2014-089408 PAR No. 0085 to 0092 can be used as the epoxy compound. It might be. These contents are incorporated herein.

When the composition for forming a partition contains a curable compound, the content of the curable compound is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, among all solids of the composition for forming a barrier wall. Do. As an upper limit, 50 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is especially preferable. Moreover, it is also preferable that the composition for partition formation does not contain a curable compound substantially. When the composition for partition formation does not substantially contain a curable compound, it is easy to make the refractive index of the partition wall obtained smaller. In addition, when the composition for partition formation does not contain a curable compound substantially, it means that the content of the curable compound is 0.005% by mass or less, and preferably 0.001% by mass or less, of the total solid content of the composition for partition formation. It is more preferable not to contain.

(Photopolymerization initiator)

When the composition for forming a partition contains a polymerizable compound as a curable compound, it is preferable to further contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays from the ultraviolet region to the visible region is preferred. Moreover, it may be a compound which generates an active radical by generating any action with a photoexcited sensitizer. It is preferable that a photopolymerization initiator is a photoradical polymerization initiator.

As a photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, a hexaaryl biimidazole, an oxime compound, organic And peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and metallocene. Compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin Compounds are preferred, compounds selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds are more preferred, and oxime compounds are more preferred. As for the photopolymerization initiator, reference can be made to the descriptions in paragraphs 0065 to 0111 of JP 2014-130173 and paragraphs 0274 to 0306 of JP 2013-029760 A, which are incorporated herein by reference.

Commercially available products of the α-hydroxyketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (above, manufactured by BASF). Examples of commercial products of the α-aminoketone compound include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379 EG (above, manufactured by BASF). As a commercial item of an acylphosphine compound, IRGACURE-819, DAROCUR-TPO (above, BASF Corporation make), etc. are mentioned. As a commercial product of the oxime compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF) are also suitably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Archles NCI-930, Adeka Optomer N-1919 (Photopolymerization initiator 2 of Unexamined-Japanese-Patent No. 2012-014052) (above, ADEKA Corporation) are mentioned.

The present invention may use a bifunctional or trifunctional or higher photopolymerization initiator as a photopolymerization initiator. As specific examples of such a photopolymerization initiator, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. WO2015 / 004565, Japanese Patent Application Publication No. 2016-532675, paragraph numbers 0417 to 0412, International Dimers of oxime compounds described in paragraph numbers 0039 to 0055 of WO2017 / 033680, and compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, International Publication WO2016 / 034963 And Cmpd1 to 7 described in the heading.

When the composition for forming a partition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, among all solids of the composition for forming a partition. Do. As an upper limit, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is especially preferable. Moreover, it is also preferable that the composition for partition formation does not contain a photoinitiator substantially. In addition, when the composition for partition formation does not substantially contain a photopolymerization initiator, it means that the content of the photopolymerization initiator is 0.005 mass% or less in the total solid content of the composition for partition formation, preferably 0.001 mass% or less, and the photopolymerization initiator It is more preferable not to contain.

(Alkali soluble resin)

The composition for partition formation may contain an alkali-soluble resin. The alkali-soluble resin can be appropriately selected from resins having groups that promote alkali dissolution. Examples of the group (hereinafter also referred to as an acid group) that promotes alkali dissolution include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxyl groups, and carboxyl groups are preferred. As for the kind of acid group which an alkali-soluble resin has, only 1 type may be sufficient and 2 or more types may be sufficient as it.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000. Moreover, as for the number average molecular weight (Mn) of alkali-soluble resin, 1000-20000 are preferable.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Moreover, from a viewpoint of developability control, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferable.

The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain. For example, copolymers having repeating units derived from monomers such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, partially esterified maleic acid, furnace And alkali-soluble phenolic resins such as convex resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers in which an acid anhydride is added to a polymer having a hydroxyl group.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. (Meth) allyl group, (meth) acryloyl group, etc. are mentioned as a polymerizable group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in a side chain or the like is useful. As commercially available products of the alkali-soluble resin having a polymerizable group, Diana NR series (Mitsubishi Rayon Co., Ltd.), Photomer6173 (polyurethane acrylate oligomer containing a carboxyl group, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R -264, KS resist 106 (all manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Flaxel CF200 series (all manufactured by Daicel), Ebecryl3800 (Daicel Yushibi) Acrecure RD-F8 (made by Nippon Shokubai Co., Ltd.), DP-1305 (made by Fuji Fine Chemical Co., Ltd.), etc. are mentioned.

The alkali-soluble resin is a compound represented by the following formula (ED1) and at least one compound selected from compounds represented by formula (1) of JP 2010-168539 (hereinafter, these compounds are referred to as "ether dimer") It is also preferable to include a polymer formed by polymerizing a monomer component containing ().

[Formula 7]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

As a specific example of the ether dimer, for example, paragraph No. 0317 of JP 2013-029760 A can be referred to, and this content is incorporated herein. As for the ether dimer, only 1 type may be sufficient and 2 or more types may be sufficient as it.

For the alkali-soluble resin, reference may be made to Japanese Patent Application Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding U.S. Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700), the contents of this specification. Is used for. Moreover, the copolymer (B) described in paragraph No. 0029 to 0063 of JP 2012-032767 A and the alkali-soluble resin used in Examples, and the binder resin described in JP 2012-208474 A of paragraph No. 0088-0098 And the binder resin used in Examples, the binder resin used in Examples and Binder Resins of Japanese Patent Application Publication No. 2012-137531, and the binder resins used in Examples, Paragraph Nos. 0132 to 0143 of Japanese Patent Application Publication No. 2013-024934 Binder resins used in Examples and Binder resins used in Examples, Paragraph Nos. 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and Paragraph Nos. 0030-0072 of Japanese Patent Laid-Open Nos. 2012-032770 You can also use the binder resin described in. These contents are incorporated herein.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, even more preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.

When the composition for forming a partition wall contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more of the total solid content of the composition for forming a partition. Especially preferred. As an upper limit, 50 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is especially preferable. Moreover, it is also preferable that the composition for partition formation does not contain an alkali-soluble resin substantially. In addition, when the composition for partition formation does not substantially contain an alkali-soluble resin, it means that the content of the alkali-soluble resin is 0.005% by mass or less, and preferably 0.001% by mass or less, in the total solid content of the composition for partition formation. It is more preferable not to contain an alkali-soluble resin.

(Other additives)

Various additives other than the above, for example, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, an antioxidant, a latent antioxidant, and the like can be added to the composition for forming a partition wall, if necessary.

<Composition for forming colored pixels>

Next, a composition (composition for forming a colored pixel) that can be preferably used for formation of a colored pixel in the structure of the present invention will be described. It is preferable that the composition for forming a colored pixel contains a coloring agent. As a coloring agent, chromatic coloring agents, such as a yellow coloring agent, an orange coloring agent, a red coloring agent, a green coloring agent, a purple coloring agent, and a blue coloring agent, are mentioned. The colorant may be a pigment or a dye.

The following are mentioned as a specific example of a pigment.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 (above, yellow pigment);

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 (above, orange pigment);

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 (or higher, Red pigment);

C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment);

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 58, 59 (above, purple pigment);

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 (above, blue pigment).

Further, as the green colorant, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in the molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms can also be used. As a specific example, the compound described in international publication WO2015 / 118720 is mentioned.

Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue colorant. As a specific example, the compound etc. which are described in paragraph No. 0022-0030 of Unexamined-Japanese-Patent No. 2012-247591 and the unexamined-Japanese-Patent No. 2011-157478 of Paragraph No. 0047 are mentioned.

As dyes, for example, Japanese Patent Application Publication No. 64-090403, Japanese Patent Application Publication No. 64-091102, Japanese Patent Application Publication No. Hei 1-094301, Japanese Patent Application Publication No. Hei 6-011614, and US Patent Publication 4808501 And dyes disclosed in Japanese Unexamined Patent Publication No. Hei 5-333207, Japanese Unexamined Patent Publication No. Hei 6-035183, Japanese Unexamined Patent Publication No. Hei 6-051115, Japanese Unexamined Patent Publication No. Hei 6-194828, and the like. . When divided into chemical structures, pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, And cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds.

Moreover, you may use a dye multimer as a coloring agent. It is preferable that the dye multimer is a dye used by being dissolved in a solvent, but particles may be formed. When the dye multimer is particles, it is used by dispersing the dye multimer in a solvent or the like. The pigment multimer in the form of particles can be obtained, for example, by emulsion polymerization. Examples of the particulate multimer in the form of particles include, for example, compounds described in JP 2015-214682 A. In addition, compounds described in Japanese Patent Laid-Open No. 2011-213925, Japanese Patent Laid-Open No. 2013-041097, Japanese Patent Laid-Open No. 2015-028144, Japanese Patent Laid-Open No. 2015-030742, etc. may be used as the dye multimer. .

The content of the colorant is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more with respect to the total solid content of the composition for forming a colored pixel. And more preferably 60% by mass or more, and most preferably 65% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. The coloring agent contained in the composition for forming a colored pixel may be one type, or two or more types. When 2 or more types of coloring agents are included, it is preferable that a total amount becomes said range.

It is preferable that the composition for forming a colored pixel contains a resin. Examples of the resin include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene etherphosphine. And oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the use of a binder. Further, a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such use of the resin is an example, and may be used for purposes other than such use. The weight average molecular weight (Mw) of the resin is preferably 5000 to 100,000. Moreover, as for the number average molecular weight (Mn) of resin, 1000-20000 are preferable.

It is also preferable that an alkali-soluble resin is used as the composition for forming a colored pixel. The above-mentioned thing is mentioned as alkali-soluble resin.

The composition for forming a colored pixel may also use a resin as a dispersant. Examples of the dispersant include the pigment dispersant described in JP-A-2015-151530, paragraphs 0173 to 1179, the contents of which are incorporated herein.

The composition for forming a colored pixel may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group, or a phthalimidemethyl group. As a chromophore constituting the pigment derivative, quinoline-based skeleton, benzimidazole-based skeleton, diketopyrrolopyrrole-based skeleton, azo-based skeleton, phthalocyanine-based skeleton, anthraquinone-based skeleton, quinacridone-based skeleton, dioxazine-based skeleton , Perinone skeleton, perylene skeleton, thio indigo skeleton, isoindoline skeleton, isoindoline skeleton, quinophthalone skeleton, tren skeleton, metal complex framework skeleton, etc., and quinoline skeleton , Benzimidazole-based skeleton, diketopyrrolopyrrole-based skeleton, azo-based skeleton, quinophthalone-based skeleton, isoindoline-based skeleton and phthalocyanine-based skeleton are preferred, and azo-based skeleton and benzimidazole-based skeleton It is more preferable. As an acid group which a pigment derivative has, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable, and a tertiary amino group is more preferable. As a specific example of a pigment derivative, the description of Paragraph No. 0162-183 of Unexamined-Japanese-Patent No. 2011-252065 can be referred to, for example, and this content is incorporated in this specification.

The composition for forming a colored pixel may further contain a curable compound, a photopolymerization initiator, a solvent, and a surfactant. These may include the aforementioned materials.

The composition for forming a colored pixel may further contain additives such as a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, an antioxidant, and a potential antioxidant.

<Composition for forming transparent pixels>

Next, a composition (a composition for forming a transparent pixel) that can be preferably used for formation of a transparent pixel in the structure of the present invention will be described. It is preferable that the composition for forming a transparent pixel contains a curable compound. The above-mentioned material is mentioned as a curable compound, The preferable range is also the same. The composition for forming a transparent pixel is also at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S. It may contain particles of an oxide containing an element (also called inorganic particles). When containing the above-mentioned inorganic particle, it is preferable that content of an inorganic particle is 20-70 mass% with respect to the total solid content of the composition for transparent pixel formation. The lower limit is more preferably 25% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably 65% by mass or less, and even more preferably 60% by mass or less. The composition for forming a transparent pixel may further contain additives such as a photopolymerization initiator, a solvent, and a surfactant. These may include the aforementioned materials. Moreover, the composition for forming a transparent pixel may further contain additives such as a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, an antioxidant, and a potential antioxidant.

<Composition for forming an infrared transmission layer>

Next, a composition (a composition for forming an infrared transmission layer) that can be preferably used for formation of a pixel of the infrared transmission layer in the structure of the present invention will be described. In the composition for forming an infrared transmission layer, it is preferable that A / B, which is the ratio between the minimum value A of the absorbance in the range of wavelength 400 to 640 nm and the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm, is 5 or more, and is 7.5 or more. It is preferable, it is more preferable that it is 15 or more, and it is more preferable that it is 30 or more.

In the composition for forming an infrared transmission layer, the conditions of the absorbance can be suitably achieved, for example, by adjusting the type of light-shielding material and the content thereof.

The absorbance Aλ at a predetermined wavelength λ is defined by the following equation (1).

Aλ = -log (Tλ / 100)… (One)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.

In the present invention, the absorbance value may be a value measured in a solution state, or may be a value in a film formed using a composition for forming an infrared transmission layer. In the case of measuring the absorbance in the film state, a composition for forming an infrared transmission layer is coated on a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and using a hot plate at 100 ° C, It is preferable to measure using a membrane prepared by drying for 120 seconds. The thickness of the film can be measured on a substrate having a film using a stylus surface shape measuring device (DEKTAK150 manufactured by ULVAC).

It is preferable that the composition for forming an infrared transmission layer contains a light-shielding material. It is preferable that the light-shielding material is a color material that absorbs light in a wavelength range from purple to red. Moreover, it is preferable that a light shielding material is a color material which shields light in the wavelength range of 400-640 nm wavelength. Moreover, it is preferable that a light-shielding material is a color material which transmits light of wavelength 1100-1300 nm. It is preferable that the light shielding material satisfies at least one of the following (A) and (B).

(1): Two or more kinds of chromatic colorants are included, and a combination of two or more kinds of chromatic colorants forms black.

(2): An organic black colorant is included. In the aspect of (2), it is also preferable to further contain a chromatic colorant.

It is preferable that A / B which is a ratio of the minimum value A of the absorbance in the range of wavelength 400-640 nm and the maximum value B of the absorbance in the range of wavelength 1100-1300 nm is 4.5 or more, for example. The above characteristics may be satisfied by one type of material, or may be satisfied by a combination of a plurality of materials. For example, in the case of the aspect (1), it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral properties. Moreover, in the case of the aspect (2), the organic black colorant may satisfy the spectral properties. In addition, the above spectral properties may be satisfied by a combination of an organic black colorant and a chromatic colorant.

It is preferable that a light-shielding material contains 2 or more types selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. That is, it is preferable that the light-shielding material forms black with a combination of two or more kinds of colorants selected from red colorants, blue colorants, yellow colorants, purple colorants, and green colorants. As a preferable combination, the following are mentioned, for example.

(1) The aspect containing a red colorant and a blue colorant.

(2) Aspect which contains a red colorant, a blue colorant, and a yellow colorant.

(3) Aspect which contains a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(4) The aspect which contains a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(5) Aspect which contains a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(6) Aspect which contains a red colorant, a blue colorant, and a green colorant.

(7) The aspect containing a yellow colorant and a purple colorant.

In the aspect of (1), the mass ratio between the red colorant and the blue colorant is preferably a red colorant: a blue colorant = 20 to 80:20 to 80, more preferably 20 to 60:40 to 80, It is more preferable that it is 20-50: 50-80.

In the aspect of (2), the mass ratio of the red colorant and the blue colorant to the yellow colorant is preferably a red colorant: a blue colorant: a yellow colorant = 10 to 80:20 to 80:10 to 40, and 10 to 60: It is more preferable that it is 30-80: 10-30, and it is more preferable that it is 10-40: 40-80: 10-20.

In the aspect of the above (3), the mass ratio of the red colorant and the blue colorant to the yellow colorant and the purple colorant is a red colorant: a blue colorant: a yellow colorant: a purple colorant = 10 to 80: 20 to 80: 5 to 40: 5 It is preferably ~ 40, more preferably 10-60: 30 ~ 80: 5 ~ 30: 5 ~ 30, and more preferably 10 ~ 40: 40 ~ 80: 5 ~ 20: 5 ~ 20.

In the aspect of the above (4), the mass ratio of the red colorant and the blue colorant to the yellow colorant and the purple colorant and the green colorant is a red colorant: a blue colorant: a yellow colorant: a purple colorant: a green colorant = 10 to 80: 20 to 80: It is preferable that it is 5-40: 5-40: 5-40, it is more preferable that it is 10-60: 30-80: 5-30: 5-30: 5-30, and it is 10-40: 40-80: 5 It is more preferable that it is ~ 20: 5-20: 5-20.

In the aspect of the above (5), the mass ratio of the red colorant and the blue colorant to the yellow colorant and the green colorant is a red colorant: a blue colorant: a yellow colorant: a green colorant = 10 to 80: 20 to 80: 5 to 40: 5 to It is preferably 40, more preferably 10 to 60:30 to 80: 5 to 30: 5 to 30, and more preferably 10 to 40:40 to 80: 5 to 20: 5 to 20.

In the aspect of the above (6), the mass ratio of the red colorant and the blue colorant to the green colorant is preferably a red colorant: a blue colorant: a green colorant = 10 to 80:20 to 80:10 to 40, and 10 to 60: It is more preferable that it is 30-80: 10-30, and it is more preferable that it is 10-40: 40-80: 10-20.

In the aspect of the above (7), the mass ratio of the yellow colorant to the purple colorant is preferably a yellow colorant: a purple colorant = 10-50: 40-80, more preferably 20-40: 50-70, 30 It is more preferable that it is ~ 40: 60-70.

As the yellow colorant, C. I. Pigment Yellow 139, 150, 185 is preferable, C. I. Pigment Yellow 139, 150 is more preferable, and C. I. Pigment Yellow 139 is more preferable. As the blue colorant, C. I. Pigment Blue 15: 6 is preferred. As the purple colorant, C. I. Pigment Violet 23 is preferred. As the red colorant, C. I. Pigment Red 122, 177, 224, 254 is preferable, C. I. Pigment Red 122, 177, 254 is more preferable, and C. I. Pigment Red 254 is more preferable. As the green colorant, C. I. Pigment Green 7, 36, 58, 59 is preferable.

When using an organic black colorant as a light-shielding material, it is preferable to use it in combination with a chromatic colorant. By using together an organic black colorant and a chromatic colorant, excellent spectral properties are easily obtained. As a chromatic colorant used in combination with an organic black colorant, a red colorant, a blue colorant, a purple colorant, etc. are mentioned, for example, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more. The mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, relative to 100 parts by mass of the organic black colorant.

The content of the pigment in the light-shielding material is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more with respect to the total amount of the light-shielding material.

It is preferable that content of a light-shielding material is 5-60 mass% with respect to the total solid content of the composition for infrared transmission layer formation. The lower limit is more preferably 9% by mass or more, and even more preferably 13% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less.

The composition for forming an infrared transmission layer may also contain an infrared absorber. In the composition for forming an infrared transmission layer, the infrared absorber has a role of limiting the light (infrared rays) that transmits to the longer wavelength side. As the infrared absorber, a compound having a maximum absorption wavelength in the infrared region (preferably in the range of 700 to 1300 nm in wavelength, more preferably in the range of 700 to 1000 nm in wavelength) can be preferably used.

Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, and dimonium At least one selected from compounds, dithiol compounds, triarylmethane compounds, pyrometene compounds, azomethane compounds, anthraquinone compounds and dibenzofuranone compounds is preferred, and pyrrolopyrrole compounds, cyanine compounds, and scoo At least one member selected from an aryllium compound, a phthalocyanine compound, a naphthalocyanine compound and a dimonium compound is more preferable, and at least one member selected from a pyrrolopyrrole compound, a cyanine compound and a squarylium compound is further used. Pyropyrrole compounds are particularly preferred. Specific examples of the pyrrolopyrrole compound include compounds described in Japanese Patent Application Laid-open No. 2009-263614, paragraphs 0016 to 0058, compounds disclosed in Japanese Patent Laid-Open No. 2011-068731, paragraphs 0037 to 0052, paragraphs in International Publication No. WO2015 / 166873 And compounds described in Nos. 0010 to 0033, etc., these contents are incorporated herein. As a specific example of a squarylium compound, the compound as described in paragraph No. 0044-0049 of JP 2011-208101 A, the compound as described in paragraph No. 0060-0061 of JP-A-6065169, paragraph number 0040 of WO2016 / 181987 The compound described in, the compound described in Japanese Unexamined Patent Publication No. 2015-176046, the compound described in paragraph No. 0072 of International Publication No. WO2016 / 190162, etc. may be mentioned, and these contents are incorporated herein. As a specific example of a cyanine compound, the compound described in paragraph No. 0044 to 0045 of JP 2009-108267 A, the compound described in paragraph No. 0026 to 0030 of JP 2002-194040 A, and JP 2015-172004 A The compounds described, the compounds described in Japanese Unexamined Patent Publication No. 2015-172102, the compounds described in Japanese Unexamined Patent Publication No. 2008-088426, the compounds described in paragraph No. 0090 of International Publication No. WO2016 / 190162, etc. may be mentioned. It is used in the specification. As a specific example of a dimonium compound, the compound of Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, and this content is incorporated in this specification. As a specific example of a phthalocyanine compound, for example, the compound described in paragraph No. 0093 of JP 2012-077153 A, the oxytitanium phthalocyanine described in JP 2006-343631 A, JP 2013-2013 The compounds described in paragraph numbers 0013 to 0029 of 195480 are mentioned, and these contents are incorporated in this specification. As a specific example of a naphthalocyanine compound, the compound described in paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, and this content is incorporated in this specification. Moreover, as an infrared absorbing compound, the compound of Unexamined-Japanese-Patent No. 2016-146619 can also be used, and this content is incorporated in this specification.

When the composition for forming an infrared transmitting layer contains an infrared absorbing agent, the content of the infrared absorbing agent is preferably 1 to 30% by mass relative to the total solid content of the composition for forming an infrared transmitting layer. The upper limit is more preferably 20% by mass or less, and even more preferably 10% by mass or less. The lower limit is more preferably 3% by mass or more, and still more preferably 5% by mass or more. Moreover, it is preferable that the total amount of an infrared absorber and a light-shielding material is 10-70 mass% of the total solid content of the composition for infrared transmission layer formation. The lower limit is more preferably 20% by mass or more, and even more preferably 25% by mass or more. Moreover, it is preferable that content of an infrared absorber in the total amount of an infrared absorber and a light-shielding material is 5-40 mass%. The upper limit is more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is more preferably 10% by mass or more, and even more preferably 15% by mass or more.

The composition for forming the infrared transmission layer includes additives such as resins, curable compounds, photopolymerization initiators, pigment derivatives, solvents, surfactants, silane coupling agents, polymerization inhibitors, ultraviolet absorbers, fillers, adhesion promoters, antioxidants, and latent antioxidants You may further include. The material mentioned above is mentioned about these details.

<Accommodation container>

There is no restriction | limiting in particular as a storage container of each composition mentioned above, A well-known storage container can be used. In addition, for the purpose of suppressing the mixing of impurities into the raw materials or the composition as a storage container, it is also preferable to use a multi-layer bottle comprising 6 types of 6 layers of resin inside the container or a bottle made of 6 types of resins in 7 layers. Do. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation method of composition>

Each composition mentioned above can be prepared by mixing the above-mentioned components. When preparing the composition, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, prepare two or more solutions or dispersions in which each component is appropriately blended in advance, and when using (when applying). ) May be mixed to prepare a composition.

Moreover, when a composition contains particles, such as a pigment, it is preferable to include the process of dispersing a particle. In the process of dispersing the particles, examples of the mechanical force used for dispersing the particles include compression, compression, impact, shearing, and cavitation. Specific examples of these processes include beads mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, float jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, in the grinding of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter, or to increase the filling rate of the beads, etc., to treat them under conditions of increasing the grinding efficiency. Moreover, it is preferable to remove the granulator by filtration, centrifugation, etc. after the crushing treatment. In addition, the process of dispersing the particles and the dispersing machine, "Dispersed Technology Daejeon, issued by Joho Kiko Co., Ltd., July 15, 2005" or "Suspension (solid / liquid dispersion system) -based dispersion technology and practical application of industrial applications The publication and publication of the Business Development Center Publication, October 10, 1978 ", Japanese Patent Application Publication No. 2015-157893, paragraph No. 0022, can be suitably used. Further, in the process of dispersing the particles, the particle may be refined in a salt milling step. For materials, equipment, processing conditions, and the like used in the salt milling process, reference may be made to, for example, Japanese Unexamined Patent Publication No. 2015-194521 and Japanese Unexamined Patent Publication No. 2012-046629.

In the preparation of the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances or reducing defects. As a filter, if it is a filter conventionally used for filtration use, etc., it is not specifically limited and can be used. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). And filters using materials such as (including high-density and ultra-high molecular weight polyolefin resins). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The hole diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the hole diameter of the filter is within the above range, fine foreign matter can be surely removed. Moreover, it is also preferable to use a fibrous filter medium. As a fibrous filter medium, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. Specifically, filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Rocky Techno Corporation are exemplified.

When using a filter, you may combine other filters (for example, a 1st filter and a 2nd filter, etc.). In that case, filtration in each filter may be performed only once, or may be performed two or more times. Moreover, you may combine filters of different hole diameters within the range mentioned above. The hole diameter here can refer to the nominal value of a filter maker. As a commercially available filter, for example, you can select from various filters provided by Nippon Paul Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nihon Integris Co., Ltd. (Kunihon Microlois Co., Ltd.) or Kitz Micro Filter Co., Ltd. As the second filter, one formed of the same material or the like as the first filter can be used. In addition, filtration in the first filter may be performed only on the dispersion liquid, and other components may be mixed before filtration with the second filter.

<Method of manufacturing structure>

Next, the manufacturing method of the structure of this invention is demonstrated.

In the structure of the present invention, a process for forming a partition on a support and a composition for forming a pixel by applying various composition for pixel formation to a region on the support and partitioned by a partition, to form a composition layer for pixel formation It can be manufactured through a process of forming a pattern and forming a pixel. Examples of the composition for forming a pixel include the above-described composition for forming a colored pixel, a composition for forming an infrared transmission layer, and the like. In addition, a partition wall may be formed after the pixels are formed.

The partition wall can be formed using a conventionally known method. For example, a partition wall can be formed as follows.

First, a barrier rib material layer is formed by applying a composition for forming a barrier rib on a support. As a method of applying the composition for forming a partition wall, a known method can be used. For example, the dropping method (drop cast); Slit coat method; Spray method; Roll coat method; Spin coating (spin coating); Flexible coating method; Slit and spin method; The free wet method (for example, the method described in JP 2009-145395 A); Various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle-jet printing systems, flexo printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; Transfer method using a mold or the like; And nanoimprint methods. The method of application in the inkjet is not particularly limited, and for example, the method indicated by "diffused and usable inkjet-infinite possibility to see as a patent-published in February 2005, Sumibe Techno Research" ~ 133 pages) However, Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830, Japanese Patent Application Publication No. 2006-169325 And the methods described in the above.

After forming the partition material layer, drying (pre-baking) may be performed. When prebaking, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and even more preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C or higher, or 80 ° C or higher. The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, a pattern is formed on the partition material layer to form a partition. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. It is preferable that it is a pattern formation method using a dry etching method from the reason that a partition wall with good rectangularity is easy to be obtained.

As a pattern forming method using the dry etching method, a resist pattern is formed on the partition wall material layer using a mask having a pattern along the shape of the partition wall, and then, using the resist pattern as a mask, dry etching is performed on the partition wall material layer. Etching is performed by a method, and then the resist pattern is peeled off from the barrier material layer, whereby the barrier rib can be formed. For the dry etching method, reference may be made to Japanese Patent Application Publication No. 2016-014856, the contents of which are incorporated herein.

The pattern forming method in the photolithography method preferably includes a step of exposing the barrier material layer in a pattern (exposure step) and a step of developing and removing the barrier material layer of the unexposed portion to form a pattern (development step). Do. If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each process is demonstrated.

In the exposure process, the barrier material layer is exposed in a pattern. For example, the barrier material layer can be pattern exposed by exposing the barrier material layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed portion of the barrier material layer can be cured. As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferable, and i-rays are more preferable. Irradiation dose (exposure dose) of, for example 0.03 ~ 2.5J / cm ² are preferred, 0.05 ~ 1.0J / cm ² is more preferred, 0.08 ~ 0.5J / cm ² is most preferred. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19 vol% or less (eg, 15 vol%, 5 vol%, substantially oxygen-free) ), Or may be exposed under a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) having an oxygen concentration exceeding 21% by volume. In addition, the exposure illumination may be selected from is possible, and usually in the range of ^{1000W / m 2 ~ 100000W / m} 2 ( for ^{example, 5000W / m 2, 15000W /} m 2, 35000W / m 2) to set properly. Oxygen concentration and the exposure light intensity is properly and the condition may be combined, for example, 10% by volume of oxygen concentration and illumination 10000W / m ^2, an oxygen concentration of 35% by volume and may be a roughness 20000W / m ² and the like.

Next, the barrier material layer of the unexposed portion in the barrier material layer after exposure is developed and removed to form a pattern. The development and removal of the barrier material layer of the unexposed portion can be performed using a developer. Thereby, the barrier material layer of the unexposed portion in the exposure step elutes into the developer, and only the photocured portion remains on the support. As the developer, an alkali developer is preferred. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the process of shaking off the developer every 60 seconds and supplying the developer more newly may be repeated several times.

Examples of the alkali agent used in the developer are ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethyl Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, Organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and metasilicate And inorganic alkaline compounds such as sodium. As for the alkali agent, a compound having a large molecular weight is preferable from the environmental and safety aspects. As the developer, an alkaline aqueous solution in which these alkali agents are diluted with pure water is preferably used. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Moreover, you may add surfactant to a developing solution and use it. The surfactant mentioned above is mentioned as an example of surfactant, Non-ionic surfactant is preferable. The developer may be prepared as a concentrate once from the viewpoint of convenience of transport or storage, and may be diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set, for example, in a range of 1.5 to 100 times. Moreover, when using the developing solution which consists of such an alkaline aqueous solution, it is preferable to wash | clean (rinse) with pure water after image development.

After development, after drying, heat treatment (post-baking) may be performed. Post-baking is a post-development heat treatment for making the film hard to be complete. In the case of post-baking, the post-baking temperature is preferably 50 to 240 ° C, for example. From the viewpoint of film curing, 200 to 230 ° C is more preferable. Moreover, when an organic electroluminescent (organic EL) element is used as a light-emitting light source, or when the photoelectric conversion film of the image sensor is composed of an organic material, the post-baking temperature is preferably 150 ° C or less, more preferably 120 ° C or less It is preferable, 100 ° C or less is more preferable, and 90 ° C or less is particularly preferable. The post-baking can be carried out continuously or in a batch manner by using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater so that the film after development is in the above conditions.

The pixel can be formed using a conventionally known method. For example, it can be formed by applying a composition for pixel formation to a region partitioned by a partition on a support to form a composition layer for pixel formation, and then forming a pattern on the composition layer for pixel formation.

As a method of applying the composition for pixel formation, a known method can be used. For example, the method mentioned above is mentioned.

After forming the composition layer for pixel formation, you may dry (prebak). When prebaking, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and even more preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C or higher, or 80 ° C or higher. The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, a pattern is formed on the composition layer for pixel formation to form a pixel. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method.

The pattern forming method in the photolithography method preferably includes a step of exposing the composition layer for pixel formation on a support in a pattern, and a step of developing and removing the composition layer for pixel formation of an unexposed portion to form a pattern. . If necessary, a step of baking the developed pattern (post-baking step) may be provided. The details of these steps are as described above.

In the pattern formation in the dry etching method, the composition layer for pixel formation on the support is cured to form a cured product layer, and then a patterned resist layer is formed on the cured product layer, and then the patterned resist layer is masked. It can be carried out by a method such as dry etching of the cured product layer using an etching gas. For pattern formation in the dry etching method, reference can be made to the descriptions in paragraphs 0010 to 0067 of JP 2013-064993 A, which are incorporated herein by reference.

<Solid imaging device>

The solid-state imaging element of the present invention has the structure of the present invention described above. The structure of the solid-state imaging device of the present invention is not particularly limited as long as it is provided with the structure of the present invention and functions as a solid-state imaging device, but the following structures are exemplified.

On the substrate, a transfer electrode made of a plurality of photodiodes, polysilicon, or the like constituting a light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), A light-shielding film having only a light-receiving portion of a photodiode open on a photodiode and a transfer electrode, a device protective film made of silicon nitride or the like formed to cover the entire light-shielding film and the photodiode light-receiving portion on the light-shielding film, and the structure of the present invention on the device protective film The structure which has is mentioned. Further, it may be a structure having a condensing means (for example, a micro lens or the like, hereinafter the same) on the device protective film and under the structure of the present invention (the side closer to the substrate), or a structure having a condensing means on the structure of the present invention. . Further, a low-refractive layer may be provided between the structure of the present invention and the light collecting means. The low-refractive layer can be formed, for example, by using the composition for forming a partition wall of the present invention.

The imaging device provided with the solid-state imaging element of the present invention can be used not only for a digital camera or an electronic device (such as a mobile phone) having an imaging function, but also for an on-vehicle camera or a surveillance camera.

<Image display device>

The structure of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. For the definition of the image display device and the details of each image display device, for example, "electronic display device (Akio Sasaki, published by Kyoko Sakai Co., Ltd. 1990)", "Display device (Sumaki Ibuki, Sankyo Tosho) (Co., Ltd. issued by the first year of Heisei). In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (Edited by Tatsuo Uchida, published by Kyoko Sakai Co., Ltd. 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, it can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, amounts, proportions, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "part" and "%" are based on mass.

<Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)>

The weight average molecular weight and the number average molecular weight of the cage-type siloxane compound and resin were measured under the following conditions by gel permeation chromatography (GPC).

Column types: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000.

Development solvent: tetrahydrofuran

Column temperature: 40 ° C

Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass%)

Device name: Tosoh HLC-8220GPC

Detector: RI (refractive index) detector

Calibration curve base resin: Polystyrene resin

<Preparation of composition for forming bulkhead>

The composition for forming a partition was prepared by mixing the raw materials shown in the following table. The numerical value described in the column of the compounding amount is parts by mass.

[Table 1]

(Cage-type siloxane compound 1)

A-1: Polymer having a structure represented by the following formula (S2-1-1) (Mw = 200,000, Mw / Mn = 3.0)

A-2: Polymer having a structure represented by the following formula (S2-1-1) (Mw = 149,000, Mw / Mn = 2.8)

A-3: Polymer of the structure represented by the following formula (S2-1-1) (Mw = 51,000, Mw / Mn = 2.6)

A-4: Polymer having a structure represented by the following formula (S2-1-1) (Mw = 246,000, Mw / Mn = 3.1)

A-5: Polymer of the structure represented by the following formula (S2-1-1) (Mw = 298,000, Mw / Mn = 3.3)

A-6: Polymer of structure represented by the following formula (S2-1-2) (Mw = 199,000, Mw / Mn = 2.9)

A-7: a polymer having a structure represented by the following formula (S2-1-3) (Mw = 204,000, Mw / Mn = 2.9)

(Cage-type siloxane compound 2)

A-8: Compound of structure represented by the following formula (A-8)

[Formula 8]

(Other siloxane compounds)

B-1: MS-1001 (manufactured by Toray Dow Corning Co., Ltd.)

(Surfactants)

F-1: Compound of the following structure (Mw = 14,000,% representing the proportion of repeating units is mol%)

[Formula 9]

(solvent)

S-1: Propylene glycol monomethyl ether acetate (PGMEA)

S-2: 1,3-butylene glycol diacetate

S-3: Propylene glycol monomethyl ether

S-4: ethyl lactate

S-5: butyl acetate

<Preparation of a composition for forming a colored pixel>

The raw materials shown below were mixed and stirred, followed by filtration with a filter made of nylon having a pore diameter of 0.45 µm (manufactured by Nippon Pole Co., Ltd.) to prepare a composition for forming a red pixel, a composition for forming a green pixel, and a composition for forming a blue pixel. Each was prepared.

(Red pixel formation composition)

Red pigment dispersion… 51.7 parts by mass

Suzy 1 ... 0.6 parts by mass

Curable compound 1… 0.6 parts by mass

Photopolymerization initiator 1 ... 0.3 parts by mass

Surfactant 1… 4.2 parts by mass

PGMEA… 42.6 parts by mass

(Composition for forming green pixels)

Green pigment dispersion ... 73.7 parts by mass

Suzy 1 ... 0.3 parts by mass

Curable compound 2 ... 1.2 parts by mass

Photopolymerization initiator 1 ... 0.6 parts by mass

Surfactant 1… 4.2 parts by mass

UV absorber 1… 0.5 parts by mass

PGMEA… 19.5 parts by mass

(Composition for forming blue pixels)

Blue pigment dispersion… 44.9 parts by mass

Suzy 1 ... 2.1 parts by mass

Curable compound 1… 1.5 parts by mass

Curable compound 3 ... 0.7 parts by mass

Photopolymerization initiator 2 ... 0.8 parts by mass

Surfactant 1… 4.2 parts by mass

PGMEA… 45.8 parts by mass

The raw materials used for the composition for forming a colored pixel are as follows.

Red pigment dispersion

A mixture of 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, 6.8 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was added to a bead mill (zirconia beads). After mixing and dispersing for 3 hours using 0.3 mm diameter), further using a high pressure disperser NANO-3000-10 (manufactured by Nippon BEI Co., Ltd.) equipped with a decompression mechanism, flow rate under a pressure of 2000 kg / cm ³ Dispersion treatment was performed at 500 g / min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

· Green pigment dispersion

A mixture of 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was added to a bead mill (zirconia beads). After mixing and dispersing for 3 hours using 0.3 mm diameter), using a high pressure disperser NANO-3000-10 (manufactured by Nippon BEI Co., Ltd.) equipped with a decompression mechanism, flow rate under a pressure of 2000 kg / cm ³ Dispersion treatment was performed at 500 g / min. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

Blue pigment dispersion

A mixture of 9.7 parts by weight of CI Pigment Blue 15: 6, 2.4 parts by weight of CI Pigment Violet 23, 5.5 parts by weight of dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by weight of PGMEA After mixing and dispersing for 3 hours using zirconia beads (0.3 mm diameter), using a high pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with a decompression mechanism, pressure of 2000 kg / cm ³ The dispersion treatment was performed under a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

Resin 1: 40 mass% PGMEA solution of the resin of the following structure (the numerical value added to the main chain is molar ratio. Mw = 10,000, acid value = 70mgKOH / g)

[Formula 10]

Curable compound 1: compound of the following structure

[Formula 11]

Curable compound 2: A mixture of compounds having the following structure (a mixture having a molar ratio of the left compound to the right compound of 7: 3)

[Formula 12]

Curable compound 3: Aaronix M-305 (55% to 63% by weight of triacrylate, manufactured by Doa Kosei Co., Ltd.)

Photopolymerization initiator 1: IRGACURE-OXE01 (manufactured by BASF)

Photopolymerization initiator 2: compound of the following structure

[Formula 13]

Surfactant 1: 0.2 mass% PGMEA solution of the compound of the following structure (Mw = 14,000,% representing the proportion of repeating units is mol%)

[Formula 14]

UV absorber 1: UV-503 (manufactured by Taito Chemical Co., Ltd.)

<Production of structure>

On the silicon wafer, a partition wall material layer is formed using the composition for partition wall formation described in the table below, and the partition wall material layer is subjected to a dry etching method under the conditions described in paragraph No. 0128 to 0133 of JP-A-2016856. By patterning, the partition walls (50 nm in width and 1 μm in height) were formed in a grid shape at 1 μm intervals. The dimensions of the openings of the partition walls on the silicon wafer (areas partitioned by the partition walls on the silicon wafer) were 1 µm long x 1 µm wide. Next, the composition for forming a green pixel was applied onto a silicon wafer on which a partition wall was formed by spin coating so that the film thickness after film formation was 1 μm, and then heated at 100 ° C. for 2 minutes using a hot plate. Subsequently, exposure was performed at an exposure amount of 150 mJ / cm ² through a mask having a Bayer pattern of 0.9 μm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Corporation). Subsequently, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used for puddle development at 23 ° C for 60 seconds. Thereafter, after rinsing in a spin shower, heating was performed at 220 ° C. for 5 minutes using a hot plate, and green pixels were formed in the partitioned area.

Next, the composition for forming a red pixel and the composition for forming a blue pixel were also sequentially patterned to form red and blue pixels in regions partitioned by partition walls, respectively.

<Evaluation of Filtration>

The composition for forming a partition wall immediately after production was filtered using a ROKI capsule filter (LPS-CLP-0025-N1) for 1000 g, and the filterability was evaluated based on the following criteria.

A: The total amount of the composition for forming the partition walls could be filtered.

B: Blockage occurred in 500 g or more and less than 1000 g

C: Blockage occurred in 100 g or more and less than 500 g

D: Blockage occurred below 100 g

<Etching surface smoothness>

The etching surface of the partition wall was observed with a scanning electron microscope (SEM) at a magnification of 50,000 times, and smoothness was evaluated according to the following criteria.

A: No vacancy was observed.

B: A pore having a size of 20 nm or more was not observed, but a pore having a size of less than 20 nm was observed.

C: A pore having a size of 20 nm or more was observed.

<Adhesiveness>

After forming colored pixels of each color in the region partitioned by the partition wall, cross-sectional observation was performed by SEM to evaluate adhesion according to the following criteria.

A: Peeling of a colored pixel was not observed in all the partition walls within the observation range.

B: Peeling of the colored pixels occurred in the partition walls of less than 20% of the total partition walls in the observation range.

C: Peeling of the colored pixels occurred in the partition walls of 20% or more of the total partition walls within the observation range.

<Evaluation of refractive index>

Each barrier rib-forming composition was coated on a silicon wafer to form a film having a film thickness of 0.3 μm, and the refractive index at a wavelength of 550 nm was measured using an ellipsometer UVISEL / 460-FUV-AGAS (manufactured by Horiba Seisakusho).

[Table 2]

As shown in the above table, the examples were able to manufacture a structure having a low refractive index and excellent partition walls. When the structure of the example was introduced into a solid-state imaging element, the light-converging rate of the pixel was high, the sensitivity was good, and a clear image could be obtained.

1: Support
2: bulkhead
4: Pixel

Claims (10)

A support,
A partition provided on the support,
A pixel provided in an area partitioned by the partition wall,
The partition wall is a partition wall formed using a composition containing a cage-type siloxane compound. The method according to claim 1,
The cage-type siloxane compound comprises a cage-type siloxane compound having an O / Si ratio of 1.3 to 1.7, which is a ratio between the number of oxygen atoms and the number of silicon atoms. The method according to claim 1 or claim 2,
A structure in which the cage-type siloxane compound comprises a partial structure represented by the following formula (S1);
(* -SiO _1.5 ) _n … (S1)
In the formula, * represents a connecting hand, and n represents an integer from 6 to 16. The method according to any one of claims 1 to 3,
A structure in which the cage-type siloxane compound comprises at least one selected from a compound represented by the following formula (S2) and a polymer obtained by polymerizing the compound;
(R ^S1 -SiO _1.5 ) _n … (S2)
Wherein, R ^S1 is an alkyl group or polymerizable group, n is an integer of 6 ~ 16, n of 2 or more R R ^S1 of ^S1 is a polymerizable group. The method according to any one of claims 1 to 4,
The cage-type siloxane compound has a partial structure represented by the following formula (S1-1), a structure;
Formula (S1-1)
[Formula 1]

The broken line in the above formula represents a bonding hand. The method according to any one of claims 1 to 5,
The cage-type siloxane compound comprises a polymer having a weight average molecular weight of 50,000 to 300,000. The method according to any one of claims 1 to 6,
The pixel structure includes a colored pixel, a transparent pixel, and at least one pixel selected from pixels of an infrared transmission layer. A composition for forming a partition used for forming the partition of a structure having a support, a partition provided on the support, and a pixel provided in an area partitioned by the partition,
A composition for forming a partition wall comprising a cage-type siloxane compound and a solvent. A solid-state imaging device having the structure according to any one of claims 1 to 7. An image display device having the structure according to any one of claims 1 to 7.

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