KR102442301B1 - Structure, composition for forming barrier ribs, solid-state imaging device, and image display device - Google Patents

Abstract

Provided is a structure having a barrier rib having a small refractive index and excellent smoothness. Moreover, the solid-state image sensor and image display apparatus containing the composition for partition formation used for this structure, and a structure are provided. The structure 100 has a support body 1, a partition wall 2 provided on the support body 1, and a pixel 4 provided in a region partitioned by the partition wall, and the partition wall 2 contains a cage-type siloxane compound. It is a barrier rib formed using a composition containing It is preferable that the cage-type siloxane compound is a compound which has a partial structure represented by "(*-SiO _1.5 ) _n ". In the formula, * represents a linking hand, and n represents an integer of 6 to 16.

Description

Structure, composition for forming barrier ribs, solid-state imaging device, and image display device

The present invention relates to a structure in which pixels are provided in a region partitioned by a partition on a support. Moreover, it is related with the composition for partition formation, a solid-state image sensor, and an image display apparatus.

DESCRIPTION OF RELATED ART In recent years, the demand of solid-state image sensors, such as a charge-coupled element (CCD) image sensor, is growing large from the spread of digital cameras, camera-equipped mobile phones, etc. A color filter is used as a key device of a display or an optical element.

As one aspect of a solid-state imaging device, the solid-state imaging device etc. which provided the structure in which the colored layer was provided in the area|region partitioned by the partition on a support body are known.

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

On the other hand, in Patent Documents 2 and 3, the invention relating to a composition containing a caged siloxane compound is described. Patent Document 2 describes forming an insulating film using a composition containing a cage-type siloxane compound. Moreover, in patent document 3, it is described that an antireflection film is formed using the composition containing a cage-type siloxane compound.

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

In the structure in which the pixel is provided in the area|region partitioned by the partition on a support body, using the material with a low refractive index as a material of a partition is considered. For example, Paragraph 0046 of Patent Document 1 describes that a low-refractive material such as glass, a porous layer of a SiO ₂ film, a fluorine-based polymer, or a siloxane polymer is used as a material of the partition wall.

For example, by making the refractive index of the barrier rib relatively smaller than the refractive index of the pixel, it is possible to increase the condensing index of light passing through the pixel or to prevent light leakage to other adjacent pixels. can increase For this reason, in recent years, it is desired to further reduce the refractive index of a partition.

On the other hand, when this inventor advanced examination about the partition using the low-refractive material described in patent document 1, it turned out that there exists room for further improvement with respect to the refractive index of a partition.

In general, barrier ribs are formed by forming a barrier rib material layer on a support and patterning the barrier rib material layer by a method such as a dry etching method. could When the smoothness of the side surface of the barrier rib is insufficient, scattering of the light passing through the pixel occurs, and the light condensing rate cannot be sufficiently increased in some cases. For this reason, it is preferable that the smoothness of the side surface of a partition is high.

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

According to the study of the present inventor, by forming the barrier ribs using a composition containing a cage siloxane compound and a solvent, it was found that a structure having a barrier rib having a small refractive index and excellent smoothness can be manufactured, thereby completing the present invention came to do Accordingly, the present invention provides the following.

<1> a support;

a partition wall provided on the support;

It has a pixel provided in a region partitioned by a partition,

The structure, wherein the barrier rib is a barrier rib formed using a composition containing a cage-type siloxane compound.

<2> The structure according to <1>, wherein the caged siloxane compound includes a caged siloxane compound in which O/Si, which is a ratio of the number of oxygen atoms to the number of silicon atoms, is 1.3 to 1.7.

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

(*-SiO _1.5 ) _n … (S1)

In the formula, * represents a linking hand, and n represents an integer of 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 polymerization of the compound;

(R ^S1 -SiO _1.5 ) _n … (S2)

In formula, R ^S1 represents an alkyl group or a polymerizable group, n represents the integer of 6-16, and 2 or more R ^S1 among n pieces of R ^S1 is a polymeric group.

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

Formula (S1-1)

[Formula 1]

A broken line in the above formula represents a bond.

<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.

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

<8> A composition for forming barrier ribs used for forming barrier ribs of a structure having a support, barrier ribs provided on the support, and pixels provided in a region partitioned by the barrier ribs, the composition for forming barrier ribs 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>.

ADVANTAGE OF THE INVENTION According to this invention, the structure which has a small refractive index and the partition which is excellent in smoothness can be provided. Moreover, the solid-state image sensor and image display apparatus containing the composition for partition formation used for the structure mentioned above, and a structure can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a side cross-sectional view which shows one Embodiment of the structure of this invention.
It is the top view seen from the direction directly 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 description not describing substitution and unsubstituted includes those having no substituent and those having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. Moreover, as light used for exposure, actinic rays or radiations, such as a bright-line spectrum of a mercury vapor lamp, and the deep ultraviolet, extreme ultraviolet (EUV light), X-rays, and an electron beam, generally typified by an excimer laser.

In this specification, the numerical range indicated using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, total solid means the total mass of the component which removed the solvent from all the components of a composition.

In this specification, "(meth)acrylate" represents both, or either of acrylate and methacrylate, "(meth)acryl" represents both, or either of acryl and methacryl, "(meth)allyl" represents both or any of allyl and methacryloyl, "(meth)acryloyl" represents both of acryloyl and methacryloyl, or either.

In the present specification, the term "process" is included in this term as long as 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, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<struct>

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

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

Since the partition wall in the structure of this invention is formed using the composition containing a cage-type siloxane compound, refractive index is small and it is excellent in smoothness. Since the cage-type siloxane compound has a structure having relatively large voids in its molecular structure, the refractive index of the partition wall can be further reduced by forming the partition wall using a composition containing the cage-type siloxane compound. Moreover, by forming a barrier rib using cage-type siloxane, the film surface roughness of the barrier rib obtained, etc. can be suppressed, and the barrier rib excellent in smoothness can be formed. For this reason, according to the structure of this invention, it can be set as the structure which has a small refractive index and the partition which is excellent in smoothness. And, since the structure of the present invention has a small refractive index of the barrier rib and excellent smoothness, it is possible to further increase the condensing rate of the light passing through the pixel. For this reason, by introducing and using the structure of the present invention in a solid-state imaging device, an image display device, or the like, it is possible to further increase the sensitivity for imaging and sensing.

Moreover, the structure of this invention is excellent also in adhesiveness between a partition and a pixel. Since the cage-type siloxane compound has a structure in which a functional group such as an organic group is bonded to the siloxane skeleton, the affinity with the pixel is improved by this functional group, or it is easy to interact with the pixel, and as a result, excellent adhesiveness is presumed to have been obtained.

The structure of the present invention can be suitably used for a solid-state imaging device, an image display device, and the like. More specifically, it can be preferably used for an image pickup device mounted on a digital still camera, a digital video camera, a surveillance camera, an on-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 body 1 is not particularly limited. It can select suitably according to a use. For example, a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, or a substrate used in various electronic devices such as solid-state imaging devices (silicon wafer, silicon carbide wafer) , a silicon nitride wafer, a sapphire wafer, a glass wafer, etc.) can be used. Moreover, on the support body, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed. Moreover, on the support body, the black matrix comprised from light-shielding materials, such as tungsten, may be formed. Moreover, on the support body, if necessary, the base layer may be provided for the improvement of adhesiveness with an upper layer, diffusion prevention of a substance, or planarization of a board|substrate surface.

The partition wall 2 is formed on the support body 1 . In this embodiment, as shown in FIG. 2, the partition 2 is the top view seen from the direction just above the support body 1 WHEREIN: It is formed in the grid|lattice shape. In addition, in this embodiment, the shape of the area|region partitioned by the partition 2 on the support body 1 (henceforth the shape of the opening part of a partition) comprises the square shape, but the shape of the opening part of the partition is , is not particularly limited, and may be, for example, a rectangular shape, a circular shape, an elliptical shape, or a polygonal shape.

The partition wall 2 is formed using the composition containing a cage type siloxane compound. Here, the cage-type siloxane compound is a compound which has a cage-type siloxane structure. It is preferable that the partition 2 has a cage-type siloxane structure. The cage-type siloxane structure may be a complete cage-type siloxane structure or an incomplete cage-type siloxane structure. It is preferable that it is a siloxane structure. Here, the complete cage-type siloxane structure means a polyhedral siloxane structure including a closed space formed by siloxane bonds, and the incomplete cage-type siloxane structure means a complete cage-type siloxane structure It means a siloxane structure in which a part of the ring-opened structure.

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

Moreover, it is preferable that the 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 linking hand, and n represents an integer of 6 to 16.

It is preferable that n is 8, 10, 12, 14, or 16, It is more preferable that it is 8, 10, or 12, It is more preferable that it is 8.

As a specific example of the partial structure represented by Formula (S1), the structure represented by Formula (S1-1) - (S1-7) below is mentioned, It is refractive index and smoothness that it is a partial structure represented by Formula (S1-1). It is preferable from the point of view of In addition, each broken line in Formula (S1-1) - (S1-7) shows a bond.

Formula (S1-1)

[Formula 2]

[Formula 3]

As a form of a cage-type siloxane compound, although a monomer may be sufficient and a polymer may be sufficient, it is preferable to contain a polymer at least from a viewpoint of the refractive index of the partition obtained, and smoothness. Moreover, it is preferable that it is 50 mass % or more, and, as for content of the polymer in the total mass of a cage type siloxane compound, it is more preferable that it is 70 mass % or more, It is more preferable that it is 90 mass % or more.

It is preferable that the molecular weight of a monomer (a cage type siloxane compound of a monomer type) is 400-2,000.

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

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

It is preferable that the cage type siloxane compound contains at least 1 sort(s) chosen from the compound represented by following formula (S2), and the polymer obtained by superposing|polymerizing this compound, It is more preferable that the above-mentioned polymer is included.

(R ^S1 -SiO _1.5 ) _n … (S2)

In formula, R ^S1 represents an alkyl group or a polymerizable group, n represents the integer of 6-16, and 2 or more R ^S1 among n pieces of R ^S1 is a polymeric group.

1-10 are preferable, as for carbon number of the alkyl group which R ^S1 represents, 1-8 are more preferable, 1-5 are still more preferable, and 1-3 are especially preferable. Any of linear, branched, and cyclic|annular chain may be sufficient as an alkyl group, It is preferable that it is linear or cyclic, and it is more preferable that it is linear. Specific examples of the alkyl group include a methyl group, an 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- 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 , a methyl group or an ethyl group, more preferably a 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. Examples of the group containing a carbon-carbon double bond or a carbon-carbon triple bond include a vinyl group, an allyl group, a 1-propenyl group, a 1-butenyl group, a 2-buten-1-yl group, and a 1-butene-4 group. -yl group, 1-hexen-6-yl group, ethynyl group, propargyl group, and 2-butyn-1-yl group are mentioned. These groups may have a substituent. Preferably, a vinyl group, the vinyl group which has a substituent, an ethynyl group, or the ethynyl group which has a substituent, etc. are mentioned. As a substituent in the above, a C1-C6 alkyl group, an aryl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group etc. are mentioned, for example.

The polymerizable group represented by R ^S1 may be composed of a group containing a carbon-carbon double bond or a carbon-carbon triple bond, and 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 The divalent linking group which can combine these arbitrarily is mentioned. (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 others, -[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.

A vinyl group and an ethynyl group are preferable and, as for the polymeric group which R ^S1 represents, a vinyl group is more preferable.

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

As an initiator used for radical polymerization, an organic peroxide and an organic azo type compound are mentioned, An organic peroxide is preferable. About the detail of an organic peroxide and an organic azo type compound, Paragraph No. 0041 of Unexamined-Japanese-Patent No. 2007-254506 - the compound of 0042 are mentioned, This content is integrated in this specification.

It is preferable to perform superposition|polymerization by the hydrosilylation reaction of the compound represented by Formula (S2) with the compound and silane compound represented by Formula (S2) in presence of a radical generator or a transition metal catalyst. Examples of the radical generator include organic peroxides and organic azo compounds. As a transition metal catalyst, a platinum catalyst, a rhodium catalyst, a nickel catalyst, a cobalt catalyst, a rhenium catalyst, a manganese catalyst, a chromium catalyst, and an iridium catalyst are mentioned, A platinum catalyst is preferable. For the detail of a transition metal catalyst, Paragraph No. 0048 of Unexamined-Japanese-Patent No. 2007-254506 can be considered into consideration, and this content is integrated in this specification. Moreover, when superposing|polymerizing by 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, or the like can be preferably used.

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

Formula (S2-1)

[Formula 4]

In the 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 which R ^S11 -R ^S18 represent, it is synonymous with the alkyl group and polymeric group which R ^S1 of Formula (S2) represents, and a preferable range is also the same.

As a specific example of the compound represented by Formula (S2), the compound of Paragraph No. 0023 of Unexamined-Japanese-Patent No. 2007-254506 - Paragraph No. 0039, The compound of Paragraph No. 0021 - 0024 of Unexamined-Japanese-Patent No. 2008-214455 are mentioned, These The content is incorporated herein by reference. 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 formation of the partition 2 can further contain external components, such as a solvent, in addition to a cage-type siloxane compound. The composition (composition for partition formation) used for formation of the partition 2 is mentioned later.

It is preferable that the width W1 of the partition 2 is 20-500 nm. As for a minimum, it is more preferable that it is 30 nm or more, It is more preferable that it is 40 nm or more, It is still more preferable that it is 50 nm or more. As for an upper limit, it is more preferable that it is 300 nm or less, It is more preferable that it is 200 nm or less, It is still more preferable that it is 100 nm or less.

It is preferable that it is 200-1000 nm, and, as for height H1 of the partition 2, it is more preferable that it is 300-700 nm. Further, the height H1 of the barrier rib 2 is preferably equal to or less than the thickness of the pixel 4 × 200%, more preferably equal to or less than the thickness of the pixel 4 × 150%, and is substantially equal to the thickness of the pixel 4 It is more preferable to say that it is the same as

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

The pitch P1 of the partition 2 is not specifically limited. It can select suitably according to a use. For example, in the solid-state image sensor use of a high pixel, it is preferable that it is 500-2000 nm, It is more preferable that it is 500-1500 nm, It is more preferable that it is 500-1000 nm.

It is preferable that it is 1.10-1.40, as for the refractive index of the light of wavelength 550nm of the partition 2, it is more preferable that it is 1.15-1.37, It is more preferable that it is 1.20-1.35.

On the support body 1, the pixel 4 is formed in the area|region (opening part of the partition wall) partitioned by the partition 2nd. There is no limitation in particular as a kind of pixel. Color pixels, such as red, blue, green, magenta, and cyan, a pixel of an infrared ray transmission layer, a transparent pixel, etc. are mentioned. Although the type and arrangement of pixels can be arbitrarily selected, it is preferable that the pixel 4 includes at least one type of pixel selected from a color pixel and a pixel of an 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, It is more preferable that it is 95 % or more.

As a pixel of an infrared transmission layer, it is preferable, for example that it is a pixel of a filter layer which has the spectral characteristic which transmits at least a part of light in the wavelength range of 700-2500 nm, The spectral characteristic which transmits at least a part of light in the wavelength range of 700-2000 nm It is more preferable that it is a pixel of the filter layer having It is more preferably a pixel of the filter layer having a spectral characteristic, and particularly preferably a pixel of the filter layer having a spectral characteristic that transmits at least a part of light in a wavelength range of 700 to 1000 nm. Moreover, the infrared transmission layer may be comprised by the film|membrane of one layer (single layer film), and may be comprised by the laminated body (multilayer film) of two or more layers of film|membrane. In the case where the infrared transmitting layer is constituted by a multilayer film, the multilayer film as a whole may have the above-described spectral characteristics, and the one-layer film itself may not have the above-described spectral characteristics.

As a preferable example of the pixel of an infrared transmission layer, the pixel of the filter layer which has the spectral characteristic in any one of the following (1)-(4) is mentioned, for example.

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

(2): the maximum value in the range of 400-750 nm wavelength of the transmittance|permeability of the light in the thickness direction is 20 % or less (preferably 15 % or less, More preferably, 10 % or less) in the thickness direction The pixel of the filter layer whose minimum value in the range of wavelength 900-1300 nm of the light transmittance is 70% or more (preferably 75% or more, More preferably, 80% or more). 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 400-850 nm wavelength of the transmittance|permeability of the light in the thickness direction is 20 % or less (preferably 15 % or less, More preferably, 10 % or less) in the thickness direction The pixel of the filter layer whose minimum value in the range of the wavelength of 1000-1300 nm of the light transmittance is 70% or more (preferably 75% or more, More preferably, 80% or more). According to this pixel, light in a wavelength range of 400 to 850 nm can be shielded, and light having a wavelength of 940 nm or more can be transmitted.

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

The height H2 of the pixel 4 can be appropriately selected according to the use. For example, in a solid-state image sensor use, it is preferable that it is 300-1000 nm, It is more preferable that it is 300-800 nm, It is more preferable that it is 300-600 nm. Moreover, it is preferable that it is 50-150% of the height H1 of the partition 2, as for the height H2 of the pixel 4, it is more preferable that it is 70-130%, It is more preferable that it is 90-110%. do.

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

In the structure of the present invention, an organic material layer may be provided between the partition wall 2 and the pixel 4 . According to this aspect, the adhesiveness of the partition 2 and the pixel 4 can be improved more. The organic layer can be formed using a composition containing a resin, a curable compound, or the like. As resin, (meth)acrylic resin, an epoxy resin, polyester resin etc. are mentioned, for example. The material etc. mentioned later are mentioned as a sclerosing|hardenable compound.

In the structure of the present invention, a condensing lens or the like may be provided on the pixel 4 . Further, the condensing lens may be provided on the surface of the pixel, or an intermediate layer may be further provided between the pixel 4 and the condensing lens. As an intermediate|middle layer, the said organic substance layer, a low refractive layer, etc. are mentioned. The low refractive layer may be a film formed using the composition for forming a barrier rib of the present invention.

<Composition for forming barrier ribs>

Next, the composition (composition for partition formation) used for formation of the partition in the structure of this invention is further demonstrated in detail.

(cage-type siloxane compound)

The composition for forming a barrier rib contains a cage-type siloxane compound. The above-mentioned thing is mentioned about the cage-type siloxane compound.

It is preferable that it is 1 mass % or more, and, as for content of the cage type siloxane compound in the composition for partition formation, it is more preferable that it is 5 mass % or more.

It is preferable that content of the cage-type siloxane compound in the total solid of the composition for partition formation is 40 mass % or more, It is more preferable that it is 60 mass % or more, It is more preferable that it is 80 mass % or more. The refractive index is low and it is easy to form the partition excellent in smoothness, so that there is much content of the cage-type siloxane compound in the total solid of the composition for partition formation.

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

Further, 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 barrier ribs is preferably 50 mass% or more, more preferably 70 mass% or more, 90 It is more preferable that it is mass % or more. It is also preferable that the caged siloxane compound is substantially only a caged siloxane compound of a polymer type. In addition, when the cage type siloxane compound contained in the composition for partition formation is substantially only a polymer type cage type siloxane compound, it is a polymer type cage type siloxane compound in the total mass of a 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 cage-type siloxane compound of a polymer type.

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. By using both together, sclerosis|hardenability of the composition for partition formation can be improved. Moreover, adhesiveness with a pixel can also be improved. When using both together, it is preferable that it is 0.01-10 mass parts of monomeric cage type siloxane compound with respect to 100 mass parts of polymer type cage type siloxane compound, It is more preferable that it is 0.1-1.0 mass part.

(Other low refractive materials)

The composition for forming a barrier rib of the present invention may contain other low-refractive materials other than the cage-type siloxane compound. Examples of other low-refractive materials include siloxane resins other than cage-type siloxane compounds, fluororesins, colloidal silica particles, and the like.

As a siloxane resin, resin obtained through a hydrolysis reaction and a condensation reaction using an alkoxy silane raw material is mentioned. Siloxane resin which has a cage-type silsesquioxane structure may be sufficient as siloxane resin.

As a fluororesin, resin containing a fluorine in a molecule|numerator is mentioned. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/ethylene copolymer Copolymer, hexafluoropropylene/propylene copolymer, polyvinylidene fluoride, vinylidene fluoride/ethylene copolymer, etc. are mentioned. Moreover, an amorphous fluororesin is also used preferably, and CYTOP (made by Asahi Glass) etc. are mentioned as a commercial item. The range of 100,000-10 million is preferable, and, as for the weight average molecular weight of fluororesins, such as polytetrafluoroethylene, 100,000-1 million are more preferable. As a commercial product of polytetrafluoroethylene, Mitsui DuPont Fluorochemicals Co., Ltd. Teflon (registered trademark) 6-J, Teflon (registered trademark) 6C-J, Teflon (registered trademark) 62-J, Asahi ICI Fluoro Fluon CD1 and CD076 manufactured by Raw Polymers Co., Ltd. are mentioned. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available from Mitsubishi Rayon Co., Ltd. as "Metablen (registered trademark)" A series, "Metablen (registered trademark)" Registered trademark)" A-3000, "Metablen (registered trademark)" A-3800 and the like are commercially available. In addition, in this specification, about resin which contains a siloxane bond and a fluorine atom in a molecule|numerator, it shall correspond to siloxane resin.

As a preferable aspect of a colloidal silica particle, the following 1st - 3rd aspects are mentioned.

1st aspect: The average particle diameter D ₁ measured by the dynamic light scattering method is 25-1000 nm, and the average particle diameter calculated from the average particle diameter D ₁ and the specific surface area S of the colloidal silica particles measured by the nitrogen adsorption method _The aspect in which ratio D1/D2 _with D2 is ₃ or more.

A second aspect: an aspect in which a plurality of spherical silica particles are planarly connected.

A third aspect: an aspect in which a plurality of spherical silica particles are connected in the form of beads.

The colloidal silica particle of a 1st aspect may further satisfy|fill the requirements of the colloidal silica particle of a 2nd aspect or 3rd aspect. Moreover, the colloidal silica particle of a 2nd aspect may further satisfy|fill the requirements of a 1st aspect. Moreover, the colloidal silica particle of a 3rd aspect may further satisfy|fill the requirements of the colloidal silica particle of a 1st aspect.

In addition, in this specification, what is necessary is just to be substantially spherical with "spherical shape", and it is the range which shows the effect of this invention, and it is the meaning which you may deform|transform. For example, the meaning also includes the shape which has an unevenness|corrugation on the surface, and the flat shape which has a long axis in a predetermined direction.

In addition, "a plurality of spherical silica particles are connected in a bead shape" means a structure in which a plurality of spherical silica particles are connected in a linear and/or branched form. For example, the structure in which several spherical silica particles were connected by the junction part whose outer diameter is smaller than this is mentioned. Moreover, in this invention, as a structure "in which a plurality of spherical silica particles are connected in a bead shape", not only a structure in a form connected in a ring shape but also a structure in a chain form having a terminal is included.

Moreover, "a some spherical silica particle is planarly connected" means the structure in which some spherical silica particle was connected in substantially the same plane. In addition, "substantially on the same plane" means not only the case of being on the same plane, but also the meaning which may shift vertically in the same plane. For example, you may shift|shift up and down in the range of 50% or less of the particle diameter of a silica particle.

In the colloidal silica particles used in the present invention, it is preferable that the ratio D ₁ /D ₂ of the average particle diameter D ₁ measured by the dynamic light scattering method to the average particle diameter D ₂ is 3 or more. _Although there is no upper limit in particular _of D1/D2, It is preferable that it is 1000 or less, It is more preferable that it is 800 or less, It is more preferable that it is 500 or less. By making D ₁ /D ₂ into such a range, favorable optical properties can be expressed, and aggregation at the time of drying can be suppressed effectively by extension. In addition, the value of D ₁ /D ₂ in the colloidal silica particles is also an index of the degree of coupling of the spherical silica particles.

The said average particle diameter D2 _of a colloidal silica particle can be considered as the average particle diameter approximated to the primary particle of a spherical silica. It is preferable that average particle diameter D2 is ₁ nm or more, It is more preferable that it is 3 nm or more, It is more preferable that it is 5 nm or more, It is especially preferable that it is 7 nm or more. As an upper limit, it is preferable that it is 100 nm or less, It is more preferable that it is 80 nm or less, It is more preferable that it is 70 nm or less, It is still more preferable that it is 60 nm or less, It is especially preferable that it is 50 nm or less.

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

The said average particle diameter D ₁ of a colloidal silica particle can be considered as the number average particle diameter of the secondary particle which several spherical silica particle gathered. Therefore, the relationship of D ₁ >D ₂ is usually established. It is preferable that average particle diameter D1 is ₂₅ nm or more, It is more preferable that it is 30 nm or more, It is especially preferable that it is 35 nm or more. As an upper limit, it is preferable that it is 1000 nm or less, It is more preferable that it is 700 nm or less, It is more preferable that it is 500 nm or less, It is especially preferable that it is 300 nm or less.

Unless otherwise specified, the measurement of the said average particle diameter D1 _of colloidal silica particles is performed using the dynamic-light-scattering type particle size distribution analyzer (Nikkiso Nanotrac Wave-EX150 [brand name]). The procedure is as follows. The dispersion of colloidal silica particles is aliquoted into a 20 ml sample bottle, and dilution is adjusted with toluene so that the solid content concentration is 0.2 mass %. The sample solution after dilution is irradiated with 40 kHz ultrasonic wave for 1 minute, and is used for the test immediately after that. Data retrieval was performed 10 times at a temperature of 25 DEG C using a quartz cell for measurement of 2 ml, and the obtained &quot;number average" For other detailed conditions, etc., if necessary, refer to the description of JISZ8828: 2013 "Particle diameter analysis-dynamic light scattering method". 5 samples per level are produced and the average value is adopted.

As for the colloidal silica particle, it is preferable that the spherical silica particle with an average particle diameter of 1-80 nm is connecting two or more via a coupling material. As an upper limit of the average particle diameter of a spherical silica particle, it is preferable that it is 70 nm or less, It is more preferable that it is 60 nm or less, It is more preferable that it is 50 nm or less. Moreover, as a minimum 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, It is more preferable that it is 7 nm or more. In addition, in this invention, the value of the average particle diameter calculated|required from the equivalent circle diameter in the projected image of the spherical part measured with the transmission electron microscope (TEM) is used for the value of the average particle diameter of a spherical silica particle.

As a coupling material which connects spherical silica particles, a metal oxide containing silica is mentioned. Examples of the metal oxide 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 a reaction product and a mixture of these metal oxides and silica (SiO ₂ ). For the connecting material, reference can be made to the description of International Publication No. WO2000/015552, the content of which is incorporated herein by reference.

As the number of connections of a spherical silica particle, 3 or more are preferable and 5 or more are more preferable. 1000 or less are preferable, as for an upper limit, 800 or less are more preferable, and 500 or less are still more preferable. The number of connections of the spherical silica particles can be measured by TEM.

You may use the colloidal silica particle in the state of a particle liquid (sol). For example, the silica sol etc. which are described in Unexamined-Japanese-Patent No. 4328935 can be used. As a medium for dispersing colloidal silica particles, alcohol (eg, methanol, ethanol, isopropanol (IPA)), ethylene glycol, glycol ether (eg, propylene glycol monomethyl ether) ), glycol ether acetate (eg, propylene glycol monomethyl ether acetate) and the like. Moreover, solvent A1, solvent A2, etc. which are mentioned later can also be used. Particle liquid (sol) _WHEREIN : It is preferable that SiO2 density|concentration is 5-40 mass %. A commercial item can also be used for the particle liquid (sol). For example, "Snotex OUP", "Snowtex UP", "IPA-ST-UP", "Snowtex PS-M", "Snotex PS-MO", "Snotex PS" manufactured by Nissan Chemical Industries, Ltd. -S", "Snotex PS-SO", "Fine Cataloid F-120" by Shokubai Kasei Kogyo Co., Ltd., "Quatron PL" by Fuso Chemical Co., Ltd., etc. are mentioned.

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 still more preferably 10 parts by mass or less with respect to 100 parts by mass of the cage-type siloxane compound.

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

(solvent)

The composition for forming a barrier rib contains a solvent. Examples of the solvent include organic solvents (aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, aromatic compounds) and water. Each example is listed below.

・aliphatic compounds

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

・Halogenated hydrocarbon compound

Methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, HCFC, monochloromethyl acetate, Monochloroethyl acetate, 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 ether, diethylene glycol monobenzyl ether, tripropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, etc.

・Ester compound

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

・Ketone compounds

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.

・Nitrile group compound

acetonitrile groups and the like.

・Amide compound

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-methylpropaneamide, hexamethylphosphoric triamide, 3-methoxy-N,N- Dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, and the like.

·Sulphoxide compound

dimethyl sulfoxide and the like.

· Aromatic compounds

benzene, toluene, etc.

The composition for partition formation WHEREIN: It is preferable that content of a solvent is 70-99 mass % with respect to the whole quantity of the composition for partition formation. As for an upper limit, it is more preferable that it is 97 mass % or less, It is more preferable that it is 95 mass % or less, It is still more preferable that it is 93 mass % or less. It is more preferable that a minimum is 75 mass % or more, It is more preferable that it is 80 mass % or more, It is still more preferable that it is 85 mass % or more.

(Surfactants)

The composition for partition formation may contain surfactant. As surfactant, you may use either a nonionic surfactant, a cationic surfactant, and an anionic surfactant. In a nonionic surfactant, a fluorochemical surfactant is preferable. In particular, a fluorine-type surfactant, an anionic surfactant, and a cationic surfactant are preferable, and a fluorine-type surfactant is more preferable.

In this invention, it is preferable to contain surfactant which has 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, and specific examples thereof include an ethylene oxide (EO) structure and a propylene oxide (PO) structure. The polyoxyalkylene structure may constitute a graft chain of the acrylic polymer.

When the surfactant is a high molecular compound, the weight average molecular weight is preferably 1500 or more, more preferably 2500 or more, still 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, It is especially preferable that it is 17500 or less.

It is preferable that it is a polymer (polymer) surfactant which has a polyethylene main chain as a fluorochemical surfactant. Especially, the polymer (polymer) surfactant which has 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 a fluorinated alkyl acrylate structural unit is preferable.

Moreover, as a fluorine-type surfactant, the compound which has a fluoroalkyl group or a fluoroalkylene group (C1-C24 is preferable, 2-12 are more preferable) at any one site|part can be used suitably. Preferably, a polymer compound having the fluoroalkyl group or fluoroalkylene group in the side chain may be used. It is preferable to have the said polyoxyalkylene structure further, and, as for a fluorochemical surfactant, it is more preferable to have a polyoxyalkylene structure in a side chain. For a compound having a fluoroalkyl group or a fluoroalkylene group, reference may be made to paragraphs 0034 to 0040 of International Publication No. WO2015/190374, the contents of which are incorporated herein by reference.

As a fluorochemical surfactant, For example, Megapac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F559, F780, F781F (above, DIC Corporation) ), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Sufflon 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 Glass Co., Ltd.), Ftop EF301, EF303, EF351, EF352 (above, manufactured by Gemco), PF636, PF656, PF6320, PF6520, PF7002 (above, the OMNOVA company make) etc. are mentioned.

Moreover, a block polymer can also be used for a fluorine-type surfactant. For example, the compound of Unexamined-Japanese-Patent No. 2011-089090 is mentioned. The fluorine-based surfactant has two or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meth) ) A fluorine-containing high molecular 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 said compound becomes like this. Preferably it is 3,000-50,000, for example, 14,000. Among the above compounds, % indicating the proportion of the repeating unit is mol%.

For nonionic surfactants other than fluorine-based surfactants, anionic surfactants, and cationic surfactants, paragraphs 0042 to 0045 of International Publication No. WO2015/190374 can be referred to, the content of which is incorporated herein by reference.

When the composition for forming barrier ribs contains a surfactant, the content of the surfactant is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and particularly preferably 0.1 mass % or more, based on the total solids of the composition for forming barrier ribs. 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. One type may be sufficient as surfactant, and 2 or more types may be included. When 2 or more types are included, it is preferable that those sum total is the said range.

Moreover, it is also preferable that the composition for partition formation does not contain surfactant substantially. When the composition for partition formation does not contain surfactant substantially, it is easy to improve adhesiveness with a pixel more. In addition, the case where surfactant is not substantially included means that the content of surfactant is 0.005 mass % or less in the total solid content of the composition for partition formation, preferably 0.001 mass % or less, and does not contain surfactant more preferably.

(curable compound)

The composition for forming a barrier rib may further contain a curable compound as a component other than the cage-type siloxane compound. Examples of the curable compound include a compound having an ethylenically unsaturated bond group, a compound having an epoxy group, and the like. As an ethylenically unsaturated bond group, a vinyl group, (meth)allyl group, (meth)acryloyl group, etc. are mentioned. As a compound which has an ethylenically unsaturated bond group, it is preferable that it is a polymeric compound, and it is more preferable that it is a radically polymerizable compound.

Although any of chemical forms, such as a monomer, a prepolymer, and an oligomer, may be sufficient as a compound which has an ethylenically unsaturated bond group used as a sclerosing|hardenable compound, A monomer is preferable. As for the molecular weight of the compound which has an ethylenically unsaturated bond group, 100-3000 are preferable. As for an upper limit, 2000 or less are more preferable, and 1500 or less are still more preferable. 150 or more are more preferable, and, as for a minimum, 250 or more are still more preferable.

It is preferable that it is a compound containing 3 or more ethylenically unsaturated bond groups, and, as for the compound which has an ethylenically unsaturated bond group, it is more preferable that it is a compound containing 3-15 ethylenically unsaturated bond groups, It is ethylenically unsaturated bond group 3- It is more preferable that it is a compound containing six. Moreover, it is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for the compound which has an ethylenically unsaturated bond group, it is more preferable that it is a 3-6 functional (meth)acrylate compound. As a specific example of the compound which has an ethylenically unsaturated bond group, Paragraph No. 0095 of Unexamined-Japanese-Patent No. 2009-288705 - Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph No. 0254 of Unexamined-Japanese-Patent No. 2008-292970 - Paragraph 0257 described compounds, the contents of which are incorporated herein by reference.

It is preferable that it is a compound which has 1-100 epoxy groups in 1 molecule as a compound (henceforth an epoxy compound) used as a sclerosing|hardenable compound which has an epoxy group. As for the minimum of an epoxy group, 2 or more are more preferable. The upper limit of the epoxy group may be, for example, 10 or less, and may be 5 or less.

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

The epoxy compound may be a low-molecular compound (eg, molecular weight less than 1000) or a macromolecule (eg, molecular weight 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more). 200-100000 are preferable and, as for the weight average molecular weight of an epoxy compound, 500-50000 are more preferable. As for the upper limit of a weight average molecular weight, 10000 or less are more preferable, 5000 or less are still more preferable, and 3000 or less are still more preferable.

As an epoxy compound, Paragraph Nos. 0034 to 0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph Nos. 0147 to 0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph No. 0085 of Unexamined-Japanese-Patent No. 2014-089408 Paragraph Nos. 0085 to 0092 of Unexamined-Japanese-Patent No. may be These contents are integrated in this specification.

When the composition for forming barrier ribs contains a curable compound, the content of the curable compound is preferably 1 mass % or more, more preferably 5 mass % or more, and particularly preferably 10 mass % or more, based on the total solids of the composition for barrier rib formation. 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 sclerosing|hardenable compound substantially. When the composition for partition formation does not contain a sclerosing|hardenable compound substantially, it is easy to make smaller the refractive index of the partition obtained. In addition, when the composition for partition formation does not contain a curable compound substantially, it means that content of a curable compound is 0.005 mass % or less in the total solid of the composition for partition formation, It is preferable that it is 0.001 mass % or less, and a curable compound It is more preferable not to contain

(Photoinitiator)

When the composition for partition formation contains a polymeric compound as a sclerosing|hardenable compound, it is preferable to contain a photoinitiator further. There is no restriction|limiting in particular as a photoinitiator as long as it has the ability to initiate polymerization of a polymeric compound, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the visible region from the ultraviolet region is preferable. Moreover, the compound which generate|occur|produces a certain action with the photo-excited sensitizer and produces|generates an active radical may be sufficient. It is preferable that a photoinitiator is a photoradical polymerization initiator.

As a photoinitiator, for example, a halogenated hydrocarbon derivative (For example, the compound which has a triazine skeleton, the compound which has an oxadiazole skeleton, etc.), an acylphosphine compound, hexaarylbiimidazole, an oxime compound, an organic and peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. A photoinitiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, (alpha)-hydroxyketone compound, (alpha)-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene from a viewpoint of exposure sensitivity. compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin A compound is preferable, the compound selected from an oxime compound, (alpha)-hydroxyketone compound, (alpha)-amino ketone compound, and an acylphosphine compound is more preferable, and an oxime compound is still more preferable. About a photoinitiator, Paragraph No. 0065 of Unexamined-Japanese-Patent No. 2014-130173 - Paragraph 0111 of Unexamined-Japanese-Patent No. 2013-029760 Paragraph No. 0274 - Description of 0306 can be considered into consideration, and these content is integrated in this specification.

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

In this invention, you may use the photoinitiator more than bifunctional or trifunctional as a photoinitiator. As a specific example of such a photoinitiator, Paragraph No. 0417-0412 of Unexamined-Japanese-Patent No. 2010-527339, Unexamined-Japanese-Patent No. 2011-524436, International Publication WO2015/004565, Unexamined-Japanese-Patent No. 2016-532675, International The dimer of the oxime compound described in Paragraph Nos. 0039 to 0055 of Unexamined Publication No. WO2017/033680, the compound (E) and the compound (G) described in Japanese Unexamined Patent Publication No. 2013-522445, International Publication WO2016/034963 and Cmpd1 to 7 described in the preceding paragraph.

When the composition for partition formation contains a photoinitiator, the content of the photoinitiator is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, based on the total solid content of the composition for partition formation. 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 contain a photoinitiator substantially, it means that content of a photoinitiator is 0.005 mass % or less in the total solid of the composition for partition formation, It is preferable that it is 0.001 mass % or less, and a photoinitiator It is more preferable not to contain

(Alkali-soluble resin)

The composition for forming a barrier rib may contain an alkali-soluble resin. Alkali-soluble resin can be suitably selected from resin which has a group which accelerates|stimulates alkali dissolution. As a group which accelerates|stimulates alkali dissolution (henceforth an acidic radical), a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, etc. are mentioned, for example, A carboxyl group is preferable. One type may be sufficient as the kind of acidic radical which alkali-soluble resin has, and 2 or more types may be sufficient as it.

As for the weight average molecular weight (Mw) of alkali-soluble resin, 5000-100000 are preferable. 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-based resin, polysiloxane-based resin, acrylic resin, acrylamide-based resin, and acryl/acrylamide copolymer resin are preferable. Moreover, from a viewpoint of developability control, an acryl-type resin, acrylamide-type resin, and acryl/acrylamide copolymer resin are preferable.

As for alkali-soluble resin, the polymer which has a carboxyl group in a side chain is preferable. 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, and partially esterified maleic acid; Alkali-soluble phenol resins, such as bolac-type resin, the acidic cellulose derivative which has a carboxyl group in a side chain, and the polymer which added the acid anhydride to the polymer which has a hydroxyl group is mentioned.

Alkali-soluble resin which has a polymeric group can also be used for alkali-soluble resin. As a polymeric group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. As alkali-soluble resin which has a polymeric group, alkali-soluble resin etc. which have a polymeric group in a side chain are useful. Commercially available alkali-soluble resins having a polymerizable group include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscot R -264, KS resist 106 (all manufactured by Osaka Yuki Chemical Co., Ltd.), Cyclomer P series (eg, ACA230AA), Flaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (Daisel Yushibi) Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), DP-1305 (manufactured by Fuji Fine Chemicals), and the like.

Alkali-soluble resin is at least 1 sort(s) of compound chosen from the compound represented by the following formula (ED1), and the compound represented by Formula (1) of Unexamined-Japanese-Patent No. 2010-168539 (Hereinafter, when these compounds are called "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 an ether dimer, Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-029760 can be considered into consideration, for example, This content is integrated in this specification. The number of ether dimers may be one, and 2 or more types may be sufficient as them.

For alkali-soluble resin, Paragraph Nos. 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (paragraph Nos. 0685 to 0700 of U.S. Patent Application Laid-Open No. 2012/0235099 corresponding to) can be referred to, the content of which is this specification is used in Moreover, the copolymer (B) of Paragraph No. 0029-0063 of Unexamined-Japanese-Patent No. 2012-032767, alkali-soluble resin used in the Example, Paragraph No. 0088 of Unexamined-Japanese-Patent No. 2012-208474 Binder resin of 0098 And the binder resin used in the Example, the binder resin of Paragraph Nos. 0022 to 0032 of Unexamined-Japanese-Patent No. 2012-137531, The binder resin used in the Example, Paragraph No. 0132-0143 of Unexamined-Japanese-Patent No. 2013-024934. The binder resin described in and the binder resin used in the Examples, Paragraph Nos. 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752, and the binder resin used in the Examples, Paragraph Nos. 0030 to 0072 of Japanese Patent Application Laid-Open No. 2012-032770 The binder resin described in can also be used. These contents are incorporated herein by reference.

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

When the composition for partition formation contains alkali-soluble resin, 1 mass % or more is preferable in the total solid of the composition for partition formation, as for content of alkali-soluble resin, 5 mass % or more is more preferable, 10 mass % or more 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 alkali-soluble resin substantially. In addition, when the composition for partition formation substantially does not contain alkali-soluble resin, it means that the content of alkali-soluble resin is 0.005 mass % or less in the total solid of the composition for partition formation, and it is preferable that it is 0.001 mass % or less, It is more preferable not to contain alkali-soluble resin.

(Other additives)

Various additives other than the above, for example, a polymerization inhibitor, a ultraviolet absorber, a filler, an adhesion promoter, antioxidant, a latent antioxidant, etc. can be mix|blended with the composition for partition formation as needed.

<Composition for Forming Colored Pixels>

Next, the composition (composition for color pixel formation) which can be used suitably for formation of the colored pixel in the structure of this invention is demonstrated. It is preferable that the composition for colored pixel formation 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. A pigment may be sufficient as a coloring agent, and dye may be sufficient as it.

Specific examples of the pigment include the following.

Color Index (C.I.) 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);

C. I. 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);

C. I. 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).

Moreover, as a green coloring agent, the average number of halogen atoms in a molecule|numerator is 10-14, the average number of bromine atoms is 8-12, and the halogenated zinc phthalocyanine pigment whose average number of chlorine atoms is 2-5 can also be used. As a specific example, the compound of international publication WO2015/118720 is mentioned.

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

As a dye, Unexamined-Japanese-Patent No. 64-090403, Unexamined-Japanese-Patent No. 64-091102, Unexamined-Japanese-Patent No. Hei 1-094301, Unexamined-Japanese-Patent No. 6-011614, U.S. Patent 4808501, for example. and dyes disclosed in Japanese Patent Application Laid-Open No. Hei 5-333207, Japanese Unexamined Patent Publication No. Hei 6-035183, Japanese Unexamined Patent Publication No. 6-051115, and Japanese Patent Application Laid-Open No. Hei 6-194828. . When classified as a chemical structure, a pyrazolazo compound, a pyromethene compound, an anilinoazo compound, a triarylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazolazo compound, a pyridonazo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazol azomethine compound, etc. are mentioned.

Moreover, you may use a dye multimer as a coloring agent. Although it is preferable that a dye multimer is a dye used by melt|dissolving in a solvent, it may form particle|grains. When a dye multimer is particle|grains, it disperse|distributes a dye multimer etc. and is used. The particle-form dye multimer can be obtained by emulsion polymerization, for example. As a particle-form dye multimer, the compound described in Unexamined-Japanese-Patent No. 2015-214682 is mentioned, for example. Moreover, the compound described in Unexamined-Japanese-Patent No. 2011-213925, Unexamined-Japanese-Patent No. 2013-041097, Unexamined-Japanese-Patent No. 2015-028144, Unexamined-Japanese-Patent No. 2015-030742, etc. can also be used as a dye multimer. .

It is preferable that content of a coloring agent is 20 mass % or more with respect to the total solid of the composition for colored pixel formation, 30 mass % or more is more preferable, 40 mass % or more is still more preferable, 50 mass % or more is still more preferable and 60 mass % or more is especially preferable, and 65 mass % or more is the most preferable. It is preferable that it is 80 mass % or less, and, as for an upper limit, 75 mass % or less is more preferable, and its 70 mass % or less is still more preferable. One type may be sufficient as the coloring agent contained in the composition for colored pixel formation, and 2 or more types may be sufficient as it. When 2 or more types of coloring agents are contained, it is preferable that a total amount becomes the said range.

It is preferable that the composition for colored pixel formation contains resin. As the resin, (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. are mentioned. The resin is blended for, for example, a use of dispersing particles such as a pigment in a composition, or a use of a binder. In addition, a resin mainly used for dispersing particles such as a pigment is also called a dispersing agent. However, such a use of resin is an example, and it can also use for purposes other than such a use. As for the weight average molecular weight (Mw) of resin, 5000-100000 are preferable. Moreover, as for the number average molecular weight (Mn) of resin, 1000-20000 are preferable.

It is also preferable that the composition for colored pixel formation uses alkali-soluble resin as resin. As alkali-soluble resin, the thing mentioned above is mentioned.

The composition for color pixel formation can also use resin as a dispersing agent. As a dispersing agent, Paragraph 0173 of Unexamined-Japanese-Patent No. 2015-151530 - the pigment dispersant of 0179 are mentioned, This content is integrated in this specification.

The composition for color pixel formation can 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. Examples of the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, and a dioxazine skeleton. , perinone skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, threne skeleton, metal complex skeleton, etc., quinoline skeleton , benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinophthalone skeleton, isoindoline skeleton and phthalocyanine skeleton are preferred, azo skeleton and benzimidazolone skeleton This is more preferable. As an acidic radical 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, Paragraph No. 0162 of Unexamined-Japanese-Patent No. 2011-252065 - description of 0183 can be considered into consideration, for example, This content is integrated in this specification.

The composition for colored pixel formation can further contain a sclerosing|hardenable compound, a photoinitiator, a solvent, and surfactant. These include the above-mentioned materials.

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

<Composition for forming transparent pixels>

Next, the composition (composition for transparent pixel formation) which can be used suitably for formation of the transparent pixel in the structure of this invention is demonstrated. It is preferable that the composition for transparent pixel formation contains a sclerosing|hardenable compound. Examples of the sclerosing compound include the materials described above, and the preferable ranges are also the same. The composition for forming a transparent pixel further comprises 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 referred to as inorganic particles). When containing the inorganic particle mentioned above, it is preferable that content of an inorganic particle is 20-70 mass % with respect to the total solid of the composition for transparent pixel formation. 25 mass % or more is more preferable, and, as for a minimum, 30 mass % or more is still more preferable. 65 mass % or less is more preferable, and, as for an upper limit, 60 mass % or less is still more preferable. The composition for transparent pixel formation may further contain additives, such as a photoinitiator, a solvent, and surfactant. These include the above-mentioned materials. Moreover, the composition for transparent pixel formation may further contain additives, such as a silane coupling agent, a polymerization inhibitor, a ultraviolet absorber, a filler, an adhesion promoter, antioxidant, and a latent antioxidant.

<Composition for forming an infrared transmission layer>

Next, the composition (composition for forming an infrared transmission layer) which can be preferably used for formation of the pixel of the infrared transmission layer in the structure of this invention is demonstrated. The composition for forming an infrared transmission layer preferably has an A/B ratio of the minimum value A of absorbance in the wavelength range of 400 to 640 nm and the maximum absorbance value B in the wavelength range of 1100 to 1300 nm of 5 or more, and 7.5 or more It is preferable, and 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 permeable layer, the conditions of the absorbance can be suitably achieved, for example, by adjusting the type and content of the light-shielding material to be described later.

The absorbance Aλ at a predetermined wavelength λ is defined by the following formula (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 value of the absorbance may be a value measured in a solution state, or may be a value in a film formed using the composition for forming an infrared transmission layer. When measuring the absorbance in a film state, the composition for forming an infrared transmission layer is applied 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 the membrane prepared by drying for 120 seconds. The thickness of a film|membrane can be measured with respect to the board|substrate which has a film|membrane using the stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC).

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

(1): Two or more types of chromatic colorants are included, and black is formed by the combination of 2 or more types of chromatic colorants.

(2): Contains an organic black colorant. Aspect of (2) WHEREIN: It is also preferable to contain a chromatic coloring agent further.

The light-shielding material preferably has an A/B ratio of, for example, the minimum value A of the absorbance in the wavelength range of 400 to 640 nm and the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm of 4.5 or more. 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 to combine a plurality of chromatic colorants to satisfy the spectral properties. Moreover, in the case of the aspect of said (2), the organic type black coloring agent may satisfy|fill the said spectral characteristic. Moreover, the said spectral characteristic may be satisfy|filled by the combination of an organic type black coloring agent and a chromatic coloring agent.

It is preferable that a light-shielding material contains 2 or more types chosen 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 the combination of 2 or more types of coloring agents chosen from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and a green coloring agent. As a preferable combination, the following are mentioned, for example.

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

(2) An aspect containing a red colorant, a blue colorant, and a yellow colorant.

(3) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(4) An aspect containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(5) Aspects containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(6) Aspects containing a red colorant, a blue colorant, and a green colorant.

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

In the aspect of the above (1), the mass ratio of the red colorant and the blue colorant is preferably red colorant: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 the above (2), the mass ratio of the red colorant, the blue colorant, and 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, the blue colorant, the yellow colorant, and the purple colorant is: red colorant:blue colorant:yellow colorant:purple colorant=10 to 80:20 to 80:5 to 40:5 It is preferable that it is -40, It is more preferable that it is 10-60:30-80:5-30:5-30, It is more preferable that it is 10-40:40-80:5-20:5-20.

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

In the aspect of the above (6), the mass ratio of the red colorant, the blue colorant, and 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 and the purple colorant is preferably yellow colorant:purple colorant=10-50:40-80, more preferably 20-40:50-70, 30 It is more preferable that it is -40:60-70.

As a yellow colorant, C.I. Pigment Yellow 139, 150, and 185 are preferable, C. I. Pigment Yellow 139, 150 are more preferable, C. I. Pigment Yellow 139 is still 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 a red coloring agent, C.I. Pigment Red 122, 177, 224, 254 is preferable, C. I. Pigment Red 122, 177, 254 is more preferable, C.I. Pigment Red 254 is still more preferable. As the green colorant, C. I. Pigment Green 7, 36, 58, and 59 are 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 type black coloring agent and a chromatic coloring agent, the outstanding spectral characteristic is easy to be obtained. As a chromatic coloring agent used in combination with an organic type black coloring agent, a red coloring agent, a blue coloring agent, a purple coloring agent, etc. are mentioned, for example, A red coloring agent and a blue coloring agent are preferable. These may be used independently and may use 2 or more types together. Moreover, 10-200 mass parts of a chromatic coloring agent is preferable with respect to 100 mass parts of organic type black coloring agents, and, as for the mixing ratio of a chromatic coloring agent and an organic type black coloring agent, 15-150 mass parts is more preferable.

It is preferable that content of the pigment in a light-shielding material is 95 mass % or more with respect to the whole quantity of a light-shielding material, It is more preferable that it is 97 mass % or more, It is more preferable that it is 99 mass % or more.

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

The composition for forming an infrared transmission layer may further contain an infrared absorber. In the composition for forming an infrared transmission layer, the infrared absorber has a role of limiting the transmitted light (infrared rays) 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 wavelength 700 to 1300 nm, more preferably in the range of wavelength 700 to 1000 nm) can be preferably used.

Examples of the infrared absorber include a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterrylene compound, a merocyanine compound, a croconium compound, an oxonol compound, and dimonium. At least one selected from a compound, a dithiol compound, a triarylmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and a pyrrolopyrrole compound, a cyanine compound, and scu At least one selected from an arylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a dimonium compound is more preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, and a squarylium compound is further preferred, particularly preferred are pyrrolopyrrole compounds. As a specific example of a pyrrolopyrrole compound, Paragraph Nos. 0016 to 0058 of Unexamined-Japanese-Patent No. 2009-263614, Paragraph Nos. 0037-0052 of Unexamined-Japanese-Patent No. 2011-068731 Paragraph of Paragraph of International Publication No. WO2015/166873 The compounds of numbers 0010 - 0033 etc. are mentioned, These content is integrated in this specification. As a specific example of a squarylium compound, Paragraph No. 0040 of Paragraph No. 0044 of Unexamined-Japanese-Patent No. 2011-208101 - 0049, Paragraph No. 0060 of Unexamined-Japanese-Patent No. 6065169 - 0061, Paragraph No. 0040 of International Publication No. WO2016/181987 The compound described in , the compound of Unexamined-Japanese-Patent No. 2015-176046, the compound of Paragraph No. 0072 of international publication WO2016/190162, etc. are mentioned, These content is integrated in this specification. As a specific example of a cyanine compound, the compound of Paragraph Nos. 0044-0045 of Unexamined-Japanese-Patent No. 2009-108267, the compound of Paragraph No. 0026-0030 of Unexamined-Japanese-Patent No. 2002-194040, Unexamined-Japanese-Patent No. 2015-172004 The compound described in Japanese Patent Application Laid-Open No. 2015-172102, the compound described in Japanese Patent Application Laid-Open No. 2008-088426, the compound described in Paragraph No. 0090 of International Publication No. WO2016/190162, etc. are mentioned, These contents are this incorporated in the specification. As a specific example of a dimonium compound, the compound of Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, This content is integrated in this specification. As a specific example of a phthalocyanine compound, For example, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153, The oxytitanium phthalocyanine of Unexamined-Japanese-Patent No. 2006-343631, Unexamined-Japanese-Patent No. 2013- Paragraph Nos. 0013-0029 of 195480 are mentioned, These content is integrated in this specification. As a specific example of a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, This content is integrated 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 integrated in this specification.

When the composition for infrared transmission layer formation contains an infrared absorber, it is preferable that content of an infrared absorber is 1-30 mass % with respect to the total solid of the composition for infrared transmission layer formation. 20 mass % or less is more preferable, and, as for an upper limit, 10 mass % or less is still more preferable. 3 mass % or more is more preferable, and, as for a minimum, 5 mass % or more is still more preferable. 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 of the composition for infrared transmission layer formation. 20 mass % or more is more preferable, and, as for a minimum, 25 mass % or more is still more preferable. Moreover, it is preferable that content of the infrared absorber in the total amount of an infrared absorber and a light-shielding material is 5-40 mass %. 30 mass % or less is more preferable, and, as for an upper limit, 25 mass % or less is still more preferable. As for a minimum, 10 mass % or more is more preferable, and 15 mass % or more is still more preferable.

The composition for forming an infrared transmission layer is an additive such as a resin, a curable compound, a photoinitiator, a pigment derivative, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, an antioxidant, and a latent antioxidant may further include About these details, the above-mentioned material is mentioned.

<Containing container of composition>

There is no limitation in particular as a container for each composition mentioned above, A well-known container can be used. In addition, for the purpose of suppressing the mixing of impurities into raw materials or the composition as a storage container, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin or a bottle in which 6 types of resins have a 7-layer structure. do. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Method for preparing the composition>

Each of the above-mentioned compositions 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, two or more solutions or dispersions in which each component is appropriately blended are prepared in advance, and at the time of use (at the time of application) ), these may be mixed to prepare a composition.

Moreover, when a composition contains particle|grains, such as a pigment, it is preferable to include the process of disperse|distributing particle|grains. In the process of dispersing particles, examples of the mechanical force used to disperse the particles include compression, compression, impact, shear, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. Moreover, in the grinding|pulverization of the particle|grains in a sand mill (bead mill), it is preferable to process under the conditions which improved the grinding|pulverization efficiency by using small diameter beads, increasing the filling rate of beads, etc. After the pulverization treatment, it is preferable to remove the coarse particles by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing particles are "Dispersion Technology Exhibition, Published by Johokiko Co., Ltd., July 15, 2005" and "Suspension (solid/liquid dispersion system) centered on dispersion technology and practical synthesis of industrial applications" The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Moreover, in the process of dispersing the particle|grains, you may perform the refinement|miniaturization process of particle|grains in a salt milling process. As for the raw material, apparatus, processing conditions, etc. used for a salt milling process, description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be referred, for example.

Preparation of the composition WHEREIN: It is preferable to filter a composition with a filter for the purpose of removal of a foreign material, reduction of a defect, etc. As a filter, if it is a filter conventionally used for a filtration use, etc., it will not specifically limit, It can be used. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) A filter using a material such as (including a high-density and ultra-high molecular weight polyolefin resin) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

As for the pore diameter of a filter, about 0.01-7.0 micrometers is suitable, Preferably it is about 0.01-3.0 micrometers, More preferably, it is about 0.05-0.5 micrometers. If the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Moreover, it is also preferable to use a fibrous filter medium. As a fibrous filter medium, a polypropylene fiber, a nylon fiber, a glass fiber, etc. are mentioned, for example. Specifically, the filter cartridge of the SBP type series (SBP008 etc.), the TPR type series (TPR002, TPR005 etc.) made by Rocky Techno, and the SHPX type series (SHPX003 etc.) is mentioned.

When using a filter, you may combine other filters (for example, a 1st filter, a 2nd filter, etc.). In that case, the filtration in each filter may be performed only once or may be performed twice or more. Moreover, you may combine filters of different pore diameters within the above-mentioned range. The hole diameter here can refer to the nominal value of a filter manufacturer. As a commercially available filter, for example, Nippon Pole Co., Ltd. (DFA4201NIEY etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (Kunihon Microliss Co., Ltd.), or Kits Microfilter Co., Ltd. can select from various filters provided. The second filter may be formed of the same material as the first filter or the like. Moreover, after performing filtration with a 1st filter only with respect to a dispersion liquid and mixing another component, you may filter with a 2nd filter.

<Method for manufacturing structure>

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

The structure of the present invention comprises a step of forming a barrier rib on a support; It can be manufactured through the process of performing pattern formation and forming a pixel. As a composition for pixel formation, the composition for colored pixel formation, the composition for infrared transmission layer formation, etc. which were mentioned above are mentioned. Moreover, you may form a partition after making a pixel.

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

First, a barrier rib material layer is formed by applying a composition for forming barrier ribs on a support. A well-known method can be used as an application method of the composition for partition formation. For example, the drip method (drop cast); slit coat method; spray method; roll coat method; spin coating (spin coating); flexible application method; slit and spin method; free wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); Various printing methods, such as discharge system printing, such as inkjet (For example, an on-demand method, a piezo method, a thermal method), a nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and the metal mask printing method; a transfer method using a mold or the like; The nanoimprint method etc. are mentioned. The method of application in inkjet is not particularly limited, and for example, the method indicated by "Diffuse and usable inkjet -infinite possibilities viewed as a patent -, published in February 2005, Sumibe Techno Research" (particularly page 115) ~133 pages), Japanese Unexamined Patent Publication No. 2003-262716, Japanese Unexamined Patent Publication No. 2003-185831, Japanese Unexamined Patent Publication No. 2003-261827, Japanese Unexamined Patent Publication No. 2012-126830, Japanese Unexamined Patent Publication No. 2006-169325 The method described in etc. is mentioned.

After forming the barrier rib material layer, drying (pre-baking) may be performed. When prebaking, 150 degrees C or less is preferable, as for prebaking temperature, 120 degrees C or less is more preferable, and 110 degrees C or less is still more preferable. The lower limit can be, for example, 50°C or higher, or 80°C or higher. 10 second - 3000 second are preferable, as for prebaking time, 40-2500 second is more preferable, 80-220 second is still more preferable. Pre-baking can be performed using a hot plate, an oven, etc.

Next, the barrier rib material layer is patterned to form barrier ribs. As a pattern formation method, the pattern formation method using the photolithography method, and the pattern formation method using the dry etching method are mentioned. It is preferable that it is the pattern formation method using the dry etching method from the reason that it is easy to obtain the partition with favorable rectangular property.

As a pattern forming method using the dry etching method, a resist pattern is formed on the barrier rib material layer using a mask having a pattern along the shape of the barrier rib, and then, using this resist pattern as a mask, dry etching is performed on the barrier rib material layer. The barrier rib can be formed by etching by a method and then peeling and removing the resist pattern from the barrier rib material layer. About the dry etching method, description of Unexamined-Japanese-Patent No. 2016-014856 can be considered into consideration, and this content is integrated in this specification.

The pattern formation method in the photolithography method preferably includes a step of exposing the barrier rib material layer in a pattern (exposure step) and a step of forming a pattern by developing and removing the barrier rib material layer of an unexposed portion (development step). do. You may provide the process (post-baking process) of baking the developed pattern as needed. Hereinafter, each process is demonstrated.

In the exposure step, the barrier rib material layer is exposed in a pattern shape. For example, the barrier rib material layer can be pattern-exposed by exposing the barrier rib material layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the exposed portion of the barrier rib material layer can be cured. As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-rays and i-rays are preferable, and i-rays are more preferable. The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² , and most preferably 0.08 to 0.5 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to carrying out under the atmosphere, for example, in a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic) ) or in a high oxygen atmosphere (eg, 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume. Moreover, exposure illuminance can be set suitably, and can select from the range of 1000W/m< ² >-100000W/m< ² > (for example, 5000W/m< ² >, 15000W/m< ² >, 35000W/m< ² > normally). The oxygen concentration and exposure illuminance may suitably combine conditions, for example, an illuminance of 10000 W/m ^{2 with an oxygen concentration of 10 vol%, an illuminance of 20,000 W/m 2 with} an oxygen concentration of 35 vol%, or the like.

Next, the barrier rib material layer of the unexposed part in the barrier rib material layer after exposure is developed and removed to form a pattern. Development and removal of the barrier rib material layer of an unexposed part can be performed using a developing solution. Thereby, the partition material layer of the unexposed part in an exposure process elutes to a developing solution, and only the photocured part remains on a support body. As a developing solution, an alkali developing solution is preferable. As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. As for image development time, 20 to 180 second is preferable. Moreover, in order to improve residue removability, you may shake off a developing solution every 60 second, and you may repeat the process of supplying a developing solution anew several times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, 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, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, metasilicic acid Inorganic alkaline compounds, such as sodium, are mentioned. As for the alkali agent, a compound with a large molecular weight is preferable from the viewpoint of environment and safety. As the developer, an alkaline aqueous solution obtained by diluting these alkali agents with pure water is preferably used. 0.001-10 mass % is preferable and, as for the density|concentration of the alkali agent of alkaline aqueous solution, 0.01-1 mass % is more preferable. Moreover, you may add and use surfactant to a developing solution. As an example of surfactant, the surfactant mentioned above is mentioned, A nonionic surfactant is preferable. The developer may be once prepared as a concentrate from the viewpoints of transport and storage convenience, and then diluted to a concentration required at the time of use. Although the dilution ratio is not specifically limited, For example, it can set in the range of 1.5-100 times. Moreover, when using the developing solution which consists of such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

After image development, after drying, you can also heat-process (post-baking). A post-baking is heat processing after image development for making hardening of a film|membrane complete. When performing post-baking, 50-240 degreeC of post-baking temperature is preferable, for example. From a viewpoint of film hardening, 200-230 degreeC is more preferable. In addition, when an organic electroluminescence (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, and more preferably 120°C or less. Preferably, 100°C or less is more preferable, and 90°C or less is particularly preferable. The post-baking can be performed continuously or batchwise using heating means, such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater, so as to satisfy the above conditions for the developed film.

A pixel can be formed using a conventionally well-known method. For example, after applying the composition for pixel formation to the area|region partitioned by the partition on a support body to form the composition layer for pixel formation, it can form by pattern-forming with respect to this composition layer for pixel formation.

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

After forming the composition layer for pixel formation, you may dry (pre-baking). When prebaking, 150 degrees C or less is preferable, as for prebaking temperature, 120 degrees C or less is more preferable, and 110 degrees C or less is still more preferable. The lower limit can be, for example, 50°C or higher, or 80°C or higher. 10 second - 3000 second are preferable, as for prebaking time, 40-2500 second is more preferable, 80-220 second is still more preferable. Pre-baking can be performed using a hot plate, an oven, etc.

Next, pattern formation is performed with respect to the composition layer for pixel formation to form a pixel. As a pattern formation method, the pattern formation method using the pattern formation method using the photolithography method, and the pattern formation method using the dry etching method are mentioned.

The pattern forming method in the photolithography method preferably includes a step of exposing the composition layer for forming a pixel on a support in a pattern shape, and a step of forming a pattern by developing and removing the composition layer for forming a pixel in an unexposed portion. . You may provide the process (post-baking process) of baking the developed pattern as needed. The details of these steps are as described above.

Pattern formation in the dry etching method is to form a cured product layer by curing the composition layer for forming pixels on a support, then a patterned resist layer is formed on the cured material layer, and then the patterned resist layer is masked It can be carried out by a method such as dry etching the cured product layer using an etching gas. About pattern formation by the dry etching method, Paragraph No. 0010 of Unexamined-Japanese-Patent No. 2013-064993 - description of 0067 can be considered into consideration, and this content is integrated in this specification.

<Solid-State Imaging Device>

The solid-state imaging device of the present invention has the above-described structure of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the structure of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

A plurality of photodiodes constituting a light-receiving area of a solid-state image sensor (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) The structure of the present invention has a light-shielding film on the photodiode and the transfer electrode, in which only the light-receiving portion of the photodiode is opened, and a device protective film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion on the light-shielding film, and on the device protective film A configuration having a In addition, a configuration having a light collecting means (for example, a microlens, etc., the same hereinafter) on the device protective film and below the structure of the present invention (the side close to the substrate), a structure having a light collecting means on the structure of the present invention, etc. may be used. . 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 using, for example, the composition for forming a barrier rib 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 and an electronic device having an imaging function (such as a cellular phone), 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 an image display apparatus and the details of each image display apparatus, for example, "Electronic display device (author Akio Sasaki, Kokocho Chosakai published in 1990)", "display device (author Sumiaki Ibuki, Tosho Sangyo)" Co., Ltd. published in the first year of the Heisei year)" and the like. Moreover, about a liquid crystal display device, it describes, for example in "next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Chosakai, 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 above-mentioned "next generation liquid crystal display technology".

Example

Hereinafter, the present invention will be described in more detail by way of Examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. 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 indicated, "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 caged siloxane compound and resin were measured by gel permeation chromatography (GPC) under the following conditions.

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

Developing solvent: tetrahydrofuran

Column temperature: 40°C

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

Device name: Tosoh agent HLC-8220GPC

Detector: RI (Refractive Index) Detector

Calibration curve base resin: polystyrene resin

<Preparation of the composition for forming a barrier rib>

The raw materials described in the following table were mixed to prepare a composition for forming a partition wall. The numerical value described in the column of the compounding quantity is a mass part.

[Table 1]

(cage-type siloxane compound 1)

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

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

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

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

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

A-6: A polymer having a 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: a compound of the 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: a compound of the following structure (Mw=14,000, % indicating 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 the composition for color pixel formation>

The raw materials shown below are mixed and stirred, and then filtered with a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 µm to obtain a composition for forming a red pixel, a composition for forming a green pixel, and a composition for forming a blue pixel. each prepared.

(Composition for forming red pixel)

Red pigment dispersion… 51.7 parts by mass

Resin 1… 0.6 parts by mass

Curable compound 1... 0.6 parts by mass

Photoinitiator 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

Resin 1… 0.3 parts by mass

Curable compound 2... 1.2 parts by mass

Photoinitiator 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

Resin 1… 2.1 parts by mass

Curable compound 1... 1.5 parts by mass

Curable compound 3... 0.7 parts by mass

Photoinitiator 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 colored pixel formation are as follows.

Red pigment dispersion

A mixture consisting 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 dispersant (Disperbyk-161, manufactured by BYK Chemie) and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads). 0.3 mm diameter) using a high pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with a pressure reducing mechanism after mixing and dispersing for 3 hours, 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 consisting 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 mixed with a bead mill (zirconia beads). 0.3mm diameter) using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with an additional pressure-reducing mechanism after mixing and dispersing for 3 hours, 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 consisting of 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill ( 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 BEI Co., Ltd.) equipped with an additional pressure reducing mechanism, a 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 the molar ratio. Mw = 10,000, acid value = 70 mgKOH/g)

[Formula 10]

Curable compound 1: a compound of the following structure

[Formula 11]

Curable compound 2: A mixture of a compound of the following structure (a mixture in which the molar ratio of the compound on the left to the compound on the right is 7:3)

[Formula 12]

-Curable compound 3: Aronix M-305 (triacrylate is 55-63 mass %, Toagosei Co., Ltd. product)

·Photoinitiator 1: IRGACURE-OXE01 (manufactured by BASF)

·Photoinitiator 2: a compound of the following structure

[Formula 13]

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

[Formula 14]

・Ultraviolet absorber 1: UV-503 (manufactured by Daito Chemical Co., Ltd.)

<Preparation of structure>

A barrier rib material layer was formed on a silicon wafer using the composition for forming barrier ribs described in the table below, and the barrier rib material layer was dried by a dry etching method under the conditions described in Paragraph Nos. 0128 to 0133 of Japanese Patent Application Laid-Open No. 2016-014856. By patterning, barrier ribs (width 50 nm, height 1 µm) were formed in a lattice shape at intervals of 1 µm. The dimension of the opening of the barrier rib on the silicon wafer (region partitioned by the barrier rib on the silicon wafer) was 1 µm in length x 1 µm in width. Next, on the silicon wafer in which the partition was formed, the composition for green pixel formation was apply|coated by the spin coating method so that the film thickness after film-forming might become 1 micrometer, Then, it heated at 100 degreeC for 2 minute(s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at an exposure amount of 150 mJ/cm ² through a mask having a 0.9 µm Bayer pattern. Then, puddle image development was performed at 23 degreeC for 60 second using the tetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Then, after rinsing by a spin shower, it heated at 220 degreeC for 5 minutes using a hotplate, and formed the green pixel in the area|region partitioned by the partition.

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

<Evaluation of filterability>

About the composition for partition formation immediately after manufacture, 1000 g was filtered using the ROKI-made capsule filter (LPS-CLP-0025-N1), and the following references|standards evaluated filterability.

A: The whole amount of the composition for partition formation was able to be filtered

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

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

D: Clogging occurred in less than 100 g

<Smoothness of etching surface>

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

A: No voids were observed.

B: No voids with a size of 20 nm or more were observed, but voids with a size of less than 20 nm were observed.

C: Voids having a size of 20 nm or more were observed.

<Adhesiveness>

After forming the colored pixel of each color in the area|region partitioned by the partition, cross-sectional observation with SEM was carried out, and the following reference|standard evaluated adhesiveness.

A: All the partitions within the observation range WHEREIN: Peeling of a colored pixel was not observed.

B: In the number of partitions of less than 20% among all the partitions in the observation range, peeling of the colored pixel was generate|occur|produced.

C: In the partition wall of 20% or more of all the partition walls within the observation range, peeling of the colored pixel was generate|occur|produced.

<Evaluation of refractive index>

Each composition for forming barrier ribs was apply|coated on a silicon wafer, the film|membrane with a film thickness of 0.3 micrometer was formed, and the refractive index in wavelength 550nm was measured using the ellipsometer UVISEL/460-FUV-AGAS (made by Horiba Seisakusho).

[Table 2]

As shown in the above table, in the Example, a structure having a low refractive index and excellent smoothness of the barrier ribs could be manufactured. When the structure of the example was introduced into a solid-state imaging device, the light-converging rate of the pixel was high, the sensitivity was good, and a clear image was obtained.

1: support
2: bulkhead
4: Pixel

Claims (11)

support and
a partition wall provided on the support;
and a pixel provided in an area partitioned by the partition wall;
The barrier rib is a barrier rib formed using a composition containing a cage-type siloxane compound in an amount of 40% by mass or more in total solid content,
The cage-type siloxane compound includes a polymer having a weight average molecular weight of 100,000 to 240,000,
The refractive index of the light having a wavelength of 550 nm of the barrier rib is 1.15 to 1.37, the structure. The method according to claim 1,
The cage-type siloxane compound includes a cage-type siloxane compound in which O/Si, which is a ratio of the number of oxygen atoms to the number of silicon atoms, is 1.3 to 1.7. The method according to claim 1 or 2,
a structure in which the cage-type siloxane compound includes a partial structure represented by the following formula (S1);
(*-SiO _1.5 ) _n … (S1)
In the formula, * represents a linking hand, and n represents an integer of 6 to 16. The method according to claim 1 or 2,
a structure in which 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)
In formula, R ^S1 represents an alkyl group or a polymerizable group, n represents the integer of 6-16, and 2 or more R ^S1 among n pieces of R ^S1 is a polymeric group. The method according to claim 1 or 2,
The cage-type siloxane compound is a structure having a partial structure represented by the following formula (S1-1);
Formula (S1-1)
[Formula 1]

A broken line in the above formula represents a bond. delete The method according to claim 1 or 2,
The pixel includes at least one type of pixel selected from a colored pixel, a transparent pixel, and a pixel of an infrared transmitting layer. A composition for forming barrier ribs used for forming the barrier rib of a structure having a support, a barrier rib provided on the support, and a pixel provided in a region partitioned by the barrier rib,
Containing a cage-type siloxane compound and a solvent,
The content of the cage-type siloxane compound in the total solid content of the composition for forming barrier ribs is 40 mass % or more,
The cage-type siloxane compound includes a polymer having a weight average molecular weight of 100,000 to 240,000,
a composition for forming barrier ribs in which the cage-type siloxane compound includes 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)
In formula, R ^S1 represents an alkyl group or a polymerizable group, n represents the integer of 6-16, and 2 or more R ^S1 among n pieces of R ^S1 is a polymeric group. A solid-state imaging device having the structure according to claim 1 or 2 . An image display device having the structure according to claim 1 or 2. delete

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