JPWO2020017187A1 - Photosensitive composition, infrared light cut filter, solid-state image sensor - Google Patents

Abstract

Provided are a photosensitive composition capable of forming a pattern having an excellent rectangular cross-sectional shape and a cured film having an excellent heat resistance, an infrared light cut filter, and a solid-state image sensor. The photosensitive composition is a photosensitive composition containing metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor, and absorbs ultraviolet rays with respect to the content of the polymerization inhibitor. The mass ratio of the content of the agent is 0.08 to 330.

Description

The present invention relates to a photosensitive composition, an infrared light cut filter, and a solid-state image sensor.

A solid-state image sensor for a color image is used in a video camera, a digital still camera, a mobile phone with a camera function, and the like. Since these solid-state image sensors use a silicon photodiode that is sensitive to infrared rays (infrared light) in the light receiving portion, it is necessary to correct the luminosity factor, and an infrared light cut filter is used. There are many.

Patent Document 1 discloses a photosensitive composition containing a predetermined tungsten oxide and / or composite tungsten oxide as a composition for forming an infrared light cut filter.

International Publication No. 2011/067998

When forming a pattern using a photosensitive composition, it is required that the cross-sectional shape of the pattern is excellent in rectangularity.

Further, the cured film formed by using the photosensitive composition is required to be less likely to change in transmittance even after being heat-treated. In particular, even when various color filters and the cured film are arranged adjacent to each other, it is desirable that the change in transmittance is unlikely to occur after the heat treatment. Hereinafter, the fact that the transmittance does not easily change after heat treatment is said to be excellent in heat resistance.

When the present inventors evaluated the above characteristics using the photosensitive composition described in Patent Document 1, they could not satisfy both characteristics in a well-balanced manner.

In view of the above circumstances, it is an object of the present invention to provide a photosensitive composition capable of forming a pattern having excellent rectangular cross-sectional shape and forming a cured film having excellent heat resistance.

Another object of the present invention is to provide an infrared light cut filter formed by using a photosensitive composition and a solid-state image sensor including an infrared light cut filter.

As a result of diligent studies on the problems of the prior art, the present inventors have found that the above problems can be solved by the following configurations.

(1) A photosensitive composition containing metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor.

A photosensitive composition in which the mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330.

(2) The photosensitive composition according to (1), wherein the surface of the metal-containing tungsten oxide particles is coated with a metal oxide.

(3) The photosensitive composition according to (2), wherein the metal oxide is an oxide containing at least one element selected from the group consisting of Si, Ti, Zr, and Al.

(4) The ultraviolet absorber is an ultraviolet absorber having a mass reduction rate of 5% or less at 150 ° C. and a mass reduction rate of 40% or more at 220 ° C. in thermogravimetric analysis (1) to The photosensitive composition according to any one of (3).

(5) The photosensitive composition according to any one of (1) to (4), wherein the ultraviolet absorber is at least one selected from a dibenzoylmethane-based compound and an aminobutadiene-based compound.

(6) The photosensitive composition according to any one of (1) to (5), which contains two or more kinds of polymerization inhibitors.

(7) The polymerization inhibitor is at least two or more selected from the group consisting of hindered phenol-based compounds, phenol-based compounds other than hindered phenol-based compounds, benzoquinone-based compounds, and hydroquinone-based compounds (6). ). The photosensitive composition.

(8) One or more first polymerization inhibitors selected from the group consisting of hindered phenol-based compounds, benzoquinone-based compounds, and hydroquinone-based compounds, and phenol-based agents other than hindered phenol-based compounds. The photosensitive composition according to (7), which comprises a compound.

(9) The photosensitive composition according to (8), wherein the mass ratio of the content of the phenolic compound other than the hindered phenolic compound to the total content of the first polymerization inhibitor is 0.0009 to 0.17. Stuff.

(10) The photosensitive composition according to any one of (1) to (9), further comprising an alkali-soluble binder having a double bond group.

(11) An infrared light cut filter formed by using the photosensitive composition according to any one of (1) to (10).

(12) A solid-state image sensor including the infrared light cut filter according to (11).

According to the present invention, it is possible to provide a photosensitive composition capable of forming a pattern having an excellent rectangular cross-sectional shape and forming a cured film having an excellent heat resistance.

Further, according to the present invention, it is also possible to provide an infrared light cut filter formed by using a photosensitive composition and a solid-state image sensor including an infrared light cut filter.

It is schematic cross-sectional view which shows the structure of one Embodiment of the solid-state image sensor of this invention. It is a functional block diagram of the image pickup apparatus to which the solid-state image sensor of this invention was applied. It is a figure for demonstrating the pattern rectangularness evaluation.

Hereinafter, preferred embodiments of the photosensitive composition of the present invention, an infrared light cut filter, and a solid-state image sensor will be described in detail.

In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl.

Further, in the present specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.

In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. A polymerizable functional group is a group involved in a polymerization reaction.

In the present specification, the total solid content means the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is the solid content at 25 ° C.

First, a feature of the present invention is that the mass ratio of the ultraviolet absorber and the polymerization inhibitor is adjusted. By adjusting the mass ratio to a predetermined range, it has been found that heat resistance and pattern rectangularity (rectangularity of the formed pattern) can be compatible with each other in a better balance.

The photosensitive composition contains metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor.

Hereinafter, each component contained in the photosensitive composition (hereinafter, also simply referred to as “composition”) will be described in detail.

(Metal-containing tungsten oxide particles)

The metal-containing tungsten oxide particles (hereinafter, also referred to as “specific particles”) are tungsten oxide particles containing metal atoms.

The specific particles selectively block infrared light (light having a wavelength of about 800 to 1200 nm) depending on the crystal structure, and thus have an effect as an infrared absorber. Therefore, the infrared light cut filter containing specific particles has high light-shielding property in the infrared region and high translucency in the visible light region.

In addition, the specific particles absorb less light than the visible region used for exposure such as high-pressure mercury lamp, KrF, and ArF used for image formation. Therefore, as will be described later, the photosensitive composition of the present invention has excellent pattern forming properties, and the shape of the infrared light cut filter can be finely controlled.

The type of metal atom contained in the specific particle is not particularly limited, but an alkali metal can be mentioned because it is more excellent in shielding infrared light.

The specific particles are preferably represented by the following general formula (composition formula) (I).

M _x W _{y Oz} ... (I)

M represents an alkali metal, W represents tungsten, and O represents oxygen.

0.001 ≤ x / y ≤ 1.1

2.2 ≤ z / y ≤ 3.0

The alkali metal of M may be one kind or two or more kinds.

As the alkali metal of M, Rb or Cs is preferable, and Cs is more preferable.

When x / y is 0.001 or more, infrared light can be sufficiently shielded, and when it is 1.1 or less, it is possible to further avoid the formation of an impurity phase in specific particles.

When z / y is 2.2 or more, the chemical stability as a material can be further improved, and when it is 3.0 or less, infrared light can be further blocked.

Specific examples of the specific particles containing an alkali metal represented by the above general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Cs _0.33 WO ₃ or Rb _0.33 WO. ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

The surface of the metal-containing tungsten oxide particles is preferably coated with the metal oxide in that the effect of the present invention is more excellent. That is, the photosensitive composition is preferably coated particles containing the metal-containing tungsten oxide particles and the metal oxide arranged so as to cover the surface of the metal-containing tungsten oxide particles.

The type of metal oxide is not particularly limited, and is preferably an oxide containing at least one element selected from the group consisting of Si, Ti, Zr, and Al.

The metal oxide may be arranged so as to cover the entire surface of the metal-containing tungsten oxide particles, or may be arranged so as to cover a part thereof.

The average particle size of the specific particles is not particularly limited, but is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle size is in the above range, it becomes difficult for the specific particles to block visible light due to light scattering, so that the translucency in the visible light region is more excellent. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the more preferable it is.

The average particle size is measured by measuring the particle size (diameter) of at least 50 specific particles with a known electron microscope (for example, a transmission electron microscope) and arithmetically averaging them. .. If the specific particle is not a perfect circle, the major axis is measured as the particle diameter.

The content of the specific particles in the photosensitive composition is not particularly limited, but is preferably 1 to 20% by mass, preferably 3 to 15% by mass, based on the total mass of the photosensitive composition in that the infrared light shielding property is more excellent. More preferably by mass.

Further, it is possible to use two or more kinds of specific particles, and in that case, the total content is preferably in the above range.

Although the specific particles are available as commercial products, they can be obtained by a method of heat-treating a tungsten compound containing an alkali metal in an inert gas atmosphere or a reducing gas atmosphere (see Patent No. 4096205).

It is also available as a dispersion of fine particles of tungsten oxide containing an alkali metal such as YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.

(Polymerizable compound)

As the polymerizable compound, any compound having a polymerizable group (a group that reacts with at least one of an acid, a radical, and heat) in the molecule may be used, and a plurality of polymerizable groups in the molecule may be used. A polyfunctional polymerizable compound having the above is preferable.

Examples of the polymerizable compound having a polymerizable group that reacts with at least one of an acid, a radical, and heat include an unsaturated ester functional group (for example, an acryloyl group and a methacryloyl group), an unsaturated amide group, and a vinyl ether group. Examples thereof include an ethylenically unsaturated group-containing compound having an ethylenically unsaturated group such as an allyl group; a methylol compound; a bismaleimide compound; a benzocyclobutene compound; a bisallyl nadiimide compound; and a benzoxazine compound.

The polymerizable compound may be a monomer or a polymer.

As the polymerizable compound, a radically polymerizable compound is preferable, and a compound having an ethylenically unsaturated double bond is more preferable.

Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters thereof, and amides thereof, and is unsaturated. Preferably, an ester of a carboxylic acid ester, an ester of an unsaturated carboxylic acid and an aliphatic polyvalent alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound.

In particular, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound can exhibit high hydrophobicity in an exposed portion, so that a pattern having a desired shape can be easily formed by alkaline development, and a highly durable pattern can be easily formed. Is preferable in that

The polymerizable compound is an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, and a mercapto group, and a monofunctional or polyfunctional isocyanate or an epoxy. Can be mentioned.

Further, examples of the polymerizable compound include a dehydration condensation reaction product of the unsaturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid.

Examples of unsaturated carboxylic acid esters include methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, and maleic acid ester.

As the polymerizable compound, a urethane-based addition-polymerizable compound produced by using an addition reaction between isocyanate and a hydroxyl group is also suitable, and specific examples thereof are described in, for example, Japanese Patent Publication No. 48-41708. Two or more polymerizable vinyl groups are added to one molecule in which a vinyl monomer having a hydroxyl group represented by the following general formula (E) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. Examples thereof include vinyl urethane compounds contained.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (E)

[However, R ⁴ and R ⁵ independently indicate H or CH _{3, respectively.} ]

The number of ethylenically unsaturated double bonds in the radically polymerizable compound is not particularly limited, and from the viewpoint of curing sensitivity, 2 or more are preferable, 3 or more are more preferable, and 4 or more are further preferable. The upper limit is not particularly limited, but in many cases, the number is 10 or less.

Further, from the viewpoint of curing sensitivity and developability of the unexposed portion, the polymerizable compound is preferably a polymerizable compound containing an EO (ethylene oxide) modified product.

Further, from the viewpoint of curing sensitivity and the strength of the exposed portion, the polymerizable compound is preferably a compound containing a urethane bond.

Further, from the viewpoint of developability at the time of pattern formation, the polymerizable compound is preferably a compound having an acid group.

Examples of the polymerizable compound include bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropanetri (acryloyloxypropyl) ether, trimethylol ethanetriacrylate, tetraethylene glycol diacrylate, and pentaerythritol. Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyl) Oxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, tricyclodecanedimethanol diacrylate and the like.

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Alternatively, a modified dipentaerythritol hexaacrylate EO is preferable.

Commercially available products include urethane oligomers UAS-10, UAB-140 (above, manufactured by Sanyo Kokusaku Pulp Co., Ltd.), KAYARAD RP-1040, DPHA-40H, KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DPCA-20 (above, Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), NK ester A-BPE- 20, A-DCP, NK Ester A-TMMT, NK Ester A-DPH-12E (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), TO-756, TO-1382, M-305, Aronix M-510 (above, Toa) Examples thereof include Ogsol EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.).

The content of the polymerizable compound in the photosensitive composition is not particularly limited, but is preferably 1 to 20% by mass with respect to the total mass of the photosensitive composition in that the strength of the infrared light cut filter is more excellent. More preferably, 10% by mass.

The polymerizable compound may be used alone or in combination of two or more. Among them, it is preferable to use two or more kinds in combination because the pattern rectangularity is more excellent.

(Polymerization initiator)

Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferable.

The photopolymerization initiator is a compound having an ability to initiate polymerization by being exposed to light, and is preferably photosensitive from an ultraviolet light region to a visible light region.

The thermal polymerization initiator is a compound having an ability to initiate polymerization by heat, and an initiator that decomposes at 150 to 250 ° C. is preferable.

As the polymerization initiator, a compound having at least an aromatic group is preferable, and for example, an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a thioxanthone compound, an oxime compound, a hexaarylbiimidazole compound, and a trihalo Examples thereof include methyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, onium salt compounds, organic boron salt compounds, and disulfone compounds.

From the viewpoint of sensitivity, an oxime compound, a hydroxyacetophenone compound, an aminoacetophenone compound, an acylphosphine compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, or a thiol compound is preferable, and an oxime compound is more preferable.

Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF).

Examples of the aminoacetophenone compound include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF).

Examples of the acylphosphine compound include IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF).

Examples of the oxime compound include IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)]) and IRGACURE OXE 02 (etanon, 1- [9-]). Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (o-acetyloxime)), IRGACUREOXE03 (trade name: manufactured by BASF), IRGACUREOXE04 (trade name: manufactured by BASF) Can be mentioned.

Examples of the oxime compound include the formulas (OX-1), (OX-2) or (OX-1) after paragraph 0513 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099 <0632>). The description of the compound represented by OX-3) can be taken into consideration, and these contents are incorporated in the present specification.

Examples of the oxime compound include polymerization initiators described in paragraphs 0092 to 0906 of JP2012-113104A, and these contents are incorporated in the present specification.

Commercially available oxime compounds include TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD). ) Made).

The content of the polymerization initiator in the photosensitive composition is not particularly limited, but is preferably 0.1 to 10% by mass, preferably 0.5 to 10% by mass, based on the total mass of the photosensitive composition in terms of excellent drying resistance. 5.0% by mass is more preferable.

The polymerization initiator may be used alone or in combination of two or more.

(Polymerization inhibitor)

Examples of the polymerization inhibitor include known polymerization inhibitors. It is presumed that the polymerization inhibitor has a function of capturing radicals generated when a color filter arranged adjacent to the cured layer is heat-treated.

For example, phenolic compounds, hindered amine compounds, phosphorus compounds, and phenothiazine compounds can be mentioned.

Among them, a hindered phenol-based compound, a phenol-based compound other than the hindered phenol-based compound, a benzoquinone-based compound, or a hydroquinone-based compound is preferable because the effect of the present invention is more excellent.

The hindered phenolic compound is a phenolic compound having a substituent other than a hydrogen atom at at least one of the two ortho positions of the phenolic hydroxyl group. Examples of the substituent include an alkyl group (preferably an alkyl group other than a methyl group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, a substituted amino group and a thioalkyl group. Groups include groups, thiophenyl groups, and halogen atoms.

As the hindered phenolic compound, a compound represented by the formula (X) is preferable.

In formula (X), R ¹ and R ² each independently represent a substituent. The definition of the substituent is as described above, and among them, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group is preferable, and an alkyl group having 4 or more carbon atoms is more preferable.

R ³ represents a substituent. The definition of the substituent is as described above, and among them, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group is preferable, and an alkyl group is preferable. When n is 2 or more, the plurality of R ^3s may be the same or different.

n represents an integer from 0 to 3. Of these, 1 is preferable.

As the phenolic compound other than the hindered phenolic compound, the compound represented by the formula (Y) is preferable.

In formula (Y), R ⁴ represents a substituent. The definition of the substituent is as described above, and among them, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an alkoxy group is preferable, and an alkoxy group is more preferable.

m represents an integer from 0 to 3. Of these, 1 is preferable.

As the benzoquinone compound, the compound represented by the formula (Z) is preferable.

In formula (Z), R ^{5 to} R ⁸ each independently represent a hydrogen atom or a substituent. The definition of the substituent is as described above, and among them, an aryl group, an amino group, a substituted amino group, or a halogen atom is preferable.

Examples of benzoquinone compounds include ortho-benzoquinone and para-benzoquinone.

As the hydroquinone-based compound, a compound represented by the formula (V) is preferable.

In formula (V), R ⁹ represents a substituent. The definition of the substituent is as described above, and among them, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an alkoxy group is preferable, and an alkyl group is more preferable. When p is 2 or more, the plurality of R ^9s may be the same or different.

p represents an integer from 0 to 4. Of these, 1 is preferable.

The polymerization inhibitor may be used alone or in combination of two or more. Among them, the photosensitive composition preferably contains two or more kinds of polymerization inhibitors because the effect of the present invention is more excellent.

When the photosensitive composition contains two or more kinds of polymerization inhibitors, the polymerization inhibitor comprises a hindered phenol-based compound, a phenol-based compound other than the hindered phenol-based compound, a benzoquinone-based compound, and a hydroquinone-based compound. It is preferably at least two or more selected from the group.

Further, in that the effect of the present invention is more excellent, the polymerization inhibitor includes one or more first polymerization inhibitor selected from the group consisting of a hindered phenolic compound, a benzoquinone compound, and a hydroquinone compound, and hindered. It is preferable to include a phenolic compound other than the phenolic compound.

Further, the mass ratio of the content of the phenolic compound other than the hindered phenolic compound to the total content of the first polymerization inhibitor is not particularly limited, but the effect of the present invention is more excellent, and it is 0.0009 to 0. It is preferably .17.

The content of the polymerization inhibitor in the photosensitive composition is not particularly limited, but 0.0001 to 0.30% by mass is preferable with respect to the total mass of the photosensitive composition in that the effect of the present invention is more excellent. More preferably 0.002 to 0.20% by mass.

(UV absorber)

The ultraviolet absorber refers to an agent that does not have a function of initiating the polymerization of a polymerizable compound by light or heat (that is, does not correspond to a polymerization initiator). Here, "does not have a function of initiating the polymerization of the polymerizable compound" means that the ultraviolet absorber substantially starts the polymerization of the polymerizable compound even when it receives the energy of light or heat. It means that it does not generate active species.

It is preferable that the ultraviolet absorber does not have the function of initiating the polymerization of the polymerizable compound and also does not have the characteristics of the sensitizer described later. Here, the property of the sensitizer refers to the property of initiating polymerization by passing the energy obtained by absorbing light to another substance (polymerization initiator or the like).

The ultraviolet absorber preferably has a maximum absorption wavelength in the wavelength range of 300 to 430 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 330 to 420 nm.

The UV absorber has a maximum absorption wavelength in at least one of (I) a wavelength range of 340 to 380 nm, (II) a wavelength range of 380 to 420 nm, and (III) a wavelength range of 420 to 450 nm. It is more preferable to have.

When the thermogravimetric analysis of the ultraviolet absorber is performed, the mass reduction rate at 150 ° C. is preferably 5% or less, more preferably 3% or less. The lower limit is not particularly limited, but 0% can be mentioned. When the mass reduction rate at 150 ° C. is within the above range, the ultraviolet absorber is less likely to be decomposed during the exposure described later, and the function as the ultraviolet absorber is likely to be exhibited.

Further, when the thermogravimetric analysis of the ultraviolet absorber is performed, the mass reduction rate at 220 ° C. is preferably 40% or more, more preferably more than 40%, still more preferably 70% or more. The upper limit is not particularly limited, but 100% can be mentioned. When the mass reduction rate at 220 ° C. is within the above range, the ultraviolet absorber is decomposed during the heat treatment performed after the exposure, and the coloring derived from the ultraviolet absorber is suppressed.

The conditions for measuring the thermogravimetric analysis of the ultraviolet absorber are as follows.

That is, in an atmosphere of nitrogen gas, the temperature of the ultraviolet absorber is raised from 25 ° C. to 100 ° C. under the condition of a temperature rising rate of 10 ° C./min. After holding at 100 ° C. for 30 minutes, the ultraviolet absorber is heated to 220 ° C. at a heating rate of 10 ° C./min and held at 220 ° C. for 30 minutes.

When the UV absorber is held at 100 ° C. for 30 minutes, the average value of the mass of the UV absorber 24 to 29 minutes from the start of holding is set as the reference value (100%) of the mass of the UV absorber, and the value is at 150 ° C. and 220. The mass of the ultraviolet absorber after heating at ° C. for 30 minutes is measured, and the mass reduction rate is calculated based on the following formula.

Mass reduction rate at 150 ° C. (%) = 100- (standard value of mass of UV absorber / mass of UV absorber at 150 ° C) x 100

Mass reduction rate at 220 ° C. (%) = 100- (standard value of mass of UV absorber / mass of UV absorber after 30 minutes at 220 ° C.) x 100

The type of the ultraviolet absorber is not particularly limited, and examples thereof include dibenzoylmethane compounds, aminobutadiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, substituted acrylonitrile compounds, and triazi compounds. Of these, dibenzoylmethane-based compounds or aminobutadiene-based compounds are preferable.

Examples of the dibenzoylmethane compound (dibenzoylmethane ultraviolet absorber) include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4. -Dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane (abobenzon) ), 2-Methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, and 2,4-dimethyl-4'-methoxydibenzoyl. Examples include methane, 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.

Examples of the aminobutadiene compound (aminobutadiene ultraviolet absorber) include a compound having a partial structure represented by the formula (1). In equation (1), * represents the bond position.

Examples of the salicylate compound (salicylate-based ultraviolet absorber) include phenylsalicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate.

Examples of benzophenone compounds (benzophenone-based ultraviolet absorbers) include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-. Examples include tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone.

Examples of the benzotriazole-based compound (benzotriazole-based ultraviolet absorber) include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy). -3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole , 2- (2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- [2'- Hydroxy-5'-(1,1,3,3-tetramethyl) phenyl] benzotriazole can be mentioned.

Examples of the substituted acrylonitrile-based compound (substituted acrylonitrile-based ultraviolet absorber) include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

Examples of triazine-based compounds (triazine-based ultraviolet absorbers) include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and other mono (hydroxyphenyl) triazine Compounds; 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-3) Methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- ( Bis (hydroxyphenyl) triazine compounds such as 2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxy) Phenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy- Examples thereof include tris (hydroxyphenyl) triazine compounds such as 4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.

In addition to the above, a diethylamino-phenylsulfonyl-pentadienoate-based ultraviolet absorber (manufactured by FUJIFILM Fine Chemicals, trade name: DPO) can also be mentioned.

Further, compounds represented by any of the general formulas (1) to (8) after paragraph 0103 of Japanese Patent Application Laid-Open No. 2012-32556 (corresponding to page 30 of WO2012 / 015076) and specific examples thereof. (1-1) to (8-3) can be taken into consideration, and these contents are incorporated in the present specification.

The content of the ultraviolet absorber in the photosensitive composition is not particularly limited, but is preferably 0.01 to 10.0% by mass, preferably 0.05 to 1.50% by mass, based on the total mass of the photosensitive composition. More preferred.

The ultraviolet absorber may be used alone or in combination of two or more.

In the photosensitive composition, the mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330, and 0.1 to 200 is in that the effect of the present invention is more excellent. Preferably, 3 to 30 is more preferable. From the viewpoint of excellent rectangularness, 20 or more is more preferable.

The photosensitive composition may contain components other than those described above, such as resin binders, sensitizers, solvents, surfactants, dispersants, cross-linking agents, and curing accelerators. Can be mentioned.

Hereinafter, each component will be described in detail.

(Resin binder)

Examples of the resin binder include (meth) acrylic resin, urethane resin, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamide, polyester, polyimide, and polybenzoxazole, and the (meth) acrylic resin or , Urethane-based resin is preferable.

Further, as the resin binder, an alkali-soluble binder (alkali-soluble resin) is also preferable. When the photosensitive composition contains an alkali-soluble binder, when the coating film obtained from the photosensitive composition is exposed, the unexposed portion can be easily removed with an alkali developer.

Examples of the alkali-soluble binder include (meth) acrylic resin, urethane resin, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamide, polyester, polyimide or its precursor, and polybenzoxazole or its precursor. , (Meta) acrylic resin or urethane resin is preferable.

As the polyimide or its precursor, and polybenzoxazole or its precursor, the polyimide resin described in paragraphs 0012 to 0046 of WO2011 / 067998 and paragraphs 0020 to 0054 of JP2013-050593A. The explanations of the above can be taken into consideration, and these contents are incorporated in the specification of the present application.

The alkali-soluble binder preferably has an acid group.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonic acid group, and a carboxylic acid group is preferable from the viewpoint of obtaining a raw material.

As the alkali-soluble binder having an acid group, a polymer obtained by using a polymerizable compound having an acid group is preferable, and from the viewpoint of adjusting the acid value, the polymerizable compound having an acid group and the polymer having no acid group are not present. A copolymer obtained by copolymerizing with a polymerizable compound is more preferable.

Examples of the polymerizable compound having an acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, and p-carboxystyrene, and acrylic acid, methacrylic acid, or p. -Carboxyrene is preferred.

Polymerizable compounds having no acid group include, for example, (meth) acrylic acid esters (alkyl esters, aryl esters, aralkyl esters, etc.).

The alkyl group at the alkyl ester moiety of the (meth) acrylic acid ester may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl having 1 to 6 carbon atoms. Groups are more preferred.

As the aryl group in the aryl ester moiety of the (meth) acrylic acid ester, an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.

As the aralkyl group in the aralkyl ester moiety of the (meth) acrylic acid ester, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 12 carbon atoms is more preferable.

The content of the acid group in the alkali-soluble binder is not particularly limited, but is preferably 0.5 to 4.0 meq / g, preferably 0.5 to 3.0 meq, from the viewpoint of alkali developability and the strength of the obtained cured film. / G is more preferable.

The alkali-soluble binder preferably further has a crosslinkable group. As a result, both the curability of the exposed portion and the alkali developability of the unexposed portion can be improved, and a highly durable pattern can be obtained.

The crosslinkable group is a group that crosslinks the resin binder in the process of the polymerization reaction that occurs in the coating film when the coating film obtained from the photosensitive composition is exposed or heated. Examples of the crosslinkable group include a polymerizable group (for example, an ethylenically unsaturated group as a functional group capable of an addition polymerization reaction), an amino group, an epoxy group and the like. Of these, a double bond group is preferable, and an ethylenically unsaturated double bond group is more preferable.

Further, the crosslinkable group may be a functional group that can become a radical by light irradiation, and examples thereof include a thiol group and a halogen group.

Of these, the crosslinkable group is preferably an ethylenically unsaturated double bond group. As the ethylenically unsaturated double bond group, a styryl group, a (meth) acryloyl group, or an allyl group is preferable, and a (meth) acryloyl group is more preferable.

The content of the crosslinkable group in the alkali-soluble binder is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g, and 1.5 to 2.8 meq. / G is particularly preferable.

Here, the content (meq / g) can be measured by, for example, iodine value titration.

The alkali-soluble binder having a crosslinkable group is described in detail in Japanese Patent Application Laid-Open No. 2003-262958, and the compound described therein can also be used in the present invention.

As one of the preferred embodiments of the alkali-soluble binder, a polymer obtained by polymerizing a monomer component containing a compound represented by the following general formula (ED) (hereinafter, also referred to as "ether dimer") (hereinafter, "" Also referred to as "specific polymer"). If a specific polymer is used, the pattern forming property of the infrared light cut filter is more excellent.

In the general formula (ED), R ₁ and R ₂ represent hydrocarbon groups having 1 to 25 carbon atoms, which may have hydrogen atoms or substituents, respectively.

The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is a linear or branched alkyl group; an aryl group; an alicyclic group; an alkoxy. Examples include an alkyl group substituted with a group; an alkyl group substituted with an aryl group such as benzyl; and the like.

Of these, a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group is preferable because the substituent has excellent heat resistance.

Specific examples of the ether dimer include the specific examples of the ether dimer described in paragraph 0565 of JP2012-208494A (paragraph 0694 of the corresponding US Patent Application Publication No. 2012/235099). The content is incorporated herein by reference.

Among them, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (Methylene)] bis-2-propenoate or dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate is preferable.

These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

The content of the repeating unit derived from the ether dimer in the specific polymer is preferably 1 to 50 mol%, more preferably 1 to 20 mol%, based on all the repeating units in the alkali-soluble binder.

Other monomers may be copolymerized with the ether dimer.

Examples of other monomers include a monomer for introducing an acid group, a monomer for introducing a radically polymerizable double bond, a monomer for introducing an epoxy group, and these. Other copolymerizable monomers include.

As such a monomer, only one kind may be used, or two or more kinds may be used.

Examples of the monomer for introducing an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, and maleic anhydride. And monomers having a carboxylic anhydride group such as itaconic anhydride. Of these, (meth) acrylic acid is preferable.

Further, the monomer for introducing an acid group may be a monomer capable of imparting an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. Examples thereof include a monomer having an epoxy group such as glycidyl (meth) acrylate and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate.

When a monomer capable of imparting an acid group after polymerization is used, it is necessary to carry out a treatment for imparting an acid group after polymerization. As a treatment for imparting an acid group after polymerization, for example, when a monomer having a hydroxyl group is used, an acid anhydride of succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride is added. Processing can be mentioned.

When the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an acid group, the content of the monomer for introducing an acid group is the monomer component. It is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass.

Examples of the monomer for introducing a radically polymerizable double bond include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; and a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Monomers having: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and o- (or m-, or p-) vinylbenzyl glycidyl ether;

When a monomer for introducing a radically polymerizable double bond is used, it is necessary to carry out a treatment for imparting a radically polymerizable double bond after the polymerization. As the treatment for imparting a radically polymerizable double bond after the polymerization, for example, when a monomer having a carboxyl group is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and , O- (or m-, or p-) vinylbenzyl glycidyl ether or the like, and a treatment for adding a compound having an epoxy group and a radically polymerizable double bond.

When the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing a radically polymerizable double bond, the monomer for introducing a radically polymerizable double bond is used. The content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass of the monomer components.

Examples of the monomer for introducing the epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and o- (or m- or p-) vinylbenzyl glycidyl ether. Can be mentioned.

When the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content of the monomer for introducing an epoxy group is the monomer component. It is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass.

When the polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) contains another copolymerizable monomer, the content ratio is not particularly limited, but is 95% by mass. The following is preferable, and it is more preferable that it is 85% by mass or less.

The weight average molecular weight of the specific polymer is not particularly limited, but from the viewpoint of heat resistance of the coating film formed by the photosensitive composition, 2000 to 200,000 is preferable, 5000 to 100,000 is more preferable, and 5000 to 20000 is further preferable.

When the specific polymer has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.

As the polymerization method applied to the synthesis of the specific polymer, various conventionally known polymerization methods can be adopted, and the solution polymerization method is preferable. Specifically, for example, a weight obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) according to the method for synthesizing the polymer (a) described in JP-A-2004-300204. The coalescence can be synthesized.

Hereinafter, exemplary compounds of the specific polymer will be shown, but the present invention is not limited thereto.

The composition ratio of the exemplified compounds shown below is mol%. Examples of commercially available products include Acrycure RD-F8 (acrylic resin) (manufactured by Nippon Shokubai Co., Ltd.).

The content of the resin binder (particularly, the alkali-soluble binder) in the photosensitive composition is not particularly limited, but the intensity of the infrared light cut filter is more excellent, and the entire photosensitive composition is improved in terms of photolithography and residue improvement. It is preferably 5 to 50% by mass, more preferably 10 to 25% by mass, based on the mass.

(solvent)

The type of solvent is not particularly limited, and examples thereof include water and organic solvents.

Examples of the solvent include solvent A having a boiling point of 170 to 200 ° C. at 1 atm.

The boiling point of the solvent A is 170 to 200 ° C, preferably 180 to 193 ° C.

As one of the preferred embodiments of the solvent A, the solvent A preferably contains 3 or more oxygen atoms in the molecule, and the number of oxygen atoms is more preferably 3 to 5, and even more preferably 3.

Preferable embodiments of the solvent A include a solvent represented by the following formula (X) or formula (Y).

Equation (X) R ¹ O- (LO) _n- R ²

Equation (Y) R ¹ O- (LO) _m- CO-R ²

In formula (X) and formula (Y), R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 3 is preferable, and 1 is more preferable.

R ² represents an alkyl group. The number of carbon atoms contained in the alkyl group is preferably 1 to 3, more preferably 1.

L represents an alkylene group. The number of carbon atoms contained in the alkylene group is preferably 3 to 5, and more preferably 3.

n represents an integer of 2-4.

m represents an integer of 1 to 2.

Specific examples of the solvent A include dipropylene glycol monomethyl ether (boiling point 188 ° C.), cyclohexanol acetate (boiling point 173 ° C.), dipropylene glycol dimethyl ether (boiling point 171 ° C.), ethylene glycol monobutyl ether acetate (boiling point 192 ° C.), and diethylene glycol. Diethyl ether (boiling point 189 ° C), diethylene glycol monomethyl ether (boiling point 194 ° C), propylene glycol diacetate (boiling point 190 ° C), 3-methoxybutyl acetate (boiling point 171 ° C), propylene glycol-n-butyl ether (boiling point 170 ° C), Examples thereof include diethylene glycol ethyl methyl ether (boiling point 176 ° C.) and diethylene glycol isopropyl methyl ether (boiling point 179 ° C.).

As one of the preferred embodiments of the solvent A, it is preferable that the solvent A contains the solvent represented by the above formula (X) or the formula (Y) as a main component. The principal component is intended that the content of the solvent represented by the formula (X) or the formula (Y) is more than 50% by mass with respect to the total mass of the solvent A.

As one of the other preferred embodiments of the solvent A, it is preferable that the solvent A contains the solvent (for example, dipropylene glycol monomethyl ether) mentioned as a specific example of the solvent A as a main component. The main component is intended that the content of the solvent mentioned as a specific example of the solvent A is more than 50% by mass with respect to the total mass of the solvent A.

The content of the solvent A in the photosensitive composition is preferably 0.1 to 20% by mass, more preferably 0.3 to 5.0% by mass, based on the total mass of the photosensitive composition.

The photosensitive composition preferably contains a solvent B selected from the group consisting of a solvent B1 having a boiling point of 100 to 130 ° C. at 1 atm and a solvent B2 having a boiling point of more than 130 ° C. and less than 170 ° C. at 1 atm.

The boiling point of the solvent B1 at 1 atm is 100 to 130 ° C, preferably 120 to 130 ° C.

The boiling point of the solvent B2 at 1 atm is more than 130 ° C. and less than 170 ° C., preferably 140 to 150 ° C.

Examples of the solvent B1 include butyl acetate (boiling point 126 ° C.), ethylene glycol monomethyl ether (boiling point 125 ° C.), methyl-n-butylketone (boiling point 127 ° C.), and tetrahydrofuran (boiling point 126 ° C.).

The solvent B2 includes propylene glycol 1-monomethyl ether 2-acetylate (boiling point 145 ° C.), ethylene glycol monomethyl ether acetate (boiling point 145 ° C.), ethyl lactate (boiling point 155 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.), 3-methoxy. Butanol (boiling point 161 ° C.) and propylene glycol-n-propyl ether (boiling point 150 ° C.) can be mentioned.

The content of the solvent B in the photosensitive composition is preferably 20 to 90% by mass, more preferably 40 to 70% by mass, based on the total mass of the photosensitive composition.

The mass ratio of solvent A to solvent B (mass of solvent A / mass of solvent B) in the photosensitive composition is preferably 0.005 to 0.500, more preferably 0.010 to 0.200.

When the photosensitive composition contains the solvent B1, the content of the solvent B1 in the photosensitive composition is preferably 0.1 to 10% by mass, and 0.5 to 5% by mass, based on the total mass of the photosensitive composition. .0% by mass is more preferable.

When the photosensitive composition contains the solvent B2, the content of the solvent B1 in the photosensitive composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the photosensitive composition. preferable.

Only one type of solvent B may be used, or two or more types may be used in combination. Among them, it is preferable to use the solvent B1 and the solvent B2 in combination because the effect of the present invention is more excellent.

When the solvent B1 and the solvent B2 are used in combination, the mass ratio of the solvent B1 and the solvent B2 (mass of the solvent B1 / mass of the solvent B2) is preferably 0.005 to 0.500, preferably 0.010 to 0.200. More preferred.

(Surfactant)

The photosensitive composition may contain a surfactant from the viewpoint of further improving the coatability. Further, since the surfactant is contained in the photosensitive composition, the pattern rectangularity is more excellent.

Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant, and the fluorine-based surfactant or silicone. Surfactants are preferred.

Examples of fluorine-based surfactants include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F479. F482, F554, F780, F781, F781F (above, DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo 3M Ltd.), Surfron S-382, SC- 101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.) , PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. Further, the surfactants described in paragraph 0552 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/0235099 <0678>) and the like are mentioned, and the contents thereof are described in the present specification. Be incorporated.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerin fatty acid ester, and oxyethylene. Examples thereof include oxypropylene block copolymers, acetylene glycol-based surfactants, and acetylene-based polyoxyethylene oxides.

Examples of the cationic surfactant include the cationic surfactant described in paragraph 0554 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/0235099 <0680>). Is incorporated herein by reference.

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

Examples of the silicone-based surfactant include the silicone-based surfactants described in paragraph 0556 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/0235099 <0682>). These contents are incorporated in the specification of the present application.

The content of the surfactant in the photosensitive composition is preferably 0.0001 to 0.1000% by mass, preferably 0, based on the total mass of the photosensitive composition in that the strength of the infrared light cut filter is more excellent. More preferably, it is 0010 to 0.0700% by mass.

(Dispersant)

The photosensitive composition may contain a dispersant. The inclusion of the dispersant improves the dispersion stability of the specific particles in the photosensitive composition. The dispersant also functions as the binder described above.

Dispersants include high molecular weight dispersants [for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylics. Copolymers and Naphthalene Sulfonic Acid Formalin Condensates], polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, and alkanol amines.

Examples of the polymer dispersant include linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers.

Examples of the terminal-modified polymer include a polymer having a phosphoric acid group at the terminal, a polymer having a sulfonic acid group at the terminal, a polymer having a partial skeleton of an organic dye or a heterocycle, and a hydroxyl group at one end. Examples thereof include polymers produced by modifying an oligomer or polymer having an amino group with an acid anhydride.

Examples of the graft type polymer include a reaction product of poly (lower alkyleneimine) and polyester, a reaction product of polyallylamine and polyester, an amphoteric dispersion resin having a basic group and an acidic group, and a partial skeleton of an organic dye. Examples thereof include a graft-type polymer having a heterocycle and a copolymer of a macromonomer and an acid group-containing monomer.

Examples of the macromonomer used when producing the graft-type polymer by radical polymerization include known macromonomers, and macromonomer AA-6 (polymethylmethacrylate having a methacrylic group as a terminal group) manufactured by Toa Synthetic Co., Ltd. ), AS-6 (polyester whose terminal group is a methacryloyl group), AN-6S (polymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyacrylic acid whose terminal group is a methacryloyl group). Butyl), PLAXEL FM5 (additional product of ε-caprolactone of 2-hydroxyethyl methacrylate with 5 molar equivalent), FA10L (addition of ε-caprolactone of 2-hydroxyethyl acrylate with 10 molar equivalent), manufactured by Daicel Chemical Industry Co., Ltd., Examples thereof include polyester-based macromonomers described in Japanese Patent Application Laid-Open No. 2-272009. Of these, polyester-based macromonomers are preferable because they are excellent in flexibility and solvent resistance.

As the block type polymer, the block type polymer described in JP-A-2003-49110, JP-A-2009-52010 and the like is preferable.

Examples of the dispersant include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polypolymer), 161, 162, 163, manufactured by BYK Chemie. 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, 4010 (polyurethane type), EFKA 4330, 4340 ( Block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ”, Ajinomoto Fine Techno Co., Ltd.“ Ajispar PB821, PB822, PB880, PB881 ”, Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)", Kusumoto Kasei Co., Ltd. "Disparon KS-860, 873SN, 874, # 2150 ( (Adioxy polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonate formalin polycondensate), MS , C, SN-B (aromatic sulfonate formalin polycondensate) "," homogenol L-18 (polymer polycarboxylic acid) "," emalgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) " , "Acetamine 86 (stearylamine acetate)", Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000 , 28000, 32000, 38500 (graft type polymer) ", Nikko Chemical Co., Ltd." Nikkor T106 (polyoxyethylene sorbitan monooleart), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemicals Co., Ltd. Hinoact T-8000E, etc., Organosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Industry Co., Ltd., "W001: Cationic surfactant" manufactured by Yusho Co., Ltd., Polyoxyethylene lauryl ether, Polyoxyethylene stearyl ether, Poly Oxyethylene oleyl ether, polyoxyethylene octylphenyle Nonionic surfactants such as polymer, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo Co., Ltd. "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", Sannopco Co., Ltd. "Disperse Aid 6, Disperse Aid 8, Disperse Aid" Polymer dispersants such as "15, Disperse Aid 9100", "Adecapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101," manufactured by ADEKA Co., Ltd. Examples thereof include "P103, F108, L121, P-123" and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd.

When a dispersant is used, first, a dispersion composition is prepared with specific particles (and other infrared light shielding agents, if necessary), a dispersant, and an appropriate solvent, and then blended into the composition. Is preferable from the viewpoint of improving dispersibility.

The content of the dispersant in the photosensitive composition is preferably 10 to 70% by mass, more preferably 30 to 60% by mass, based on the total mass of the specific particles.

(Sensitizer)

The photosensitive composition may contain a sensitizer. By including the sensitizer in the photosensitive composition, the pattern rectangularity is more excellent.

As the sensitizer, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

The type of sensitizer used is not particularly limited, and examples thereof include the compounds exemplified in paragraph 0202 of JP2012-1222045.

The content of the sensitizer in the photosensitive composition is preferably 0.01 to 10.0% by mass, more preferably 0.10 to 4.0% by mass, based on the total solid content in the photosensitive composition. preferable.

(Crosslinking agent)

The photosensitive composition may contain a cross-linking agent. By including the cross-linking agent in the photosensitive composition, it is expected that the strength of the infrared light cut filter will be improved.

The cross-linking agent is preferably a compound having two or more cross-linking groups. Examples of the crosslinkable group include an oxetan group, a cyanate group, and a group similar to that described for the crosslinkable group that the alkali-soluble binder may have, and an epoxy group, an oxetane group, or a cyanate group is preferable. That is, as the cross-linking agent, an epoxy compound, an oxetane compound or a cyanate compound is preferable.

The type of the cross-linking agent used is not particularly limited, and examples thereof include compounds exemplified in paragraphs 0204 to 0209 of JP2012-12204.

(Curing accelerator)

The photosensitive composition may contain a curing accelerator.

The type of the curing accelerator used is not particularly limited, and examples thereof include the compounds exemplified in paragraph 0211 of JP2012-1222045.

The photosensitive composition can be prepared by mixing each of the above components.

The use of the photosensitive composition is not particularly limited, but it is preferably used for forming an infrared light shielding layer, and more preferably used for forming an infrared light cut filter. That is, the cured film formed by using the photosensitive composition is preferably used for the infrared light shielding layer.

The infrared light cut filter formed by using the photosensitive composition of the present invention includes, for example, an infrared light cut filter on the light receiving side of the solid-state image sensor and a back surface side (opposite side of the light receiving side) of the solid-state image sensor. ) Can also be used as an infrared light cut filter.

Further, the photosensitive composition of the present invention may be directly applied on a color filter or a flattening layer to form a coating film.

Since the photosensitive composition of the present invention can be supplied in a coatable state, an infrared light cut filter can be easily formed at a desired member or position of the solid-state image sensor.

<Infrared light cut filter>

Next, the infrared light cut filter of the present invention will be described.

The infrared light cut filter of the present invention is formed by using the above-mentioned photosensitive composition of the present invention.

The film thickness of the infrared light cut filter can be appropriately selected depending on the intended purpose, and is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more in order to maintain the light-shielding ability.

The maximum transmittance of the infrared light cut filter at a wavelength of 400 to 1300 nm is not particularly limited, but is preferably 60% or more, more preferably 65% or more.

The maximum transmittance of the infrared light cut filter at a wavelength of 900 to 1300 nm is not particularly limited, but is preferably 20% or less, more preferably 10% or less, and most preferably 5% or less.

The infrared light cut filter is a lens having a function of absorbing or cutting infrared light (lenses for cameras such as digital cameras, mobile phones, and in-vehicle cameras, and optical lenses such as f-θ lenses and pickup lenses). , Optical filter for semiconductor light receiving element, Infrared light cut filter for proximity illuminance sensor, Infrared light cut filter or infrared light absorption plate that blocks heat rays for energy saving, Agriculture for selective use of sunlight Coatings, recording media that utilize the heat of absorption of infrared light, near-infrared light cut filters for electronic devices or photographs, protective glasses, sunglasses, heat ray blocking film, optical character reading and recording, confidential document copy protection, electronic It is used for photographic photoconductors and laser welding.

In particular, it is useful for a noise cut filter for a CCD (Charge Coupled Device) camera or a filter for a CMOS (Complementary Metal Oxide Semiconductor) image sensor.

The method for producing the infrared light cut filter is not particularly limited, but the infrared light cut filter can be produced through a step of forming a coating film by applying the photosensitive composition of the present invention to a support.

Further, as will be described later, a step of forming a pattern may be performed.

As a method for forming a coating film, for example, the above-mentioned photosensitive composition is dropped onto a support by a drop casting method, a spin coater method, a slit spin coater method, a slit coater method, a screen printing method, and an applicator coating. The law can be mentioned.

The support to which the photosensitive composition of the present invention is applied may be a transparent substrate made of glass or the like. Further, it may be each base material in the solid-state image sensor. Further, another substrate provided on the light receiving side of the solid-state image sensor may be used. Further, it may be a layer such as a flattening layer provided on the light receiving side of the solid-state image sensor.

Examples of a method for producing a patterned infrared light cut filter include a step of applying the photosensitive composition of the present invention on a support to form a coating film, and a step of exposing the coating film in a pattern. , A method including a step of developing and removing an unexposed portion to form a pattern can be mentioned.

The term "exposure" is used to include not only light of various wavelengths but also radiation irradiation such as electron beam and X-ray.

The exposure is preferably performed by irradiation with radiation, and examples of the radiation include ultraviolet light, visible light, and electron beam, and more specifically, KrF, ArF, g line, h line, and i line. Can be mentioned.

Examples of the exposure method include stepper exposure and exposure with a high-pressure mercury lamp.

Exposure is preferably 5~3000mJ / cm ^2, and more preferably 10 to 2000 mJ / cm ^2.

Although the method of forming the pattern by the development process has been described above, the pattern may be formed by the dry etching method.

Other steps may be included in the method for manufacturing an infrared light cut filter. Examples of other steps include a surface treatment step of the support, a preheating step (pre-baking step), and a post-heating step (post-baking step).

The heating temperature in the preheating step is preferably 80 to 200 ° C, more preferably 90 to 150 ° C. The heating time in the preheating step is preferably 30 to 240 seconds when a hot plate is used.

The heating temperature in the post-heating step is preferably 120 ° C. to 250 ° C., more preferably 160 ° C. to 220 ° C. The heating time in the post-heating step is preferably 3 minutes to 180 minutes when a hot plate is used.

<Solid image sensor>

The infrared light cut filter can be suitably applied to a solid-state image sensor.

Hereinafter, an embodiment of the solid-state image sensor of the present invention will be described with reference to FIG.

In the solid-state image sensor (infrared light sensor) 100 shown in FIG. 1, FIG. 110 is a solid-state image sensor substrate.

An infrared light cut filter 111 and a color filter 112 are arranged on the solid-state image sensor substrate 110.

A region 114 is provided between the infrared light transmission filter (color filter that transmits infrared light) 113 and the solid-state image sensor substrate 110. In the region 114, a resin layer (for example, a transparent resin layer) capable of transmitting light having a wavelength transmitted through the infrared light transmission filter 113 is arranged. Infrared light transmission filter 113 may be formed in the region 114. That is, the infrared light transmission filter 113 may be formed on the solid-state image sensor substrate 110.

A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared light transmission filter 113. The flattening layer 116 is formed so as to cover the microlens 115.

In FIG. 1, the film thickness of the color filter 112 and the film thickness of the infrared light transmission filter 113 are the same, but the film thicknesses of both may be different.

In FIG. 1, the color filter 112 is provided on the incident light hν side of the infrared light cut filter 111, but the order of the infrared light cut filter 111 and the color filter 112 is changed to cut the infrared light. The filter 111 may be provided on the incident light hν side of the color filter 112. Another layer may be formed between the infrared light cut filter 111 and the color filter 112.

The color filter 112 is selected from a group consisting of a color filter that transmits light in the red wavelength region, a color filter that transmits light in the green wavelength region, and a color filter that transmits light in the blue wavelength region. It is preferable that at least one is contained.

The color filter 112 may be impregnated with an infrared light absorbing substance so that the color filter 112 has a function as an infrared light cut filter.

Since the solid-state image sensor of the present invention is provided with an infrared light cut filter inside, the infrared light cut filter as a member of the camera module becomes unnecessary, the number of parts of the camera module can be reduced, and the size of the camera module can be reduced. Can be planned.

The color filter 112 is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be referred to. The content is incorporated herein by reference.

The characteristics of the infrared light transmission filter 113 are selected according to the emission wavelength of the light source.

One of the preferred embodiments of the solid-state imaging device is a color filter that transmits light in the red wavelength region (red color filter), a color filter that transmits light in the green wavelength region (green color filter), and a blue wavelength region. A filter layer containing at least one selected from the group consisting of a color filter (blue color filter) that transmits light and a color filter (infrared light transmission filter) that transmits infrared light, and a filter layer that contains more than a filter layer. It is preferable to provide an infrared light cut filter arranged on the light incident side.

For example, a filter layer having a red color filter, a green color filter, a blue color filter, and an infrared light transmission filter on the same plane, and an infrared light cut that is arranged on the light incident side of the filter layer and is arranged on the entire surface of the filter layer. Examples thereof include a solid-state image sensor provided with a filter.

The infrared light cut filter may be arranged on the light incident side of the substrate 110.

For example, the infrared light cut filter may be arranged on the red color filter, the green color filter, and the blue color filter, and the infrared light cut filter may be arranged on the infrared light transmission filter.

Further, a flattening layer may be arranged between the filter layer and the infrared light cut filter.

Next, an image pickup device (camera system) will be described as an example to which the solid-state image pickup device of the present invention is applied.

FIG. 2 is a functional block diagram of the imaging device. The image pickup device emits infrared light from the lens optical system 1, the solid-state image sensor 10, the signal processing unit 20, the signal switching unit 30, the control unit 40, the signal storage unit 50, the light emission control unit 60, and the light emission control unit 60. An infrared LED (light emitting diode) 70 of the light emitting element and image output units 80 and 81 are provided. As the solid-state image sensor 10, the solid-state image sensor 100 described above can be used. Further, all or a part of the configurations other than the solid-state image sensor 10 and the lens optical system 1 can be formed on the same semiconductor substrate. For each configuration of the image pickup apparatus, paragraphs 0032 to 0036 of JP2011-233983A can be referred to, and the contents thereof are incorporated in the present specification.

As the image pickup device, there are a motion sensor, a proximity sensor, a gesture sensor and the like.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. Unless otherwise specified, "part" and "%" are based on mass.

<Preparation of composition (photosensitive composition)>

The components shown in Table 1 below were dissolved in the solvent shown in the same table to prepare a photosensitive composition.

The various components used in Table 1 above are summarized below.

(Resin binder)

Resin A: Acrycure RD-F8 manufactured by Nippon Shokubai (corresponding to an alkali-soluble binder having a double bond group)

(Polymerizable compound)

DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Polymerization initiator)

IRGACURE 369: IRGACURE 369 (manufactured by BASF)

(Sensitizer)

DETX-S: Kayace DETX-S (2,4-diethylthioxanthone) (manufactured by Shoji Sangyo Co., Ltd.)

(solvent)

PGMEA: 1-methoxy-2-propanol acetate

(Surfactant)

Megafac F-781-F (manufactured by DIC Corporation)

(UV absorber (ultraviolet absorber))

The results of the thermogravimetric measurements of UV1 to UV-6 are shown in Table 2 below.

(Polymerization inhibitor)

(Specific particles)

The specific particle 1 was produced according to the following procedure.

A mixture of tungsten fine particles (composition: Cs _0.33 WO ₃ , average particle size: 20 nm) (100 parts by mass), ethyl silicate (10 parts by mass), and methanol (90 parts by mass) was stirred at 0 ° C. for 10 hours. Then, the mixture was stirred at 20 ° C. for 20 hours. The solid content was collected by filtration from the obtained mixture, and the recovered solid content was dried at 25 ° C. for 24 hours, 100 ° C. for 10 hours, and 200 ° C. for 1 hour, then pulverized and coated with _{specific particles 1 (coated with SiO 2).} Tungsten fine particles) were obtained.

As shown in Table 3 described later, the specific particles 2 to 4 were produced according to the same procedure as above except that the type of the coupling agent was changed. The specific particles 2 were _{tungsten fine particles coated with TiO 2} , the specific particles 3 were _{tungsten fine particles coated with Al 2} O ₃ , and the specific particles 4 were tungsten fine particles coated with _{ZrO 2.}

The tungsten fine particles that were not coated were designated as the specific particles 5.

The above composition further contains a dispersant. The dispersant has a function of dispersing the specific particles.

Using the composition obtained above, the following various measurements were carried out. The results are summarized in Table 5 above.

<Heat resistance evaluation>

The raw materials shown in Table 4 below are mixed at the ratio (parts by mass) shown in Table 4, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to form a Green composition and Red composition. A product and a Blue composition were prepared.

The numerical values in the table represent parts by mass.

The pigment dispersion liquid 1 is a composition containing the following components.

・ C. I. Pigment Green 58 ・ ・ ・ 11.4 parts by mass

・ C. I. Pigment Yellow 185 ... 2.3 parts by mass

-Compound 1 with the following structure: 1.4 parts by mass

Dispersant 1 (resin having the following structure (acid value = 49 mgKOH / g, Mw = 24000, the numerical value added to the main chain is the molar ratio)) ... 7.2 parts by mass

-Propylene glycol methyl ether acetate: 81.9 parts by mass

The pigment dispersion liquid 2 is a composition containing the following components.

・ C. I. Pigment Red 254 ... 11.4 parts by mass

・ C. I. Pigment Yellow 139 ... 2.3 parts by mass

-Compound 1 with the above structure: 1.4 parts by mass

-The above-mentioned dispersant 1 ... 7.2 parts by mass

-Propylene glycol methyl ether acetate: 77.77 parts by mass

The pigment dispersion liquid 3 is a composition containing the following components.

・ C. I. Pigment Blue 15: 6 ... 11.4 parts by mass

・ C. I. Pigment Bio Red 23 ... 2.3 parts by mass

-Compound 1 with the above structure: 1.4 parts by mass

-The above-mentioned dispersant 1 ... 7.2 parts by mass

-Propylene glycol methyl ether acetate: 81.9 parts by mass

Resin A: A resin having the following structure (acid value = 70 mgKOH / g, Mw = 11000, the numerical values added to the main chain are molar ratios. Synthesized by the method described in paragraphs 0304 to 0307 of JP2012-173356A. did.)

-Monomer A: M-350 (Toagosei Co., Ltd.)

-Photopolymerization initiator 1: IRGACUREOXE03 (BASF)

-Photopolymerization initiator 2: IRGACUREOXE04 (BASF)

-Polymerization inhibitor: p-methoxyphenol

-Organic solvent: PGMEA

-Epoxy compound: EHPE-3105 (Daicel Chemical Industry Co., Ltd.)

-Surfactant: Megafac-781F (DIC Corporation)

The photosensitive composition of Example 1 was applied onto a glass wafer by a spin coating method so that the film thickness after film formation was 2.7 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. Then, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the obtained coating film was ^{exposed to the entire surface at 1000 mJ / cm 2} , and further heated at 220 ° C. for 5 minutes on a hot plate. A cured layer was obtained.

Next, the Green composition was applied onto the cured layer by a spin coating method so that the film thickness after film formation was 1.5 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. Then, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the obtained coating film was ^{exposed to the entire surface at 1000 mJ / cm 2} , and further heated at 220 ° C. for 5 minutes on a hot plate. A Green film was laminated on the cured layer to obtain a sample G1 containing the cured layer and the Green film.

A Red composition or a Blue composition was used instead of the Green composition to obtain a sample R1 containing a cured layer and a Red film, and a sample B1 containing a cured layer and a Blue film.

Various samples were prepared by using the photosensitive compositions of other examples and comparative examples instead of the photosensitive composition of Example 1 above.

The light transmittance of the obtained sample was measured in the wavelength range of 400 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).

Next, the obtained sample was heated on a hot plate at 240 ° C. for 300 seconds, and the change in transmittance (ΔT) in the wavelength range of 400 to 1300 nm before and after heating was measured and used as an index of heat resistance. The smaller the value of ΔT, the better the heat resistance, and the judgment criteria are as follows.

The ΔT represents a change in transmittance at a wavelength showing the largest change in transmittance in the wavelength range of 400 to 1300 nm. Practically, A or B is preferable.

"A": ΔT <2%

"B": 2% ≤ ΔT% <5%

"C": ΔT% ≥ 5%

In Table 5, which will be described later, the results of each sample formed by using the Green composition, Red composition, and Blue composition are shown.

<Evaluation of pattern rectangleness>

The photosensitive compositions of each Example and Comparative Example were applied onto a silicon substrate, dried at 100 ° C. for 2 minutes, and then photophotographed using an exposure apparatus UX3100-SR (manufactured by Ushio, Inc.). ^{Light irradiation (exposure amount: 100-2000 mJ / cm 2} ) was performed through a mask (mask pattern: 50 μm line and space). The pattern-exposed coating film is paddle-developed at room temperature for 60 seconds using a 60% aqueous solution of an organic alkaline developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.), and then spin showered for another 20 seconds. Rinse with pure water. Then, it was washed with pure water. Then, water droplets were blown off with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a cured film (thickness: 2.7 μm) as a line portion. The rectangularity was evaluated by evaluating the cross section of the obtained line portion. Specifically, as shown in FIG. 3, the value of the angle θ formed by the line portion 202 with respect to the silicon substrate 200 was obtained and evaluated according to the following criteria. Practically, A or B is preferable.

"A": θ is 80 to 100 °

"B": θ is 70 ° or more and less than 80 °, or more than 100 ° and 110 ° or less.

"C": θ is less than 70 ° or more than 110 °

As shown in Table 5 above, when the photosensitive composition of the present invention was used, a predetermined effect was obtained.

In particular, as shown in Examples 1 to 9, in the thermogravimetric measurement of the ultraviolet absorber, the mass reduction rate at 150 ° C. is 5% or less, and the mass reduction rate at 220 ° C. is 40% or more. , Excellent heat resistance. As shown in Examples 2 to 9, in the thermogravimetric measurement of the ultraviolet absorber, when the mass reduction rate at 150 ° C. is 5% or less and the mass reduction rate at 220 ° C. is more than 40%, the heat resistance Was particularly good at.

In Example 6, a photosensitive composition was prepared and evaluated in the same procedure except that the resin A was replaced with the resin B (structure below) as a binder. As a result, the same results as in Example 6 were obtained. Obtained.

Resin B: The following structure. (Acid value = 95 mgKOH / g, Mw = 41000, the values added to the main chain are molar ratios.)

In Example 6, the resin A is similarly photosensitive except that the resin A is replaced with a mixture of the resin A and the resin C (the following structural formula) (resin A / resin C = 7.85 / 7.85). When the composition was prepared and evaluated in various ways, the same results as in Example 6 were obtained.

Resin C: The following structure. (Acid value = 217 mgKOH / g, Mw = 11000, the values added to the main chain are molar ratios.)

In Example 6, a photosensitive composition was prepared in the same manner and evaluated in various ways except that DPHA was replaced with Aronix M-510 (manufactured by Toagosei Co., Ltd.) as a polymerizable compound. As a result, the same results as in Example 6 were obtained. was gotten.

In Example 6, the photosensitive compositions were prepared in the same manner and evaluated in various ways except that DPHA was replaced with DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable compound. As a result, the same results as in Example 6 were obtained. was gotten.

In Example 6, a photosensitive composition was prepared in the same manner and evaluated in various ways except that DPHA was replaced with Oxol EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.) as a polymerizable compound. Results were obtained.

In Example 6, the photosensitive composition was similarly prepared except that DPHA was replaced with a mixture of DPHA and Aronix M-510 (DPHA: Aronix M-510 (mass ratio) = 1: 1) as the polymerizable compound. As a result of preparation and various evaluations, the pattern shortness was further excellent as compared with Example 6. From this result, it is considered that the pattern shortness was further improved by using two or more kinds of polymerizable compounds.

In Example 6, a photosensitive composition was prepared in the same manner and various evaluations were made except that IRGACURE369 was replaced with IRGACUREOXE01 (manufactured by BASF) as an initiator. As a result, the pattern shortenness was further excellent as compared with Example 6. Was there. From this result, it is considered that the pattern shortness was further improved by using the oxime compound (oxime-based initiator).

In Example 6, a photosensitive composition was prepared in the same manner and various evaluations were made except that IRGACURE369 was replaced with IRGACUREOXE03 (manufactured by BASF) as an initiator. As a result, the pattern shortenness was further excellent as compared with Example 6. Was there. From this result, it is considered that the pattern shortness was further improved by using the oxime compound (oxime-based initiator).

In Example 6, a photosensitive composition was prepared in the same manner and various evaluations were made except that IRGACURE369 was replaced with IRGACUREOXE04 (manufactured by BASF) as an initiator. As a result, the pattern shortenness was further excellent as compared with Example 6. Was there. From this result, it is considered that the pattern shortness was further improved by using the oxime compound (oxime-based initiator).

In Example 6, a photosensitive composition was prepared in the same manner except that IRGACURE369 was replaced with a mixture of IRGACURE369 and IRGACUREOXE04 (IRGACURE369: IRGACUREOXE04 (mass ratio) = 0.75: 0.75) as an initiator. As a result of various evaluations, the pattern shortness was further excellent as compared with Example 6. From this result, it is considered that the pattern shortness was further improved by using the oxime compound (oxime-based initiator).

In Example 6, the photosensitive compositions were prepared in the same manner and evaluated in various ways except that the sensitizer was not used. As a result, the same results were obtained except that the pattern shortness was B. It is considered that the pattern shortness was further improved by using the sensitizer.

In Example 6, except that no surfactant was used, the photosensitive compositions were prepared in the same manner and evaluated in various ways. As a result, the same results were obtained except that the pattern shortness was B. It is considered that the pattern shortness was further improved by using the surfactant.

In Example 6, a photosensitive composition was prepared in the same manner and various evaluations were made except that butyl acetate was used instead of ethylene glycol monobutyl ether acetate. As a result, the same results as in Example 6 were obtained.

In Example 6, the photosensitive compositions were prepared in the same manner and evaluated in various ways except that PGMEA was used instead of butyl acetate. As a result, the same results as in Example 6 were obtained.

1: Lens optical system, 10: Solid-state image sensor, 20: Signal processing unit, 30: Signal switching unit, 40: Control unit, 50: Signal storage unit, 60: Light emission control unit, 70: Infrared LED, 80, 81 : Image output unit, 100: Solid-state image sensor, 110: Solid-state image sensor substrate, 111: Infrared light cut filter, 112: Color filter, 113: Infrared light transmission filter, 114: Region, 115: Microlens, 116 : Flattening layer, 200: Silicon substrate, 202: Line part, hν: Incident light

Claims (12)

A photosensitive composition comprising metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor.

A photosensitive composition in which the mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330.

The photosensitive composition according to claim 1, wherein the surface of the metal-containing tungsten oxide particles is coated with a metal oxide.

The photosensitive composition according to claim 2, wherein the metal oxide is an oxide containing at least one element selected from the group consisting of Si, Ti, Zr, and Al.

Claims 1 to 3 say that the ultraviolet absorber is an ultraviolet absorber having a mass reduction rate of 5% or less at 150 ° C. and a mass reduction rate of 40% or more at 220 ° C. in thermogravimetric analysis. The photosensitive composition according to any one of the following items.

The photosensitive composition according to any one of claims 1 to 4, wherein the ultraviolet absorber is at least one selected from a dibenzoylmethane-based compound and an aminobutadiene-based compound.

The photosensitive composition according to any one of claims 1 to 5, which contains two or more of the polymerization inhibitors.

6. The polymerization inhibitor is at least two or more selected from the group consisting of a hindered phenol-based compound, a phenol-based compound other than the hindered phenol-based compound, a benzoquinone-based compound, and a hydroquinone-based compound. The photosensitive composition according to.

The polymerization inhibitor is other than one or more first polymerization inhibitors selected from the group consisting of the hindered phenol-based compound, the benzoquinone-based compound, and the hydroquinone-based compound, and the hindered phenol-based compound. The photosensitive composition according to claim 7, which comprises a phenolic compound.

The photosensitive composition according to claim 8, wherein the mass ratio of the content of the phenolic compound other than the hindered phenolic compound to the total content of the first polymerization inhibitor is 0.0009 to 0.17. ..

The photosensitive composition according to any one of claims 1 to 9, further comprising an alkali-soluble binder having a double bond group.

An infrared light cut filter formed by using the photosensitive composition according to any one of claims 1 to 10.

A solid-state image sensor including the infrared light cut filter according to claim 11.

Images