KR102147630B1 - Resin composition for lamination, and its use - Google Patents

Abstract

(Problem) Provided is a laminate having excellent heat resistance obtained by forming a laminating resin composition having excellent heat resistance as a material for forming a layer on a substrate, and a layer comprising the laminating resin composition on a substrate. Moreover, a light selective transmission filter and an image pickup device using such a laminate are also provided.
(Solution means) As a resin composition used as a material for forming a layer on a substrate, the resin composition contains an oxirane compound having at least one oxirane ring in a molecule, and a dye, and the oxirane compound is a hydroxyl group and/or Or a resin composition for lamination containing a compound having an ester group, wherein the dye contains a dye having an absorption maximum in a wavelength range of 600 to 900 nm.

Description

Resin composition for lamination and its use {RESIN COMPOSITION FOR LAMINATION, AND ITS USE}

The present invention relates to a resin composition for lamination and a use thereof. More specifically, it relates to a resin composition used as a material for forming a layer on a substrate, a laminate obtained by forming a layer made of the resin composition on a substrate, a light selective transmission filter, and an imaging device.

In recent years, in order to achieve multifunctionality in various fields such as optical devices such as display elements and image pickup devices, members and materials of a laminate structure in which several layers are formed on a substrate made of glass or the like (also referred to as a laminate or laminate) ) Is supposed to be widely used. As a layer to be formed on the substrate, for example, an ITO (indium-tin composite oxide) transparent conductive layer used for a touch panel, an infrared (IR) cut layer for reducing optical noise in an image pickup device, and a substrate surface And an antireflection (AR) layer that reduces reflection of light.

The imaging device is also called a solid-state imaging device or an image sensor chip, and is an electronic component that converts light from a subject into an electrical signal and outputs it as an electrical signal. For example, a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, and a display It is used in devices (LEDs, etc.). Such an image pickup device is generally composed of a configuration including a detection device (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), and a lens, but to achieve multifunctional and high performance, image processing There is a growing demand for reduction of optical noise that interferes with the like.

The reduction of optical noise in the imaging device is conventionally performed by providing an absorbing glass such as blue glass doped with copper ions, and a resin filter having a light absorbing or reflecting function to reduce optical noise in a resin component. come. However, although the absorbent glass is very excellent in heat resistance, cracks (cracks) and chipping (defects) are likely to occur, and workability 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, compared to glass, the heat resistance is not sufficient, and the occurrence of warpage due to linear expansion cannot be denied. Therefore, in recent years, development of an optical filter of a laminated structure in which a layer having a light absorbing function or a reflecting function is formed on a substrate such as glass has been developed.

As a conventional optical filter of a laminated structure, for example, a light absorption filter including a first layer containing a light absorbing agent and a second layer having a different refractive index on a glass substrate (refer to Patent Document 1); A near-infrared absorption filter in which an organic film layer made of a resin binder and a near-infrared absorbing dye and an inorganic film layer are formed on a transparent substrate such as a polyester film base material (refer to Patent Document 2); A color filter having a colored film made of a colored curable composition containing a phthalocyanine compound on a glass substrate (refer to Patent Document 3); A near-infrared cut filter having an organic polymer layer made of a liquid resin composition or the like on a glass substrate, and a near-infrared reflecting film made of a dielectric multilayer film (refer to Patent Document 4); A near-infrared cut filter (refer to Patent Document 5) which includes a laminated plate having a resin layer containing a near-infrared absorber on a glass substrate and exhibits a predetermined transmittance; A solid-state imaging device (refer to Patent Document 6) and the like having a layer formed of a curable composition for a solid-state imaging device containing a binder resin and an infrared shielding material on a substrate are disclosed.

Japanese Patent Application Publication No. 2008-51985 Japanese Unexamined Patent Publication No. 2006-106570 Japanese Patent Application Publication No. 2012-167145 Japanese Unexamined Patent Publication No. 2013-50593 Japanese Unexamined Patent Publication No. 2012-103340 Japanese Patent Application Publication No. 2012-189632

As described above, in recent years, development of a laminate in which an IR cut layer or the like is formed on a substrate is in progress, and examination of a laminate material for obtaining the same has been made.

By the way, when forming a layer such as an IR cut layer on a substrate, a method of vapor deposition at a high temperature is desired from the viewpoint of forming a dense layer. Therefore, high heat resistance is required for the material of the layer formed on the substrate (material for lamination).

Further, for example, since imaging elements such as digital camera modules are mounted on a mobile phone or the like, miniaturization is progressing and cost reduction is also required, and therefore, as an imaging lens, a resin lens is being adopted instead of the conventional inorganic glass. In such a member mounting step, in order to achieve a lower cost, it is becoming mainstream to employ a solder reflow method. Therefore, the material of the layer formed on the surface of the lens or the like is required to have heat resistance that the cured product (molded product) can withstand the reflow process.

As described above, in Patent Documents 1 to 6, IR cut filters and the like of a multilayer structure have been proposed. However, in the prior art, there has been room for further investigation into a resin composition that provides a molded article having excellent properties such as heat resistance in the high-temperature vapor deposition as described above and heat resistance in the reflow step.

The present invention has been made in view of the above-described conditions, and has excellent heat resistance as a material for forming a layer on a substrate, and a lamination resin composition having excellent heat resistance, and a laminate having excellent heat resistance obtained by forming a layer made of the resin composition for lamination on a substrate It aims to provide a sieve. It is also an object of the present invention to provide a light selective transmission filter and an image pickup device using such a laminate.

The inventors of the present invention have conducted various studies on the resin composition for lamination as a material for forming a layer on a substrate (also referred to as a substrate). As a result, the resin composition has at least one oxirane ring in the molecule, and additionally has a hydroxyl group and/or an ester group. As long as it contains an oxirane compound and a dye having an absorption maximum in a wavelength range of 600 to 900 nm as a dye, the resin composition is excellent in heat resistance and is preferable as a material for forming a layer by high temperature vapor deposition on a substrate. I figured out what could be used. Further, it was found that the cured product of the laminated structure obtained by laminating such a resin composition on the substrate (also referred to as a laminate or laminate) has heat resistance capable of withstanding the reflow process. Then, it was found that the light selective transmission filter and the image pickup device including such a laminated body were very useful in the field of optical and opto-devices, and conceived that the above problems could be satisfactorily solved, thus reaching the present invention.

That is, the present invention is a resin composition used as a material for forming a layer on a substrate, wherein the resin composition contains an oxirane compound having at least one oxirane ring in a molecule, and a pigment, and the oxirane compound is a hydroxyl group and /Or a compound having an ester group, and the dye is a resin composition for lamination containing a dye having an absorption maximum in a wavelength range of 600 to 900 nm.

The present invention is also a laminate obtained by forming a layer made of the above-described resin composition for lamination on a substrate.

The present invention is also a light selective transmission filter comprising the laminate.

The present invention is also an imaging device comprising the laminate.

The present invention is described in detail below. Further, a combination of two or three or more of the individual preferred embodiments of the present invention described below is also a preferred aspect of the present invention.

In the present specification, the term ``maximum absorption'' means that the relationship between the wavelength and the absorbance is represented by a two-dimensional graph of the X-axis and the Y-axis (however, the X-axis is the wavelength and the Y-axis is the absorbance). It means a peak that changes to and the wavelength of this peak is called "absorption maximum wavelength". In addition, among the maximum absorption wavelengths (also referred to as absorption peak wavelengths), those having the maximum absorbance are referred to as "maximum absorption wavelength" or "maximum absorption peak wavelength".

The "absorption width (also referred to as absorption band)" is a wavelength width at an arbitrary transmittance intensity. When the absorption width is wide (large side), the light selective transmittance is more excellent, and the design conditions of the reflective film are expanded, so that the manufacture of a light selective transmission filter (infrared cut filter, etc.) becomes easy.

[Resin composition for lamination]

The resin composition for lamination of the present invention (referred to simply as ``resin composition'') contains an oxirane compound having at least one oxirane ring in a molecule and a pigment as essential components, but other than the range that does not interfere with the effect of the present invention Components may be contained, and each of these components can be used alone or in combination of two or more.

-Color-

In the resin composition for lamination of the present invention, the dye contains a dye having an absorption maximum in the wavelength range of 600 to 900 nm (hereinafter, also referred to as a specific dye). By containing such a pigment|dye, it becomes possible to reduce the infrared rays of 780 nm-10 micrometers in particular, and it becomes possible to remove the optical noise resulting from this. In the present invention, a dye having an absorption maximum in the short wavelength side among conventional near-infrared absorbers with an absorption maximum of 600 to 900 nm as described above is essential, however, the optical transmittance of visible light is high and the blocking performance in the near-infrared region is excellent. A desirable performance is obtained for noise reduction. The specific dye is preferably a dye having an absorption maximum in a wavelength range of 600 to 800 nm, and more preferably a dye having an absorption maximum in a wavelength range of 650 to 750 nm.

The specific dye may have a plurality of absorption maximums in a wavelength range of 600 to 900 nm. Of the absorption maximums in the wavelength range of 600 to 900 nm, it is preferable that the absorption maximum on the shortest wavelength side is in the wavelength range of 650 to 750 nm.

It is preferable that the specific dye also has substantially no absorption maximum in the wavelength range of 400 nm or more and less than 600 nm.

In the resin composition, it is preferable that the dye is dispersed or dissolved in the resin composition. More preferably, it is a form in which a dye is dissolved and contained in a resin composition. That is, it is preferable that the dye is dissolved in a resin component or a solvent contained in the resin composition. One or two or more kinds of pigments can be used.

The dye contained in the resin composition is preferably a dye having a π electron bond in the molecule. As the dye having a π electron bond in the molecule, it is preferable that it is a compound containing an aromatic ring. More preferably, it is a compound containing two or more aromatic rings in one molecule.

Further, it is particularly preferable that the dye having a π electron bond in the molecule has an absorption maximum in the above-described wavelength range, that is, a specific dye.

As a dye having a π electron bond in the molecule, for example, a phthalocyanine dye, a porphyrin dye, a cyanine dye, a quarterrylene dye, a squarylium dye, a naphthalocyanine dye, a nickel complex dye, a copper ion series Pigments and the like, and one or two or more of these can be used. From the viewpoint of heat resistance and weather resistance, a dye having neither a zwitterionic structure nor a cationic structure is preferred, and particularly, a phthalocyanine dye and/or a porphyrin dye is preferred. More preferably, they are metal phthalocyanine complexes and/or metal porphyrin complexes.

As the porphyrin-based dye, metal porphyrin complexes such as tetraazaporphyrin are preferable.

The phthalocyanine-based dye is preferably a metal phthalocyanine complex, and for example, metal elements such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead are used as the central metal. Metal phthalocyanine complexes to be mentioned. Among these metal elements, it is preferable to use at least one of copper, vanadium, and zinc as the central metal from the viewpoint of more excellent solubility or dispersibility (for example, dissolution or dispersibility in a resin component), visible light transmittance, and light resistance. . That is, copper, zinc or vanadium is preferable as the central metal, and copper and zinc are more preferable. Phthalocyanine using copper does not deteriorate due to light even if it is dispersed in any resin component (binder resin), and has very excellent light resistance. Further, a phthalocyanine complex (phthalocyanine-based dye) containing zinc as a central metal is preferable because it has excellent solubility in a resin component and easy to obtain a laminate having higher light selective transmittance.

Among the phthalocyanine-based dyes, particularly preferably, it is a compound represented by the following general formula (I). When a resin composition containing such a compound is used, the occurrence of cracks, chipping and warping is more suppressed, and it becomes possible to obtain a laminate that can more fully withstand high temperature vapor deposition and reflow processes. In addition, when such a laminate is applied to an image pickup device application, the occurrence of flares and ghosts can be sufficiently suppressed, and the incidence angle dependence, which may become a problem when combined with a reflective film, can be sufficiently reduced. Further, when the laminate is used in combination with, for example, a reflective film or an interference film, it becomes possible to exhibit light selective transmittance close to the sensitivity of the human eye. Moreover, when a phthalocyanine-based dye represented by the following general formula (I) is used, the laminate obtained by using the resin composition of the present invention tends to have an absorption maximum in the wavelength range of 650 to 680 nm.

[Formula 1]

In the formula, M represents a metal atom, a metal oxide, or a metal halide. R ^a1 to R ^a4 , R ^b1 to R ^b4 , R ^c1 to R ^c4 and R ^d1 to R ^d4 are the same or different, and a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), an iodine atom (I), or the OR ⁱ group which may have a substituent is shown. The OR ⁱ group represents an alkoxy group, a phenoxy group, or a naphthoxy group. However, neither of R ^a1 to R ^a4 and R ^d1 to R ^d4 represents a hydrogen atom (H) or a fluorine atom (F).

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 the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms is preferable, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms . Among R ⁱ , preferably a phenyl group or a phenyl group having a substituent.

Examples of the substituent which the OR ⁱ group may have include electron withdrawing groups such as an alkoxycarbonyl group (-COOR), a halogen group (halogen atom), a cyano group (-CN), and a nitro group (-NO ₂ ); Electron donating groups such as an alkyl group (-R) and an alkoxy group (-OR) may be mentioned, and one or two or more of these may be contained. Further, the electron withdrawing group is preferably an alkoxycarbonyl group, a chlor group (a chlorine atom) or a cyano group, and more preferably a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chlor group or a cyano group.

Further, R constituting the alkoxycarbonyl group (-COOR) is preferably an alkyl group having 1 to 4 carbon atoms, and R constituting the alkyl group (-R) is preferably an alkyl group having 1 to 4 carbon atoms. 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 the substituent is not particularly limited, but it is preferably 1 to 4, for example. More preferably, they are 1 or 2.

In addition, when one OR ⁱ group has two or more substituents, the substituents may be the same or different. In addition, the position of the substituent in the OR ⁱ group is not particularly limited.

As said R ^a1 to R ^a4 , R ^b1 to R ^b4 , R ^c1 to R ^c4, and R ^d1 to R ^d4 , at least one of them preferably represents an OR ⁱ group. Thereby, the light resistance becomes more excellent.

Here, the carbon to which the OR ⁱ group is bonded is the α-position carbon in the four aromatic rings of the phthalocyanine skeleton (abbreviated as “C _α ”, and the 1, 4, 8, 11, 15, 18, 22, 25 positions of the phthalocyanine ring) It may be a carbon of the β position) or β-position carbon (abbreviated as ``C _β '' and represents the carbon in the 2, 3, 9, 10, 16, 17, 23, 24 position of the phthalocyanine ring), but at least the α position It is preferably carbon (C _α ). Among them, α position carbon (C _α) of the average 2 OR ⁱ groups are bonded to one or more carbon-type, more preferably from OR ⁱ groups are bonded to one or more α position carbon (C _α) on each aromatic ring It is in the form. Moreover, it is also preferable that a hydrogen atom or a fluorine atom is bonded to an average of 4 or more carbons among the β-position carbon (C _β ). More preferably β position carbon (C _β) of an hydrogen atom or a fluorine atom is bonded to the average of 6 or more carbon form, the more preferably a hydrogen atom or a fluorine atom is bonded to any carbon in the β position carbon (C _β) Form. By setting it as such a form, it becomes possible to exhibit more the effect by using the phthalocyanine-type dye represented by the above-mentioned general formula (I).

In the 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, and for example, copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, lead, etc. These are mentioned, and 1 type or 2 or more types of these can be used. Among them, it is preferable to use at least one of copper, vanadium, and zinc as a central metal from the viewpoint of more excellent solubility, visible light transmittance, and light resistance. More preferably, they are copper or zinc. The phthalocyanine-based dye containing copper as a central metal does not deteriorate due to light even when dispersed in any resin component (binder resin), and has very excellent light resistance. A phthalocyanine complex (phthalocyanine-based dye) containing zinc as a central metal is preferable because it is excellent in solubility in a resin component and it is easy to obtain a laminate having higher light selective transmittance.

The halogen atom constituting the metal halide is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The compound represented by the said general formula (I) can be synthesize|combined using the usual method described, for example, in JP-A6-31239. Specifically, one selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides, and organic acid metals (these are collectively referred to as ``metal compounds'') and the following general formula (i):

[Formula 2]

(In the formula, R ^a to R ^d 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. The OR ⁱ group is an alkoxy group, a phenoxy group, or a naphthoxy group. It is preferable to obtain by heating and reacting the phthalonitrile derivative represented by) in the presence of a solvent or an organic solvent, and among them, it is preferable to react in an organic solvent. The cyclization reaction of the phthalonitrile derivative is not particularly limited, and a conventionally known method described in Japanese Patent Publication No. Hei 6-31239, Japanese Patent No.3721298, Japanese Patent No. 3226504, Japanese Patent Laid-Open No. 2010-77408, etc. Can be applied alone or by appropriately modifying. Specific forms of the substituent and the OR ⁱ group are as described above for the general formula (I).

In the general formula (i), as R ^a to R ^d , preferably at least one or more of them represents an OR ⁱ group. Especially, it is preferable that R ^a and/or R ^d (α position) is an OR ⁱ group. Moreover, it is preferable that R ^b and/or R ^c (beta position) is a hydrogen atom or a fluorine atom, and more preferably, both R ^b and R ^c are a hydrogen atom or a fluorine atom.

In the above reaction, further, as a phthalonitrile derivative represented by the general formula (i), two or more compounds having at least one different from R ^a to R ^d may be used in combination.

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). Metals such as iron, copper, zinc, vanadium, titanium, indium, and tin; Metal halide compounds such as chloride, bromide, and iodide of the metal; Metal oxides such as vanadium oxide, titanyl oxide, and copper oxide of the metal; Organic acid metals such as acetates of the metal; Complex compounds such as acetylacetonate of the metal, and metal carbonyls such as carbonyl iron.

Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; Metal halide compounds such as chloride, bromide, and iodide of the metal (for example, vanadium chloride, titanium chloride, copper chloride, 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, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, indium bromide, aluminum bromide, copper fluoride, gallium fluoride Indium, etc.); Vanadium monoxide, vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron trioxide, iron tetraoxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt trioxide, cobalt dioxide, copper oxide, copper oxide, copper oxide Metal oxides such as copper oxide, vanadium oxide, zinc oxide, germanium monoxide, and 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 cobaltcarbonyl, ironcarbonyl, and nickelcarbonyl.

Among the above metal compounds, more preferably a metal halide, more preferably vanadium iodide, vanadium chloride, copper chloride, copper iodide and zinc iodide, and particularly preferably copper chloride, vanadium chloride and zinc iodide. When zinc iodide is used, the central metal in the general formula (I) becomes zinc.

When the reaction of the metal compound with the phthalonitrile derivative represented by the general formula (i) is carried out in an organic solvent, examples of the organic solvent include benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichloro Inert solvents such as benzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; Pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide, dimethylsulfone, sulfolane, etc. One type or two or more types, such as an aprotic polar solvent, can be used. Among them, it is preferable to use 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene, and ethylene glycol. More preferably, they are trimethylbenzene and benzonitrile.

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

Regarding the above reaction, the reaction temperature is not necessarily constant depending on the kind of raw material, the kind of solvent, and other conditions, but it is generally 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 less, still more preferably 240°C or less, and particularly preferably 200°C or less. Moreover, in order to control an exothermic reaction, you may raise the temperature step by step. The reaction time is also not particularly limited, but it is usually 2 to 24 hours, more preferably 5 to 20 hours.

The reaction may also be carried out in an atmospheric atmosphere, but depending on the type of the metal compound, in an inert gas or an oxygen-containing gas atmosphere (for example, in a flow of nitrogen gas, helium gas, argon gas, or oxygen/nitrogen mixture gas, etc.) It is preferred to be implemented.

After the cyclization reaction, crystallization, filtration, washing, and/or drying may be performed according to a conventionally known method.

The resin composition may further contain two or more dyes. Among them, when the two or more dyes contain at least a dye α and a dye β having different absorption properties, and the dye α is a phthalocyanine-based dye, and when the absorption spectrum of a cured product comprising the dye α and the measurement resin is measured, The absorption maximum is shown in the wavelength ranges of 600 to 650 nm and 680 to 750 nm, respectively, and the dye β is in the wavelength range of 650 to 680 nm when the absorption spectrum of the cured product composed of the dye β and the measurement resin is measured. It is desirable to show the maximum absorption. Thereby, when the resin composition or laminate of the present invention is applied to an image pickup device, a sufficient light absorption width can be ensured, and the occurrence of flares and ghosts can be sufficiently suppressed, and when combined with a reflective film Incident angle dependence, which can be a problem, can be sufficiently reduced. Further, for example, when used in combination with a reflective film or an interference film, it becomes possible to exhibit light selective transmittance close to the sensitivity of the human eye.

The pigment α is a phthalocyanine pigment, but the pigment β is also preferably a phthalocyanine pigment. The phthalocyanine-based pigment is as described above. Especially, it is preferable that the dye α and the dye β are a phthalocyanine-based dye represented by the above-described general formula (I).

When the absorption spectrum of the cured product composed of the dye α and the measurement resin is measured, the dye α represents an absorption maximum in the wavelength ranges of 600 to 650 nm and 680 to 750 nm, respectively. Among these two maximum absorption wavelengths, if the maximum absorption wavelength in the wavelength range of 680 to 750 nm is λ _α1 and the maximum absorption wavelength in the wavelength range of 600 to 650 nm is λ _{α 2} , the absorption rate is the most. It is preferable that the wavelength of the large peak (that is, the wavelength of the peak having the lowest transmittance) is λ _{α 1} . That is, if the absorbance at the maximum absorption wavelength in the wavelength range of 680 to 750 nm is Aα1, and the absorbance at the maximum absorption wavelength in the wavelength range of 600 to 650 nm is Aα2, it is preferable that Aα2 <Aα1. . Thereby, more excellent light selective transmittance can be exhibited when used in combination with the dye β.

It is preferable that the maximum absorption wavelength λ _α2 in the wavelength range of 600 to 650 nm that the dye α has is 600 to 630 nm. Moreover, it is preferable that the maximum absorption wavelength λ _α1 in the wavelength range of 680 to 750 nm is 680 to 730 nm.

Α is the pigment that is the maximum absorption wavelength absorbance Aα2 at λ _{α 2} present in the wavelength range of 600 ~ 650 ㎚ 0.3 or less. It is more preferably 0.25 or less, still more preferably 0.2 or less. Further, it is preferable that the absorbance Aα1 at the maximum absorption wavelength λ _{α 1} present in the wavelength range of 680 to 750 nm is 0.1 or more. It is more preferably 0.2 or more, and still more preferably 0.4 or more.

When the absorption spectrum of the cured product composed of the dye β and the measurement resin is measured, the dye β exhibits an absorption maximum in a wavelength range of 650 to 680 nm. When the absorbance at the maximum absorption wavelength existing in the wavelength range of 650 to 680 nm is Aβ, the following relational expression;

Aα2 <Aβ <Aα1

It is desirable to satisfy. That is, of the maximum absorption of the dye α, the absorbance at the maximum absorption wavelength in the wavelength range of 680 to 750 nm (Aα1), the absorbance at the maximum absorption wavelength in the wavelength range 600 to 650 nm (Aα2), And the absorbance (Aβ) at the maximum absorption wavelength in the wavelength range of 650 to 680 nm of the dye β satisfies the above relational expression. Thereby, when the absorption spectrum of the cured product (e.g., resin layer, laminate) obtained from the above resin composition is measured, the absorption maximum peaks of each dye are superimposed, and absorption characteristics showing a broad absorption peak as a whole are obtained. That is, it is possible to secure a more sufficient absorption band.

As described above, the resin composition contains two or more pigments, and the two or more pigments contain at least a pigment α and a pigment β having different absorption properties, and the pigment α is a phthalocyanine pigment, and the pigment α and the measurement resin When the absorption spectrum of the cured product consisting of is measured, the absorption maximum is shown in the wavelength ranges of 600 to 650 nm and 680 to 750 nm, respectively, and the dye β is the absorption spectrum of the cured product composed of the dye β and the measurement resin. At this time, the mode in which the absorption maximum is shown in the wavelength range of 650 to 680 nm is one of the preferred embodiments of the present invention.

Hereinafter, more preferable forms as the dye α and the dye β will be further described.

(i) pigment α

The dye α is a phthalocyanine-based dye exhibiting maximum absorption in the wavelength ranges of 600 to 650 nm and 680 to 750 nm, respectively, when the absorption spectrum of the cured product comprising the dye α and the measurement resin is measured. The dye α is preferably a phthalocyanine-based dye described above, but among them, it is more preferably a compound represented by the following general formula (II).

[Formula 3]

In the formula, M ² represents a metal atom, a metal oxide or a metal halide. Among them, an atom at the α position (Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ ), and an atom at the β position (Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ , Z ¹⁵ ) may be substituted with a substituent represented by the following formula (ii-a), (ii-b) or (ii-c), or a halogen atom, or a hydrogen atom. do.

[Formula 4]

In formula (ii-a), X ¹ represents an oxygen atom or a sulfur atom. R ¹ is the same or different, and is a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. It represents an alkoxy group or -COOR ² . R ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ¹ is an integer of 0-5.

In formula (ii-b), X ² represents an oxygen atom or a sulfur atom. R ³ is the same or different, and is a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. It represents an alkoxy group or -COOR ⁴ . R ⁴ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ² is an integer of 0-7.

In formula (ii-c), X ³ represents an oxygen atom or a sulfur atom. R ⁵ represents an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

Here, in order to show two absorption maxima by dividing into wavelength ranges of 600 to 650 nm and 680 to 750 nm, it is preferable that the atom at the α-position is substituted. When the substituent is (ii-a) or (ii-b), at least one of R ¹ and R ³ is preferably bonded to the ortho position or the meta position, and more preferably is bonded to the ortho position. When the substituent is (ii-c), among the 16 atoms of Z ¹ to Z ^16, the number of atoms substituted by (ii-c) is preferably 4 to 16, more preferably 8 to 16, and 12 More preferably, there are 16 to 16. Although the atom at the β-position may or may not be substituted (that is, it may be in the state of a hydrogen atom), from the viewpoint of solubility, a substituent represented by (ii-a), (ii-b) or (ii-c), Or it is preferably substituted with a halogen atom or the like, and more preferably substituted with a substituent represented by (ii-c) or a halogen atom from the viewpoint of destroying the planarity of the molecule and suppressing the degree of association. Due to the above, since the dye α becomes difficult to form an aggregate, when the absorption spectrum of the cured product consisting of the dye α and the measurement resin is measured, it is divided into a wavelength range of 600 to 650 nm and 680 to 750 nm, and two absorption maximums Becomes easier to show.

(ii) pigment β

The dye β may be any one having the above-described absorption characteristics, but, for example, a phthalocyanine dye, a porphyrin dye, a chlorine dye, a choline dye, a cyanine dye, a quaterylene dye, a squarylium dye, and a naphthalocyanine dye. It is preferably a dye, a nickel complex dye, a copper ion dye, or the like. Among these, a phthalocyanine-based dye is preferable from the viewpoint of light resistance and heat resistance.

As the dye β, it is particularly preferably a compound represented by the following general formula (III). By using the dye β having such a structure, when the absorption spectrum of the cured product composed of the dye β and the measurement resin is measured, it becomes easy to have an absorption maximum in the wavelength range of 650 to 680 nm.

[Formula 5]

In the formula, M ³ represents a metal atom, a metal oxide, or a metal halide. Among these, an atom at the α position (Z ¹⁷ , Z ²⁰ , Z ²¹ , Z ²⁴ , Z ²⁵ , Z ²⁸ , Z ²⁹ , Z ³² ), and an atom at the β position (Z ¹⁸ , Z ¹⁹ , Z ²² , Z ²³ , Z ²⁶ , Z ²⁷ , Z ³⁰ , Z ³¹ ) may be substituted with a substituent represented by the following formula (iii-a), (iii-b) or (iii-c), or a halogen atom, or a hydrogen atom. do.

[Formula 6]

In formula (iii-a), X ⁴ represents an oxygen atom or a sulfur atom. R ⁶ is the same or different, and having a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. It represents an alkoxy group or -COOR ⁷ . R ⁷ represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. m ³ is an integer of 0-5.

In formula (iii-b), X ⁵ represents an oxygen atom or a sulfur atom. R ⁸ is the same or different, and a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 1 to 20 carbon atoms which may have a substituent. It represents an alkoxy group or -COOR ⁹ . R ⁹ represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. m ⁴ is an integer of 0-7.

In formula (iii-c), X ⁶ represents an oxygen atom or a sulfur atom. R ¹⁰ represents an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

Here, in order to show the maximum absorption in the wavelength range of 650 to 680 nm, it is preferable that the atom at the β-position is substituted. The introduced substituent is preferably a structure that maintains the planarity of the phthalocyanine structure, and is preferably substituted with a structure such as (iii-a) or (iii-b). Especially, it is more preferable that at least one of R ⁶ and R ⁸ is bonded to the meta-position or the para-position, and even more preferably bonded to the para-position. Further, the residue is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, but from the high solubility, it is more preferable that they are a hydrogen atom, a fluorine atom, or a chlorine atom, further preferably a hydrogen atom, a fluorine atom, and It is particularly preferred that it is an atom. The atom at the α-position may be substituted, and those substituted with (iii-a), (iii-b), hydrogen atom (i.e., unsubstituted), fluorine atom, chlorine atom, bromine atom, or iodine atom desirable.

From the viewpoint of high planarity, (iii-a), a hydrogen atom (unsubstituted), a fluorine atom, a chlorine atom, a bromine atom, or more preferably substituted with an iodine atom, and a hydrogen atom (unsubstituted), a fluorine atom, chlorine What is substituted with an atom, a bromine atom, or an iodine atom is more preferable, and what is substituted with a hydrogen atom (unsubstituted) or a fluorine atom is particularly preferable.

From the viewpoint of high solubility, (iii-a), (iii-b), a hydrogen atom (unsubstituted), a fluorine atom, or more preferably a chlorine atom substituted, and a hydrogen atom (unsubstituted), or a fluorine atom substituted It is more preferable that it is substituted, and it is particularly preferable that it is substituted with a fluorine atom.

When the dye represented by the above formula (III) is used, the association of the dye β becomes higher, and when the absorption spectrum of the cured product composed of the dye β and the measurement resin is measured, it is easy to have an absorption maximum in the wavelength range of 650 to 680 nm. Lose. Therefore, it is particularly preferable to use a dye represented by the formula (III).

More preferably as the dye β, the following general formula (IV):

[Formula 7]

(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 a hydrogen atom (H), a fluorine atom (F) or a substituent have optionally represents a group oR ^i. oR ⁱ group is an alkoxy group, a phenoxy or naphthoxy group. However, X ¹ and Y At least one of the ^first, at least one of X ² and Y ² dogs, X ³ and Y ³ At least one of them, and at least one of X ⁴ and Y ⁴ represent the OR ⁱ group which may have a substituent.) It is a compound represented by. Thereby, it becomes possible to exhibit more fully the effect of being able to exhibit excellent light selective transmittance and high heat resistance. Further, the light resistance of the laminate is further improved.

In the general formula (IV), the group M, OR ⁱ and the substituent are the same as those in the general formula (I). In the present invention, it is preferable that at least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ in the general formula (IV) represents a phenoxy group which may have a substituent. Thereby, due to the fact that the association of the phthalocyanine-based dye is higher, it is possible to sharply block the wavelength region to be blocked, and to show a high transmittance in the wavelength region to be transmitted. In addition to being able to exhibit more, it becomes possible to further significantly reduce the dependence of the incident angle due to the reflective film.

At least ¹ of X ¹ and Y ¹ , at least 1 of X ² and Y ² , at least 1 of X ³ and Y ³ , and at least 1 of X ⁴ and Y ⁴ may have a substituent OR ⁱ group Show. Preferably, it is a phenoxy group which may have a substituent (ie, 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 them, a phenoxy group having a substituent is preferable. As the substituent, an electron withdrawing group is preferable.

The compound represented by the general formula (IV) can be obtained in the same manner as the compound represented by the above general formula (i). Specifically, the metal compound and the following general formula (iv):

[Formula 8]

(In the formula, X ^a and Y ^a represents a group OR, which may the same or different, a hydrogen atom (H), fluorine (F) or a substituent ^i, OR ⁱ groups are an alkoxy group, a phenoxy group or a naphthoxy group It is preferable to obtain by reacting the phthalonitrile derivative represented by) by heating in the presence of a solvent or an organic solvent, and among them, it is preferable to react in an organic solvent. The cyclization reaction of the phthalonitrile derivative is as described above, and the metal compound, the kind and amount of the organic solvent, and reaction conditions are as described above.

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

In the above reaction, as the phthalonitrile derivative represented by the general formula (iv), it is preferable to use at least a compound having an OR ⁱ group in which at least one of X ^a and Y ^a may have a substituent. In addition, a compound in the form of a group (atom) other than the OR ⁱ group in which both of X ^a and Y ^a may have a substituent, and a form in which at least one of X ^a and Y ^a represents an OR ⁱ group which may have a substituent You may use the compound of together.

Here, since the extinction coefficient is generally different depending on the skeleton of the dye, and it is impossible to define the mass ratio for the dyes of the various skeletons, it is difficult to define the mass ratio of the dye α and the dye β, but, for example, the dye α/ It is preferable that it is dye β (mass ratio) = 80/20-40/60. Thereby, it becomes possible to exhibit more sufficiently the effect of having a more sufficient absorption band, exhibiting sharp transmission absorption characteristics, and sufficiently reducing the incident angle dependence when combined with a reflective film. The mass ratio is more preferably 70/30 to 50/50.

In the above resin composition, the total amount of all dyes is preferably 0.0001% by mass or more and 15% by mass or less with respect to, for example, 100% by mass of the total amount of the resin composition. Thereby, it becomes possible to obtain a cured product having a higher visible light transmittance and more excellent blocking performance in the near-infrared region. The lower limit of the content of the dye is more preferably 0.001% by mass or more, still more preferably 0.005% by mass or more, particularly preferably 0.1% by mass or more, and most preferably 1% by mass or more. Moreover, as an upper limit, it is more preferably 10 mass% or less, still more preferably 7 mass% or less, and even more preferably 5 mass% or less.

The resin composition may contain other dyes as long as it contains a dye having an absorption maximum (specific dye) in a wavelength range of 600 to 900 nm. For example, in each band of near-infrared, infrared, ultraviolet, and visible light other than the wavelength range of 600 to 900 nm, a dye having characteristic absorption at a specific wavelength can be appropriately selected according to the purpose of use, and can be applied to various uses of optical materials. I can.

The content of the other dye is preferably 50% by mass or less with respect to 100% by mass of the total amount of the dye. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less. In other words, it is preferable that the dye having an absorption maximum in the wavelength range of 600 to 900 nm is 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass with respect to 100% by mass of the total amount of the dye. That's it.

-Oxirane compound-

The resin composition for lamination of the present invention contains an oxirane compound (also simply referred to as an oxirane compound) having one or more oxirane rings in a molecule, and the oxirane compound contains a compound having a hydroxyl group and/or an ester group. That is, the resin composition for lamination of the present invention contains an oxirane compound having a hydroxyl group and/or an ester group, and in addition to the oxirane compound having a hydroxyl group and/or an ester group, other oxirane compounds not containing a hydroxyl group or an ester group You may contain it.

The oxirane compound is a compound (a cation-curable compound) which has a cation-curable group called an oxirane ring and is cured (polymerized) by heat or light. When the resin composition contains an oxirane compound, it is possible to sufficiently reduce the amount of shrinkage of the cured product, and the time to cure is shortened to increase productivity, and the resulting cured film (resin layer) also has heat resistance (thermal decomposition resistance and heat coloring resistance). And chemical resistance is excellent. Further, when the oxirane compound is a compound having a hydroxyl group and/or an ester group, the resin composition is excellent in adhesiveness.

In the present specification, compounds that are cured (polymerized) by heat or light are collectively referred to as ``curable compounds'' or ``resin components'', and among them, curable compounds having a cation curable group are collectively referred to as ``cationic curable compounds''. .

In addition, a group containing an oxirane ring, which is a 3-membered ring ether, is referred to as an "epoxy group". In ``epoxy group'', in addition to an epoxy group in the narrow sense, a group in which an oxirane ring is bonded to carbon such as a glycidyl group, a group containing an ether bond or an ester bond such as a glycidyl ether group and a glycidyl ester group, epoxy It is assumed that a cyclohexane ring or the like is contained.

As the oxirane compound having a hydroxyl group and/or an ester group, an epoxy compound having a hydroxyl group and/or an ester group is preferable. Moreover, as an epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound, or an aliphatic epoxy compound is preferable. Among them, a polyfunctional epoxy compound is preferred from the viewpoint of obtaining a cured product in a shorter time.

Regarding the epoxy compound, the alicyclic epoxy compound is a compound having an alicyclic epoxy group. Examples of the alicyclic epoxy group include an epoxy cyclohexane group (also referred to as an epoxycyclohexane skeleton), an epoxy group added directly or via a hydrocarbon to a cyclic aliphatic hydrocarbon (particularly preferably an oxirane ring), and the like. . As an alicyclic epoxy compound, it is especially preferable that it is a compound which has an epoxy cyclohexane group. In addition, a polyfunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in the molecule is preferable because the curing rate can be further increased. Further, a compound having one alicyclic epoxy group in the molecule and having 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, etc. are preferable. In addition, as an alicyclic epoxy compound other than the epoxy compound having an epoxy cyclohexane group, for example, 1,2-epoxy-4-(2-oxiranyl of 2,2-bis(hydroxymethyl)-1-butanol ) Alicyclic epoxides such as heterocycle-containing epoxy resins such as cyclohexane adducts and triglycidyl isocyanurate.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound. 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, more preferably hydrogen of an aromatic polyfunctional glycidyl ether compound It is an additive. 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 preferably, they 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 a molecule. As an aromatic epoxy compound, an epoxy compound etc. which have an aromatic ring conjugated system, such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, an anthracene ring, etc. are preferable, for example. Among them, in order to realize a lower water absorption rate and a higher refractive index, a compound having a bisphenol skeleton and/or a fluorene skeleton is preferable. More preferably, it is a compound having a fluorene skeleton, whereby the refractive index can be further remarkably increased, and the releasability can be further improved. In addition, in the aromatic epoxy compound, a compound in which the epoxy group is a glycidyl group is preferable, but among them, a compound (also referred to as an aromatic glycidyl ether compound) is more preferable. Further, even by using a brominated compound of an aromatic epoxy compound, it is preferable because it can achieve a higher refractive index, but since the Abbe number slightly increases, it is preferable to use it appropriately depending on the application.

As the aromatic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, an aromatic epoxy compound having a bromo substituent, and the like are preferably mentioned, for example. Among them, a bisphenol A type epoxy compound and a fluorene type epoxy compound are preferable.

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.

Examples of the epibis-type glycidyl ether-type epoxy resin include those obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S and fluorene bisphenol with epihalohydrin. I can.

As the high molecular weight epibis type glycidyl ether type epoxy resin, for example, the epibis type glycidyl ether type epoxy resin is used with bisphenols such as bisphenol A, bisphenol F, bisphenol S and fluorene bisphenol. What is obtained by further addition reaction is preferably mentioned.

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

The said aliphatic epoxy compound is a compound which has an aliphatic epoxy group. Among them, an aliphatic glycidyl ether type epoxy resin is preferable.

As the aliphatic glycidyl ether type epoxy resin, for example, a polyhydroxy compound (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG600), propylene glycol, dipropylene glycol, tripropylene Glycol, tetrapropylene glycol, polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, glucose, fructose, lactose, maltose, etc. Mono/polysaccharides and the like) obtained by condensation reaction of epihalohydrin and the like are preferably mentioned. Among them, an aliphatic glycidyl ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton in the central skeleton is more preferable.

Among the above oxirane compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds or aromatic epoxy compounds are particularly preferred. These are not easily colored by the epoxy compound (oxirane compound) itself during curing, and are not easily colored or deteriorated by light, that is, they are excellent in transparency, low coloring property, and light resistance. Therefore, when it is made into a resin composition containing these, the resin layer and the laminated body excellent in colorlessness and light resistance more excellent can be obtained with high productivity. As described above, the form in which the oxirane compound contains at least one selected from the group consisting of an alicyclic epoxy compound, a hydrogenated epoxy compound, and an aromatic epoxy compound is one of the preferred embodiments of the present invention. More preferably, the oxirane compound is a form containing 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 contains at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, as the content of the alicyclic epoxy compound and/or the hydrogenated epoxy compound, the total amount is oxy It is preferably 50% by mass or more with respect to 100% by mass of the total amount of the compound. Thereby, it becomes possible to exhibit more the effect of the alicyclic epoxy compound or the hydrogenated epoxy compound. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.

Further, in the present invention, a sufficiently cured cured product (resin layer) can be obtained even when the resin composition contains an aromatic epoxy compound that has not been cured well with a conventional catalyst. Therefore, by appropriately selecting the type of the aromatic epoxy compound or the content in the composition, a laminate having a more controlled refractive index or the like can be obtained. Both the form in which the aromatic epoxy compound is 100% by mass as the oxirane compound, and the form in which an aromatic epoxy compound and another oxirane compound are used in combination are preferred embodiments 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.

In the resin composition, it is essential to contain an oxirane compound having a hydroxyl group and/or an ester group as the oxirane compound, but other oxirane compounds may be contained. As other oxirane compounds, novolac-aralkyl type glycidyl ether epoxy resins and the like can be used.

In the 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 curable compound in the resin composition from the viewpoint of further improving the adhesiveness. It is more preferably 10% by mass or more, still more preferably 30% by mass or more, particularly preferably 50% by mass or more, even more preferably 80% by mass or more, and most preferably 100% by mass.

Moreover, it is preferable that content of the oxirane compound which has a hydroxyl group and/or an ester group is 50 mass% or more with respect to 100 mass% of the total amount of the oxirane compound contained in a resin composition. Thereby, it becomes possible to further increase adhesiveness (for example, adhesiveness with a base material or another layer, adhesiveness with other members/materials, etc.). More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.

It is preferable that the said oxirane compound also contains an oxirane compound with 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 mass% with respect to 100 mass% of the total amount of the oxirane compound contained in the resin composition. Thereby, the said resin composition becomes a thing more excellent in film formability when forming a resin layer on a base material (it is also called a substrate). As described above, the form in which the oxirane compound contains 10 to 100 mass% of a compound having a weight average molecular weight of 2000 or more relative to the total 100 mass% of the oxirane compound is one of the preferred embodiments of the present invention. It is more preferably 30 to 100% by mass, still more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass.

In the oxirane compound having a weight average molecular weight of 2000 or more, it is preferable that the weight average molecular weight is 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 formation property, and from the viewpoint of maintaining a glass transition temperature of a cured product (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 device: HLC-8120GPC (brand name, manufactured by Tosoh Corporation)

Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series and used

Eluent: Tetrahydrofuran (THF)

Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)

Measurement method: The object to be measured is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using the filtered product as a measurement sample.

-Other curable compounds-

In addition to the above-described oxirane compound, the resin composition for lamination of the present invention may contain one or more organic compounds (referred to as other curable compounds) having a curable functional group.

The curable functional group refers to a functional group that undergoes a curing reaction by heat or light (i.e., means a group that causes a resin composition to be cured), and for example, in addition to an oxirane group (oxirane ring) or an epoxy group, an oxetane group ( Oxetane ring), an ethylene sulfide group, a dioxolane group, a trioxorane group, a vinyl ether group, and a cation curable group such as a styryl group; Radical curable groups, such as an acrylic group, a methacrylic group, and a vinyl group, etc. are preferable. Accordingly, as the other curable compound, a compound having a cation curable group (also referred to as ``a cation curable compound'' or a ``cation curable resin''), and/or a compound having a radical curable group (``radical curable resin'' or ``radical It is also preferably referred to as "curable compound"). Thereby, the time until hardening becomes a short time, and productivity becomes higher, and the hardened|cured material obtained also becomes the thing which is more excellent in heat resistance (thermal decomposition resistance, heat coloring resistance). Among them, it is more preferable to contain a cation-curable compound from the viewpoint that it is easy to impart a shape in a mold or the like because the curing shrinkage rate is low. In addition, the oxirane compound mentioned above is contained in a cation-curable compound.

It is preferable that the cation-curable compound (oxirane compound and other cation-curable compound) also contains a compound having two or more cation-polymerizable groups in one molecule, that is, a polyfunctional cation-curable compound. Thereby, curing property can be further improved, and a cured product having more excellent various properties can be obtained. The compound having two or more cation polymerizable groups in one molecule may be a compound having two or more identical cation polymerizable groups, or a compound having two or more different cation polymerizable groups. In the present invention, a polyfunctional alicyclic epoxy compound and a polyfunctional hydrogenated epoxy compound are particularly preferable as the polyfunctional cation-curable compound. By using these, it becomes possible to obtain a cured product in a shorter time.

Specifically as said other curable compound, a compound (referred to as an oxetane compound) which has one or more oxetane groups (oxetane ring) in a molecule|numerator is mentioned, for example. When the resin composition contains an oxetane compound, it is preferable to use it together with an alicyclic epoxy compound and/or a hydrogenated epoxy compound from the viewpoint of a curing rate.

As the oxetane compound, it is preferable to use an oxetane compound which does not have an aryl group or an aromatic ring from the viewpoint of improving light resistance. Further, 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 not having an aryl group or an aromatic ring, examples of monofunctional oxetane compounds include 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 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, ethyldiethylene glycol (3-ethyl-3-oxygen) Cetanylmethyl) ether and the like are preferred.

Among the oxetane compounds not having an aryl group or an aromatic ring, examples of the polyfunctional oxetane compound include di[1-ethyl(3-oxetanyl)]methyl ether, 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 glycolbis(3-ethyl-3-oxetanylmethyl)ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropanetris (3-ethyl) -3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaeryth Litholtris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycolbis (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 and the like are preferred.

Specifically as the oxetane compound, for example, ETERNACOLL (R) EHO, ETERNACOLL (R) OXBP, ETERNACOLL (R) OXMA, ETERNACOLL (R) HBOX, ETERNACOLL (R) OXIPA (above, manufactured by Ube Hungsan); OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610 (above, manufactured by Toa Synthetic Corporation) and the like are preferable.

-Hardener-

It is preferable that the resin composition further contains a curing agent. Curing agents can be used alone or in combination of two or more.

The curing agent may be appropriately selected depending on the curing reaction or the type of curable compound (also referred to as curable resin). For example, when performing thermal curing, in addition to the thermally latent cation curing catalyst, a commonly used curing agent such as a thermally latent radical curing catalyst, an acid anhydride type, a phenol type, or an amine type can be used. Among them, it is preferable to use a thermally latent cation curing catalyst and a thermally latent radical curing catalyst, and for the purpose of reducing the amount of shrinkage of the cured product, it is particularly preferable to use a thermally latent cation curing catalyst. Moreover, in the case of performing curing by irradiation with active energy rays, a photoinitiator can be used as the curing agent. Among them, it is preferable to use a photo-latent cation curing catalyst and a photo-latent radical curing catalyst, and for the purpose of reducing the amount of shrinkage of the cured product, it is particularly preferable to use a photo-latent cation curing catalyst. As described above, the curing agent is particularly preferably a cation curing catalyst.

In addition, in this specification, a catalyst which accelerates a cation hardening reaction, such as a thermal latent cation hardening catalyst and a photo latent cation hardening catalyst, is also called a "cation hardening catalyst." The cation curing catalyst has a different function from the curing accelerator in the acid anhydride curing reaction, for example.

Among the curing agents, the thermally latent cation curing catalyst is different from acid anhydrides, amines, phenol resins, etc. that are generally used as curing agents, and even if it is contained in the resin composition, the viscosity increase or gelation of the resin composition over time at room temperature. In addition, as a function of a thermally latent cation curing catalyst, a curing reaction can be sufficiently promoted to exert an excellent effect, and a one-component resin composition (also referred to as a ``one-component material'') superior in handling properties can be provided. have.

In addition, by using a thermally latent cation curing catalyst, the moisture resistance of the cured product formed from the obtained resin composition is dramatically improved, and the excellent optical properties of the resin composition are maintained even in harsh use environments, which is more preferable for various applications. It becomes something that can be used easily. In general, when moisture with a low refractive index is contained in the resin composition or its cured product, it causes turbidity, but when a thermally latent cation curing catalyst is used, excellent moisture resistance can be exhibited, so that such turbidity can be suppressed. do. As the moisture resistance is improved, moisture absorption into the resin composition is suppressed, and the generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed.Therefore, excellent heat resistance can be exhibited over a long period of time without causing yellowing or decrease in strength of the resin composition. I can.

As the thermally latent cation curing catalyst, for example, the following general formula (1):

(R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^+m (AX _n ) ^-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 positive numbers, and the sum of a, b, c and d is equal to the valence of Z. Cations (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^+m represents an onium salt A represents a metal element or a metalloid that is a central atom of a halide complex, and B, P, As, Al, Ca, In, Ti , Zn, Sc, V, Cr, Mn, Co. X represents a halogen element, m is the net charge of the halide complex ion, and n is the net charge of the halide complex ion. It is the number of halogen elements.) The compound represented by is preferable.

Anion (AX _n) in the formula ⁽¹⁾ Specific examples of ^m are tetrafluoroborate (BF ₄ ^-), phosphate (PF ₆ ^-), hexafluorophosphate, antimonate hexafluorophosphate (SbF ₆ ^- there may be mentioned), etc. ^-), it is Senate hexafluorophosphate (AsF ₆ ^-), hexachloro antimonate (SbCl _6. An anion represented by the general formula AX _n (OH)- can also be used. In addition, those with other anions, perchlorate ion (ClO ₄ ^-) a, toluenesulfonic acid ion, trinitrotoluene sulfonic acid ion such as methyl sulfite ion trifluoroacetate ^{_{(CF 3 SO 3 - -)}} , sulfonate ion fluoro (FSO ₃₎ Can be lifted.

Specific products of the thermally latent cation curing catalyst include, for example, diazonium salt types such as AMERICURE series (manufactured by American Kan), ULTRASET series (manufactured by Adeka Corporation), and WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.); UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicon), Photoinitiator 2074 (manufactured by Long Franc (now Rhodia)), WPI series (manufactured by Wako Junyaku Ind.), etc. Iodonium salt type; CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), Optomer SP series, Optomer CP series (manufactured by Adeka), Sulfonium salt types, such as San-Aid SI series (manufactured by Sanshin Chemical Industries, Ltd.), CI series (manufactured by Nippon Soda Corporation), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), and CPI series (manufactured by San Apro Corporation), etc.

As the thermally latent radical curing catalyst, for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate organic peroxides such as t-butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl2,2 Azo compounds, such as'-azobis (2-methylpropionate), etc. can be shown.

As the photoinitiator, it is preferable to use a photolatent cation curing catalyst or a photolatent radical curing catalyst as described above. The photolatent cation curing catalyst is also called a photocationic polymerization initiator, and exhibits a practical function as a curing agent by irradiation with light. By using a photo-latent cation curing catalyst, the compound containing a cation species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds.

Examples of the photo-latent cationic curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p-(phenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, p -(Phenylthio)phenyldiphenylsulfoniumhexafluorophosphate, 4-chlorphenyldiphenylsulfoniumhexafluorophosphate, 4-chlorphenyldiphenylsulfoniumhexafluoroantimonate, bis[4-(diphenyl Sulfonio)phenyl]sulfidebishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl)benzene]-Fe-hexafluorophosphate, diallyliodonium hexafluoroantimonate, etc. are preferable. These can be easily obtained from the market, and, for example, SP-150, SP-170 (manufactured by Asahi Telephone Company); Irgacure 261 (manufactured by Chiba-Keigi); UVR-6974, UVR-6990 (manufactured by Union Carbide); CD-1012 (manufactured by Satomer) and the like are preferred. Among these, it is preferable to use an onium salt. Further, as the onium salt, it is preferable to use at least one of a triarylsulfonium salt and a diaryliodonium salt.

As the photo-latent radical curing catalyst, for example, acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylaceto Phenone, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4 -Thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl Acetophenones such as vinyl)phenyl]propanone oligomer and 1,1-dichloroacetophenone; Benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzo Phenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoyl Benzophenones, such as benzyl) trimethyl ammonium chloride; 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2,4-dichloro thioxanthone Thioxanes such as santon, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-onemesochloride Tonnage; Xanthones; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -One ; And acylphosphine oxides. 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 cation curing catalyst or a radical curing catalyst is used as the curing agent, the blending amount is the amount of an active ingredient that does not contain a solvent, etc. (meaning the amount in terms of solid content. A Lewis acid and a Lewis base represented by the general formula (2) described later) In the case of using a cation curing catalyst, it is the total amount of the Lewis acid and the Lewis base.) As, it is preferable to set it as 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the cation curable compound or the total amount of the radical curable compound, respectively. . Thereby, the curing rate can be further increased, the productivity can be further improved, and the fear of coloring during curing, heating, use, etc. can be further suppressed. Further, for example, in the case of reflow mounting a cured product or a laminate obtained using the above resin composition, heat resistance of 200°C or higher is required, and therefore it is preferable to be 10 parts by mass or less from the viewpoint of colorlessness and transparency. It is more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.

When using a commonly used curing agent such as an acid anhydride type, a phenol type, or an amine type as the curing agent, a commonly used curing agent may be used.

For example, as an acid anhydride curing agent, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, hetic acid Anhydride, Hymic acid anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro phthalic anhydride-maleic anhydride addition Alicyclic carboxylic anhydrides such as water, chlorendic anhydride, and methylendomethylenetetrahydrophthalic anhydride; Anhydrides of aliphatic carboxylic acids such as dodecenyl succinic anhydride, polyazelaic anhydride, polysebacic anhydride, and polydodecanedioic anhydride; And aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, and biphenyltetracarboxylic anhydride.

Examples of the phenolic curing agent include bisphenol A, tetrabrombisphenol 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'-butyrylene-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; Novolac resins using various phenols as raw materials such as polyphenol compounds such as phenolic polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, and naphthol : Various novolac resins, such as a xylylene skeleton-containing phenol novolak resin, a dicyclopentadiene skeleton-containing phenol novolac resin, and a fluorene skeleton-containing phenol novolac resin, are mentioned.

Among the commonly used curing agents such as acid anhydride, phenol or amine, preferably, it is an acid anhydride curing agent, more preferably methyltetrahydro phthalic anhydride, tetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, hexa It is hydrophthalic anhydride. More preferably, they are methylhexahydro phthalic anhydride and hexahydro phthalic anhydride.

In the case of using a commonly used curing agent such as the acid anhydride type, phenol type, or amine type, the content of the curing agent is preferably 25 to 70% by mass with respect to 100% by mass of the resin composition. More preferably, it is 35 to 60 mass %. In addition, the mixing ratio of the curable compound (also referred to as curable resin) and these curing agents is preferably 0.5 to 1.6 equivalents of the curing agent per chemical equivalent of the curable resin. The mixture is more preferably 0.7 to 1.4 equivalents, still more preferably 0.9 to 1.2 equivalents.

As the curing agent, preferably as described above, a cation curing catalyst such as a thermal latent cation curing catalyst or a photo latent cation curing catalyst is used. Thereby, since the curing reaction can preferably proceed in a short time and a cured product can be formed quickly, the manufacturing efficiency is further improved. In addition, a cured product having higher heat resistance and releasability can be obtained, and the resin composition may stably exist as a one-component composition (one-component) excellent in handling properties. As described above, the form in which the resin composition further contains a cation curing catalyst is also one of the preferred embodiments of the present invention. Among them, it is preferable to use at least a thermally latent cation curing catalyst.

In addition, a cation hardening catalyst is a catalyst which accelerates a cation hardening reaction, and has a different action from a hardening accelerator in an acid anhydride hardening reaction, for example.

The cation curing catalyst preferably contains a boron compound, and more preferably contains an aromatic fluorine compound.

Particularly preferably as the cationic curing catalyst, the following general formula (2):

[Formula 9]

(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, the same or different, and represents the number of fluorine atoms bonded to the aromatic ring. a Is an integer greater than or equal to 1, b is an integer greater than or equal to 0, and satisfies a + b = 3.) is a form consisting of a Lewis acid (organoborane) represented by and a Lewis base.

As a result, since cation curing can be employed as a curing method, the resulting cured product is required for optical applications such as heat resistance, chemical stability, and moisture resistance, compared to the case of adopting addition type curing such as acid anhydride curing. It becomes a more excellent characteristic. In addition, as compared with the case of using a conventional cation curing catalyst such as an antimony sulfonium salt, coloration by heat (when curing, film formation, use environment) is reduced, and durability such as moist heat resistance and temperature shock resistance is reduced. A better cured product is obtained.

In addition, the presence/absence and degree of coloring of the cured product based on the catalyst to be used can be confirmed also from the change in transmittance at 400 nm in general. In short, by measuring the transmittance of the cured product at 400 nm, the presence and degree of coloring of the cured product can be evaluated.

R in the general formula (2) is the same or different, and represents a hydrocarbon group which may have a substituent. The hydrocarbon group is not particularly limited, but is preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as the total number of carbon atoms is 1 to 20, but is preferably an alkyl group, an aryl group, or an alkenyl group. The said alkyl group, aryl group, and alkenyl group may be an unsubstituted group, and 1 or 2 or more of hydrogen atoms may be a group substituted by another organic group or a halogen atom. Examples of 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 as a whole corresponds to an unsubstituted alkyl group), an aryl group, an alkenyl group, an alkoxy group, and a hydroxyl group.

In the general formula (2), x is an integer of 1 to 5, the same or different, and represents the number of fluorine atoms bonded to the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. As x, it is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.

In addition, a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, in the Lewis acid, an aromatic ring to which a fluorine atom is bonded is bonded to at least one boron atom. As a, it is more preferably 2 or more, and particularly preferably 3, that is, 3 aromatic rings to which a fluorine atom is bonded to a boron atom.

Specifically as the Lewis acid, for example, tris(pentafluorophenyl)borane (referred to as "TPB"), bis(pentafluorophenyl)phenylborane, pentafluorophenyl-diphenylborane, tris(4- Fluorophenyl) borane and the like are preferred. Among these, TPB is more preferable because the heat resistance, moist heat resistance, temperature shock resistance, and the like of the cured product can be improved. In addition, among the cationic curing catalysts, those containing TPB as Lewis acid are also referred to as "TPB-based catalysts".

The Lewis base is not limited as long as it is capable of coordinating to the Lewis acid, that is, forming a coordination bond with the boron atom of the Lewis acid, and any commonly used Lewis base may be used. A compound having an atom having is preferred. Specifically, it is preferably a compound having a nitrogen atom, a phosphorus atom or a sulfur atom. In this case, the Lewis base forms a coordinating bond by donating a non-shared electron pair of a nitrogen atom, a phosphorus atom, or a sulfur atom to the boron atom of the Lewis acid. Further, the Lewis base is more preferably a compound having a nitrogen atom or a phosphorus atom.

As the compound having a nitrogen atom, preferably, amines (monoamine, polyamine), ammonia, and the like can be mentioned. More preferably, they are an amine having a hindered amine structure, an amine having a low boiling point, and ammonia, and still more preferably, a polyamine or ammonia having a hindered amine structure. When a polyamine having a hindered amine structure is used as the Lewis base, oxidation of the cured product can be prevented due to the radical trapping effect, and the resulting cured product is more excellent in heat resistance (moist heat resistance). On the other hand, when ammonia or an amine having a low boiling point is used as the Lewis base, the resulting cured product has excellent low water absorption and UV irradiation resistance. Since ammonia or a low-boiling amine is volatilized in the curing step, the salt structure derived from ammonia or a low-boiling amine in the final molded product (cured product) decreases, so it is estimated that the absorption rate of the cured product can be reduced. In particular, ammonia is preferable because it is excellent in the above-described effect.

Here, as described later, in the present invention, since it is preferable to contain a nitrogen-containing compound having a boiling point of 120°C or less, it is also preferable to use a nitrogen-containing compound having a boiling point of 120°C or less as the Lewis base. That is, it is also preferable that the nitrogen-containing compound having a boiling point of 120° C. or lower is contained in the resin composition as a part of forming the cation curing catalyst.

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

As the low-boiling amine, it is preferable to use an amine having a boiling point of 120° C. or less, more preferably 80° C. or less, still more preferably 50° C. or less, even more preferably 30° C. or less, particularly preferably It is preferably 5 ℃ or less. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, and ethylenediamine; Secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine, and piperidine; Tertiary amines, such as trimethylamine and triethylamine, etc. are mentioned.

The compound having a phosphorus atom is preferably phosphines. Specifically, triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis(diphenylphosphino)ethane, diphenylphosphine, etc. are mentioned.

The compound having a sulfur atom is preferably thiols and sulfides. Specific examples of thiols include methylthiol, ethylthiol, propylthiol, hexylthiol, decanethiol, and phenylthiol. As a specific example of sulfides, diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide, etc. are mentioned.

In the cationic curing catalyst comprising a Lewis acid and a Lewis base represented by the general formula (2), the mixing ratio of the Lewis acid and the Lewis base may not necessarily be a stoichiometric ratio. That is, any one of Lewis acid and Lewis base (converted by base point amount) may be contained in excess of the theoretical amount (equivalent). Specifically, the ratio of the number of atoms serving as the Lewis base point n (b) to the number of atoms n (a) of boron at the Lewis acid point in the mixing ratio of Lewis acid and Lewis base in the cation curing catalyst (n (b )/n (a)), and acts as a cation curing catalyst even if it is not 1 (stoichiometric ratio). Here, the ratio n (b)/n (a) in the cation curing catalyst affects the storage stability of the resin composition and the cation curing properties (curing rate, curing degree of cured product, etc.).

In addition, when the Lewis base has two Lewis base points in the molecule, such as diamines, the ratio n (b)/ when the mixing molar ratio of the Lewis base to the Lewis acid constituting the cation curing catalyst is 0.5. n (a) = 1 (quantitative ratio). In this way, the ratio n (b)/n (a) is calculated.

In the above cation curing catalyst, from the viewpoint of the storage stability of the resin composition containing this, if the Lewis acid is excessively present with respect to the Lewis base, the storage stability may not be sufficient, so that the resin composition having more excellent storage stability can be obtained. In order to do so, it is preferable that the ratio n (b)/n (a) is 0.5 or more. For the same reason, it is more preferably 0.8 or more, still more 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 the cation curing properties, if the Lewis base is excessively excessive, the low-temperature curing property of the cured product may not be sufficient. In order to obtain a composition having more excellent cation curing properties, n (b)/n (a ) Is preferably 100 or less. For the same reason, it is more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less.

In the ratio n (b)/n (a), the Lewis base is composed of a compound having a nitrogen atom, a sulfur atom, or a phosphorus atom, and a structure in which two or more carbons are substituted (a structure in which two or more carbons are substituted is to Means a structure in which two or more organic groups are bonded through a carbon atom), from the viewpoint of cation hardening properties, the acid dissociation constant is high and steric hindrance is large, the ratio n (b)/n (a ) Is preferably 2 or less. It is more preferably 1.5 or less, and still more preferably 1.2 or less. For a structure such as, for example, hindered amine, this range is preferable.

In addition, when the Lewis base is a nitrogen-containing compound having a boiling point of 120°C or less (especially ammonia or a low-boiling amine having small steric hindrance), in particular, in the case of ammonia, the ratio n (b)/n (a) is greater than 1 It is desirable to have a large one. It is more preferably 1.001 or more, still more preferably 1.01 or more, particularly preferably 1.1 or more, and most preferably 1.5 or more.

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

As a cationic curing catalyst consisting of a Lewis acid and a Lewis base represented by the general formula (2), specifically, for example, TPB alkyl such as TPB/monoalkylamine complex, TPB/dialkylamine complex, TPB/trialkylamine complex, etc. Organic borane/amine complexes such as amine complexes and TPB/hindered amine complexes; Organic borane/ammonia complexes such as TPB/NH ₃ complexes; Organic borane/phosphine complexes such as TPB/triarylphosphine complex, TPB/diarylphosphine complex, and TPB/monoarylphosphine complex; Organic borane/thiol complexes such as TPB/alkylthiol complexes; And organic borane/sulfide complexes such as TPB/diarylsulfide complexes and TPB/dialkylsulfide complexes. Among them, TPB/alkylamine complex, TPB/hindered amine complex, TPB/NH ₃ complex, and TPB/phosphine complex are preferable.

In the above resin composition, the content of the cation curing catalyst refers to the amount of the active ingredient (in terms of solid content) not containing a solvent, etc. A cation curing catalyst comprising a Lewis acid and a Lewis base represented by the general formula (2) is used. In this case, the total amount of the Lewis acid and Lewis base) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the cation-curable compound contained in the resin composition. Thereby, the curing speed can be further increased, productivity can be further improved, and the fear of coloring during curing, heating, use, etc. can be further suppressed. Further, for example, in the case of reflow mounting a laminate obtained by using the resin composition, heat resistance of 200°C or higher is required, and therefore, from the viewpoint of colorlessness and transparency, it is preferably 10 parts by mass or less. More preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, particularly preferably It is less than 2 parts by mass.

-Nitrogen-containing compound-

It is preferable that the resin composition further contains a nitrogen-containing compound (also simply referred to as a "nitrogen-containing compound") having a boiling point of 120°C or less. As a result, the resin composition is excellent in storage stability due to the presence of the nitrogen-containing compound during storage (storage) or during transport, while some or all of the nitrogen-containing compound vaporizes during curing. It becomes possible to easily obtain a cured product which is excellent and exhibits a high appearance. As described above, the form in which the resin composition further contains a nitrogen-containing compound having a boiling point of 120°C or lower is also one of the preferred embodiments of the present invention.

The boiling point of the nitrogen-containing compound is preferably 100°C or less, more preferably 80°C or less, still more preferably 50°C or less, particularly preferably 30°C or less, from the viewpoint of further expressing the above effect. Preferably it is 5 degrees C or less.

The boiling point of the nitrogen-containing compound is also the temperature at the time of forming the resin layer with the resin composition on the substrate (for example, the temperature at the time of forming the resin layer by a solution coating method described later such as spin coating). When it is A (degreeC), it is preferable that it is (A + 80) degreeC or less. That is, for example, when A = room temperature 25°C, the boiling point of the nitrogen-containing compound is preferably 105°C or less. Thereby, it becomes possible to exhibit more fully the effect by using the nitrogen-containing compound mentioned above. It is more preferably (A + 60) °C or less, still more preferably (A + 30) °C or less, and particularly preferably (A + 10) °C or less.

Specifically as the nitrogen-containing compound, for example, ammonia (boiling point: -33.34°C); Monomethylamine (boiling point: -6°C), monoethylamine (boiling point: 16.6°C), monopropylamine (boiling point: 48°C), monobutylamine (boiling point: 78°C), monopentylamine, ethylenediamine (boiling point: 117°C) and other primary amines; Dimethylamine (boiling point: 6.9 ℃), diethylamine (boiling point: 55.5 ℃), dipropylamine, methylethylamine (boiling point: 36-37 ℃), methylpropylamine (boiling point: 78 ℃), methylbutylamine (boiling point : 90-92 degreeC), secondary amines, such as ethylpropylamine (boiling point: 80-85 degreeC), and piperidine (boiling point: 106 degreeC); Tertiary amines, such as trimethylamine (boiling point: 2.9°C) and triethylamine (boiling point: 89.7°C), are preferable. Among them, ammonia is particularly preferable because the above-described effects can be more expressed. Thus, the form in which the nitrogen-containing compound is ammonia is one of the preferred embodiments of the present invention.

In the resin composition, the content of the nitrogen-containing compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the curable compound. More preferably, it is 0.01-5 mass parts. In the present invention, it is also preferable to use a cation curing catalyst composed of a Lewis acid represented by the general formula (2) and a nitrogen-containing compound as a Lewis base. In this case, it is preferable to appropriately set the content ratio of the nitrogen-containing compound so as to be within the preferable range of the ratio n (b)/n (a) described above.

-Coupling agent-

It is preferable that the said resin composition also contains a coupling agent. By containing a coupling agent, the heat-and-moisture resistance of the resin composition and the cured product (laminate) can be remarkably improved, and adhesiveness can be improved. Therefore, it is possible to suppress peeling and the like in the solder reflow process and in use in a humid and heat environment.

As the coupling agent, it is preferable to contain silicon, zirconium, titanium and/or aluminum, etc. as the central metal, and among them, silicon is preferably used as the central metal. More preferably, it is a silane coupling agent. By using a silane coupling agent, it becomes possible to further improve the moist heat resistance. As described above, the form in which the resin composition further contains a silane coupling agent is one of the preferred embodiments of the present invention.

The coupling agent is also preferably a coupling agent having a vinyl group, a (meth)acryl group, an oxirane group (oxirane ring), an amino group, a mercapto group, an isocyanate and the like as a reactive group. Especially, it is preferable to have an oxirane group as a reactive group.

Specifically, as the coupling agent, a silane coupling agent such as Z-6040 and Z-6043 manufactured by Tore Dow Corning is preferably used.

In the above resin composition, the content of the coupling agent is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the total amount of the curable resin (curable compound). Thereby, the said effect by a coupling agent can be exhibited more. It is more preferably 5 to 50 parts by mass, still more preferably 10 to 30 parts by mass.

Moreover, it is preferable that the content of the silane coupling agent occupied by 100 mass% of the total amount of the coupling agent is 50 to 100 mass %. It is more preferably 70 to 100 mass%, still more preferably 90 to 100 mass%, and particularly preferably 100 mass%.

-menstruum-

It is preferable that the resin composition also contains a solvent. This makes it possible to obtain a resin composition with high fluidity, and is particularly preferable 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; Ester solvents, such as ethyl acetate, butyl acetate, and cellosolve acetate, are mentioned. One or two or more of these solvents can be used.

In the case of containing the solvent, the content is preferably 10 parts by mass or more with respect to 100 parts by mass of the total amount of the curable compound (resin component). Thereby, the resin composition can exhibit more excellent fluidity as a material for forming a layer on a substrate (preferably a transparent inorganic material layer). It is more preferably 50 parts by mass or more, still more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more. On the other hand, the content of the solvent is preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less, and still more preferably 1000 parts by mass or less.

By the way, what can fully dissolve another component (for example, a curable compound and a dye) in a solvent, for example; When the solution is coated on a substrate, there is little variation in film thickness; What does not cause surface roughness due to bumps or the like even when heated to advance hardening of the coating film; Do not lower the strength of the film as it becomes a hardening inhibiting factor; Even when the solution is stored for a long time, it is required that it does not cause changes in physical properties such as thickening, and based on such conditions, the components contained in the resin composition used (for example, curable compounds, dyes, curing catalysts, etc.) It is preferable to select an appropriate solvent according to the type of.

Therefore, as a result of the inventors' investigation, as a solvent, acetone, γ-butyrolactone, diethyldiglycol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), It was found that when propylene glycol monomethyl ether (PGME), tetrahydrofuran (THF) or the like was used, a good film was formed. In particular, PGMEA has a relatively high boiling point at 145°C, but it has high volatility, so when PGMEA is used as the main component of the solvent, there is little non-uniformity in the film thickness, there is no roughness on the surface due to stony stones, and cure is inhibited. It turned out that there were few degrees and the storage stability was also favorable, and the resin composition (resin solution) containing PGMEA found out that the quality of the coating film which used it was high, and it turned out to be a solution which can produce stably. It has been found that substantially the same effect is exhibited for solvents having a relatively large molecular structure other than PGMEA having a dielectric constant of less than 10 and a molecular weight of more than 100. In this way, the resin composition further contains a solvent, and the solvent is a solvent having a dielectric constant of less than 10 and a molecular weight of more than 100 ("solvent having a dielectric constant of less than 10 and a molecular weight of more than 100" The form containing "") is also one of the preferred forms of the present invention.

The present inventors also found out that another problem arises when solvent A such as PGMEA is used together with a dye having high association, such as, for example, the dye β described above. That is, when the solvent A was used, the probability of association of dye molecules having high association with each other increased, and when the degree of association became more than a certain level, it was found to crystallize and the dye precipitated in the solution. If precipitation in the solution occurs, there is a possibility that it becomes a foreign substance during coating, and the quality cannot be made higher, and since the dye concentration also changes, stable production may become difficult.

Therefore, as a result of further investigation, when the solvent A is used as the main solvent and a dye having a high association such as, for example, a dye β is used in combination, a solvent having a dielectric constant of 10 or more, and/or a dielectric constant of 5 A solvent having a dielectric constant of 10 or more and 100 or less (hereinafter referred to as a ``solvent B1'' with a dielectric constant of 10 or more, and a solvent having a dielectric constant of 5 or more and less than 10 and a molecular weight of 100 or less) B2", and these solvents B1 and B2 are collectively referred to as "solvent B"), it was found that precipitation of the dye β can be suppressed. When the solvent B is used, crystallization of a highly associative dye is suppressed regardless of the use of the solvent A or not. In particular, by adding the solvent B so that the content ratio of the solvent B is 5% by mass or more with respect to 100% by mass of the total solvent components, crystallization of the highly associative dye is further suppressed, resulting in a more stable coating solution.

When a relatively high polarity solvent B1 having a dielectric constant of 10 or more is used, not only associations between dye molecules but also associations with solvent molecules are formed, and in that case, since crystallinity does not increase, precipitation can be suppressed. In addition, even in a solvent having a dielectric constant of 5 or more and less than 10, when a solvent B2 having a relatively small structure such as a molecular weight of 100 or less is used, the solvent is trapped between the dye molecules and an association between the dye and the solvent is formed. Likewise, the crystallinity can be suppressed from increasing and precipitation can be suppressed. On the other hand, in the case of a solvent having a dielectric constant of 5 or more and less than 10 and a molecular weight of more than 100, it is difficult to squeeze between the dye molecules, and the association between the dye molecules proceeds to form crystals and precipitate in some cases. In addition, in the case of a solvent having a dielectric constant of less than 5, even if the molecular weight is 100 or less and can be squeezed between molecules, the force to form an association with the dye molecules is weak, so that the dye molecules associate with each other and become crystals. It may precipitate.

On the other hand, if the content ratio of the solvent B (that is, the solvent B1 and/or the solvent B2) is 5% by mass or more with respect to 100% by mass of the total solvent component, the ratio of the solvent molecules forming an association with the dye molecules increases, so that crystallization Is suppressed more, and it becomes possible to further prevent precipitation of a pigment|dye. Since the effect of suppressing the precipitation of the dye in this way is higher as the content ratio of the solvent B increases, the content ratio of the solvent B may be increased. More preferably, it contains 50 mass% or more of solvent B with respect to 100 mass% of all solvent components, More preferably, it contains 100 mass %.

In addition, when the solvent A and the solvent B are used in combination, the content ratio of the solvent B may be increased within a range that does not impair the coating performance derived from the solvent A.

As described above, the resin composition further contains a solvent, and the solvent contains a solvent B1 having a dielectric constant of 10 or more, and/or a solvent B2 having a dielectric constant of 5 or more and less than 10, and a molecular weight of 100 or less. It is one of the preferred forms. Further, the resin composition further contains a solvent, and the solvent contains a solvent B1 having a dielectric constant of 10 or more, and/or a solvent B2 having a dielectric constant of 5 or more and less than 10, and a molecular weight of 100 or less, and the solvent B1 and One of the preferred embodiments of the present invention is that the content ratio of the solvent B2 is 5 mass% or more with respect to 100 mass% of all solvent components. In addition, the resin composition further contains a solvent, the solvent is a solvent A having a dielectric constant of less than 10 and a molecular weight greater than 100, a solvent B1 having a dielectric constant of 10 or more, and/or a dielectric constant of 5 or more and less than 10, Further, a solvent B2 having a molecular weight of 100 or less is contained, and the content ratio of the solvent B1 and the solvent B2 is 5% by mass or more with respect to 100% by mass of all solvent components is also one of the preferred embodiments of the present invention. The resin composition of the above aspect becomes preferable as an ink solution for a light selective transmission filter (for example, an infrared absorption filter), for example.

-Photosensitizer-

The said resin composition may further contain 1 type or 2 or more types of photosensitizers as needed. In particular, in the case of performing curing by irradiation of the above-described active energy rays, it is preferable to use a photosensitizer in combination with the photopolymerization initiator.

Examples of the photosensitizer include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid (2-dimethylamino ) Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, and the like are preferable.

In the case of containing the photosensitizer, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the curable resin (curable compound). More preferably, it is 0.5-10 mass parts.

-Hardening accelerator-

The said resin composition may further contain 1 type or 2 or more types of hardening accelerators as needed. In particular, in the case of using a commonly used curing agent such as an acid anhydride type, phenol type, or amine type described above, it is preferable to use a curing accelerator in combination.

Examples of the curing accelerator include an acid salt of an organic base or an aromatic compound having tertiary nitrogen. As the acid salt of an organic base, an organic onium salt such as an organic phosphonium salt or an organic ammonium salt, or an organic acid having tertiary nitrogen Acid salts of bases. Examples of the organic phosphonium salt include phosphonium bromide having four phenyl rings such as tetraphenylphosphonium bromide and triphenylphosphine toluene bromide, and examples of the organic ammonium salt include tetraoctylammonium Tetra(C1-C8) alkylammonium bromide such as bromide, tetrabutylammonium bromide, and tetraethylammonium bromide. Examples of the acid salt of an organic base having tertiary nitrogen include alicyclic salts having tertiary nitrogen in the ring. The organic acid salt of a table base and the organic acid salt of various imidazoles are mentioned.

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

Examples of the organic acid salts of the various imidazoles include salts of imidazoles and organic acids such as polyhydric carboxylic acids. Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazole, etc. are mentioned. Preferred imidazoles include, for example, imidazoles similar to the phenyl group substituted imidazoles in the aromatic compound having tertiary nitrogen described later.

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

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

Among the curing accelerators, particularly preferred curing accelerators include phenol salts of 1,8-diazabicyclo(5,4,0)undecene-7, and 1,8-diazabicyclo(5,4,0)undecene- 7 octylate, 2,4,6-tri(dimethylaminomethyl)-phenol, tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimida They are trimellitic acid salt of sol, tetraphenylphosphonium bromide, and triphenylphosphine toluene bromide.

In the case of containing the curing accelerator, the content is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the curable resin (curable compound). More preferably, it is 0.03-3 mass parts.

-Flexible ingredients-

It is preferable that the said resin composition further contains a component (referred to as a "flexible component") which has flexibility. Thereby, it becomes possible to obtain a resin composition having a sense of unity, that is, having high toughness. Moreover, by containing a flexible component, the hardness of a resin layer is improved more.

In addition, the flexible component may be a compound different from the curable resin, and at least one of the curable resin may be a flexible component.

As the flexible component, for example, a compound having an oxyalkylene skeleton represented by -[-(CH ₂ ) _n -O-] _m- (n is an integer of 2 or more, and m is an integer of 1 or more. Preferably, n Is 2 to 12, m is an integer of 1 to 1000, more preferably n is an integer of 3 to 6, and m is an integer of 1 to 20.) An epoxy compound containing, for example, an oxybutylene group ( Japan Epoxy Resin Co., Ltd. make, YL-7217, epoxy equivalent 437, liquid epoxy compound (10 degreeC or more)) are preferable. Further, as other preferable flexible components, liquid rubber such as liquid nitrile rubber, polymer rubber such as polybutadiene, and fine particle rubber having a particle diameter of 100 nm or less are preferable.

Among these, the flexible component is preferably a compound containing an epoxy group, more preferably an oxybutylene group (-[-(CH ₂ ) ₄ -O-] _m- (m is the same as above)) It is a compound.

When the flexible component is contained, the content is preferably 40% by mass or less with respect to 100% by mass of the total amount of the curable compound 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 above-described essential components and preferred containing components, the above-described resin composition for lamination is a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, as long as it does not impair the effect of the present invention. 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 enhancer other than coupling agent, heat stabilizer, Antibacterial and mold inhibitor, flame retardant, gloss remover, defoaming agent, leveling agent, wetting/dispersing agent, anti-settling agent, thickening agent, anti-flow agent, color separation inhibitor, emulsifier, slip and scratch inhibitor, film inhibitor, drying agent, antifouling agent, antistatic agent, conductive Agents (electrostatic aids) and the like may be contained.

When the resin composition contains an inorganic filler, it is possible to reduce the coefficient of linear expansion, and it is possible to suppress expansion due to heat in a solder reflow process, an inorganic oxide deposition process, or the like. As an inorganic filler, it is preferable to mix|blend nanoparticles from a viewpoint of not impairing transparency, and it is preferable to contain silica, titanium oxide, zinc oxide, and zirconium oxide having a particle diameter of 40 nm or less. For example, Nissan Chemical Industries, Ltd. MEK-ST or the like is preferably used.

In the resin composition, the number of foreign matters having a particle diameter of 10 µm or more per 1 cm 3 of the resin composition is preferably 1000 or less, more preferably 100 or less, and still more preferably 10 or less.

In addition, foreign matter contained in the resin composition can be removed by filtration when preparing the resin composition.

-How to prepare-

The method for preparing the resin composition for lamination of the present invention is not particularly limited, and can be obtained by mixing the contained components by a conventional method. When mixing the contained components, each component or mixture may be heated and mixed so as to obtain a uniform composition as necessary. The heating temperature is not particularly limited as long as it is less than or equal to the decomposition temperature of the curable resin (curable compound) or less than or equal to the reaction temperature, but if it is before addition of the curing agent (catalyst), it is preferably 140 to 20°C, more preferably 120 to 40°C. to be.

-Viscosity-

It is preferable that the viscosity of the resin composition is 10000 Pa·s or less. Thereby, it is excellent in processing characteristics, and it becomes possible, for example, to obtain a film with a smooth surface during coating. More preferably 1000 Pa·s or less, still more preferably 200 Pa·s or less, even more preferably 10000 mPa·s or less, particularly preferably 100 mPa·s or less, most preferably 50 mPa·s 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 evaluated using an E-type viscometer (manufactured by Toki Industries, Ltd.) for a resin composition. It is preferable that the value of the viscosity is a value evaluated under the conditions of 25°C.

-Curing method-

The curing method of the resin composition is not particularly limited, and various methods such as thermal curing or photo curing (curing by irradiation with active energy rays) can be preferably used. The thermal curing furnace is preferably cured at about 30 to 400°C, and the optical curing furnace is preferably cured at 10 to 10000 mJ/cm 2. Curing may be performed in one step, or may be performed in two steps, such as primary curing (pre-curing) and secondary curing (main curing).

Hereinafter, the case of performing two-stage hardening is explained in full detail.

In the two-stage curing method, as a first step corresponding to the first 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 is It is preferable to employ a method including a second step corresponding to secondary curing of thermally curing the obtained cured product at more than 200°C and not more than 500°C.

In the case of thermal curing in the first step, the curing temperature is preferably 80 to 200°C. More preferably, it is 100 degreeC or more and 160 degreeC or less. In addition, the curing temperature may be changed stepwise within the range of 80 to 200°C.

The curing time in the thermal curing step is, for example, preferably within 10 minutes, more preferably within 5 minutes, and still more preferably within 3 minutes. Moreover, it is preferably 10 seconds or more, more preferably 30 seconds or more.

The thermal curing step can also be carried out in air or in an inert gas atmosphere such as nitrogen, under reduced pressure, or under pressure. Further, photocuring (curing by irradiation with active energy rays) may be combined.

In the curing method, in the second step, it is preferable to thermally cure the cured product obtained in the first step at more than 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, even more preferably 250° C. or higher, even more preferably 300° C. or higher, particularly preferably 330° C. or higher, most preferably It is more than 350 ℃. The upper limit is more preferably 400°C or less. Further, the curing temperature may be changed stepwise within a temperature range of more than 150°C and not more than 500°C.

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 in consideration of production efficiency, it is preferably, for example, from 10 minutes to 30 hours. More preferably, it is 30 minutes-10 hours.

The second step can also be carried out in air or in an inert gas atmosphere such as nitrogen. Among them, it is particularly preferable to perform the second step in an atmosphere with a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is 10% by volume or less. It is more preferably 3% by volume or less, still more preferably 1% by volume or less, particularly preferably 0.5% by volume or less, and most preferably 0.3% by volume or less.

By carrying out the said 1st process, it becomes possible to suppress aggregation, cratering, etc. of the coating liquid with respect to the coated substrate. Moreover, by performing the said 2nd process, it becomes possible to improve heat resistance to a reflow process and a vapor deposition process.

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

As another curing method, it is also preferable to use one-step curing. In particular, when the resin composition for lamination of the present invention contains a nitrogen-containing compound having a boiling point of 120° C. or lower, the curing property is particularly excellent, so that it is not necessary to undergo a photo-curing process as a pre-curing, that is, a thermal curing process as the main curing. A cured product exhibiting a sufficiently excellent appearance can be efficiently imparted by itself. Therefore, in this case, compared to the case of performing two-stage curing of photocuring and thermal curing, for example, the photocuring step is omitted, thereby reducing the process, and thus the productivity and workability of the cured product are excellent.

As the curing method by the one-step curing, it is particularly preferably a thermal curing method. Thermal curing is preferably cured at about 20 to 400°C, and may be changed stepwise within this temperature range.

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

The one-step curing process can be carried out in air or in an inert gas atmosphere such as nitrogen. Especially, it is preferable to carry out in an atmosphere with a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is 10% by volume or less. It is more preferably 3% by volume or less, still more preferably 1% by volume or less, particularly preferably 0.5% by volume or less, and most preferably 0.3% by volume or less.

The resin composition for lamination of the present invention can impart a cured product excellent in heat resistance, moist heat resistance, temperature shock resistance, light resistance, and the like as described above. Therefore, in the case where a resin layer made of the resin composition of the present invention is formed on a substrate, the resin layer has high heat resistance, excellent surface appearance, and sufficiently suppressed reduction in visible light transmittance and coloring, The resin composition of the present invention and a laminate obtained by using the same are useful as members of various elements for forming a film (for example, optical materials such as light selective transmission filters typified by IR cut filters). In addition, for various devices such as mobile phones, televisions, PCs, and vehicle-mounted applications, for reasons such as simplification of the manufacturing process and low cost, there is a flow of adopting a solder reflow process. As a result, the resin composition of the present invention and the use thereof Since the obtained laminate is sufficiently suppressed from deterioration of optical properties even when applied to a solder reflow process, members of various elements employing a solder reflow process (e.g., optical selective transmission filters typified by IR cut filters) It is particularly useful as a material). Especially, when a transparent inorganic material layer is used as a base material, it can suppress generation|occurrence|production of crack, chipping, and warpage, and since a laminated body excellent also in heat resistance can be obtained, it is preferable. Thus, a cured product (laminate) obtained by forming a layer made of the above-described resin composition for lamination on a substrate is also one of the present invention.

[Laminate]

The laminate of the present invention (also referred to as “laminate”) has a layer (also referred to as “resin layer”) made of the above-described resin composition for lamination on a substrate. That is, the resin composition for lamination of the present invention can be used as a material for forming a layer on a substrate. The resin layer may have only one side of the substrate, or may have both sides. Moreover, the base material and the resin layer may each be either a single layer structure or a multilayer structure.

The laminate is obtained by forming a resin layer on a substrate, but a method of forming it by coating and curing a resin composition on a substrate is preferable as a method of formation thereof. That is, a method of forming a coating film on a substrate is preferred. Moreover, it is preferable that the resin composition for lamination used for the laminated body of this invention is for coating.

Here, "having a resin layer on a base material" means not only a form in which the resin layer is directly in contact with the base material, but also includes a form in which a resin layer is provided through other constituent members present on the base material. The same applies to "forming a resin layer on a substrate", and includes not only the case where the resin layer is directly formed on the substrate, but also the case where the resin layer is formed via other constituent members present on the substrate. . The same applies to "coating a resin composition on a substrate", and includes not only the case where the resin composition is applied directly onto the substrate, but also the case where the resin composition is applied via other constituent members present on the substrate. .

In the form in which the resin composition is applied via the other constituent member, from the viewpoint of improving adhesion, for example, after surface treatment of the constituent member with a liquid containing a metal oxide precursor such as a silane coupling agent , It is preferable to apply a resin composition. This makes it possible to further suppress peeling and the like in, for example, a solder reflow process and use in a moist heat environment. As the silane coupling agent, a compound having an oxirane ring is preferable, and Tore Dow Corning Co., Ltd. Z-6040, Z-6043, and the like are preferably used.

As a method of forming a coating film made of a resin composition on the substrate (or other constituent member), a solution coating method is preferable. Specifically, a commonly used method such as a spin coating method, a cast method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a screen printing method, a flexo printing method, and an ink jet method may be mentioned. Among these, the spin coating method is preferable from the viewpoint of reducing the variation of the coating layer on the substrate. When forming a coating film by the spin coating method, it is preferable to dry the solvent while rotating the transparent inorganic material layer (or another constituent member) at 500 to 4000 rpm for about 10 to 60 seconds near room temperature (25°C). Further, it is also preferable to perform the inkjet method from the viewpoint of reducing the variation while obtaining a sample other than the annular shape which is difficult to obtain by spin coating. Further, it is preferable to perform photocuring and/or thermal curing as necessary after spin coating or ink jetting.

As one of the preferred embodiments of the laminate, 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 is exemplified. As such a layered product, specifically, a phthalocyanine-based dye exhibiting absorption characteristics 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 is required. Can be mentioned. According to this aspect, it becomes possible to manufacture a laminate having high heat resistance, and it becomes possible to obtain a spectrum that does not have an absorption maximum at 400 to 680 nm by combination with an inorganic reflective film or an inorganic interference film. As a result, the laminate can exhibit light selective transmittance close to the sensitivity of a human eye, and thus it becomes a very useful laminate for use in imaging devices. In addition, when the laminate is applied to an image pickup device, the occurrence of flares and ghosts can be sufficiently suppressed, and incidence angle dependence, which may be a problem when combined with a reflective film, can be sufficiently reduced. More preferably, the layered product 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 750 nm. Thereby, the above effect can be exhibited more.

Here, "having only one absorption maximum in the wavelength range of 400 to 680 nm" means that only one peak (absorption maximum) that changes from increase to decrease in absorbance in the wavelength range of 400 to 680 nm is observed. . The peak with this absorption maximum as the peak may be sharp or broad. In the latter case, when two or more sharp absorption peaks are overlapped, a broad absorption peak is formed as a whole, and the peak at which the absorbance changes from an increase to a decrease (absorption maximum) may be formed of only one.

It is preferable that the above-described laminate further has a transmittance of 80% or more at a wavelength of 550 nm. When the transmittance is 80% or more at a wavelength of 550 nm, more excellent light selective transmittance can be exhibited. The transmittance is more preferably 83% or more, still more preferably 85% or more, particularly preferably 87% or more, and most preferably 89% or more.

It is preferable that the above-described laminate further has a transmittance of 60% or less at an absorption maximum wavelength or maximum absorption wavelength existing in a wavelength range of 650 to 680 nm. It is more preferably 50% or less, still more preferably 40% or less, still more preferably 30% or less.

It is preferable that the absorbance of the layered product is higher in the wavelength range of 600 to 680 nm, so that the longer wavelength side is. In other words, it is preferable that the transmittance is lower in the wavelength range of 600 to 680 nm, the longer the wavelength side is. For example, in the wavelength range of 600 to 680 nm, when the transmittance is measured every 1 nm, the transmittance at any wavelength It is preferable to exceed the transmittance at a longer wavelength than this. Thereby, since the transmittance spectrum becomes a smoother curve, more excellent light selective transmittance can be expressed.

In the present specification, the absorption characteristics and transmittance of the layered product, the resin layer, and the transparent inorganic material layer are, for example, an absorption spectrum using an absorbance meter (also referred to as a spectrophotometer. Shimadzu Corporation make, spectrophotometer UV-3100), for example. Alternatively, it can be determined by measuring the transmittance spectrum.

In addition, it is preferable that the resin layer also has the same characteristics as the absorption characteristics and transmission characteristics of the above-described laminate. Among them, it is particularly preferable that the resin layer has a higher absorbance in a wavelength range of 600 to 680 nm as the light absorbance increases toward the longer wavelength side.

The thickness of the laminate is preferably 1 mm or less, for example. Thereby, it is possible to sufficiently meet the request for miniaturization of the imaging device. More preferably, it is 500 µm or less, still more preferably 300 µm or less, particularly preferably 150 µm or less, and most preferably 100 µm or less. Moreover, it is preferable that it is 30 micrometers or more. More preferably, it is 50 micrometers or more.

As described above, a form in which the laminate 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 is one of the preferred embodiments of the present invention.

<material>

Although it does not specifically limit as a base material in the said laminated body, For example, it is preferable to use 1 type, or 2 or more types, such as an organic material, an inorganic material, an organic-inorganic composite material, and a metal material. As an organic material or an organic-inorganic composite material, a resin film etc. which consist of these materials are mentioned, for example. As an inorganic material, glass, crystal, metal oxide, etc. are mentioned, for example.

Moreover, it is preferable that the material of a base material is a material which has a reflow property.

Among the above substrates, it is preferable to use a transparent inorganic material as a material. That is, the substrate is preferably a layer made of a transparent inorganic material (referred to as a transparent inorganic material layer). This is preferable because the occurrence of cracks, chipping, and warping can be further suppressed, and a laminate having more excellent heat resistance can be obtained. A laminate obtained by forming a resin layer made of the resin composition on the transparent inorganic material layer in this manner is one of the preferred embodiments of the present invention.

Examples of the transparent inorganic material include glass and crystal.

The transparent inorganic material may also be obtained by containing transition metal ions in a material for forming glass or crystal. As the transition metal ion, one or two or more commonly used ones having light absorbing ability may be used. For example, Ag ⁺ , Fe ⁺ , Co ^{2 +} , Ni ^{2 +} , Cu ^{2 +} , Zn ^{2 +} And the like. In addition, the form in which the substrate is a glass or quartz substrate is one of the preferred embodiments of the present invention.

In the transparent inorganic material layer, "transparent" preferably has a transmittance of 80% or more at a wavelength of 550 nm. It is more preferably 85% or more, and still more preferably 90% or more.

The thickness of the substrate (preferably the transparent inorganic material layer) is not particularly limited, but is preferably 30 to 1000 µm, for example. More preferably, it is 50 micrometers or more.

It is preferred that the substrate is also treated with a coupling agent. Thereby, adhesiveness is further improved, and peeling etc. can be further suppressed in the use in a solder reflow process and a moist heat environment, for example.

In addition, the substrate treated with a coupling agent is preferably a substrate surface-treated with a coupling agent.

Preferred forms of the coupling agent and the like are as described above, and it is preferable to contain silicon, zirconium, titanium and/or aluminum as the central metal. Among them, it is preferable to have silicon as a central metal. More preferably, it is a silane coupling agent.

As described above, the substrate has been treated with a coupling agent, and the coupling agent contains silicon, zirconium, titanium and/or aluminum as a central metal is also one of the preferred embodiments of the present invention.

<resin layer>

The thickness of the layer (resin layer) made of the laminating resin composition is not particularly limited, but from the viewpoint of heat resistance and transparency during film formation or reflow, and from the viewpoint of preventing peeling or cracking at the interface due to thermal expansion, 50 μm It is preferably not more than 30 µm, more preferably not more than 10 µm, particularly preferably not more than 5 µm, and most preferably not more than 2 µm. In addition, from the viewpoint of preventing defects by making the film thickness sufficiently thicker than the general foreign material size, from the viewpoint of reducing the concentration of the dye dissolved in the resin composition and suppressing the association or precipitation of the dye, it is preferably 0.1 μm or more, and more preferably Is 0.5 μm or more.

<UV cut layer>

It is also preferred that the laminate further has a UV (ultraviolet) cut layer. Thereby, since deterioration due to ultraviolet rays can be sufficiently suppressed, the weather resistance of the laminate can be significantly improved. As described above, the form in which the laminate has an additional UV cut layer is one of the preferred forms of the present invention.

It is preferable that the UV cut layer is disposed on the light incident side of the laminate. Moreover, in the said laminated body, one UV cut layer may be sufficient, and two or more layers may be sufficient as it.

The UV cut layer can be formed by, for example, a resin composition containing at least a resin component and an ultraviolet absorber. As the ultraviolet absorber, for example, a compound having an absorption ability in a wavelength range of 350 to 400 nm is preferable. Specifically, it is preferable to use a phthalocyanine-based dye having an absorption ability in a wavelength range of 350 to 400 nm. In addition, for example, one or two or more such as TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, TINUVIN 326 (manufactured by BASF) may be used.

[Use of laminate]

The laminate of the present invention is particularly suitable for use in imaging devices. The resin composition for lamination of the present invention is also particularly preferred for use in an imaging device. 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 resin composition is more preferably used as a (near) infrared absorbing layer (also simply referred to as an absorbing layer) among the light selective transmission filters. A light selective transmission filter comprising such a laminate is also one of the present invention, and an image pickup device comprising the laminate is also included in the present invention. In addition, it is particularly preferable that the imaging device includes a light selective transmission filter comprising the laminate.

However, the resin composition and laminate for lamination are not limited to the above uses, and for example, optical materials (members), mechanical parts materials, electrical/electronic parts materials, automobile parts materials, civil engineering building materials, molding materials, etc. In addition, it is also useful for various applications such as materials for paints and adhesives.

Hereinafter, a light selective transmission filter and an image pickup device will be described.

<Light selective transmission filter>

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

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

As described above, in a form in which the light selective transmission filter has different functions, it is preferable to form a reflective film on one surface of the laminate of the present invention and to form a functional material layer for imparting different functions to the other surface. . The functional material layer is formed directly on the laminate by, for example, a CVD method, a sputtering method, or a vacuum evaporation method, or obtained by adhering a functional material layer formed on the release-treated temporary substrate to the laminate with an adhesive. I can. Moreover, it can also be obtained by coating and drying a liquid composition containing a raw material to the said laminated body to form a film. For example, as a countermeasure against the deterioration of the light of the absorbing layer, the layer blocking ultraviolet rays is applied by applying a liquid resin composition containing an ultraviolet absorber on the absorbing layer formed on a substrate (for example, a glass substrate), and drying or curing the ultraviolet absorber. It is also preferable to film-produce a resin layer containing.

The light selective transmission filter selectively reduces light transmittance. The light to be reduced may be between 10 nm and 1000 nm, and may be selected according to 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, etc. can be used, but among them, infrared light of 750 nm to 1000 nm (more preferably infrared light of 650 nm to 1000 nm) It is preferable to reduce ultraviolet light of and 200 to 350 nm, and to transmit other light. That is, it is preferable that the light selective transmission filter of the present invention is an infrared/ultraviolet cut filter.

The infrared cut filter may be a filter having a function of selectively reducing light of a certain wavelength (range) among light having a wavelength of 650 nm to 10000 nm, which is an infrared region. The range of the wavelength to be selectively reduced is preferably 650 nm to 2500 nm, 650 nm to 1000 nm, or 800 nm to 1000 nm. A filter for selectively reducing at least one of the 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 that has a function of blocking ultraviolet rays. The range of the wavelength selectively reduced is preferably 200 to 350 nm.

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

In the form in which the light selective transmission filter of the present invention is an infrared cut filter, it is preferable to selectively reduce the transmittance of infrared rays 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 of light in the wavelength range of 480 to 550 nm is 85% or more, and more preferably 90% or more among visible light. In addition, in the infrared cut filter, the transmittance of wavelengths outside (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 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 form 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 rays of 200 to 350 nm to 5% or less.

In the form 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.

As the light selective transmission filter, a reflective film (preferably a (near) infrared reflecting film) is formed on at least one surface of the laminate. That is, it is preferable that it is a light selective transmission filter including the said laminated body and a reflective film. With such a configuration, it is possible to more sufficiently reduce the incident angle dependence of the light blocking characteristics. 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. As the inorganic multilayer film, it is preferable that it is a refractive index controlled multilayer film in which a low refractive index material and a high refractive index material are alternately laminated on the surface of a substrate, an absorbing layer, or another constituent member by vacuum vapor deposition or sputtering. 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 them, an inorganic multilayer film is preferable.

The inorganic multilayer film is preferably a dielectric multilayer film in which a dielectric layer A and a dielectric layer 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 generally used. Preferably, the refractive index ranges from 1.2 to 1.6.

As the material, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, and the like are preferable.

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 ranges from 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, and indium oxide as main components, and contain a small amount of titanium oxide, tin oxide, cerium oxide, etc. What made it, etc. are preferable.

The thickness of each of the dielectric layers A and B is preferably 0.1 λ to 0.5 λ, as long as the wavelength of light to be blocked is λ (nm). When the thickness is outside the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is greatly different from the optical film thickness calculated by λ/4, and the relationship between the optical properties of reflection and refraction is broken, There is a fear that the control of blocking and transmitting a specific wavelength may become impossible.

The method of laminating the dielectric layer A and the dielectric layer B is not particularly limited as long as a dielectric multilayer film stacked with these material layers is formed, but the dielectric layer A and the dielectric layer B are formed by, for example, a CVD method, a sputtering method, a vacuum evaporation method, or the like. Dielectric multilayer films can be formed by alternately stacking them.

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

It is preferable that the thickness of the reflective film is 0.5 to 10 µm. More preferably, it is 2 to 8 micrometers. Further, it is preferable that the total thickness of the reflective film of the light selective transmission filter and the image pickup device is within the above range.

As a preferred form of the reflective film and the absorbing layer, from the viewpoint of obtaining a smooth transmittance spectrum as an optical filter with respect to the maximum absorption wavelength of the absorbing layer in the infrared region (650 to 750 nm), the wavelength of the reflective film having a lower transmittance than the absorbing layer. It is preferably present at +30 nm or less, more preferably +20 nm or less, still more preferably +10 nm or less, particularly preferably 0 nm or less. On the other hand, from the viewpoint of reducing the angle dependence as an optical filter, it is preferably -10 nm or more, more preferably 0 nm or more, still more preferably 10 nm or more, and particularly preferably 20 nm or more.

Here, in the case where the resin layer, which is a part of the laminate of the present invention, is used as an absorbing layer of a reflective light selective transmission filter and a reflective film is formed on at least one surface of the laminate, it is preferable to form a multilayer film of 10 or more layers as the reflective film. desirable. Further, after forming the reflective film, it is also preferable to form a resin layer formed of the resin composition.

It is preferable that the reflective film is present directly on the base material or resin layer constituting the laminated body or through other constituent members. For example, it is preferable to form a reflective film on these surfaces by using a CVD method, a sputtering method, a vacuum evaporation method, or the like. Among them, it is preferable to use a vacuum evaporation method. More preferably, it is a method of forming a reflective film by forming a vapor deposition layer on a temporary substrate such as a release-treated glass, and transferring the vapor deposition layer to a transparent inorganic material layer or a resin layer. Accordingly, it is possible to reduce the likelihood that the light selective transmission filter is deformed and curled or cracks occur due to vapor deposition. Further, in this case, it is preferable to form an adhesive layer on the transparent inorganic material layer or resin layer to which the vapor deposition layer is to be transferred.

In this way, for forming a reflective film (preferably an inorganic multilayer film), a vapor deposition method is preferably used, but the vapor deposition temperature is preferably 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, thereby improving various resistances and improving yield. For this reason, it is very meaningful to use a transparent inorganic material layer, a resin component, and a dye that can withstand such vapor deposition temperatures. When the laminate of the present invention is used, not only can it be deposited at high temperatures, but even when deposited at a low temperature, the difference in the coefficient of linear expansion with the inorganic film is small, so that, for example, a heating environment in a manufacturing process such as a reflow process or harsh Even in the use environment, cracks in the inorganic layer due to the difference in the 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 substrate is excellent in light blocking performance, but has an incidence angle dependence (also referred to as ``viewing angle dependence'') in which the reflective characteristics change depending on the incident angle of light, that is, by the incident angle. Since the spectral transmittance curves are different, the improvement is a problem.

The incidence angle dependence of the light blocking characteristic is, for example, the transmittance (e.g., 0°, 20°, 25°, 30°, etc.) using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation) and changing the incident angle. The transmittance at an incident angle of 0° is the transmittance measured by allowing light to enter from the thickness direction of the light selective transmission filter, and the transmittance at an incident angle of 20° is a direction inclined by 20° to the thickness direction of the light selective transmission filter. It is the transmittance measured by allowing light to enter from .), and it can be evaluated by the amount of spectral change.

Further, the dependence of the angle of incidence of the light blocking characteristic needs to be sufficiently reduced by absorption of the absorbing layer, and it is preferable that the transmittance spectrum does not change with respect to the change of the incident angle, or that the degree of change is small. Specifically, even if the incident angle of 0° is changed to 20° (more preferably, it is changed to 25°), it is preferable that the transmittance spectrum does not change in a region of 80% or more of transmittance, and more preferably, transmittance of 70 The transmittance spectrum does not change in the region of% or more, and more preferably, the transmittance spectrum does not change in the transmittance region of 60% or more. Most preferably, the spectrum does not change in any transmittance region.

The light selective transmission filter of the present invention is particularly excellent in light resistance, heat resistance, and light selective transmittance, and can sufficiently reduce the dependence of the incident angle of the light blocking characteristic, so that, for example, a heat ray cut filter mounted on glass, such as a car or a building. In addition to being useful as a camera module (also referred to as a solid-state imaging device), it is also useful as a filter for correcting visibility by blocking optical noise in applications. Among them, the light selective transmission filter of the present invention is useful as a filter used in a camera module such as a digital still camera or a camera for a mobile phone. That is, it is preferable that the light selective transmission filter is a light selective transmission filter for an image pickup device. As described above, an image pickup device including the light selective transmission filter is also one of the preferred embodiments of the present invention.

<Imaging element>

The imaging device of the present invention includes one or two or more of the above-described laminates, but may further have one or two or more other members as necessary. Typically, the imaging device has a detection device (sensor) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS), and a lens, but additionally, an optical filter or an adhesive for fixing the member may be used.

The image pickup device is preferably in a form in which a reflective film is formed on at least one surface of the laminate. That is, it is preferable that it is an imaging element including the said laminated body and a reflective film. With such a configuration, it is possible to more sufficiently reduce the incident angle dependence of the light blocking characteristics. In this case, the arrangement form (configuration) of the reflective film in the imaging device is not particularly limited. For example, by forming a reflective film directly on a lens, the lens and the reflective film are integrated (also referred to as form (a)); When the imaging device includes an optical filter including a reflective film, a form having a reflective film as a constituent member independent from the lens (also referred to as form (b)), etc. can be mentioned.

In addition, the reflective film is as described above.

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

In the above aspect (b), the optical filter including the reflective film may have only a function of reflecting (near) infrared rays, or may have a function of absorbing (near) infrared rays.

The optical filter including the reflective film may be a light selective transmission filter including the laminate of the present invention and a reflection film, or an optical filter other than the light selective transmission filter. Moreover, you may have 1 or 2 or more optical filters containing a reflective film, and the arrangement form is also not specifically limited. For example, when the imaging device has two or more lenses, the filter having the reflective film may be disposed between the lenses.

In addition, the reflective film is preferably formed on one surface or both surfaces of the lens and/or on one surface or both surfaces of the substrate.

Since the resin composition for lamination of the present invention has the above-described configuration, it is possible to provide a cured product (laminate) excellent in film formation, adhesiveness, heat resistance, moist heat resistance, and temperature shock resistance. Such a laminate can be suitably applied to various applications such as optical materials, and is particularly useful as a material constituting an IR cut filter.

1 is a transmittance spectrum in each step in Example 7.
2 is a transmittance spectrum in each step in Example 8.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, "part" means "part by mass" and "%" means "mass%".

<Preparation of cation curing catalyst>

Preparation Example 1 (Synthesis of TPB-containing powder B)

According to the synthesis method described in International Publication No. 1997/031924, 255 g of an isopa E solution having a 7% TPB (tris(pentafluorophenyl) borane) content was prepared. Water was added dropwise to this solution at 60°C. White crystals precipitated during the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. After drying the obtained cake under reduced pressure at 60° C., 18.7 g of a white crystal TPB-water complex (TPB-containing powder B) was obtained. This complex had a water content of 9.2% (Carl Fischer water system) and a TPB content of 90.8%. The complex after drying was subjected to ¹⁹ F-NMR analysis and GC analysis, but no peaks other than TPB were detected.

The measurement results of ¹⁹ F-NMR are shown below.

Preparation Example 2 (Preparation of cation curing catalyst A)

To TPB-containing powder B: 2 g (TPB pure powder: 1.816 g (3.547 mmol), water: 0.184 g (10.211 mmol)) obtained in Preparation Example 1, 2.1 g of γ-butyrolactone was added, and at room temperature Mix for 10 minutes. Then, 0.778 g (0.984 mmol, mole number of N group is 3.934 mol) of Adecastab LA-57 (hindered amine, manufactured by ADEKA) was added, mixed at room temperature for 10 minutes, and further 20 at 60°C. It mixed for a minute, and it was set as a homogeneous solution of a cation hardening catalyst (TPB catalyst). This was referred to as a cation curing catalyst A.

Preparation Example 3 (Preparation of cation curing catalyst B)

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

<Preparation of resin composition and cured product (laminate)>

Example 1

As an oxirane compound, 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, cyclo as a solvent 330 parts of hexanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 6 parts of TX-EX-609K (phthalocyanine-based dye, absorption maximum wavelength: 715 nm, manufactured by Nippon Catalyst) as a dye were uniformly mixed at 80°C. Thereafter, the temperature was lowered to 40°C, 1 part of the cation curing catalyst A was uniformly mixed as a curing agent, and the foreign material was filtered through a 0.45 μm filter (manufactured by GL Science, non-aqueous 13N). The resin composition (1) was obtained by the above. Using the resin composition, film formation and curing were performed by a method described later to obtain a cured product (laminate).

Examples 2 to 6

Resin compositions (2) to (6) were obtained in the same manner as in Example 1, except that the amount of the dye constituting the resin composition and the kind of the curing agent were changed as shown in Table 1. Using the resin composition, film formation and curing were performed by a method described later to obtain a cured product (laminate).

Comparative Example 1

100 parts of DPE-6A (manufactured by Kyoeisha Chemical) as an acrylic curable resin, 330 parts of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, TX-EX-609K as a colorant (phthalocyanine-based dye, absorption maximum wavelength: 715 nm , Nippon Catalyst Co., Ltd.) 6 parts were uniformly mixed. Then, the temperature was lowered to 40°C, and 1 part of Perhexyl I (manufactured by Nichiyu Corporation) was uniformly mixed as a curing agent, and the foreign matter was filtered through a 0.45 µm filter (manufactured by GL Science, 13N non-aqueous). By the above, a resin composition for comparison (Comparative 1) was obtained. Using the resin composition, film formation and curing were performed by a method described later to obtain a cured product (laminate).

Comparative Example 2

100 parts of UN-904 (manufactured by Negami Industries) as a urethane acrylic curable resin, 330 parts of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, TX-EX-609K as a pigment (phthalocyanine pigment, absorption maximum wavelength: 715 nm) , Nippon Catalyst Co., Ltd.) 6 parts were uniformly mixed. Then, the temperature was lowered to 40°C, and 1 part of Perhexyl I (manufactured by Nichiyu Corporation) was uniformly mixed as a curing agent, and the foreign matter was filtered through a 0.45 µm filter (manufactured by GL Science, 13N non-aqueous). By the above, a resin composition for comparison (Comparative 2) was obtained. Using the resin composition, film formation and curing were performed by a method described later to obtain a cured product (laminate).

Using the resin composition obtained in the above Examples and Comparative Examples, film formation and curing were performed by the following method to obtain a cured product (laminate).

<Membrane formation and curing method of Examples 1 to 6 and Comparative Examples 1 to 2>

1, film formation method

After dropping each resin composition onto a glass substrate (manufactured by Matsunami Glass Industries, Sunokma slide glass, S9213, 76 mm × 52 mm × 1.2 to 1.5 mm) washed with an isopropanol solvent, a spin coater ( Using the Mikasa Co., Ltd. product, 1H-DX2), a predetermined rotational speed was maintained over 3 seconds, and the rotational speed was returned to 0 rpm over 3 seconds to form a film. Table 2 shows specific film formation conditions.

2, curing method

(1) light curing (UV curing)

As a radiation irradiation light source, an exposure apparatus equipped with a 250 W ultra-high pressure mercury lamp (USH-250BY, manufactured by Ushio Electric Corporation) (basic configuration unit "ML-251B/D", irradiation optical unit "PM25C-135", manufactured by Ushio Electric Corporation. ) Was used. Irradiation was performed so that the illuminance on the surface of the substrate on the irradiation side was 33 mW/cm2 at a wavelength of 365 nm, and the accumulated amount of light was 2 J/cm2.

(2) heat curing

Using an inner gas oven (manufactured by Koyo Thermosystems, INL-45N1-S), the temperature was raised from 30° C. to 250° C. for 1 hour in an N2 atmosphere (oxygen concentration 30 ppm or less), and 250° C. After holding at for 1 hour, the temperature was lowered to 30°C.

Table 2 shows specific curing conditions. As shown in Table 2, the resin compositions obtained in Examples 1, 4 and 6 and Comparative Examples 1 and 2 were subjected to thermal curing, and the resin compositions obtained in Examples 2, 3 and 5 were thermally cured after photocuring. Was carried out.

(3) After the final curing, the outer circumferential portion of the glass was removed using a diamond cutter so as to become even, and six evaluation samples having a size of 15 mm x 15 mm were taken out from one glass substrate.

For the resin composition or cured product (laminate) obtained in the above Examples and Comparative Examples, the coating film thickness, film formation property, adhesion, transmittance of the cured product, heat resistance (film formation heat resistance and reflow heat resistance), moist heat resistance, resistance Temperature shock was evaluated by the following method. The results are shown in Table 2.

<Evaluation method of each physical property, etc. of Examples 1-6 and Comparative Examples 1-2>

1, coat thickness

The thickness of the glass substrate before film formation and the thickness of the sample for evaluation after film formation and curing were completed were measured using a micrometer, and the coating film thickness was determined from the difference between the two.

2, film formation

Five samples for evaluation of the cured product after final curing (that is, the cured product obtained by the curing method of the above 2) were visually checked and a 20-fold stereoscopic microscope, and evaluated according to the following criteria.

◎: Only a defect of less than 0.1 mm occurred.

○: A defect of 0.1 mm or more and less than 1 mm occurred in length (diameter).

?: A defect of 1 mm or more and less than 2 mm in length (diameter) occurred.

X: A defect of 2 mm or more in length (diameter) occurred.

3, adhesiveness

Using a cutter (manufactured by OLFA, NT Cutter, A300) for the cured product after the final curing, an incision line was placed on the cured product, and 11 crosscut wires were prepared at 1 mm intervals in vertical and horizontal rows, respectively. 100 masses of squares were made. A tape (manding tape 810, manufactured by 3M Co., Ltd.) was affixed on the cured product so that air did not enter at room temperature, and allowed to stand for 30 seconds. Thereafter, a sample for evaluation was prepared by performing a peeling operation within 1 second so that the peeling force of the cured product became constant.

The evaluation sample was evaluated according to the following criteria.

(Circle): Among the squares of the manufactured 100 masses, peeling did not occur even for 1 mass.

?: Peeling occurred in 1 to 10 masses among the squares of 100 masses produced.

X: Out of the square of 100 masses produced, peeling occurred in 11 to 100 masses.

4, the transmittance of the cured product (with or without coloring)

Using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100), at the time after final curing, the transmittance of the cured product in a wavelength of 400 nm, which is a short wavelength region of visible light, and 550 nm, which is a central region of visible light, is measured. , The presence or absence of coloring was evaluated.

5, heat resistance test (film formation heat resistance test)

The cured product after final curing was dried at 300°C in the air for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and then the transmittance of the cured product at a wavelength of 400 nm and 550 nm was measured by an absorbance meter (manufactured by Shimadzu Corporation). , A spectrophotometer UV-3100) was used. In addition, cracks and peeling were confirmed visually.

6, heat resistance test (reflow heat resistance test)

The cured product after final curing was dried for 20 minutes at 260°C in air using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and then the transmittance of the cured product at a wavelength of 400 nm and 550 nm was measured by an absorbance meter (manufactured by Shimadzu Corporation). , A spectrophotometer UV-3100) was used. In addition, cracks and peeling were confirmed visually.

7, moist heat resistance test

The cured product after final curing is stopped still for 100 hours in an environment at a temperature of 85°C and a relative humidity of 85% using a thermo-hygrostat (manufactured by ESPEC, SH-211), and the transmittance of the cured product at a wavelength of 400 nm and 550 nm Was measured using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). In addition, cracks and peeling were confirmed visually.

8, temperature impact resistance test

The cured product after final curing was put into a cold/heat cycle machine in which a temperature cycle was performed between 115°C x 30 minutes and -40°C x 30 minutes, and the transmittance of the cured product at wavelengths 400 nm and 550 nm at 100 cycles was measured by an absorbance meter ( It measured using the Shimadzu Corporation make, spectrophotometer UV-3100). In addition, cracks and peeling were confirmed visually.

9, evaluation of cracks and peeling

About the five evaluation samples, it evaluated according to the following criteria.

○: No cracking and peeling occurred.

×: Cracks or peeling occurred even in one sheet.

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, manufactured by Daicel Chemical Industries, Ltd.

EHPE-3150: alicyclic epoxy resin, weight average molecular weight 2900, manufactured by Daicel Chemical Industries, Ltd.

TX-EX-609K: Phthalocyanine dye, absorption maximum wavelength: 715 nm, manufactured by Nippon Catalyst

CPI-101A: Photo-latent cation curing catalyst (antimony sulfonium salt (SbF ₆ salt)), manufactured by San Apro

SI-100L: Thermal latent cation curing catalyst "San-Aide SI-100L" (antimony sulfonium salt (SbF ₆ salt)), manufactured by Sanshin Chemical Industries, Ltd., 50% solid content

DPE-6A: Acrylic curable resin "Light Acrylate DPE-6A", manufactured by Kyoeisha Chemicals

UN-904: Urethane acrylic curable resin "Art Resin UN-904", manufactured by Nagami Industries

Perhexyl I: radical polymerization initiator, manufactured by Nichiyu

From the results of Table 2, the following was found.

1, about film formation and adhesion

It was found that Examples 1 to 6 containing an oxirane compound were superior in film formation properties and adhesiveness as compared to Comparative Examples 1 to 2 not containing an oxirane compound.

In addition, among Examples 1 to 6, when a photo-latent cation curing catalyst was used as a curing agent (Examples 2, 3 and 5), the film formation was more than when a different cation curing catalyst was used (Examples 1, 4 and 6). It was found that the property was excellent.

2, about the transmittance after final curing

In Examples 1 to 6, it was found that the transmittance (especially the transmittance of 550 nm) after the final curing had a high value. This shows that in Examples 1 to 6, coloring at the time of final curing can be reduced. In addition, it was found that the transmittance of 400 nm was lower in Examples 4 to 6 having a large amount of the dye, but the transmittance of 550 nm was about the same compared to Examples 1 to 3 having a small amount of the dye.

In addition, among Examples 1 to 6, the case of using a TPB-based catalyst as a curing agent (Examples 1, 3 and 4) has a higher transmittance than the case of using another cation curing catalyst (Examples 2, 5 and 6). , It was found that the coloring reduction effect was high.

3, film formation heat resistance, reflow heat resistance, moist heat resistance, temperature shock resistance

In Examples 1 to 6, cracks and peeling did not occur at all even after each test, and since the transmittance did not change before and after the test, it was found that the film formation heat resistance, reflow heat resistance, moist heat resistance, and temperature shock resistance were excellent. Could

In addition, among Examples 1 to 6, when a TPB-based catalyst was used as the curing agent (Examples 1, 3 and 4), compared to the case of using another cation curing catalyst (Examples 2, 5 and 6), film formation heat resistance and ripple It was found that the low heat resistance, moist heat resistance, and temperature shock resistance were excellent.

In the above examples, a cured product having excellent film formation, adhesion, heat resistance (film formation heat resistance, reflow heat resistance), moist heat resistance, and temperature shock resistance by using a resin composition containing a specific oxirane compound and a pigment It has been found that such a resin composition can be preferably used as a lamination material (especially an optical material such as an IR cut filter) for forming a layer on a substrate. In addition, it is considered that the same functional groups as in the above examples are expressed in the same manner in the resin composition of the present invention.

Therefore, from the results of the above examples, it can be said that the present invention can be applied throughout the technical scope of the present invention and in various aspects disclosed in the present specification, and advantageous effects can be exhibited.

Synthesis Example 1 (Synthesis of phthalocyanine (1))

(1) Step 1

Tetrafluorophthalonitrile 54 g (0.27 mol), potassium fluoride 34.5 g (0.59 mol), and 126 g of acetone were added to a 1000 ml four-neck separable flask, and 3-chloro-4-hydroxyl was added to a dropping funnel. 127 g (0.55 mol) of methoxyethyl benzoate and 216 g of acetone were injected. While stirring the reaction vessel under ice-cooling, the 3-chloro-4-hydroxybenzoic acid methoxyethyl ester solution was added dropwise from the dropping funnel over about 2 hours, and then stirring was continued for further 2 hours. Then, the reaction temperature was stirred overnight while slowly increasing to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate by a rotary evaporator, and methanol was added to perform recrystallization. The obtained crystal was filtered, and 108.7 g (yield 64.8%) of the intermediate (1) was obtained by vacuum drying.

The reaction of this step 1 is briefly shown below.

[Formula 10]

(2) Step 2

20.0 g (0.032 mol), zinc iodide (II) 2.57 g (0.0081 mol), and 30.0 g of benzonitrile were poured into a 200 ml four-neck flask, followed by stirring at 160°C for 24 It was reacted for time. After completion of the reaction, 52.7 g of methylcellosolve was added to the reaction solution, and then it was added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The resulting cake was washed again with a mixed solution of methanol and water, followed by suction filtration. After drying the obtained cake at 90°C for 24 hours using a vacuum dryer, 17.78 g (yield 87.1%) of phthalocyanine (1) as the target product was obtained.

The reaction of this step 2 is briefly shown below.

[Formula 11]

The phthalocyanine (1) obtained in Synthesis Example 1 has a structure in which a substituent shown on the right is substituted in each of the portions (8 in total) indicated by "*" in the main skeleton.

Synthesis Example 2 (Synthesis of phthalocyanine (2))

(1) Step 1

Into a 1000 ml four neck separable flask, 75 g (0.37 mol) of tetrafluorophthalonitrile, 52.3 g (0.90 mol) of potassium fluoride, and 167 g of acetonitrile were added, and 2,6-dichlorophenol 123.4 was added to the dropping funnel. g (0.76 mol) and 133 g of acetonitrile were injected. While stirring, after dropping the 2,6-dichlorophenol solution from the dropping funnel over about 2 hours, stirring was continued for further 2 hours. After that, it was stirred and reacted overnight. The reaction solution was filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered, and 148.1 g (yield 80.2%) of the intermediate (2) was obtained by vacuum drying.

The reaction of this step 1 is briefly shown below.

[Formula 12]

(2) Step 2

140 g (0.29 mol) of the intermediate (2), 107.8 g (0.78 mol) of potassium carbonate, 92.1 g (0.61 mol) of methyl p-hydroxybenzoate and 280 g of acetone were injected into a 500 ml four-neck separable flask. After the reaction solution was stirred at 60° C. overnight to react, the reaction solution was filtered, acetone was distilled off from the filtrate by a rotary evaporator, and a mixture of methanol and water was added to perform recrystallization. The obtained crystal was filtered, and 202.3 g (yield 93.1%) of the intermediate (3) was obtained by vacuum drying.

The reaction of this step 2 is briefly shown below.

[Formula 13]

(3) Step 3

22.5 g (0.030 mol), zinc iodide (II) 2.37 g (0.0074 mol), and 52.5 g of benzonitrile were poured into a 200 ml four-necked flask and stirred at 160°C for 24 hours. Reacted. After completion of the reaction, 30.3 g of methylcellosolve was added to the reaction solution, and then it was added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The resulting cake was washed again with a mixed solution of methanol and water, followed by suction filtration. After drying the obtained cake at 90°C for 24 hours using a vacuum dryer, 17.83 g (yield 86.1%) of phthalocyanine (2) as the target product was obtained.

The reaction of this step 3 is briefly shown below.

[Formula 14]

In the phthalocyanine (2) obtained in Synthesis Example 2, 8 of the parts represented by ``*'' in the main skeleton (16 in total) have a substituent shown in the upper right, and the remaining 8 have a substituent shown in the lower right. It consists of a substituted (or bonded) structure.

Synthesis Example 3 (Synthesis of phthalocyanine (3))

(1) Step 1

3-nitrophthalonitrile 100 g (0.58 mol), potassium carbonate 159.7 g (1.16 mol), 2,6-dichlorophenol 104.6 g (0.64 mol) and acetonitrile 400 g were injected into a 1000 ml three-neck reaction vessel . After stirring and reacting at 60° C. overnight, the reaction solution was filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered, and 100.9 g (yield 60.2%) of the intermediate (4) was obtained by vacuum drying.

The reaction of this step 1 is briefly shown below.

[Formula 15]

(2) Step 2

60.0 g (0.21 mol), copper chloride (I) 5.65 g (0.057 mol), and 140.0 g of diethylene glycol monomethyl ether were poured into a 300 ml four-necked flask, and at 160°C It was reacted for 24 hours while stirring. After completion of the reaction, 100.0 g of methylcellosolve was added to the reaction solution, and then it was added dropwise to a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The resulting cake was washed again with a mixed solution of methanol and water, followed by suction filtration. After drying the obtained cake at 90°C for 24 hours using a vacuum dryer, 51.48 g (yield 80.4%) of phthalocyanine (3) as the target product was obtained.

The reaction of this step 2 is briefly shown below.

[Formula 16]

Phthalocyanine (3) obtained in Synthesis Example 3 has a substituent shown in the upper right in four of the moieties represented by ``*'' in the main skeleton (8 in total) and a substituent shown in the lower right in the remaining four (i.e. Hydrogen atoms) are each substituted (or bonded).

<Preparation of resin composition and cured product (laminate)>

Example 7

Celoxide CEL-2021P 15 parts, EHPE-3150 85 parts, propylene glycol monomethyl ether acetate (PGMEA) 240 parts, tetrahydrofuran (THF) 40 parts, and 8 parts of phthalocyanine (1) obtained in Synthesis Example 1 And uniformly mixed at 80°C. Thereafter, the temperature was lowered to 40°C, 5.6 parts of the cation curing catalyst B was uniformly mixed as a curing agent, and the foreign material was filtered with a 0.45 μm filter (manufactured by GL Science, non-aqueous 13N). The resin composition (7) was obtained by the above. About the obtained resin composition, storage stability was evaluated by the method mentioned later.

Moreover, film formation and hardening were performed by the method mentioned later using the obtained resin composition, and the film formation property, each transmittance, and heat resistance (reflow heat resistance) were evaluated. The results are shown in Fig. 1 and Table 4.

Example 8 and Reference Examples 1 to 4

Except having changed the kind and amount of dyestuff as Table 3, it carried out similarly to Example 7, and obtained the resin composition (8) and resin compositions (1)-(4) for a reference.

About the obtained resin composition, storage stability was evaluated by the method mentioned later.

Further, film formation and curing were performed in the same manner as in Example 7 using the obtained resin composition, and film formation properties, respective transmittances and heat resistance (reflow heat resistance) were evaluated. The results are shown in Fig. 2 (only Example 8) and Table 4.

<Storage stability of resin composition>

Using an E-type viscometer (manufactured by Toki Industries, Ltd.), viscosity measurement was performed under conditions of 25°C. The viscosity before and after standing at 40°C for 1 week was measured, and evaluated according to the following criteria.

(Circle): The amount of change from the initial viscosity was less than 30%.

X: The amount of change from the initial viscosity was 30% or more, or gelled.

<Method of film formation, curing (thermal curing) and deposition film formation of Examples 7 to 8 and Reference Examples 1 to 4>

1, film formation method

After dropping each resin composition on a glass substrate (manufactured by SCHOTT, glass, D263, 8 inch ring shape) washed with an isopropanol solvent, using a spin coater (manufactured by Mika Corporation, 1H-DX2), it was determined over 3 seconds. The predetermined time was maintained as the number of revolutions of the film, and the number of revolutions was returned to 0 rpm over 3 seconds to form a film (ie, coating). Specific film formation conditions are shown in Table 4 (2500 rpm). Moreover, the transmittance spectrum after this film formation (coating) was obtained.

2, curing method (heat curing)

The film obtained by the film formation method of 1 was cured. Specifically, using an inner gas oven (manufactured by Koyo Thermosystems, INL-45N1-S), in a N ₂ atmosphere (oxygen concentration 30 ppm or less) from 30 °C to 250 °C for 1 hour with a program The temperature was raised and the temperature was lowered to 30°C after holding at 250°C for 1 hour. Further, the transmittance spectrum after curing was obtained.

3, deposition film formation method

On the opposite side of the coating layer obtained by the curing method of 2 above, an alternate deposition layer of 20 titanium oxide/20 silica layers (infrared reflective layer) is formed, and an alternate deposition layer of 3 titanium oxide/silica 3 layers (antireflection layer) on the coating layer ) Was formed.

<Evaluation method of each physical property, etc. of Examples 7-9 and Reference Examples 1-4>

1, film formation

The range of a square having a center of 3 cm x 3 cm of the cured product after final curing (that is, the cured product obtained by the curing method of 2) was confirmed with a stereoscopic microscope of 20 times, and evaluated according to the following criteria.

(Double-circle): Only a defect of less than 0.03 mm occurred.

○: A defect of 0.03 mm or more and less than 1 mm in length or diameter occurred.

Δ: A defect of 1 mm or more and less than 2 mm in length or diameter occurred.

X: A defect of 2 mm or more in length or diameter occurred.

2, transmittance

The transmittance spectrum at each step was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100). Spectra are shown in Figs. 1 and 2 (only in Examples 7 and 8). Table 4 shows the transmittances in each step 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 the dye.

In addition, the transmittance after formation of the vapor deposition film was measured by arranging the laminate so as to be in the order of the infrared reflecting layer/glass/coating layer/antireflection layer from the incident light source side. In addition, when the laminate is provided so as to be perpendicular to the incident light (the transmittance spectrum measured in this way is also referred to as a 0 degree spectrum. It is measured by allowing the light to enter from the thickness direction (vertical direction) of the laminate) and, When the laminate was installed so that light was incident from a direction inclined at 30 degrees with respect to the thickness direction (vertical direction) of the laminate (the transmittance spectrum measured in this way is referred to as a 30 degree spectrum), it was measured for each.

3, heat resistance (reflow heat resistance)

The cured product after final curing (that is, the cured product obtained by the curing method of the above 2) was dried in air at 260° C. for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and the wavelength of 430 nm, 550 nm, and The transmittance of the cured product at 650 nm was measured using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). In addition, cracks and peeling were confirmed visually. The evaluation of cracks and peeling was evaluated based on the following criteria for five evaluation samples.

○: No cracking and peeling occurred.

×: Cracks or peeling occurred even in one sheet.

Among the abbreviations in Table 3, those not described in Table 1 are as follows.

PGMEA: Propylene glycol monomethyl ether acetate (nickname: 1,2-propanediol monomethyl ether acetate)

THF: tetrahydrofuran

Phthalocyanine (1): Phthalocyanine pigment obtained in Synthesis Example 1

Phthalocyanine (2): Phthalocyanine pigment obtained in Synthesis Example 2

Phthalocyanine (3): Phthalocyanine pigment obtained in Synthesis Example 3

Antimony catalyst SI-60L: Brand name "San-Aide SI-60L", manufactured by Sanshin Chemical Industries, Ltd.

Curing catalyst A: Cation curing catalyst A obtained in Preparation Example 2

Curing catalyst B: Cation curing catalyst B obtained in Preparation Example 3

From Table 4, the following was found.

The resin compositions obtained in Examples 7 and 8 contain ammonia as a nitrogen-containing compound having a boiling point of 120°C or less by using the curing catalyst B as the cation curing catalyst. In this case, it was found that the storage stability was excellent, the film formation property was also very excellent, and the cured product had high transparency and heat resistance.

Example 9

Celoxide CEL-2021P 15 parts, EHPE-3150 85 parts, propylene glycol monomethyl ether acetate (PGMEA) 240 parts, tetrahydrofuran (THF) 40 parts, and 8 parts of phthalocyanine (1) obtained in Synthesis Example 1 And uniformly mixed at 80°C. Thereafter, the temperature was lowered to 40° C., 20 parts of Z-6043 (manufactured by Toray Dow Corning) as a silane coupling agent, and 5.6 parts of a cation curing catalyst B as a curing agent were uniformly mixed, and the foreign matter was mixed with a 0.45 μm filter (GL Science). Produced and filtered through non-aqueous 13 N). The resin composition (9) was obtained by the above.

Using the obtained resin composition, film formation and curing were performed by the method described later, and film formation properties, transmittances, heat resistance, and adhesion were evaluated. Table 6 shows the results.

Example 10, Examples 7'and 8', Reference Examples 5 to 6

In Example 10 and Reference Examples 5 to 6, a resin composition (10) and a reference resin composition (5) to (6) were carried out in the same manner as in Example 9, except that the kind and amount of the contained components were changed as shown in Table 5 ). In addition, in Examples 7'and 8', the resin composition (7) obtained in Example 7 and the resin composition (8) obtained in Example 8 were used, respectively.

Using each resin composition, film formation and curing were performed in the same manner as in Example 9, and film formation properties, respective transmittances, heat resistance, and adhesion were evaluated. Table 6 shows the results.

<Film formation and curing (thermal curing) method of Examples 7', 8', 9, 10 and Reference Examples 5-6>

1, film formation method

(1) pretreatment coating

a) As a pretreatment coating liquid, a composition of the following formulation was used.

As a silane coupling agent, 40 parts of Z-6043 (manufactured by Tore Dow Corning), 40 parts of ethanol, 10.3 parts of water, and 4 parts of formic acid were uniformly mixed at 25°C for 1 hour. Next, 1 part of this mixed solution and 99 parts of ethanol were mixed uniformly at 25 degreeC, and the foreign material was filtered with a 0.45 micrometer filter (manufactured by GL Science, non-aqueous 13N). By the above, a pretreatment coating solution was obtained.

b) In the same manner as the coating of the resin composition described later, after dropping the pretreatment coating solution on a glass substrate (manufactured by SCHOTT, glass, D263, 8 inch annular shape) cleaned with an isopropanol solvent, a spin coater (manufactured by Mikasa, 1H) -DX2) was used to maintain a predetermined time at a predetermined rotational speed (2500 rpm) over 3 seconds, and a film was formed by returning the rotational speed to 0 rpm over 3 seconds (that is, coating).

In addition, pretreatment coating was performed only in Examples 7'and 8'.

(2) coating of resin composition

After dropping each resin composition on a glass substrate (manufactured by SCHOTT, glass, D263, 8 inch ring shape) washed with an isopropanol solvent, using a spin coater (manufactured by Mika Corporation, 1H-DX2), it was determined over 3 seconds. A predetermined time was maintained at the number of revolutions (2500 rpm), and the number of revolutions was returned to 0 rpm over 3 seconds to form a film (that is, coated).

2, curing method (heat curing)

The film obtained by the film formation method of 1 was cured. Specifically, by using an inner gas oven (manufactured by Koyo Thermosystems, INL-45N1-S), in a N ₂ atmosphere (oxygen concentration 30 ppm or less) from 30° C. to 250° C. for 1 hour. The temperature was raised, and after holding at 250°C for 1 hour, the temperature was lowered to 30°C.

3, deposition film formation method

On the opposite side of the coating layer obtained by the curing method of 2 above, an alternate deposition layer of 20 titanium oxide/20 silica layers (infrared reflective layer) is formed, and an alternate deposition layer of 3 titanium oxide/silica 3 layers (antireflection layer) on the coating layer ) Was formed.

<Evaluation method of each physical property, etc. of Examples 7', 8', 9, 10 and Reference Examples 5-6>

Film formation, transmittance, and heat resistance (reflow heat resistance) were evaluated in the same manner as in Example 7.

1, adhesion (both test)

The cured product after final curing was allowed to stand still for 5 hours in a boiling environment using a boiling bath. Thereafter, an incision line was put on the cured product using a cutter (manufactured by OLFA, NT Cutter, A300), and 11 crosscut wires were manufactured at 1 mm intervals in vertical and horizontal rows, and a square of 1 mm2 was 100 Mass was prepared. A tape (manding tape 810, manufactured by 3M Co., Ltd.) was affixed on the cured product at room temperature so that air did not enter, and allowed to stand for 30 seconds. Thereafter, a sample for evaluation was prepared by performing a peeling operation within 1 second so that the peeling force of the cured product became constant. About the evaluation sample, it evaluated according to the following criteria.

(Circle): Among the squares of the manufactured 100 masses, peeling did not occur even for 1 mass.

?: Peeling occurred in 1 to 10 masses among the squares of 100 masses produced.

X: Out of the square of 100 masses produced, peeling occurred in 11 to 100 masses.

2, adhesiveness (pressure cooker (PCT) test)

The cured product after final curing was stopped still at 120° C./2 atmospheres/humidity 100% for 50 hours using a PCT tester, and then the adhesiveness was evaluated in the same manner as in the above 1.

Among the abbreviations in Table 5, those not described in Tables 1 and 3 are as follows.

Z-6043: Silane coupling agent, brand name "Z-6043", manufactured by Tore Dow Corning

Z-6040: Silane coupling agent, brand name "Z-6040", manufactured by Tore Dow Corning

From Table 6, the following was found.

It can be seen that peeling, etc., is sufficiently suppressed even after exposure to a moist heat environment by performing pretreatment coating using a silane coupling agent on the substrate or using a silane coupling agent as one of the components contained in the resin composition forming the resin layer. there was.

Claims (14)

As a resin composition used as a material for forming a layer on a substrate,
The resin composition contains an oxirane compound having at least one oxirane ring in a molecule, a dye and a cation curing catalyst,
The oxirane compound contains a compound having a hydroxyl group and/or an ester group,
The dye contains a dye having an absorption maximum in a wavelength range of 600 to 900 nm,
The resin composition for lamination, wherein the cation curing catalyst contains a boron compound. The method of claim 1,
The said oxirane compound contains 10-100 mass% of the compound with a weight average molecular weight of 2000 or more with respect to the total 100 mass% of the oxirane compound. The method of claim 1,
The cation curing catalyst is 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, the same or different, and represents the number of fluorine atoms bonded to the aromatic ring. a Is an integer greater than or equal to 1, b is an integer greater than or equal to 0, and satisfies a + b = 3.) A resin composition for lamination, comprising a Lewis acid represented by and a Lewis base. The method of claim 1,
The resin composition for lamination, characterized in that the dye is a phthalocyanine-based dye and/or a porphyrin-based dye. The method of claim 1,
The resin composition for lamination, characterized in that for coating. The method of claim 1,
The resin composition for lamination contains two or more dyes,
The two or more dyes contain at least a dye α and a dye β having different absorption properties,
The dye α is a phthalocyanine-based dye, and when the absorption spectrum of the cured product composed of the dye α and the measurement resin is measured, the maximum absorption is shown in the wavelength ranges of 600 to 650 nm and 680 to 750 nm,
The dye β exhibits a maximum absorption in a wavelength range of 650 to 680 nm when the absorption spectrum of the cured product comprising the dye β and the measurement resin is measured. The method of claim 1,
The resin composition for lamination further comprises a silane coupling agent. The method of claim 1,
The resin composition for lamination further contains a solvent,
The solvent is a resin composition for lamination, characterized in that it contains at least one solvent selected from the following.
-A solvent having a dielectric constant of 10 or more,
-A solvent having a dielectric constant of 5 or more and less than 10 and a molecular weight of 100 or less. The method of claim 1,
The resin composition for lamination further comprises a nitrogen-containing compound having a boiling point of 120°C or less. A laminate obtained by forming a layer made of the resin composition for lamination according to any one of claims 1 to 9 on a substrate. The method of claim 10,
The substrate is treated with a coupling agent,
A laminate, characterized in that the coupling agent contains silicon, zirconium, titanium and/or aluminum as a central metal. The method of claim 10,
The layered product, wherein the layered product 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. A light selective transmission filter comprising the laminate according to claim 10. An imaging device comprising the laminate according to claim 10.

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