KR102129747B1 - Composition, cured film, infrared transmission filter, solid-state imaging element and infrared sensor - Google Patents

Abstract

Provided is a composition capable of forming a cured film having excellent pattern formability and solvent resistance, and a cured film using the above-described composition, an infrared transmission filter, a solid-state imaging device, and an infrared sensor. As a composition comprising a near-infrared transmission black colorant, a curable compound, and a solvent, the near-infrared transmission black colorant contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound , A/B which is the ratio of the minimum value A of the absorbance in the range of wavelength 400 to 700 nm of the composition and the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm is 4.5 or more.

Description

Composition, cured film, infrared transmission filter, solid-state imaging element and infrared sensor

The present invention relates to a composition that can be used for formation of an infrared transmission filter or the like. Moreover, it is related with the cured film using an composition, an infrared transmission filter, a solid-state imaging element, and an infrared sensor.

The solid-state imaging element is utilized as an optical sensor for various purposes. For example, infrared rays have a longer wavelength than visible light, making it difficult to scatter, and can be used for distance measurement, 3D measurement, and the like. In addition, since infrared rays are invisible to humans, animals, etc., it is used to shoot a nocturnal wild animal because the subject is not aware even when the subject is illuminated with an infrared light source at night, or to shoot without stimulating the opponent for crime prevention. It can also be used. As described above, the optical sensor (infrared sensor) that detects infrared rays can be deployed for various purposes, and development of a film that can be used for the infrared sensor is desired.

Patent Document 1 describes a color filter composition containing a near-infrared transmission black color material. Moreover, in paragraph number 0019 of patent document 1, there is a description that the near-infrared transmission black color material is preferably a pigment.

Patent Document 1: Japanese Patent Application Publication No. 2014-130173

In recent years, further refinement of the pattern size is desired. The composition using a dye-type near infrared-transmitting black colorant can improve resolution compared to a composition using a pigment-type near-infrared-transmitting black colorant. In addition, when preparing the composition, the dye-type near-infrared transmission black colorant has an advantage that it is possible to omit hassle such as dispersion. However, the cured film using a composition containing a dye-type near-infrared-transmitting black colorant tends to have poor solvent resistance compared to a cured film using a composition containing a pigment-type near-infrared-transmitting black colorant.

Accordingly, an object of the present invention is to provide a composition capable of forming a cured film excellent in pattern formation and solvent resistance. Moreover, it is providing the cured film using the above-mentioned composition, an infrared transmission filter, a solid-state imaging element, and an infrared sensor.

As a result of careful examination, the present inventors used a dye compound having a crosslinkable group-containing dye compound and/or a dye multimer having a structure derived from a dye compound having a crosslinkable group as a near-infrared transmission black color material, thereby forming pattern and solvent resistance. It has been found that an excellent cured film can be formed, and the present invention has been completed. The present invention provides the following.

<1> A composition comprising a near-infrared transmission black color material, a curable compound, and a solvent,

The near-infrared transmission black color material contains at least one kind selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound,

The composition in which A/B which is the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 700 nm of the composition and the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm is 4.5 or more.

<2> The composition according to <1>, wherein the crosslinkable group of the dye compound is at least one selected from a group having an ethylenically unsaturated bond, an epoxy group, and an alkoxysilyl group.

<3> The composition according to <1> or <2>, wherein the dye compound having a crosslinkable group is at least one selected from xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds.

<4> The composition according to any one of <1> to <3>, wherein the dye multimer is formed by bonding two or more of a structure derived from a dye compound to a divalent or higher linking group.

<5> The composition according to any one of <1> to <3>, wherein the dye multimer has a repeating unit having a structure derived from a dye compound.

<6> The composition according to any one of <1> to <5>, further comprising a chromatic colorant.

<7> A cured film obtained by curing the composition according to any one of <1> to <6>.

<8> An infrared transmission filter having the cured film according to <7>.

<9> A solid-state imaging device having the cured film according to <7>.

<10> An infrared sensor having the cured film according to <7>.

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the cured film excellent in pattern formation property and solvent resistance can be provided. Moreover, a cured film using the above-described composition, an infrared transmission filter, a solid-state imaging element, and an infrared sensor can be provided.

1 is a schematic cross-sectional view showing a configuration of an embodiment of an infrared sensor of the present invention.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the entire composition.

In the description of the group (atomic group) in the present specification, the notation that does not describe substituted or unsubstituted includes a group having a substituent together with a group not 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, unless otherwise specified. Further, examples of the light used for exposure include a bright spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams or radiation.

In the present specification, "(meth)acrylate" represents both or both of acrylates and methacrylates, and "(meth)acrylic" represents both of acrylics and methacryls, or either, "(Meth)acryloyl" represents both or both of acryloyl and methacryloyl.

In the present specification, the term "process" is included in this term when the desired action of the process is achieved even if it is not an independent process, but can not be clearly distinguished from other processes.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation) as a column. , 6.0 mmID (inner diameter) x 15.0 cm), and can be obtained by using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

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

<Composition>

The composition of the present invention is a composition comprising a near-infrared transmission black color material, a curable compound, and a solvent,

The near-infrared transmission black color material contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from a dye compound having a crosslinkable group,

It is characterized in that A/B, which is the ratio of the minimum value A of the absorbance in the range of wavelength 400 to 700 nm of the composition and the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm, is 4.5 or more.

The composition of the present invention can form a cured film excellent in solvent resistance by using a dye compound having a structure derived from a dye compound having a crosslinkable group and/or a dye compound having a crosslinkable group as a near-infrared transmission black color material. have. In addition, this composition shields visible light because A/B, which is the ratio of the minimum value A of the absorbance in the range of wavelength 400 to 700 nm and the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm, is 4.5 or more, A cured film that transmits infrared rays in a specific wavelength region can be formed. For this reason, by using the composition of the present invention, it is possible to form an infrared transmission filter or the like having excellent solvent resistance.

Moreover, in the manufacturing process of devices, such as an infrared sensor, a color filter, a protective film, etc. may be laminated|stacked on an infrared transmission filter. When the solvent resistance of the infrared transmission filter is inferior, when these films are laminated on the infrared transmission filter, the near-infrared transmission black colorant or the like elutes from the infrared transmission filter, and the spectral characteristics of the infrared transmission filter may fluctuate. On the other hand, according to the composition of the present invention, since a cured film excellent in solvent resistance can be formed, even when a color filter or a protective film is formed on the cured film formed using the composition of the present invention, near infrared rays from the cured film The elution of the transparent black color material can be suppressed.

Moreover, since the composition of the present invention uses a dye compound having a crosslinkable group and/or a dye multimer having a structure derived from a dye compound as a near-infrared transmission black color material, the pattern formation property is good and a finer pattern is used. Can form.

Further, since the near-infrared transmittance black color material has low permeability such as i-line (365 nm), the pattern size may become high resolution and the rectangularity of the pattern may decrease, or pattern peeling may occur. By using a dye compound having a crosslinkable group (preferably a group having an ethylenically unsaturated bond), even a small exposure amount can be cured to the bottom of the film, and even a high resolution pattern can form a pattern excellent in rectangularity and adhesion. Can.

In the composition of the present invention, the conditions of the absorbance may be achieved by any means. For example, by adjusting the type and content of the near-infrared-transmitting black color material, or further containing a chromatic colorant and/or an infrared absorber, and adjusting these types and content, the conditions of the absorbance can be suitably achieved. have. In addition, the infrared absorber has a role of limiting the light (infrared rays) to be transmitted to the longer wavelength side.

For the spectral properties of the composition of the present invention, the above-mentioned value of A/B is preferably 7 or more, more preferably 7.5 or more, more preferably 10 or more, even more preferably 15 or more, and 30 or more This is particularly preferred.

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

Aλ=-log(Tλ/100)...(1)

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

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

Absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions of the absorbance are not particularly limited, but the maximum value B of the absorbance in the range of the wavelength 1100 to 1300 nm is measured under the condition that the minimum value A of the absorbance in the range of the wavelength 400 to 700 nm is adjusted to 0.1 to 3.0. It is desirable to do. By measuring the absorbance under these conditions, the measurement error can be made smaller. There is no particular limitation as a method for adjusting the minimum value A of the absorbance in the range of 400 to 700 nm to be 0.1 to 3.0. For example, when measuring the absorbance in the state of a composition, a method of adjusting the optical path length of the sample cell can be mentioned. Moreover, when measuring the absorbance in the state of being a film, the method of adjusting the film thickness, etc. are mentioned.

The specific example of the measuring method, such as the spectral characteristic and film thickness of the film formed by the composition of this invention is shown below.

The composition of the present invention is coated on a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and is dried at 100°C for 120 seconds using a hot plate. The thickness of the film is measured by using a stylus-type surface shape measuring device (DEKTAK150 manufactured by ULVAC) to measure the substrate after drying with the film. The dried substrate having this film was measured for transmittance in the range of wavelength 300 to 1300 nm using an ultraviolet visible near infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

Since the composition of the present invention transmits infrared rays, it can also be referred to as an infrared-transmissive composition. Below, each component which can constitute the composition of this invention is demonstrated.

<<Near infrared transmission black color material>>

The composition of the present invention contains a near-infrared transmission black color material. The near-infrared transmission black color material in this invention contains at least 1 sort(s) selected from the dye compound which has a crosslinkable group, and the dye multimer which has the structure derived from the dye compound which has a crosslinkable group.

The near-infrared transmission black color material is preferably a material that absorbs light in a wavelength range from purple to red. It is preferable that the near-infrared transmission black color material is a color material that blocks light in a range of 400 to 700 nm in wavelength. In the near-infrared transmission black color material, it is preferable that A1/B1, which is the ratio of the minimum value A1 of the absorbance in the range of wavelength 400 to 700nm and the minimum value B1 of the absorbance in the range of wavelength 900 to 1300nm, is 4.5 or more. It is preferable that the near-infrared transmission black color material is a color material that transmits at least a portion of light in a wavelength range of 800 to 1300 nm.

(Dye compound having a crosslinkable group)

The dye compound having a crosslinkable group (also referred to as a crosslinkable dye) is preferably at least one compound selected from xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds, and more preferably xanthene compounds.

The crosslinkable dye is preferably a compound that dissolves 1 g or more with respect to 100 g of propylene glycol monomethyl ether acetate at 23°C, and more preferably a compound that dissolves 3 g or more.

The type of the crosslinkable group of the crosslinkable dye is not particularly limited. And groups capable of causing a crosslinking reaction due to the action of heat, light, and radicals. As a specific example of a crosslinkable group, the group which has an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, a methylol group, etc. are mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth)allyl group, and (meth)acryloyl group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. 1-5 are preferable, as for carbon number of the alkoxy group in an alkoxysilyl group, 1-3 are more preferable, and 1 or 2 is more preferable. As a crosslinkable group, an epoxy group and an alkoxysilyl group are preferable, and an epoxy group is more preferable. According to this aspect, there is no difference in the crosslinking rate in the upper part (surface side) and the lower part (support side) of the film, so that the entire film can be crosslinked substantially evenly. Moreover, pattern formation property is favorable and the obtained pattern shape is favorable. Furthermore, pattern peeling can be effectively suppressed.

The crosslinkable dye preferably has 1 to 4 crosslinkable groups in 1 molecule, more preferably 1 to 3, and more preferably 1 to 2. According to this aspect, the effect that resistance to a solvent improves can be expected.

It is preferable that a crosslinkable dye is a monomer type compound. It is preferable that a crosslinkable dye is a compound which has one pigment|skeleton skeleton in 1 molecule. Further, the molecular weight of the crosslinkable dye is preferably 300 to 3000, more preferably 500 to 1500. In addition, the molecular weight value of a crosslinkable dye is a value calculated from a structural formula.

The following compounds are mentioned as a specific example of a crosslinkable dye. Moreover, a commercial item can also be used for a crosslinkable dye. For example, K01 (made by Wako Pure Chemical Industries, Ltd., xanthene compound), R56 (made by Wako Pure Chemical Industries, Ltd., xanthene compound), etc. are mentioned. In the following structural formulae, Me is a methyl group.

[Formula 1]

(Pigment multimer)

The dye multimer used as a near-infrared transmission black color material is a dye multimer (hereinafter also referred to as dye multimer A) having a structure derived from a dye compound having a crosslinkable group.

The dye multimer A is preferably dissolved in 1 g or more with respect to 100 g of propylene glycol monomethyl ether acetate at 23°C, and more preferably dissolved in 3 g or more.

It is preferable that the dye multimer A has two or more structures derived from the above-mentioned crosslinkable dye in one molecule, and more preferably three or more. The upper limit is not particularly limited, but may be 100 or less.

It is preferable that the dye multimer A is a compound having a structure in which a structure derived from a dye compound (crosslinkable dye) is bonded to two or more linking groups. Examples of the divalent or higher linking group include an alkylene group, an arylene group, -O-, -S-, -SO-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR-(R is a hydrogen atom or , Represents an alkyl group having 1 to 20 carbon atoms), or a combination of these.

Moreover, it is preferable that dye multimer A is a compound (polymer) which has a repeating unit derived from a dye compound (crosslinkable dye). It is preferable that the dye multimer A is a polymer containing a repeating unit represented by formula (A). As for the dye multimer A, it is preferable that the ratio of the repeating unit represented by Formula (A) is 10-100 mass% of all the repeating units which comprise dye multimer A. The lower limit is more preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less.

[Formula 2]

In Formula (A), X ¹ represents a main chain of a repeating unit, and L ¹ represents a single bond or a divalent linking group. DyeI represents the pigment structure.

In Formula (A), X ¹ represents the main chain of a repeating unit. The main chain of a repeating unit differs depending on the kind of crosslinkable group of the crosslinkable dye. For example, when the crosslinkable dye is a compound having an ethylenically unsaturated bond as a crosslinkable group, examples of X ¹ include structures represented by the following (XX-1) to (XX-24), and (XX-1) ) Or (XX-24) is preferred.

[Formula 3]

In the formula, * represents a linkage with L ¹ . Me represents a methyl group. Moreover, R in (XX-18) and (XX-19) represents a hydrogen atom, a C1-C5 alkyl group, or a phenyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, and -COO- , -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by connecting two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The carbon number of the alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and more preferably 3 or more. The alkylene group may be either straight chain, branched or cyclic. As for carbon number of an arylene group, 6-20 are more preferable, and 6-12 are more preferable. The heterocyclic linking group is preferably a 5- or 6-membered ring. As for the hetero atom which a heterocyclic linking group has, an oxygen atom, a nitrogen atom, and a sulfur atom are preferable. As for the number of hetero atoms which a heterocyclic linking group has, 1-3 are preferable.

The dye structure represented by DyeI is a dye structure derived from a crosslinkable dye. Examples include a xanthene dye structure, a perylene dye structure, an azo dye structure, and a bisbenzofuranone dye structure.

It is preferable that the repeating unit represented by Formula (A) is a repeating unit represented by the following Formulas (A-1) to (A-3).

[Formula 4]

In the formula (A-1), R ^1A represents a hydrogen atom or an alkyl group, L ^1A represents a single bond or a divalent linking group, and DyeI represents a pigment structure. In Formula (A-2), L ^2A represents a single bond or a divalent linking group, and DyeI represents a pigment structure. In the formula (A-3), R ^3A represents an alkyl group or an aryl group, L ^3A represents a single bond or a divalent linking group, a represents 0 or 1, and DyeI represents a pigment structure.

The divalent linking group represented by L ^1A to L3 ^A in formulas (A-1) to (A-3) is synonymous with the divalent linking group represented by L ¹ in formula (A), and the preferred range is also the same. . The dye structure represented by DyeI in formulas (A-1) to (A-3) is synonymous with the dye structure represented by DyeI in formula (A), and the preferred range is also the same.

1-5 are preferable, as for carbon number of the alkyl group represented by R<^1A> in Formula (A-1), 1-3 are more preferable, and 1 is more preferable. R ^1A is preferably a hydrogen atom or a methyl group.

As for carbon number of the alkyl group in Formula (A-3), 1-10 are preferable, 1-8 are more preferable, and 1-6 are more preferable. Moreover, any of linear, branched, and cyclic may be sufficient as an alkyl group, and a straight chain is preferable. 6-20 are preferable, as for carbon number of the aryl group in Formula (A-3), 6-14 are more preferable, and 6-10 are more preferable.

The dye multimer A may contain other repeating units in addition to the repeating units represented by formula (A). Other repeating units may contain functional groups such as crosslinkable groups and acid groups. Moreover, another repeating unit does not need to contain a functional group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, and a methylol group. As an acidic radical, a carboxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned.

When the dye multimer A contains a repeating unit having a crosslinkable group, the proportion of the repeating units having a crosslinkable group is preferably greater than 0% by mass and 50% by mass or less of all the repeating units constituting the dye multimer A. The lower limit is more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.

When the dye multimer A contains a repeating unit having an acid group, the proportion of the repeating units having an acid group is preferably greater than 0% by mass and 50% by mass or less of all the repeating units constituting the dye multimer A. The lower limit is more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.

In the composition of the present invention, the content of the near-infrared transmission black color material is preferably 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less.

When the composition of the present invention contains a crosslinkable dye as a near-infrared transmission black color material, the content of the crosslinkable dye is preferably 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less. Moreover, the content of the crosslinkable dye in the total mass of the near-infrared transmission black color material is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and even more preferably 50 to 100% by mass. As for a crosslinkable dye, only 1 type may be used and 2 or more types may be used together. When using 2 or more types of crosslinkable dyes together, it is preferable that a total amount is the said range.

When the composition of the present invention contains the dye multimer A as a near-infrared transmission black color material, it is preferable that the content of the dye multimer A is 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less. Moreover, the content of the dye multimer A in the total mass of the near-infrared transmission black color material is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and even more preferably 50 to 100% by mass. As for the dye multimer A, only 1 type may be used and 2 or more types may be used together. When using two or more types of dye multimers A, it is preferable that the total amount is the said range.

It is also preferable that the composition of the present invention uses a crosslinkable dye and dye multimer A as a near-infrared transmission black color material. When both are used together, the content of the crosslinkable dye is preferably 10 to 90 parts by mass, more preferably 25 to 75 parts by mass, and even more preferably 40 to 60 parts by mass relative to 100 parts by mass of the dye multimer A .

(Other near-infrared transmission black color materials)

The composition of the present invention may contain, as a near-infrared transmission black color material, a near-infrared transmission black color material other than the above-mentioned crosslinkable dye and the above-mentioned dye multimer A (hereinafter also referred to as another near-infrared transmission black color material). The other near-infrared transmission black color material is a pigment type near-infrared transmission black color material or a dye type near-infrared transmission black color material, and a dye compound having no crosslinkable group can be mentioned. Examples of other near-infrared transmission black color materials include bisbenzofuranone compounds, azomethane compounds, perylene compounds, azo-based compounds, and the like, and bisbenzofuranone compounds and perylene compounds are preferred.

Examples of the bisbenzofuranone compound include those described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, and the like, for example, "Irgaphor Black" manufactured by BASF. It is available as ".

C. I. Pigment Black 31, 32, etc. are mentioned as a perylene compound.

Examples of the azomethine compound include those described in Japanese Unexamined Patent Application Publication No. Hei 1-170601, Japanese Patent Application Publication No. Hei 2-034664, and the like, for example, available as "Chromofine Black A1103" manufactured by Dainichi Seika Co., Ltd. can do.

Although an azo-type compound is not specifically limited, The compound etc. which are represented by following formula (A-1) are mentioned suitably.

[Formula 5]

It is preferable that the bisbenzofuranone compound is a compound represented by the following general formula and a mixture thereof.

[Formula 6]

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, and a and b each independently represent an integer of 0 to 4. When a is 2 or more, a plurality of R ³ may be the same or different, and a plurality of R ³ may be bonded to form a ring. When b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality of R ⁴ may be bonded to form a ring.

For details of the bisbenzofuranone compound, reference may be made to the description of paragraphs 0014 to 0037 in Japanese Patent Publication No. 2010-534726, the contents of which are incorporated herein.

When the composition of the present invention contains another near-infrared transmission black color material, the content of the other near-infrared transmission black color material is preferably 1 to 60% by mass, more preferably 1 to 30% by mass of the total solids of the composition. Moreover, it is preferable that content of the other near-infrared transmission black color material in the total amount of a near-infrared transmission black color material is 5-50 mass %, and it is more preferable that it is 5-30 mass %.

Moreover, it is also possible that the composition of this invention does not contain other near-infrared transmission black color materials substantially. When the content of the other near-infrared transmission black color material is not substantially contained, the content of the other near-infrared transmission black color material in the near-infrared transmission black color material is preferably 3% by mass or less, more preferably 1% by mass or less, and is not contained. More preferred.

<< infrared absorbent >>

The composition of the present invention may contain an infrared absorber. In the infrared transmission filter, the infrared absorber has a role of limiting the transmitted light (near infrared) to the longer wavelength side.

In the present invention, as the infrared absorber, a compound having a maximum absorption wavelength in the wavelength region of the infrared region (preferably, the wavelength of 700 nm or more and 1300 nm or less) can be preferably used. The infrared absorber may be a pigment or a dye.

Examples of the infrared absorber include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, diimium compounds, transition metal oxides, squarylium compounds, naphthalocyanine compounds, quaterylene compounds, and di A thiol metal complex compound, a croconium compound, and the like. Examples of the pyrrolopyrrole compound include the compounds described in Japanese Patent Application Laid-Open No. 2009-263614, paragraphs 0016 to 0058, and the compounds described in Japanese Patent Laid-Open Publication No. 2011-068731, Paragraph Nos. 0037 to 0052, and the like. The content is incorporated herein. As a squarylium compound, the compound described in paragraph No. 0044-0049 of Unexamined-Japanese-Patent No. 2011-208101 is mentioned, for example, and this content is incorporated in this specification. Examples of the cyanine compound include compounds described in Japanese Patent Application Laid-Open No. 2009-108267, Paragraph Nos. 0044 to 0045, and Japanese Patent Laid-Open No. 2002-194040, Paragraph Nos. 0026 to 0030, and their contents are It is incorporated herein. As a diimium compound, the compound of Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, and this content is incorporated in this specification. As a phthalocyanine compound, for example, the compound described in paragraph No. 0093 of JP 2012-077153 A, and the oxytitanium phthalocyanine described in JP 2006-343631 A, JP 2013-195480 A The compounds described in paragraph numbers 0013 to 0029 are mentioned, and the contents of these are incorporated herein. As a naphthalocyanine compound, the compound described in paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, and this content is incorporated in this specification. Further, as the cyanine compound, phthalocyanine compound, diimium compound, squarylium compound, and croconium compound, the compounds described in paragraphs 0010 to 0081 of JP 2010-111750 A may be used, and this content Is incorporated herein. In addition, the cyanine-based compound can refer to, for example, "functional pigment, Ogawara Makoto/Matsuoka Masaru/Kitao Daisiro/Hirashima Tsuneaki, Godansha Scientific", the contents of this specification. Is used.

In the present invention, as the infrared absorber, the compound described in Japanese Patent Application Laid-open No. Hei 07-164729, paragraphs 0004 to 0016, the compound described in Japanese Patent Laid-Open No. 2002-146254, Paragraph Nos. 0027 to 0062, 2011-2011 You may use near-infrared absorbing particle which consists of crystallites of the oxide containing Cu and/or P described in paragraph number 0034-0067 of 164583 and has a number average aggregate particle diameter of 5-200 nm. The contents of these are incorporated herein. In addition, FD-25 (manufactured by Yamada Chemical Industry Co., Ltd.), IRA842 (naphthalocyanine compound, manufactured by Exiton), etc. can also be used.

As the infrared absorber, inorganic fine particles can also be used. The inorganic fine particles are preferably metal oxide fine particles or metal fine particles from the viewpoint of more excellent infrared shielding properties. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine-doped tin dioxide (F-doped) SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal fine particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. Moreover, a tungsten oxide type compound can be used as an inorganic fine particle. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, reference may be made to Japanese Patent Laid-Open No. 2016-006476, paragraph number 0080, which is incorporated herein by reference. The shape of the inorganic fine particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape, regardless of spherical shape or non-spherical shape.

When the composition of the present invention contains an infrared absorber, the content of the infrared absorber is preferably 1 to 60% by mass, more preferably 10 to 40% by mass of the total solids of the composition. The content of the infrared absorber is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and even more preferably 30 to 80 parts by mass, relative to 100 parts by mass of the near-infrared transmission black color material. The infrared absorbers may be used alone or in combination of two or more. When using 2 or more types of infrared absorbers together, it is preferable that the total is the said range.

<< chromatic colorant >>

It is preferable that the composition of this invention contains a chromatic coloring agent. In addition, in this specification, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant having a maximum absorption wavelength in the range of 400 to 650 nm.

The chromatic colorant may be a pigment or a dye. It is preferably a dye. Moreover, it is preferable that a chromatic colorant is a compound which has a crosslinkable group.

It is preferable that a pigment is an organic pigment, and the following are mentioned. However, the present invention is not limited to these.

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

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

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

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

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (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, etc. (above, blue pigment).

These organic pigments can be used alone or in various combinations.

There is no restriction|limiting in particular as a dye, A well-known dye can be used. Examples of the chemical structure include pyrazole azo-based, anilino-azo-based, triarylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole-azo-based, pyridone-azo-based, cyanine-based, and phenothiazines. And dyes such as pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene.

You may use a dye multimer as a chromatic colorant. It is preferable that the dye multimer is a dye used by being dissolved in a solvent, but particles may be formed. When the dye multimer is a particle, it is used by dispersing the dye multimer in a solvent or the like. The dye multimer in the form of particles can be obtained, for example, by emulsion polymerization, and examples thereof include compounds and production methods described in JP 2015-214682 A. Further, as the dye multimer, compounds described in Japanese Patent Application Laid-open No. 2011-213925, Japanese Patent Application Laid-Open No. 2013-041097, Japanese Patent Application Laid-Open No. 2015-028144, Japanese Patent Application Laid-Open No. 2015-030742 can also be used. have.

The following compounds are mentioned as a chromatic coloring agent which has a crosslinkable group. This compound is a red dye.

[Formula 7]

As the chromatic colorant, the composition of the present invention preferably contains at least one colorant selected from a red colorant, a blue colorant, and a purple colorant, and more preferably contains a red colorant and/or a blue colorant. According to this aspect, the light-shielding property of a visible region can be improved more effectively.

When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 60% by mass in the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less.

The content of the chromatic colorant is preferably 1 to 100 parts by mass, more preferably 30 to 100 parts by mass, relative to 100 parts by mass of the near-infrared transmission black color material. Moreover, 1-100 mass parts is preferable with respect to 100 mass parts of total of the above-mentioned crosslinkable dye and the above-mentioned dye multimer A, and, as for content of a chromatic coloring agent, 30-100 mass parts is more preferable.

The chromatic colorants may be used alone or in combination of two or more. When using 2 or more types of chromatic coloring agents, it is preferable that the total amount is in the said range.

<<curable compound>>

The composition of the present invention contains a curable compound. As a curable compound, a polymerizable compound, resin, etc. are mentioned. The resin may be a non-crosslinkable resin (a resin having no crosslinkable group) or a crosslinkable resin (a resin having a crosslinkable group). Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, and an alkoxysilyl group. In this invention, it is preferable to use together a polymerizable compound (preferably a radically polymerizable compound) and resin as a curable compound. Moreover, it is preferable that resin contains alkali-soluble resin mentioned later. In addition, in this invention, curable compound is a component other than a near-infrared transmission black color material.

In the composition of the present invention, the content of the curable compound is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more with respect to the total solid content of the composition. This is particularly preferred. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

<<<polymerizable compound>>>

The polymerizable compound may be either a monomer or a polymer, but a monomer is preferred. The monomeric polymerizable compound preferably has a molecular weight of 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. Moreover, it is also preferable that a polymeric compound is a compound which does not have a molecular weight distribution substantially. Here, it is preferable that the dispersion degree (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the compound is 1.0 to 1.5, and 1.0 to 1.3 is more preferable that the molecular weight distribution is not substantially provided. The polymerizable compound is preferably a compound that can be polymerized by the action of a radical. That is, it is preferable that a polymerizable compound is a radically polymerizable compound. The polymerizable compound is preferably a compound having at least one group having an ethylenically unsaturated bond, more preferably a compound having at least two groups having an ethylenically unsaturated bond, and a compound having at least three groups having an ethylenically unsaturated bond. This is more preferred. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include vinyl groups, styryl groups, (meth)allyl groups, (meth)acryloyl groups, and the like, and (meth)acryloyl groups are preferred. It is preferable that a polymerizable compound is a 3-15 functional (meth)acrylate compound, and it is more preferable that it is a 3-6 functional (meth)acrylate compound.

As an example of a polymerizable compound, description of paragraph No. 0033-0034 of JP 2013-253224 A can be referred to, and this content is incorporated herein. As the compound, ethyleneoxy-modified pentaerythritol tetraacrylate (a commercially available product, NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (a commercially available product, KAYARAD D-330; Nippon Kayaku Co., Ltd., dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (KAYARAD D- as a commercial product) 310; Nippon Kayaku Co., Ltd., dipentaerythritol hexa(meth)acrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) Preferred are structures wherein the (meth)acrylic and (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. Moreover, these oligomer types can also be used. In addition, description of the polymerizable compounds in paragraphs 0034 to 0038 of JP 2013-253224 A can be referred to, and the contents thereof are incorporated herein. Moreover, the polymerizable monomers etc. which are described in paragraph No. 0477 of the Japanese Unexamined Patent Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099 of Paragraph No. 0585) are mentioned, the contents of which are incorporated herein by reference. .

Moreover, diglycerin EO (ethylene oxide) modified (meth)acrylate (M-460 as a commercial item; manufactured by Doa Kosei Co., Ltd.) is preferable. Pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferable. Oligomer types of these can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

The polymerizable compound may have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polymerizable compound in which an acid group is added by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferably, in the above-mentioned ester, a compound in which the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol is more preferable. As a commercial item, Aaronix M-510, M-520 (made by Toa Kosei Co., Ltd.), CBX-0, CBX-1 (made by Shin-Nakamura Kagaku High School Co., Ltd.) etc. are mentioned. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g. The lower limit is more preferably 5 mgKOH/g or more. The upper limit is more preferably 30 mgKOH/g or less. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the developing and dissolving properties are good, and if it is 40 mgKOH/g or less, it is advantageous for production or handling. Furthermore, it is excellent in curability.

The polymerizable compound is also a preferred embodiment of a compound having a caprolactone structure.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythrate Polyfunctional polyfunctional ε-caprolactone modified obtained by esterifying polyhydric alcohols such as itol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and (meth)acrylic acid and ε-caprolactone ( And meth)acrylates. The compound having a caprolactone structure can refer to the description of paragraphs 0153 to 0170 of International Publication No. WO2015/166779, the contents of which are incorporated herein. As a commercial item, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and DPCA-60 which is a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. And TPA-330, a trifunctional acrylate having three isobutyleneoxy chains.

As the polymerizable compound, isocyanurate ethylene oxide-modified (meth)acrylate is also preferable. As commercial products, Aaronix M-315, M-313 (manufactured by Toa Kosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), SR368 (manufactured by Satomer Corporation), and the like are listed. As a polymerizable compound used in combination with a titanyl phthalocyanine pigment, a high SP value (Solubility Parameter) is preferable from the viewpoint of heat resistance. Examples of the polymerizable compound having a high SP value include Aaronix M-315 and M-313 (manufactured by Toagosei Co., Ltd.).

As a polymerizable compound, it is as described in Unexamined-Japanese-Patent No. 48-041708, Unexamined-Japanese-Patent No. 51-037193, Unexamined-Japanese-Patent No. 2-032293, Unexamined-Japanese-Patent No. 2-016765. Ethylene acrylate, ethylene oxide described in Japanese Patent Application Publication No. 58-049860, Japanese Patent Application Publication No. 56-017654, Japanese Patent Application Publication No. 62-039417, Japanese Patent Application Publication No. 62-039418 Uretain compounds having a system skeleton are also suitable. By using addition polymerizable compounds having an amino structure or sulfide structure in a molecule, as described in Japanese Patent Application Laid-open No. 63-277653, Japanese Patent Application Laid-open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 , It is possible to obtain a composition having a very good photosensitive speed.

As a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp), UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha Chemical Co., Ltd.), etc. are mentioned.

The content of the polymerizable compound in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more, for example. As an upper limit, 45 mass% or less is more preferable, for example, 40 mass% or less is more preferable. The polymerizable compound may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<<<resin>>>

The composition of the present invention may contain a resin as a curable compound. As resin, alkali-soluble resin etc. are mentioned. The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and still more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and more preferably 5,000 or more. It is preferable that content of resin is 10 to 80 mass% of the total solid content of a composition, and it is more preferable that it is 20 to 60 mass %. The composition may contain only one type of resin, or may contain two or more types. When 2 or more types of resin are included, it is preferable that the total amount becomes the said range.

(Alkali-soluble resin)

It is preferable that the composition of this invention contains alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation property are improved.

The molecular weight of the alkali-soluble resin is not particularly limited, but it is preferable that the weight average molecular weight (Mw) is 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000.

As the alkali-soluble resin, a resin having a group that promotes alkali dissolution can be appropriately selected. Examples of the group (hereinafter also referred to as an acid group) that promotes alkali dissolution include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxy group is preferable. As for these acid groups, only 1 type may be sufficient and 2 or more types may be sufficient as them.

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

The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain. Specific examples include alkali-soluble phenol resins such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolac resins, and carboxy groups on the side chains. And acidic cellulose derivatives and resins having an acid anhydride added to the polymer having a hydroxy group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, and vinyl compounds. As alkyl (meth)acrylate and aryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate , Pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate , As a vinyl compound such as cyclohexyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydro And furfuryl methacrylate, polystyrene macromonomers, and polymethyl methacrylate macromonomers. As another monomer, the N-position substituted maleimide monomer described in JP-A-10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide, or the like may be used. Moreover, only 1 type may be sufficient as other monomers copolymerizable with these (meth)acrylic acid, and 2 or more types may be sufficient as them.

In order to improve the crosslinking efficiency of the membrane, an alkali-soluble resin having a polymerizable group may be used. (Meth)allyl group, (meth)acryloyl group etc. are mentioned as a polymerizable group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group in a side chain or the like is useful. Examples of the alkali-soluble resin containing a polymerizable group include Diana NR series (Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 (All manufactured by Osaka Yuki Chemical Industry Co., Ltd.) Cyclomer P series (e.g., ACA230AA), Fracel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (made by Daicel Yushibi Co., Ltd.), And Acricure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

The alkali-soluble resin includes benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl(meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, and benzyl (meth)acrylate A /(meth)acrylic acid/polypolymer composed of other monomers can be preferably used. 2-hydroxyethyl (meth)acrylate copolymer, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid described in Japanese Patent Application Laid-open No. Hei 7-140654. Copolymer, 2-hydroxy-3-phenoxypropylacrylate/polymethylmethacrylate macromonomer/benzylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/polystyrene macromonomer/methylmeth A acrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc. can also be preferably used.

The alkali-soluble resin is a polymer formed by polymerizing a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers") It is also preferable to include.

[Formula 8]

In the 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.

[Formula 9]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of Formula (ED2), the description of JP 2010-168539 A can be referred to.

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have substituents represented by R ¹ and R ² is not particularly limited, but is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl , Linear or branched alkyl groups such as isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecaneyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; Alkyl groups substituted with alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl; And an alkyl group substituted with an aryl group such as benzyl. Among these, substituents of primary or secondary carbons, which are difficult to desorb by acid or heat, such as methyl, ethyl, cyclohexyl, and benzyl, are preferred from the viewpoint of heat resistance.

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

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

[Formula 10]

In Formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. . n represents the integer of 1-15.

In Formula (X), 2 to 3 carbon atoms of the alkylene group of R ₂ are preferable. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group, 2-phenyl (iso)propyl group, and the like.

The following is mentioned as a specific example of alkali-soluble resin. Among the following resins, the numerical value added to the main chain is a molar ratio.

[Formula 11]

For the alkali-soluble resin, reference may be made to Japanese Patent Application Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, 0685 to 0700), the contents of which are described herein. Is used. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP 2012-032767 and alkali-soluble resins used in Examples, and the binder resins described in JP 2012-208474 of PAR Nos. 0088 to 0098 And the binder resin used in Examples, the binder resin used in Examples and Binder Resins disclosed in Japanese Patent Application Publication No. 2012-137531, and the binder resin used in Examples, Paragraph Nos. 0132 to 0143 in Japanese Patent Application Publication No. 2013-024934 Binder resins used in Examples and binder resins used in Examples, Binder resins used in Examples No. 2011-242752, and binder resins used in Examples, paragraphs in Japanese Patent Publication No. 2012-032770 The binder resin described in No. 0030-0072 can also be used. The contents of these are incorporated herein.

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

As for content of alkali-soluble resin, 0.1-20 mass% is preferable with respect to the whole solid content of a composition. The lower limit is more preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and even more preferably 10% by mass or less. The composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

(Other resins)

The composition of the present invention may contain other than the above-mentioned alkali-soluble resin (also called other resins). As other resins, for example, (meth)acrylic resin, (meth)acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin , Polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, epoxy resin, and the like. . As a cyclic olefin resin, norbornene resin can be used preferably from a viewpoint of improving heat resistance. As a commercial item of norbornene resin, the ARTON series (for example, ARTON F4520) by JSR Co., Ltd. is mentioned, for example.

As an epoxy resin, for example, the epoxy resin which is a glycidyl etherate of a phenol compound, the epoxy resin which is a glycidyl etherate of various novolak resins, alicyclic epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, Glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, epoxy resins glycidylated with halogenated phenols, condensates of silicon compounds having an epoxy group and other silicon compounds, and polymerizable unsaturated polymers having an epoxy group And copolymers of the compound with other polymerizable unsaturated compounds. As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, products available on the market include Mapru G-0150M, G-0105SA, G-0130SP, G-0250SP, and G- And 1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by Nichiyu Co., Ltd.).

The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g/eq, more preferably 310 to 1700 g/eq, and even more preferably 310 to 1000 g/eq. Epoxy resins may be used alone or in combination of two or more.

As the epoxy resin, commercial products may be used. As a commercial item, the following epoxy resin is mentioned, for example. As bisphenol A type epoxy resin, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above) Note)). Bisphenol F-type epoxy resins, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (Above, Nippon Kayaku Co., Ltd. product) etc. are mentioned. As a phenol novolak-type epoxy resin, jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) And the like. As a cresol novolac-type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. As an aliphatic epoxy resin, ADEKA RESIN EP-4080S, copper EP-4085S, copper EP-4088S (above, manufactured by ADEKA Corporation), celloxide 2021P, celloxide 2081, celloxide 2083, celloxide 2085, EHPE3150, EPOLEAD PB 3600, copper PB 4700 (above, manufactured by Daicel Co., Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase Chemtex Co., Ltd.), etc. Can be lifted. In addition, ADEKA RESIN EP-4000S, copper EP-4003S, copper EP-4010S, copper EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, manufactured by Adeka Corporation), jER1031S (Mitsubishi Chemical Corporation).

As for content of an epoxy resin, 1-30 mass% is preferable with respect to the whole solid content of a composition. The lower limit is more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 25% by mass or less, and even more preferably 20% by mass or less. The composition of the present invention may contain only one type of epoxy resin, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

In addition, when the composition contains an epoxy resin and a polymerizable compound, the mass ratio of the polymerizable compound and the epoxy resin is preferably a polymerizable compound: epoxy resin = 100:1 to 100:400, and 100:1 to 100:100. It is more preferable.

<<<polyfunctional thiol compound>>>

The composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in a molecule for the purpose of promoting the reaction of the polymerizable compound and the like. It is preferable that a polyfunctional thiol compound is a 2nd class alkane thiol, and it is especially preferable that it is a compound which has a structure represented by the following general formula (T1).

Formula (T1)

[Formula 12]

(In formula (T1), n represents the integer of 2-4, and L represents a 2-4 tetravalent coupling group.)

The content of the polyfunctional thiol compound is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass relative to the total solid content of the composition. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<< photopolymerization initiator >>

When using a polymerizable compound as a curable compound, it is preferable that the composition of this invention contains a photoinitiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the visible region from the ultraviolet region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound such as acylphosphine oxide, and hexaaryl biimi And oxime compounds such as dazol and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. The compound described in Japan, 42, 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, J. Org by FC Schaefer, etc. . Chem.; 29, 1527 (1964), the compound described in Japanese Patent Application Laid-open No. 62-058241, the compound described in Japanese Patent Application Laid-open No. Hei 5-281728, the compound described in Japanese Patent Application Laid-open No. Hei 5-034920, USA And the compounds described in Patent Publication No. 4212976.

The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, or a metallocene from the 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 Preferred are compounds selected from the group consisting of compounds. Particularly, when the composition of the present invention is used for a solid-state imaging device, it is important to develop a fine pattern in a sharp shape, and therefore it is important to develop the unexposed portion without residue along with curability. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, in the case of forming a fine pattern in a solid-state imaging device, a stepper exposure machine is used for exposure for curing. This exposure machine may be damaged by halogen, and the addition amount of the photopolymerization initiator needs to be suppressed low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, reference may be made to paragraphs 0265 to 0268 of JP 2013-029760 A, and the contents thereof are incorporated herein.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be suitably used. For example, the α-aminoketone compound described in Japanese Patent Application Laid-open No. Hei 10-291969 and the acylphosphine compound described in Japanese Patent Publication No. 4225898 can also be used. As the α-hydroxyketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (above, manufactured by BASF) can be used. As the α-aminoketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF) can be used. As the α-aminoketone compound, a compound described in JP 2009-191179 A can be used. As an acylphosphine compound, commercially available products IRGACURE-819 and DAROCUR-TPO (above, BASF Corporation make) can be used.

It is preferable to use an oxime compound as a photoinitiator. Specific examples of the oxime compound include compounds described in Japanese Unexamined Patent Publication No. 2001-233842, Japanese Unexamined Patent Publication No. 2000-080068, Japanese Unexamined Patent Publication No. 2006-342166, and Japanese Unexamined Patent Publication No. 2016-021012. Examples of the oxime compound which can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy )Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. JCS Perkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Publication 2000 -066385, Japanese Unexamined Patent Publication No. 2000-080068, Japanese Unexamined Patent Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2006-342166, and the like.

In commercial products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF) are also suitably used. TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Arkles NCI-831 (manufactured by Adeka), Adeka Arkles NCI- 930 (made by ADEKA Corporation) and Adeka Optomer N-1919 (made by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-014052 A) can also be used.

As an oxime compound other than the above, a compound described in Japanese Patent Publication No. 2009-519904, wherein an oxime is connected to the N position of the carbazole ring, a compound described in U.S. Patent Publication No. 7626957 in which a hetero substituent is introduced at the benzophenone site, and a night at the pigment site The compound described in Japanese Unexamined Patent Publication No. 2010-015025 and U.S. Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No. WO2009/131189, the triazine skeleton and the oxime skeleton, contained in the same molecule The compound described in U.S. Patent Publication No. 7556910, the compound described in JP 2009-221114 A, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, may be used.

The oxime compound is preferably a compound represented by the following formula (OX-1). Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Formula 13]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. For details of formula (OX-1), reference may be made to the description of paragraphs 0276 to 0304 in JP 2013-029760 A, and this content is incorporated herein.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. As specific examples of the oxime compound having a fluorine atom, the compound described in JP 2010-262028 A, the compound 24, 36-40 in JP 2014-500852 A, the compound described in JP 2013-164471 A (C-3) and the like. This content is incorporated herein.

As the photopolymerization initiator, an oxime compound having a nitro group can also be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 and 0008 to 0012 and 0070 to 0079 of JP 2014-137466, Japanese Patent Publication The compound described in paragraph number 0007-0025 of 4223071, Adeka Acles NCI-831 (made by ADEKA Corporation) is mentioned.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated herein.

As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include compounds OE-01 to OE-75 described in International Publication No. WO2015/036910.

Preferred specific examples of the oxime compound are shown below, but the present invention is not limited to them.

[Formula 14]

[Formula 15]

The oxime compound is preferably a compound having an absorption maximum in the wavelength region of 350 nm to 500 nm, and more preferably a compound having an absorption maximum in the wavelength region of 360 nm to 480 nm. The oxime compound is preferably a compound having a high absorbance of 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2, 000 to 300,000, and even more preferably 5,000 to 200,000, from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

It is also preferable that the photopolymerization initiator contains an oxime compound and an α-aminoketone compound. By using both together, developability is improved and it is easy to form a pattern excellent in rectangularity. When the oxime compound and the α-aminoketone compound are used in combination, with respect to 100 parts by mass of the oxime compound, the α-aminoketone compound is preferably 50 to 600 parts by mass, and more preferably 150 to 400 parts by mass.

As for content of a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid content of a composition, 0.5-30 mass% is more preferable, and 1-20 mass% is more preferable. When the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formability are obtained. The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

<< solvent >>

The composition of the present invention may contain a solvent. An organic solvent is mentioned as a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition, but is preferably selected in consideration of the coatability and safety of the composition.

Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. As a specific example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate. For the details of the organic solvent, reference can be made to the description in paragraph No. 0223 of WO2015/166779, the content of which is incorporated herein.

However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be preferably reduced due to environmental reasons, for example, 50 ppm by mass based on the total amount of the organic solvent ( parts per million) or less, more preferably 10 ppm by mass or less, and more preferably 1 ppm by mass or less.

The organic solvents may be used alone or in combination of two or more. When using two or more organic solvents in combination, 3-ethoxypropionate methyl, 3-ethoxypropionic acid ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-meth Mixture consisting of two or more selected from methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate Solutions are preferred.

It is preferable to use a solvent having a small metal content, and the metal content of the solvent is preferably 10 parts by mass (ppb) or less, for example. If necessary, you can use a solvent at a parts per trillion (ppt) level, and such high-purity solvents are provided by, for example, Toyo Kosei Co., Ltd. (Kagaku High School Nippo, November 13, 2015).

As a method of removing impurities, such as metal, from a solvent, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter is mentioned, for example. As a filter hole diameter of the filter used for filtration, 10 nm or less is preferable, 5 nm or less is more preferable, and 3 nm or less is more preferable. The material of the filter is preferably polytetrachloroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds of the same atomic number and different structures). The isomer may contain only one type or may contain multiple types.

The organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably does not substantially contain peroxide.

The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass relative to the total amount of the composition.

<< polymerization inhibitor >>

The composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert -Butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine first cerium salt and the like. Especially, paramethoxyphenol is preferable.

The content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition.

<<silane coupling agent>>

The composition of the present invention may further contain a silane coupling agent. In addition, the silane coupling agent in this invention is a component different from the near-infrared transmission black color material mentioned above.

In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent capable of generating a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction, directly connected to a silicon atom. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. The functional group other than the hydrolysable group is preferably a group that exhibits affinity by forming an interaction or bond with the resin. Examples include vinyl groups, styryl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and the like. Diary and epoxy groups are preferred.

Specific examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3 -Aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-amino Propyl trimethoxysilane, hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyl Triethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxy Silane, and the like. In addition to the above, an alkoxy oligomer can be used. The following compounds can also be used.

[Formula 16]

As commercially available products, KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM- made by Shin-Etsu Silicone Co., Ltd. 3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE- 9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41- 1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40- 9238 and the like. As a silane coupling agent, the compound described in paragraph No. 0018 to 0036 of JP 2009-288703, the compound described in paragraph No. 0056 to 0066 of JP 2009-242604, paragraph No. 0229 of WO2015/166779 The compound described in -0236 is mentioned, and this content is incorporated in this specification.

As for content of a silane coupling agent, 0.1-30 mass% is preferable with respect to the total solid content of a composition, 0.5-20 mass% is more preferable, and 1-10 mass% is more preferable.

<<<surfactant>>>

The composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. As the surfactant, reference may be made to International Publication No. WO2015/166779, paragraphs 0238 to 0245, the contents of which are incorporated herein.

By incorporating the fluorine-based surfactant in the composition of the present invention, liquid properties (especially, fluidity) when prepared as a coating liquid are further improved, and uniformity and liquid-liquidity of the coating thickness can be further improved. When a film is formed by using a coating solution to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating solution is lowered, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is improved. For this reason, it is possible to more appropriately form a film having a uniform thickness with a small thickness variation.

As for the fluorine-containing rate in a fluorine-type surfactant, 3-40 mass% is suitable, 5-30 mass% is more preferable, and 7-25 mass% is more preferable. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid-repellency, and solubility in the composition is also good.

Specifically, as the fluorine-based surfactant, the surfactants described in Japanese Patent Application Laid-open No. 2014-041318, paragraphs 0060 to 0064 (corresponding international publication 2014/17669, paragraphs 0060 to 0064), Japanese Patent Application Laid-Open No. 2011-132503 The surfactants described in paragraph numbers 0117 to 0132 are exemplified, and their contents are incorporated herein. Commercially available products of the fluorine-based surfactant include, for example, Megapak F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482, Copper F554, Copper F780 (above, manufactured by DIC Corporation), Fluorad FC430, Copper FC431, Copper FC171 (above, Sumitomo 3M Co., Ltd.), SUPRON S-382, Copper SC-101, Copper SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 (above, manufactured by Asahi Garas Co., Ltd.), And PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA).

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heated, an acrylic compound in which a portion of the functional group containing a fluorine atom is cut to volatilize the fluorine atom can also be suitably used. As such a fluorine-based surfactant, DIC Corporation's Megapak DS series (Kagaku High School Nippo, February 22, 2016) (Nikkei Sangyo status, February 23, 2016), for example Megapak DS- 21, and these can be used.

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

[Formula 17]

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

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain may be used. As a specific example, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, for example, Megapak RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation And -72-K. As the fluorine-based surfactant, the compounds described in Japanese Patent Application Laid-Open No. 2015-117327, paragraphs 0015 to 1158 may also be used.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sobitan Fatty Acid Ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspur 20000 (Nihon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Junyaku High School Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Yoshi Takemoto ( Note), Olfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like.

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass relative to the total solid content of the composition. As surfactant, only 1 type may be used and 2 or more types may be combined. When using 2 or more types, it is preferable that the total amount becomes the said range.

<< other ingredients >>

The composition of the present invention may contain various additives such as a thermal polymerization initiator, a thermal polymerization component, an ultraviolet absorber, an antioxidant, a plasticizer, a developing agent such as a low molecular weight organic carboxylic acid, and other fillers, antioxidants, and aggregation inhibitors. . As the ultraviolet absorber, an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, or a triazine compound can be used, and as a specific example, Japanese Patent Application Publication No. 2013-068814 And the compounds described in the heading. As a benzotriazole compound, you may use MYUA series (made by Miyoshi Yushi Co., Ltd., Kagaku High School Nippo, February 1, 2016). As the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, a compound described in paragraph No. 0042 of JP 2011-090147 A), a thioether compound, or the like can be used. As a commercial item, for example, the Adeka Stab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, manufactured by ADEKA Corporation), AO-330, etc.).

Depending on the raw material to be used, a metal element may be contained in the composition, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 element (calcium, magnesium, etc.) in the composition is preferably 50 ppm by mass or less, and 0.01 to 10 mass ppm is more preferred. It is preferable that the total amount of the inorganic metal salt in a composition is 100 mass ppm or less, and 0.5-50 mass ppm is more preferable.

<Preparation method of composition>

The composition of the present invention can be prepared by mixing the above-described components.

When preparing a composition, you may mix|blend each component collectively, or you may mix|blend sequentially after dissolving or dispersing each component in a solvent. The mixing order and working conditions when compounding are not particularly limited. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, prepare two or more solutions or dispersions in which each component is appropriately blended in advance, and use them at the time of use (when applying). You may mix and prepare as a composition.

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

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

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

When using a filter, you may combine other filters (for example, a 1st filter and a 2nd filter, etc.). In that case, filtration using each filter may be performed only once, or may be performed two or more times.

Filters of different hole diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of a filter manufacturing company. Examples of commercially available filters include, for example, Nippon Paul Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (Kunihon Microlois Co., Ltd.) or Kabuki Co., Ltd. Kits micro filters, etc. You can choose from various filters.

As the second filter, one formed of the same material or the like as the first filter can be used.

Filtration using the first filter may be performed only on the dispersion, and after mixing the other components, the second filter may be filtered.

The total solid content (solid content concentration) of the composition varies depending on the application method, but is preferably 1 to 50% by mass, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

In the composition of the present invention, when a film having a film thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed, the maximum value in the range of 400 to 700 nm of light transmittance in the thickness direction of the film is 20% or less. It is preferable that the minimum value in the range of wavelength 1100-1300 nm of the light transmittance in the thickness direction of the film satisfies the spectral characteristics of 70% or more. The maximum value in the wavelength range of 400 to 700 nm is more preferably 15% or less, and still more preferably 10% or less. The minimum value in the wavelength range of 1100 to 1300 nm is more preferably 75% or more, and more preferably 80% or more.

It is more preferable that the composition of the present invention satisfies any one of the following spectral properties (1) to (3).

(1) When a film having a film thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed, the maximum value in the range of 400 to 750 nm of light transmittance in the thickness direction of the film is 20% or less (preferably Is 15% or less, more preferably 10% or less), and the minimum value in the range of wavelength 900 to 1300 nm of the light transmittance in the film thickness direction is 70% or more (preferably 75% or more, more preferably) Is 80% or more).

(2) When a film having a film thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed, the maximum value in the range of the wavelength of 400 to 830 nm of the light transmittance in the thickness direction of the film is 20% or less (preferably Is 15% or less, more preferably 10% or less), and the minimum value in the range of wavelength 1000 to 1300 nm of light transmittance in the thickness direction of the film is 70% or more (preferably 75% or more, more preferably Is 80% or more).

(3) When a film having a film thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed, the maximum value in the range of the wavelength of 400 to 950 nm of the light transmittance in the thickness direction of the film is 20% or less (preferably Is 15% or less, more preferably 10% or less), and the minimum value in the range of wavelengths 1100 to 1300 nm of light transmittance in the thickness direction of the film is 70% or more (preferably 75% or more, more preferably) Is 80% or more).

<Pattern formation method>

Next, a method for forming a pattern using the composition of the present invention will be described. It is preferable that the pattern forming method includes a step of forming a composition layer on a support using the composition of the present invention and a step of forming a pattern on the composition layer by a photolithography method or a dry etching method.

Pattern formation in the photolithography method includes a step of forming a composition layer on a support using the composition of the present invention, a step of exposing the composition layer in a pattern shape, and a step of developing and removing unexposed portions to form a pattern. It is preferred to include.

The pattern formation in the dry etching method is a step of forming a composition layer on a support using the composition of the present invention and curing to form a cured product layer, and a process of forming a photoresist layer on the cured product layer, It is preferable to include a process of patterning a photoresist layer by exposure and development to obtain a resist pattern, and a process of forming a pattern by using a resist pattern as an etching mask and dry etching the cured product layer. Hereinafter, each process is demonstrated.

<<Process for forming composition layer>>

In the step of forming the composition layer, the composition layer is formed on the support using the composition of the present invention.

As a method of applying the composition to the support, a known method can be used. For example, the dropping method (drop cast); Slit coat method; Spray method; Roll coat method; Spin coating (spin coating); Flexible coating method; Slit and spin method; The free wet method (for example, the method described in JP 2009-145395 A); Various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle jet and other ejection system printing, flexo printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; Transfer method using a mold or the like; And nanoimprint methods. The method of application in the inkjet is not particularly limited, and for example, the method described in the patent publication shown in "diffused and usable inkjet-infinite potential to be viewed as a patent-, published in February 2005, Sumibe Techno Research". (Especially pages 115 to 133), Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830, Japanese Patent Application Publication 2006-169325, etc. are mentioned.

The composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, prebaking is not required. In the case of prebaking, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit may be, for example, 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 2200 seconds. Drying can be performed with a hot plate, an oven, or the like.

(When pattern is formed by photolithography method)

<<exposure process>>

Next, the composition layer is exposed in a pattern shape (exposure step). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed portion can be cured.

As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferably used (particularly preferably i-rays). Irradiation dose (exposure dose) of, for example 0.03 ~ 2.5J / cm ² are preferred, 0.05 ~ 1.0J / cm ² is more preferred, 0.08 ~ 0.5J / cm ² is more preferred.

The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed under the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19 vol% or less (preferably 15 vol% or less, more preferably 5 vol% or less) , More preferably substantially oxygen-free, and under a high oxygen atmosphere (preferably 22 vol% or more, more preferably 30 vol% or more, more preferably 50) having an oxygen concentration exceeding 21 vol% (Volume% or more). Exposure illuminance is possible to appropriately set, and usually ^{1000W / m 2 ~ 100000W / m} 2 ( preferably 5000W / m ^2, and more preferably at 15000W / m ² or more, more preferably 35000W / m ² or greater) You can choose from the range of. Oxygen concentration and the exposure illumination may be the appropriate combination of conditions, for example, an oxygen concentration of 10 volume% and the roughness 10000W / m ^2, an oxygen concentration of 35% by volume and may be a roughness 20000W / m ² and the like.

<<development process>>

Next, the unexposed portion is developed and removed to form a pattern. The development of the unexposed portion can be removed using a developer. Thereby, the composition layer of the unexposed portion in the exposure process is eluted into the developer, and only the photocured portion remains on the support.

As the developer, an alkali developer that does not cause damage to a solid-state imaging device or circuit under the ground is preferable.

The temperature of the developer is preferably 20 to 30°C, for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, the developer may be shaken off every 60 seconds, and the process of supplying the developer again may be repeated several times.

Examples of the alkali agent used in the developer are ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethyl Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, Organic alkaline compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate Can. As the developer, an alkaline aqueous solution in which these alkali agents are diluted with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. A surfactant may be used for the developer. Examples of the surfactant include the surfactants described in the above-mentioned composition, and nonionic surfactants are preferred. When using a developer composed of such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

After drying after the development step, a curing step of curing by heat treatment (post-baking) or post-exposure may be performed.

Post-baking is a post-development heat treatment to make curing complete. The heating temperature in the post-baking is preferably 100 to 240°C, for example, and more preferably 200 to 240°C. When an organic electroluminescent (organic EL) element is used as the light emitting light source, or when the photoelectric conversion film of the image sensor is composed of an organic material, the heating temperature is preferably 150°C or less, more preferably 120°C or less, and more preferably 100°C The following are more preferable, and 90 degrees C or less is especially preferable. The lower limit can be, for example, 50°C or higher. The post-baking can be performed continuously or in a batch mode by using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to achieve the above-described conditions.

The post-exposure can be performed by g-rays, h-rays, i-rays, excimer lasers such as KrF or ArF, electron beams, X-rays, etc., but is preferably performed at a low temperature of about 20 to 50°C with a conventional high-pressure mercury lamp. The irradiation time is preferably 10 seconds to 180 seconds, and more preferably 30 seconds to 60 seconds. In the case of using a combination of post-exposure and post-heating, it is preferable to perform post-exposure first.

(In case of pattern formation by dry etching method)

Pattern formation in a dry etching method can be performed using an etching gas by curing the composition layer formed on the support to form a cured product layer, and then the obtained cured product layer using a patterned photoresist layer as a mask. . In forming the photoresist layer, it is preferable to further perform a prebaking treatment. Particularly, as a photoresist layer formation process, a mode in which a post-exposure heat treatment and a post-development heat treatment (post-baking treatment) is performed is preferable. For the pattern formation in the dry etching method, reference can be made to descriptions in paragraphs 0010 to 0067 of JP 2013-064993 A, which are incorporated herein by reference.

By performing each of the steps described above, a pattern of pixels having specific spectral characteristics of the present invention can be formed. An infrared transmission filter may be composed of only pixels having specific spectral characteristics of the present invention, and a combination of pixels having specific spectral characteristics of the present invention and other pixels such as red, green, blue, magenta, sulfur, cyan, black, and colorless The infrared transmission filter may be configured. When an infrared transmission filter is formed by combining a pixel having a specific spectral characteristic of the present invention and a pixel of a different color, a pattern of a pixel having the specific spectral characteristic of the present invention may be formed first, or a pattern of a pixel other than the above After forming, a pattern of a pixel having specific spectral characteristics of the present invention may be formed.

<cured film>

Next, the cured film in the present invention will be described. The film of the present invention is formed by curing the above-described composition of the present invention. The cured film of the present invention can be preferably used as an infrared transmission filter.

The cured film of the present invention has a maximum value in the range of 400 to 700 nm of light transmittance in the thickness direction of the film of 20% or less (preferably 15% or less, more preferably 10% or less), and the film thickness. It is preferable that the minimum value in the range of wavelength 1100-1300 nm of the light transmittance in the direction is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the range of 400 to 700 nm in wavelength can be shielded, and a film capable of transmitting infrared rays in a state where there is little noise derived from visible light can be formed.

It is preferable that the cured film of this invention has any one of the following spectral characteristics (1)-(3). In the present specification, the spectral characteristics of the cured film indicate a value obtained by measuring transmittance in the range of wavelength 300 to 1300 nm using an ultraviolet visible near infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

(1) The maximum value in the range of the wavelength of 400 to 750 nm of the light transmittance in the thickness direction of the film is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The aspect in which the minimum value in the range of the wavelength of 900-1300 nm of the light transmittance of 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light having a wavelength in the range of 400 to 750 nm is shielded, and a film capable of transmitting infrared rays having a wavelength of 900 nm or more in a state where there is little noise derived from visible light can be used.

(2) The maximum value in the range of the wavelength of 400 to 830 nm of the light transmittance in the thickness direction of the film is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The aspect in which the minimum value in the range of the wavelength of 1000-1300 nm of the light transmittance of 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light having a wavelength in the range of 400 to 830 nm can be shielded, and a film capable of transmitting infrared rays having a wavelength of 1000 nm or more in a state where there is little noise derived from visible light can be used.

(3) The maximum value in the range of the wavelength of 400 to 950 nm of the light transmittance in the thickness direction of the film is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The aspect in which the minimum value in the range of the wavelength of 1100-1300 nm of the light transmittance of 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light having a wavelength in the range of 400 to 950 nm is shielded, and a film capable of transmitting infrared rays having a wavelength of 1100 nm or more in a state where there is little noise derived from visible light can be used.

The cured film having the spectral properties of the above (1) can be formed by using the composition of the present invention containing a near-infrared transmission black color material. It is easy to adjust the spectroscopy of said (1) to a preferable range by further containing a chromatic coloring agent.

The cured film having the spectral properties of (2) can be formed by using the composition of the present invention further comprising an infrared absorber in addition to the near-infrared transmission black color material. It is preferable that the infrared absorber is a compound having a maximum absorption wavelength in a range of 800 nm or more and less than 900 nm. Moreover, it is easy to adjust the spectroscopy of said (2) to a preferable range by further containing a chromatic coloring agent.

The cured film having the spectral properties of the above (3) can be formed by using the composition of the present invention further comprising an infrared absorber in addition to the near-infrared transmission black color material. It is preferable that the infrared absorber is a compound having a maximum absorption wavelength in a range of 900 nm or more and less than 1000 nm. Moreover, it is easy to adjust the spectroscopy of said (3) to a preferable range by further containing a chromatic colorant and/or a compound which has a maximum absorption wavelength in the range of 800 nm or more and less than 900 nm in wavelength.

Although the film thickness of the cured film of this invention is not specifically limited, 0.1-20 micrometers is preferable and 0.5-10 micrometers is more preferable.

<Infrared transmission filter>

Next, the infrared transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the cured film of the present invention.

It is preferable to use the infrared transmission filter of the present invention by laminating it on a support. Examples of the support include substrates made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. A charge bonding element (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, etc. may be formed on the support. In some cases, a black matrix for isolating each pixel is formed on the support. If necessary, an undercoat layer may be provided to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate, if necessary.

The infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using the coloring composition containing a chromatic coloring agent. As a chromatic colorant, the chromatic colorant demonstrated by the composition mentioned above is mentioned. The coloring composition may further contain a resin, a polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, and an ultraviolet absorber. About these details, the material demonstrated by the above-mentioned composition is mentioned, and they can be used.

It is also preferable that the infrared transmission filter of the present invention has a pixel of the film or laminate of the present invention and a pixel selected from red, green, blue, magenta, sulfur, cyan, black and colorless.

<Solid imaging device>

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

On the support, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, and the like, and only the photodiode and the light receiving portion of the photodiode on the transfer electrode It has a light-shielding film made of tungsten or the like that has been opened, and has a device protective film made of silicon nitride or the like formed to cover the entire light-shielding film surface and a photodiode light-receiving portion on the light-shielding film, and has a cured film of the present invention on the device protective film. Further, it is on the device protective film, and has a condensing means (for example, a micro lens or the like, hereinafter the same) under the cured film of the present invention (the side closer to the support), or a condensing means on the cured film of the present invention It may be configured.

<Infrared sensor>

The infrared sensor of the present invention has the cured film of the present invention. The configuration of the infrared sensor of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to FIG. 1.

In the infrared sensor 100 shown in Fig. 1, reference numeral 110 is a solid-state imaging element.

The imaging area provided on the solid-state imaging element 110 includes an infrared cut filter 111 and a color filter 112.

The infrared cut filter 111 transmits light in the visible region (for example, light having a wavelength of 400 to 700 nm) and transmits light in the infrared region (for example, at least a part of light having a wavelength of 800 to 1300 nm, preferably It is a filter that shields at least a portion of light having a wavelength of 900 to 1200 nm, more preferably at least a portion of light having a wavelength of 900 to 1000 nm).

The color filter 112 is a color filter in which pixels for transmitting and absorbing light of a specific wavelength in the visible light region are formed, and for example, red (R), green (G), and blue (B) pixels are formed. Color filters and the like are used.

Between the infrared transmission filter 113 and the solid-state imaging element 110, an area 114 in which the infrared cut filter 111 is not formed is provided. In the region 114, a resin layer (for example, a transparent resin layer) capable of transmitting light having a wavelength transmitted through the infrared transmission filter 113 is disposed.

The infrared transmission filter 113 is a filter that has visible light shielding property and transmits infrared rays of a specific wavelength, and is composed of the cured film of the present invention.

A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 113. The planarization layer 116 is formed to cover the micro lens 115.

In the embodiment shown in FIG. 1, a resin layer is disposed in the region 114, but an infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state imaging element 110.

In the embodiment shown in Fig. 1, the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thickness of both may be different.

In the embodiment shown in Fig. 1, the color filter 112 is provided on the incident light hv side than the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to cut off the infrared light. The filter 111 may be provided on the incident light hν side than the color filter 112.

In the embodiment shown in Fig. 1, the infrared ray cut filter 111 and the color filter 112 are stacked adjacently, but both filters are not necessarily adjacent, and another layer may be provided between them.

According to this infrared sensor, since image information can be read in real time, motion sensing or the like that recognizes an object for detecting motion is possible. Furthermore, since distance information can be acquired, it is also possible to shoot an image including 3D information.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples, unless it goes beyond the spirit. In addition, unless otherwise specified, "part" and "%" are based on mass.

<Preparation of composition>

(Composition 1; Example 1)

9.0 parts by mass of resin A1, 2.0 parts by mass of coloring material D1, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 1.5 parts by mass of photopolymerization initiator, and propylene glycol as a solvent Colmonomethyl ether acetate (PGMEA) was mixed with 86.0 parts by mass, stirred, and then filtered through a nylon filter (made by Nippon Paul Co., Ltd.) having a pore diameter of 0.5 µm to obtain composition 1.

(Composition 2; Example 2)

Composition 2 was obtained in the same manner as in Composition 1, except that the coloring material D2 was used instead of the coloring material D1.

(Composition 3; Example 3)

Composition 3 was obtained in the same manner as in Composition 1, except that the coloring material D3 was used instead of the coloring material D1.

(Composition 4; Example 4)

Resin A2 is 9.0 parts by mass, color material D4 is 2.0 parts by mass, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 1.5 parts by mass of a photopolymerization initiator, PGMEA of 86.0 as a solvent. After mixing and stirring parts by mass, a filter made of nylon (made by Nippon Paul Co., Ltd.) having a pore diameter of 0.5 µm was filtered to obtain composition 4.

(Composition 5; Example 5)

9.0 parts by mass of resin A2, 0.5 parts by mass of coloring material D5, 1.5 parts by mass of coloring material D3, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable compound, and 1.5 parts by mass of photopolymerization initiator 86.0 parts by mass of PGMEA as a part and a solvent were mixed and stirred, followed by filtration through a nylon filter (manufactured by Nippon Paul Co., Ltd.) having a pore diameter of 0.5 µm to obtain composition 5.

(Composition 6; Example 6)

8.0 mass parts of resin A1, 1.0 mass parts of resin A3, 2.0 mass parts of coloring material D1, 1.5 mass parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 1.5 mass parts of photopolymerization initiator 70.0 parts by mass of parts, PGMEA, and 16.0 parts by mass of methylene chloride were mixed and stirred, followed by filtration through a nylon filter (made by Nippon Paul Co., Ltd.) having a pore diameter of 0.5 µm to obtain composition 6.

(Composition 7; Example 7)

8.0 mass parts of resin A1, 1.0 mass parts of resin A4, 2.0 mass parts of color material D3, 0.2 mass parts of color material D7, and 1.5 mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound 1.5 parts by weight of the part and a photopolymerization initiator and 86.0 parts by weight of PGMEA were mixed and stirred, followed by filtration through a nylon filter (made by Nippon Paul Co., Ltd.) having a pore diameter of 0.5 µm to obtain composition 7.

(Composition 8; Comparative Example 1)

A composition 8 was obtained in the same manner as in composition 1, except that the coloring material D6 was used instead of the coloring material D1.

(Composition 9; Comparative Example 2)

Composition 9 was obtained in the same manner as in Composition 8, except that the content of the colorant D6 was changed to 0.5 parts by mass.

(Composition 10; Comparative Example 3)

600.0g of black pigment (Irgaphor Black S0100CF manufactured by BASF), and acrylic resin A (methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30, Mw=10,000, acid value=110mgKOH/g)) A 35 mass% solution of propylene glycol monomethyl ether acetate of 321.4 g, a dispersant (BYK21116; manufactured by BIC Chemie) 93.8 g, and propylene glycol monomethyl ether acetate (PGMEA) of 1984.8 g in a tank. The mixture was added and stirred for 1 hour with a homo mixer (Tokushu Gikaze) to obtain a preliminary dispersion 1. Thereafter, a pre-dispersion solution 1 was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 70% zirconia beads (made of Toray) having a diameter of 0.10 mm, and rotated at 8 m/s for 2 hours Dispersion was performed to obtain a black pigment dispersion 1 having a solid content concentration of 25% by mass and a pigment/resin (mass ratio)=80/20.

To PGMEA 29.52 g, 0.38 g of Adeka Acles (registered trademark) NCI-831 as a photopolymerization initiator was added and stirred until the solid content dissolved. Further, PGMEA 35 mass% solution of acrylic resin A is 16.03 g, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 3.38 g as a polymerizable compound, and propylene glycol monomethyl ether of silicone surfactant BYK333 as a surfactant. 0.24 g of a 10% by mass acetate (PMA) solution was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. Composition 10 was prepared by adding 10.46 g of black pigment dispersion 1 to this photosensitive resist.

Color materials D1 to D7: compounds of the following structure. D1, D3, and D4 are near-infrared transmission black color materials made of a dye compound having a crosslinkable group. D2 is a dye multimer formed by polymerizing D1 (n in the formula is 5, Mw=3000). D5 is a red colorant composed of a dye compound having a crosslinkable group. D6 is a near-infrared transmission black color material which consists of a dye compound which does not have a crosslinkable group. The coloring materials D1 to D7 are compounds that dissolve 3 g or more in 100 g of propylene glycol monomethyl ether acetate at 23°C.

[Formula 18]

Resin A1: Resin having the following structure (Mw=40,000). The figures added to the main chain are molar ratios.

Resin A2: Resin having the following structure (Mw=14,000). The figures added to the main chain are molar ratios.

Resin A3: ARTON F4520 (made by JSR Corporation, norbornene resin)

Resin A4: Mapruof G-0150M (manufactured by Nichiyu Co., Ltd., methacrylic acid glycidyl skeleton random polymer)

[Formula 19]

Photopolymerization initiator: a compound having the structure

[Formula 20]

[Measurement of absorbance]

Each composition was spin-coated on a glass substrate so that the film thickness after post-baking was 1.1 µm, and dried by heating at 100° C. for 120 seconds using a hot plate. After drying, it was further heated (post-baked) at 220° C. for 300 seconds using a hot plate to form a cured film. Using the ultraviolet visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi Hi-Technologies), the glass substrate on which the cured film is formed is a transmittance in the range of 300 to 1300 nm in wavelength and a minimum value of absorbance in the range of 400 to 700 nm in wavelength A , The maximum value B of absorbance in the range of wavelengths 1100 to 1300 nm was measured. The values of the spectral properties A/B of each composition are shown in the table below.

[Pattern formation]

Each composition was spin-coated on a silicon wafer so that the film thickness after post-baking was 1.1 µm, and dried by heating at 100° C. for 120 seconds using a hot plate. Then, i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), using a photomask which is a square pixel pattern of 1.1μm everywhere formed 50mJ / in ^{cm 2 750mJ / cm 2 50mJ /} cm 2 by using By increasing each, the optimum exposure amount for resolving the square pixel pattern was determined, and exposure was performed at this optimal exposure amount. Thereafter, the silicon wafer on which the exposed coating film was formed was placed on a horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemtronics Co., Ltd.), and CD-2060 (aqueous solution of tetramethylammonium hydroxide) , Puddle development at 23° C. for 60 seconds using Fujifilm Electronics Materials Co., Ltd. to form a pattern on the silicon wafer. The patterned silicon wafer was rinsed with pure water and then spin dried. Subsequently, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 220°C to obtain a silicon wafer (infrared transmission filter) having a pattern.

<Evaluation of solvent resistance>

The infrared transmission filter was immersed in PGMEA for 300 seconds, and the transmittance (unit %) of light having a wavelength of 400 to 700 nm before and after immersion in PGMEA was measured to obtain a change in transmittance by the following equation. In addition, the change in transmittance was evaluated as the transmittance at the wavelength where the change in transmittance before and after immersion in PGMEA was the largest.

Change in transmittance=|(Transmittance after immersion in PGMEA(%)-Transmittance before immersion in PGMEA(%))|

The solvent resistance was evaluated according to the following criteria.

3: Change in transmittance before and after immersion is less than 3%

2: Change in transmittance before and after immersion is 3% or more and less than 5%.

1: Change in transmittance before and after immersion is 5% or more

<Pattern resolution (pattern formability)>

The obtained pattern shape was evaluated according to the following criteria.

3: A clear square shape can be recognized.

2: can recognize a square shape

1: The shape is broken

<spectral recognition>

The obtained infrared transmission filter was introduced into a solid-state imaging element according to a known method. The resulting solid-state imaging device was irradiated with a near-infrared LED (light emitting diode) light source with a light emission wavelength of 940 nm in a low-light environment (0.001 Lux), and images were read to compare and evaluate image performance.

Spectroscopic recognition was evaluated according to the following criteria.

3: The subject can be reliably recognized on a good image.

2: The subject can be recognized on a slightly good image.

1: The subject cannot be recognized on an insufficient image.

[Table 1]

As shown in the above table, the examples were excellent in pattern resolution and solvent resistance. Moreover, the infrared transmission filter formed using the composition of the Example had good spectral recognition. On the other hand, in the comparative example, at least one of solvent resistance or pattern resolution was inferior.

In Example 1, the same effect can be obtained by using the crosslinkable dye of the dye skeleton of the perylene compound, azo compound, or bisbenzofuranone compound instead of the colorant D1.

100: infrared sensor
110: solid-state imaging element
111: infrared cut filter
112: color filter
113: infrared transmission filter
114: area (resin layer)
115: micro lens
116: planarization layer
hν: incident light

Claims (13)

As a composition comprising a near-infrared transmission black color material, a curable compound, and a solvent,
The near-infrared transmission black color material contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound,
The crosslinkable group of the dye compound is at least one selected from epoxy groups and alkoxysilyl groups,
A/B which is the ratio of the minimum value A of the absorbance in the range of the wavelength of 400 to 700 nm of the composition and the maximum value B of the absorbance in the range of the wavelength of 1100 to 1300 nm is 4.5 or more. As a composition comprising a near-infrared transmission black color material, a curable compound, and a solvent,
The near-infrared transmission black color material contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound,
The content of the near-infrared transmission black color material is 1 to 60% by mass of the total solids of the composition,
A/B which is the ratio of the minimum value A of the absorbance in the range of the wavelength of 400 to 700 nm of the composition and the maximum value B of the absorbance in the range of the wavelength of 1100 to 1300 nm is 4.5 or more. The method according to claim 1,
The crosslinkable group of the dye compound is an epoxy group. The method according to claim 2,
The crosslinkable group possessed by the dye compound is at least one selected from a group having an ethylenically unsaturated bond, an epoxy group, and an alkoxysilyl group. The method according to any one of claims 1 to 4,
The dye compound having a crosslinkable group is at least one selected from xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds. The method according to any one of claims 1 to 4,
The dye compound having the crosslinkable group is a xanthene compound. The method according to any one of claims 1 to 4,
The dye multimer, a composition in which a structure derived from the dye compound is bonded to two or more linking groups. The method according to any one of claims 1 to 4,
The dye multimer has a repeating unit having a structure derived from the dye compound. The method according to any one of claims 1 to 4,
The composition further comprises a chromatic colorant. A cured film obtained by curing the composition according to claim 1. An infrared transmission filter having the cured film according to claim 10. A solid-state imaging device having the cured film according to claim 10. An infrared sensor having the cured film according to claim 10.

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