JP5965639B2 - Infrared cut filter manufacturing method, infrared absorbing liquid composition used in the manufacturing method, and camera module manufacturing method - Google Patents

Description

  The present invention relates to a method for producing an infrared cut filter, an infrared absorbing liquid composition used in the production method, an infrared cut filter, a camera module, and a method for producing the same.

  In recent years, CCDs and CMOS image sensors, which are solid-state image sensors for color images, have been used in video cameras, digital still cameras, mobile phones with camera functions, etc., but these solid-state image sensors are sensitive to near infrared rays in their light receiving parts. Therefore, it is necessary to perform visibility correction, and an infrared cut filter is often used.

As such an infrared cut filter, a type using a dielectric multilayer film and a type using an infrared absorber are known.
As a type of infrared cut filter using a dielectric multilayer film, for example, a filter using a glass substrate as a base material (for example, Patent Document 1), or a resin film as a base material (for example, Patent Document 2). )It has been known.
However, infrared cut filters of the type using a dielectric multilayer film tend to have poor incident angle dependency.
As a type using an infrared absorber, an infrared cut filter in which most of the constituent material is glass is mainly known. Such an infrared cut filter has a problem that the manufacturing cost is high and the processability is inferior because the glass is doped or kneaded with an infrared absorber.

JP 2011-121792 A JP 2009-258362 A

  However, the above-described conventional infrared cut filter requires processing accuracy with respect to the substrate constituting the infrared cut filter and the infrared cut filter itself, and its manufacturing suitability is not necessarily high. Therefore, the fact is that it is required to satisfy the various performances required for the infrared cut filter as well as having good manufacturing aptitude.

This invention is made | formed in view of this present condition, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide an infrared cut filter that can easily (with good manufacturing aptitude) produce an infrared cut filter having a small film thickness distribution, excellent film thickness uniformity, and excellent incident angle dependency. It is to provide a manufacturing method.
Another object of the present invention is to provide an infrared absorbing liquid composition used in the above manufacturing method, an infrared cut filter manufactured by the above manufacturing method, a camera module, and a manufacturing method thereof.

The present invention has the following configuration, whereby the above object of the present invention is achieved.
<1>
In the light receiving side of the solid-state imaging device substrate, an infrared absorbing agent, polymerizable compound, a solvent, and an infrared absorptive liquid composition containing a fluorine-based surfactant have a step of forming a film by spin coating, the A method for producing an infrared cut filter, wherein the infrared absorber is at least one selected from a metal oxide and a diimmonium dye .
<2>
In the light receiving side of the solid-state imaging device substrate, an infrared absorbing agent, polymerizable compound, a solvent, and the infrared absorbing liquid composition containing a polymerization initiator it has a step of forming a film by spin coating, the infrared absorption The manufacturing method of the infrared cut filter whose agent is at least 1 type selected from a metal oxide and a diimmonium pigment | dye .
<3>
The method for producing an infrared cut filter according to <1>, wherein the infrared absorbing liquid composition further contains a polymerization initiator.
<4>
The method for producing an infrared cut filter according to <2> or <3>, wherein the polymerization initiator is a compound having an aromatic group.
<5>
Production of an infrared cut filter according to <2> or <3>, wherein the polymerization initiator is an oxime compound, an acetophenone compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, or a thiol compound. Method.
<6>
The manufacturing method of the infrared cut filter of any one of <1>-<5> whose rotation speed of the said spin application is 1000 rpm to 4000 rpm.
<7>
<1>-<6> The manufacturing method of the infrared cut filter of any one of <1>-<6> whose film thickness of the film | membrane formed by spin-coating is 0.5 micrometer-5 micrometers.
<8>
An infrared absorbing liquid composition containing an infrared absorbent, a polymerizable compound, a solvent, and a fluorine-based surfactant, which is used in the method for producing an infrared cut filter according to <1>.
<9>
An infrared-absorbing liquid composition containing an infrared absorbent, a polymerizable compound, a solvent, and a polymerization initiator, which is used in the method for producing an infrared cut filter according to <2>.
<10>
<8> or <9>, wherein the infrared absorber is at least one selected from a metal oxide and a diimmonium dye represented by the following general formula (III-1) or (1) . Liquid composition.

In general formula (III-1), R ³¹¹ , R ³¹² , R ³²¹ , R ³²² , R ³³¹ , R ³³² , R ³⁴¹ and R ³⁴² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, R ³⁰³ , R ³¹³ , R ³²³ , R ³³³ and R ³⁴³ each independently represent a substituent, and n ₃₀₃ , n ₃₁₃ , n ₃₂₃ , n ₃₃₃ and n ₃₄₃ each independently represent an integer of 0 to 4, Represents a monovalent or divalent anion, n ₃₅₃ represents 1 or 2, and the product of the valence of X and n ₃₅₃ is 2.

In the general formula (1), each R independently represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group, a phenylalkylene group or an alkoxy group, and R ¹ represents a fluorine atom or a fluorine atom. Represents an alkyl group.
<11>
The infrared absorbing liquid composition according to <10>, wherein the metal oxide is cesium tungsten oxide .
< 12 >
A method for manufacturing a camera module, comprising: a solid-state image sensor substrate; and an infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is any one of <1> to <7>. The manufacturing method of a camera module manufactured by the manufacturing method of the infrared cut filter of description.
In addition, although this invention has the structure as described in said <1>-< 12 >, the following was also described for reference below.

[1]
An infrared cut filter manufacturing method comprising a step of forming a film by spin-coating an infrared absorbing liquid composition on a light receiving side of a solid-state imaging device substrate.
[2]
The method for producing an infrared cut filter according to [1] above, wherein the spin coating has a rotation speed of 1000 rpm to 4000 rpm.
[3]
The method for producing an infrared cut filter according to the above [1] or [2], wherein the film formed by the spin coating has a film thickness of 0.5 μm to 5 μm.
[4]
An infrared absorbing liquid composition used in the method for producing an infrared cut filter according to any one of [1] to [3].
[5]
The infrared absorbing liquid composition according to [4] above, which contains an infrared absorber, a polymerizable compound, and a solvent.
[6]
The infrared absorbing liquid composition according to the above [5], wherein the infrared absorbing agent is at least one selected from a metal oxide and a diimmonium dye.
[7]
The infrared-absorbing liquid composition according to the above [6], wherein the metal oxide is cesium tungsten oxide.
[8]
The infrared cut filter manufactured by the manufacturing method of the infrared cut filter of any one of said [1]-[3].
[9]
A camera module having a solid-state image pickup device substrate and an infrared cut filter disposed on a light receiving side of the solid-state image pickup device substrate, wherein the infrared cut filter is the infrared cut filter according to [8]. .
[10]
A method for manufacturing a camera module, comprising: a solid-state image pickup device substrate; and an infrared cut filter disposed on a light receiving side of the solid-state image pickup device substrate, wherein the infrared cut filter is any one of [1] to [3]. The manufacturing method of the camera module manufactured by the manufacturing method of the infrared cut filter of claim | item.

The present invention preferably further has the following configuration.
[11]
The infrared absorbing liquid composition according to the above [6], wherein the metal oxide is represented by the following general formula (I).
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
[12]
The infrared absorbing liquid composition according to [11], wherein M is an alkali metal.

According to the present invention, manufacture of an infrared cut filter that can easily (with good manufacturing aptitude) produce an infrared cut filter having a small film thickness distribution, excellent film thickness uniformity, and excellent incident angle dependency. Can provide a method.
Moreover, according to this invention, the infrared rays absorptive liquid composition used for the said manufacturing method, the infrared cut filter manufactured by the said manufacturing method, a camera module, and its manufacturing method can be provided.

It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor which concerns on embodiment of this invention. It is a schematic sectional drawing of the solid-state image sensor board | substrate which concerns on embodiment of this invention.

Hereinafter, the manufacturing method of the infrared cut filter of this invention is demonstrated in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, in this specification, a viscosity value points out the value in 25 degreeC.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a mass average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

The method for producing an infrared cut filter according to the present invention includes a step of forming a film by spin-coating an infrared-absorbing liquid composition on the light-receiving side of a solid-state imaging device substrate.
The reason why an infrared cut filter having a small film thickness distribution, excellent film thickness uniformity, and excellent incident angle dependence characteristics can be easily manufactured (with good manufacturing aptitude) by the manufacturing method of the infrared cut filter of the present invention. It is estimated as follows.
As described above, the type of infrared cut filter using a dielectric multilayer film tends to have poor incident angle dependency. This is because normal light and oblique incident light have different optical distances in the multilayer film, so that the cutoff wavelength of the filter action caused by multiple interference between layers shifts. On the other hand, according to the method for producing an infrared cut filter of the present invention, a film is formed by spin-coating the infrared absorbing liquid composition, so that the incident angle dependent characteristics depend on the absorption characteristics of the infrared absorbing liquid composition itself. This is considered to be excellent in incident angle dependence characteristics.
Further, it is considered that the film thickness distribution can be reduced by selectively using spin coating from various coating methods, and excellent film thickness uniformity can be achieved. This is presumed to be because spin coating volatilizes the solvent while spreading the infrared-absorbing liquid composition applied by centrifugal force on the substrate.
In addition, according to the present invention, since the infrared cut filter can be easily manufactured by spin coating, a process for forming a dielectric multilayer film as in the past, a glass substrate is doped with an infrared absorber, or kneaded. Such a complicated process is not necessary, and the production suitability is improved. That is, the manufacturing method of the infrared cut filter of the present invention having good manufacturing aptitude is expected to contribute to the reduction of the manufacturing cost of the infrared cut filter. In addition, since a film can be easily formed even on a large-area substrate by spin coating, a large-area infrared cut filter is manufactured first, and then the infrared cut filter is cut to a desired size to obtain a solid-state imaging device. It is also possible to mount it on the board, and further reduction in manufacturing cost is expected.
It is preferable that the manufacturing method of the infrared cut filter of this invention is a manufacturing method of the infrared cut filter for solid-state image sensors.

  In order to form an infrared cut filter, first, a film is formed from an infrared absorbing liquid composition described later. The film is not particularly limited as long as it is a film formed including the infrared absorbing liquid composition, and the film thickness, the laminated structure, and the like can be appropriately selected according to the purpose.

  As the method for forming the film, on the support, the infrared absorbing liquid composition of the present invention (coating solution in which the solid content in the composition is dissolved, emulsified or dispersed in a solvent described later) is directly spin-coated, The method of forming by making it dry is mentioned.

The support is provided on the light receiving side of the solid-state imaging device substrate, whether it is a solid-state imaging device substrate or another substrate (for example, a glass substrate 30 described later) provided on the light-receiving side of the solid-state imaging device substrate. A layer such as a flattening layer may also be used.
The method of spin-coating the infrared absorbing liquid composition (coating liquid) on the support can be carried out by using, for example, a spin coater, a slit spin coater or the like.
The rotational speed of the spin coating is preferably 1000 rpm to 4000 rpm, more preferably 1500 rpm to 2500 rpm from the viewpoint of film thickness uniformity.
The spin time of the spin coating is preferably in the range of 5 seconds to 500 seconds, more preferably 10 seconds to 400 seconds, and even more preferably 15 seconds to 300 seconds.
Moreover, as drying conditions of a coating film, although it changes also with each component, the kind of solvent, a usage rate, etc., it is about 30 seconds-15 minutes normally at the temperature of 60 to 150 degreeC.

  The film thickness of the film formed by spin coating is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5 μm to 5 μm is preferable, and 0.5 μm to 3 μm is more preferable. 0.5 μm to 2 μm is more preferable.

The method for forming an infrared cut filter using the infrared absorbing liquid composition of the present invention may include other steps.
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a preheating process (prebaking process), a hardening process process, a post-heating process (post-baking) Process).

<Pre-heating process / Post-heating process>
The heating temperature in the preheating step and the postheating step is usually 80 ° C to 200 ° C, and preferably 90 ° C to 150 ° C.
The heating time in the preheating step and the postheating step is usually 30 seconds to 400 seconds, and preferably 60 seconds to 300 seconds.

<Curing process>
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably. Here, in the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used. Preferably, KrF, g line, h line, and i line are preferable.
As an exposure method. Examples include stepper exposure and exposure with a high-pressure mercury lamp.
Exposure is more preferably ^5mJ / cm ^{2 ~3000mJ} / cm 2 is preferably ^{10mJ / cm 2 ~2000mJ / cm 2} , 50mJ / cm 2 ~1000mJ / cm 2 being most preferred.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the infrared absorbing liquid composition contains a polymerizable compound, curing of the polymerization component in the film formed from the composition is promoted by overall exposure, and the curing of the film further proceeds, mechanical strength, Durability is improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Moreover, as a method of the whole surface heat treatment, a method of heating the entire surface of the formed film can be mentioned. By heating the entire surface, the film strength of the pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, more preferably 150 ° C to 250 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the components in the film are decomposed and the film quality is prevented from becoming weak and brittle.
The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

The present invention also relates to an infrared-absorbing liquid composition used in the above-described method for producing an infrared cut filter.
The infrared absorbing liquid composition of the present invention preferably contains an infrared absorber, a polymerizable compound and a solvent.
The infrared absorbing liquid composition of the present invention is preferably an infrared absorbing liquid composition for a solid-state imaging device.
Below, the structure of an infrared absorptive liquid composition is demonstrated.

[1] Infrared absorber The infrared absorber used in the infrared absorbing liquid composition of the present invention is not particularly limited as long as it has the property of absorbing infrared rays, but is at least one selected from metal oxides and diimmonium dyes. It is preferable that
The metal oxide that can be used in the infrared-absorbing liquid composition of the present invention preferably has a maximum absorption wavelength (λ _max ) within a wavelength range of 800 nm to 2000 nm, and includes, for example, a tungsten oxide compound (an oxide containing tungsten). Can be preferably mentioned.
Tungsten oxide compounds have high absorption for infrared rays (especially light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) for infrared rays) and low absorption for visible light. It is a shielding material. Therefore, when the composition of the present invention contains a tungsten compound, an infrared cut filter having a high light-shielding property (infrared shielding property) in the infrared region and a high light-transmitting property (visible light transmittance) in the visible region. Can be manufactured.

The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following general formula (composition formula) (I).
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  As the metal of M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Examples include Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, and an alkali metal is preferable. The metal of M may be one type or two or more types.

M is preferably an alkali metal, preferably Rb or Cs, and more preferably Cs.
That is, the metal oxide is more preferably cesium tungsten oxide.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when 1.1 or less, the generation of an impurity phase in the tungsten oxide compound is more reliably avoided. Can do.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The metal oxide is preferably fine particles. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal oxide to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible, but for reasons such as ease of handling during production, the average particle size of the metal oxide is usually 1 nm or more.

The content of the metal oxide is preferably 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 50% by mass or less with respect to the total solid mass of the composition of the present invention. More preferably, it is 5 mass% or more and 40 mass% or less.
Two or more tungsten compounds can be used.

A metal oxide is available as a commercial product. When the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide compound is a method in which the tungsten compound is heat-treated in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4,096,205).
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.

  The diimmonium dye that can be used in the infrared absorbing liquid composition of the present invention is preferably a compound represented by the following general formula (III-1).

In general formula (III-1), R ³¹¹ , R ³¹² , R ³²¹ , R ³²² , R ³³¹ , R ³³² , R ³⁴¹ and R ³⁴² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, R ³⁰³ , R ³¹³ , R ³²³ , R ³³³ and R ³⁴³ each independently represent a substituent, and n ₃₀₃ , n ₃₁₃ , n ₃₂₃ , n ₃₃₃ and n ₃₄₃ each independently represent an integer of 0 to 4, Represents a monovalent or divalent anion, n ₃₅₃ represents 1 or 2, and the product of the valence of X and n ₃₅₃ is 2.

R ³¹¹ , R ³¹² , R ³²¹ , R ³²² , R ³³¹ , R ³³² , R ³⁴¹ and R ³⁴² are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group and an aryl group, more preferably a hydrogen atom, carbon An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, carbon An alkenyl group having 2 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 8 carbon atoms, and most preferably 2 to 6 carbon atoms. It is an alkyl group.
It is also preferred that all of R ³¹¹ , R ³¹² , R ³²¹ , R ³²² , R ³³¹ , R ³³² , R ³⁴¹ and R ³⁴² are the same.

R ³⁰³ , R ³¹³ , R ³²³ , R ³³³ and R ³⁴³ are preferably halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, cyano groups, hydroxyl groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups. , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, A oxyoxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group, more preferably a halogen atom, an alkyl group, an alkenyl group , Aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, amino group, alkylthio group, arylthio group, imide group, silyl group, more preferably halogen atom, alkyl group, aryl A group, an alkoxy group, an aryloxy group, a silyloxy group, and an amino group, and most preferably an alkyl group.
It is also preferred that all of R ³¹³ , R ³²³ , R ³³³ and R ³⁴³ are the same.
n ₃₀₃ , n ₃₁₃ , n ₃₂₃ , n ₃₃₃ and n ₃₄₃ are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.

  X represents a monovalent or divalent anion, and X is preferably a perchlorate ion, a carboxylate ion, a sulfonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, or a hexafluoroantimonate ion, More preferred are perchlorate ion, sulfonate ion, hexafluorophosphate ion, tetrafluoroborate ion or hexafluoroantimonate ion, and more preferred are sulfonate ion, hexafluorophosphate ion and tetrafluoroborate ion. Or hexafluoroantimonate ions, more preferably hexafluorophosphate ions, tetrafluoroborate ions or hexafluoroantimonate ions.

  Although the specific example of a compound represented by general formula (III-1) of this invention below is shown, this invention is not limited to these.

  These compounds can be easily synthesized, for example, by the synthesis method described in JP-A-2007-254682.

  As the diimmonium dye that can be used in the infrared absorbing liquid composition of the present invention, a compound represented by the following general formula (1) is also preferable.

(In the formula, each R independently represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group, a phenylalkylene group or an alkoxy group, and R ¹ represents a fluorine atom or a fluorinated alkyl group. Indicate)

In the general formula (1), R ¹ is a fluorine atom is a diimonium salt compound containing bis (fluorosulfonyl) imidic acid as an anion component. In the general formula (1), R ¹ is a fluorinated alkyl group. Some are diimonium salt compounds containing alkanesulfonyl fluoride-fluorosulfonylimide acid as an anionic component.

The fluorinated alkyl group in R ¹ of the general formula (1) is not particularly limited in the number of substituted fluorine atoms or the number of carbon atoms, but preferred examples thereof include a C 1-8 perfluoroalkyl group. In particular, trifluoromethane, pentafluoroethane, and the like are more preferable in terms of near infrared absorption ability.

  Examples of a method for synthesizing the diimonium salt compound of the general formula (1) include a synthesis method described in JP-A-2006-298899.

  Commercially available products can also be used as the diimmonium dye that can be used in the infrared absorbing liquid composition of the present invention. Examples of commercially available diimmonium dyes include EPOLIGHT 1178, EPOLIGHT 7551 (manufactured by Epolin), and the like.

The content of the diimmonium dye is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, with respect to the total solid mass of the composition of the present invention. More preferably, it is 20 mass% or more and 40 mass% or less.
Two or more diimmonium dyes can be used.

  The dye is preferably a fine particle. The average particle size of the dye is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter is in such a range, the dye is less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the dye is usually 1 nm or more.

The content of the infrared absorber (when containing a plurality of types, the total content thereof) is preferably 3% by mass or more and 80% by mass or less with respect to the total solid mass of the composition of the present invention. It is more preferably 5% by mass or more and 70% by mass or less, and further preferably 5% by mass or more and 60% by mass or less.
Two or more infrared absorbers can be used.

[2] Polymerizable compound The infrared absorbing liquid composition of the present invention can be suitably constituted by containing at least one polymerizable compound.

  Specifically, the polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronic series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid value of the entire polyfunctional monomer should be adjusted so that it falls within the above range. Is essential.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  In addition, the polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - a represents , Y each independently represents an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  As the polymerizable compound, ethylenically unsaturated compounds having an acid group are also suitable. The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

  In addition, examples of the high heat-resistant polymerizable compound include benzocyclobutene (BCB), bisallylnadiimide (BANI), benzoxazine, melamine, and analogs thereof.

Two or more polymerizable compounds can be used.
The content of the polymerizable compound is preferably 3% by mass or more and 80% by mass or less, and preferably 5% by mass or more and 70% by mass or less with respect to the total solid content mass of the infrared absorbing liquid composition of the present invention. It is more preferable.

[3] Solvent The infrared absorbing liquid composition of the present invention contains a solvent.
The solvent is not particularly limited and can be appropriately selected depending on the purpose as long as it can uniformly dissolve or disperse each component of the infrared absorbing liquid composition of the present invention. For example, methanol, ethanol , Alcohols such as normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone, cyclopentanone; ethyl acetate, butyl acetate Esters such as methyl acetate, normal-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate, and methoxypropyl acetate; Aromatic hydrocarbons such as len, benzene and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl Ethers such as ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  The infrared absorbing liquid composition of the present invention thus obtained preferably has a solid content concentration of 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and most preferably. Is 15 mass% or more and 30 mass% or less.

  As described above, if a liquid composition is prepared by adding a solvent to the composition, an infrared cut filter can be easily manufactured by a simple process of forming a film by spin-coating the liquid composition. Insufficient manufacturing suitability in the conventional infrared cut filter described above can be improved.

[4] Polymerization initiator The infrared-absorbing liquid composition of the present invention may contain a polymerization initiator. As the polymerization initiator, polymerization of the polymerizable compound is initiated by light, heat, or both. As long as it has the ability to do so, it is not particularly limited and can be appropriately selected according to the purpose, but is preferably a photopolymerizable compound. When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
Moreover, when starting superposition | polymerization with a heat | fever, the initiator decomposed | disassembled at 150 to 250 degreeC is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group, such as an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, and a ketal derivative. Compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds, etc. Onium salt compounds, organoboron salt compounds, disulfone compounds, and the like.
From the viewpoint of sensitivity, oxime compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred.
Examples of the polymerization initiator suitable for the present invention will be given below, but the present invention is not limited thereto.

  Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-methyl -1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  As the trihalomethyl compound, more preferably, an s-triazine derivative 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, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compound, IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1- [9-ethyl) manufactured by BASF Japan -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) thioxanthen-9-one and the like.
Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, * represents the bonding position between Y and the adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

  R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that are suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has a high absorbance at 365 nm and 455 nm. Particularly preferred.

From the viewpoint of sensitivity, the oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The photopolymerization initiator is more preferably a compound selected from the group consisting of oxime compounds, acetophenone compounds, and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, and the oxime initiator described above, As the oxime initiator, compounds described in JP-A No. 2001-233842 can also be used.
As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The content of the polymerization initiator relative to the total solid mass of the infrared absorbing liquid composition of the present invention is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and 1% by mass to 15% by mass is particularly preferable.

[5] Binder The infrared absorbing liquid composition of the present invention preferably contains a binder (resin). The binder is preferably an alkali-soluble binder (alkali-soluble resin).

The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, and can be appropriately selected according to the purpose. Examples thereof include (meth) acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, and polyvinyl formal. , Polyamide, polyester, and the like, and (meth) acrylic resins or urethane resins are preferable.
The binder may have an acid group.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, and a carboxylic acid group is preferable from the viewpoint of obtaining raw materials.

  The binder having an acid group is not particularly limited, but is preferably a polymer obtained by using a polymerizable compound having an acid group as a monomer component. From the viewpoint of adjusting the acid value, polymerization having an acid group is preferable. More preferably, the copolymer is a copolymer obtained by copolymerizing a polymerizable compound and a polymerizable compound having no acid group.

  There is no restriction | limiting in particular as a polymeric compound which has an acid group, According to the objective, it can select suitably, For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl Styrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxyl styrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

Although there is no restriction | limiting in particular as a polymeric compound which does not have an acid group, For example, (meth) acrylic acid ester (an alkyl ester, an aryl ester, an aralkyl ester etc.) can be mentioned suitably.
The alkyl group in the alkyl ester moiety of the (meth) acrylate ester may be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, and 1 to 6 carbon atoms. The alkyl group is more preferably.
The aryl group in the aryl ester moiety of the (meth) acrylic acid ester is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
The aralkyl group in the aralkyl ester moiety of the (meth) acrylic acid ester is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 12 carbon atoms.

The molar ratio of the monomer corresponding to the polymerizable compound having an acid group and the monomer corresponding to the polymerizable compound not having an acid group is usually more preferably 1:99 to 99: 1.
The content of the acid group in the binder is not particularly limited, but is preferably 0.1 meq / g to 4.0 meq / g.

  The binder preferably further has a crosslinkable group, which is preferable in that it can improve the curability particularly when exposed to light and can provide a highly durable film. Here, the crosslinkable group is a group that crosslinks the binder polymer in the course of a polymerization reaction that occurs in the layer when the layer obtained from the infrared absorbing liquid composition is exposed or heated. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, etc. are mentioned, for example. Of these, an ethylenically unsaturated bond group is preferable. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable. From the viewpoint of achieving both the stability of the crosslinkable group before exposure and the strength of the film, the (meth) acryloyl group It is more preferable that

  In the binder, for example, free radicals (polymerization initiating radicals or growth radicals in the polymerization process of a polymerizable compound) are added to the crosslinkable functional group, and addition polymerization is performed directly between polymers or via a polymerization chain of the polymerizable compound. As a result, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.

The content of the crosslinkable group in the binder is not particularly limited, but is preferably 0.5 meq / g to 3.0 meq / g, more preferably 1.0 meq / g to 3.0 meq / g, 1.5 meq / g Particularly preferred is g to 2.8 meq / g. When the content is 0.5 meq / g or more, the curing reaction amount is sufficient and high sensitivity is obtained, and when the content is 3.0 meq / g or less, the storage stability of the infrared absorbing liquid composition Can be high.
Here, the content (meq / g) can be measured by, for example, iodine value titration.
The binder having a crosslinkable group is described in detail in JP-A No. 2003-262958, and the compounds described herein can also be used in the present invention.
The binder containing these crosslinkable groups is preferably a binder having an acid group and a crosslinkable group, and typical examples thereof are shown below.
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin.
(2) An unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule.
(3) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

  Moreover, as the binder having an acid group and a crosslinkable group, a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain, and having a bisphenol A skeleton and a bisphenol F skeleton, Examples thereof include novolak resins having an acid group and an ethylenically unsaturated bond, and resole resins. These resins can be obtained by the technique described in paragraph Nos. [0008] to [0027] of JP-A No. 11-240930.

  As described above, the alkali-soluble binder is preferably a (meth) acrylic resin or a urethane resin, and the “(meth) acrylic resin” includes (meth) acrylic acid, (meth) acrylic acid ester ( It is preferably a copolymer having a (meth) acrylic acid derivative such as an alkyl ester, aryl ester, aralkyl ester, etc.), (meth) acrylamide, and (meth) acrylamide derivative as a polymerization component. The “urethane resin” is preferably a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups.

  A suitable example of the (meth) acrylic resin is a copolymer having a repeating unit containing an acid group. Preferred examples of the acid group include those described above. As the repeating unit containing an acid group, a repeating unit derived from (meth) acrylic acid or one represented by the following general formula (I) is preferably used.

(In General Formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an n + 1 valent linking group, A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom. Or, it represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5.)

The linking group represented by R ² in the general formula (I) is composed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. The number of atoms constituting the linking group represented by R ² is preferably 1-80. Specific examples include an alkylene group, an arylene group, and the like, and these divalent groups have a structure in which a plurality of these are connected by any of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. May be. R ² is preferably a single bond, an alkylene group, or a structure in which a plurality of alkylene groups are linked by at least one of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond.
The alkylene group preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
The arylene group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.
The alkylene group and the arylene group may further have a substituent, and examples of such a substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, and a halogen atom (—F, -Br, -Cl, -I), hydroxyl group, cyano group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group , Aryloxycarbonyl group, carbamoyl group, aryl group, alkenyl group, alkynyl group and the like.

The hydrocarbon group for R ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
R ³ is most preferably a hydrogen atom or a methyl group.
n is preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

  The ratio (mol%) of the repeating unit having an acid group in all repeating unit components of the (meth) acrylic resin is preferably 10 to 90%.

  As described above, the (meth) acrylic resin preferably further has a crosslinkable group, and specific examples of the crosslinkable group and the content thereof are the same as those described above.

  The (meth) acrylic polymer used in the present invention includes, in addition to the above-described polymer unit having an acid group and polymer unit having a crosslinkable group, a polymer unit of (meth) acrylic acid alkyl or aralkyl ester, (meth) acrylamide. Alternatively, it may have a polymer unit of a derivative thereof, a polymer unit of α-hydroxymethyl acrylate, or a polymer unit of a styrene derivative. The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms and an alkyl group having the aforementioned substituent having 2 to 8 carbon atoms, and a methyl group is more preferable. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate. Examples of (meth) acrylamide derivatives include N-isopropylacrylamide, N-phenylmethacrylamide, N- (4-methoxycarbonylphenyl) methacrylamide, N, N-dimethylacrylamide, morpholinoacrylamide and the like. Examples of the α-hydroxymethyl acrylate include ethyl α-hydroxymethyl acrylate and cyclohexyl α-hydroxymethyl acrylate. Examples of styrene derivatives include styrene and 4-tertbutylstyrene.

  As alkali-soluble binders other than (meth) acrylic resins and urethane resins, acetal-modified polyvinyl alcohol-based binder polymers having acid groups described in European Patent 993966, European Patent 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 are suitable. . In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers, and [allyl (meth) acrylate / (meth) acrylic acid / necessary Accordingly, the other addition polymerizable vinyl monomer] copolymer is preferable because it is excellent in the balance of film strength and sensitivity.

The weight average molecular weight of the binder polymer that can be used in the infrared absorbing liquid composition of the present invention is preferably 3,000 or more, more preferably 5,000 to 300,000, and most preferably 10,000. ˜30,000, the number average molecular weight is preferably 1,000 or more, more preferably 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binders may be any of random polymers, block polymers, graft polymers and the like.

  The binder can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and butyl acetate. These solvents are used alone or in combination of two or more.

A binder may be used individually by 1 type and may use 2 or more types together.
The content of the binder is preferably 5% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass with respect to the total solid mass of the infrared absorbing liquid composition of the present invention. When the content is in the above range, exposure sensitivity is good, processing time is short, and good TCT resistance is obtained.

[6] Dispersant The infrared absorbing liquid composition of the present invention may be used by dispersing with a known dispersant for the purpose of improving the dispersibility and dispersion stability of the metal oxide and the dye.

Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and alkanol amine.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the surface include a polymer having a phosphate group at its terminal described in JP-A-3-112992, JP-T2003-533455, and the like. A polymer having a sulfonic acid group at its terminal described in JP-A-273191, a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, or the like in JP-A-2008-29901 Examples thereof include a polymer produced by modifying an oligomer or polymer having a hydroxyl group or an amino group at one end and an acid anhydride. In addition, a high molecular weight terminal in which two or more anchor portions (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) to the surface of the infrared shielding material are introduced at the polymer ends described in JP-A-2007-277514. Molecules are also preferred because of their excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the surface include poly (lower alkyleneimine) described in JP-A No. 54-37082, JP-A No. 8-507960, JP-A No. 2009-258668, and the like. Reaction product of polyester and polyester, reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, amphoteric dispersion resin having basic group and acidic group described in JP-A-2009-203462, Copolymers of macromonomer and nitrogen atom monomer described in Kaihei 10-339949, JP-A-2004-37986, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A-2008- JP-A-201032, a graft polymer having a partial skeleton of an organic dye or a heterocyclic ring, They include copolymers of macromonomer and acid group-containing monomers described in 6268 JP like.

  As a macromonomer used when producing a graft polymer having an anchor site on the surface by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal group) manufactured by Toa Gosei Co., Ltd. Is a methacryloyl group polymethyl methacrylate), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (terminal Polybutyl acrylate whose group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate, ε-caprolactone 5 molar equivalent addition product), FA10L (ε of 2-hydroxyethyl acrylate) -Caprolactone 10 molar equivalent addition product), and JP-A-2-272009 Polyester macromonomer described in the publication No. and the like. Among these, a polyester-based macromonomer that is particularly flexible and excellent in solvent-solubility is particularly preferable from the viewpoints of dispersibility and dispersion stability of the infrared shielding material in the composition, and further described in JP-A-2-272009. Most preferred is a polyester macromonomer represented by the following polyester macromonomer.

  As the block polymer having an anchor site to the surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

As the dispersant, for example, a known dispersant or surfactant can be appropriately selected and used.
Specific examples include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, and 163, manufactured by BYK Chemie. 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050-4010-4165 (polyurethane system), EFKA4330, manufactured by EFKA. -4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ", Ajinomoto Fan Techno "Ajispa" “PB821, PB822, PB880, PB881”, “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon” manufactured by Enomoto Kasei Co., Ltd. KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725, “Demol RN, N” manufactured by Kao Corporation (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935” , 985 (polyoxyethylene nonylphenyl ether), “acetamine 86 (stearyl amine) N-acetate ”, manufactured by Nippon Lubrizol Co., Ltd.“ Solsperse 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (Graft type polymer) ", Nikko Chemical's" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, etc. Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic Surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl Nonionic surfactants such as ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017” Agents, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450” manufactured by Morishita Sangyo Co., Ltd., “Disperse Aid 6, Disp. Polymer dispersants such as Perth Aid 8, Disperse Aid 15, Disperse Aid 9100, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F manufactured by ADEKA Corporation 68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.

These dispersants may be used alone or in combination of two or more. In addition, the dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the surface of the infrared shielding material. . Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.
From the viewpoints of dispersibility and sedimentation, the following resins described in JP 2010-106268 A are preferable, and in particular, from the viewpoint of dispersibility, a polymer dispersant having a polyester chain in the side chain is preferable. Also preferred are resins having acid groups and polyester chains. As a preferable acid group in the dispersant, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorptivity, and carboxylic acid, sulfonic acid, and phosphoric acid are particularly preferable.

The dispersion resin described in JP 2010-106268 A, which is preferably used in the present invention, will be described below.
A preferred dispersant is a graft copolymer having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 in the molecule. It is preferable that at least a structural unit represented by any one of the following formulas (1) to (4) is included, and at least the following formula (1A), the following formula (2A), the following formula (3A), the following formula ( 3B) and a structural unit represented by any one of the following formulas (4) are more preferable.

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis restrictions, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom. In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited, Specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, it is preferable to have a steric repulsion effect particularly from the viewpoint of improving dispersibility, and the monovalent substituents represented by Z ^{1 to} Z ³ are each independently an alkyl group having 5 to 24 carbon atoms or carbon. An alkoxy group having 5 to 24 carbon atoms is preferable, and among them, an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable. The monovalent substituent represented by Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred. In Formula (1)-Formula (4), n, m, p, and q are integers of 1 to 500, respectively.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of dispersion stability.

In the formula (3), R ′ represents a branched or straight chain alkylene group. R ′ in formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
Further, as R ′ in the formula (3), two or more types of R ′ having different structures may be mixed and used in the dispersion resin. In formula (4), R represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom. An atom or an alkyl group. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
Moreover, as R in Formula (4), two or more types of R having different structures may be mixed and used in the specific resin.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.
The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoint of dispersion stability.

Wherein (3A) or ^{(3B), X 3, Y} 3, Z 3 and p, the formula ^{(3) X 3, Y 3} , have the same meaning as ^{Z 3} and p in, preferred ranges are also the same.

  Specific examples include the following compounds. In addition, in the following exemplary compounds, the numerical value written together with each structural unit (the numerical value written together with the main chain repeating unit) represents the content of the structural unit [described as mass%: (wt%)]. The numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.

When the infrared-absorbing liquid composition of the present invention contains a polymerizable compound and a dispersant, first, the infrared-absorbing liquid composition is prepared by preparing a dispersion composition of the above-described infrared absorber and dispersant using an appropriate solvent. From the viewpoint of improving dispersibility, it is preferable to blend the product.
The infrared absorbing liquid composition may or may not contain a dispersant, but when it is contained, the content of the dispersant in the composition is relative to the mass of the infrared absorber in the composition. 1 mass%-90 mass% is preferable, and 3 mass%-70 mass% is more preferable.

[7] Sensitizer The infrared absorbing liquid composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable. Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg, Thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthrone) Laquinone), squalium (for example, squalium), acridine orange, coumarins (for example, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, Distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone , Aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. And the like.
The infrared absorbing liquid composition may or may not contain a sensitizer, but if included, the content of the sensitizer is relative to the total solid mass of the infrared absorbing liquid composition of the present invention. The content is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less.

[8] Crosslinking agent The infrared absorbing liquid composition of the present invention may further contain a crosslinking agent for the purpose of improving the strength of the infrared cut filter.
The crosslinking agent is preferably a compound having a crosslinkable group, and more preferably a compound having two or more crosslinkable groups. As specific examples of the crosslinkable group, oxetane group, cyanate group, and the same groups as those mentioned for the crosslinkable group which the alkali-soluble binder may have can be suitably exemplified. , An oxetane group or a cyanate group. That is, the crosslinking agent is particularly preferably an epoxy compound, an oxetane compound or a cyanate compound.
Examples of the epoxy compound that can be suitably used as a crosslinking agent in the present invention include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule. Compound etc. are mentioned.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include a bixylenol type or biphenol type epoxy compound (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy compounds (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by BASF Japan”, etc.), bisphenol A type epoxy compounds, novolac type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol A types Epoxy compounds, bisphenol S type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, halogenated epoxy compounds (for example, low brominated epoxy compounds, high halogenated epoxy compounds) Compound, brominated phenol novolac type epoxy compound, etc.), allyl group-containing bisphenol A type epoxy compound, trisphenol methane type epoxy compound, diphenyldimethanol type epoxy compound, phenol biphenylene type epoxy compound, dicyclopentadiene type epoxy compound (" HP-7200, HP-7200H; manufactured by DIC Corporation, etc.), glycidylamine type epoxy compounds (diaminodiphenylmethane type epoxy compounds, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy compounds (diphthalic acid diphthalate) Glycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy compound, alicyclic ring Epoxy compounds (3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate,

Bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries, Ltd.”), imide type alicyclic epoxy compound, trihydroxy Phenylmethane type epoxy compound, bisphenol A novolak type epoxy compound, tetraphenylol ethane type epoxy compound, glycidyl phthalate compound, tetraglycidyl xylenoyl ethane compound, naphthalene group-containing epoxy compound (naphthol aralkyl type epoxy compound, naphthol novolak type epoxy compound) Tetrafunctional naphthalene type epoxy compounds, commercially available products are “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-”. 700; manufactured by DIC Corporation, etc.), a reaction product of a polyphenol compound obtained by addition reaction of a phenol compound with a diolefin compound such as divinylbenzene or dicyclopentadiene, and epichlorohydrin, 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid or the like, epoxy compound having a linear phosphorus-containing structure, epoxy compound having a cyclic phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy compound, dibenzoyloxybenzene type liquid crystal epoxy Compound, azophenyl type liquid crystal epoxy compound, azomethine phenyl type liquid crystal epoxy compound, binaphthyl type liquid crystal epoxy compound, azine type epoxy compound, glycidyl methacrylate copolymer epoxy compound (“CP-50S, CP-50M; NOF Corporation) Etc.), epoxy compounds copolymerized with cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy compounds, bis (glycidyloxyphenyl) adamantane type epoxy compounds, etc. is not. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

Examples of the oxetane compound include oxetane resins having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, ether compounds such as silsesquioxanes and the like, and other compounds having an oxetane ring and alkyl (meth) acrylate. A polymer etc. are also mentioned.
Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2′-bis- [4- (4-maleimide). Phenoxy) phenyl] propane, and the like.

  Examples of the cyanate compound include a bis A type cyanate compound, a bis F type cyanate compound, a cresol novolac type cyanate compound, and a phenol novolac type cyanate compound.

Moreover, a melamine or a melamine derivative can be used as the crosslinking agent.
Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like).
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together. The crosslinking agent has good storage stability and is effective in improving the surface hardness of the cured film (the film after the crosslinking reaction by the crosslinking agent is performed by energy such as light or heat) or the film strength itself. Melamine or alkylated methylol melamine is preferred, and hexamethylated methylol melamine is particularly preferred.

  The infrared-absorbing liquid composition may or may not contain a crosslinking agent, but when included, the content of the crosslinking agent is 1 mass relative to the total solid mass of the infrared-absorbing liquid composition of the present invention. % To 40% by mass, and more preferably 3% to 20% by mass.

[9] Curing Accelerator The infrared absorbing liquid composition of the present invention may further contain a curing accelerator for the purpose of accelerating the thermal curing of the crosslinking agent such as the epoxy compound or the oxetane compound. .
Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl- N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole) 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl 4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyl) Oxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxy Ethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. The curing accelerator is preferably melamine or dicyandiamide.
A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
The infrared absorbing liquid composition may or may not contain a curing accelerator, but when it is contained, the content of the curing accelerator with respect to the total solid content of the composition is usually 0.01 to 15% by mass. It is.

[10] Elastomer The infrared absorbing liquid composition of the present invention may further contain an elastomer.
By containing an elastomer, the adhesiveness between the substrate and the infrared cut filter can be further improved, and the heat resistance, thermal shock resistance, flexibility and toughness of the infrared cut filter can be further improved.

  There is no restriction | limiting in particular as an elastomer which can be used for this invention, According to the objective, it can select suitably, For example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer And silicone elastomers. These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Among these, polyester elastomers are advantageous in terms of compatibility with other materials.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like. As a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used in addition to styrene. Specifically, Tufprene, Solprene T, Asaprene T, Tuftec (Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (Aron Kasei Co., Ltd.), Clayton G, Super Reflex (October, Shell Japan Co., Ltd.), JSR- TR, TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Co., Ltd.), Quintac (manufactured by Nippon Zeon Co.), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Examples include Lavalon (manufactured by Mitsubishi Chemical Corporation), Septon, Hybler (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (manufactured by Riken Vinyl Industry Co., Ltd.) and the like.

  The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM) and the like. The olefin-based elastomer includes dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and the like. Examples include coalesced and epoxidized polybutadiene. Examples of the olefin-based elastomer include carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid. Further, as the olefin elastomer, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer Rubber etc. are mentioned.

  Specific examples of olefin-based elastomers include milastoma (manufactured by Mitsui Petrochemical), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (manufactured by Nippon Synthetic Rubber) ), Butadiene-acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.), “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.), polybutadiene Examples thereof include “BF-1000” (manufactured by Nippon Soda Co., Ltd.), which is partially epoxidized epoxidized polybutadiene.

  Urethane elastomers are composed of structural units of a hard segment composed of low molecular (short chain) diol and diisocyanate and a soft segment composed of high molecular (long chain) diol and diisocyanate. Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene-neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500. Specific examples of the urethane-based elastomer include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), sylactolan E790, and the like.

  The polyester elastomer is obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; Examples include alicyclic diol, bisphenol A, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxy-3-methylphenyl) -propane, resorcin and the like. These compounds can be used alone or in combination of two or more. In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. Polyester elastomers are available in various grades depending on the types and ratios of hard segments and soft segments, and the difference in molecular weight. Specific examples of polyester elastomers include Hytrel (Du Pont-Toray), Perprene (Toyobo), Espel (Hitachi Chemical Industries), and the like.

  Polyamide elastomers are composed of hard segments made of polyamide and soft segments made of polyether or polyester, and are roughly divided into two types: polyether block amide type and polyether ester block amide type. The Examples of the polyamide include polyamide 6, polyamide 11, and polyamide 12. Examples of the polyether include polyoxyethylene, polyoxypropylene, polytetramethylene glycol and the like. Specific examples of polyamide-based elastomers include UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MS Japan), Novamid (manufactured by Mitsubishi Chemical Corporation). ), Gleasing (manufactured by DIC Corporation) and the like.

  Acrylic elastomers are acrylic esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, monomers having an epoxy group such as glycidyl methacrylate, allyl glycidyl ether, and / or vinyls such as acrylonitrile and ethylene. It is obtained by copolymerizing with a monomer. Examples of the acrylic elastomer include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  Silicone elastomers are mainly composed of organopolysiloxane, and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Further, a part of organopolysiloxane modified with a vinyl group, an alkoxy group or the like may be used. Specific examples of the silicone elastomer include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above-mentioned elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin is, for example, a part or all of the epoxy groups such as the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, or cresol novolak type epoxy resin. Is obtained by modification with carboxylic acid-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.

  Among elastomers, from the viewpoints of shear adhesion and thermal shock resistance, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers, espels having hydroxyl groups which are polyester elastomers (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), epoxy Polybutadiene is preferred.

  The infrared absorbing liquid composition of the present invention may or may not contain an elastomer, but when it is contained, the elastomer content relative to the total solid mass of the infrared absorbing liquid composition is not particularly limited, Although it can select suitably according to the objective, 0.5 mass%-30 mass% in solid content are preferable, 1 mass%-10 mass% are more preferable, 3 mass%-8 mass% are especially preferable. When the content is within a preferable range, it is advantageous in that the shear adhesiveness and the thermal shock resistance can be further improved.

[11] Surfactant Various surfactants may be added to the infrared absorbing liquid composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the infrared-absorbing liquid composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved, so that the coating thickness is uniform. And liquid-saving properties can be further improved.
That is, in the case of forming a film using a coating solution to which an infrared absorbing liquid composition containing a fluorosurfactant is applied, the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating solution. The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in an infrared-absorbing liquid composition. .

  Examples of the fluorosurfactant include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, and F-143. F-144, R-30, F-437, F-475, F-479, F-482, F-554, F-780, F-781 (above, DIC ( Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The infrared absorbing liquid composition may or may not contain a surfactant, but when it is included, the content of the surfactant is based on the total solid mass of the infrared absorbing liquid composition of the present invention. The content is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.5% by mass or less.

[12] Other components In the infrared absorbing liquid composition of the present invention, in addition to the essential components and the preferred additives, other components are appropriately selected depending on the purpose as long as the effects of the present invention are not impaired. May be used.
Examples of other components that can be used in combination include thermosetting accelerators, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further adhesion promoters to the substrate surface and other assistants. Agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents, etc.) may be used in combination.
By appropriately containing these components, it is possible to adjust properties such as stability and film physical properties of the target infrared absorption filter.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The colorant is described in detail, for example, in paragraphs [0105] to [0106] of JP-A-2008-250074 and paragraphs [0038] and [0039] of JP-A-2009-205029.
The adhesion promoter is described in detail, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074.
Any of the additives described in these publications can be used in the infrared-absorbing liquid composition of the present invention.

The use of the infrared absorbing liquid composition of the present invention is not particularly limited, but for an infrared cut filter on the light receiving side of the solid-state image sensor substrate (for example, an infrared cut filter for a wafer level lens), the back surface of the solid-state image sensor substrate Examples include an infrared cut filter on the side (opposite to the light receiving side), and preferably for a light shielding film on the light receiving side of the solid-state imaging device substrate.
When the infrared-absorbing liquid composition of the present invention is for an infrared cut filter on the light-receiving side of a solid-state imaging device substrate, the solid content concentration is 30% by mass or more and 80% by mass in order to form a relatively thick coating film. % Or less, more preferably 35% by mass or more and 70% by mass or less, and most preferably 40% by mass or more and 60% by mass or less.
The viscosity of the infrared absorbing liquid composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s, most preferably. Is in the range of 100 mPa · s to 1500 mPa · s.
When the infrared-absorbing liquid composition of the present invention is for an infrared cut filter on the light-receiving side of a solid-state imaging device substrate, in the range of 10 mPa · s or more and 3000 mPa · s or less from the viewpoint of thick film formation and uniform coating properties. Preferably, it is in the range of 500 mPa · s to 1500 mPa · s, and most preferably in the range of 700 mPa · s to 1400 mPa · s.

The present invention also relates to an infrared cut filter manufactured by the above-described method for manufacturing an infrared cut filter of the present invention. Since such an infrared cut filter is formed by the method of manufacturing an infrared cut filter of the present invention, the infrared cut filter has a small film thickness distribution, excellent film thickness uniformity, and excellent incident angle dependence characteristics. It is.
The infrared cut filter of the present invention is preferably an infrared cut filter for a solid-state imaging device.

  Further, the present invention is a camera module having a solid-state image sensor substrate and an infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is the infrared cut filter of the present invention. Also related to camera modules.

Hereinafter, although the camera module which concerns on embodiment of this invention is demonstrated, referring FIG.1 and FIG.2, this invention is not limited by the following specific examples.
Throughout FIGS. 1 and 2, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are the sides closer to the silicon substrate 10. Point to.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state imaging device.
A camera module 200 shown in FIG. 1 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 is provided on the first main surface side (light receiving side) of the solid-state image sensor substrate 100 and the solid-state image sensor substrate 100 provided with an image sensor section on the first main surface of the silicon substrate. The flattening layer 46 (not shown in FIG. 1), the infrared cut filter 42 provided on the flattening layer 46, and the glass substrate 30 (light transmissive substrate) disposed above the infrared cut filter 42 A lens holder 50 having an imaging lens 40 disposed in an internal space above the glass substrate 30, and a light shielding / electromagnetic shield 44 disposed to surround the solid-state imaging device substrate 100 and the glass substrate 30. Configured. Each member is bonded by an adhesive 20 (not shown in FIG. 1) and 45.
The present invention is a method for manufacturing a camera module having a solid-state image sensor substrate and an infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is a method for manufacturing the infrared cut filter of the present invention. The present invention also relates to a camera module manufacturing method manufactured by the method.
Therefore, in the camera module according to the present embodiment, for example, a film is formed on the planarizing layer 46 by spin-coating the infrared absorbing liquid composition of the present invention to form the infrared cut filter 42. . The method for forming an infrared cut filter by forming a film by spin coating is as described above.
In the camera module 200, incident light hν from the outside passes through the imaging lens 40, the glass substrate 30, the infrared cut filter 42, and the flattening layer 46 in order, and then reaches the imaging device portion of the solid-state imaging device substrate 100. It has become.
The camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in FIG.
The solid-state image sensor substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a micro The lens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are configured.
However, the solder resist layer 24 may be omitted.

First, the configuration on the first main surface side of the solid-state imaging device substrate 100 will be mainly described.
As shown in FIG. 2, an imaging element unit in which a plurality of imaging elements 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of the silicon substrate 10 that is a base of the solid-state imaging element substrate 100. ing.
An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13. Furthermore, on the base layer 14, a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) Are arranged.
A light shielding film (not shown) may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit. This light shielding film can be produced using, for example, a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).
The planarizing layer 46 is provided on the microlens 17.

In addition, a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit. Has been.
Furthermore, an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
A base layer 14 is formed on the element surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.

The above is the configuration of the first main surface side of the solid-state imaging device substrate 100, but instead of providing the infrared cut filter 42 on the planarization layer 46, between the base layer 14 and the color filter 15, or An infrared cut filter may be provided between the color filter 15 and the overcoat 16.
On the first main surface side of the solid-state image sensor substrate 100, an adhesive 20 is provided around the image sensor section, and the solid-state image sensor substrate 100 and the glass substrate 30 are bonded via the adhesive 20.

  The silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole. The imaging element portion and the circuit board 70 are electrically connected by the through electrode.

Next, the configuration on the second main surface side of the solid-state imaging device substrate 100 will be mainly described.
On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
On the insulating film 22, a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the image pickup element portion in the solid-state image pickup element substrate 100 and the circuit board 70.
The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective layer) is provided on the second main surface side, which covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a portion on the metal electrode 23. Insulating film).
Further, on the second main surface side, there is provided a light shielding film 18 that covers the second main surface on which the solder resist layer 24 is formed and has an opening through which a part of the metal electrode 23 is exposed. It has been.
In FIG. 2, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24).
The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

  A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode (not shown) of the circuit board 70 are connected via the solder ball 60. , Are electrically connected.

As mentioned above, although the structure of the solid-state image sensor substrate 100 was demonstrated, the method as described in Paragraph 0033-0068 of Unexamined-Japanese-Patent No. 2009-158863, the method as described in Paragraph 0036-0065 of Unexamined-Japanese-Patent No. 2009-99951, etc. It can be formed by a known method.
The interlayer insulating film 13 is formed as a SiO ₂ film or a SiN film by sputtering, CVD (Chemical Vapor Deposition), or the like, for example.
The color filter 15 is formed by photolithography using a known color resist, for example.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
The microlens 17 is formed by using styrene resin or the like, for example, by photolithography.
The solder resist layer 24 is preferably formed by photolithography using a known solder resist including, for example, a phenol resin, a polyimide resin, or an amine resin.
The solder ball 60 is formed using, for example, Sn—Ag, Sn—Cu, Sn—Ag—Cu as Sn—Pb (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder. . The solder ball 60 is formed in a spherical shape having a diameter of 100 μm to 1000 μm (preferably a diameter of 150 μm to 700 μm), for example.
The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example. The metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers. The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used. Although the thickness of the substrate is not limited, for example, a silicon wafer having a thickness of 20 μm to 200 μm (preferably 30 to 150 μm) is used.
The through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).

  As mentioned above, although one Embodiment of the camera module was described with reference to FIG.1 and FIG.2, the said one embodiment is not restricted to the form of FIG.1 and FIG.2.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation of infrared absorbing liquid composition>
[Composition A]
The following compound was mixed with a stirrer and dissolved to prepare an infrared absorbing liquid composition A.
・ 80 parts by mass of cyclohexanone ・ YMF-02A (Cesium tungsten oxide (Cs _0.33 WO ₃ ) manufactured by Sumitomo Metal Mining Co., Ltd., concentration 18.5% by mass, average particle size 15 nm, refractive index 1.66)
6 parts by mass-KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound) 7.78 parts by mass-Irgacure OXE01 (manufactured by BASF Japan, polymerization initiator)
1.00 parts by mass Resin (binder, repeating unit derived from benzyl methacrylate / repeating unit derived from methacrylic acid = 80/20 (molar ratio), Mw = 30000)
6.2 parts by mass-Surfactant (F-781 manufactured by DIC Corporation) 0.02 parts by mass

[Composition B]
Similarly, the following compound was mixed and dissolved with a stirrer to prepare an infrared absorbing liquid composition B.
Propylene glycol monomethyl ether acetate (PGMEA) 80 parts by mass YMF-02A (Cesium Tungsten Oxide (Cs _0.33 WO ₃ ) manufactured by Sumitomo Metal Mining Co., Ltd., concentration 18.5% by mass, average particle diameter 15 nm, refractive index 1.66)
6.2 parts by mass-KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound) 7.75 parts by mass-Irgacure OXE02 (manufactured by BASF Japan Ltd., polymerization initiator)
1.00 parts by mass-The following resin (D-1 ') (binder) 6 parts by mass-Surfactant (F-171 manufactured by DIC Corporation) 0.05 parts by mass

[Composition C]
Similarly, the following compound was mixed with a stirrer and dissolved to prepare an infrared absorbing liquid composition C.
Propylene glycol monomethyl ether acetate (PGMEA) 80 parts by mass EPOLIGHT 1178 (Epolin, diimmonium dye)
6.2 parts by mass Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound)
13.75 parts by mass Irgacure OXE01 (manufactured by BASF Japan, polymerization initiator)
1.00 parts by mass Surfactant (DIC-made F-171) 0.05 parts by mass

(Examples 1-5 and Comparative Examples 2-4)
Using the obtained infrared absorbing liquid compositions A to C, the film thickness distribution evaluation and the incident angle dependence characteristic evaluation were performed as follows.

<Evaluation of film thickness distribution>
On the substrate (8 inch silicon substrate), the infrared absorbing liquid composition described in the following Table 1 is applied by the application method described in the following Table 1, and then heat-treated for 120 seconds using a 100 ° C. hot plate ( A dry film was obtained by performing pre-baking. When spin coating was employed as the coating method, spin coating was performed at the number of revolutions described in Table 1, and a dry film having a dry film thickness described in Table 1 was obtained. Further, when bar coating was adopted as the coating method, the dry film was formed so that the dry film thickness was 1.0 μm. Next, the film thickness of the dry film is measured at 10 arbitrary positions on the wafer surface. The difference between the maximum value and the minimum value of the film thickness is less than 0.03 μm, and the difference between 0.03 μm and less than 0.05 μm is Δ. 0.05 μm or more was taken as x.
In Comparative Example 1, since the film was formed by vapor deposition as described later, the film thickness distribution evaluation was not performed.
Below, the application | coating method of Table 1 is demonstrated.

(Spin coating)
Using 1H-D7 (Mikasa spin coater), spin coating was performed at the rotational speeds shown in Table 1.

(Bar coating)
Bar coating was performed using a doctor blade YD-2 type (manufactured by Yoshimi Seiki Co., Ltd.).

<Evaluation of incident angle dependency>
Each of the infrared-absorbing liquid compositions described in the following Table 1 is applied on a glass wafer by the coating method (that is, spin coating or bar coating) described in the column of “Coating Method” in Table 1 below. Then, after preheating (pre-baking) at 100 ° C. for 120 seconds, the entire surface was exposed at 2000 mJ / cm ² using an i-line stepper. Subsequently, post heating (post-baking) was performed at 200 ° C. for 300 seconds to obtain an infrared cut filter having a film thickness of 1.0 μm. In addition, when the coating method described in the column of “Coating method” in Table 1 is spin coating, spin coating was performed at a rotational speed of 2000 rpm.
The spectral characteristics on the long wavelength side of the infrared cut filter obtained as described above were evaluated using a phase difference measuring device (COBRA-WR, manufactured by Oji Scientific). Incident angle is changed perpendicularly to the infrared cut filter surface (angle 0 degree) and 35 degrees, and the slope on the high wavelength side in the p-polarized transmission band (visible light region) (here, “the slope on the high wavelength side” is , Which means a slope due to a decrease in spectral transmittance in the visible to near-infrared region having a wavelength of 600 nm or more), the shift amount of the wavelength at which the transmittance becomes 50% is less than 25 nm, Δ is 25 nm or more and less than 30 nm, 30 nm or more is shown as x.
In Comparative Example 1, the incident angle dependence characteristics were evaluated in the same manner as described above for the infrared cut filter produced as follows.

(Comparative Example 1)
A SiO ₂ layer and a TiO ₂ layer are alternately deposited on a glass substrate by electron beam evaporation (EB), and a dielectric multilayer film is formed on both surfaces of the glass substrate. A glass substrate (infrared cut filter) was obtained. The dielectric multilayer film layer formed on the glass substrate had a film thickness of 110 to 120 nm, and constituted 17 layers (the outermost surface layer was an SiO ₂ layer) for each side of the glass substrate.

  The above results are shown in Table 1.

As can be seen from the results in Table 1, Examples 1 to 5 using spin coating as the coating method have a film thickness distribution of the formed film as compared with Comparative Examples 2 to 4 using bar coating as the coating method. Small and excellent in film thickness uniformity.
In addition, the infrared cut filters of Examples 1 to 5 manufactured by spin coating have a smaller wavelength shift amount due to a change in incident angle than the infrared cut filter of Comparative Example 1 manufactured by vapor deposition (that is, incident angle dependence). The incident angle dependence characteristics were excellent.

As described above, according to the method for manufacturing an infrared cut filter of the present invention, it was found that an infrared cut filter having a small film thickness distribution, excellent film thickness uniformity, and excellent incident angle dependence characteristics can be produced. .
In addition, since the infrared absorbing liquid composition according to the present invention is a liquid, an infrared cut filter can be easily manufactured by a simple process of forming a film by spin coating. Insufficient production suitability can be improved.
In the above example, the silicon substrate was used as the substrate for the film thickness distribution evaluation, and the glass wafer was used as the substrate for the incident angle dependence characteristic evaluation. However, when a film was formed on the light receiving side using a solid-state image sensor substrate. It is considered that a similar result can be obtained.
Thus, the infrared cut filter manufacturing method of the present invention is a manufacturing method suitable for manufacturing a camera module having a solid-state image sensor substrate and an infrared cut filter disposed on the light-receiving side of the solid-state image sensor substrate. It is.

DESCRIPTION OF SYMBOLS 10 Silicon substrate 12 Image pick-up element 13 Interlayer insulating film 14 Base layer 15 Color filter 16 Overcoat 17 Micro lens 18 Light shielding film 20 Adhesive 22 Insulating film 23 Metal electrode 24 Solder resist layer 26 Internal electrode 27 Element surface electrode 30 Glass substrate 40 Imaging Lens 42 Infrared cut filter 44 Light shielding / electromagnetic shield 45 Adhesive 46 Flattening layer 50 Lens holder 60 Solder ball 70 Circuit board 100 Solid-state imaging device substrate 200 Camera module

Claims (12)

In the light receiving side of the solid-state imaging device substrate, an infrared absorbing agent, polymerizable compound, a solvent, and an infrared absorptive liquid composition containing a fluorine-based surfactant have a step of forming a film by spin coating, the A method for producing an infrared cut filter, wherein the infrared absorber is at least one selected from a metal oxide and a diimmonium dye . In the light receiving side of the solid-state imaging device substrate, an infrared absorbing agent, polymerizable compound, a solvent, and the infrared absorbing liquid composition containing a polymerization initiator it has a step of forming a film by spin coating, the infrared absorption The manufacturing method of the infrared cut filter whose agent is at least 1 type selected from a metal oxide and a diimmonium pigment | dye .   The method for producing an infrared cut filter according to claim 1, wherein the infrared absorbing liquid composition further contains a polymerization initiator.   The manufacturing method of the infrared cut filter of Claim 2 or 3 whose said polymerization initiator is a compound which has an aromatic group.   The method for producing an infrared cut filter according to claim 2 or 3, wherein the polymerization initiator is an oxime compound, an acetophenone compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, or a thiol compound.   The manufacturing method of the infrared cut filter of any one of Claims 1-5 whose rotation speed of the said spin application is 1000 rpm to 4000 rpm.   The manufacturing method of the infrared cut filter of any one of Claims 1-6 whose film thickness of the film | membrane formed by the said spin coating is 0.5 micrometer-5 micrometers.   An infrared-absorbing liquid composition containing an infrared absorbent, a polymerizable compound, a solvent, and a fluorine-based surfactant, which is used in the method for producing an infrared cut filter according to claim 1.   An infrared absorbing liquid composition containing an infrared absorbent, a polymerizable compound, a solvent, and a polymerization initiator, which is used in the method for producing an infrared cut filter according to claim 2. The infrared absorbing liquid composition according to claim 8 or 9, wherein the infrared absorber is at least one selected from a metal oxide and a diimmonium dye represented by the following general formula (III-1) or (1). object.

In general formula (III-1), R ³¹¹ , R ³¹² , R ³²¹ , R ³²² , R ³³¹ , R ³³² , R ³⁴¹ and R ³⁴² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, R ³⁰³ , R ³¹³ , R ³²³ , R ³³³ and R ³⁴³ each independently represent a substituent, and n ₃₀₃ , n ₃₁₃ , n ₃₂₃ , n ₃₃₃ and n ₃₄₃ each independently represent an integer of 0 to 4, Represents a monovalent or divalent anion, n ₃₅₃ represents 1 or 2, and the product of the valence of X and n ₃₅₃ is 2.

In the general formula (1), each R independently represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group, a phenylalkylene group or an alkoxy group, and R ¹ represents a fluorine atom or a fluorine atom. Represents an alkyl group.   The infrared absorbing liquid composition according to claim 10, wherein the metal oxide is cesium tungsten oxide.   It is a manufacturing method of the camera module which has a solid-state image sensor board | substrate and the infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor board | substrate, Comprising: The said infrared cut filter is any one of Claims 1-7. The manufacturing method of the camera module manufactured by the manufacturing method of the infrared cut filter.