KR20160127663A - Radiation-sensitive resin composition, infrared shielding film, formation method for same, and solid-state imaging device, light sensor - Google Patents

Abstract

According to the present invention, a radiation sensitive resin composition can be used to form a film having high capability of blocking infrared rays. The infrared ray blocking film can be used to a solid state imaging device and a luminance sensor. The radiation sensitive resin composition comprises: [A] a polymer; [B] a quinone diazide compound; and [C] an infrared ray blocking material.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation sensitive resin composition, an infrared ray shielding film, a method for forming the same, and a solid-state image sensor, a radiation sensor,

The present invention relates to a radiation sensitive resin composition, an infrared ray shielding film, a method of forming the same, and a solid state image pickup device and an illuminance sensor.

CMOS image sensor chips, which are solid-state image pickup devices for color images, are used in smart phones, video cameras and the like. These solid-state image pickup devices use a silicon photodiode having sensitivity to near-infrared rays in the light-receiving portion thereof, and therefore correction of visual sensitivity is required, and an infrared cut filter is used (for example, see Patent Document 1).

In addition, an illumination sensor is mounted on a smart phone or the like, and is used for adjusting the brightness of a screen in an indoor or outdoor environment, and uses an infrared cut filter (see, for example, Patent Document 2).

However, if the surface of the solid-state imaging device substrate or the like and the infrared cut filter are opposed to each other with the space therebetween, the incident angle dependence of the light received by the solid-state imaging device becomes large, which causes malfunction.

Attempts have been made to form a film of a curable resin composition on a substrate in order to reduce the dependence of the incident angle on the infrared cut filter (see, for example, Patent Document 3).

However, these curable resin compositions are difficult to form patterns of the infrared shielding film with high sensitivity and good patterning property.

In view of the above, from the viewpoint of improving the productivity of the solid-state image sensor and the light intensity sensor, a radiation-sensitive resin composition capable of forming a pattern of the infrared ray shielding film with high sensitivity and excellent in patterning property is required.

Japanese Laid-Open Patent Publication No. 2012-28620 Japanese Laid-Open Patent Publication No. 2011-60788 Japanese Laid-Open Patent Publication No. 2012-189632

The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a radiation-sensitive resin composition which can form a pattern of an infrared shielding film with high sensitivity and is excellent in infrared shielding property, chemical resistance and refractive index And an object of the present invention is to provide a solid-state image pickup device having an infrared ray shielding film formed from the radiation sensitive resin composition, an illuminance sensor, and a method of forming an infrared ray shielding film.

According to an aspect of the present invention,

Is achieved by a radiation-sensitive resin composition comprising a polymer [A], a [B] quinone diazide compound, and a [C] infrared shielding material, wherein the polymer [A] is a polymer comprising a carboxyl group in the same or different polymer molecules And a polymer having a polymerizable group-containing structural unit.

Further, another invention made to solve the above problems is achieved by an infrared ray shielding film formed of the radiation sensitive resin composition, a solid-state image pickup element having the infrared ray shielding film or an illuminance sensor.

It is also possible to form an infrared shielding film having a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film with radiation, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film As a method, the above-mentioned coating film is formed by the method of forming an infrared shielding film by using the radiation sensitive resin composition of the present invention.

An infrared ray shielding film formed of the radiation sensitive resin composition, a method of forming the same, and a solid state image pickup device having the infrared ray shielding film.

Therefore, the radiation sensitive resin composition, the infrared ray shielding film and the forming method thereof can be suitably used for a manufacturing process of a solid-state imaging element, an illumination sensor, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing a configuration of a camera module including a solid-state image pickup device according to an embodiment of the present invention. Fig.
2 is a schematic view showing a configuration of an illuminance sensor according to an embodiment of the present invention.

(Mode for carrying out the invention)

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition of the present invention is a radiation sensitive resin composition containing a [A] polymer, a [B] quinone diazide compound, and a [C] infrared shielding material. The polymer is not particularly limited as long as it is a polymer, and a polymer having developability from the viewpoint of pattern formation is preferable. Particularly preferred polymers from this viewpoint are polymers having structural sites having phenolic hydroxyl groups, carboxyl groups, silanol groups and the like. As such a polymer, an acrylic resin, a novolac resin, a polyamic acid, a polyimide, a polybenzoxazole, a polysiloxane, a polyether and the like are preferable, and an acrylic resin, a novolac resin, a polyamic acid, Polymers are preferred.

It is particularly preferable that the polymer is a polymer having a structural unit containing a carboxyl group and a structural unit containing a polymerizable group in the same or different polymer molecules.

The radiation sensitive resin composition may contain other optional components as long as the effect of the present invention is not impaired. Each component will be described in detail below.

<[A] Polymer>

The polymer [A] contained in the radiation sensitive resin composition of the present embodiment is a resin that is soluble in an alkaline solvent and has alkali developability. The polymer [A] is preferably one selected from, for example, an acrylic resin having a carboxyl group, a polyimide and a polyimide precursor, a polysiloxane and a novolak resin. Hereinafter, each of the acrylic resin having a carboxyl group, the polyimide resin, the polysiloxane and the novolak resin will be described in more detail.

[Acrylic resin having carboxyl group]

The acrylic resin having a carboxyl group preferably contains a structural unit having a carboxyl group and a structural unit having a polymerizable group. In this case, it is not particularly limited as long as it contains a constituent unit having a carboxyl group and a constituent unit having a polymerizable group and having alkali developability (alkali solubility).

The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. The acrylic resin having a carboxyl group contains the specific structural unit described above to form a film having excellent surface curability and deep curability so that the cured film of the embodiment of the present invention can be formed.

Examples of the structural unit having a (meth) acryloyloxy group include a method of reacting (meth) acrylic acid with an epoxy group in the copolymer, a method of reacting a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer, A method of reacting a (meth) acrylic acid ester having an isocyanate group in the hydroxyl group in the copolymer, and a method of reacting a (meth) acrylic acid hydroxy ester to an acid anhydride portion in the copolymer. Of these, a method of reacting a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer is preferred.

The acrylic resin comprising a constituent unit having a carboxyl group and a constituent unit having an epoxy group as a polymerizable group is at least one selected from the group consisting of (A1) unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(A1) ), And (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as &quot; (A2) compound &quot;). In this case, the acrylic resin having a carboxyl group is a copolymer comprising at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carbonic acid anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound.

The acrylic resin having a carboxyl group can be produced, for example, by copolymerizing a compound (A1) imparting a carboxyl group-containing structural unit and a compound (A2) imparting an epoxy group-containing structural unit in a solvent in the presence of a polymerization initiator have. The copolymer (A3) may also be made by further adding a hydroxyl group-containing unsaturated compound (hereinafter also referred to as &quot; (A3) compound) &quot; In the production of an acrylic resin having a carboxyl group, the above-mentioned compound (A1), the compound (A2) and the compound (A3) described above (A4) ) Unsaturated compound giving a constituent unit other than the constituent unit derived from the compound), may be further added to the copolymer. Next, each compound of (A1) to (A3) will be described in detail.

((A1) compound)

Examples of the compound (A1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, and a mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.

Examples of the anhydrides of unsaturated dicarboxylic acids include anhydrides of the compounds exemplified as the unsaturated dicarboxylic acids.

Of these compounds (A1), acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability.

These compounds (A1) may be used alone or in combination of two or more.

The proportion of the compound (A1) used is preferably 5% by mass to 30% by mass based on the total amount of the compound (A1) and the compound (A2) (optionally, the compound (A3) , And more preferably 10% by mass to 25% by mass. By setting the proportion of the compound (A1) to 5% by mass to 30% by mass, it is possible to optimize the solubility of the acrylic resin having a carboxyl group in an aqueous alkali solution and form a film having excellent radiation sensitivity.

((A2) compound)

(A2) is an epoxy group-containing unsaturated compound having a radical polymerizing property. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl - epoxy tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate.

These compounds (A2) may be used alone or in combination of two or more.

The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the total amount of the compound (A1) and the compound (A2) (optionally, the compound (A3) , And more preferably 10% by mass to 50% by mass. By setting the proportion of the compound (A2) to be 5% by mass to 60% by mass, the cured film of the present embodiment having excellent curability and the like can be formed.

((A3) compound)

(A3) compounds include (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid esters having a phenolic hydroxyl group, and hydroxystyrene.

Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass, based on the total amount of the compound (A1), the compound (A2) and the compound (A3) , And more preferably from 5% by mass to 25% by mass.

((A4) compound)

(A4) compound is not particularly limited so long as it is an unsaturated compound other than the above-mentioned (A1) compound, (A2) compound and (A3) compound. (A4) compounds include, for example, methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

These (A4) compounds may be used alone or in combination of two or more. The proportion of the compound (A4) used is preferably 10% by mass to 80% by mass, based on the total amount of the compound (A1), the compound (A2) and the compound (A4).

As specific examples of these monomers and polymerization methods, polymerization can be carried out by a known method, and Japanese Patent Publication No. 2961722, Japanese Patent Publication No. 3241399, Japanese Patent Publication No. 5607364, Japanese Patent Publication No. 3838626, Japanese Patent Publication No. 4853228, Japanese Patent Publication No. 4947300, Japanese Patent Publication No. 5002275, and the like.

&Lt; Polyimide and polyimide precursor >

The polyimide is preferably a polyimide having an alkali-soluble group in the constituent unit of the polymer. The alkali-soluble group includes, for example, a carboxyl group. By having an alkali-soluble group, for example, a carboxyl group, in the constituent unit, the alkali developability (alkali solubility) is provided, and scum expression in the exposed area can be suppressed during alkali development. Likewise, the polyimide precursor may also have an alkali-soluble group, for example, an alkali-soluble group such as a carboxyl group.

When the polyimide has a fluorine atom in the constituent unit, water repellency is imparted to the interface of the film when it is developed with an aqueous alkaline solution, so that permeation of the interface is suppressed. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less from the viewpoint of solubility in an aqueous alkali solution, in order to sufficiently obtain the effect of preventing the surface from seeping.

The polyimide used in the composition of the present embodiment is, for example, a polyimide obtained by condensing an acid component and an amine component. As the acid component, tetracarboxylic acid dianhydride is preferably selected, and as the amine component, diamine is preferably selected.

Examples of the tetracarboxylic acid dianhydride used for forming the polyimide include 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarbon Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane Bis (3,4-dicarboxyphenyl) fluorene dianhydride or 9,9-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] Rylene dianhydride and the like are preferable. Two or more of these may be used.

Specific examples of the diamine used for forming the polyimide include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, m-phenyl P-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene or 9,9-bis (4-aminophenyl) fluorene. Two or more of these may be used.

As such polyimide and polyimide precursors, for example, polymers disclosed in Japanese Unexamined Patent Publication (Kokai) No. 2001-133699 and Japanese Unexamined Patent Publication No. 2009-258634 may be used.

[Polysiloxane]

The polysiloxane is not particularly limited as long as it is a polymer of a compound having a siloxane bond. The polysiloxane is usually cured using, for example, an acid generated from a photo acid generator or a base generated from a photo base generator as a catalyst.

The polysiloxane is preferably a hydrolyzed condensate of a hydrolyzable silane compound represented by the following formula (2B).

(Wherein R ²⁰ is a non-hydrolyzable organic group having 1 to ²⁰ carbon atoms, R ²¹ is an alkyl group having 1 to 4 carbon atoms, q is an integer of 0 to 3, and R ²⁰ or R ²¹ is a , They may be the same or different)

Examples of the non-hydrolyzable organic group represented by R ²⁰ include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. These may be linear, branched or cyclic. Some or all of the hydrogen atoms of these alkyl groups, aryl groups and aralkyl groups may be substituted with a vinyl group, a (meth) acryloyl group or an epoxy group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and a butyl group. q is an integer of 0 to 3, but is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 1. When q is the above-mentioned value, progress of the hydrolysis-condensation reaction becomes easier, and as a result, the rate of the curing reaction increases, and the strength and adhesion of the resulting cured film can be improved.

Of the hydrolyzable silane compounds represented by the above formula (2B), silane compounds substituted with four hydrolysable groups and silane compounds substituted with one nonhydrolyzable group and three hydrolyzable groups are preferable, and one nonhydrolyzable group A silane compound substituted with three hydrolyzable groups is more preferable. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, Ethyltriethoxy silane, ethyl tri butoxy silane, butyl trimethoxy silane, gamma -glycidoxypropyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, and And 3-methacryloxypropyltriethoxysilane. These hydrolyzable silane compounds may be used singly or in combination of two or more.

The conditions for hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (2B) are as follows: at least a part of the hydrolyzable silane compound represented by the formula (2B) is hydrolyzed, the hydrolyzable group is converted into a silanol group, But is not limited to, it can be carried out as an example as follows.

As the water used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (2B), it is preferable to use water purified by reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.

Examples of the solvent that can be used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (2B) include, but not limited to, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether , Propylene glycol monoalkyl ether acetate, propionic acid esters and the like.

As the polysiloxane, for example, polysiloxanes disclosed in Japanese Patent Laid-Open Publication No. 2011-28225 and Japanese Patent Laid-Open Publication No. 2006-178436 may be used.

<Cyclic Olefin Resin>

The cyclic olefin resin is not particularly limited and may be a resin containing a cyclic olefin moiety. For example, a cyclic olefin resin described in WO2013 / 054864 can be used.

<Polycarbonate>

The polycarbonate is not particularly limited and may be a polycarbonate resin containing a fluorene moiety. For example, a polycarbonate described in JP-A-2008-163194 can be used.

[Novolac resin]

The novolac resin which is suitable as the resin for use in the radiation sensitive resin composition of the present embodiment can be obtained by polycondensation of phenols with aldehydes such as formalin by a known method.

Examples of phenols for obtaining novolac resins preferable in the present embodiment include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4- Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , 2,4,5-trimethylphenol, methylenebisphenol, methylenebisp-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o- chlorophenol, m- Phenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, 2,5-diethylphenol, p-isopropylphenol,? -Naphthol,? -Naphthol, and the like. Two or more of these may be used.

In the present embodiment, examples of the aldehydes for obtaining the preferred novolak resin include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Two or more of these may be used.

The weight average molecular weight of the novolak resin as a resin to be used in the radiation sensitive resin composition of the present embodiment is preferably 2000 to 50000 in terms of polystyrene by GPC (gel permeation chromatography), more preferably 3000 ~ 40000.

&Lt; [B] Quinone diazide compound >

The [B] quinone diazide compound, which the radiation sensitive resin composition may contain as a suitable component, generates carbonic acid by irradiation with radiation. The positive radiation-sensitive resin composition of the present invention can impart a positive radiation-sensitive property to the radiation-sensitive resin composition in which the exposed portion is removed by the developing process, by further containing the [B] quinone diazide compound.

The [B] quinone diazide compound is preferably a condensate of a compound having a phenolic hydroxyl group and a halide of naphthoquinone diazidesulfonic acid.

Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formulas.

Of these, compounds having a phenolic hydroxyl group include 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1- methylethyl] phenyl] ethylidene] bisphenol, 1,1,1 -Tri (p-hydroxyphenyl) ethane is preferred.

Examples of the naphthoquinone diazidesulfonic acid halide include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. The ester compound (quinone diazide compound) obtained from 1,2-naphthoquinonediazide-4-sulfonic acid chloride is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. On the other hand, an ester compound (quinone diazide compound) obtained from 1,2-naphthoquinonediazide-5-sulfonic acid chloride is suitable for exposure at a wide wavelength because absorption is present in a wide wavelength range.

Examples of the [B] quinone diazide compound include 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1- methylethyl] phenyl] ethylidene] bisphenol and 1,2- Diazide-5-sulfonic acid chloride, condensates of 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic chloride are preferable.

The Mw of the [B] quinone diazide compound is preferably 300 to 1,500, and more preferably 350 to 1,200. By setting the Mw of the [B] quinone diazide compound to 300 or more, the transparency of the formed interlayer insulating film can be kept high. On the other hand, by lowering the Mw of the [B] quinone diazide compound to 1,500 or less, deterioration of the pattern forming property of the radiation-sensitive resin composition can be suppressed.

[B] quinone diazide compounds may be used alone or in combination of two or more. The content of the [B] quinone diazide compound in the radiation-sensitive resin composition is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 100 parts by mass, per 100 parts by mass of the polymer [A] 50 parts by mass. When the content of the [B] quinone diazide compound is within the above-specified range, the difference in solubility between the irradiated portion of the alkali solution and the unexposed portion of the alkali aqueous solution becomes large, and consequently, the patterning performance is improved. In addition, the obtained interlayer insulating film has good solvent resistance.

[C] Infrared shielding material

The infrared shielding material used in the present invention may be any of a metal oxide, a copper compound, an infrared absorbing dye, and an infrared absorbing pigment, as long as it is a compound absorbing light having a wavelength of 800 to 1200 nm. The term "shielding" refers to blocking a space portion from the influence of an external force field such as an electric field or a magnetic field, and an infrared shielding material means a compound having an effect of blocking the influence of infrared rays.

The metal oxide used in the present invention has a high shielding property against infrared light and has an infrared shielding property in view of resolution and sensitivity in pattern formation using a light source having a wavelength of 500 nm or less, More preferably a metal boride, and most preferably a tungsten compound.

The tungsten compound is an infrared shielding material having a high absorption (that is, a high shielding property to infrared rays) for infrared rays (light having a wavelength of about 800 to 1200 nm) and a low absorption for visible light. Therefore, the curable composition for a solid-state imaging device of the present invention contains a tungsten compound, so that not only the shielding property in the infrared region is high, but also the pattern can be formed with high sensitivity.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, and a tungsten sulphide compound, and more preferably a tungsten oxide compound represented by the following formula (I) (composition formula).

M _x W _y O _z ... (I)

(M represents a metal, W represents tungsten, and O represents oxygen).

0.001? X / y?

2.2? Z / y? 3.0

As the metal of M, alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, , Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi. The metal of M may be one or more.

M is preferably an alkali metal, preferably Rb or Cs, more preferably Cs.

When x / y is 0.001 or more, infrared rays can be shielded sufficiently, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be avoided more reliably.

Since z / y is 2.2 or more, the chemical stability as a material can be further improved, and 3.0 or less, whereby infrared rays can be sufficiently shielded.

The formula (I) Specific examples of the tungsten oxide based compounds represented _{by, Cs 0.33 WO 3, Rb 0} .33 WO 3, K 0 .33 and the like _{WO 3, Ba 0 .33 WO 3} , Cs 0. ₃₃ WO ₃ or Rb _{0 .33} WO ₃ , more preferably Cs _{0 .33} WO ₃ .

The tungsten compound is preferably a fine particle. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. Since the average particle diameter is in this range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be more assured. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better, but the average particle size of the tungsten fine particles is usually 1 nm or more for ease of handling at the time of production.

When the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere Patent Publication No. 4096205).

The tungsten oxide-based compound is also available as a dispersion of tungsten microparticles such as YMF-02 manufactured by Sumitomo Chemical Co., Ltd.

Like the tungsten compound, the metal boride has high absorption for infrared rays (light having a wavelength of about 800 to 1,200 nm), low absorption for visible light, and high-pressure mercury lamps such as KrF, ArF The absorption is small even for light having a shorter wavelength than that of the visible region used in the visible region. Therefore, when the curable composition for a solid-state imaging device of the present invention contains a metal boride, as in the case of containing a tungsten compound, the shielding property in the infrared region is high and the transmittance in the visible light region is high, A pattern excellent in sensitivity can be obtained.

As the metal boride, boride, lanthanum (LaB _6), boride, praseodymium (PrB _6), boride, neodymium (NdB _6), boride, cerium (CeB _6), boride, yttrium (YB _6), titanium diboride (TiB _2), boride, zirconium ( ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB) (W ₂ B ₅ ), and the like, and more preferably lanthanum boride (LaB ₆ ).

The metal boride is preferably fine particles. The average particle diameter of the metal boride particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. Since the average particle diameter is in this range, the light transmittance in the visible light region can be further ensured because the metal boride fine particles are hardly shielded from visible light by light scattering. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better, but the average particle size of the metal boride fine particles is usually 1 nm or more for ease of handling at the time of production.

The metal boride is available as a commercially available product, and is also available as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Chemical Co., Ltd.

The copper compound used in the present invention is not particularly limited as long as it is a copper compound having a maximum absorption wavelength within a wavelength range of 700 nm to 1200 nm (near-infrared region).

The copper compound used in the present invention is not necessarily a copper complex or a copper complex, but is preferably a copper complex.

In the case where the copper compound used in the present invention is a copper complex, the ligand (L) to be coordinated to copper is not particularly limited as long as it is capable of coordinating with the copper ion, and examples thereof include sulfonic acid, phosphoric acid, phosphoric acid ester, phosphonic acid, , A phosphonic acid ester, a carbonic acid, a carbonyl (ester, a ketone), an amine, an amide, a sulfonamide, a urethane, a urea, an alcohol, a thiol and the like. Among them, sulfonic acid, phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphonic acid and phosphinic acid ester are preferable, and sulfonic acid, phosphoric acid ester, phosphonic acid ester and phosphinic acid ester are more preferable.

As specific examples of the copper compound used in the present invention, a phosphorus-containing copper compound, a copper sulfonate compound, or a copper carbide compound is more preferable. As the phosphorus-containing compound, specifically, the compounds described in WO2005 / 030898 may be taken into consideration, and the contents thereof are incorporated herein.

Hereinafter, the phosphate ester copper compound used in the present invention will be described in detail.

The composition of the present invention preferably contains a phosphate ester copper compound and an antioxidant. The composition of the present invention comprises a phosphate ester copper compound, and is preferably contained in an amount of from 20 to 95 mass%, more preferably from 30 to 80 mass%, based on the solid content of the composition. The phosphoric acid ester copper compound may be used singly or in combination of two or more, and in the case of two or more types, the total amount is in the above range.

The phosphate ester copper compound used in the present invention is preferably formed using a phosphoric acid ester compound and more preferably formed using a compound represented by the following formula (II).

The formula (II)

_{(HO) n -P (= O} ) - (ORa 2) 3-n

(Wherein, Ra ² represents an alkenyl group of an aralkyl group, having 1 to 18 carbon atoms or an aryl group, having 1 to 18 carbon atoms in the alkyl group, having a carbon number of 6-18 having 1 to 18 carbon atoms, or an -ORa ^2, carbon atoms, 4 to (Meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, n is 1 or 2, n is an integer of 1 to 100, , Ra &lt; ² &gt; may be the same or different).

In the above formulas, it is preferable that at least one of -ORa ² represents a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloylpolyoxyalkyl group having 4 to 100 carbon atoms, More preferably from 4 to 100 (meth) acryloyloxyalkyl groups.

The number of carbon atoms of the polyoxyalkyl group having 4 to 100 carbon atoms, the (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or the (meth) acryloylpolyoxyalkyl group having 4 to 100 carbon atoms is preferably 4 to 20 And more preferably from 4 to 10.

In the formula (II), Ra ² is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, More preferably an aryl group having 1 to 10 carbon atoms, and particularly preferably a phenyl group.

In the present invention, when n is 1, one of Ra ² is -ORa ² , a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloylpolyoxyalkyl group having 4 to 100 carbon atoms , And the other is -ORa ² or an alkyl group.

Examples of the phosphoric acid ester compound of the present invention include phosphoric acid monoesters (n = 2 in the formula (II)) and phosphoric acid diesters (n = 1 in the formula (II)). In view of near infrared ray shielding property and solubility A phosphoric acid diester is preferable.

The phosphoric acid ester copper complex is in the form of a copper complex (copper compound) for phosphoric acid esters in copper which is a central metal. Copper in the phosphoric acid ester copper complex is bivalent copper, and can be produced, for example, by reacting a copper salt with a phosphoric acid ester. Therefore, it is presumed that a near infrared ray absorbing composition containing copper and a phosphate ester compound forms a phosphate ester copper complex in the composition.

The molecular weight of the phosphate ester copper compound used in the present invention is preferably 300 to 1500, more preferably 320 to 900.

As specific examples of the phosphoric acid ester compound, mention may be made of the description of JP-A-2001-354945, the contents of which are incorporated herein. Further, regarding the synthesis method and preferred examples of the phosphate ester copper compound used in the present invention, the description of WO99 / 26952 can be taken into consideration, and the contents of these specifications are incorporated herein by reference.

In the synthesis of the phosphate ester copper compound, phosphonic acid such as Phosmer M, Phosmer PE, and Phosmer PP (manufactured by Unichemical Co.) may be used as a commercially available product.

The content of at least one of the metal oxide and the copper compound is preferably 5% by mass or more and 70% by mass or less with respect to the total solids mass of the radiation sensitive resin composition.

Examples of the infrared absorbing dye that can be used as the infrared ray shielding material in the present invention include a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, an iminium dye, an iminium dye, an aminium dye, a quinolinium dye, a pyrilium dye, At least one member selected from the group consisting of pyrrolopyrrole dye, copper complex, quaternary dye, azo dye, anthraquinone dye, diimonium dye, squarylium dye and porphyrin dye.

In the present invention, the coloring matter which can be used as an infrared ray shielding material is also available as a commercial product, and for example, the following commercially available coloring matter is suitably used.

Manufactured by FEW Chemicals, S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, S0484

American Dye Source, Inc. Preparation ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, ADS816EI, ADS818HT, ADS819MT, ADS821NH, ADS822MT, ADS838MT, ADS840MT , ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T, ADS1120F

YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR- YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132,

NK-123, NK-124, NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508 and NKX-114 manufactured by Hayashibara Seibutsukagakuken , NK-2545, NK-3555, NK-3509, NK-3519

Specific examples of the cyanine dyes and quaternary dyes include compounds described in JP-A-2012-215806, JP-A-2008-009206, and the like.

Specific examples of the phthalocyanine dye (phthalocyanine compound) are disclosed in JP-A-60-224589, JP-A-2005-537319, JP-A-4-23868, JP-A-4-39361, Japanese Patent Application Laid-Open Nos. 5-78364, 5-222047, 5-222301, 5-222302, 5-345861, Japanese Patent Application Laid- Japanese Patent Application Laid-Open Nos. 6-25548, 6-107663, 6-192584, 6-228533, 7-118551, Japanese Patent Application Laid- Japanese Patent Application Laid-Open Nos. 7-118552, 8-120186, 8-225751, 9-202860, 10-120927, Japanese Unexamined Patent Application Publication No. 10-182995, Japanese Unexamined Patent Publication No. 11-35838, Japanese Unexamined Patent Publication No. 2000-26748, The compounds described in JP-A 2000-63691, JP-A 2001-106689, JP-A 2004-18561, JP-A 2005-220060 and JP-A 2007-169343.

Specific examples of azo dyes, anthraquinone dyes (anthraquinone dyes) and squarylium dyes (squarylium dyes) are described in JP-A-2012-215806 and the like.

These dyes are commercially available, for example, Lumogen IR765, Lumogen IR788 (manufactured by BASF); ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (manufactured by Exciton); SDA3598, SDA6075, SDA8030, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by H. W. SANDS); Excolor TX-EX720, Excolor TX-EX720 as a phthalocyanine colorant, and Excolor TX-EX720 as a phthalocyanine coloring agent. Examples of the cyanine dye include Daito chemix 1371F (manufactured by Daito Kikusui K.K.) (Manufactured by Nippon Shokubai Co., Ltd.), and the like.

These dyes may be used alone or in combination of two or more of them for the purpose of developing good shielding properties.

Examples of the infrared absorbing pigment that can be used as an infrared ray shielding material in the present invention include zinc oxide, lead white, ritofone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, (Ferrocyanide potassium), zircon (ferricyanide), iron oxide, iron oxide red, chrome yellow, zinc sulfur (one kind of zinc sulfur and two kinds of zinc sulfur) Chrome tungsten yellow, chrome green, peachock, victorian green, tapping (unrelated to prussian blue), vanadium zirconium blue, chromium tin pink, manganese pink, salmon pink, titanium black, tungsten compounds, And a metal pigment such as a black pigment containing at least one metal element selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag. Metal oxides, metal nitrogen water or mixtures thereof And the like can be used.

The content of the dye is preferably 1% by mass or more and 30% by mass or less with respect to the total solids mass of the radiation sensitive resin composition.

The content of the infrared shielding material is preferably 0.1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 45% by mass or less, and still more preferably 5% by mass or less, based on the total solids mass of the curable composition for a solid- Or more and 40 mass% or less, and most preferably 5 mass% or more and 20 mass% or less. It is also possible to use two or more types of infrared shielding materials.

&Lt; Other optional components >

The radiation sensitive resin composition may contain, if necessary, a photoacid generator (other than a quinone diazide compound), an antioxidant, a polyfunctional acrylate, a surfactant, an adhesion aid, an inorganic oxide Particles, a compound having a cyclic ether group, a solvent, and the like. The other optional components may be used singly or in combination of two or more.

<Acid Generator (Except Quinone Diazide Compound)>

In the acid generator of the present invention, it is preferable that the acid generated from the acid generator by irradiation with an actinic ray or radiation generates an acid having a pKa of 3 or less. The acid generator may be a compound capable of generating an acid by heat. Examples of the acid generated from the acid generator by irradiation with an actinic ray or radiation include quaternary acids such as carbonic acid, sulfonic acid, phosphoric acid, sulfinic acid, sulfuric acid, sulfurous acid, sulfuric acid monoester, hydrochloric acid, hexafluorophosphoric acid and tetrafluoroboric acid Boric acid, and the like. Examples of the acid generating compound include organic halogenated compounds, organic boron compounds, disulfonic acid compounds, oxime ester compounds, and onium salt compounds.

Specific examples of the organic halogenated compound include those described in Wakabayashi et al., &Quot; Bull. Chem. Soc. Japan, 42, 2924 (1969), U.S. Patent No. 3,905,815, JP-A-46-4605, JP-A-48-36281, JP-A-55-32070, JP- 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 62-212401, and the like in Japanese Patent Application Laid- 63-98249, MP Hutt, Journal of Heterocyclic Chemistry, 1 (No 3), (1970). Particularly, compounds in which a trihalomethyl group is substituted Oxazole compounds: S-triazine compounds.

More suitably, s-triazine derivatives in which at least one mono, di or trihalogen substituted methyl group is bonded to the s-triazine ring, specifically, for example 2,4,6-tris (monochloromethyl) - s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine and the like.

Examples of the organoboron compound include compounds described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP- Japanese Patent Application Laid-Open Nos. 9-188710, 2000-131837, 2002-107916, 2764769, 2000-310808, and Kunz, Martin, RadTech 98, Proceeding April 19-22, 1998, Chicago, etc., organic boron compounds described in JP-A No. 6-157623, JP-A No. 6-175564 and JP-A No. 6-175561 Sulfonium complex or organic boron oxosulfonium complex, organic boron iodonium complexes described in JP-A-6-175554 and JP-A-6-175553, organo boron complexes described in JP-A-9-188710 Boron phosphonium complex, JP-A-6-348011, Japan Organic boron transition metal coordination complexes such as those disclosed in Japanese Patent Application Laid-Open Nos. 7-128785, 7-140589, 7-306527, and 7-292014, .

Examples of the disulfone compound include compounds described in JP-A-61-166544, JP-A-2002-328465, and the like.

Examples of the oxime ester compound include compounds described in JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232 and JP-A 2000-66385 However, from the viewpoint of sensitivity, it is preferable to be a sulfonic acid ester.

Examples of the onium salt compounds include those described in S. I. Schlesinger, Photogr. Sci. Ammonium salts described in U.S. Patent No. 4,069,055, JP-A-4-365049, and the like, as disclosed in U.S. Pat. 4,069,055, 4,069,056, EP 104,143, US 339,049, EP 410,201, JP 2-150848, JP-A No. 2-150848, JP- Iodonium salts described in JP-A No. 2-296514, European Patent No. 370,693, EP 390,214, JP 233,567, EP 297,443, EP 297,442, US 4,933,377, EP 161,811, EP 410,201, EP 339,049, JV Crivelloetal, Macromolecules, 10 (6), 1307 (1977), JV Crivello et al., U.S. Patent Nos. 4,760,013, 4,734,444 and 2,833,827, German Patents 2,904,626, 3,604,580 and 3,604,581, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), C. S. Wenetal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and the like.

Particularly, from the viewpoints of reactivity and stability, the acid generator is preferably the oxime ester compound or the onium salt compound.

As the onium salt compounds, diazonium salts, iodonium salts and sulfonium salts are suitably used.

The content of the acid generator is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or less, relative to the total solid content of the radiation sensitive resin composition of the present invention. By mass or more and 15% by mass or less.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and an amine-based antioxidant, but a phenol-based antioxidant is particularly preferable. The antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 part by mass to 10 parts by mass, particularly preferably 0.2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymer component [A] contained in the radiation sensitive resin composition of the present embodiment Mass part. When used in this range, heat resistance of the infrared shielding film formed of the radiation sensitive resin composition can be further improved.

As the antioxidant, an antioxidant described in Japanese Laid-Open Patent Publication No. 2011-227106 can be used.

The polyfunctional acrylate is preferably 100 parts by mass or less, more preferably 0.1 parts by mass or more and 80 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or less, And not more than 25 parts by mass. When used in this range, heat resistance and solvent resistance of the infrared shielding film formed of the radiation sensitive resin composition can be further improved.

As polyfunctional acrylates, polyfunctional acrylates described in JP-A-2005-227525 can be used.

The surfactant is a component for enhancing the film-forming property of the radiation-sensitive resin composition. By containing the surfactant, the radiation sensitive resin composition of the present invention can improve the surface smoothness of the coating film, and as a result, the uniformity of the thickness of the infrared shielding film formed of the radiation sensitive resin composition can be further improved.

The adhesion assisting agent is a component that improves the adhesion between the film forming object such as a substrate and the infrared shielding film. The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the infrared shielding film.

As the adhesion auxiliary agent, a functional silane coupling agent is preferred.

As the inorganic oxide particles, inorganic oxide particles which are oxides containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium can be used . The inorganic oxide particles described in JP-A-2011-128385 can be used.

The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer having the [A] polymer component. The radiation sensitive resin composition contains a compound having a cyclic ether group to accelerate the crosslinking of the polymer component or the like by the thermal reactivity of the compound having a cyclic ether group to form an infrared shielding film The hardness of the radiation-sensitive resin composition can be further increased, and the radiation sensitivity of the radiation-sensitive resin composition can be increased.

As the compound having a cyclic ether group, a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule is preferable. As the compound having an epoxy group as the compound having a cyclic ether group, the compounds described in JP-A No. 2011-257537 can be used.

Among them, the compound having a cyclic ether group is preferably a compound having at least two oxetanyl groups in the molecule, and the isophthalic acid bis [(3-ethyloxetan-3-yl) methyl], 1,4-bis [ Epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1- EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.)) is more preferable.

The content of the cyclic ether group-containing compound is preferably 150 parts by mass or less, more preferably 0.5 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the polymer component [A] And more preferably 10 parts by mass or more and 25 parts by mass or less. By setting the content of the compound having a cyclic ether group within the above range, the hardness of the infrared shielding film formed of the radiation sensitive resin composition can be further increased.

&Lt; Preparation method of radiation-sensitive resin composition >

The radiation sensitive resin composition is prepared by dissolving or dispersing the [A] polymer, the [B] quinone diazide compound, and the [C] infrared shielding material, a suitable component and other optional components in a solvent . For example, the radiation-sensitive resin composition can be prepared by mixing the respective components in a predetermined ratio in a solvent.

<Solvent>

As the solvent, those which do not react with other components in the radiation-sensitive resin composition are uniformly dissolved or dispersed and suitably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates , Aromatic hydrocarbons, ketones, and other esters. As the solvent, a solvent described in JP-A-2011-232632 can be used.

&Lt; Polymer composition >

The polymer composition of the present invention contains a polymer component having at least one selected from the group consisting of a structural unit containing a carboxyl group, a structural unit containing a polymerizable group and other structural units. This polymer component is the same as the polymer component [A] of the radiation-sensitive resin composition.

<Infrared shielding film>

The infrared shielding film of the present invention is formed of the radiation sensitive resin composition. Since the infrared ray shielding film is formed of the radiation sensitive resin composition, it has excellent water repellency, appearance characteristics of the coating film, and uniformity of the film thickness. Such an infrared shielding film having such characteristics can be suitably used as an infrared shielding film of a solid-state image pickup device, an illuminance sensor, a proximity sensor or the like. The method for forming the infrared ray shielding film is not particularly limited, but it is preferable to apply the infrared ray shielding film formation method described below.

&Lt; Method of Forming Infrared Shielding Film &

The radiation sensitive resin composition can be suitably used for forming an infrared shielding film.

A method of forming an infrared shielding film of the present invention is a method of forming a coating film on a substrate (hereinafter also referred to as &quot; step (1) &quot;) using the radiation sensitive resin composition, (Hereinafter, also referred to as &quot; step (3) &quot;) for heating the coated film (hereinafter also referred to as &quot; (4) &quot;).

According to the method of forming the infrared ray shielding film, an infrared ray shielding film having high pattern stability can be formed. In addition, since the film thickness variation amount of the unexposed portion can be suppressed, the production process margin can be consequently improved and the yield can be improved. Further, by forming a pattern by exposure, development and heating using photosensitivity, an infrared shielding film having a fine and precise pattern can be easily formed.

[Step (1)]

In this step, the radiation-sensitive resin composition is applied to a substrate to form a coating film. When the radiation sensitive resin composition contains a solvent, it is preferable to remove the solvent by pre-baking the coated surface.

Examples of the substrate include glass, quartz, silicon, resin, and the like. Examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, cyclic olefin, and hydrogenated products thereof. The conditions of the prebaking differ depending on the kind of each component, the mixing ratio, etc., but are usually about 70 to 120 DEG C and about 1 to 10 minutes.

[Step (2)]

In this step, at least a part of the coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for the exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable. The exposure dose is preferably 500 J / m2 to 6,000 J / m2, more preferably 1,500 J / m2 to 1,800 J / m2. The exposure dose is a value measured by a light meter (OAI model 356, manufactured by OAI Optical Associates) of the intensity of the radiation at a wavelength of 365 nm.

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (irradiated portions) are removed to form a predetermined pattern.

As the developer used in this step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like.

As the developer containing an organic solvent, an organic solvent such as a ketone-based organic solvent or an alcohol-based organic solvent may be used. By using a developing solution containing such an organic solvent, a negative, positive reversed pattern can be formed (see, for example, JP-A-2014-199272).

To the aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining suitable developability.

Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. The developing time varies depending on the composition of the radiation sensitive resin composition, but is usually about 10 seconds to 180 seconds.

Following this development processing, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with compressed air or compressed nitrogen, for example, to form a desired pattern.

The rate of change of the film thickness after development relative to the development film thickness of the coating film before development is preferably 90% or more. As described above, according to the formation method using the radiation sensitive resin composition, the amount of change in the film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90% or more of the film thickness before development .

[Step (4)]

In this step, the developed coating film is heated. For the heating, the patterned thin film is heated by using a heating device such as a hot plate or an oven to accelerate the curing reaction of the [A] polymer component to form an infrared shielding film. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, but is, for example, about 5 minutes to 30 minutes on a hot plate and about 30 minutes to 90 minutes in an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, the patterned thin film corresponding to the intended infrared ray shielding film can be formed on the surface of the substrate. The film thickness of the infrared ray shielding film is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m.

<Solid-state image sensor>

1 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image pickup device.

The camera module 200 shown in Fig. 1 is connected to a circuit board 70, which is a mounting board, via a solder ball 60 which is a connecting member.

More specifically, the camera module 200 includes a solid-state imaging element substrate 100 having an imaging element portion on a first main surface of a silicon substrate and a first main surface side 1), a glass substrate 30 (light transmitting substrate) disposed above the infrared shielding film formed on the planarization layer, and a glass substrate 30 (light transmitting substrate) And a light shielding and electromagnetic shield (not shown) disposed around the solid-state imaging element substrate 100 and the glass substrate 30 so as to surround the solid-state imaging element substrate 100 and the glass substrate 30 44 as shown in Fig. Each member is bonded by an adhesive (not shown in Fig. 1).

The present invention relates to a method of manufacturing a camera module having a solid-state imaging element substrate and an infrared ray shielding film disposed on a light receiving side of the solid-state imaging element substrate, The infrared shielding film is formed by applying the composition.

Therefore, in the camera module according to the present embodiment, the infrared ray shielding film is formed, for example, by applying the radiation sensitive resin composition of the present invention on the planarizing layer. The method of forming the infrared shielding film is as described above.

In the camera module 200, incident light hν from the outside sequentially passes through the imaging lens 40, the glass substrate 30, the infrared shielding film 42, and the flattening layer, And reaches the imaging element portion.

The camera module 200 is connected to the circuit board 70 via the solder balls 60 (connection material) on the second main surface side of the solid-state imaging element substrate 100. [

<Light intensity sensor>

The configuration of the light intensity sensor according to the present embodiment will be described with reference to Fig. 2 is a cross-sectional view showing the configuration of the illuminance sensor. As shown in this figure, the illuminance sensor comprises a glass epoxy resin substrate 4, an illuminance sensor light receiving element 6, a distance detecting light receiving element 8, an infrared light emitting element 10, a gold wire 12 ), A resin (16), and an infrared ray shielding film (18). In the illuminance sensor 1, the infrared rays emitted from the infrared ray emitting element 10 and reflected by the object are incident on the distance detecting light receiving element 8 to detect the distance. The illuminance sensor unit 2 is provided with a glass epoxy resin substrate 4, an illuminance sensor light receiving element 6, a gold wire 12, a resin 16, and an infrared ray shielding film 18.

(Example)

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. The weight average molecular weight (Mw) of the polymer component [A] was measured by the following method.

[Weight average molecular weight (Mw)]

Was measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: "GPC-101" manufactured by Showa Denko K.K.

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

&Lt; Synthesis of polymer component [A]

[Synthesis Example 1] (Synthesis of polymer (A-1)

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were placed. Subsequently, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of? -Methyl-p-hydroxystyrene, 10 parts by mass of styrene, 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of cyclohexylmaleimide and 10 parts by mass of n-lauryl methacrylate were charged, and after replacing with nitrogen, the temperature of the solution was raised to 70 DEG C while stirring slowly, and this temperature was maintained for 5 hours to polymerize To obtain a solution containing the polymer (A-1). The Mw of the polymer (A-1) was 8000.

[Synthesis Example 2] (Synthesis of polymer (A-2)) [

(0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Garris Co., Ltd.) 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Kasei Kogyo K.K.) as a terminal endblock were dissolved in 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) &Lt; / RTI &gt; Then, 31.2 g (0.1 mole) of bis (3,4-dicarboxyphenyl) ether anhydride (Mannock Corp.) was added together with 20 g of NMP, and the mixture was reacted at 20 ° C for 1 hour and then at 50 ° C for 4 hours . Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 캜 for 5 hours while water was azeotropically mixed with xylene. After completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 캜 for 20 hours to obtain a polymer (A-2) having a structure represented by the following formula.

[Synthesis Example 3] (Synthesis of polymer (A-3)

In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was added. Subsequently, 50 parts by mass of methyltrimethoxysilane, 30 parts by mass of phenyltrimethoxysilane and 20 parts by mass of? -Glycidoxypropyltrimethoxysilane were added and heated until the solution temperature reached 60 占 폚. After the solution temperature reached 60 占 폚, 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were added, and the mixture was heated to 75 占 폚 and stored for 4 hours. The solution temperature was adjusted to 40 캜, and this was kept at this temperature to remove the generated methanol by ion exchange water and hydrolysis and condensation. Thus, a polymer (A-3) was obtained as a polysiloxane which is a hydrolysis-condensation product. The polymer (A-3) which is a polysiloxane had an Mw of 5,000.

<Synthesis Example of Phosphoric Acid Copper Complex>

(180 mL, manufactured by Wako Pure Chemical Industries, Ltd.), 73.6 g (0.42 mol, manufactured by Tokyo Kasei Kogyo K. K.) of 2-hydroxyethyl methacrylate (0.38 mol, Wako Pure Chemical Industries, Ltd.) 116 g (0.38 mol, manufactured by Tokyo Kasei Kogyo K.K.) of pyridine solution (400 mL) of 1,3,5-triisopropylsulfonic acid chloride was added at 5 ° C or less. After the addition, the reaction was completed by stirring at room temperature for 6 hours. 2.9 L of a 10% aqueous solution of sodium hydrogencarbonate was added so that the temperature did not rise above 30 DEG C, followed by washing with ethyl acetate. Concentrated hydrochloric acid was added to the aqueous layer to adjust the pH to 1, and the desired product was extracted with ethyl acetate. After removal of the solvent, chloroform / water solution was added to remove the 1,3,5-triisopropyl sulfonic acid produced as a by-product during the reaction. Finally, 10 mg of para-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the solvent of the organic layer was distilled off to obtain a phosphoric acid ester compound (22 g, yield 20%).

The phosphoric acid ester (3.15 g, 11.0 mmol) and methanol (16.6 g) were mixed to prepare a methanol solution of phosphoric acid ester. Copper acetate (1 g, 5.5 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the methanol solution of phosphoric acid ester, and the temperature was raised to 50 占 폚 and the reaction was carried out for 2 hours. After completion of the reaction, the acetic acid and the solvent generated in this separator were distilled off to obtain phosphoric acid ester copper complex 1 (3.5 g).

[Preparation of radiation-sensitive resin composition]

The [B] quinone diazide compound, the [C] infrared shielding compound and other optional compounds used for preparing the radiation sensitive resin composition are shown below.

([A] polymer)

A-1: The polymer (A-1) obtained in Synthesis Example 1

A-2: Polymer (A-2) obtained in Synthesis Example 2

A-3: The polymer (A-3) obtained in Synthesis Example 3

A-4: A novolak resin (trade name: XPS-4958G, m-cresol / p-cresol ratio = 55/45 (weight ratio), manufactured by Hirokaku Kogyo K.K.)

([B] quinone diazide compound)

B-1: 4,4'- [1- [4- [1- (4-hydroxyphenyl) -1- methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide- A condensate of sulfonic acid chloride

B-2: Condensation product of 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride

([C] Infrared shielding material)

C-1: YMF-02 (Sumitomo Keene joku kojan prepared cesium tungsten oxide manufactured by right or wrong (Cs _{0 .33} WO ₃ (18.5% by mass dispersion of the average dispersed particle diameter less than 800nm)))

C-2: Cyanine dye (Daito chemix 1371F manufactured by Daito Kikusui Co., Ltd., maximum absorption wavelength (? Max = 805 nm)

C-3: Phosphoric acid ester copper complex 1 obtained by the synthesis of the phosphoric acid ester copper complex

(Compound having [D] cyclic ether group)

D-1: Isophthalic acid bis [(3-ethyloxetan-3-yl) methyl]

D-2: 1,4-Bis [(3-ethyloxetan-3-yl) methoxymethyl] benzene represented by the following formula (D-

([F] antioxidant)

F-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60 from Adeka Co., Ltd.)

[Preparation of radiation-sensitive resin composition 1]

25 parts by mass of the [B] quinonediazide compound (B-1) was added to a polymer solution (polymer component (A-1) 100 parts by mass (solid content) , 18 parts by mass of (C-1) as the infrared shielding material, 5 parts by mass of the compound (D-1) as the compound having the cyclic ether group [D] and 0.5 parts by mass of the [F] Were mixed to prepare a radiation-sensitive resin composition 1 (hereinafter also referred to as &quot; Composition 1 &quot;).

[Preparation of radiation-sensitive resin composition 2]

(B-2) 30 as the [B] quinone diazide compound was added to a polymer solution (Polymer A-2) containing 100 parts by mass (solid content) (Hereinafter referred to as &quot; Composition 2 &quot;), 30 parts by mass of [C] infrared shielding material (C-2) and 5 parts by mass of (D- ).

[Preparation of radiation-sensitive resin composition 3]

(B-1) as the [B] quinone diazide compound was added to a polymer solution (polymer component (A-3) in an amount corresponding to 100 parts by mass (solid content)) of polymer [A] , 20 parts by mass of (C-3) as the infrared shielding material, and 1 part by mass of (F-1) as the antioxidant were mixed to obtain a radiation-sensitive resin composition 3 ).

[Preparation of radiation-sensitive resin composition 4]

(B-1) as a [B] quinone diazide compound was added to a polymer solution (Polymer (A-4) in an amount corresponding to 100 parts by mass (solid content)) of polymer [A] , 20 parts by mass of (C-3) as the infrared shielding material, and 1 part by mass of (F-1) as the antioxidant were mixed to obtain a radiation-sensitive resin composition 4 ).

In the comparative example, the same preparation was made except that the compound (C-1) was not contained in the preparation of the radiation-sensitive resin composition 1 (hereinafter also referred to as "comparative composition").

<Evaluation>

Radiation-sensitive resin compositions 1 to 4 and radiation-sensitive resin compositions of comparative examples were used to evaluate the radiation sensitivity, the infrared shielding property, the chemical resistance and the refractive index of the infrared shielding film.

Example 5 was evaluated in the same manner except that the radiation-sensitive resin composition 1 was used and butyl acetate was used as a developer. In the case of Example 5, the unexposed portion is developed with butyl acetate, and a pattern can be obtained in the exposed portion. The evaluation results are shown in Table 1.

[Evaluation of radiation sensitivity]

The radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then baked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 25.0 mu m. Subsequently, exposure was carried out using a photomask having an island pattern of 200 mu m square shape using an exposure machine ("MPA-600FA" (ghi line mixing) manufactured by Canon Inc.) And irradiated with radiation. Thereafter, it was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 캜 for 80 seconds by a puddle method. Next, water washing was performed for 1 minute with ultra-pure water, and then dried to form a pattern. At this time, the amount of exposure necessary to completely dissolve the island pattern having a square shape of 200 mu m was examined. When the value of the exposure dose is less than 300 mJ / cm 2, it can be judged that the radiation sensitivity is good.

Evaluation criteria are shown below.

A: Less than 300 mJ / cm 2

B: 300 mJ / cm 2 or more, less than 400 mJ / cm 2

[Evaluation of infrared shielding property]

A radiation-sensitive resin composition was applied to a glass substrate under the above conditions using a spinner, and then a photosensitive layer (curable composition layer) coating film having a thickness of 25 mu m was formed, and a spectrophotometer (manufactured by Hitachi Seisakusho Quot; 150-20 type double beam &quot;) was used to measure the transmittance of the coating film at a wavelength of 1200 nm. The lower the value, the better the infrared shielding. When the transmittance is less than 2%, it can be said that it shows practically good infrared ray shielding property.

[Evaluation of Chemical Resistance of Infrared Shielding Film]

The chemical resistance of the infrared shielding film was evaluated as swelling (swelling) due to the peeling liquid. The radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then baked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 25.0 mu m. Subsequently, the substrate was baked for 30 minutes using an oven heated to 230 deg. C to form an infrared shielding film. This film was immersed in N-methylpyrrolidone solvent heated to 40 占 폚 for 3 minutes, and the film thickness change ratio (%) before and after immersion was determined and used as an index of chemical resistance. A: Change in film thickness is less than 5%, B: Change in film thickness is not less than 5% and less than 10%, C: Change in film thickness is not less than 10% and less than 15% . The film thickness was measured at 25 占 폚 using a light interference film thickness measuring apparatus (Lambda Ace VM-1010).

[Evaluation of refractive index (optical refractivity)] [

For the substrate having the infrared shielding film formed in the evaluation of the chemical resistance, the refractive index was measured by "Prism coupler model 2010" of Metricon. The refractive index was measured at three wavelengths of 408 nm, 633 nm and 828 nm. The refractive index was evaluated as &quot; A &quot; when the measured value at 633 nm was 1.60 or more, and &quot; B &quot; When the refractive index is high, it can be said that it is good in terms of optical characteristics.

As is evident from the results in Table 1, the radiation sensitive resin compositions of Examples 1 to 5 were excellent in radiation sensitivity, excellent in infrared ray shielding property, chemical resistance and refractive index.

On the other hand, the radiation sensitive resin compositions of the comparative examples were found to be excellent in radiation sensitivity and chemical resistance, but had a poor infrared shielding property and a low refractive index.

30: glass substrate
40: imaging lens
42: Infrared shielding film
44: Shielding and Electronic Shield
50: Lens holder
60: solder ball
70: circuit board
100: Solid-state imaging element substrate
200: camera module
1: Light sensor
2: illuminance sensor unit
4: Glass epoxy resin substrate (substrate)
6: Illumination sensor Light receiving element
8: Light receiving element for distance detection
10: Infrared light emitting element (light emitting element)
12: Gold wire
16: Resin
18: Infrared shielding film

Claims (13)

[A] Polymer,
[B] quinone diazide compound, and
[C] Infrared shielding material
By weight of the radiation-sensitive resin composition. The method according to claim 1,
Wherein the polymer [A] is at least one polymer selected from an acrylic resin having a carboxyl group, a polyamic acid, a polyimide resin, a polysiloxane and a novolac resin. The method according to claim 1,
Wherein the infrared ray shielding material [C] is at least one selected from metal oxides, copper compounds and pigments. The method of claim 3,
Wherein the metal oxide is tungsten oxide cesium. The method of claim 3,
Wherein the copper compound is a phosphorus-containing copper compound. The method of claim 3,
Wherein the dye is a cyanine dye, a phthalocyanine dye, a quaternary dye, an aminium dye, an iminium dye, an azo dye, an anthraquinone dye, a diimonium dye, a squarylium dye or a porphyrin dye. The method of claim 3,
Wherein the content of at least one of the metal oxide and the copper compound is not less than 5 mass% and not more than 70 mass% with respect to the total solid mass of the radiation sensitive resin composition. The method of claim 3,
Wherein the content of the coloring matter is 1% by mass or more and 30% by mass or less based on the total solids mass of the radiation sensitive resin composition. An infrared shielding film formed using the radiation sensitive resin composition according to any one of claims 1 to 8. A solid-state imaging device having the infrared shielding film according to claim 9. An illuminance sensor having the infrared ray shielding film according to claim 9. (1) a step of forming a coating film of the radiation sensitive resin composition according to any one of claims 1 to 8 on a substrate,
(2) a step of irradiating at least a part of the coating film formed in the step (1)
(3) a step of developing the coated film irradiated with the radiation in the step (2)
(4) a step of heating the developed coating film in the step (3)
Wherein the infrared ray shielding film is formed on the substrate. 13. The method of claim 12,
A method of forming an infrared shielding film, wherein in the step (2), a developer containing an organic solvent is used.

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