CN110506224A - The forming method of solid-state imager composition and solid-state imager infrared ray shielding film - Google Patents

Abstract

The present invention is a kind of solid-state imager composition, it includes inorganic compound, polymer, organic pigment and solvents, the amine value of the polymer is 90mgKOH/g or more and 200mgKOH/g or less, the solvent includes that solubility parameter is 8.8 or more and 12.0 specific solvents below, the specific solvent relative to the solid-state imager is 40 mass % or more and 90 mass % with the content of composition entirety hereinafter, the solubility of the organic pigment in the solvent at 20 DEG C, 0.1MPa is 2 mass % or more.

Description

The shape of solid-state imager composition and solid-state imager infrared ray shielding film At method

Technical field

The present invention relates to the formation of a kind of solid-state imager composition and solid-state imager infrared ray shielding film Method.

Background technique

Equipped with charge-coupled device in video camera, digital camera, mobile phone with camera-enabled etc. (Charge-Coupled Device, CCD) imaging sensor or complementary metal oxide semiconductor (Complementary Metal oxide semiconductor, CMOS) solid-state imagers such as imaging sensor.Have in the solid-state imager The sensitivity of standby photodiode crosses over visible light region to infrared spectral range.Therefore, in solid-state imager, it is arranged useful To interdict the optical filter of infrared ray.Optical filter is interdicted using the infrared ray, the mode that can be close to the visual acuity of the mankind is corrected The sensitivity of solid-state imager.

Contain organic pigment or the inorganic compound (ginseng as infrared ray smoke agent for shielding in infrared ray blocking optical filter According to Japanese Patent Laid-Open 2013-137337 bulletin, Japanese Patent Laid-Open 2013-151675 bulletin).Infrared ray blocking filters Piece can usually be formed and coating includes the composition of infrared ray smoke agent for shielding on substrate.Optical filter is interdicted in the infrared ray In, the film of the composition is functioned as the film for covering infrared ray.

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2013-137337 bulletin

Patent document 2: Japanese Patent Laid-Open 2013-151675 bulletin

Summary of the invention

Problem to be solved by the invention

Solid-state imager composition is required to be formed and has both good visible light permeability and infrared ray masking The optical filter of property.In addition, requiring dispersion stabilization or ageing stability high solid-state imager composition.Institute State it is insufficient in the case where, the generation or productivity of the defect of resulting optical filter (infrared ray shielding film) can be caused Decline.In addition, also resulting in influence to visible light permeability or infrared ray shielding.In turn, also have film is exposed and The case where developing and forming patterned infrared ray shielding film, but in this case, used solid-state imager is used Composition requires good pattern.

The present invention is formed in view of the situation, and its purpose is to provide a kind of solid-state imager composition and uses The forming method of the solid-state imager shielding film of the solid-state imager composition, the solid-state imager group Closing object can form that dispersion stabilization and ageing stability are high, defect is few, have both good visible light permeability and infrared ray masking The solid-state imager optical filter of property.

Technical means to solve problem

The invention completed in order to solve the problem is a kind of solid-state imager composition, and it includes inorganic chemicals Object, polymer, organic pigment and solvent, the amine value of the polymer is 90mgKOH/g or more and 200mgKOH/g is hereinafter, described Solvent includes that solubility parameter is 8.8 (cal/cm³)^1/2Above and 12.0 (cal/cm³)^1/2Specific solvent below, it is described specific Solvent is 40 mass % or more relative to the content of the solid-state imager composition entirety and 90 mass % are hereinafter, 20 DEG C, the solubility of the organic pigment in the solvent under 0.1MPa be 2 mass % or more.

Another invention completed in order to solve the problem is a kind of shape of solid-state imager infrared ray shielding film At method comprising in a step of surface side of substrate forms film, formed by this solid-state imager with composition The film.

The effect of invention

According to the present invention, it is possible to provide a kind of solid-state imager composition and use solid-state imager combination The forming method of the solid-state imager shielding film of object, the solid-state imager composition can be formed dispersion stabilization and Ageing stability is high, defect is few, has both good visible light permeability and the solid-state imager optics of infrared ray shielding Optical filter.

Specific embodiment

Hereinafter, to the solid-state imager composition and solid-state imager infrared ray of one embodiment of the present invention The forming method of shielding film is described in detail.

< solid-state imager composition >

The solid-state imager composition (hereinafter, also referred to as " composition ") of one embodiment of the present invention includes [A] inorganic compound, [B] polymer, [C] organic pigment and [D] solvent.[B] polymer be amine value be 90mgKOH/g or more and 200mgKOH/g polymer below.[D] solvent includes that solubility parameter (hereinafter also referred to as " SP value ") is 8.8 (cal/cm³)^1/2 Above and 12.0 (cal/cm³)^1/2Specific solvent below (hereinafter also referred to as " [D1] solvent ").[D1] solvent is relative to described The content of solid-state imager composition entirety is 40 mass % or more and 90 mass % or less.In addition, in 20 DEG C, 0.1MPa Under [D] solvent in [C] organic pigment solubility be 2 mass % or more.

In this composition, by using [B] polymer with specific amine value, the dispersibility of [A] inorganic compound It improves.In turn, by [D1] solvent with specific solubility parameter containing specified amount, [A] inorganic compound can be improved Dispersibility.In the case where the dispersibility of [A] compound is high, the visible light permeability or infrared ray of resulting optical filter Shielding also becomes good.In addition to this, by can further change high [C] organic pigment of dissolubility and [D] solvent combination It is apt to the visible light permeability or infrared ray shielding etc..Therefore, according to this composition, can be formed dispersion stabilization and through when it is steady Qualitative height, defect is few, has both good visible light permeability and the solid-state imager optical filter of infrared ray shielding.

This composition preferably also includes [E] polymerizable compound, in addition to this preferably includes [F] polymerization initiator. This composition can also include other compositions.Hereinafter, each ingredient is described in detail.

([A] inorganic compound)

[A] inorganic compound is the ingredient functioned as infrared ray smoke agent for shielding.[A] inorganic compound can be so-called Pigment.[A] inorganic compound preferably has maximum absorption wavelength more than wavelength 800nm and in the range of 2,000nm or less. [A] inorganic compound is particle shape, disperses to exist in this composition.

As [A] inorganic compound, the preferably oxide of metal or semimetal (silicon etc.).As [A] inorganic compound, It is specifically preferably tungsten oxide caesium, quartz, magnetic iron ore, aluminium oxide, titanium dioxide, zirconium oxide, spinelle or the combination. The inorganic compound, which can be used alone, one kind or to be used in mixed way two or more.

As [A] inorganic compound, it is described in preferably tungsten oxide caesium.Tungsten oxide caesium is to infrared ray (especially wavelength About 800nm or more and 1,200nm infrared ray below) absorb high (that is, the shielding to infrared ray is high), low to visible absorption Infrared ray smoke agent for shielding.Therefore, by using tungsten oxide caesium, the good visible light-transmissive of resulting optical filter can be maintained Property and improve infrared ray shielding.

Tungsten oxide caesium is for example indicated using following formula (a).

Cs_xWO_y···(a)

In formula (A), 0.001≤x≤1.1.2.2≦y≦3.0.

It is 0.001 or more by the x in the formula (a), can sufficiently covers infrared ray.The lower limit of x is preferably 0.01, more excellent It is selected as 0.1.It on the other hand, is 1.1 hereinafter, can more reliably avoid generating impurity phase in tungsten oxide caesium by x.The upper limit of x Preferably 1, more preferably 0.5.

It is 2.2 or more by the y in the formula (a), can further improve the chemical stability as material.The lower limit of y Preferably 2.5.It on the other hand, is 3.0 hereinafter, infrared ray can sufficiently be covered by y.

As the concrete example of tungsten oxide caesium represented by the formula (a), Cs can be enumerated_0.33WO₃Deng.

[A] inorganic compound is preferably particulate.The upper limit of average grain diameter (D50) as [A] inorganic compound, preferably For 500nm, more preferably 200nm, and then preferably 50nm, and then more preferably 30nm, it is even more preferably 20nm.Pass through Average grain diameter is the upper limit hereinafter, can further improve visible light permeability.On the other hand, handling easiness when just manufacturing Deng reason for, the average grain diameter of [A] inorganic compound is usually 1nm or more, can also be 10nm or more.Furthermore it is described flat Equal partial size (D50) aggregate particle size in composition thus.

Well known method synthesis can also be used in [A] inorganic compound, can be used as commercially available product and obtains.Such as tungsten oxide caesium It can be used as the dispersion of the tungsten oxide caesium particulate of " YMF-02 " of mine company, Sumitomo Metal Industries etc. and obtain.

The lower limit of the content shared in all solids ingredient in this composition as [A] inorganic compound, preferably 1 Quality %, more preferably 10 mass %, and then preferably 20 mass %, and then more preferably 30 mass %.On the other hand, as The upper limit of the content, preferably 70 mass %, more preferably 60 mass %.By the way that the content of [A] inorganic compound is set as In the range, the visible light permeability and infrared ray shielding of resulting optical filter reach more good balance.In addition, The dispersion stabilization of this composition or ageing stability can be made to become better.Furthermore so-called all solids ingredient refers to that [D] is molten Whole components other than agent.

([B] polymer)

[B] polymer is the ingredient for improving the dispersibility of [A] inorganic compound etc..[B] polymer may include a kind of polymerization Object can also be the mixture of the two or more polymer with identical or different amine value.Amine value is the polymerization of 0mgKOH/g Object is not included in [B] polymer of the mixture as multiple polymers.

The lower limit of the amine value of [B] polymer is 90mgKOH/g, preferably 110mgKOH/g, more preferably 130mgKOH/g. On the other hand, the upper limit of the amine value is 200mgKOH/g.By using the polymer with the amine value, [A] inorganic chemical The dispersibility of object improves, and can further improve the visible light permeability and infrared ray shielding of resulting optical filter.Furthermore So-called " amine value " is the mg number with the KOH for neutralizing HCl equivalent required for polymer solids ingredient 1g.As [B] polymer, In In the case where being used in mixed way the multiple polymers with different amine values, the amine value of [B] polymer by described in is set as being weighted and averaged Value.

[B] polymer is preferably block copolymer.As block copolymer, preferably following block copolymer is described embedding Section copolymer includes the A block containing the functional group comprising nitrogen-atoms and the B block with said solvophilic.The packet of A block The functional group of nitrogen atom shows the good adsorptivity to [A] inorganic compound.Therefore, by using with A block and B The block copolymer of block can further improve the dispersibility of [A] inorganic compound.

A block preferably has structural unit represented by such as following formula (1).

[changing 1]

In formula (1), X is bivalence linking base.R¹For hydrogen atom or methyl.R²And R³It is separately hydrogen atom or can Chain or cricoid alkyl or R with substituent group²With R³It is mutually bonded and is formed together with the be bonded nitrogen-atoms Ring structure.

It as the X, can enumerate: methylene, the alkylidene of carbon number 2~10, arlydene ,-CONH-R⁷Represented by (*) Base ,-COO-R⁸Base represented by (*) etc..R⁷And R⁸Separately for methylene, the alkylidene of carbon number 2~10 or carbon number 2~ 10 alkyleneoxyalkylene group.(*) indicates the bond position with N.As X, preferably-COO-R⁸Represented base, as R⁸, The preferably alkylidene of carbon number 2~6.

As R²And R³, preferably chain alkyl, more preferably the chain alkyl of carbon number 1~5, and then preferably methyl, second Base and propyl.

As the monomer of structural unit represented by the formula (1) is provided, can enumerate: (methyl) acrylate Ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate propyl ester, (methyl) acrylic acid diethyl Amino propyl ester etc..

A block also may include the structural unit other than structural unit represented by the formula (1).As in block copolymer A block content ratio, preferably such as 30 mass % or more and 70 mass % or less.

B block preferably has structural unit represented by such as following formula (2).

[changing 2]

In formula (2), R⁴It is separately the alkylidene of carbon number 2~4.R⁵For hydrogen atom or the alkyl of carbon number 1~6.R⁶For Hydrogen atom or methyl.The integer that n is 1~150.

As R⁴, preferably ethylidene and methyl ethylidene.As R⁵, preferably methyl, ethyl, propyl and butyl.N's The upper limit is preferably 20, and more preferably 10, and then preferably 5.

As the monomer of structural unit represented by the formula (2) is provided, can enumerate: polyethylene glycol (n=1~5) methyl ether (methyl) acrylate, polyethylene glycol (n=1~5) ether (methyl) acrylate, polyethylene glycol (n=1~5) propyl ether (first Base) acrylate, polypropylene glycol (n=1~5) methyl ether (methyl) acrylate, polypropylene glycol (n=1~5) ether (methyl) third Olefin(e) acid ester, polypropylene glycol (n=1~5) propyl ether (methyl) acrylate etc..

B block also may include the structural unit other than structural unit represented by the formula (2).May include as B block Other structures unit, the structural unit from (methyl) acrylate can be enumerated.Specifically, as other structures list is provided The monomer of member, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) propylene Isopropyl propionate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) propylene Sour cyclohexyl etc..

As the content ratio of the B block in block copolymer, preferably such as 30 mass % or more and 70 mass % with Under.

The lower limit of average molecular weight as [B] polymer, for example, 3,000, preferably 6,000.On the other hand, as The upper limit, for example, 30,000, preferably 20,000.

Block copolymer can be synthesized using conventionally known method.In addition, block copolymer and other [B] polymer can also Use commercially available product.[B] polymer can also be at least part of point of the surface of [A] inorganic compound coating in this composition Powder.

The lower limit of the content of [B] polymer preferably 5 mass parts relative to 100 mass parts of [A] inorganic compound, it is more excellent It is selected as 10 mass parts, and then preferably 20 mass parts.On the other hand, the upper limit of the content is preferably 200 mass parts, more preferably For 100 mass parts, and then preferably 60 mass parts.

([C] organic pigment)

[C] organic pigment is the ingredient functioned with [A] inorganic compound together as infrared ray smoke agent for shielding.Pass through group It closes and uses [A] inorganic compound and [C] organic pigment, good visible light permeability and infrared ray shielding can be played.[C] has Machine pigmentolysis is in [D] solvent.

As [C] organic pigment, organic dyestuff or organic pigment, preferably organic dyestuff can be enumerated.By using organic Dyestuff improves the dissolubility of [D] solvent, can further suppress the generation of cohesion foreign matter.

The solubility of [C] organic pigment in [D] solvent at 20 DEG C, 0.1MPa is 2 mass % or more.Therefore, this Composition can get the high dissolubility with [C] organic pigment, dispersion stabilization or ageing stability raising and then defect is few The optical filter of good characteristic.The solubility refers to is dissolving the maximum amount of [C] organic color for [D] solvent The concentration (quality %) of the solution of element, [C] organic pigment i.e. in saturated solution.In the case where [D] solvent is mixed solvent It is using the concentration of [C] organic pigment in saturated solution of the mixed solvent as solvent.The solubility of [C] organic pigment It can be reached by [C] organic pigment and the combination of [D] solvent.Furthermore as the upper limit of the solubility, have no special limit It is fixed, such as can also be 50 mass %.

[C] organic pigment preferably has maximum absorption wave more than wavelength 600nm and in the range of 1,000nm or less It is long.The lower limit of the maximum absorption wavelength is more preferably 650nm.On the other hand, the upper limit is preferably 900nm, and then preferably 850nm.It is logical to use [C] organic pigment with the maximum absorption wavelength, the visible light of resulting optical filter can be made saturating The property crossed or infrared ray shielding are better.

It can be suitable for selecting using conventionally known organic in the range of meeting the solubility as [C] organic pigment Pigment.As [C] organic pigment, diimine compounds, side sour inner salt compound, cyanine compound, phthalocyanine compounds can be used Object, naphthalene phthalocyanine compound, quaterrylene compound, ammonium compounds, group with imine moiety, azo-compound, anthraquinone compounds, porphyrin Compound, pyrrolopyrrole compound, oxonol compound, gram ketone compound, hexa-atomic porphyrin compound or the combination. It preferably include phthalocyanine compound as [C] organic pigment.Phthalocyanine compound color, heat resistance, in terms of it is excellent It is different.

[C] organic pigment, which can be used alone, one kind or to be applied in combination two or more.This composition preferably include two kinds with Upper [C] organic pigment.It in turn, sometimes also more preferably include three kinds or more [C] organic pigments.By the way that a variety of [C] are applied in combination Organic pigment can make the visible light permeability of resulting optical filter or infrared ray shielding better.On the other hand, existing Using a variety of organic pigments, dispersion stabilization or ageing stability etc. decline sometimes.But according to this combination Object can also play good dispersion stabilization or ageing stability even with a variety of organic pigments.As used [C] The upper limit of the species number of organic pigment, is not particularly limited, and may be, for example, 10 kinds, can also be 5 kinds, can also be 3 kinds.

The lower limit of the content shared in all solids ingredient in this composition as [C] organic pigment, preferably 0.1 Quality %, more preferably 0.5 mass %, and then preferably 1 mass %.On the other hand, the upper limit as the content, preferably 30 mass %, more preferably 15 mass %, and then preferably 10 mass %.By the way that the content of [C] organic pigment is set as described In range, the visible light permeability and infrared ray shielding of resulting optical filter reach more good balance.

([D] solvent)

[D] solvent be as [A] inorganic compound decentralized medium function and make the dissolutions such as [C] organic pigment at Point.

[D] solvent includes [D1] solvent.[D1] solvent is that SP value is 8.8 (cal/cm³)^1/2Above and 12.0 (cal/cm³)^1/2 Solvent below.As the lower limit of the SP value, preferably 9.5 (cal/cm³)^1/2.On the other hand, as the upper limit, preferably For 11.0 (cal/cm³)^1/2, more preferably 10.5 (cal/cm³)^1/2.By using [D1] of the SP value with the particular range The dispersibility of [A] inorganic compound or the dissolubility of [C] organic pigment can be improved in solvent.Herein, so-called SP value is to utilize R.F. Take Dare, is recorded in Polym Eng Sci (R.F.Fedors, Polym.Eng.Sci.) 14,147 (1974) below The value that the formula of expense Dare is found out.

Take the formula of Dare:

SP value (δ)=(E_v/v)_1/2=(Σ Δ e_i/ΣΔv_i)_1/2

E_v: evaporation energy

V: molal volume

Δe_i: the atom of each ingredient or the evaporation energy of atomic group

Δv_i: the molal volume of each atom or atomic group

As [D1] solvent, such as can enumerate: normal propyl alcohol (SP value: 11.8), 1,2,5,6- tetrahydro benzylalcohols (SP value: 11.3), diethylene glycol ether (SP value: 10.9), 3- methoxybutanol (SP value: 10.9), glycerol triacetate (SP value: 10.2), propylene glycol monomethyl ether (SP value: 10.2), cyclopentanone (SP value: 10.0), gamma-butyrolacton (SP value: 9.9), cyclohexanone (SP Value: 9.9), propylene glycol-positive propyl ether (SP value: 9.8), propylene glycol-n-butyl ether (SP value: 9.7), dipropylene glycol methyl ether (SP value: 9.7), 1,4- butanediol diacetate esters (SP value: 9.6), 3- methoxybutyl acetic acid esters (SP value: 8.7), propylene-glycol diacetate (SP value: 9.6), lactic acid ethylhexoate (SP value: 9.6), 6-caprolactone (SP value: 9.6), 1,3 butylene glycol diacetate esters (SP , dipropylene glycol-positive propyl ether (SP value: 9.5), 1,6-HD diacetate esters (SP value: 9.5), the positive fourth of dipropylene glycol-value: 9.5) Ether (SP value: 9.4), tripropylene glycol methyl ether (SP value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), adnoral acetate (SP , diethylene glycol ether acetic acid esters (SP value: 9.0), ethylene glycol monomethyl ether acetate (SP value: 9.0), diethylene glycol mono butyl value: 9.2) Ether acetic acid ester (SP value: 8.9), ethylene glycol monomethyl ether acetate (SP value: 8.9), toluene (SP value: 8.9), methyl acetic acid ester (SP Value: 8.8) etc..Furthermore the unit ((cal/cm of SP value³)^1/2) suitably omit.[D1] solvent can be used a kind of or be used in mixed way two Kind or more.

[D1] solvent is 40 mass % relative to the lower limit of the content of this composition entirety, preferably 50 mass %, more excellent It is selected as 60 mass %, and then preferably 65 mass %.By the way that the content of [D1] solvent is set as the lower limit or more, [A] is inorganic The dispersibility of compound or the dissolubility of [C] organic pigment further increase.On the other hand, the upper limit of the content of [D1] solvent is 90 mass %, preferably 80 mass %, more preferably 75 mass %.By by the content of [D1] solvent be set as the upper limit with Under, adjustable an adequate amount of other compositions, that is, by the way that the content of [D1] solvent is set as the range, this composition can be improved Dispersion stabilization and ageing stability, using this composition, can be formed defect is few, have both good visible light permeability with it is red The solid-state imager optical filter of outside line shielding.

[D] solvent also may include [D2] solvent other than [D1] solvent.[D2] solvent is the less than 8.8 (cal/cm of SP value³)^1/2 Or more than 12.0 (cal/cm³)^1/2Solvent.As [D2] solvent, the less than 8.8 (cal/cm of SP value can be enumerated³)^1/2Or it is more than 12.0(cal/cm³)^1/2(poly-) alkane glycol monoalkyl ether, (ring) alkylol, keto-alcohol (poly-) alkane glycol monoalkyl ether acetic acid esters, Ketone, diacetate esters, carboxylate, lactams, aromatic hydrocarbon etc..For example, as the less than 8.8 (cal/cm of SP value³)^1/2(poly-) alkane Glycol monoalkyl ether can enumerate propylene glycol methyl ether acetate (SP value: 8.7) etc..

As the SP value of [D2] solvent, preferably less than 8.8 (cal/cm³)^1/2.In addition, SP value as [D2] solvent Lower limit, preferably 7 (cal/cm³)^1/20, more preferably 8 (cal/cm³)^1/2, and then preferably 8.5 (cal/cm³)^1/2。

The lower limit of content as [D1] solvent in [D] solvent, preferably 50 mass %, more preferably 70 mass %, And then preferably 80 mass %, and then more preferably 90 mass %.[D] solvent substantially can only include [D1] solvent.Passing through will The content of [D1] solvent in [D] solvent is set as the lower limit or more, the dispersibility or [C] organic pigment of [A] inorganic compound Dissolubility further increase, effect of the invention is more fully played.

[D] solvent includes preferably the solvent with cyclic structure.By using the solvent with cyclic structure, dissolubility Or dispersibility becomes better.Solvent with cyclic structure can be [D1] solvent, can also be [D2] solvent, but preferably [D1] Solvent.The cyclic structure can be carbocyclic ring, can also be heterocycle.In addition, the cyclic structure can be polycyclic, it can also be monocycle.Separately Outside, the cyclic structure can be aromatic rings, can also be cycloaliphatic ring.

As the solvent with cyclic structure, preferably cyclic ketone, cyclic ether, lactone (gamma-butyrolacton, 6-caprolactone Deng), lactams, aromatic hydrocarbon (toluene etc.) and the combination.In described, preferably cyclic ketone, lactone and aromatic hydrocarbon, more Preferably cyclic ketone and lactone.

It as cyclic ketone, can enumerate: cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone etc..In described, preferably Cyclopentanone, cyclohexanone and cycloheptanone, more preferably cyclopentanone and cyclohexanone.

As cyclic ether, tetrahydrofuran, oxinane etc. can be enumerated.

As lactone, gamma-butyrolacton, 6-caprolactone etc., preferably gamma-butyrolacton can be enumerated.

It as lactams, can enumerate: amyl- 4- lactams, 5- N-methyl-2-2-pyrrolidone N, hex- 6- lactams, 6- acyl in oneself Amine etc..

The lower limit of content as the solvent with cyclic structure in [D] solvent, preferably 50 mass %, more preferably 70 mass %, and then preferably 80 mass %, and then more preferably 90 mass %.[D] solvent substantially can be only comprising having ring The solvent of shape structure.By the way that the content of the solvent with cyclic structure in [D] solvent is set as the lower limit or more, [A] nothing The dispersibility of machine compound or the dissolubility of [C] organic pigment further increase, and effect of the invention is more fully played.

As under the solid component concentration (total concentration of each ingredient other than [D] solvent) in this composition Limit, preferably 5 mass %, more preferably 10 mass %.On the other hand, the upper limit as the solid component concentration, preferably 50 mass %, more preferably 40 mass %.By the way that solid component concentration is set as in the range, dispersibility, stability, coating Property etc. become better.

([E] polymerizable compound)

In the case where this composition contains [E] polymerizable compound, good hardenability or resulting optics can be played Good heat resistance of optical filter etc..So-called [E] polymerizable compound refers to the compound with more than two polymerizable bases. As polymerizable base, such as ethylene unsaturated group, Oxyranyle, oxetanylmethoxy, N- alkoxy methyl ammonia can be enumerated Base etc..[E] polymerizable compound can be polymer, can also be monomer, but preferably monomer.It is excellent as [E] polymerizable compound It is selected as the compound with more than two (methyl) acryloyl groups and the change with more than two N- alkoxy methyl amino Object is closed, more preferably with the compound of more than two (methyl) acryloyl groups.[E] polymerizable compound can be used it is a kind of or It is used in mixed way two or more.

As the compound with more than two (methyl) acryloyl groups, can enumerate: as aliphatic polyhydroxylated conjunction The multifunctional (methyl) acrylate of the reactant of object and (methyl) acrylic acid etc., multifunctional (methyl) third through caprolactone modification Olefin(e) acid ester, through the modified multifunctional (methyl) acrylate of alkylene oxide, as with hydroxyl (methyl) acrylate and more officials Can isocyanates reactant etc. polyfunctional carbamate (methyl) acrylate, as (methyl) propylene with hydroxyl The multifunctional (methyl) acrylate etc. with carboxyl of the reactant of acid esters and acid anhydrides etc..

Herein, as the aliphatic polyhydroxy compound, such as can enumerate: ethylene glycol, polyethylene glycol, gathers at propylene glycol The bivalent aliphatics such as propylene glycol polyol or glycerol, trimethylolpropane, pentaerythrite, dipentaerythritol etc. three Aliphatic polyhydroxy compound more than valence.As described (methyl) acrylate with hydroxyl, such as (methyl) can be enumerated Acrylic acid 2- hydroxy methacrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, two seasons penta Tetrol five (methyl) acrylate, glycerine dimethacrylate etc..As the polyfunctional isocyanate, such as can enumerate: Toluene di-isocyanate(TDI), hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate Deng.As the acid anhydrides, such as can enumerate: succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, The dibasic acid anhydrides such as hexahydrophthalic anhydride or pyromellitic acid anhydride, biphenyltetracarboxylic dianhydride, benzophenone tetrabasic carboxylic acid two The quaternarys acid dianhydride such as acid anhydride.

As the concrete example of the compound with more than two (methyl) acryloyl groups, such as can enumerate: ω-carboxyl is poly- Caprolactone list (methyl) acrylate, ethylene glycol (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonyl Glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, poly- the third two Alcohol two (methyl) acrylate, double phenoxetol fluorenes two (methyl) acrylate, dihydroxymethyl tristane two (methyl) third Olefin(e) acid ester, 2- hydroxyl -3- (methyl) acryloxypropyl acrylate, (methyl) acrylic acid 2- (2'- ethyleneoxy second Oxygroup) ethyl ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, four (first of pentaerythrite Base) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three (2- (methyl) Acryloyl-oxyethyl) phosphate, ethylene-oxide-modified dipentaerythritol hexaacrylate, succinate modified pentaerythrite 3 third Olefin(e) acid ester, carbamate (methyl) acrylate compounds etc..

In compound with more than two (methyl) acryloyl groups, preferably multifunctional (methyl) acrylate, more Preferably with the multifunctional (methyl) acrylate of 3 or more and 10 (methyl) acryloyl groups below.Specifically, excellent It is selected as trimethylolpropane trimethacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate and two Ji Wusi Six acrylate of alcohol.

As the compound with more than two N- alkoxy methyl amino, such as can enumerate with melamine knot Structure, benzoguanamine structure, compound of urea structure etc..As the compound with more than two N- alkoxy methyl amino Concrete example can be enumerated: N, N, N', N', N ", N "-six (alkoxy methyl) melamine, N, N, N', N'- tetra- (alkoxy methyl) Benzoguanamine, N, N, N', N'- tetra- (alkoxy methyl) glycoluril etc..

The lower limit of the content shared in all solids ingredient of this composition as [E] polymerizable compound, preferably 5 Mass parts, more preferably 10 mass parts, and then preferably 20 mass parts.On the other hand, the upper limit as the content, preferably 60 mass %, more preferably 50 mass %.

([F] polymerization initiator)

[F] polymerization initiator is the ingredient for starting the polymerization reaction of [E] polymerizable compound.It polymerize as [F] and causes Agent can enumerate Photoepolymerizationinitiater initiater, thermal polymerization etc., preferably Photoepolymerizationinitiater initiater.This composition can be assigned as a result, Photonasty (radioactivity-sensitive).So-called Photoepolymerizationinitiater initiater refers to through luminous ray, ultraviolet light, far ultraviolet, electron beam, X The compound for the reactive species that the exposure of the radioactive ray such as ray and generating starts the polymerization of [E] polymerizable compound.[F] polymerization is drawn Hair agent can be used a kind of or be used in mixed way two or more.

It as [F] polymerization initiator, such as can enumerate: thioxanthones based compound, acetophenone based compound, bisglyoxaline system Close object, triazine based compound, O- acyl group oxime compound, salt based compound, styrax based compound, benzophenone series chemical combination Object, α-diketone based compound, multicore oxime-based compound, two azo compounds, acid imide sulfonate based compound, salt system Close object etc..In described, preferably thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound Or O- acyl group oxime compound, more preferably O- acyl group oxime compound.

It as thioxanthones based compound, can enumerate: thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthones, 2- isopropylthioxanthones Ketone, 4-isopropylthioxanthone, bis- clopenthixal ketone of 2,4-, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2,4- diisopropyl Base thioxanthones etc..

It as acetophenone based compound, such as can enumerate: 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinopropane- 1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) butane -1- ketone, 2- (4- methylbenzyl) -2- (dimethylamino Base) -1- (4- morpholino phenyl) butane -1- ketone etc..

As bisglyoxaline based compound, such as can enumerate: 2,2'- bis- (2- chlorphenyls) -4,4', 5,5'- tetraphenyl -1, Bis- (2,4 dichloro benzene base) -4,4', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of 2'- bisglyoxaline, 2,2'-, the bis- (2,4,6- tri- of 2,2'- Chlorphenyl) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxaline etc..

Furthermore using bisglyoxaline based compound, so that it may for the aspect for improveing sensitivity, preferably and use hydrogen Donor." hydrogen donor " described herein, which refers to, to be supplied the free radical as caused by bisglyoxaline based compound by exposure The compound of hydrogen atom.As hydrogen donor, such as the mercaptan system hydrogen such as can enumerate 2-mercaptobenzothiazole, 2- mercaptobenzoxazole Donor；The amine systems hydrogen donor such as bis- (dimethylamino) benzophenone of 4,4'-, bis- (diethylamino) benzophenone of 4,4'-.

As triazine based compound, such as Japan Patent examined patent publication 57-6096 bulletin, Japanese Patent Laid-Open can be enumerated The compound recorded in the paragraph [0063] of 2003-238898 bulletin~paragraph [0065].

It as O- acyl group oxime compound, can enumerate: 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl Base oxime), ethyl ketone -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base methoxybenzoyl base) -9H- carbazole -3- base] -1- (O- acetyl group oxime), second Ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolyl) methoxybenzoyl base } -9H- click Azoles -3- base] -1- (O- acetyl group oxime) etc..Commercially available product as O- acyl group oxime compound, it is possible to use NCI-831, NCI- 930 (the above are the manufactures of Ai Dike (ADEKA) limited liability company), (the above are BASF (BASF) companies by OXE-03, OXE-04 Manufacture) etc..

Using Photoepolymerizationinitiater initiater, can also and sensitizer be used.As the sensitizer, such as can enumerate: Bis- (dimethylamino) benzophenone of 4,4'-, bis- (diethylamino) benzophenone of 4,4'-, 4- diethyl amino benzoylformaldoxime, 4- Dimethylamino propiophenone, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid 2- ethylhexyl, 2,5- are bis- (4- diethylamino benzal) cyclohexanone, 7- diethylamino -3- (4- diethylamino benzoyl) cumarin, 4- (two Ethylamino) chalcone etc..

The lower limit of the content of [F] polymerization initiator preferably 1 mass relative to 100 mass parts of [E] polymerizable compound Part, more preferably 5 mass parts.On the other hand, the upper limit as the content, preferably 100 mass parts, more preferably 40 mass Part.

(adhesive resin)

Adhesive resin can also also be contained in this composition.Furthermore [B] polymer is not contained in adhesive resin.Make It for adhesive resin, is not particularly limited, it is however preferred to have the resin of the acid functional groups such as carboxyl, phenolic hydroxyl group.Wherein, preferably For the polymer with carboxyl (hereinafter also referred to as " carboxylic polymer ").As carboxylic polymer, such as can enumerate Ethylene unsaturated monomer (hereinafter also referred to as " unsaturated monomer (1) ") with more than one carboxyl is copolymerizable with other Ethylene unsaturated monomer (hereinafter also referred to as the copolymer of " unsaturated monomer (2) ".

It as the unsaturated monomer (1), such as can enumerate: (methyl) acrylic acid, maleic acid, maleic anhydride, succinic acid Single [2- (methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid Deng.

As the unsaturated monomer (2), such as can enumerate:

The N- substituted maleimide amine such as N-phenylmaleimide, N- N-cyclohexylmaleimide,

Styrene, α-methylstyrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to vinyl benzyl shrink The aromatic ethenyl compounds such as glycerin ether, acenaphthene,

(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) propylene Sour 2- hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (first Base) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polyethylene glycol (degree of polymerization 2~10) list (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10) single (methyl) acrylate, (methyl) cyclohexyl acrylate, (first Base) isobornyl acrylate, tricyclic [5.2.1.0^2,6] decane -8- base (methyl) acrylate, (methyl) acrylic acid dicyclopentenyl Ester, glycerol list (methyl) acrylate, (methyl) acrylic acid 4- hydroxylphenyl ester, p -cumylphenol ethylene-oxide-modified (methyl) Acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- expoxycyclohexyl methyl esters, 3- [(methyl) third Alkene pivaloyloxymethyl] (methyl) propylene such as oxetanes, 3- [(methyl) acryloyloxymethyl] -3- Ethyloxetane Acid esters,

Cyclohexyl vinyl ether, isobornyl vinyl ethers, tricyclic [5.2.1.0^2,6] decane -8- base vinyl ethers, five rings The vinyl ethers such as pentadecyl vinyl ethers, 3- (ethyleneoxy methyl) -3- Ethyloxetane,

Polystyrene, poly- (methyl) methyl acrylate, poly- (methyl) n-butyl acrylate, polysiloxanes etc. are in polymer point The end of subchain has the macromonomer etc. of single (methyl) acryloyl group.

In addition, as adhesive resin, it is possible to use there are the polyunsaturated bonds such as (methyl) acryloyl group in side chain Carboxylic polymer.In addition, polysiloxanes etc. also can be used as adhesive resin and use.

(additive)

This composition can also optionally contain various additives.

As additive, such as can enumerate: surfactant, antioxidant, ultraviolet absorbing agent, is prevented contiguity promotor Flocculating agent, residue improver, developability improver etc..

As surfactant, fluorinated surfactant, silicone surfactant etc. can be enumerated.Herein as surfactant Shared content in all solids ingredient of composition, such as 0.01 mass % or more and 5 mass % or less can be set as.

As contiguity promotor, can enumerate: vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- amino second Base) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidoxypropyl trimethoxy Silane, 3- glycidoxypropyl dimethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silicon Alkane, 3-mercaptopropyi trimethoxy silane etc..

It as antioxidant, can enumerate: 2,2- thiobis (4- methyl-6-tert-butylphenol), 2,6- di-t-butyl benzene Phenol, pentaerythrite four [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester], the bis- [2- [3- (3- tert-butyl -4- hydroxyls of 3,9- Base -5- aminomethyl phenyl)-propionyloxy] -1,1- dimethyl ethyl] four oxa-s of -2,4,8,10--spiral shell [5.5] hendecane, thio two Ethylene bis- [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic esters] etc..As antioxidant this composition all solids Shared content in ingredient, such as 0.01 mass % or more and 5 mass % or less can be set as.

As ultraviolet absorbing agent, 2- (3- tert-butyl -5- methyl -2- hydroxy phenyl) -5- chlorobenzotriazole, alkane can be enumerated Oxygroup benzophenone etc..

As anti-flocculating agent, Sodium Polyacrylate etc. can be enumerated.

As residue improver, can enumerate: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2- ethylaminoethanol, 3- amino -1- propyl alcohol, 5- amino -1- amylalcohol, 3- amido-1,2-propanediol, 2- amino -1,3- propylene glycol, 4- Amino -1,2- butanediol etc..

It as developability improver, can enumerate: mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid Agent such as single [2- (methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate etc..

(preparation method)

It as the preparation method of this composition, is not particularly limited, can be prepared and mixing each ingredient.For example, can With the following method: the dispersion liquid containing [A] inorganic compound, [B] polymer and [D] solvent is prepared first, in the dispersion [C] organic pigment or other compositions are added in liquid and are mixed.At this point, [D] solvent can also be added further.Dispersion liquid or this Composition optionally can also implement filtration treatment and remove condensation product.

The forming method > of < solid-state imager infrared ray shielding film

The forming method of the solid-state imager infrared ray shielding film of one embodiment of the present invention includes:

(the step 1) the step of formation film in a surface side of substrate,

The film is formed with composition using this solid-state imager.

This forming method is preferably further include:

The step of radioactive ray are irradiated at least part of the film (step 2) and

The step of developing to the film after radioactive ray irradiation (step 3).

According to this forming method, by using the high composition of dispersion stabilization and ageing stability, can be formed defect it is few, Have both the solid-state imager optical filter of good visible light permeability and infrared ray shielding.In addition, being formed herein In the case that method includes step 2 and step 3, there is good pattern.

(step 1)

In step 1, film is formed in a surface side of substrate (support) using this composition.As the base Plate can enumerate glass substrate, synthetic resin substrate etc..Furthermore the shape of substrate is not limited to plate.Furthermore will be infrared In the case that line shielding film is set into aftermentioned solid-state imager, the transparent base of the component parts as solid-state imager Plate, lenticule, colored filter etc. are equivalent to the substrate.

The formation of film can usually be carried out using the coating of this composition.It is described coating can be used spray-on process, rolling method, The suitable rubbing method such as method of spin coating (spin-coating method), slot coating processes (slot coated method), stick rubbing method.

After coating, prebake conditions are carried out and evaporates solvent, film is consequently formed.Heat drying as the prebake conditions Condition, for example, 70 DEG C or more and 110 DEG C or less, 1 minute or more and 10 minutes or less Zuo You.

(step 2)

In step 2, radioactive ray are irradiated at least part of the film.It is radiated used in exposure as film The light source of line, such as can enumerate: xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, The lamp sources such as middle medium pressure mercury lamp, Cooper-Hewitt lamp or argon laser, yttrium-aluminium-garnet (yttrium aluminum garnet, YAG) laser light sources such as laser, XeCl excimer laser, nitrogen lasers etc..As exposure light source, it is possible to use luminescence-utraviolet Diode (light emitting diode, LED).Wavelength is preferably the radiation in the range of 190nm or more and 450nm or less Line.The light exposure of radioactive ray is usually 10J/m²Above and 50,000J/m²Left and right below.

(step 3)

In step 3, develop to the film after radioactive ray irradiation.It is usually alkaline as the developer solution Developer solution or organic solvent developer solution.Furthermore it is usually washed after development.

As alkaline-based developer, such as preferably sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethyl hydrogen-oxygen Change ammonium (tetramethylammonium hydroxide, TMAH), choline, 1,8- diazabicylo-[5.4.0] -7- 11 The aqueous solution of alkene, 1,5- diazabicylo-[4.3.0] -5- nonene etc..Suitable first can also be for example added in alkaline-based developer The water-miscible organic solvents such as alcohol, ethyl alcohol or surfactant etc..

As organic solvent developer solution, it is preferable to using acetone, methyl ethyl ketone, methyln-hexyl ketone, methyl n-heptyl ketone, 2-HEPTANONE, The ketones, second such as 3- heptanone, 4- heptanone, methyl-n-butyl ketone, 3- hexanone, diisobutyl ketone, methyl cyclohexanone, acetophenone, methyl acetophenone Propyl propionate, butyl acetate, isobutyl acetate, pentyl acetate, acetic acid butene esters, isoamyl acetate, propyl formate, butyl formate, Iso-butyl formate, amyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, M Cr, butenoic acid ethyl, propionic acid Methyl esters, ethyl propionate, 3- ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, lactic acid isobutyl Ester, amyl lactate, isoamyl lactate, 2- hydroxy-methyl isobutyl acid, 2- ethyl butyrate of hydroxyl iso, methyl benzoate, benzoic acid second Ester, phenylacetate, benzyl acetate, phenylacetate, benzyl formate, formic acid phenyl chlorocarbonate, 3- phenylpropionic acid methyl ester, propionic acid benzyl The esters such as ester, ethyl phenylacetate, acetic acid 2- phenyl chlorocarbonate.

It, can be using spray development method, spray development method, dipping (dip) development method, sheathed submergence as development treatment method (puddle) (covering liquid) development method etc..Development conditions are 5 seconds or more and 300 seconds or less Zuo You at normal temperature.

By the development, the non-exposed portion of film is dissolved removal.Thereafter, it by being toasted after optionally carrying out, can obtain Obtain the patterned infrared ray shielding film for regulation shape.As the condition of rear baking, usually 180 DEG C or more and 280 DEG C with Under, 1 minute or more and 60 minutes or less Zuo You.

Furthermore in the case where this composition is free of [E] polymerizable compound and [F] polymerization initiator, with the formation Method is different, can also be without cure process such as exposures.In addition, can also without development treatment, in this case, can be formed without Patterned infrared ray shielding film.

As the solid-state imager formed in this way the lower limit of the average film thickness of infrared ray shielding film, usually 0.5 μm, preferably 1 μm.On the other hand, the upper limit as the average film thickness, usually 5 μm, preferably 3 μm.By infrared The average film thickness of line shielding film is in the range, it is seen that the balance of photopermeability and infrared ray shielding becomes better.

The infrared ray shielding film is preferably used as a member of formation and is set into solid-state imager.This situation Under, infrared ray shielding film is individually used as optical filter (infrared intercepting filter) to function.By in solid-state image pickup Group enters infrared ray shielding film in element, can get big process margin etc. and it is preferred that.Solid is set into infrared ray shielding film In the case where in photographing element, infrared ray shielding film is for example configured in the outer surface side, micro- of the lenticule of solid-state imager Between lens and colored filter, between colored filter and photodiode etc..Infrared ray shielding film is preferably laminated in micro- Between lens and colored filter or between colored filter and photodiode.

It, can also be to be laminated with infrared ray shielding film and winner on the surface of transparent substrate as the optical filter.Make For the transparent substrate, glass or transparent resin etc. can be used.As the transparent resin, polycarbonate, polyester, virtue can be enumerated Fragrant polyamide, polyamidoimide, polyimides etc..The optical filter also can be used as infrared in solid-state imager Line edge filter and be preferably used.

The solid-state imager for having infrared ray shielding film (optical filter) is used in digital still camera, mobile phone Camera, digital camera, personal computer (Personal Computer, PC) camera, supervision camera, automobile are shone It is useful in camera, portable-type information terminal, computer, video-game, medical machine etc..

[embodiment]

Hereinafter, being illustrated based on embodiment to the present invention, but the present invention is not limited to the embodiments.Again The characteristic of person, the polymer obtained by synthesis example are measured using following methods.

[weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (Mw/Mn)]

The Mw and Mn of polymer are gel permeation chromatography (the Gel Permeation using Tosoh company Chromatography, GPC) tubing string (G2000HXL 2, G3000HXL 1, G4000HXL 1), in following analysis item It is measured under part using gel permeation chromatography (GPC).

Dispersion degree (Mw/Mn) is the measurement result according to Mw and Mn and calculates.

(analysis condition)

Dissolve out solvent: tetrahydrofuran

Flow: 1.0mL/ minutes

Sample solution concentration: 1.0 mass %

Sample injection rate: 100 μ L

Tubing string temperature: 40 DEG C

Detector: Differential refractometer

Standard substance: monodisperse polystyrene

1 > of < synthesis example (synthesis of organic pigment (C-1))

Use the side recorded in paragraph [0020]~paragraph [0025] (embodiment 1) of Japanese Patent Laid-Open 05-25177 Method synthesizes the organic pigment (C-1) as phthalocyanine compound represented by following formula.

[changing 3]

2 > of < synthesis example (synthesis of organic pigment (C-2))

Using the method recorded in the paragraph [0075] (embodiment 4) of Japanese Patent Laid-Open 2016-204536 bulletin, close At the organic pigment (C-2) as phthalocyanine compound represented by following formula.

[changing 4]

3 > of < synthesis example (synthesis of organic pigment (C-3))

Using the method recorded in Japanese Patent Laid-Open 1-228960 bulletin, synthesize as side represented by following formula The organic pigment (C-3) of sour inner salt compound.

[changing 5]

4 > of < synthesis example (synthesis of organic pigment (C-4))

Using the method recorded in Japanese Patent Laid-Open 2-138382 bulletin, synthesize as phthalein represented by following formula The organic pigment (C-4) of cyanine compound.

[changing 6]

In addition to this, used organic pigment is as described below.

Organic pigment (C-5): " FDN-002 " (phthalocyanine compound) of hillside plot chemical industrial company

Organic pigment (C-6): " FDR-004 " (phthalocyanine compound) of hillside plot chemical industrial company

Organic pigment (C-7): " FDN-001 " (phthalocyanine compound) of hillside plot chemical industrial company

5~synthesis example of < synthesis example, 7 > (synthesis of polymer (B-1)~polymer (B-3))

Using the method recorded in document (macromolecular (Macromolecules) 1992,25, p5907-5913), carry out down State polymer (B-1)~polymer (B-3) synthesis of monomer composition ratio (mass ratio) recorded in table 1.Can get includes pair Inorganic compound as pigment has the block of the monomer (DAMA) of adsorptivity base, the diblock knot with the block of other compositions The polymer of structure.Furthermore the solution after reaction is quenched using methanol, by resulting reaction solution 7 mass % carbonic acid Hydrogen sodium water solution is then cleaned in water.Thereafter, propylene glycol methyl ether acetate is replaced as by carrying out solvent (Propylene Glycol Monomethyl Ether Acetate, PGMEA) is obtained with 80 mass %-82 mass % of yield Obtain the polymer solution recorded in following table 1.Indicated in table 1 amine value, Mw, Mw/Mn and the solid of resulting each polymer at Component.In addition, DAMA indicates dimethylaminoethyl methacrylate in table, EHMA indicates 2-Ethylhexyl Methacrylate, NBMA indicates that n-BMA, PME-200 (" Blanc is not (Blemmer) " of the manufacture of You limited liability company) indicate Methoxy poly (ethylene glycol) monomethacrylates.Specifically, PME-200 is CH₂=C (CH₃)COO(C₂H₄O)_n-CH₃(n≒4) The polymer of represented monomer.

8 > of < synthesis example (synthesis of polymer (B-8))

Other than polymerizeing together to whole monomers, the method recorded with 5~synthesis example of synthesis example 7 is carried out similarly The synthesis of the polymer (B-8) for the monomer composition ratio (mass ratio) recorded in following table 1.Polymer (B-8) is random copolymer.

[table 1]

9 > of < synthesis example (synthesis of tungsten oxide caesium powder)

Using the method recorded in the paragraph [0113] of No. 4096205 bulletins of Japanese Patent No., tungsten oxide caesium is synthesized (Cs_0.33WO₃) powder.

Polymer and solvent used in preparation example described below, Examples and Comparative Examples.

(polymer)

B-1~B-3: the polymer (B-1) of the table 1 synthesized in the 5~synthesis example of synthesis example 7~polymer (B-3)

" BYK-LPN6919 " (61 mass % of solid component concentration, amine of B-4: Bi Ke chemical (BYK-Chemie) company Value 120mgKOH/g)

" BYK-2001 " (46 mass % of solid component concentration, amine value of B-5: Bi Ke chemical (BYK-Chemie) company 29mgKOH/g)

" BYK-2000 " (40 mass % of solid component concentration, amine value of B-6: Bi Ke chemical (BYK-Chemie) company 4mgKOH/g)

" BYK-LPN22102 " (38.5 matter of solid component concentration of B-7: Bi Ke chemical (BYK-Chemie) company Measure %, amine value 23mgKOH/g)

B-8: the polymer (B-8) of the table 1 synthesized in the synthesis example 8

(solvent)

CPN: cyclopentanone (SP value: 10.0)

CHN: cyclohexanone (SP value: 9.9)

GBL: gamma-butyrolacton (SP value: 9.9)

Tol: toluene (SP value: 8.9)

PGMEA: propylene glycol methyl ether acetate (SP value: 8.7)

[preparation example 1] (preparation of dispersion liquid (X-1))

Prepare 25.00 mass parts of tungsten oxide caesium, 13.11 mass parts of polymer (B-4) and as solvent (dispersion Medium) 61.89 mass parts of cyclopentanone (CPN).It will be filled in together with 2000 mass parts of zirconia particles with 0.1mm diameter In container, dispersed using paint mixer, the dispersion liquid (X-1) for being 19nm thus to obtain average grain diameter (D50).Furthermore Average grain diameter is using determination of light scattering device (German ALV company " ALV-5000 ") and to utilize dynamic light scattering (dynamic Light Scattering, DLS) method measures.

[2~preparation example of preparation example 15] (preparation of dispersion liquid (X-2)~dispersion liquid (X-15))

Other than using each ingredient shown in table 2, dispersion liquid (X-2)~dispersion is obtained respectively in the same manner as preparation example 1 Liquid (X-15).The average grain diameter (D50) of particle in resulting dispersion liquid is shown together in table 2.CsWO in table 2 indicates to close At tungsten oxide caesium obtained in example 9.

[table 2]

[embodiment 1]

50.00 mass parts of the dispersion liquid (X-1), 0.75 mass parts of organic pigment (C-1) are measured in a reservoir, as poly- " Ka Yala get (KAYARAD) DPHA " (dipentaerythritol hexaacrylate and two seasons of the Japanese chemical drug company of conjunction property compound The mixture of penta tetrol, five acrylate) 6.26 mass parts, as polymerization initiator Ai Dike (ADEKA) company " NCI- 930 " (O- acetyl group oxime compound) 1.46 mass parts, as surfactant Nai Aosi (NEOS) company " FTX- 0.02 mass parts of 218D " (fluorine system surfactant), as antioxidant BASF AG " easy fine jade Northey (Irganox) 1010 " (phenolic antioxidant) 0.01 mass parts and 41.50 mass parts of cyclopentanone (CNP) as additional solvent, using stirring The machine of mixing is mixed.Existed using 0.5 μm of polytetrafluoroethylene (PTFE) (Polytetrafluoroethylene, PTFE) filter processed Pressure filtration in 3 minutes is carried out to the mixture 200mL under 0.5MPa, thus to obtain the composition (Z-1) of embodiment 1.20 DEG C, the organic pigment (C-1) under 0.1MPa in the solubility in solvent (CPN) be 2 mass % or more.

Herein, solubility is found out using following methods.Firstly, adding organic pigment (additive amount at this time in a solvent It is the amount for being equivalent to 10 mass % relative to solution entirety), after resulting solution is heated to be 50 DEG C, under room temperature (20 DEG C) It places 12 hours.Solubility of each dyestuff relative to solvent is calculated based on the amount for dissolving remaining each organic pigment after placement (20℃)。

[2~embodiment of embodiment 23,1~comparative example of comparative example 13]

Other than being set as shown in 3~table of table 7 by the composition of each ingredient, embodiment 2~reality is obtained similarly to Example 1 Apply each composition (Z-2)~composition (Z-23), the composition (Y-1)~composition of example 23 and 1~comparative example of comparative example 13 (Y-13).Solubility of the organic pigment relative to used solvent used in being shown together in 3~table of table 7.Furthermore In Also comprising the solvent from polymer solution in each composition.Value in table is to also allow for the value.

[evaluation]

Using resulting each composition, conduct the following evaluation.It shows the results of the evaluation in 3~table of table 7.

(dispersion stabilization)

Using 0.5 μm of polytetrafluoroethylene (PTFE) (PTFE) filter processed, 3 points are carried out to each composition 200mL at 0.5MPa Clock pressure filtration.Based on the rate of recovery of filtered fluid at this time, and utilize following benchmark evaluation dispersion stabilization (filterability, precipitation Inhibition).In the case where A or B, it is good to be evaluated as dispersion stabilization, in the case where A, is evaluated as especially excellent.Furthermore The trapping of condensation product etc. is more, the rate of recovery less than 90% (C) in the case where, filtering becomes inadequate, and productivity is remarkably decreased.

A:95% or more

B:90% or more and less than 95%

C: less than 90%

Evaluation below is implemented using the filtered composition.

Each composition is coated with using spin-coating method in a manner of becoming regulation film thickness on the glass substrate.Thereafter, at 100 DEG C Film heat within 120 seconds, using i ray stepper to become 1000mJ/cm²Mode be exposed.Then, by It carries out heating for 300 seconds at 220 DEG C, and makes 1.40 μm~1.60 μm of average film thickness of infrared ray shielding film on the glass substrate. Each average film thickness is shown in 3~table of table 7.Furthermore utilize (big and scientific company " the α stepping (Step) of contact pin type scale meter IQ ") measurement film thickness.Secondly, using spectrophotometer (" V-7300 " of Japanese light splitting company), with glass substrate comparative determination institute State the transmitance in each wavelength region of the infrared ray shielding film made on glass substrate.According to resulting spectrum, by following The evaluation criteria is evaluated.

(visible light permeability)

Calculate the mean transmissivity of the visible light of wavelength 450nm-550nm.Mean transmissivity it is less than 70% the case where Under, as infrared ray shielding film come using when solid-state imager sensitivity decline.In addition, about the mean transmissivity, It is evaluated using following benchmark.

A:80% or more

B:70% or more and less than 80%

C: less than 70%

(infrared ray shielding 1)

Calculate the mean transmissivity of the infrared ray of wavelength 700nm-900nm.The feelings for being 20% or more in mean transmissivity Under condition, as infrared ray shielding film come using when solid-state imager noisiness increase.In addition, about the average transmission Rate is evaluated using following benchmark.

A: less than 15%

B:15% or more and less than 20%

C:20% or more

(infrared ray shielding 2)

The transmitance of infrared ray about wavelength 1200nm, it may be said that permeability less than 15% and show practical good Infrared ray shielding.About the transmitance of wavelength 1200nm, evaluated using following benchmark.

A: less than 10%

B:10% or more and less than 15%

C:15% or more

(S/N ratio)

Obtain the mean transmissivity (S) and infrared region (700nm-900nm) of the visible light region (450nm-550nm) Mean transmissivity (N) ratio (S/N ratio), practical performance is speculated.The numerical value of S/N ratio is higher, and performance is the better, for In the case where 5 or more, it is judged as realistic scale and can be used.About S/N ratio, evaluated using following benchmark.

A:5 or more

B: less than 5

(defect inhibition)

1 μm of film thickness of cured film is formed using method identical with paragraph [0139].Use defect/foreign body detecting device (" KLA 2351 " of Ke Lei (KLA-Tencor) company) measures the defect concentration (Defect density) of cured film.It can sentence Break smaller for the value of the defect concentration, defect inhibition is higher.Furthermore so-called defect refers to the detection having a size of 1 μm or more Point.Based on the defect concentration, following benchmark evaluation defect inhibition is utilized.

A:10/cm²Below

B: more than 10/cm²It and is 50/cm²Below

C: more than 50/cm²

(ageing stability: thickening efficiency)

After composition is taken care of 3 at 40 DEG C, the viscosity of measurement keeping front and back.Furthermore viscosity is using E type viscosimeter (the E type viscosimeter RE-80L of eastern machine industry (stock) manufacture), is measured in the state that coating fluid is remained 20 DEG C.It is inciting somebody to action Viscosity before keeping is set as the viscosity after V1, keeping when being set as V2, and the value of (| V2-V1 |/V1) × 100 is defined as thickening efficiency (%).Based on the thickening efficiency, evaluated using following benchmark.The the numerical value of thickening efficiency the low the better, less than 10% In the case of be judged as there is practicability.

A: less than 5%

B:5% or more and less than 10%

C:10% or more

(ageing stability: defect number)

After taking care of composition 3 at 40 DEG C, the composition measuring defect number after keeping is used.By measuring method and Benchmark is set as identical as the evaluation of " the defect inhibition ".

(pattern)

About composition Z-1~composition Z-13, composition Z-17~composition Z-18, composition Z-23, composition Y-1 ~composition Y-8 and composition Y-10 forms the film that film thickness is 1 μm using spin-coating method on a silicon substrate.Then, at 100 DEG C Lower to carry out 120 seconds after heating, Jie utilizes i ray stepper to carry out 1000mJ/cm every the mask of the L/S pattern with 50 μm²'s Exposure.Develop in acetone removing non-exposed portion by the way that the substrate after exposure to be impregnated in.Then, by 220 DEG C It carries out heating in 300 seconds and makes the infrared ray shielding film with L/S pattern.It is observed using optical microscopy, is as a result confirmed To the L/S pattern for foring 50 μm of line width.

About composition Z-14~composition Z-16, composition Z-19~composition Z-22 and composition Y-9, in addition to that will show Shadow liquid is changed to other than 2.38% TMAH solution, makes infrared ray shielding film using identical method.Utilize optical microscopy It is observed, as a result confirmed to be formed with 50 μm of L/S pattern.

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

As shown in 3~table of table 7, it is known that composition Z-1~composition Z-23 stably dispersing of 1~embodiment of embodiment 23 Property and ageing stability it is high, it may have good pattern.In addition, knowing the infrared ray shielding film obtained by the composition The defect of (optical filter) is few and has both good visible light permeability and infrared ray shielding.

Industrial availability

Solid-state imager composition of the invention is preferably used as the optical filter of solid-state imager, has more The forming material of infrared filter etc. for body.

Claims (11)

1. a kind of solid-state imager composition, it includes inorganic compound, polymer, organic pigment and solvent,

The amine value of the polymer be 90mgKOH/g or more and 200mgKOH/g hereinafter,

The solvent includes that solubility parameter is 8.8 (cal/cm³)^1/2Above and 12.0 (cal/cm³)^1/2Specific solvent below,

The specific solvent is 40 mass % or more and 90 matter relative to the content of the solid-state imager composition entirety Measure % hereinafter,

The solubility of the organic pigment in the solvent at 20 DEG C, 0.1MPa is 2 mass % or more.

2. solid-state imager composition according to claim 1, it includes the two or more organic pigments.

3. solid-state imager composition according to claim 1 or 2, wherein the solvent includes to have cyclic structure Solvent.

4. solid-state imager composition according to claim 3, wherein the solvent with cyclic structure is ring Shape ketone, cyclic ether, lactone, lactams, aromatic hydrocarbon or the combination.

5. according to claim 1 to solid-state imager composition described in any one of 4, wherein the organic pigment exists There is maximum absorption wavelength in the range of wavelength 600nm or more and 1,000nm or less.

6. solid-state imager composition according to any one of claim 1 to 5, wherein the organic pigment is two Group with imine moiety, side sour inner salt compound, cyanine compound, phthalocyanine compound, naphthalene phthalocyanine compound, quaterrylene chemical combination Object, ammonium compounds, group with imine moiety, azo-compound, anthraquinone compounds, porphyrin compound, pyrrolopyrrole compound, oxa- Cyanine compound, gram ketone compound, hexa-atomic porphyrin compound or the combination.

7. solid-state imager composition according to any one of claim 1 to 6, wherein the polymer is block Copolymer, the block copolymer include the block containing the functional group comprising nitrogen-atoms and with the embedding of said solvophilic Section.

8. solid-state imager composition according to any one of claim 1 to 7, wherein the inorganic compound is Tungsten oxide caesium, quartz, magnetic iron ore, aluminium oxide, titanium dioxide, zirconium oxide, spinelle or the combination.

9. solid-state imager composition according to any one of claim 1 to 8 also includes polymerism chemical combination Object.

10. a kind of solid-state imager forming method of infrared ray shielding film comprising

In a step of surface side of substrate forms film, pass through solid-state image pickup member as claimed in any one of claims 1-9 wherein Part composition and form the film.

11. the solid-state imager according to claim 10 forming method of infrared ray shielding film, further include:

The step of radioactive ray are irradiated at least part of the film and

The step of developing to the film after radioactive ray irradiation.