JP6251530B2 - Curable resin composition for imaging device and use thereof - Google Patents

Description

The present invention relates to a curable resin composition for an image sensor and its use. More specifically, the present invention relates to a curable resin composition used for an image sensor, a laminate using the same, a light selective transmission filter, and an image sensor.

An image sensor is also referred to as a solid-state image sensor or an image sensor chip, and is an electronic component that converts light of an object into an electrical signal and outputs the electrical signal. For example, a camera for a mobile phone, a digital camera, a vehicle camera, a monitoring It is used for cameras, display elements (LEDs, etc.). Such an image sensor is usually a CCD (Charge Coupled Device) or CMOS (Complementary).
Although it is configured with a detection element (sensor) and lens such as Metal-Oxide Semiconductor), there is an increasing demand for reducing optical noise that hinders image processing, etc., in order to increase functionality and performance. Yes.

Conventionally, optical noise reduction in imaging devices has been achieved by providing absorption glass such as blue glass doped with copper ions, resin filters with light absorption and reflection functions that reduce optical noise, and resin components. I have been. However, although the absorbing glass is very excellent in heat resistance, cracks and chipping are likely to occur, and the processability is not sufficient. On the other hand, the resin filter can suppress the occurrence of cracks and chipping and is excellent in workability. On the other hand, the heat resistance is not sufficient as compared with glass, and the occurrence of warpage due to linear expansion cannot be denied. Therefore, in recent years, development of an optical filter in which a layer having a light absorption function and a reflection function is formed on a substrate such as glass has been advanced.

As a conventional optical filter, for example, a light absorption filter comprising a first layer containing a light absorber and a second layer having a different refractive index on a glass substrate (see Patent Document 1), a polyester film substrate A near-infrared absorbing filter (see Patent Document 2) in which an organic film layer composed of a resin binder and a near-infrared absorbing dye and an inorganic film layer are formed on a transparent substrate such as a pigment, and a colored curing containing a phthalocyanine compound on a glass substrate A color filter having a colored film made of a conductive composition (see Patent Document 3), a glass substrate having an organic polymer layer made of a liquid resin composition and a near infrared reflecting film made of a dielectric multilayer film Infrared cut filter (see Patent Document 4), a near-infrared cut filter that includes a laminated plate having a resin layer containing a near-infrared absorber on a glass substrate and exhibits a predetermined transmittance Chromatography (Patent Document 5 references) have been disclosed.

Japanese Patent Laid-Open No. 2008-51985 JP 2006-106570 A JP 2012-167145 A JP 2013-50593 A JP 2012-103340 A

As described above, in recent years, in order to reduce optical noise in an image sensor, an absorption glass, a resin filter having a light absorption function and a reflection function on a resin component, and a light absorption layer and a reflection layer are formed on a substrate. Optical filters have been developed.

By the way, since it is considered that the image pickup device has the following problems in addition to the reduction of optical noise, a technique capable of solving these problems and exhibiting desired performance is required.
For example, the human eye is said to have the highest sensitivity near a wavelength of 555 nm. Therefore, in order to become a more effective image pickup device for the user, the image pickup device is required to have light selective transparency close to the sensitivity of the human eye. In addition, since the image sensor is often reflow-mounted, the members constituting the image sensor are required to have heat resistance that can withstand the reflow process. In particular, when an optical filter in which a light absorption layer or a reflection layer is formed on a substrate is used as an imaging device, the optical filter is produced by depositing the layer on the substrate at a high temperature from the viewpoint of forming a dense layer. Since a method is desired, high heat resistance is required.

However, the present condition is that the member which can express high heat resistance with the selective light transmission close | similar to the sensitivity of human eyes has not been developed yet. In addition, a filter having a reflection function has an incident angle dependency (also referred to as a viewing angle dependency) in which the reflection characteristic changes depending on the incident angle of light, although it has excellent light blocking performance. In addition to problems, ghosts and flares may occur due to irregular reflection of light incident on the lens, and there is also a problem regarding suppression thereof.

The present invention has been made in view of the above-described present situation, and can exhibit high heat resistance as well as excellent light selective transmission, and is extremely useful for imaging device applications, and a laminate using the same. The purpose is to provide. Another object of the present invention is to provide a light selective transmission filter and an image sensor including such a laminate.

The inventors of the present invention have made various studies on members used for imaging device applications. As a result, when a curable resin composition containing at least a phthalocyanine-based dye and a resin component is used, attention is focused on heat resistance and light resistance. did. And when the compound which has a predetermined structure as a phthalocyanine type pigment | dye is used, it discovered that the outstanding light selective permeability could be exhibited and it became a curable resin composition extremely useful for an image pick-up element use. If such a curable resin composition is used for an image sensor, it is possible to sufficiently suppress the occurrence of flares and ghosts, which are problems with the image sensor, and also to have sufficient incident angle dependency that can be a problem when combined with a reflective film. Can be reduced. In addition, a laminate having a resin layer formed from such a curable resin composition on a transparent inorganic material layer such as glass or crystal can suppress the occurrence of cracks, chipping, and warpage, and can be used for high-temperature deposition and reflow. It was found that the heat resistance was excellent enough to cope with the process. Furthermore, it has also been found that by using such a laminate in combination with, for example, a reflective film or an interference film, it is possible to exhibit light selective transparency close to the sensitivity of the human eye. And the light selective transmission filter and the image sensor including such a laminate for the image sensor have been found to be extremely useful in the optical field and the optical device field, and it has been conceived that the above problems can be solved brilliantly. The present invention has been reached.

That is, this invention is a curable resin composition used for an image pick-up element containing a pigment | dye and a resin component, Comprising: This pigment | dye is the following general formula (I):

(In the formula, M represents a metal atom, a metal oxide or a metal halide. X ^{1 to} X ⁴ and Y ^{1 to} Y ⁴ are the same or different and represent a hydrogen atom (H), a fluorine atom (F) or .OR ⁱ group represents an oR ⁱ group which may have a substituent, an alkoxy group, a phenoxy group or a naphthoxy group. provided that at least one of ^{X 1} and ^{Y 1,} the ^{X 2} and ^{Y 2} At least one of them, at least one of X ³ and Y ³ , and at least one of X ⁴ and Y ⁴ represents an OR ⁱ group which may have a substituent. It is a curable resin composition for an image sensor containing a phthalocyanine dye.

This invention is also a laminated body obtained by forming the resin layer which consists of the said curable resin composition for image pick-up elements on a transparent inorganic material layer.
The present invention is also a light selective transmission filter including the laminate.
The present invention is also an image pickup device including the laminate.
The present invention is described in detail below. A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

In this specification, “absorption maximum” means that the relationship between wavelength and absorbance is represented by a two-dimensional graph of the X axis and Y axis (where the X axis is the wavelength and the Y axis is the absorbance) It means the peak at which the absorbance changes from increasing to decreasing, and the wavelength at this peak is called the “absorption maximum wavelength”. Further, among absorption maximum wavelengths (also referred to as absorption peak wavelengths), those having the maximum absorbance are referred to as maximum absorption wavelengths (also referred to as “maximum absorption peak wavelengths”).
“Absorption width (also referred to as absorption band width)” is a wavelength width at an arbitrary transmission intensity. When the absorption width is wide (large), the light selective transparency is excellent, and the design conditions of the reflective film are widened, so that it becomes easy to manufacture a light selective transmission filter (such as an infrared cut filter).

[Curable resin composition for imaging element]
The curable resin composition for an image sensor of the present invention (also referred to as a curable resin composition or a resin composition) includes a dye and a resin component. Such a curable resin composition is particularly useful for imaging device applications.
In addition, the said pigment | dye and the resin component may be used individually by 1 type, or 2 or more types, respectively, and the said curable resin composition may further contain 1 type or 2 types or more of another component as needed.

-Dye-
The dye contains at least a phthalocyanine dye represented by the general formula (I). Thereby, high heat resistance and light resistance can be exhibited together with excellent light selective transparency.

In the general formula (I), R ⁱ constituting the OR ⁱ group is an alkyl group, a phenyl group, or a naphthyl group, and may have a substituent. As an alkyl group, a C1-C20 alkyl group is preferable, for example, More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Most preferably, it is C1-C4. It is an alkyl group. Among R ⁱ , a phenyl group or a phenyl group having a substituent is preferable. In the present invention, at least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ in the general formula (I), it is preferable to represent a good phenoxy group which may have a substituent. As a result, due to the higher association of the phthalocyanine dye, it is possible to sharply block the wavelength range to be blocked and to exhibit high transmittance in the wavelength range to be transmitted (blocking transmission) Characteristic) can be further exhibited, and the dependency on the incident angle by the reflective film can be greatly reduced. Thus at least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ in the general formula (I) is in the form represents an phenoxy group which may have a substituent are also suitable for the present invention One of the forms.

Examples of the substituent that the OR ⁱ group may have include electrons such as an alkoxycarbonyl group (—COOR), a halogen group (halogen atom), a cyano group (—CN), and a nitro group (—NO ₂ ). An attractive group; an electron donating group such as an alkyl group (—R) and an alkoxy group (—OR); and the like, and may include one or more of these. Among these, an electron withdrawing group is preferable from the viewpoint that the selective light transmission property is further improved due to the fact that an associated molecular structure is easily formed. The electron withdrawing group is preferably an alkoxycarbonyl group, a chloro group (chlorine atom) or a cyano group, and more preferably a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group or a cyano group.
Note that R constituting the alkoxycarbonyl group (—COOR) is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and R constituting the alkyl group (—R) is 1 to 1 carbon atom. 8 alkyl groups are preferred. The alkoxycarbonyl group is preferably a methoxycarbonyl group or a methoxyethoxycarbonyl group, and the alkyl group is preferably a methyl group or a dimethyl group.

When the OR ⁱ group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 4, for example. More preferably, it is 1 or 2.
When one OR ⁱ group has two or more substituents, the substituents may be the same or different. Further, the position of the substituent in the OR ⁱ group is not particularly limited.

At least one of the above X ¹ and Y ¹ , at least one of X ² and Y ² , at least one of X ³ and Y ³ , and at least one of X ⁴ and Y ⁴ is a substituent. Represents an OR ⁱ group which may have Preferably, it is a phenoxy group which may have a substituent (that is, a phenoxy group or a phenoxy group having a substituent). More preferably, all of X ^{1 to} X ⁴ and Y ^{1 to} Y ⁴ represent a phenoxy group which may have a substituent. Among these, a phenoxy group having a substituent is preferable, and as the substituent, an electron-withdrawing group is preferable as described above.

In the said general formula (I), M represents a metal atom, a metal oxide, or a metal halide. The metal atom and the metal atom constituting the metal oxide or metal halide are not particularly limited. For example, copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, Lead etc. are mentioned, These 1 type (s) or 2 or more types can be used. Among these, those having one or more of copper, vanadium, and zinc as the central metal are preferable because they are more excellent in solubility or dispersibility in the resin component, visible light permeability, and light resistance. More preferably, it is copper or zinc. The phthalocyanine dye having copper as a central metal is not deteriorated by light even when dispersed in any resin component (binder resin), and has very excellent light resistance. A phthalocyanine complex (phthalocyanine-based dye) having zinc as a central metal is preferable because a laminate having excellent solubility in a resin component and higher light selective permeability can be easily obtained.

The halogen atom which comprises the said metal halide is not specifically limited, For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

The compound represented by the general formula (I) can be synthesized, for example, by using a usual method described in Japanese Patent Publication No. 6-31239. Specifically, one selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides and organic acid metals (these are also collectively referred to as “metal compounds”), and the following general formula (II):

(Wherein, X ^a and Y ^a are the same or different and represent a hydrogen atom (H), a fluorine atom (F) or an OR ⁱ group which may have a substituent, and the OR ⁱ group is an alkoxy group) And a phthalonitrile derivative represented by phenoxy group or naphthoxy group) is preferably obtained by heating and reacting in the absence of a solvent or in the presence of an organic solvent. It is preferable to react. The cyclization reaction of the phthalonitrile derivative is not particularly limited, and is conventionally described in JP-B-631239, JP37212298, JP32226504, JP2010-77408, and the like. Known methods can be applied singly or appropriately modified. Specific forms of the substituent and the OR ⁱ group are as described above for the general formula (I).

In the general formula (II), X ^a and Y ^a are preferably such that at least one of them represents an OR ⁱ group which may have a substituent. More preferably, both X ^a and Y ^a are the same or different and represent an OR ⁱ group which may have a substituent.

In the above reaction, as the phthalonitrile derivative represented by the general formula (II), at least one compound in a form representing an OR ⁱ group in which at least one of X ^a and Y ^a may have a substituent is used. It is preferable to do. It should be noted that both X ^a and Y ^a are a compound in a form representing a group (atom) other than an OR ⁱ group which may have a substituent, and at least one of X ^a and Y ^a is substituted. You may use together with the compound of the form showing the ^ORi group which may have a group.

The metal compound is not particularly limited as long as it reacts with the phthalonitrile derivative to give the compound represented by the general formula (I). For example, metals such as iron, copper, zinc, vanadium, titanium, indium and tin; metal halides such as chloride, bromide and iodide of the metal; vanadium oxide, titanyl oxide and copper oxide of the metal Metal oxide; organic acid metal such as acetate of the metal; complex compound of the metal such as acetylacetonate; metal carbonyl such as carbonyl iron; and the like.

Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium and tin; metal halides such as chloride, bromide and iodide of the metal (for example, vanadium chloride, titanium chloride, chloride) Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminium, gallium iodide, copper bromide, zinc bromide, cobalt bromide, indium bromide, aluminum bromide, gallium bromide, copper fluoride, zinc fluoride, indium fluoride, etc.); vanadium monoxide, trioxide Vanadium, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron sesquioxide, iron tetroxide, Metal oxides such as manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, barium oxide, zinc oxide, germanium monoxide, germanium dioxide; Organic acid metals such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate, copper stearate and zinc stearate; complex compounds such as acetylacetonate and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl And the like.

Among the above metal compounds, metal halides are more preferable, vanadium iodide, vanadium chloride, copper chloride, copper iodide, and zinc iodide are more preferable, and copper chloride, vanadium chloride, and iodide are particularly preferable. Zinc. When zinc iodide is used, the central metal in the general formula (I) is zinc.

When the reaction between the metal compound and the phthalonitrile derivative represented by the general formula (II) is performed in an organic solvent, examples of the organic solvent include benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, Inert solvents such as trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, benzonitrile; pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, One type or two or more types of aprotic polar solvents such as tri-n-butylamine, dimethyl sulfoxide, dimethyl sulfone and sulfolane can be used. Of these, 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene, and ethylene glycol are preferably used. More preferred are trimethylbenzene and benzonitrile.

When a solvent is used in the above reaction, the amount of the organic solvent used is preferably such that the concentration of the phthalonitrile compound represented by the general formula (II) is 1 to 50% by mass. More preferably, the amount is 10 to 40% by mass.

With regard to the above reaction, the reaction temperature is not necessarily constant depending on the type of raw material, the type of solvent, and other conditions, but it is usually preferably 100 to 300 ° C. More preferably, it is 120 degreeC or more, More preferably, it is 130 degreeC or more. Further, it is more preferably 260 ° C. or lower, further preferably 240 ° C. or lower, particularly preferably 200 ° C. or lower. Further, the temperature may be raised stepwise to control the exothermic reaction. Although there is no restriction | limiting in particular also for reaction time, Usually, it is preferable to set it as 2 to 24 hours, More preferably, it is 5 to 20 hours.
The above reaction may also be performed in an air atmosphere, but depending on the type of metal compound, an inert gas or oxygen-containing gas atmosphere (for example, nitrogen gas, helium gas, argon gas, oxygen / nitrogen mixed gas, etc.) It is preferable to be carried out under the distribution of
After the cyclization reaction, crystallization, filtration, washing, and / or drying may be performed according to a conventionally known method.

The phthalocyanine dye preferably has an absorption maximum in a wavelength range of 650 to 680 nm when an absorption spectrum of a cured product composed of the phthalocyanine dye and a measurement resin is measured. Thereby, it becomes possible to fully exhibit the effect of this invention.

The phthalocyanine dye preferably has only one absorption maximum in a wavelength range of 400 to 680 nm when an absorption spectrum of a cured product composed of the phthalocyanine dye and a measurement resin is measured. As a result, the light selective permeability can be further enhanced, and the effects of the present invention can be fully exhibited. More preferably, only one absorption maximum is shown in the wavelength region of 400 to 750 nm.

The phthalocyanine dye preferably has a transmittance at a wavelength of 550 nm of 80% or more when an absorption spectrum of a cured product composed of the phthalocyanine dye and a measurement resin is measured. More preferably, it is 83% or more, still more preferably 85% or more, particularly preferably 87% or more, and most preferably 89% or more.

The phthalocyanine dye further has a transmittance of 60% or less at an absorption maximum wavelength existing in a wavelength range of 650 to 680 nm when an absorption spectrum of a cured product composed of the phthalocyanine dye and a measurement resin is measured. Preferably it is. More preferably, it is 50% or less, More preferably, it is 40% or less, More preferably, it is 30% or less.

The above-mentioned absorption characteristics and transmission characteristics of the dye are characteristics obtained from the absorption spectrum (or transmittance spectrum) of the cured product composed of the dye and the measurement resin. Specifically, it is preferable to obtain by a resin film evaluation method.
The resin film evaluation method is a method for evaluating absorbance characteristics in a film state in which a dye is dispersed or dissolved in a measurement resin.
“A film in which a dye is dispersed or dissolved in a measurement resin” is a film composed of a dye to be measured and a measurement resin, and the conditions under which the absorbance at the absorption maximum wavelength can be evaluated (the absorbance at the absorption maximum wavelength is spectroscopic). Any film may be used as long as the content of the dye and the thickness of the film are selected so as to satisfy the conditions under which the absorbance can be measured without exceeding the measurement limit of the photometer.

In the resin film evaluation method, the evaluation film is preferably selected from a range in which the content ratio of the pigment to be measured is 0.01 to 15% by mass and a thickness of the film is 0.1 to 10 μm. More preferably, the content of the specific dye in the film is 10% by mass and the thickness of the film is 1 μm.
The film for evaluation contains a pigment and a measurement resin (may contain a solvent if necessary), and is formed (applied, dried if necessary) on a transparent substrate (glass, transparent resin film). Can be obtained. The absorbance of the dye can be determined by measuring the absorbance of the thus obtained film-coated substrate.

The measurement resin for evaluation is not particularly limited, but is selected from the group consisting of, for example, epoxy resins, acrylic resins, fluorinated aromatic polymers, poly (amide) imide resins, polyamide resins, aramid resins, and polycycloolefin resins. It is preferable that it is 1 type. Among these, epoxy resins and acrylic resins are more preferable, and epoxy resins are more preferable.
The absorbance can be measured using, for example, a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100).

In the present invention, other dyes may be further contained as necessary. Although it does not specifically limit as another pigment | dye, The thing which has an absorption maximum in the wavelength range of 600-800 nm is suitable. More preferably, it has an absorption maximum in a wavelength region of 680 to 750 nm. Thus, the form in which the said pigment | dye further contains the pigment | dye which has an absorption maximum in a wavelength range of 680-750 nm is one of the suitable forms of this invention. As a result, a sufficient absorption band width can be secured, so that the light selective transmission can be further increased, and the occurrence of flares and ghosts and the dependency on the incident angle when combined with a reflective film can be further reduced. Can do.
The absorption characteristic of the dye is preferably a characteristic shown when the absorbance characteristic is evaluated by the resin film evaluation method described above.

When a dye having an absorption maximum in the wavelength range of 680 to 750 nm (also referred to as dye α) is further used as the other dye, the dye α has an absorption maximum substantially in the wavelength range of 400 nm or more and less than 600 nm. It is preferable that it is not. In addition, from the viewpoint of improving the transparency in the visible light region, a material having high transparency in the 400 to 450 nm region is preferable. Specifically, it is preferable to show a transmittance of 87% or more at 430 nm, and more preferably 88% or more.
In addition, the pigment | dye (alpha) can use 1 type (s) or 2 or more types.

The dye α also preferably has an absorption maximum in the wavelength region of 600 to 650 nm. That is, it is preferable that the absorption maximum is shown in the wavelength range of 600 to 650 nm and the wavelength range of 680 to 750 nm, respectively (this kind of dye α is referred to as dye α ′). As a result, an even more sufficient absorption band width can be secured, so that the light selective transparency is further improved. In addition, when the laminate of the present invention using such a pigment is combined with a reflective film, the incident angle dependency due to the reflective film can be greatly reduced.
In addition, it is also suitable to use together the pigment | dye which has an absorption maximum in the wavelength range of 680-750 nm, and the pigment | dye which has an absorption maximum in the wavelength range of 600-650 nm.

The maximum absorption wavelength in the wavelength range of 680 to 750 nm of the dye α ′ is preferably 680 to 730 nm. The maximum absorption wavelength in the wavelength region of 600 to 650 nm is preferably 600 to 630 nm.

Here, among the phthalocyanine dyes essential for the laminate of the present invention, a dye that has an absorption maximum in the wavelength range of 650 to 680 nm and only one absorption maximum in the wavelength range of 400 to 680 nm (dye β In addition, when the dye α ′ is used in combination, the absorbance (Aα1) at the maximum absorption wavelength in the wavelength range of 680 to 750 nm out of the absorption maximum of the dye α ′, in the wavelength range of 600 to 650 nm The absorbance (Aα2) at the maximum absorption wavelength and the absorbance (Aβ) at the maximum absorption wavelength in the wavelength range of 650 to 680 nm of the dye β are the following relational expressions:
Aα2 <Aβ <Aα1
It is preferable to satisfy. Thereby, the absorption maximum peaks of the respective dyes are overlapped, and the laminate of the present invention has an absorption characteristic showing a broad absorption peak as a whole, that is, a sufficient absorption band width can be secured. The effect can be more fully exhibited.

The other dyes also preferably have a transmittance at a wavelength of 550 nm of 80% or more when the absorbance characteristics are evaluated by a resin film evaluation method. More preferably, it is 83% or more, still more preferably 85% or more, particularly preferably 87% or more, and most preferably 89% or more.

Specific examples of the other dyes include, for example, phthalocyanine dyes other than the phthalocyanine dyes represented by the general formula (I), porphyrin dyes, chlorin dyes, choline dyes, cyanine dyes, quaterylene dyes. , Squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like, and one or more of these can be used. Among these, phthalocyanine dyes are preferable from the viewpoint of light resistance and heat resistance.

In the curable resin composition, the total amount of the dye (total concentration of all the dyes) is preferably 0.0001% by mass or more and 15% by mass or less with respect to 100% by mass of the total amount of the resin components, for example. Thereby, it is possible to obtain a laminate having a high visible light transmittance and excellent in blocking characteristics in the near infrared region. More preferably, it is 0.001 mass% or more, More preferably, it is 0.1 mass% or more, Especially preferably, it is 1 mass% or more, More preferably, it is 10 mass% or less, More preferably, it is 7 mass% or less, Especially preferably, it is 5 mass% or less.

Here, since the extinction coefficient generally varies depending on the skeleton of the dye, and it is impossible to define the mass ratio for dyes of various skeletons, the phthalocyanine dye essential in the present invention and other dyes are used in combination. It is difficult to define these mass ratios in cases. However, for example, when the phthalocyanine dye represented by the general formula (I) is used, the dye α is used as the other dye, and the dye α is a low association phthalocyanine dye, the general formula ( The mass ratio of the content of the phthalocyanine dye represented by I) and the dye α (phthalocyanine dye / dye α) is, for example, preferably 20/80 to 60/40. As a result, it has a sufficient absorption band width, shows a sharp transmission absorption characteristic, and when it is combined with a reflective film, the effect of the present invention that can sufficiently reduce the incident angle dependency is more fully exhibited. It becomes possible to do. The mass ratio is more preferably 30/70 to 50/50.

In the present invention, the content of the phthalocyanine dye represented by the general formula (I) in the total amount of the dye of 100% by mass is preferably 10 to 100%. More preferably, it is 15-100 mass%.

The dye of the present invention may contain a phthalocyanine dye represented by the above-mentioned general formula (I) and a dye that does not fall under either of the dyes α. The content of such a dye has the effect of the present invention. In order to fully exhibit, it is suitable that it is 50 mass% or less with respect to 100 mass% of total amounts of a pigment | dye. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it does not contain substantially the pigment | dye which does not correspond to any of the phthalocyanine dye represented by the general formula (I) mentioned above, and the pigment | dye (alpha). That is.

The said curable resin composition may also contain the compound which has an absorptivity in the wavelength range of 350-400 nm. Thereby, deterioration of a laminated body resulting from light (substantially purple light) in a wavelength range of 350 to 400 nm can be sufficiently suppressed.
Examples of the compound having an absorptivity in the wavelength range of 350 to 400 nm include one or two ultraviolet absorbing compounds such as TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, and TINUVIN 326 (manufactured by BASF). More than seeds can be used.
In addition, the pigment | dye as used in the field of this invention does not contain the compound which has an absorptivity in the wavelength range below 400 nm represented by the compound which has an absorptivity in the wavelength range of 350-400 nm.

-Resin component-
In the curable resin composition of the present invention, the resin component is preferably one that can sufficiently dissolve or disperse the dye. That is, it is preferable that the pigment is uniformly dispersed or dissolved in a curable resin composition containing the pigment and a resin component. In addition, by appropriately selecting the resin component, the high transmittance in the wavelength region (for example, visible region) to be transmitted and the high absorbency in the wavelength region (for example, infrared region) to be blocked are more compatible. Is possible.

As the resin component, for example, at least one selected from the group consisting of a solvent-soluble resin, a solvent-soluble resin material, and a liquid resin material is suitable. Such a resin component has a high dispersibility of the dye, so that it can form a light absorbing film excellent in light selective absorption and can disperse the dye at a high concentration, so that the resin layer can be made thin. is there. Further, when the resin component is used, a resin layer can be formed (film formation) by a coating method described later, so that the pigment can be uniformly dispersed at a high concentration in the resin layer, and the resin layer can be formed at a relatively low temperature. Can be formed.

Here, the “solvent-soluble resin” means a resin soluble in an organic solvent, for example, 100 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone, tetrahydrofuran, acetone, or methyl isobutyl ketone. A resin that dissolves 1 part by mass or more is preferable. The “solvent-soluble resin raw material” means a solvent-soluble resin raw material, that is, a resin raw material that is solvent-soluble. For example, propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone, tetrahydrofuran, acetone Or what melt | dissolves 1 mass part or more with respect to 100 mass parts of methyl isobutyl ketone is suitable. The “liquid resin raw material” means a liquid resin raw material, that is, a resin raw material that is liquid. The term “liquid” means that the viscosity of the product itself is 100 Pa · s or less at room temperature (25 ° C.). The viscosity can be measured with a B-type viscometer.
The “resin raw material” includes a precursor of the resin, a raw material of the precursor, and a monomer (such as a curable monomer) for forming the resin.

As the solvent-soluble resin, an organic compound having a curable functional group (also referred to as a curable compound) is preferable. The curable functional group refers to a functional group that undergoes a curing reaction by heat or light (a group that causes the resin composition to undergo a curing reaction). For example, an oxirane group (oxirane ring), an epoxy group, an oxetane group (oxetane ring), and ethylene. Preferred are cationic curable groups such as sulfide groups, dioxolane groups, trioxolane groups, vinyl ether groups, and styryl groups; radical curable groups such as acrylic groups, methacryl groups, and vinyl groups. Therefore, the resin component includes a compound having a cationic curable group (also referred to as a cationic curable resin or a cationic curable compound) and / or a compound having a radical curable group (also referred to as a radical curable resin or a radical curable compound). Preferably). As a result, the time until curing is shortened and the productivity is further increased, and the cured film (resin layer) obtained is also more excellent in heat resistance (heat decomposition resistance and color resistance). Among these, it is more preferable to contain at least a cationic curable compound from the viewpoint of lower cure shrinkage.

In the resin component, the content of the cationic curable compound is preferably 10 to 100% by mass with respect to 100% by mass of the total amount of the resin component. More preferably, it is 50-100 mass%.

The cationic curable compound may be a compound having one cationic polymerizable group in one molecule (referred to as a monofunctional cationic curable compound), or two or more cationic polymerizable groups in one molecule. Although it may be a compound (referred to as a polyfunctional cation curable compound), it is preferable to use at least a polyfunctional cation curable compound. Thereby, sclerosis | hardenability is improved more.

The polyfunctional cation curable compound may be a compound having two or more identical cation polymerizable groups or a compound having one or more different cation polymerizable groups. As the polyfunctional cation curable compound, a polyfunctional alicyclic epoxy compound and / or a polyfunctional hydrogenated epoxy compound are particularly preferable. By using these, a cured product can be obtained in a shorter time.

Among the above cationic curable compounds, compounds having one or more oxirane rings in one molecule (also referred to as oxirane compounds) are preferable. Thereby, the laminate and the curable resin composition of the present invention have excellent chemical resistance. Thus, the form in which the resin component contains a compound having one or more oxirane rings in the molecule is also a preferred form of the present invention.

In this specification, a group containing an oxirane ring which is a three-membered ether is referred to as an “epoxy group”. “Epoxy group” includes, in addition to a narrowly defined epoxy group, a group in which an oxirane ring is bonded to carbon such as a glycidyl group, a group containing an ether or ester bond such as a glycidyl ether group and a glycidyl ester group, epoxy A cyclohexane ring etc. shall be included.

The oxirane compound is preferably a compound having a hydroxyl group and / or an ester group (referred to as an oxirane compound having a hydroxyl group and / or an ester group). By using the oxirane compound in such a form, the laminate and the curable resin composition of the present invention are more excellent in adhesiveness. In addition, you may use together the oxirane compound which does not contain a hydroxyl group and an ester group with the oxirane compound which has a hydroxyl group and / or an ester group.

Specifically, an epoxy compound having a hydroxyl group and / or an ester group is preferable as the oxirane compound having a hydroxyl group and / or an ester group. Moreover, as an epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound, or an aliphatic epoxy compound is preferable.

Regarding the epoxy compound, the alicyclic epoxy compound is a compound having an alicyclic epoxy group. Examples of the alicyclic epoxy group include an epoxycyclohexane group (epoxycyclohexane skeleton), an epoxy group added to a cyclic aliphatic hydrocarbon directly or via a hydrocarbon (particularly preferably an oxirane ring), and the like. The alicyclic epoxy compound is particularly preferably a compound having an epoxycyclohexane group. Moreover, the polyfunctional alicyclic epoxy compound which has two or more alicyclic epoxy groups in a molecule | numerator is suitable at the point which can raise a hardening rate more. A compound having one alicyclic epoxy group in the molecule and an unsaturated double bond group such as a vinyl group is also preferably used as the alicyclic epoxy compound.

Examples of the epoxy compound having an epoxycyclohexane group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4 ′. -Epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate and the like are preferred. Examples of the alicyclic epoxy compound other than the epoxy compound having the epoxycyclohexane group include 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include adducts and alicyclic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferred. Such a hydrogenated epoxy compound is preferably a complete or partial hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably an aromatic polyfunctional compound. It is a hydrogenated product of a glycidyl ether compound. Specifically, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like are preferable. More preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. Preferred examples of the aromatic epoxy compound include epoxy compounds having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, and an anthracene ring. Among these, a compound having a bisphenol skeleton and / or a fluorene skeleton is preferable in order to realize a lower water absorption rate and a higher refractive index. More preferably, it is a compound having a fluorene skeleton, whereby the refractive index can be remarkably increased and the releasability can be further enhanced. Moreover, the compound whose epoxy group is a glycidyl group in an aromatic epoxy compound is preferable, but the compound (aromatic glycidyl ether compound) which is a glycidyl ether group is more preferable. Also, it is preferable to use a brominated compound of an aromatic epoxy compound because a higher refractive index can be achieved. However, since the Abbe number slightly increases, it is preferably used as appropriate depending on the application.

Preferred examples of the aromatic epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene type epoxy compounds, and aromatic epoxy compounds having a bromo substituent. Of these, bisphenol A type epoxy compounds and fluorene type epoxy compounds are preferred.

Examples of the aromatic glycidyl ether compound include an epibis type glycidyl ether type epoxy resin and a high molecular weight epibis type glycidyl ether type epoxy resin.

Preferred examples of the epibis type glycidyl ether type epoxy resin include those obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol with epihalohydrin.

As the high molecular weight epibis type glycidyl ether type epoxy resin, for example, the above epibis type glycidyl ether type epoxy resin is further subjected to addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like. Those obtained by (1) are preferably mentioned.

Preferable specific examples of the aromatic glycidyl ether compound include bisphenol A type compounds such as 828EL, 1003, and 1007 (manufactured by Japan Epoxy Resin Co., Ltd.); Oncoat EX-1020, Oncoat EX-1010, Oxol EG-210 And fluorene-based compounds such as Ogsol PG (manufactured by Osaka Gas Chemical Co., Ltd.) and the like. Of these, Ogsol EG-210 is preferred.

The said aliphatic epoxy compound is a compound which has an aliphatic epoxy group. Of these, aliphatic glycidyl ether type epoxy resins are preferred.

Examples of the aliphatic glycidyl ether type epoxy resin include polyhydroxy compounds (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. , Polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose and maltose) and epihalohydrins Those obtained by a condensation reaction with are preferably mentioned. Among these, aliphatic glycidyl ether type epoxy resins having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton as the central skeleton are more preferable.

Among the oxirane compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds, or aromatic epoxy compounds are particularly suitable. These are hard to be colored of the epoxy compound (oxirane compound) itself at the time of curing, and are not easily colored or deteriorated by light, that is, excellent in transparency, low colorability, and light resistance. Therefore, if it is set as the curable resin composition containing these, the resin layer and laminated body which are excellent in light resistance without coloring can be obtained with high productivity. Thus, the form in which the said oxirane compound contains at least 1 sort (s) selected from the group which consists of an alicyclic epoxy compound, a hydrogenated epoxy compound, and an aromatic epoxy compound is one of the suitable forms of this invention. More preferably, the oxirane compound includes at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound.

In the form in which the oxirane compound includes at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, the content of the alicyclic epoxy compound and / or the hydrogenated epoxy compound is the sum of these. The amount is preferably 50% by mass or more based on 100% by mass of the total amount of oxirane compounds. Thereby, it becomes possible to exhibit the effect by an alicyclic epoxy compound or a hydrogenated epoxy compound more. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.

In the present invention, a sufficiently cured product (resin layer) can be obtained even when the resin component contains an aromatic epoxy compound that is difficult to cure with a conventional catalyst. Therefore, a laminate in which the refractive index and the like are more controlled can be obtained by appropriately selecting the type of aromatic epoxy compound and the content in the composition. Both the form in which the aromatic epoxy compound is 100% by mass as the oxirane compound and the form in which the aromatic epoxy compound and another oxirane compound are used in combination are preferred forms of the present invention. In the latter, it is more preferable to contain an aromatic epoxy compound and at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound as another oxirane compound.

As the oxirane compound, a novolak aralkyl type glycidyl ether type epoxy resin or the like can be used as a compound other than the oxirane compound having a hydroxyl group and / or an ester group.

In the curable resin composition, the content of the oxirane compound is preferably 5% by mass or more with respect to 100% by mass of the total amount of the resin components in the curable resin composition from the viewpoint of further improving the adhesiveness. . More preferably, it is 10 mass% or more, More preferably, it is 30 mass% or more, Most preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 100 mass%.

The content of the oxirane compound having a hydroxyl group and / or an ester group is preferably 50% by mass or more with respect to 100% by mass of the total amount of oxirane compounds contained in the resin component in the curable resin composition. Thereby, it becomes possible to improve adhesiveness (for example, adhesiveness with a base material or another layer, adhesiveness with another member and material, etc.) more. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.

The oxirane compound preferably also contains an oxirane compound having a weight average molecular weight of 2000 or more. The content of the oxirane compound having a weight average molecular weight of 2000 or more is preferably 10 to 100% by mass with respect to 100% by mass of the total amount of oxirane compounds contained in the resin component in the curable resin composition. Thereby, the said curable resin composition becomes the thing excellent in the film formability at the time of forming a resin layer on a base material (preferably transparent inorganic material layer). More preferably, it is 30-100 mass%, More preferably, it is 50-100 mass%, Most preferably, it is 70-100 mass%.

In the oxirane compound having a weight average molecular weight of 2000 or more, the weight average molecular weight is preferably 2200 or more. More preferably, it is 2500 or more. Moreover, it is preferable that it is 1 million or less from a viewpoint of film-forming property and maintaining the glass transition temperature of hardened | cured material (resin layer) high. More preferably, it is 100,000 or less, More preferably, it is 10,000 or less.

In the present specification, the weight average molecular weight can be determined by GPC (gel permeation chromatography) measurement under the following conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

The resin component may also contain a compound having one or more oxetane groups (oxetane ring) in the molecule (referred to as an oxetane compound). When the said resin component contains an oxetane compound, it is preferable to use together with an alicyclic epoxy compound and / or a hydrogenated epoxy compound from a viewpoint of a cure rate.

As the oxetane compound, it is preferable to use an oxetane compound having no aryl group or aromatic ring from the viewpoint of improving light resistance. From the viewpoint of improving the strength of the cured product, it is preferable to use a polyfunctional oxetane compound, that is, a compound having two or more oxetane rings in one molecule.

Among the oxetane compounds having no aryl group or aromatic ring, examples of the monofunctional oxetane compound include 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3- Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether and the like are preferable.

Among the oxetane compounds having no aryl group or aromatic ring, examples of the polyfunctional oxetane compound include di [1-ethyl (3-oxetanyl)] methyl ether and 3,7-bis (3-oxetanyl) -5. -Oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis ( 3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-o Cetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether Etc. are preferred.

Specific examples of the oxetane compound include, for example, ETERNACOLL (R) EHO, ETERNCOLL (R) OXBP, ETERNCOLL (R) OXMA, ETERNCOLL (R) HBOX, ETERNCOLL (R) OXIPA (manufactured by Ube Industries, Ltd.); -101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610 (manufactured by Toagosei Co., Ltd.) and the like are suitable.

-Curing agent-
It is preferable that the curable resin composition further contains a curing agent. A hardening | curing agent can be used 1 type or in combination of 2 or more types.

What is necessary is just to select the said hardening | curing agent suitably according to hardening reaction, the kind of curable resin, etc. For example, when heat curing is performed, a commonly used curing agent such as a heat latent radical curing catalyst, an acid anhydride system, a phenol system, or an amine system can be used in addition to the heat latent cationic curing catalyst. Among them, it is preferable to use a heat latent cationic curing catalyst and a heat latent radical curing catalyst, and it is particularly preferable to use a heat latent cationic curing catalyst for the purpose of reducing the shrinkage of the cured product. Moreover, when hardening by active energy ray irradiation, a photoinitiator can be used as a hardening | curing agent. Among them, it is preferable to use a photolatent cationic curing catalyst and a photolatent radical curing catalyst, and it is particularly preferable to use a photolatent cationic curing catalyst for the purpose of reducing the shrinkage of the cured product. Thus, a cationic curing catalyst is particularly preferable as the curing agent.
In the present specification, a catalyst that promotes a cationic curing reaction, such as a heat latent cationic curing catalyst or a photolatent cationic curing catalyst, is also referred to as a “cation curing catalyst”. The cationic curing catalyst functions differently from, for example, a curing accelerator in an acid anhydride curing reaction.

Among the curing agents, the heat-latent cationic curing catalyst is different from acid anhydrides, amines, phenol resins, etc. that are generally used as curing agents, and even if contained in the resin composition, the resin composition It does not cause an increase in viscosity or gelation over time at room temperature, and as a function of the heat latent cationic curing catalyst, it can sufficiently promote the curing reaction and exert an excellent effect, and it is excellent in handling properties In addition, a one-component resin composition (one-component material) can be provided.

Also, by using a heat-latent cationic curing catalyst, the moisture resistance of the cured product formed from the resulting resin composition is dramatically improved, and the excellent optical properties of the resin composition are maintained even in harsh usage environments. However, it can be suitably used for various applications. Normally, when water having a low refractive index is contained in the resin composition or its cured product, it causes turbidity.However, when a heat-latent cationic curing catalyst is used, excellent moisture resistance can be exhibited, and thus such turbidity is exhibited. Will be suppressed. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. Excellent heat resistance over time.

Examples of the heat latent cationic curing catalyst include the following general formula (1):
_{^{(R 1 a R 2 b R}} 3 c R 4 d Z) + m (AXn) -m (1)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements. R ¹ , R ² , R ³ and R ⁴ is the same or different and represents an organic group, a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. Cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^{+ m} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element, and m is the net charge of the halide complex ion. N is the number of halogen elements in the halide complex ion Is preferred).

Specific examples of the anion (AXn) ^-m of the general formula (1) include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexafluoro arsenates ^{(AsF 6-),} hexachloroantimonate (SbCl ^6-), and the like.
Further formula AXn (OH) ^- anions may be used which is represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

Specific products of the above-mentioned heat-latent cationic curing catalyst include, for example, diazonium salt types such as AMERICURE series (American Can), ULTRASET series (Adeka), and WPAG series (Wako Pure Chemical Industries). UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc (now Rhodia)), WPI series (Wako Pure Chemical Industries) CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), Optomer SP series Optomer CP Sulfonium salts such as Leeds (manufactured by Adeka), Sun-Aid SI series (manufactured by Sanshin Chemical Industry), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San Apro) Type.

Examples of the thermal latent radical curing catalyst include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butyl peroxide. Organic peroxides such as oxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbo) Nitriles), azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like are shown.

As the photopolymerization initiator, it is preferable to use a photolatent cationic curing catalyst or a photolatent radical curing catalyst as described above. The photolatent cationic curing catalyst is also called a photocationic polymerization initiator, and exhibits a substantial function as a curing agent when irradiated with light. By using a photolatent cationic curing catalyst, a compound containing a cationic species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds.

Examples of the photolatent cationic curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) Phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methyl) Ethyl) benzene] -Fe- hexafluorophosphate, diaryliodonium hexafluoroantimonate and the like. These can be easily obtained from the market. For example, SP-150, SP-170 (manufactured by Asahi Denka); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide) CD-1012 (manufactured by Sartomer) and the like are suitable. Among these, it is preferable to use an onium salt. Moreover, as an onium salt, it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.

Examples of the photolatent radical curing catalyst include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 1,1-dichloroacetophenone, etc. Acetophenones; benzoin, benzoin methyl ether Benzoins such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4 , 4′-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl Benzophenones such as benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxa , 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9- Thioxanthones such as onmesochloride; xanthones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides Etc. are shown. Among these, acetophenones, benzophenones, and acylphosphine oxides are preferably used, and in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4- Thiomethylphenyl) propan-1-one is preferably used.

When a cationic curing catalyst or a radical curing catalyst is used as the curing agent, the blending amount is the amount of an active ingredient not containing a solvent or the like (meaning a solid content equivalent amount. Lewis represented by the general formula (2) described later) In the case of using a cation curing catalyst comprising an acid and a Lewis base, the total amount of the Lewis acid and the Lewis base.), Respectively, the total amount of the cationic curable compound or the total amount of the radical curable compound is 100 parts by mass. On the other hand, it is preferable to set it as 0.01-10 mass parts. As a result, the curing rate can be further increased, productivity can be further improved, and the possibility of coloring during curing, heating, use, or the like can be further suppressed. In addition, for example, when reflow mounting a laminate obtained using the curable resin composition, heat resistance of 200 ° C. or higher is necessary, and from the viewpoint of colorlessness and transparency, 10 parts by mass or less. It is preferable to do. More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it is 2 mass parts or less.

In the usually used curing agent such as acid anhydride, phenol or amine, the acid anhydride curing agent includes, for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride , Hexahydrophthal, acid anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, het acid anhydride, hymic acid anhydride, 5- (2,5-dioxotetrahydrofuryl)- Alicyclic carboxylic acid anhydrides such as 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, chlorendic acid, methylendomethylenetetrahydrophthalic anhydride; Dodecenyl succinic anhydride, poly azelaic anhydride, poly sebacic anhydride, Aliphatic carboxylic anhydrides such as lidodecanedioic anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyltetracarboxylic acid Examples thereof include aromatic carboxylic acid anhydrides such as anhydrides.

Examples of the phenolic curing agent include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol). ), 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4′-butylene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene ; Polyphenols such as phenolized polybutadiene Novolak resins made from various phenols such as diol compounds, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols: xylylene skeleton-containing phenol novolac Various novolak resins such as resins, dicyclopentadiene skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins are exemplified.

Of the usually used curing agents such as acid anhydrides, phenols or amines, acid anhydrides are preferred, more preferably methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydro. Phthalic anhydride, hexahydrophthalic anhydride. More preferred are methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

When using the normally used curing agents such as acid anhydrides, phenols, or amines, the content of the curing agent is 25 to 70% by mass with respect to 100% by mass of the curable resin composition. Is preferred. More preferably, it is 35-60 mass%. Moreover, it is preferable that the mixing ratio of a resin component and these hardening | curing agents mixes a hardening | curing agent in the ratio of 0.5-1.6 equivalent with respect to 1 chemical equivalent of a resin component. More preferably, the mixing is performed at a ratio of 0.7 to 1.4 equivalents, more preferably 0.9 to 1.2 equivalents.

The curing agent is preferably a cationic curing catalyst such as a thermal latent cationic curing catalyst or a photolatent cationic curing catalyst as described above. Thereby, since a hardening reaction can be suitably advanced in a short time and a hardened | cured material can be formed rapidly, manufacturing efficiency will be improved more. In addition, a cured product having higher heat resistance and releasability can be obtained, and the resin composition can stably exist as a one-component composition (one-component property) excellent in handling properties. Thus, the form in which the said hardening | curing agent contains a cationic hardening catalyst is also one of the suitable forms of this invention. Among these, it is preferable to use at least a heat latent cationic curing catalyst.

More preferred as the cationic curing catalyst is a boron compound, and an aromatic fluorine compound is even more preferred.
As the cation curing catalyst, the following general formula (2):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. A is an integer equal to or greater than 1, b is an integer equal to or greater than 0, and a + b = 3 is satisfied.) And a Lewis base (organic borane). . Thus, the form in which the said curable resin composition contains the cationic curing catalyst which consists of a Lewis' acid represented by General formula (2) and a Lewis base is one of the suitable forms of this invention.

As described above, since the curable resin composition contains the cationic curing catalyst, cationic curing can be employed as a curing method. Therefore, compared with a case where addition type curing such as acid anhydride curing is employed. Thus, the cured product obtained is more excellent in properties required for optical applications such as heat resistance, chemical stability, and moisture resistance. In addition, compared to the case of using a conventional cationic curing catalyst such as antimony sulfonium salt, coloring due to heat (during curing, film formation, environment of use) is reduced, and durability such as moisture and heat resistance and temperature impact resistance is reduced. A cured product superior in properties can be obtained.
The presence / absence or degree of coloring of the cured product based on the catalyst to be used can usually be confirmed from the change in transmittance at 400 nm. That is, by measuring the 400 nm transmittance of the cured product, the presence / absence or degree of coloring of the cured product can be evaluated.

R in the said General formula (2) is the same or different, and represents the hydrocarbon group which may have a substituent. Although the said hydrocarbon group is not specifically limited, It is preferable that it is a C1-C20 hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be an unsubstituted group, or may be a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom. Other organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group corresponds to an unsubstituted alkyl group as a whole), An aryl group, an alkenyl group, an alkoxy group, a hydroxyl group, etc. are mentioned.

X in the said General formula (2) is an integer of 1-5, and is the same or different and represents the number of the fluorine atoms couple | bonded with the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. x is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.
A is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom. a is more preferably 2 or more, and particularly preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.

Specific examples of the Lewis acid include tris (pentafluorophenyl) borane (TPB), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, and tris (4-fluorophenyl) borane. Among these, TPB is more preferable because it can improve the heat resistance, moist heat resistance, temperature impact resistance, and the like of the cured product. Of the cationic curing catalysts, those containing TPB as a Lewis acid are also referred to as TPB-based catalysts.

The Lewis base is not limited as long as it can be coordinated to the Lewis acid, that is, can form a coordinate bond with the boron atom of the Lewis acid, and those commonly used as Lewis bases are used. However, compounds having atoms with lone pairs are preferred. Specifically, a compound having a nitrogen atom, a phosphorus atom or a sulfur atom is preferred. In this case, the Lewis base forms a coordinate bond by donating a non-shared electron pair possessed by a nitrogen atom, a phosphorus atom, or a sulfur atom to the boron atom of the Lewis acid. Moreover, the compound which has a nitrogen atom or a phosphorus atom is more preferable.

Preferred examples of the compound having a nitrogen atom include amines (monoamines and polyamines) and ammonia. More preferred are amines having a hindered amine structure, amines having a low boiling point, and ammonia, and still more preferred are polyamines having a hindered amine structure and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, the cured product can be prevented from oxidation due to the radical scavenging effect, and the resulting cured product is more excellent in heat resistance (moisture heat resistance). On the other hand, when ammonia or a low-boiling amine is used as the Lewis base, the resulting cured product is excellent in low water absorption and UV irradiation resistance. As ammonia or low boiling point amine volatilizes in the curing process, the salt structure derived from ammonia or low boiling point amine in the final molded product (cured product) is reduced, so the water absorption of the cured product is reduced. It is speculated that it can. In particular, ammonia is preferable because of its excellent effects.

As the amine having the hindered amine structure, a nitrogen atom forming a coordinate bond with a boron atom constitutes a secondary or tertiary amine from the viewpoint of storage stability of the resin composition and curability at the time of molding. It is preferable that it is polyamine more than diamine. Specific examples of the amine having a hindered amine structure include 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine; TINUVIN770, TINUVIN765, TINUVIN144, TINUVIN123, and TINUVIN744. CHIMASSORB2020FDL (above, manufactured by BASF); Adeka Stub LA52, Adekastab LA57 (above, made by ADEKA) and the like. Among these, TINUVIN770, TINUVIN765, Adeka Stab LA52, and Adeka Stub LA57 having two or more hindered amine structures per molecule are preferable.

As the low boiling point amine, it is preferable to use an amine having a boiling point of 120 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower, particularly preferably. Is 5 ° C. or lower. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine, piperidine; And tertiary amines such as trimethylamine and triethylamine.

The compound having a phosphorus atom is preferably a phosphine. Specific examples include triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and diphenylphosphine.

Preferred examples of the compound having a sulfur atom include thiols and sulfides. Specific examples of thiols include methyl thiol, ethyl thiol, propyl thiol, hexyl thiol, decane thiol, and phenyl thiol. Specific examples of the sulfides include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide and the like.

In the cationic curing catalyst composed of the Lewis acid and the Lewis base represented by the general formula (2), the mixing ratio of the Lewis acid and the Lewis base is not necessarily a stoichiometric ratio. That is, any one of Lewis acid and Lewis base (converted to the base point amount) may be contained in excess of the theoretical amount (equivalent). Specifically, the mixing ratio of the Lewis acid and the Lewis base in the cation curing catalyst is such that the atomic number n (b) of the atom serving as the Lewis base point with respect to the atomic number n (a) of boron serving as the Lewis acid point. Expressed as a ratio (n (b) / n (a)), even if it is not 1 (stoichiometric ratio), it acts as a cationic curing catalyst. Here, the ratio n (b) / n (a) in the cationic curing catalyst affects the storage stability and cationic curing characteristics (curing speed, degree of curing of the cured product, etc.) of the resin composition.
In the case where the Lewis base has two Lewis base points in the molecule, such as diamines, the ratio n is determined when the mixing molar ratio of the Lewis base to the Lewis acid constituting the cationic curing catalyst is 0.5. (B) / n (a) = 1 (stoichiometric ratio). In this way, the ratio n (b) / n (a) is calculated.

In the above cationic curing catalyst, from the viewpoint of the storage stability of the resin composition containing the catalyst, if the Lewis acid is present in an excessive amount relative to the Lewis base, the storage stability may not be sufficient. In order to obtain a more excellent resin composition, the ratio n (b) / n (a) is preferably 0.5 or more. For the same reason, it is more preferably 0.8 or more, further preferably 0.9 or more, particularly preferably 0.95 or more, and most preferably 0.99 or more.
On the other hand, from the viewpoint of cationic curing characteristics, if the Lewis base is excessively large, the low-temperature curability of the cured product may not be sufficient. Therefore, in order to obtain a composition having superior cationic curing characteristics, n (b) / n (a) is preferably 100 or less. For the same reason, it is more preferably 20 or less, further preferably 10 or less, and particularly preferably 5 or less.

As the ratio n (b) / n (a), a Lewis base is composed of a compound having a nitrogen atom, a sulfur atom, or a phosphorus atom, and is a structure in which two or more carbons are substituted (a structure in which two or more carbons are substituted) , Which means a structure in which two or more organic groups are bonded to these atoms via carbon atoms), from the viewpoint of cationic curing characteristics, the acid dissociation constant is high and the steric hindrance is large. n (b) / n (a) is preferably 2 or less. More preferably, it is 1.5 or less, More preferably, it is 1.2 or less. For example, such a range is preferable for a structure such as a hindered amine.
When the Lewis base is ammonia or a low-boiling amine having a small steric hindrance, particularly ammonia, the ratio n (b) / n (a) is preferably larger than 1. More preferably, it is 1.001 or more, More preferably, it is 1.01 or more, Especially preferably, it is 1.1 or more, Most preferably, it is 1.5 or more.

The presence form of the Lewis acid and the Lewis base constituting the cation curing catalyst is not particularly limited, but it is preferable that the Lewis base is present in an electronic interaction with the Lewis acid. More preferably, at least a part of the Lewis base is coordinated to the Lewis acid, and more preferably at least a Lewis base equivalent to an equivalent amount to the Lewis acid present is coordinated to the Lewis acid. It is a form. When the abundance ratio of Lewis base to Lewis acid is equivalent or less than equivalent, that is, when the ratio n (b) / n (a) is 1 or less, almost all of the Lewis base present is coordinated to the Lewis acid. The form formed is preferable. On the other hand, in the form in which the Lewis base is contained in excess (more than equivalent), it is preferable that the Lewis base is coordinated with the Lewis acid in an equivalent amount, and the excess Lewis base is present in the vicinity of the complex.

Specific examples of the cationic curing catalyst comprising a Lewis acid and a Lewis base represented by the above general formula (2) include TPB / monoalkylamine complexes, TPB / dialkylamine complexes, TPB / trialkylamine complexes, and the like. Organic borane / amine complexes such as TPB alkylamine complexes and TPB / hindered amine complexes; organic borane / ammonia complexes such as TPB / NH ₃ complexes; TPB / triarylphosphine complexes, TPB / diarylphosphine complexes, TPB / monoarylphosphine complexes, etc. And organic borane / phosphine complexes such as TPB / alkyl thiol complexes; organic borane / sulfide complexes such as TPB / diaryl sulfide complexes and TPB / dialkyl sulfide complexes. Of these, TPB / alkylamine complexes, TPB / hindered amine complexes, TPB / NH ₃ complexes, and TPB / phosphine complexes are preferred.

-Solvent-
It is preferable that the curable resin composition also contains a solvent. As a result, a resin composition having high fluidity can be obtained, which is particularly suitable as a resin composition for coating.

As the solvent, an organic solvent is preferable. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and diacetone alcohol; aromatic solvents such as toluene and xylene; alcohol solvents such as isopropyl alcohol and n-butyl alcohol; acetic acid And ester solvents such as ethyl, butyl acetate, and cellosolve acetate. These solvents can be used alone or in combination of two or more.

When it contains the said solvent, it is preferable that it is 10 mass% or more as the content with respect to 100 mass% of total amounts of a resin component and a pigment | dye. Thereby, the said curable resin composition can exhibit the fluidity | liquidity more excellent as a material which forms a layer on a board | substrate (preferably transparent inorganic material layer). More preferably, it is 50 mass% or more, More preferably, it is 100 mass% or more, Most preferably, it is 200 mass% or more. On the other hand, the content of the solvent is preferably 10,000% by mass or less, more preferably 5000% by mass or less, and still more preferably 1000% by mass or less.

-Photosensitizer-
The curable resin composition may further contain one or more photosensitizers as necessary. In particular, when curing by the above-mentioned active energy ray irradiation, it is preferable to use a photosensitizer in addition to the photopolymerization initiator.

Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid (2- Amines such as dimethylamino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, and 4-dimethylaminobenzoic acid 2-ethylhexyl are suitable.

When it contains the said photosensitizer, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of total amounts of a resin component as the content. More preferably, it is 0.5-10 mass parts.

-Curing accelerator-
The curable resin composition may further contain one or more curing accelerators as necessary. In particular, when a commonly used curing agent such as the above-mentioned acid anhydride type, phenol type or amine type is used, it is preferable to use a curing accelerator in combination.

Examples of the curing accelerator include organic base acid salts or aromatic compounds having tertiary nitrogen, and organic base acid salts include organic onium salts such as organic phosphonium salts and organic ammonium salts, and tertiary nitrogen. Organic base acid salts having Examples of organic phosphonium salts include phosphonium bromides having four phenyl rings such as tetraphenyl phosphonium bromide and triphenyl phosphine / toluene bromide. Examples of organic ammonium salts include tetraoctyl ammonium bromide, tetra Examples include tetra (C1-C8) alkylammonium bromides such as butylammonium bromide and tetraethylammonium bromide. Examples of acid salts of organic bases having tertiary nitrogen include alicyclic bases having tertiary nitrogen in the ring. Examples include acid salts and organic acid salts of various imidazoles.

Examples of the organic acid salt of an alicyclic base having tertiary nitrogen in the ring include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8-diazabicyclo (5,4). , 0) Diaza compounds such as octylate of undecene-7 and salts of phenols, the following polyvalent carboxylic acids or phosphinic acids.

Examples of the organic acid salts of the various imidazoles include salts of imidazoles with organic acids such as polycarboxylic acids. Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. Examples include 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, and the like. Preferable imidazoles include, for example, the same imidazoles as phenyl group-substituted imidazoles in an aromatic compound having tertiary nitrogen described later.

Examples of the polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as maleic acid and oxalic acid. Examples of preferred polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, and pyromellitic acid. Examples of preferable salts of imidazoles with organic acids such as polyvalent carboxylic acids include polyvalent carboxylates of imidazoles having a substituent at the 1-position. More preferred is, for example, trimellitic acid salt of 1-benzyl-2-phenylimidazole.

Examples of the aromatic compound having tertiary nitrogen include phenyl group-substituted imidazoles and tertiary amino group-substituted phenols. Examples of phenyl group-substituted imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Examples include 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like. Preferable examples include imidazoles having an aromatic substituent at the 1-position, and more preferable examples include 1-benzyl-2-phenylimidazole. Examples of tertiary amino group-substituted phenols include phenols having 1 to 3 di (C1-C4) alkylamino (C1-C4) alkyl groups such as 2,4,6-tri (dimethylaminomethyl) -phenol. Is mentioned.

Among the above-mentioned curing accelerators, particularly preferred curing accelerators include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt and 1,8-diazabicyclo (5,4,0) undecene-7 octyl. Acid salt, 2,4,6-tri (dimethylaminomethyl) -phenol, tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt, Tetraphenylphosphonium bromide and triphenylphosphine / toluene bromide.

When the said hardening accelerator is included, it is preferable to set it as 0.01-5 mass parts with respect to 100 mass parts of total amounts of a resin component as the content. More preferably, it is 0.03-3 mass parts.

-Flexible component-
The curable resin composition preferably also includes a flexible component (flexible component). This makes it possible to obtain a resin composition having a sense of unity, that is, having high toughness. Moreover, the hardness of the resin layer is further improved by including a flexible component.
In addition, as a flexible component, the compound different from the said resin component may be sufficient, and at least 1 sort (s) of the said resin component may be a flexible component.

Examples of the flexible component include a compound having an oxyalkylene skeleton represented by (1)-[— (CH ₂ ) _n —O—] _m — (n is 2 or more, m is an integer of 1 or more. N is preferably an integer of 2 to 12, m is an integer of 1 to 1000, and more preferably, n is an integer of 3 to 6 and m is an integer of 1 to 20. Epoxy compounds containing a butylene group (manufactured by Japan Epoxy Resin, YL-7217, epoxy equivalent 437, liquid epoxy compound (10 ° C. or higher)) are suitable. As other suitable flexible components, (2) polymer epoxy compounds (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)); 3) alicyclic solid epoxy compound (EHPE-3150 manufactured by Daicel Chemical Industries, Ltd.); (4) alicyclic liquid epoxy compound (Delcel Chemical Industries, Celoxide 2081); (5) liquid rubber such as liquid nitrile rubber, Polymer rubber such as polybutadiene, fine particle rubber having a particle size of 100 nm or less, and the like are preferable.

Among these, a cation curable compound containing a cation curable group at the terminal, side chain, main chain skeleton or the like is more preferable.
As described above, a cationically curable compound can be suitably used as the flexible component. However, the compound is preferably a compound containing an epoxy group, and more preferably an oxybutylene group (-[ - _{(CH 2)} 4 -O-] _m - (m is ibid.) is a compound having a).

When the flexible component is included, the content is preferably 40% by mass or less with respect to 100% by mass of the total amount of the resin component and the flexible component. More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. Moreover, 0.01 mass% or more is preferable, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.

-Other ingredients-
In addition to the essential components and suitable components described above, the curable resin composition is further saturated with no curing accelerator, reactive diluent, and unsaturated bond, as long as the effects of the present invention are not impaired. Compound, Pigment, Dye, Antioxidant, UV absorber, IR cut agent, Light stabilizer, Plasticizer, Non-reactive compound, Chain transfer agent, Anaerobic polymerization initiator, Polymerization inhibitor, Inorganic filler, Organic filler Adhesion improvers such as coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners and sagging prevention Agents, color separation preventing agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic aids) and the like.

When the curable resin composition contains an inorganic filler, it is possible to reduce the coefficient of linear expansion, and to suppress expansion due to heat in a solder reflow process, an inorganic oxide vapor deposition process, and the like. It is. As the inorganic filler, those containing nanoparticles are preferable from the viewpoint of not impairing transparency, and those containing silica, titanium oxide, zinc oxide and zirconia having a particle size of 40 nm or less are preferable. For example, MEK-ST manufactured by Nissan Chemical Industries, Ltd. is preferably used.

When the curable resin composition contains a silane coupling agent, it is possible to improve adhesion, and it is possible to suppress peeling and the like in use in a solder reflow process and a wet heat environment. Thus, it is also preferable that the curable resin composition contains a silane coupling agent. As the silane coupling agent, a compound having an oxirane ring is suitable, and Z-6040, Z-6043 manufactured by Toray Dow Corning Co., Ltd. are suitably used.

In the said curable resin composition, it is preferable that the foreign material with a particle diameter of 10 micrometers or more contained per 1 cm < ³ > of resin compositions is 1000 or less, More preferably, it is 100 or less, More preferably, it is 10 or less. is there.
In addition, the foreign material contained in the said curable resin composition can be removed by performing filtration when preparing a resin composition.

-Preparation method-
The preparation method of the said curable resin composition is not specifically limited, It can obtain by mixing a containing component by a normal method. When mixing the components, if necessary, each component or mixture can be heated and mixed to achieve a uniform composition. The heating temperature is not particularly limited as long as it is not higher than the decomposition temperature of the curable resin or not higher than the reaction temperature, but preferably 140 to 20 ° C., more preferably 120 to 120 before the addition of the curing agent (catalyst). 40 ° C.

-Viscosity-
The curable resin composition preferably has a viscosity of 10,000 mPa · s or less. As a result, the processing characteristics are improved. More preferably, it is 100 mPa * s or less, More preferably, it is 50 mPa * s or less. Moreover, it is preferable that it is 0.01 mPa * s or more, More preferably, it is 0.1 mPa * s or more.

The measurement of the viscosity can be performed on the resin composition using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C.

-Curing method-
It does not specifically limit as a hardening method of the said curable resin composition, For example, various methods, such as thermosetting and photocuring (curing by active energy ray irradiation), can be used suitably. As thermosetting, it is preferable to cure at about 30 to 400 ° C., and as photocuring, it is preferable to cure at 10 to 10,000 mJ / cm ² . Curing may be performed in one stage, or may be performed in two stages such as primary curing (preliminary curing) and secondary curing (main curing).
Hereinafter, the case of performing the two-stage curing will be described in detail.

As a two-step curing method, as a first step corresponding to primary curing, the resin composition is photocured at 10 to 100000 mJ / cm ² or thermally cured at 80 to ²⁰⁰ ° C., and the first step It is preferable to employ a method including a second step corresponding to the secondary curing in which the cured product obtained in the step is thermally cured at a temperature exceeding 200 ° C. and not exceeding 500 ° C.

In the first step, in the case of thermosetting, the curing temperature is preferably 80 to 200 ° C. More preferably, it is 100 degreeC or more and 160 degrees C or less. Moreover, you may change a curing temperature in steps within the range of 80-200 degreeC.
The curing time in the thermosetting step is preferably, for example, within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.

The thermosetting step can also be performed in air or in an atmosphere of an inert gas such as nitrogen, under reduced pressure, or under pressure. Moreover, you may combine photocuring (curing by active energy ray irradiation).

In the curing method, in the second step, the cured product obtained in the first step is preferably heat-cured at a temperature exceeding 150 ° C. and not more than 500 ° C. The lower limit of the curing temperature is more preferably 200 ° C. or higher, still more preferably 230 ° C. or higher. The upper limit is more preferably 400 ° C. or lower. Further, the curing temperature may be changed stepwise within a temperature range of more than 150 ° C. and 500 ° C. or less.

The curing time in the second step is not particularly limited as long as the curing rate of the cured product to be obtained is sufficient, but considering the production efficiency, for example, 10 minutes to 30 hours is preferable. . More preferably, it is 30 minutes to 10 hours.

The second step can also be performed in any atmosphere such as air or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0.5 volume% or less, Most preferably, it is 0.3 volume% or less.

By carrying out the first step, it is possible to suppress the aggregation and repellency of the coating liquid with respect to the coated substrate. Moreover, it becomes possible to improve the heat resistance with respect to a reflow process and a vapor deposition process by implementing the said 2nd process.

The curing method preferably includes the first step and the second step, but may include a curing treatment before, after, and in the middle. For example, after the first step is performed by photocuring, thermal curing is performed at 150 ° C. for 60 minutes under nitrogen, and the second step is performed by thermal curing. By performing such treatment, it is possible to further improve the film formability and heat resistance.

The curable resin composition of the present invention can give a cured product excellent in heat resistance, light resistance and the like. Therefore, when a resin layer made of the curable resin composition of the present invention is formed on a substrate, the resin layer has high heat resistance, and a reduction in visible light transmittance and coloring are sufficiently suppressed. Therefore, such a laminate is particularly useful for imaging device applications. Among these, when a transparent inorganic material layer is used as a base material, it is preferable because a laminate that can suppress generation of cracks, chipping, and warpage and has excellent heat resistance can be obtained. Thus, the laminated body obtained by forming the resin layer which consists of the said curable resin composition on a transparent inorganic material layer is also one of this invention.

[Laminate]
The laminate of the present invention has a resin layer on the transparent inorganic material layer. The resin layer may be provided only on one side of the transparent inorganic material layer, or may be provided on both sides. The transparent inorganic material layer and the resin layer may each have a single layer structure or a multilayer structure.

The laminate can be obtained by forming a resin layer on the transparent inorganic material layer. As a method for forming the laminate, a method of forming the laminate by applying and curing a curable resin composition on the transparent inorganic material layer. Is preferred. That is, a method of forming a coating film on the transparent inorganic material layer is preferable. Moreover, it is suitable for the curable resin composition used for the laminated body for image sensors of this invention for a coating.

Here, “having a resin layer on the transparent inorganic material layer” means not only the form in which the resin layer is in direct contact with the transparent inorganic material layer, but also other constituent members existing on the transparent inorganic material layer. A form having a resin layer is also included. The same applies to “forming a resin layer on a transparent inorganic material layer”, not only when the resin layer is directly formed on the transparent inorganic material layer, but also through other components existing on the transparent inorganic material layer. The case where a resin layer is formed is also included. The same applies to “applying the curable resin composition on the transparent inorganic material layer”, and not only when the curable resin composition is applied directly on the transparent inorganic material layer, but also on the transparent inorganic material layer. The case where the curable resin composition is applied through another constituent member is also included.

In the form in which the curable resin composition is applied through the other constituent member, from the viewpoint of improving the adhesiveness, for example, the surface of the constituent member by a liquid material containing a metal oxide precursor such as a silane coupling agent. It is preferable to apply a curable resin composition after the treatment. As the silane coupling agent, a compound having an oxirane ring is suitable, and Z-6040, Z-6043 manufactured by Toray Dow Corning Co., Ltd. are suitably used.

As a method for forming a coating film made of a curable resin composition on the transparent inorganic material layer (or other constituent member), a solution coating method is suitable. Specifically, it is as described later.

It is preferable that the laminate has an absorption characteristic that has an absorption maximum in a wavelength range of 650 to 680 nm and only one absorption maximum in a wavelength range of 400 to 680 nm. Thereby, for example, the combination of the inorganic reflective film and the inorganic interference film enables the laminated body to exhibit more selective light transmission close to the sensitivity of the human eye, and thus is a very useful laminated body for imaging device applications. It becomes. More preferably, it has an absorption maximum in the wavelength range of 650 to 680 nm and only one absorption maximum in the wavelength range of 400 to 750 nm.
Here, “having only one absorption maximum in the wavelength range of 400 to 680 nm” means that only one apex (absorption maximum) where the absorbance changes from increasing to decreasing is recognized in the wavelength range of 400 to 680 nm. The peak having the absorption maximum as a vertex may be sharp or broad. In the latter case, it may be a form in which two or more sharp absorption peaks overlap to form a broad absorption peak as a whole, and there is only one apex (absorption maximum) at which the absorbance changes from increase to decrease.

It is also preferable that the laminate has an absorbance at an absorption maximum wavelength existing in a wavelength range of 650 to 680 nm of 0.2 or more. More preferably, it is 0.3 or more.

Further, it is preferable that the laminate has a higher absorbance on the longer wavelength side in the wavelength range of 600 to 680 nm. In other words, it is preferable that the transmittance is lower on the longer wavelength side in the wavelength range of 600 to 680 nm. For example, when the absorbance is measured every 1 nm in the wavelength range of 600 to 680 nm, the absorbance at a certain wavelength. However, it is preferable not to exceed the absorbance at longer wavelengths. Thereby, since an absorbance spectrum becomes a smoother curve, more excellent light selective permeability can be expressed.

In this specification, the absorption characteristics and transmittance of the laminate, the resin layer, and the transparent inorganic material layer are measured using, for example, an absorptiometer (also referred to as a spectrophotometer, manufactured by Shimadzu Corporation, spectrophotometer UV-3100). It can be determined by measuring the absorption spectrum or transmittance spectrum.
It is preferable that the resin layer also has the same characteristics as the absorption characteristics and transmission characteristics of the laminate described above. In particular, the resin layer preferably has a higher absorbance in the wavelength range of 600 to 680 nm on the longer wavelength side, and such a form is also a preferred form of the present invention.

The thickness of the laminate is preferably 1 mm or less, for example. Thereby, it is possible to sufficiently meet the demand for downsizing of the image sensor. More preferably, it is 500 micrometers or less, More preferably, it is 300 micrometers or less. Moreover, it is preferable that it is 30 micrometers or more. More preferably, it is 50 μm or more.

<Transparent inorganic material layer>
In the laminate, the transparent inorganic material layer means a layer made of a transparent inorganic material.
Examples of the transparent inorganic material include glass and crystal.
The transparent inorganic material may also be obtained by including transition metal ions in a material that forms glass, crystal, or the like. As the transition metal ion, one or more kinds which are usually used as those having light absorption ability may be used. For example, Ag ⁺ , Fe ⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2+ and the} like may be used. Can be mentioned.

Although the thickness of the said transparent inorganic material layer is not specifically limited, For example, it is preferable that it is 30-1000 micrometers. More preferably, it is 50 μm or more.

In the transparent inorganic material layer, “transparent” means that the transmittance at a wavelength of 550 nm is preferably 80% or more. More preferably, it is 85% or more, More preferably, it is 90% or more.

<Resin layer>
As a method for forming a coating film made of a curable resin composition on the transparent inorganic material layer (or other constituent member), a solution coating method is suitable. Specific examples include commonly used methods such as spin coating, casting, roll coating, spray coating, bar coating, dip coating, screen printing, flexographic printing, and inkjet. Among these, the spin coating method is preferable from the viewpoint of reducing the deviation of the coating layer on the substrate. When forming a coating film by spin coating, the solvent can be dried while rotating the transparent inorganic material layer (or other constituent member) at 500 to 4000 rpm for about 10 to 60 seconds at around room temperature (25 ° C.). preferable. In addition, it is also preferable to perform the inkjet method from the viewpoint of reducing the deviation while obtaining a sample other than a round shape that is difficult to obtain by spin coating. Moreover, it is preferable to perform photocuring and / or thermosetting as needed after spin coating or inkjet.

The drying (curing) method after applying the curable resin composition to the surface of the transparent inorganic material layer or other constituent member, that is, the curing method of the curable resin composition is as described above.

Although the thickness of the resin layer is not particularly limited, it is preferably 50 μm or less, more preferably 30 μm or less, from the viewpoints of heat resistance and transparency during reflow, and prevention of peeling and cracking at the interface due to thermal expansion. More preferably, it is 10 μm or less, particularly preferably 5 μm or less, and most preferably 2 μm or less. In addition, from the viewpoint of preventing defects by making the film thickness sufficiently thicker than the general foreign matter size, reducing the concentration of the dye dissolved in the resin composition, and suppressing the association and precipitation of the dye, 0.1 μm or more Preferably, it is 0.5 μm or more.

[Use of laminate]
The laminate of the present invention is particularly suitable for imaging device applications. The curable resin composition used for the laminate of the present invention is also particularly suitable for imaging device applications. Especially, it is preferable to use the said laminated body as a constituent material of a light selective transmission filter. In this case, the resin layer formed of the curable resin composition is more preferably used as a (near) infrared absorption layer (also simply referred to as an absorption layer) in the selective light transmission filter. Such a light selective transmission filter including the laminate is also one aspect of the present invention, and an image pickup device including the laminate is also included in the present invention. In addition, it is particularly preferable that the image pickup device includes a light selective transmission filter including the laminate.
Hereinafter, the light selective transmission filter and the image sensor will be described.

<Light selective transmission filter>
The light selective transmission filter of the present invention includes one or more of the above laminates, but may further include one or more other layers as necessary. In the light selective transmission filter, it is preferable to use a transparent inorganic material layer as a base material and a resin layer formed from a curable resin composition as an absorption layer in the laminate.

The light selective transmission filter may have various other functions other than the function of selectively reducing desired light transmittance. For example, in the case of an infrared cut filter which is one of the preferred forms as a light selective transmission filter, the form having various functions other than the infrared cut such as the function of shielding ultraviolet rays and the physical properties of the infrared cut filter such as toughness and strength. The form which has the function to improve can be mentioned.

Thus, in the embodiment in which the light selective transmission filter has other functions, a functional material layer for forming a reflective film on one surface of the laminate of the present invention and imparting other functions to the other surface Is preferably formed. The functional material layer is formed directly on the laminated body by, for example, the CVD method, the sputtering method, or the vacuum vapor deposition method, or the functional material layer formed on the temporary base material that has been subjected to the release treatment. It can be obtained by laminating the laminate with an adhesive. It can also be obtained by applying a liquid composition containing a raw material to the laminate, drying it, and forming a film.

The light selective transmission filter selectively reduces the light transmittance. The light to be reduced may be between 10 nm and 1000 nm, and can be selected depending on the intended use. Depending on the wavelength of light to be reduced, an infrared cut filter, an ultraviolet cut filter, an infrared / ultraviolet cut filter, or the like can be used. Among them, infrared light of 750 nm to 1000 nm (more preferably, infrared light of 650 nm to 1000 nm). ) And 200 to 350 nm ultraviolet light, and other light is preferably transmitted. That is, the light selective transmission filter of the present invention is preferably an infrared / ultraviolet cut filter.

The infrared cut filter may be a filter having a function of selectively reducing light of any wavelength (range) among light having a wavelength of 650 nm to 10000 nm that is an infrared region. The wavelength range to be selectively reduced is preferably 650 nm to 2500 nm, 650 nm to 1000 nm, or 800 nm to 1000 nm. A filter that selectively reduces at least one of wavelengths in these ranges is also included in the infrared cut filter. The range of the wavelength to be selectively reduced is more preferably 650 nm to 1000 nm which is a near infrared region.

The ultraviolet cut filter is a filter having a function of blocking ultraviolet rays. The wavelength range to be selectively reduced is preferably 200 to 350 nm.

The infrared / ultraviolet cut filter is a filter having a function of blocking both ultraviolet rays and infrared rays. The wavelength range to be selectively reduced is preferably the same as described above.

In the embodiment in which the light selective transmission filter of the present invention is an infrared cut filter, it is preferable to selectively reduce the infrared transmittance of 750 to 1000 nm to 5% or less. For example, when the infrared cut filter is used as a camera module, it is preferable that the transmittance of infrared light is 5% or less and the transmittance of 450 to 600 nm in visible light is 70% or more. More preferably, it is 80% or more. Moreover, it is preferable that the transmittance | permeability of the light of the wavelength range of 480-550 nm is 85% or more among visible light, and it is more preferable that it is 90% or more. In the infrared cut filter, the transmittance of other wavelengths (other than the infrared region) is more preferably 85% or more, and still more preferably 90% or more. That is, the light selective transmission filter is preferably an infrared cut filter having a light transmittance of 85% or more at a wavelength of 480 to 550 nm and a transmittance of 5% or less at 750 to 1000 nm.
The transmittance can be measured using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation).

In the embodiment in which the light selective transmission filter of the present invention is an ultraviolet cut filter, it is preferable to selectively reduce the transmittance of ultraviolet light of 200 to 350 nm to 5% or less.

In the embodiment in which the light selective transmission filter of the present invention is an infrared / ultraviolet cut filter, it is preferable to selectively reduce infrared light of 650 nm to 1 μm and ultraviolet light of 200 to 350 nm to 5% or less.

The light selective transmission filter preferably has a form in which a reflective film (preferably a (near) infrared reflective film) is formed on at least one surface of the laminate. That is, a light selective transmission filter including the laminate and the reflective film is preferable. With such a configuration, the incident angle dependency of the light blocking characteristic can be more sufficiently reduced. In this case, the arrangement form (configuration) of the reflective film in the light selective transmission filter is not particularly limited.

As the reflective film, an inorganic multilayer film capable of controlling the refractive index of each wavelength is preferable from the viewpoint of excellent heat resistance. The inorganic multilayer film is a refractive index control multilayer film in which a low refractive index material and a high refractive index material are alternately laminated on the surface of a base material, an absorption layer, or other components by vacuum deposition or sputtering. Preferably there is. The reflective film is also preferably a transparent conductive film. As the transparent conductive film, a transparent conductive film as a film that reflects infrared rays, such as indium-tin oxide (ITO), is preferable. Among these, an inorganic multilayer film is preferable.

The inorganic multilayer film is preferably a dielectric multilayer film in which dielectric layers A and dielectric layers B having a refractive index higher than that of the dielectric layer A are alternately stacked.
As a material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be usually used. Preferably, the material has a refractive index range of 1.2 to 1.6.
As the material, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride sodium, and the like are suitable.

As a material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used. Preferably, the refractive index range is 1.7 to 2.5.
Examples of the material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as a main component, and small amounts of titanium oxide, tin oxide, cerium oxide, and the like. What was contained is suitable.

In general, the thickness of each of the dielectric layer A and the dielectric layer B is preferably 0.1λ to 0.5λ when the wavelength of light to be blocked is λ (nm). When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. May be lost, and control for blocking / transmitting a specific wavelength may not be possible.

The method for laminating the dielectric layer A and the dielectric layer B is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, CVD, sputtering, vacuum deposition Thus, a dielectric multilayer film can be formed by alternately laminating the dielectric layers A and B.

The reflective film is preferably a multilayer film as described above, and the number of stacked layers is preferably in the range of 10 to 80 layers as the total number of stacked reflective films of the imaging device. More preferably, it is the range of 25-50 layers.

The thickness of the reflective film is preferably 0.5 to 10 μm. More preferably, it is 2-8 micrometers. Note that the total thickness of the reflection films included in the light selective transmission filter and the imaging element is preferably in the above range.

From the viewpoint of obtaining a smooth transmittance spectrum as an optical filter with respect to the absorption maximum wavelength of the absorption layer in the infrared region (650 to 750 nm) as a preferable form of the reflection film and the absorption layer, the transmittance is higher than that of the absorption layer. It is preferable that the wavelength of the reflective film to be reduced is present at +30 nm or less, more preferably +20 nm or less, still more preferably +10 nm or less, and particularly preferably 0 nm or less. On the other hand, from the viewpoint of reducing the angle dependency as an optical filter, it is preferably −10 nm or more, more preferably 0 nm or more, further preferably 10 nm or more, and particularly preferably 20 nm or more. preferable.

Here, when the resin layer which is a part of the laminate of the present invention is used as the absorption layer of the reflection type light selective transmission filter and a reflection film is formed on at least one surface of the laminate, It is preferable to form a multilayer film of 10 layers or more. Moreover, it is also suitable to form the resin layer formed from the said curable resin composition after forming a reflecting film.

The reflective film is preferably present on the base material (preferably a transparent inorganic material layer) or the resin layer constituting the laminate directly or via another constituent member. For example, it is preferable to form a reflective film on these surfaces using a CVD method, a sputtering method, a vacuum deposition method, or the like. Among these, it is preferable to use a vacuum deposition method. More preferably, it is a method of forming a reflective film by forming a vapor deposition layer on a temporary base material such as glass that has been subjected to a release treatment, and transferring the vapor deposition layer to the base material or a resin layer. Thereby, the possibility that the light selective transmission filter is deformed and curled or cracks due to vapor deposition can be reduced. In this case, it is preferable to form an adhesive layer on the substrate or resin layer to which the vapor deposition layer is to be transferred.

Thus, for the formation of the reflective film (preferably an inorganic multilayer film), it is preferable to use a vapor deposition method, but the vapor deposition temperature is preferably set to 100 ° C. or higher. More preferably, it is 120 degreeC or more, More preferably, it is 150 degreeC or more. When vapor deposition is performed at such a high temperature, the inorganic film (inorganic film constituting the inorganic multilayer film) becomes dense and hard, and there are advantages such as improving various resistances and improving the yield. Therefore, it is very meaningful to use a transparent inorganic material layer, a resin component, and a pigment that can withstand such a deposition temperature. If the laminate of the present invention is used, not only can it be deposited at a high temperature, but even if it is deposited at a low temperature, the difference in linear expansion coefficient from the inorganic film is small. Even in a use environment, inorganic layer cracks due to differences in linear expansion coefficient do not occur.

By the way, in general, a reflective filter having a reflective film on one or both sides of a base material is excellent in light blocking performance, but has an incident angle dependency (also referred to as a viewing angle dependency) in which the reflection characteristic changes depending on the incident angle of light. ), That is, the spectral transmittance curve varies depending on the incident angle. However, when the laminate of the present invention and the reflective film are used in combination, the dependency on the incident angle can be suppressed, and various physical properties such as heat resistance and light resistance are excellent, which is very useful.

The incident angle dependence of the light blocking property is determined by, for example, using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation) and changing the incident angle (for example, 0 °, 20 °, 25 °, 30 °). Etc. The transmittance at an incident angle of 0 ° is a transmittance measured as light enters from the thickness direction of the light selective transmission filter, and the transmittance at an incident angle of 20 ° is the transmittance of the light selective transmission filter. It is a transmittance measured as light enters from a direction inclined by 20 ° with respect to the thickness direction.) Can be measured and evaluated by the amount of change in spectrum.
In addition, the incident angle dependence of the light blocking characteristic needs to be sufficiently reduced by absorption of the absorption layer, and the transmittance spectrum does not change with respect to the change in the incident angle, or the degree of the change is small. It is preferable. Specifically, even if the incident angle is changed from 0 ° to 20 ° (more preferably to 25 °), it is preferable that the transmittance spectrum does not change in the region where the transmittance is 80% or more, more preferably. Is that the transmittance spectrum does not change in a region where the transmittance is 70% or more, and more preferably, the transmittance spectrum does not change in a region where the transmittance is 60% or more. Most preferably, the spectrum does not change in any transmittance region.

As described above, the light selective transmission filter of the present invention is particularly excellent in light resistance, heat resistance and light selective transmission, and can sufficiently reduce the incident angle dependency of the light blocking characteristics. In addition to being useful as a heat ray cut filter or the like attached to glass or the like of a building or the like, it is also useful as a filter for blocking optical noise and correcting visibility in camera module (also referred to as a solid-state imaging device) application. Among these, the light selective transmission filter of the present invention is useful as a filter used in camera modules such as digital still cameras and mobile phone cameras. In other words, the light selective transmission filter is preferably a light selective transmission filter for an image sensor. Thus, an image sensor provided with the light selective transmission filter is also one preferred embodiment of the present invention.

<Image sensor>
The image pickup device of the present invention includes one or more of the laminates, but may further include one or more other members as necessary. Usually, the imaging device has a detection element (sensor) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) and a lens, but further includes an optical filter, an adhesive for fixing the member, and the like. Can be mentioned.

Preferably, the imaging element has a form in which a reflective film is formed on at least one surface of the laminate. That is, it is preferable that the imaging device includes the laminate and the reflective film. With such a configuration, the incident angle dependency of the light blocking characteristic can be more sufficiently reduced. In this case, the arrangement form (configuration) of the reflective film in the image sensor is not particularly limited. For example, by forming a reflective film directly on the lens, the lens and the reflective film are integrated with each other (also referred to as form (a)); the imaging element includes an optical filter including the reflective film. And the like (form (b)) having a reflective film as an independent component.
The reflective film is as described above.

In the form (a), when the imaging element has two or more lenses, the number of lenses on which the reflective film is formed is not particularly limited.

In the form (b), the optical filter including the reflective film may have only a function of reflecting (near) infrared light, or may have a function of absorbing (near) infrared light. May be.

The optical filter including the reflective film may be a light selective transmission filter including the laminate of the present invention and the reflective film, or may be an optical filter other than the light selective transmission filter. Moreover, you may have 1 or 2 or more of optical filters containing a reflecting film, and an arrangement | positioning form is not specifically limited, either. For example, when the image sensor has two or more lenses, the filter having the reflective film may be disposed between the lenses.
The reflective film is preferably formed on one surface or both surfaces of the lens and / or one surface or both surfaces of the substrate.

Since the curable resin composition for an image sensor of the present invention has the above-described configuration, it can provide a cured product that can exhibit high heat resistance and light resistance with excellent light selective transmission, and can be used for an image sensor. Very useful. In addition, a laminate obtained by forming a resin layer made of such a curable resin composition on a transparent inorganic material layer can be suitably applied as a member constituting an imaging element, and is particularly a light selective transmission filter, Near) Effective as a constituent member of an infrared cut filter (IRCF). In addition, the light selective transmission filter or the multilayer body including such a laminated body and a reflective film not only exhibits light selective transmission close to human eyes, but also has an incident angle that has been a problem by using a reflective filter. It is possible to capture an image in which the occurrence of color unevenness due to the above is suppressed, and to sufficiently suppress the occurrence of ghosts and flares due to irregular reflection. Since the curable resin composition and laminate for an image pickup device of the present invention can also exhibit a high level of light resistance, severe light resistance is required, such as applications that may be exposed to direct sunlight. It is also preferably used for applications.

It is the transmittance | permeability spectrum in each step in Example 1. FIG. It is the transmittance | permeability spectrum in each step in Example 2. FIG. 4 is a transmittance spectrum at each stage in Comparative Example 1. It is the transmittance | permeability spectrum in each step in the comparative example 2. FIG. It is the transmittance | permeability spectrum in each step in the comparative example 3. FIG. It is the transmittance | permeability spectrum in each step in the comparative example 4. : It is a conceptual diagram which shows the transmittance | permeability measuring method.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

Preparation Example 1 (Synthesis of TPB-containing powder B)
According to the synthesis method described in International Publication No. 1997/031924, 255 g of Isopar E solution having a TPB (tris (pentafluorophenyl) borane) content of 7% was prepared. Water was added dropwise to this solution at 60 ° C. White crystals precipitated from the middle of the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried at 60 ° C. under reduced pressure, and 18.7 g of TPB / water complex (TPB-containing powder B) as white crystals was obtained. This complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the dried complex, but no peaks other than TPB were detected.
The measurement result of ¹⁹ F-NMR is shown below.
¹⁹ F-NMR (CDCl ₃ ) ppm (standard substance: CFCl ₃ 0 ppm)
δ = −135.6 (6F, m)
δ = -156.5 (3F, dd)
δ = −163.5 (6F, d)

Preparation Example 2 (Preparation of cationic curing catalyst A)
2.1 g of γ-butyrolactone was added to 2 g of TPB-containing powder B obtained in Preparation Example 1 (TPB pure content: 1.816 g (3.547 mmol), water: 0.184 g (10.211 mmol)), Mix for 10 minutes at room temperature. Thereafter, 0.778 g (0.984 mmol, the number of moles of N group is 3.934 mol) of Adeka Stab LA-57 (hindered amine, manufactured by ADEKA) was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes. And a homogeneous solution of a cationic curing catalyst (TPB catalyst). This was designated as cationic curing catalyst A.

Preparation Example 3 (Preparation of cationic curing catalyst B)
1.6 g of γ-butyrolactone was added to 2 g of TPB-containing powder B obtained in Preparation Example 1 (TPB pure content: 1.816 g (3.547 mmol), water: 0.184 g (10.211 mmol)), Mix for 10 minutes at room temperature. Thereafter, 2.1 g of a 2 mol / L ammonia / ethanol solution was added and mixed at room temperature for 60 minutes to obtain a uniform solution of a cation curing catalyst (TPB catalyst). This was designated as cationic curing catalyst B.

Synthesis Example 1 (Synthesis of phthalocyanine (1))
(1) Step 1
A 1000 ml four-necked separable flask was charged with 54 g (0.27 mol) of tetrafluorophthalonitrile, 34.5 g (0.59 mol) of potassium fluoride, and 126 g of acetone, and 3-chloro-4-hydroxy was added to the dropping funnel. 127 g (0.55 mol) of benzoic acid methoxyethyl ester and 216 g of acetone were charged. While stirring the reaction vessel under ice cooling, the 3-chloro-4-hydroxybenzoic acid methoxyethyl ester solution was added dropwise over about 2 hours from the dropping funnel, and the stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 108.7 g (yield 64.8%) of intermediate (1).
The reaction of this step 1 is simply shown below.

(2) Step 2
In a 200 ml four-necked flask, 20.0 g (0.032 mol) of the intermediate (1) obtained in Step 1, 2.57 g (0.0081 mol) of zinc (II) iodide, and 30. 0 g was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, 52.7 g of methyl cellosolve was added to the reaction solution, and then added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again washed with stirring with a mixed solution of methanol and water, and suction filtered. The obtained cake was dried at 90 ° C. for 24 hours using a vacuum dryer, and 17.78 g (yield: 87.1%) of the target phthalocyanine (1) was obtained.
The reaction of Step 2 is simply shown below.

The phthalocyanine (1) obtained in Synthesis Example 1 has a structure in which the substituents shown on the right side are substituted on each of the portions indicated by “*” (total 8) in the main skeleton in the above structure.

Synthesis Example 2 (Synthesis of phthalocyanine (2))
(1) Step 1
A 1000 ml four-necked separable flask was charged with 75 g (0.37 mol) of tetrafluorophthalonitrile, 52.3 g (0.90 mol) of potassium fluoride, and 167 g of acetonitrile, and 2,6-dichlorophenol 123 was added to the dropping funnel. .4 g (0.76 mol) and 133 g of acetonitrile were charged. While stirring, the 2,6-dichlorophenol solution was dropped from the dropping funnel over about 2 hours, and the stirring was further continued for 2 hours. Then, it stirred overnight and was made to react. The reaction solution was filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 148.1 g of intermediate (2) (yield: 80.2%).
The reaction of this step 1 is simply shown below.

(2) Step 2
In a 500 ml four-necked separable flask, 140 g (0.29 mol) of intermediate (2), 107.8 g (0.78 mol) of potassium carbonate, 92.1 g (0.61 mol) of methyl p-hydroxybenzoate and acetone 280 g was charged. The reaction solution was stirred and reacted overnight at 60 ° C., then the reaction solution was filtered, acetone was removed from the filtrate by a rotary evaporator, and recrystallization was performed by adding a mixed solution of methanol and methanol. The obtained crystals were filtered and vacuum-dried to obtain 202.3 g (yield 93.1%) of intermediate (3).
The reaction of Step 2 is simply shown below.

(3) Process 3
Into a 200 ml four-necked flask, 22.5 g (0.030 mol) of intermediate (3) obtained in step 2, 2.37 g (0.0074 mol) of zinc (II) iodide, and 52.5 g of benzonitrile were charged. The mixture was reacted at 160 ° C. for 24 hours with stirring. After completion of the reaction, 30.3 g of methyl cellosolve was added to the reaction solution, and then added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again washed with stirring with a mixed solution of methanol and water, and suction filtered. The obtained cake was dried at 90 ° C. for 24 hours using a vacuum dryer, and 17.83 g (yield: 86.1%) of the desired phthalocyanine (2) was obtained.
The reaction of this step 3 is simply shown below.

In the above structure, the phthalocyanine (2) obtained in Synthesis Example 2 has the above-described substituents shown on the right side in the portion indicated by “*” (16 in total) in the main skeleton and the remaining 8 on the right side. Each of the substituents shown below has a substituted (or bonded) structure.

Synthesis Example 3 (Synthesis of phthalocyanine (3))
(1) Step 1
A 1000 ml three-necked reaction vessel is charged with 100 g (0.58 mol) of 3-nitrophthalonitrile, 159.7 g (1.16 mol) of potassium carbonate, 104.6 g (0.64 mol) of 2,6-dichlorophenol and 400 g of acetonitrile. It is. After stirring and reacting at 60 ° C. overnight, the reaction solution was filtered, acetonitrile was removed from the filtrate by a rotary evaporator, and recrystallization was performed by adding methanol. The obtained crystals were filtered and vacuum dried to obtain 100.9 g of intermediate (4) (yield 60.2%).
The reaction of this step 1 is simply shown below.

(2) Step 2
In a 300 ml four-necked flask, 60.0 g (0.21 mol) of the intermediate (4) obtained in step 1, 5.65 g (0.057 mol) of copper (I) chloride, and 140.0 g of diethylene glycol monomethyl ether were added. The reaction was carried out for 24 hours while stirring at 160 ° C. After completion of the reaction, 100.0 g of methyl cellosolve was added to the reaction solution, and then added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again washed with stirring with a mixed solution of methanol and water, and suction filtered. The obtained cake was dried at 90 ° C. for 24 hours using a vacuum dryer, and 51.48 g (yield: 80.4%) of the target phthalocyanine (3) was obtained.
The reaction of Step 2 is simply shown below.

In the above structure, the phthalocyanine (3) obtained in Synthesis Example 3 has four substituents shown on the right side among the parts indicated by “*” in the main skeleton (total 8), and the remaining four on the right side. Each of the substituents (ie, hydrogen atoms) shown below has a structure in which each is substituted (or bonded).

<Preparation of curable resin composition and laminate>
Example 1
Celoxide CEL-2021P (liquid alicyclic epoxy resin, epoxy equivalent 131, manufactured by Daicel Chemical Industries, Ltd.) 15 parts, EHPE-3150 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) 85 parts, propylene glycol monomethyl ether acetate ( 240 parts of PEGMEA, 40 parts of tetrahydrofuran (THF), and 8 parts of the phthalocyanine (1) obtained in Synthesis Example 1 were uniformly mixed at 80 ° C. Thereafter, the temperature was lowered to 40 ° C., 5.6 parts of cation curing catalyst B was uniformly mixed as a curing agent, and foreign matters were filtered with a 0.45 μm filter (GL Science Co., Ltd., non-aqueous 13N). Thus, a curable resin composition (1) was obtained.
Using the obtained resin composition, it formed into a film and hardened | cured by the below-mentioned method, and evaluated each transmittance | permeability and heat resistance (reflow heat resistance). The results are shown in FIG.

Example 2 and Comparative Examples 1 to 4
A curable resin composition (2) and comparative resin compositions (1) to (4) were obtained in the same manner as in Example 1 except that the type and amount of the dye were changed as shown in Table 1.
Using the obtained resin composition, film formation and curing were performed in the same manner as in Example 1, and each transmittance and heat resistance (reflow heat resistance) were evaluated. The results are shown in FIGS.

<Film formation method>
Each resin composition was hung on a glass substrate washed with an isopropanol solvent (manufactured by SCHOTT, glass, D263, 8-inch round), and then used for 3 seconds using a spin coater (Mikasa, 1H-DX2). The number of rotations was maintained at a predetermined time, and the film was formed (i.e., coated) by returning the number of rotations to 0 rpm over 3 seconds. Specific film forming conditions are shown in Table 2 (2500 rpm). A transmittance spectrum after film formation (coating) was obtained.

<Curing method (thermosetting)>
The film obtained in the above <Film formation method> was cured. Specifically, using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo Systems Co., Ltd.), a program that reaches 250 ° C. in one hour from 30 ° C. in an N ₂ atmosphere (oxygen concentration of 30 ppm or less). The temperature was raised and maintained at 250 ° C. for 1 hour, and then the temperature was lowered to 30 ° C. Specific curing conditions are shown in Table 2. In addition, the transmittance | permeability spectrum after this hardening was obtained.

<Vapor deposition film forming method>
An alternate vapor deposition layer (infrared reflective layer) of 20 layers of titanium oxide / 20 layers of silica is formed on the opposite surface of the coating layer obtained in the above <curing method>, and 3 layers of titanium oxide / 3 layers of silica are formed on the coating layer. Alternating vapor deposition layers (antireflection layers) were formed.

<Evaluation of incident angle dependency>
A light selective transmission filter (also referred to as IRCF) prepared so as to be in the order of the infrared reflection layer / glass / coating layer / antireflection layer is arranged from the incident light source side, and an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer) UV-3100) was used to perform spectral transmittance measurement (transmittance spectrum measurement). As shown in FIG. 7, when the IRCF is installed so as to be perpendicular to the incident light as shown in FIG. 7 (the transmittance spectrum measured in this way is also called a 0 degree spectrum. The thickness direction of the IRCF (vertical When the cured product and the glass IRCF are installed so that the light is incident from a direction inclined by 30 degrees with respect to the thickness direction (vertical direction) of the IRCF. (The transmittance spectrum measured in this way is referred to as a 30-degree spectrum). In addition, in order to evaluate the angle dependency in the long wavelength region of visible light of 600 nm to 700 nm, a wavelength of light incident angle 0 degree (T50 (0 °)) at a IRCF transmittance of 50% and a wavelength of 30 degrees ( The difference from T50 (30 °) was evaluated. The case where this difference was 0 nm or more and less than 20 nm was evaluated as “◯”, and the case where it was 20 nm or more was evaluated as “x”. The results are shown in Table 3.

<Transmissivity>
The transmittance spectrum at each stage was measured using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). The spectra are shown in FIGS. In addition, Table 2 shows transmittances at a wavelength of 430 nm which is a short wavelength region of visible light, 550 nm which is a central region of visible light, and 650 nm which is an absorption wavelength of a dye at each stage.

<Heat resistance test (reflow heat resistance test)>
The cured product after final curing (that is, the cured product obtained in the above <curing method>) was dried in the atmosphere at 260 ° C. for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and then the wavelength The transmittance of the cured product at 430 nm, 550 nm and 650 nm was measured using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). Moreover, the crack and peeling were confirmed visually. For the evaluation of cracks and peeling, for the five samples for evaluation, the case where no cracks or peeling occurred was evaluated as “◯”, and the case where even one piece cracked or peeled was evaluated as “x”.

Abbreviations and the like in Table 1 are as follows.
CEL-2021P: Liquid alicyclic epoxy resin “Celoxide CEL-2021P”, epoxy equivalent 131, weight average molecular weight 120, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd .: Alicyclic epoxy resin, weight average molecular weight 2900, Daicel Chemical Industries, Ltd. PGMEA: Propylene glycol monomethyl ether acetate (also known as 1,2-propanediol monomethyl ether acetate)
NIR705A: cyanine dye, manufactured by QCR Solutions Corp., near infrared dye SDA3039: cyanine dye, manufactured by HW SANDS Corp., dye curing catalyst for laser B: cation curing catalyst B obtained in Preparation Example 3
As is clear from the above structural formula, phthalocyanine (1) has a structure represented by the above general formula (I), but phthalocyanines (2) and (3) are represented by the above general formula (I). Does not have the structure represented.

From the examples and comparative examples, the following was found.
(1) Transmittance after final curing In Examples 1 and 2, the absorption spectrum after vapor deposition is smooth, and there is no absorption maximum near 667 nm in the wavelength range of 400 to 680 nm. It was confirmed to have close light selective transmission. On the other hand, Comparative Examples 1-4 did not become a smooth absorption spectrum. Regarding the angle dependency of incident light, it was found that in Examples 1 and 2, the change in the area of the transmittance spectrum in the vicinity of 600 to 700 nm was small and the angle dependency was small. Further, from Table 3, in Examples 1 and 2, the shift of the wavelength (T50) at which the transmittance of the 0 ° spectrum and the 30 ° spectrum is 50% is small, and an image having a color close to the actual state is obtained over a wide angle. I was able to. On the other hand, in Comparative Examples 1 to 4, it was confirmed that the T50 shift of the 0 ° spectrum and the 30 ° spectrum is large, and the image at the location where the incident angle to the image sensor is large deviates from the actual color.

(2) Heat resistance From Table 2, in Examples 1 and 2, no cracks or peeling occurred even after the reflow test, and the transmittance did not change before and after the test. And it was confirmed that it was excellent in reflow heat resistance. On the other hand, in Comparative Examples 3 and 4, it was difficult to endure even a curing temperature lower than the reflow low heat temperature. Therefore, evaluation of the heat resistance test was not performed in Comparative Examples 3 and 4 (shown as “−” in Table 2).

Claims (7)

A curable resin composition that includes a dye and a resin component and is used in an imaging device,
The dye has the following general formula (I):

(In the formula, M represents a metal atom, a metal oxide or a metal halide. X ^{1 to} X ⁴ and Y ^{1 to} Y ⁴ are the same or different and represent a hydrogen atom (H), a fluorine atom (F) or .OR ⁱ group represents an oR ⁱ group which may have a substituent, an alkoxy group, a phenoxy group or a naphthoxy group. provided that at least one of ^{X 1} and ^{Y 1,} the ^{X 2} and ^{Y 2} At least one of them, at least one of X ³ and Y ³ , and at least one of X ⁴ and Y ⁴ represents an OR ⁱ group which may have a substituent. A curable resin composition for an image sensor, comprising a phthalocyanine dye. At least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ in the general formula (I), imaging of claim 1, characterized in that represents an phenoxy group which may have a substituent A curable resin composition for an element. The said resin component contains the compound which has a 1 or more oxirane ring in a molecule | numerator, The curable resin composition for image sensors of Claim 1 or 2 characterized by the above-mentioned. A laminate obtained by forming a resin layer made of the curable resin composition for an imaging element according to any one of claims 1 to 3 on a transparent inorganic material layer. A light selective transmission filter comprising the laminate according to claim 4. An image pickup device comprising the laminate according to claim 4. The imaging device according to claim 6, wherein a reflective film is formed on at least one surface of the laminate.

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