KR20140091446A - Resin composition for lamination, and its use - Google Patents

Abstract

Provided by the present invention are a resin composition for laminating which has an excellent heat-resisting property as a material for forming a layer on a substrate; and a laminate having the excellent heat-resisting property which is obtained by forming a layer composed of the resin composition for laminating on the substrate. The present invention also provides an imaging device and a selective light permeability filter using the laminate forementioned. The resin composition for laminating used as a material which forms a layer on a base material contains a pigment and an oxirane compound having an oxirane ring which is equal to or greater than 1 in a molecule. The oxirane compound contains a compound which has a hydroxyl group and/or an ester group. The pigment contains a pigment which has a maximum absorption in the wavelength of 600-900 nm.

Description

RESIN COMPOSITION FOR LAMINATION AND ITS USE [0002]

The present invention relates to a resin composition for lamination and a use thereof. More specifically, the present invention relates to a resin composition used as a material for forming a layer on a substrate, a laminate obtained by forming a layer composed of the resin composition on a substrate, a photoelectrolyte filter, and an image pickup device.

2. Description of the Related Art In recent years, in order to achieve multifunctionality in various fields such as display devices and optical devices such as image pickup devices, members and materials (also referred to as a laminate or laminate) having a laminated structure in which several layers are formed on a substrate made of glass or the like ) Is widely used. Examples of the layer formed on the substrate include an ITO (indium-tin composite oxide) transparent conductive layer used for a touch panel or the like, an infrared (IR) cut layer for reducing optical noise in the image pickup device, And an anti-reflection (AR) layer for reducing reflection of light.

The image pickup device is also referred to as a solid-state image pickup device or an image sensor chip. The image pickup device is an electronic device that converts light of a subject into an electric signal and outputs the electric signal as an electric signal. Examples of such an image pickup device include a camera for a cellular phone, a digital camera, Devices (LEDs, etc.) and the like. Such an image pickup device usually has a configuration including a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) and a lens. However, in order to achieve multi- There has been a growing demand for reduction of optical noise which is an obstacle to the optical system.

Reduction of the optical noise in the image pickup element is conventionally carried out by providing absorbing glass such as blue glass doped with copper ions or a resin filter having a resin absorbing function or a reflecting function for reducing optical noise come. However, the absorbing glass is excellent in heat resistance, but cracks (cracks) and chipping (defects) are likely to occur, and the workability is not sufficient. On the other hand, the resin filter can suppress the occurrence of cracking and chipping, and is excellent in workability. On the other hand, the resin filter has insufficient heat resistance as compared with glass and can not be defeated by warping due to linear expansion. Therefore, in recent years, development of an optical filter having a laminated structure in which a layer having a light absorbing function and a reflecting function is formed on a substrate such as glass is progressing.

Examples of conventional optical filters of a laminated structure include a light absorbing filter having a first layer containing a light absorbing agent and a second layer having a different refractive index on a glass substrate (see Patent Document 1); An organic film layer made of a resin binder and a near infrared absorbing dye on a transparent substrate such as a polyester film substrate, and a near infrared absorbing filter (see Patent Document 2) in which an inorganic film layer is formed; A color filter having a colored film made of a colored curable composition containing a phthalocyanine compound on a glass substrate (see Patent Document 3); A near-infrared cut filter (see Patent Document 4) having a near-infrared reflecting film composed of a dielectric multi-layer film and an organic polymer layer made of a liquid resin composition or the like on a glass substrate; A near-infrared cut filter (see Patent Document 5) including a laminate having a resin layer containing a near infrared absorber on a glass substrate and exhibiting a predetermined transmittance; A solid-state image pickup device having a layer formed of a curable composition for a solid-state image pickup device containing a binder resin and an infrared shielding material on a substrate (see Patent Document 6) and the like.

Japanese Laid-Open Patent Publication No. 2008-51985 Japanese Laid-Open Patent Publication No. 2006-106570 Japanese Laid-Open Patent Publication No. 2012-167145 Japanese Laid-Open Patent Publication No. 2013-50593 Japanese Laid-Open Patent Publication No. 2012-103340 Japanese Laid-Open Patent 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 under development, and a lamination material for obtaining it has been studied.

However, when forming a layer such as an IR cut layer on a substrate, a method of depositing at a high temperature from the viewpoint of forming a dense layer is desired. Therefore, the material of the layer (layering material) formed on the substrate is required to have high heat resistance.

In addition, since an imaging element such as a digital camera module is mounted on a cellular phone or the like, the miniaturization is progressing and the cost is also lowered. Therefore, a resin lens is being used instead of conventional inorganic glass as an imaging lens. In the mounting process of such a member, in order to achieve a low cost, it has become mainstream to adopt a solder reflow method. Therefore, the material of the layer formed on the surface of a lens or the like is required to have heat resistance capable of enduring the reflow process of the cured product (molded product).

As described above, in the patent documents 1 to 6, a multilayered IR cut filter or the like has been proposed. However, the prior art has had to be further examined for a resin composition which gives a molded article excellent in heat resistance at the time of carrying out the above-described high-temperature vapor deposition and heat resistance in a reflow process.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described circumstances, and has as its object to provide a resin composition for lamination having excellent heat resistance as a material for forming a layer on a substrate, and a laminate having excellent heat resistance obtained by forming a layer comprising the resin composition for lamination on a substrate It is intended to provide a sieve. It is also an object of the present invention to provide an optical selective transmission filter and an imaging device using such a laminate.

The present inventors have made various studies on a resin composition for lamination as a material for forming a layer on a substrate (also referred to as a substrate). As a result, it has been found that the resin composition has at least one oxirane ring in the molecule and further has a hydroxyl group and / And a colorant having an absorption maximum in the wavelength range of 600 to 900 nm as a colorant, the resin composition is excellent in heat resistance and is preferably used as a material for forming a layer on a substrate by high-temperature deposition I found out that I can use it. It has also been found that a cured product (also referred to as a laminate or laminate) of a laminated structure obtained by laminating such a resin composition on a substrate has heat resistance capable of enduring the reflow process. It has been found that the optical selective transmission filter and the imaging element including such a laminate are very useful in the field of optics and opto-devices, and the present invention has been accomplished on the basis of being able to solve the above problems well.

That is, the present invention is a resin composition for use as a material for forming a layer on a substrate, the resin composition comprising an oxirane compound having at least one oxirane ring in the molecule and a colorant, / 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 resin composition for lamination on a substrate.

The present invention is also a photo-selective transmission filter including the above laminate.

The present invention is also an imaging device including the above-described laminate.

Hereinafter, the present invention will be described in detail. It is also a preferred embodiment of the present invention that two or three or more individual preferred embodiments of the present invention described below are combined.

In the present specification, the term "absorption maximum" means a relationship between a wavelength and an absorbance in a two-dimensional graph of the X axis and the Y axis (where the X axis is the wavelength and the Y axis is the absorbance) Quot ;, and the wavelength of this peak is referred to as " absorption maximum wavelength ". Among the maximum absorption wavelengths (also referred to as absorption peak wavelengths), the one having the maximum absorbance is referred to as a "maximum absorption wavelength" or "maximum absorption peak wavelength".

The "absorption width (also referred to as absorption width)" is a wavelength width at an arbitrary transmittance. When the absorption width is wide (larger), the optical selective permeability is better and the design conditions of the reflective film are expanded, so that the production of the optical selective transmission filter (infrared cut filter, etc.) is facilitated.

[Resin composition for lamination]

The resin composition for lamination (also referred to simply as " resin composition ") of the present invention comprises an oxirane compound having at least one oxirane ring in the molecule and a colorant as essential components, These components may be used alone or in combination of two or more.

- Coloring -

In the resin composition for lamination of the present invention, the coloring matter contains a coloring matter having an absorption maximum in the wavelength range of 600 to 900 nm (hereinafter also referred to as a specific coloring matter). By containing such a coloring matter, infrared rays of 780 nm to 10 탆 in particular can be reduced, and it is possible to eliminate the optical noise caused by this. In the present invention, a dye having an absorption maximum at a short wavelength side is essential among the conventional near infrared absorbers at an absorption maximum of 600 to 900 nm as described above. By doing so, it is possible to provide a dye having high visible light transmittance and excellent near- A desired performance is obtained for noise reduction. The specific colorant is preferably a colorant having an absorption maximum in a wavelength range of 600 to 800 nm, and more preferably a colorant having an absorption maximum in a wavelength range of 650 to 750 nm.

The specific coloring matter may have a plurality of absorption maximums in a wavelength range of 600 to 900 nm. It is preferable that the absorption peak on the shortest wavelength side among the absorption maximums in the wavelength range of 600 to 900 nm is in the wavelength range of 650 to 750 nm.

It is preferable that the specific dye also has substantially no absorption maximum in a 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, the resin composition contains a colorant dissolved therein. 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 may be used.

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

It is particularly preferable that the dye having a? -Electron linkage in the molecule has an absorption maximum at the aforementioned wavelength range, that is, a specific dye.

Examples of the dye having a π-electron bond in the molecule include a phthalocyanine dye, a porphyrin dye, a cyanine dye, a quaternary dye, a squarylium dye, a naphthalocyanine dye, a nickel complex dye, Dye, and the like, and one or more of these may be used. From the viewpoints of heat resistance and weather resistance, pigments which do not have any of a bionic ion structure and a cationic structure are preferable, and phthalocyanine pigments and / or porphyrin pigments are particularly preferable. More preferably, it is a metal phthalocyanine complex and / or a metal porphyrin complex.

As the porphyrin-based colorant, a metal porphyrin complex such as tetraazaporphyrin is preferable.

As the phthalocyanine dye, a metal phthalocyanine complex is preferable, and a metal element such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, And a metal phthalocyanine complex. Among these metal elements, it is preferable to use at least one of copper, vanadium and zinc as the center metal in view of better solubility or dispersibility (for example, dissolution or dispersibility in resin components), visible light transmittance and light resistance . That is, the center metal is preferably copper, zinc or vanadium, more preferably copper and zinc. Phthalocyanine using copper has no deterioration by light even when dispersed in a certain resin component (binder resin), and has excellent light resistance. A phthalocyanine complex (phthalocyanine dye) having zinc as a central metal is preferable because it is easy to obtain a layered product having excellent solubility in a resin component and higher optical selective permeability.

Among the phthalocyanine dyes, compounds represented by the following general formula (I) are particularly preferable. When a resin composition containing such a compound is used, it is possible to obtain a laminate in which the generation of cracks, chipping, and warpage is further suppressed, and the laminate can be sufficiently durable even in a high-temperature vapor deposition or reflow process. In addition, when such a laminated body is applied to an image pickup device application, occurrence of flare and ghost can be sufficiently suppressed, and incident angle dependency which can be a problem when combined with a reflection film can be sufficiently reduced. In addition, when the laminate is used together with, for example, a reflective film or an interference film, it is possible to exhibit optical selectivity close to that of a human eye. When a phthalocyanine dye represented by the following formula (I) is used, the laminate obtained by using the resin composition of the present invention tends to have an absorption maximum in a wavelength region of 650 to 680 nm.

[Chemical Formula 1]

In the formulas, M represents a metal atom, a metal oxide or a metal halide. R ^a1 ~ R ^a4, R ^b1 ~ R ^b4, R ^c1 ~ R ^c4 and R ^d1 ~ R ^d4 are the same or different and are a hydrogen atom (H), fluorine (F), chlorine (Cl), a bromine atom, (Br), an iodine atom (I), or an OR ⁱ group which may have a substituent. The OR ⁱ group represents an alkoxy group, a phenoxy group or a naphthoxy group. Provided that all of R ^a1 to R ^a4 and R ^d1 to R ^d4 do not represent 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. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms . Among R ⁱ , a phenyl group or a phenyl group having a substituent is preferable.

Examples of the substituent which the OR ⁱ group may have include electron-attracting groups such as an alkoxycarbonyl group (-COOR), a halogen group (halogen atom), a cyano group (-CN), and a nitro group (-NO ₂ ); An electron donating group such as an alkyl group (-R), an alkoxy group (-OR), and the like, and may contain one or two or more of them. The electron donating group is preferably an alkoxycarbonyl group, a chlorine group (chlorine atom) or a cyano group, more preferably a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chlorine group or a cyano group.

The R constituting the alkoxycarbonyl group (-COOR) is preferably an alkyl group having 1 to 4 carbon atoms, and the 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 is preferably 1 to 4, for example. More preferably 1 or 2.

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

Preferably, at least one of R ^a1 to R ^a4 , R ^b1 to R ^b4 , R ^c1 to R ^c4 and R ^d1 to R ^d4 represents an OR ⁱ group. As a result, the light resistance is more excellent.

Here, the carbon to which the OR ^{< 1} > group is bonded is a carbon in the four directional rings of the phthalocyanine skeleton (abbreviated as " C _{alpha &} quot ;, and is located at positions 1, 4, 8, 11, 15, 18, 22, and 25 of the phthalocyanine ring (Which is abbreviated as " C _{beta &} quot ;, and represents carbon at 2, 3, 9, 10, 16, 17, 23 and 24 positions of the phthalocyanine ring). However, Carbon (C _? ). 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 Respectively. It is also preferable that a hydrogen atom or a fluorine atom is bonded to an average of at least four carbons in the _? -Position carbon (C _? ). More preferably, a hydrogen atom or a fluorine atom is bonded to an average of at least six carbons in the? -Position carbon (C _? ), And more preferably, all carbons in the _{? -Position} carbon (C _? ) Are bonded to a hydrogen atom or a fluorine atom . By adopting such a form, it becomes possible to further exert the effect of using the phthalocyanine-based coloring matter represented by the above-mentioned general formula (I).

In the above 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 the metal halide are not particularly limited and examples thereof include copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, , And one or more of these may be used. Among them, it is preferable to use at least one of copper, vanadium and zinc as a central metal in view of better solubility, visible light transmittance and light resistance. More preferably copper or zinc. The phthalocyanine-based dye having copper as a central metal does not deteriorate by light even when dispersed in a certain resin component (binder resin), and has excellent light resistance. A phthalocyanine complex (phthalocyanine dye) containing zinc as a central metal is preferable because it is easy to obtain a layered product having excellent solubility in a resin component and having a higher photo-selective permeability.

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 above general formula (I) can be synthesized by a conventional method described in, for example, Japanese Patent Application Laid-Open No. 6-31239. Concretely, it is preferable to use one kind selected from the group consisting of a metal, a metal oxide, a metal carbonyl, a metal halide and an organic acid metal (collectively referred to as a "metal compound"

(2)

(Wherein, R ^a ~ R ^d are the same or different, a hydrogen atom (H), fluorine (F) or a group OR ^i, which may have a substituent. OR ⁱ groups are an alkoxy group, a phenoxy group or a naphthoxy group Is preferably obtained by heating the phthalonitrile derivative represented by the general formula (I) in the presence of a solvent or an organic solvent. Among them, the reaction is preferably carried out in an organic solvent. The ring-forming reaction of the phthalonitrile derivative is not particularly limited, and it is possible to use a conventionally known method described in JP-A-6-31239, JP-A-3721298, JP-A-3226504, JP-A-2010-77408 Can be applied alone or in an appropriate manner. The specific form of the substituent and the OR ⁱ group is as described above with respect to the general formula (I).

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

In the above reaction, as the phthalonitrile derivative represented by the general formula (i), two or more compounds having at least one of R ^a to R ^d different from each other 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 chlorides, bromides, and iodides of the metal; Metal oxides such as vanadium oxide, titanyl oxide and copper oxide of the metal; Organic acid metal such as acetic acid salt of the metal; A complex compound such as acetylacetonate of the metal, and a metal carbonyl such as carbonyl iron.

Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium and tin; Metal halide compounds (e.g., vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride Magnesium chloride, zinc iodide, cobalt iodide, indium iodide, gallium iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, indium bromide, gallium bromide, copper fluoride, zinc fluoride, fluoride Indium, etc.); A metal oxide such as vanadium pentoxide, vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, titanium dioxide, iron oxide, ferric oxide, ferric oxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt oxide, cobalt dioxide, Metal oxides such as copper oxide, vanadium oxide, zinc oxide, germanium monoxide, and germanium dioxide; Organic acid metal such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate, copper stearate and zinc stearate; Complex compounds such as acetylacetonate, and metal carbonyls such as cobalt carbonyl, iron carbonyl, nickel carbonyl and the like.

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

When the reaction between the metal compound and 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, benzonitrile and the like; N, N-dimethylacetophenone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide, dimethylsulfone, Aprotic polar solvent and the like can be used. Among them, 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene and ethylene glycol are preferably used. More preferred are trimethylbenzene and benzonitrile.

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

Regarding the above reaction, the reaction temperature is not necessarily constant depending on the kind of the raw material, the kind of the solvent, and other conditions, but it is usually preferably 100 to 300 ° C. More preferably 120 ° C or higher, and further preferably 130 ° C or higher. More preferably, it is 260 占 폚 or lower, more preferably 240 占 폚 or lower, and particularly preferably 200 占 폚 or lower. Further, the temperature may be increased stepwise to control the exothermic reaction. The reaction time is not particularly limited, but is usually from 2 to 24 hours, more preferably from 5 to 20 hours.

The reaction may also be carried out in an atmospheric atmosphere. Depending on the kind of the metal compound, the reaction may be carried out in an inert gas atmosphere or an oxygen-containing gas atmosphere (for example, nitrogen gas, helium gas, argon gas or oxygen / .

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

The resin composition may also contain two or more coloring matters. Among them, when the two or more kinds of pigments contain at least pigments alpha and beta having different absorption characteristics and the pigments alpha are phthalocyanine pigments, and when the absorption spectrum of the cured product of pigments alpha and the measurement resin is measured, And the absorption maximum of the cured product of the dye β and the measurement resin is measured. The absorption spectrum of the dye β and the wavelength of 650 to 680 nm It is preferable that it shows the absorption maximum. As a result, when the resin composition or the laminate of the present invention is applied to the use of an image pickup device, a sufficient light absorption width can be secured, occurrence of flare and ghost can be sufficiently suppressed, It is possible to sufficiently reduce the incident angle dependency which can be a problem. In addition, for example, when used in combination with a reflective film or an interference film, it is possible to exhibit optical selectivity close to that of a human eye.

The dye alpha is a phthalocyanine dye, but the dye beta is also preferably a phthalocyanine dye. The phthalocyanine dye is as described above. Among them, the dye alpha and the dye beta are preferably the phthalocyanine-based dye represented by the above-mentioned general formula (I).

The coloring matter? Represents absorption peaks at wavelengths of 600 to 650 nm and 680 to 750 nm, respectively, when the absorption spectrum of the cured product of the dye alpha and the measurement resin is measured. Assuming that the maximum absorption wavelength in the wavelength region of 680 to 750 nm is? ₁ , and the maximum absorption wavelength in the wavelength region of 600 to 650 nm is _{? 2} , among these _two absorption maximum wavelengths, The wavelength of the large peak (i.e., the wavelength of the peak with the lowest transmittance) is preferably _{? 1} . That is, when A? 1 is the absorbance at the maximum absorption wavelength in the wavelength region of 680 to 750 nm and A? 2 is the absorbance at the maximum absorption wavelength in the wavelength region of 600 to 650 nm, A? 2 <A? 1 . Thus, it is possible to exhibit better optical selectivity when used in combination with the dye beta.

It is preferable that the maximum absorption wavelength? ₂ in the wavelength range of 600 to 650 nm possessed by the coloring matter? Is 600 to 630 nm. The maximum absorption wavelength? ₁ at a wavelength region of 680 to 750 nm is preferably 680 to 730 nm.

It is preferable that the dye alpha has an absorbance A _{? 2} at a maximum absorption wavelength? ₂ existing in a wavelength range of 600 to 650 nm of 0.3 or less. More preferably 0.25 or less, and further preferably 0.2 or less. It is also preferable that the absorbance A _{? 1} at the maximum absorption wavelength? ₁ existing in the wavelength region of 680 to 750 nm is 0.1 or more. More preferably at least 0.2, still more preferably at least 0.4.

The coloring matter? Represents the absorption maximum in the wavelength region of 650 to 680 nm when the absorption spectrum of the cured product of the coloring matter? And the measurement resin is measured. Assuming that the absorbance at the maximum absorption wavelength existing in the wavelength range of 650 to 680 nm is A?

A? 2 <A? <A? 1

Is satisfied. That is, the absorbance (A? 1) at the maximum absorption wavelength in the wavelength region of 680 to 750 nm, the absorbance (A? 2) at the maximum absorption wavelength in the wavelength region of 600 to 650 nm, And the absorbance (A?) At the maximum absorption wavelength in the wavelength region of 650 to 680 nm of the dye (s) satisfy the above relational expression. Thus, when the absorption spectrum of a cured product (for example, a resin layer or a laminate) obtained from the resin composition is measured, the absorption maximum peaks of the respective dyes are overlapped with each other, and the absorption characteristics exhibiting broad absorption peaks as a whole That is, a more sufficient absorption width can be ensured.

As described above, the resin composition contains at least two kinds of coloring matter, and at least two kinds of coloring matter contain at least a coloring matter alpha and a coloring matter beta having different absorption characteristics, and the coloring matter alpha is a phthalocyanine coloring matter, , The absorption spectrum of the cured product consisting of the dye β and the measurement resin was measured. The absorption spectrum of the cured product of the dye and the measurement resin was measured at 600 to 650 nm and 680 to 750 nm, , The absorption maximum in the wavelength range of 650 to 680 nm is one of the preferable forms of the present invention.

Hereinafter, more preferable forms as the coloring matter? And the coloring matter? Are respectively described.

(i) pigment alpha

The dye alpha is a phthalocyanine dye exhibiting absorption peaks at wavelengths of 600 to 650 nm and 680 to 750 nm, respectively, when the absorption spectrum of the cured product of the dye alpha and the measurement resin is measured. The dye α is preferably the above-described phthalocyanine dye, more preferably a compound represented by the following formula (II).

(3)

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

[Chemical Formula 4]

In the formula (ii-a), X ¹ represents an oxygen atom or a sulfur atom. R ¹ is the same or different and represents 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, An alkoxy group, or -COOR &lt; ^{2 &} gt ;. R ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ¹ is an integer of 0 to 5;

In the formula (ii-b), X ² represents an oxygen atom or a sulfur atom. R ³ is the same or different and represents 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, An alkoxy group, or -COOR &lt; ^{4 &} gt ;. R ⁴ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m &lt; ² &gt; is an integer of 0 to 7;

In the 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 represent two absorption peaks divided into wavelength regions of 600 to 650 nm and 680 to 750 nm, atoms at the? -Position are preferably substituted. When the substituent is (ii-a), it is preferable that at least one of R ¹ and R ³ is bonded to the ortho or meta position, more preferably to the ortho position. When the substituent is (ii-c), the number of atoms substituted by (ii-c) among the 16 atoms of Z ¹ to Z ¹⁶ is preferably 4 to 16, more preferably 8 to 16, To 16%. (ii-a), (ii-b) or (ii-c) from the viewpoint of solubility, Or a halogen atom, and the substituent represented by (ii-c), or a halogen atom is more preferable from the viewpoint of suppressing the degree of association by breaking down the planarity of the molecule. Since the dye alpha is difficult to form the aggregate, when the absorption spectrum of the cured product of the dye alpha and the measurement resin is measured, it is divided into wavelength regions of 600 to 650 nm and 680 to 750 nm, .

(ii) pigment β

The coloring matter? May have any of the above-described absorption characteristics, but may be, for example, a phthalocyanine coloring pigment, a porphyrin coloring pigment, a chlorine coloring pigment, a choline coloring pigment, a cyanine coloring pigment, a quaternary coloring pigment, a squarylium coloring pigment, A nickel complex dye, a copper ion dye, and the like. Of these, phthalocyanine-based pigments are preferable from the viewpoint of light resistance and heat resistance.

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

[Chemical Formula 5]

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

[Chemical Formula 6]

In the formula (iii-a), X ⁴ represents an oxygen atom or a sulfur atom. R ⁶ is the same or different and represents 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, An alkoxy group, or -COOR &lt; ^{7 &} gt ;. R ⁷ represents an alkyl or alkoxy group having 1 to 20 carbon atoms which may have a substituent. and m ³ is an integer of 0 to 5.

In the formula (iii-b), X ⁵ is an oxygen atom or a sulfur atom. R ⁸ is the same or different and represents 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, An alkoxy group, or -COOR &lt; ^{9 &} gt ;. R ⁹ represents an alkyl or alkoxy group having 1 to 20 carbon atoms which may have a substituent. m ⁴ is an integer of 0 to 7;

In the 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 exhibit the absorption maximum at a wavelength range of 650 to 680 nm, it is preferable that atoms at the? -Position are substituted. The substituent to be introduced is preferably a structure which maintains the planarity of the phthalocyanine structure and is preferably substituted with a structure such as (iii-a) or (iii-b). Among them, 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 more preferably, it is bonded to the para position. The residue is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a hydrogen atom, a fluorine atom or a chlorine atom at a high solubility, more preferably a hydrogen atom or a fluorine atom, Atoms are particularly preferable. (iii-a), (iii-b), a hydrogen atom (that is, an unsubstituted), a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom desirable.

(Iii-a), a hydrogen atom (unsubstituted), a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a hydrogen atom (unsubstituted), a fluorine atom, a chlorine More preferably an atom, a bromine atom, or an iodine atom, and particularly preferably a hydrogen atom (unsubstituted) or a fluorine atom.

(Iii-a), (iii-b), a hydrogen atom (unsubstituted), a fluorine atom, or a chlorine atom, more preferably a hydrogen atom More preferably a fluorine atom, and particularly preferably a fluorine atom.

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

More preferably, the dye (3) is represented by the following general formula (IV):

(7)

X ¹ to X ⁴ and Y ¹ to Y ⁴ are the same or different and each represents a hydrogen atom (H), a fluorine atom (F) or a substituent group. 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 , And at least one of X ⁴ and Y ⁴ represents an OR ⁱ group which may have a substituent. This makes it possible to more fully exert the action and effect of exerting high heat selectivity as well as excellent optical selectivity. Further, the light resistance of the laminate is further improved.

In the general formula (IV), the M, OR ⁱ groups and substituents are the same as those in the general formula (I). In the present invention, at least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ in the general formula (IV) preferably represents a phenoxy group which may have a substituent. As a result, due to the fact that the above-mentioned phthalocyanine-based coloring matter becomes higher, it is possible to shield the wavelength region to be cut off sharply and to exhibit a high transmittance in the wavelength region to be transmitted, And it is possible to greatly reduce the dependence of the incident angle on the reflective film.

At least ^one of X ¹ and Y ¹ , at least one of X ² and Y ² , at least one of X ³ and Y ³ , and at least one of X ⁴ and Y ⁴ may be a substituted or unsubstituted OR ⁱ group . Preferably a phenoxy group which may have a substituent (i.e., a phenoxy group or a phenoxy group having a substituent). More preferably, each of X ¹ to X ⁴ and Y ¹ to Y ⁴ represents 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 above general formula (IV) can be obtained in the same manner as the compound represented by the aforementioned general formula (i). Specifically, the metal compound and the compound represented by the following general formula (iv):

[Chemical 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 Is reacted with a phthalonitrile derivative represented by the general formula (1) in the presence of a solvent or an organic solvent to effect the reaction. Among them, the reaction is preferably carried out in an organic solvent. The cyclization reaction of the phthalonitrile derivative is as described above, and the kind and amount of the metal compound, the organic solvent, and the reaction conditions are as described above.

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

In the above reaction, as the phthalonitrile derivative represented by the general formula (iv), it is preferable to use at least a compound of a form in which at least one of X ^a and Y ^a represents an OR ⁱ group which may have a substituent. In addition, the form represents an OR ⁱ is the X ^a and Y ^a may all have the at least one of forms of the compounds and, X ^a and Y ^a represent the groups (atoms) other than OR ⁱ group substituent may have a substituent May be used in combination.

Since it is impossible to specify the mass ratio of the coloring matters? And the coloring matter?, It is difficult to define the mass ratio of the coloring matter? And the coloring matter? And the coloring matter? (Mass ratio) = 80/20 to 40/60. This makes it possible to more fully exert the action and effect that the incident angle dependency can be sufficiently reduced in the case of combining with a reflective film, exhibiting a more excellent absorption width and exhibiting sharp transmission and absorption characteristics. The mass ratio is more preferably 70/30 to 50/50.

In the resin composition, the total amount of all pigments is preferably 0.0001% by mass or more and 15% by mass or less based on 100% by mass of the total amount of the resin composition. This makes it possible to obtain a cured product having a higher visible light transmittance and better blocking performance in the near infrared region. The lower limit of the content of the pigment is more preferably 0.001 mass% or more, still more preferably 0.005 mass% or more, particularly preferably 0.1 mass% or more, and most preferably 1 mass% or more. The upper limit is more preferably 10 mass% or less, still more preferably 7 mass% or less, still more preferably 5 mass% or less.

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

The content of the other pigments is preferably 50% by mass or less based on 100% by mass of the total amount of pigments. More preferably 20 mass% or less, and further preferably 10 mass% or less. In other words, the colorant having an absorption maximum in a wavelength range of 600 to 900 nm is preferably 50 mass% or more, more preferably 80 mass% or more, further preferably 90 mass% or more, relative to 100 mass% Or more.

- oxirane compound -

The resin composition for lamination of the present invention contains an oxirane compound (also referred to simply as an oxirane compound) having at least one oxirane ring in the molecule, and the oxirane compound contains a compound having a hydroxyl group and / or an ester group. That is, the resin composition for laminating according to the present invention contains an oxirane compound having a hydroxyl group and / or an ester group. In addition to the oxirane compound having a hydroxyl group and / or an ester group, another oxirane compound containing no hydroxyl group or ester group .

The oxirane compound is a compound (cationically curable compound) which has a cationic curable group called oxiranic ring and is cured (polymerized) by heat or light. The resin composition contains an oxirane compound, whereby the shrinkage amount of the cured product can be sufficiently reduced, the time to curing becomes short, the productivity is enhanced, and the cured film (resin layer) obtained also has heat resistance (thermal decomposition resistance and heat resistance coloring property) And chemical resistance. Further, when the oxirane compound is a compound having a hydroxyl group and / or an ester group, the resin composition is excellent in adhesion.

In the present specification, a compound which is cured (polymerized) by heat or light is collectively referred to as a &quot; curable compound &quot; or a &quot; resin component &quot;, and among them, a curable compound having a cationically curable group is collectively referred to as &quot; .

The group containing an oxirane ring which is an ether of a triple ring is also referred to as an &quot; epoxy group &quot;. The term "epoxy group" includes, in addition to the epoxy group in the narrow sense, a group having an oxirane ring 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, Cyclohexane ring and the like.

The oxirane compound having a hydroxyl group and / or an ester group is preferably an epoxy compound having a hydroxyl group and / or an ester group. As the 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 preferable 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 to a cyclic aliphatic hydrocarbon directly or via a hydrocarbon (particularly preferably an oxiran ring), and the like . The alicyclic epoxy compound is preferably a compound having an epoxycyclohexane group. In addition, a polyfunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in the molecule is preferable in that the curing rate can be further increased. 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 an alicyclic epoxy compound.

Examples of the epoxy compound having an epoxycyclohexane group include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, epsilon-caprolactone denatured-3,4-epoxycyclohexylmethyl -3 ', 4'-epoxycyclohexanecarboxylate, and bis- (3,4-epoxycyclohexyl) adipate. Examples of the alicyclic epoxy compound other than the epoxy compound having an epoxycyclohexane group include 1,2-epoxy-4- (2-oxiranyl (meth) acrylate of 2,2-bis (hydroxymethyl) ) Cyclohexane adducts, and heterocycle-containing epoxy resins such as triglycidylisocyanurate, and the like.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferable. 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 a hydrogenated 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 preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. The aromatic epoxy compound is preferably an epoxy compound having an aromatic ring conjugate system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, or an anthracene ring. Among them, a compound having a bisphenol skeleton and / or a fluorene skeleton is preferable in order to realize a lower absorption rate and a high refractive index. More preferably, it is a compound having a fluorene skeleton, whereby it is possible to further increase the refractive index and further increase the releasability. In the aromatic epoxy compound, a compound in which the epoxy group is a glycidyl group is preferable, and among them, a compound (also referred to as an aromatic glycidyl ether compound) which is a glycidyl ether group is more preferable. It is also preferable to use a brominated compound of an aromatic epoxy compound because a higher refractive index can be achieved, but the Abbe number is slightly higher, so that it is preferable to suitably use it according to the application.

Examples of the aromatic epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, and an aromatic epoxy compound having a bromo substituent. Among them, a bisphenol A type epoxy compound and a fluorene type epoxy compound are preferable.

As the aromatic glycidyl ether compound, for example, epibisstic granidyl ether type epoxy resin and high molecular weight epibissta granidyl ether type epoxy resin can be given.

Examples of the Epi-Vista triglycidyl ether type epoxy resin include epoxy resins obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S and fluorene bisphenol with epihalohydrin, .

Examples of the high-molecular-weight epihisterglycidyl ether type epoxy resin include epoxy resins such as bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like, And further addition reaction.

Specific examples of the aromatic glycidyl ether compound include bisphenol A type compounds such as 828EL, 1003, and 1007 (manufactured by Japan Epoxy Resins Co., Ltd.); Fluorine-based compounds such as Oncoat EX-1020, Oncoat EX-1010, Oggol EG-210 and Oggol PG (manufactured by Osaka Gas Chemical Co., Ltd.) desirable.

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

Examples of the aliphatic glycidyl ether type epoxy resin include polyhydroxy compounds such as polyhydroxy compounds (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG600), propylene glycol, dipropylene glycol, Glycol, tetrapropylene glycol, polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylol propane and its oligomers, pentaerythritol and its oligomers, glucose, fructose, lactose, maltose and the like Polysaccharides and the like) and epihalohydrin, and the like, and the like. Among them, an aliphatic glycidyl ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton is more preferable as the central skeleton.

Among the above oxirane compounds, an alicyclic epoxy compound, a hydrogenated epoxy compound or an aromatic epoxy compound is particularly preferable. They do not cause coloration of the epoxy compound (oxirane compound) per se at the time of curing, and are excellent in transparency, low coloring property, and light resistance, which do not cause coloring or deterioration due to light. Therefore, when a resin composition containing them is used, a resin layer and a laminate having no coloration and having better light resistance can be obtained with high productivity. As described above, the embodiment in which the oxirane compound contains at least one kind 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 contains at least one member 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 in the form containing at least one selected from the group consisting of the alicyclic epoxy compound and the hydrogenated epoxy compound, Is preferably 50% by mass or more based on 100% by mass of the total amount of the compound. This makes it possible to further exert the action and effect of the alicyclic epoxy compound and the hydrogenated epoxy compound. More preferably not less than 60% by mass, and still more preferably not less than 70% by mass.

Further, in the present invention, a cured product (resin layer) sufficiently cured can be obtained even when the resin composition contains an aromatic epoxy compound which has not been well cured in the conventional catalyst. Therefore, a laminate having a controlled refractive index or the like can be obtained by appropriately selecting the kind of the aromatic epoxy compound or the content in the composition. As the oxirane compound, a form in which the aromatic epoxy compound is 100% by weight and a form in which the aromatic epoxy compound and the oxirane compound are used in combination are both preferred embodiments of the present invention. In the latter case, it is more preferable to contain at least one selected from the group consisting of aromatic epoxy compounds and other oxirane compounds such as alicyclic epoxy compounds and hydrogenated epoxy compounds.

In the resin composition, it is essential that the oxirane compound contains an oxirane compound having a hydroxyl group and / or an ester group, but it may contain other oxirane compounds. As other oxirane compounds, novolak-aralkyl type glycidyl ether type 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 based on 100% by mass of the total amount of the curable compound in the resin composition from the viewpoint of further improving the adhesiveness. More preferably at least 10 mass%, further preferably at least 30 mass%, particularly preferably at least 50 mass%, even more preferably at least 80 mass%, and most preferably at most 100 mass%.

The content of the oxirane compound having a hydroxyl group and / or ester group is preferably 50% by mass or more based on 100% by mass of the total amount of the oxirane compound contained in the resin composition. This makes it possible to further improve the adhesiveness (for example, adhesiveness to a substrate or another layer, adhesion to other members and materials, and the like). More preferably not less than 60% by mass, and still more preferably not less than 70% by mass.

It is preferable that the oxirane compound further contains an oxirane compound having a weight average molecular weight of 2000 or more. The content of the oxirane compound having a weight average molecular weight of 2000 or more is preferably 10 to 100% by mass based on 100% by mass of the total amount of the oxirane compound contained in the resin composition. As a result, the resin composition is more excellent in film-forming property when a resin layer is formed on a substrate (also referred to as a substrate). As described above, the embodiment in which the oxirane compound contains 10 to 100% by mass of a compound having a weight average molecular weight of 2000 or more based on 100% by mass of the entire oxirane compound is a preferred embodiment of the present invention. 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, the weight average molecular weight is preferably 2,200 or more. More preferably, it is 2500 or more. From the viewpoint of film formability and from the viewpoint of keeping the glass transition temperature of the cured product (resin layer) high, it is preferable that it is not more than 1,000,000. More preferably 100,000 or less, and even more preferably 10,000 or less.

In the present specification, the weight average molecular weight can be determined by GPC (Gel Permeation Chromatography) measurement under the following conditions.

Measuring instrument: HLC-8120GPC (trade name, manufactured by Toso Co., Ltd.)

Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (all manufactured by Toso Co., Ltd.) are connected in series and used

Eluent: tetrahydrofuran (THF)

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

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

Other curable compounds -

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

The curable functional group refers to a functional group that undergoes a curing reaction with heat or light (that is, a group that causes a curing reaction of the resin composition). For example, an oxirane group (oxirane ring) or an epoxy group An oxetane ring), an ethylene sulfide group, a dioxolane group, a trioxoranane group, a vinyl ether group, and a styryl group; A radical-curing group such as an acryl group, a methacryl group, and a vinyl group. Therefore, as the other curable compound, a compound having a cationically curable group (also referred to as a &quot; cationically curable compound &quot; or a &quot; cationically curable resin &quot;) and / or a compound having a radical curable group Curable compound &quot;). As a result, the time to curing becomes short, resulting in higher productivity, and the resulting cured product is also superior in heat resistance (thermal decomposition resistance and heat resistance coloring property). Among them, it is more preferable to contain a cationically curable compound since the curing shrinkage rate is low and it is easy to impart a shape in a mold or the like. In addition, the oxirane compound described above is contained in the cationically curable compound.

The cationically curable compounds (oxirane compounds and other cationically curable compounds) preferably further contain a compound having two or more cationically polymerizable groups in one molecule, that is, a polyfunctional cationically curable compound. Thereby, the curability can be further increased, and a cured product having various properties can be obtained. The compound having two or more cationically polymerizable groups in one molecule may be a compound having two or more of the same cationically polymerizable groups or a compound having two or more different cationically polymerizable groups. In the present invention, a polyfunctional alicyclic epoxy compound or a polyfunctional hydrogenated epoxy compound is particularly preferable as the polyfunctional cationically curable compound. By using these, a cured product can be obtained in a shorter time.

Specific examples of the other curable compound include a compound having at least one oxetane group (oxetane ring) in the molecule (referred to as an oxetane compound). When the resin composition contains an oxetane compound, it is preferable to use it in combination with an alicyclic epoxy compound and / or a hydrogenated epoxy compound from the viewpoint of the curing rate.

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

Of the oxetane compounds having no aryl group or aromatic ring, examples of the monofunctional oxetane compound include 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) Ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, isobornyl Cetanylmethyl) ether and the like are preferable.

Among the oxetane compounds having no aryl group or aromatic ring, examples of polyfunctional oxetane compounds include di [1-ethyl (3-oxetanyl)] methyl ether, 3,7- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3- (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) 3-oxetanylmethoxy) hexane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis Ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol Pentacene (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether and the like.

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

- hardener -

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

The curing agent may be appropriately selected depending on the curing reaction, the kind of the curable compound (also referred to as a curable resin), and the like. For example, in the case of performing heat curing, a commonly used curing agent such as a thermal latent radical curing catalyst, acid anhydride system, phenol system or amine system may be used in addition to the thermal latent cationic curing catalyst. Among them, it is preferable to use a thermal latent cationic curing catalyst and a thermal latent radical curing catalyst, and it is particularly preferable to use a thermal latent cationic curing catalyst for the purpose of reducing the shrinkage of the cured product. In the case of curing by irradiation with active energy rays, a photo polymerization initiator can be used as a curing agent. Among them, it is preferable to use a light-potential cationic curing catalyst or a light-potential radical curing catalyst, and it is particularly preferable to use a light-potential cationic curing catalyst for the purpose of reducing the shrinkage of a cured product. Thus, the curing agent is particularly preferably a cationic curing catalyst.

In the present specification, a catalyst that promotes a cationic curing reaction such as a thermal latent cationic curing catalyst or a photonic latent cationic curing catalyst is also referred to as a &quot; cationic curing catalyst &quot;. The cationic curing catalyst has a function different from that of the curing accelerator in the acid anhydride curing reaction, for example.

Among the above curing agents, the thermal latent cationic curing catalyst is different from acid anhydrides, amines, phenol resins and the like which are generally used as a curing agent. Even when contained in the resin composition, the viscosity of the resin composition increases with time, (Also referred to as &quot; one-liquefying material &quot;) which can exert an excellent effect by sufficiently accelerating the curing reaction as an action of a thermal latent cationic curing catalyst and which is superior in handling properties have.

Further, by using the thermal latent cationic curing catalyst, the moisture resistance of the cured product formed from the obtained resin composition is dramatically improved, and excellent optical properties of the resin composition are maintained even in a severe use environment, It can be used. Normally, when moisture having a low refractive index is contained in the resin composition or the cured product thereof, clouding may occur. However, when the thermal latent cationic curing catalyst is used, excellent moisture resistance can be exhibited. do. As moisture resistance is improved, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals by the synergistic effect of irradiation with ultraviolet rays or exposure to heat rays is suppressed. Thus, excellent heat resistance can be exhibited over a long period of time without causing yellowing or strength deterioration of the resin composition .

As the thermal latent cationic curing catalyst, for example, a compound represented by 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 a halogen ^{atom. R 1, R 2, R} 3 and R ⁴ A, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. The cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^{+ m} represents an onium salt, A represents a metal element or a metalloid which is a central atom of a halide complex, and B, P, As, Al, Ca, In, Ti , Zn, Sc, V, Cr, Mn, and Co, where X represents a halogen element, m represents a net positive charge of a halide complex ion, Is the number of halogen atoms).

Specific examples of the anion (AX _n ) ^{- m} of the general formula (1) include tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), hexafluoroantimonate (SbF ₆ ^- ), Hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ). Anions represented by the general formula AX _n (OH) - may also be used. Examples of other anions include perchlorate ion (ClO ₄ ^- ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ^- ), fluorosulfonate ion (FSO ₃ ^- ), toluenesulfonate ion, trinitrobenzenesulfonate ion, .

Specific examples of the thermal latent cationic curing catalyst include diazonium salt type such as AMERICURE series (American Kana Co.), ULTRASET series (manufactured by Adeka) and WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.); (Manufactured by Wako Pure Chemical Industries, Ltd.), UVE series (manufactured by General Electric Co.), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicones), Photoinitiator 2074 Iodonium salt type; (Manufactured by Union Carbide), UVI series (manufactured by General Electric Co.), FC series (manufactured by 3M), CD series (manufactured by Sato MUSA), Optomer SP series and Optomer CP series (manufactured by Adeka) A sulfonium salt type such as a SANEID SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), a CI series (manufactured by Nippon Soda Co., Ltd.), a WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), and a CPI series (manufactured by SANA PRO).

Examples of the thermal latent radical curing catalyst include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate , t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, and the like; Azo compounds such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) Azo compounds such as azobis (2-methylpropionate) and the like.

As the photopolymerization initiator, it is preferable to use a photolatent cationic curing catalyst or a photocatalytic radical curing catalyst as described above. The light-potential cationic curing catalyst is also called a photocathion polymerization initiator and exhibits a substantial function as a curing agent by light irradiation. By using a photonic latent cationic curing catalyst, a compound containing a cationic species is excited by light to cause a photodecomposition reaction to proceed with photo-curing.

As the photolatent cationic curing catalyst, for example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p - (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (2,4-cyclopentadien-1-yl) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, [(1-methylethyl) benzene] -Fe-hexafluorophosphate, diallyl iodonium hexafluoroantimonate and the like are preferable. These are readily available from the market and include, for example, SP-150, SP-170 (manufactured by Asahi Kasei); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide Corporation); CD-1012 (manufactured by Sato MUSA) and the like are preferable. Of these, it is preferable to use an onium salt. As the onium salt, it is preferable to use at least one of triarylsulfonium salt and diaryliodonium salt.

Examples of the photopotential radical curing catalyst include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy- Phenol, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methyl-2-methyl- Vinyl) phenyl] propanone oligomer, and 1,1-dichloroacetophenone; Benzoin 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) Phenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- propenyloxy) ethyl] benzenemethanaminium bromide, Benzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanic acid such as 1-chloro-4-propanedioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone- Tons; Xanthones; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan- -One ; Acylphosphine oxides, and the like. Of these, acetophenones, benzophenones and acylphosphine oxides are preferably used, and in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- (4-thiomethylphenyl) propan-1-one is preferably used.

When a cationic curing catalyst or a radical curing catalyst is used as the curing agent, the amount thereof is an amount of the active ingredient (a solid content conversion amount not containing a solvent, etc.), which is the amount of the Lewis acid represented by the general formula (2) The total amount of the Lewis acid and the Lewis base when the cationic curing catalyst is used) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the cationically curable compound or the radical-curing compound, respectively . As a result, the curing rate can be further increased, productivity can be further improved, and the possibility of coloring during curing, heating, and use can be further suppressed. Further, for example, when a cured product or a laminate obtained by using the resin composition is reflow-mounted, heat resistance of 200 占 폚 or more is required, so that it is preferably 10 parts by mass or less from the viewpoint of colorlessness and transparency. More preferably not less than 0.1 part by mass, more preferably not less than 0.2 parts by mass, more preferably not more than 5 parts by mass, further more preferably not more than 3 parts by mass, particularly preferably not more than 2 parts by mass.

When a commonly used curing agent such as an acid anhydride system, phenol system or amine system is used as the curing agent, those which are conventionally used may be used as the curing agent.

Examples of the acid anhydride-based curing agent include anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, Anhydride, hydamic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Alicyclic carboxylic anhydrides such as water, chlorendic acid and methylendomethyltetrahydrophthalic anhydride; Anhydrides of aliphatic carboxylic acids such as dodecenyl succinic anhydride, polyazelaic anhydride, polysubacic anhydride, and polydodecanedioic anhydride; Aromatic carboxylic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol anhydride trimellitic acid and biphenyltetracarboxylic acid anhydride.

Examples of the phenolic curing agent include bisphenol A, tetrabromo bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenyl phenol, 2,2'-methylene-bis (4- Butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4'- , 3-tris (2-methyl-4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, diisopropylidene skeleton; Phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; Polyphenol compounds such as phenolated polybutadiene, novolac resins prepared from various phenols such as phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S and naphthol : Various novolak resins such as phenol novolak resin containing xylylene skeleton, phenol novolac resin containing dicyclopentadiene skeleton, and phenol novolac resin containing fluorene skeleton.

Of the commonly used curing agents such as acid anhydride, phenol or amine, acid anhydride type curing agents are preferable, and more preferable examples are methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexa Hydrophthalic anhydride. More preferred are methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

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

As described above, a cationic curing catalyst such as a thermal latent cationic curing catalyst or a photonic latent cationic curing catalyst is preferably used as the curing agent. As a result, the curing reaction can be progressed favorably in a short time, and the cured product can be formed promptly, thereby further improving the production efficiency. In addition, a cured product having higher heat resistance and releasability can be obtained, and the resin composition can be stably present as a single-liquid composition (one-liquid property) excellent in handling properties. Thus, a form in which the resin composition further contains a cationic curing catalyst is also one of the preferred embodiments of the present invention. Among them, it is preferable to use at least a thermal latent cationic curing catalyst.

Further, the cationic curing catalyst is a catalyst for accelerating the cationic curing reaction and has a different action from the curing accelerator in the acid anhydride curing reaction, for example.

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

As the cationic curing catalyst, compounds represented by the following general formula (2):

[Chemical Formula 9]

(Wherein R is the same or different and represents a hydrocarbon group which may have a substituent group, x represents an integer of 1 to 5, and is the same or different, and represents the number of fluorine atoms bonded to the aromatic ring. Is an integer of 1 or more and b is an integer of 0 or more and satisfies a + b = 3) and a Lewis base.

This makes it possible to employ cationic curing as a curing method. Therefore, compared with the case of employing addition curing such as, for example, acid anhydride curing, the obtained cured product is required in optical applications such as heat resistance, chemical stability, Is more excellent. Also, as compared with the case of using a conventional cationic curing catalyst such as an antimony-based sulfonium salt, coloring due to heat (curing, film formation, use environment) is reduced and durability A more excellent cured product can be obtained.

The degree of the presence or absence of coloration of the cured product based on the catalyst to be used can also be confirmed from the change in the transmittance at 400 nm. That is, by measuring the transmittance of the cured product to 400 nm, it is possible to evaluate the presence or absence of coloration of the cured product.

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 it is preferably an alkyl group, an aryl group or an alkenyl group. The alkyl group, aryl group or alkenyl group may be an unsubstituted group, and one or two or more hydrogen atoms may be replaced by other organic groups or halogen atoms. 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 is 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, and is 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. x is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.

Also, a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, the Lewis acid is a fluorine-bonded aromatic ring bound to at least one boron atom. a, more preferably 2 or more, and particularly preferably 3, that is, a form in which three aromatic rings to which a fluorine atom is bonded are bonded to a boron atom.

Specific examples of the Lewis acid include tris (pentafluorophenyl) boran (referred to as "TPB"), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, tris Fluorophenyl) borane and the like are preferable. Of these, TPB is more preferable because it can improve the heat resistance, wet heat resistance, and temperature impact resistance of the cured product. Also, among the cationic curing catalysts, those containing TPB as a Lewis acid are also referred to as &quot; TPB catalysts &quot;.

The Lewis base is not limited as long as it is capable of coordinating with the Lewis acid, that is, capable of forming a coordination bond with the boron atom of the Lewis acid, and can be any of those conventionally used as a Lewis base. Are 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 coordination bond by donating a non-covalent electron pair of a nitrogen atom, phosphorus atom or sulfur atom to the boron atom of the Lewis acid. The Lewis base is more preferably a compound having a nitrogen atom or phosphorus atom.

Preferable examples of the compound having a nitrogen atom include amines (monoamine, polyamine), ammonia, and the like. More preferably, it is an amine having a hindered amine structure, an amine having a low boiling point, ammonia, more preferably a polyamine having a hindered amine structure, and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, oxidation of the cured product can be prevented by the radical capturing effect, and the resultant cured product is more excellent in heat resistance (wet 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 low water absorption and excellent UV radiation resistance. Ammonia or a low boiling point amine is volatilized in the curing process, the salt structure derived from ammonia or an amine having a low boiling point in the final molded product (cured product) is reduced, and therefore it is presumed that the water absorption rate of the cured product can be reduced. Particularly, ammonia is preferable because the above-mentioned effect is excellent.

As described later, it is preferable in the present invention to contain a nitrogen-containing compound having a boiling point of 120 캜 or less, and therefore it is also preferable to use a nitrogen-containing compound having a boiling point of 120 캜 or lower 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 forming the cationic curing catalyst.

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

The amine having a low boiling point is preferably an amine having a boiling point of 120 占 폚 or lower, more preferably 80 占 폚 or lower, even more preferably 50 占 폚 or lower, still more preferably 30 占 폚 or lower Lt; / RTI &gt; Specific examples thereof include primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and ethylenediamine; Secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine and piperidine; And tertiary amines such as trimethylamine and triethylamine.

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

The sulfur atom-containing compound is preferably thiol and sulfide. Specific examples of the thiol include methylthiol, ethylthiol, propylthiol, hexylthiol, decanethiol, phenylthiol and the like. Specific examples of the sulfide include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, and methoxymethylphenyl sulfide.

In the cationic curing catalyst comprising the Lewis acid and the 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. In other words, either of Lewis acid and Lewis base (in terms of base weight) may be contained in excess of the theoretical amount (equivalent). Specifically, the ratio of the mixture ratio of Lewis acid and Lewis base in the cationic curing catalyst to the atomic number n (b) of the Lewis base point to the atomic number n (a) of boron which is a Lewis acid point (n ) / n (a)), and it functions as a cationic curing catalyst even if it is not 1 (stoichiometric ratio). Here, the ratio n (b) / n (a) in the cationic curing catalyst affects the storage stability of the resin composition, the cationic curing properties (curing rate, curing degree of the cured product, etc.).

When the Lewis base has two Lewis base points in the molecule, such as diamines, the ratio n / (b) / (b) of the Lewis base to the Lewis acid constituting the cationic curing catalyst is 0.5, n (a) = 1 (stoichiometric ratio). In this way, the ratio n (b) / n (a) is calculated.

From the viewpoint of the storage stability of the resin composition containing the cationic curing catalyst, when the Lewis acid is excessively present in excess of the Lewis base, the storage stability may not be sufficient. Therefore, , 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 cationic curing property, if the Lewis base is excessively excessive, the low temperature curing property of the cured product may not be sufficient. Therefore, in order to obtain a composition having better cationic curing property, n (b) / n ) Is preferably 100 or less. For the same reason, it is more preferably 20 or less, still more preferably 10 or less, particularly preferably 5 or less.

The above-mentioned ratio n (b) / n (a) also includes a structure in which the Lewis base is a compound having a nitrogen atom, a sulfur atom or a phosphorus atom, and is a structure having two or more carbon atoms (B) / n (a) in view of the high acid-dissociation constant and high steric hindrance from the viewpoint of the cationic curing property when the organosilicon compound has a structure in which two or more organic groups are bonded through a carbon atom ) Is preferably 2 or less. More preferably not more than 1.5, still more preferably not more than 1.2. For example, in a structure such as a hindered amine, this range is preferable.

When the Lewis base is a nitrogen-containing compound having a boiling point of 120 占 폚 or less (particularly, ammonia or a low boiling point amine having a small steric hindrance), the ratio n (b) / n (a) A larger one is preferable. More preferably not less than 1.001, still more preferably not less than 1.01, particularly preferably not less than 1.1, and most preferably not less than 1.5.

The form of the Lewis acid and the Lewis base constituting the cationic curing catalyst is not particularly limited, but it is preferable that the Lewis base exists in the Lewis acid in a state having electronic interaction. More preferably, at least a part of the Lewis base is added to the Lewis acid, more preferably the Lewis base equivalent to the equivalent amount to at least Lewis acid existing in the Lewis acid. When the ratio of the presence of the Lewis base to the Lewis acid is less than or equal to the equivalent, that is, when the ratio n (b) / n (a) is 1 or less, a form in which substantially all of the Lewis base present is formed in the Lewis acid Do. On the other hand, in the form in which the Lewis base is contained excessively (more than the equivalent amount), it is preferable that the Lewis base is in the equivalent coordination with the Lewis acid and the excess Lewis base is present in the vicinity of the complex.

Specific examples of the cationic curing catalyst composed of a Lewis acid and a Lewis base represented by the above general formula (2) include TPB / alkylamines such as TPB / monoalkylamine complex, TPB / dialkylamine complex and TPB / trialkylamine complex Amine complexes, organic borane / amine complexes such as 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, TPB / monoarylphosphine complex; Organic borane / thiol complexes such as TPB / alkyl thiol complex; Organic borane / sulfide complexes such as TPB / diaryl sulfide complexes, TPB / dialkyl sulfide complexes and the like. Among them, TPB / alkylamine complex, TPB / hindered amine complex, TPB / NH ₃ complex, TPB / phosphine complex are preferable.

In the resin composition, the content of the cationic curing catalyst is an amount of an effective component (a solid content conversion amount not containing a solvent, etc.). The cationic curing catalyst comprising a Lewis acid represented by the general formula (2) , 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 cationic curing compound contained in the resin composition. As a result, the curing rate can be further increased, productivity can be further improved, and the possibility of coloring during curing, heating, and use can be further suppressed. For example, when a laminate obtained by using the above resin composition is reflow-mounted, heat resistance of 200 占 폚 or more is required, so that it is preferably 10 parts by mass or less from the viewpoint of colorlessness and transparency. More preferably not less than 0.05 parts by mass, more preferably not less than 0.1 parts by mass, particularly preferably not less than 0.2 parts by mass, more preferably not more than 5 parts by mass, further preferably not more than 3 parts by mass, 2 parts by mass or less.

- nitrogen containing compounds -

It is preferable that the resin composition further contains a nitrogen-containing compound having a boiling point of 120 占 폚 or less (also simply referred to as "nitrogen-containing compound"). Thus, the resin composition is excellent in storage stability due to the presence of the nitrogen-containing compound at the time of storage (storage) or transportation, while part or all of the nitrogen-containing compound is volatilized during curing, It is possible to easily obtain a cured product excellent in appearance and high in appearance. As described above, a form in which the resin composition further contains a nitrogen-containing compound having a boiling point of 120 캜 or lower is also one of the preferred embodiments of the present invention.

The boiling point of the nitrogen-containing compound is preferably 100 占 폚 or lower, more preferably 80 占 폚 or lower, still more preferably 50 占 폚 or lower, particularly preferably 30 占 폚 or lower, Preferably 5 DEG C or less.

The boiling point of the nitrogen-containing compound may be adjusted by adjusting 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 or the like such as the spin coating method) A (占 폚), it is preferably not more than (A + 80) 占 폚. That is, for example, when A = room temperature of 25 占 폚, the boiling point of the nitrogen-containing compound is preferably 105 占 폚 or lower. This makes it possible to more fully exert the effect of using the above-mentioned nitrogen-containing compound. (A + 60) ° C or lower, more preferably (A + 30) ° C or lower, particularly preferably (A + 10) ° C or lower.

Specific examples of the nitrogen-containing compound include ammonia (boiling point: -33.34 占 폚); Monoethylamine (boiling point: 16.6 占 폚), monopropylamine (boiling point: 48 占 폚), monobutylamine (boiling point: 78 占 폚), monopentylamine, ethylenediamine (boiling point: 117 &lt; 0 &gt;C); Dimethylformamide (boiling point: 36-37 占 폚), methylpropylamine (boiling point: 78 占 폚), methylbutylamine (boiling point: : 90 - 92 캜), ethylpropylamine (boiling point: 80 - 85 캜), and piperidine (boiling point: 106 캜); Tertiary amines such as trimethylamine (boiling point: 2.9 ° C) and triethylamine (boiling point: 89.7 ° C) are preferred. Above all, ammonia is particularly preferable because it can further manifest the above-mentioned effects. 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 based on 100 parts by mass of the total amount of the curable compound. More preferably 0.01 to 5 parts by mass. In the present invention, it is also preferable to use a cationic curing catalyst comprising a Lewis acid represented by the above-mentioned general formula (2) and a nitrogen-containing compound as a Lewis base. In this case, the content ratio of the nitrogen-containing compound is desirably set appropriately so as to be in the preferable range of the above-mentioned ratio n (b) / n (a).

- Coupling agent -

The resin composition preferably further contains a coupling agent. By including the coupling agent, the heat resistance of the resin composition and the cured product (laminate) can be improved significantly, and the adhesion can be improved. Therefore, peeling and the like can be suppressed in the use in the solder reflow step and the wet heat environment.

The coupling agent preferably contains, for example, silicon, zirconia, titanium and / or aluminum as the central metal, and among these, it is preferable to have silicon as a central metal. More preferred is a silane coupling agent. By using a silane coupling agent, it is possible to further improve the resistance to humidity and humidity. Thus, the form of the resin composition further containing a silane coupling agent is one of the preferred embodiments of the present invention.

The coupling agent is also preferably a reactive group having a vinyl group, a (meth) acryl group, an oxirane group (oxirane ring), an amino group, a mercapto group, an isocyanate or the like. Among them, those having an oxirane group as a reactive group are preferable.

As the coupling agent, for example, a silane coupling agent such as Z-6040 or Z-6043 manufactured by Toray Dow Corning Inc. is preferably used.

In the resin composition, the content of the coupling agent is preferably 1 to 80 parts by mass based on 100 parts by mass of the total amount of the curable resin (curable compound). As a result, the above-mentioned effect of the coupling agent can be further exerted. More preferably 5 to 50 parts by mass, and still more preferably 10 to 30 parts by mass.

The content of the silane coupling agent in the total amount of 100 mass% of the coupling agent is preferably 50 to 100 mass%. More preferably from 70 to 100% by mass, still more preferably from 90 to 100% by mass, and particularly preferably 100% by mass.

-menstruum-

It is preferable that the resin composition further contains a solvent. As a result, a resin composition having high fluidity can be obtained, which 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; And ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate. These solvents may be used alone or in combination of two or more.

When the solvent is contained, the content thereof is preferably 10 parts by mass or more based on 100 parts by mass of the total amount of the curable compound (resin component). As a result, the resin composition can exert more excellent flowability as a material for forming a layer on a substrate (preferably, a transparent inorganic material layer). 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 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, and still more preferably 1,000 parts by mass or less.

By the way, the solvent can sufficiently dissolve, for example, other components (for example, a curable compound or a dye); The film thickness unevenness is small when the solution is coated on the substrate; Does not cause surface roughness caused by dolbis or the like even when heated to advance the hardening of the coat film; The strength of the film is not lowered due to the curing inhibiting factor; (For example, a curing compound, a coloring matter, a curing catalyst or the like) in the resin composition to be used, on the basis of such conditions, It is preferable to select an appropriate solvent depending on the type of the solvent.

As a result of conducting studies by the present inventors, it has been found that, as a solvent, acetone,? -Butyrolactone, diethyldiglycol, cyclohexanone, methylethylketone, methylisobutylketone, propylene glycol monomethylether acetate (PGMEA) Propylene glycol monomethyl ether (PGME), tetrahydrofuran (THF), or the like is used, a good film is formed. Particularly, PGMEA has a high boiling point even at a relatively high boiling point of 145 占 폚. Therefore, when PGMEA is used as a main component of the solvent, the film thickness unevenness is small, there is no surface roughness by the dolbid, (Resin solution) containing PGMEA was found to be a solution capable of producing a stable and high-quality coating film using the resin composition (resin solution) containing PGMEA. It has been found that almost the same effect is exhibited even for a solvent having a relatively large molecular structure in which the dielectric constant other than PGMEA is less than 10 and the molecular weight is more than 100. As described above, 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 ("a solvent having a dielectric constant of less than 10 and a molecular weight of more than 100" Quot;) is also one of the preferred forms of the present invention.

The present inventors have also found that another problem arises when a solvent A such as PGMEA is used together with a coloring matter having a high degree of crystallization such as the above-described coloring matter?. That is, in the case of using the solvent A, the probability of association of the high coloring matter molecules with each other is high, and when the degree of association becomes a certain value or more, it is crystallized and it is found that the coloring matter precipitates in the solution. If precipitation into a solution occurs, there is a possibility that the coating becomes a foreign matter at the time of coating, and thus the quality can not be made higher. In addition, since the coloring matter concentration also changes, stable production may become difficult.

Thus, as a result of further studies, it has been found that when a solvent A is used as a main solvent and a dye having a high recurrence such as, for example, a dye β is used in combination, a solvent having a dielectric constant of 10 or more and / (Hereinafter, referred to as &quot; a solvent having a dielectric constant of 10 or more &quot; is referred to as &quot; solvent B1 &quot;, 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 is possible to inhibit the precipitation of the dye β. When the solvent B is used, the crystallization of a coloring matter having a high crystallinity is inhibited regardless of whether or not the solvent A is used. Particularly, by adding the solvent B so that the content of the solvent B is 5% by mass or more with respect to 100% by mass of the total solvent component, the crystallization of the coloring matter with higher crystallinity is further suppressed and the solution becomes more stable coating.

When a solvent B1 having a relatively high dielectric constant of 10 or more is used, not only dye molecules are associated with each other, but also association with solvent molecules is formed. In this case, precipitation can be suppressed because the crystallinity is not increased. When a solvent B2 having a relatively small structure such as a molecular weight of 100 or less is used in a solvent having a dielectric constant of 5 or more and less than 10, the solvent is incorporated between dye molecules to form a coloring matter and a solvent, , It is possible to suppress the crystallinity from becoming large and to suppress precipitation. 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 for the solvent to intercalate between coloring matter molecules, so that association of coloring matter molecules progresses and crystals are sometimes precipitated. Further, in the case of a solvent having a dielectric constant of less than 5, even if the molecular weight is 100 or less, even if it can fit in between the molecules, since the force for forming associations with the dye molecules is weak, the association of the dye molecules progresses, And there is a case where precipitation occurs.

On the other hand, when the content ratio of the solvent B (that is, the solvent B1 and / or the solvent B2) is 5% by mass or more based on 100% by mass of the total solvent component, the proportion of the solvent molecules forming association with the pigment molecule becomes large, Is further suppressed, and it is possible to further prevent the precipitation of the dye. Since the effect of suppressing the precipitation of the coloring matter is higher as the content ratio of the solvent B is higher, the content ratio of the solvent B may be increased. More preferably, the solvent B contains 50% by mass or more, and more preferably 100% by mass, of the solvent component with respect to 100% by mass of the total solvent component.

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 is a solvent B1 having a dielectric constant of 10 or more, and / or a form containing 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. The resin composition further contains a solvent, and the solvent includes 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, The content of the solvent B2 is 5% by mass or more with respect to 100% by mass of the total solvent component, which is one of the preferred forms of the present invention. The resin composition further contains a solvent, and the solvent has a dielectric constant of less than 10 and a molecular weight of more 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, And a solvent B2 having a molecular weight of 100 or less and a content ratio of the solvent B1 and the solvent B2 of 5 mass% or more with respect to 100 mass% of the total solvent component is also one of the preferred embodiments of the present invention. The resin composition as described above is preferable as an ink solution or the like for a photo-selective transmission filter (for example, an infrared absorption filter).

- Optical sensitizer -

The resin composition may further contain one or more photo-sensitizers, if necessary. Particularly, in the case of performing the above-mentioned curing by irradiation with active energy rays, it is preferable to use a photo-sensitizer in addition to the photo-polymerization initiator.

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

When the photosensitizer is contained, the content thereof is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the curable resin (curable compound). More preferably 0.5 to 10 parts by mass.

- Curing accelerator -

The resin composition may further contain one or more curing accelerators, if necessary. Particularly, when a commonly used curing agent such as the aforementioned acid anhydride-based, phenol-based or amine-based curing agent is used, it is preferable to use a curing accelerator in combination.

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

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

Examples of the organic acid salts of the various imidazoles include salts of organic acids such as imidazoles and polyvalent carboxylic acids. The imidazoles include, for example, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl- 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl- Cyanoethyl-2-undecylimidazole, and the like. Preferable imidazoles include, for example, imidazoles similar to the phenyl group-substituted imidazoles in aromatic compounds having a tertiary nitrogen to be described later.

Examples of the polycarboxylic acids include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and naphthalenedicarboxylic acid; aliphatic polycarboxylic acids such as maleic acid and oxalic acid And preferable examples of the polyvalent carboxylic acid include aromatic polyvalent carboxylic acids such as terephthalic acid, trimellitic acid and pyromellitic acid. Preferable examples of the salts of organic acids such as imidazoles and polyvalent carboxylic acids include polyvalent carboxylic acid salts of imidazoles having substituents at the 1-position. More preferably trimellitic acid salt of 1-benzyl-2-phenylimidazole.

Examples of the aromatic compounds having tertiary nitrogen include, for example, 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, Phenylimidazole, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1- Nonyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like. Preferably imidazoles having an aromatic substituent at the 1-position, more preferably 1-benzyl-2-phenylimidazole. Examples of tertiary amino group-substituted phenols include phenols having 1 to 3 di (C1-C4) alkylamino (C1-C4) alkyl groups such as 2,4,6-tri .

Particularly preferable curing accelerators among the curing accelerators include phenol salts of 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene- Benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole, Triphenyl phosphonium bromide, and triphenylphosphine-toluene bromide.

When the curing accelerator is contained, the content thereof is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the curable resin (curable compound). More preferably 0.03 to 3 parts by mass.

- Flexible components -

The resin composition preferably also contains a component having flexibility (referred to as &quot; flexible component &quot;). This makes it possible to provide a resin composition having a sense of unity, that is, a resin having a high toughness. The hardness of the resin layer is further improved by containing the flexible component.

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

Examples of the flexible component include compounds having an oxyalkylene skeleton represented by - [- (CH ₂ ) _n --O--] m- (n is 2 or more, m is an integer of 1 or more, preferably n Is an integer of 2 to 12 and 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), and for example, an epoxy compound containing an oxybutylene group YL-7217, epoxy equivalent 437, liquid epoxy compound (10 占 폚 or higher) manufactured by Japan Epoxy Resin Co., Ltd.). As other preferable flexible components, liquid rubbers such as liquid nitrile rubbers, polymer rubbers such as polybutadiene, and particulate rubbers having a particle diameter of 100 nm or less are preferable.

Among them, the above-mentioned flexible component is preferably a compound containing an epoxy group, more preferably an oxybutylene group (- [- (CH ₂ ) ₄ -O-] m- / RTI &gt;

When the flexible component is contained, the content thereof is preferably 40% by mass or less based on 100% by mass of the total amount of the curable compound and the flexible component. More preferably 30% by mass or less, further preferably 20% by mass or less. Further, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and further preferably 0.5 mass% or more.

- Other ingredients -

The resin composition for laminating may further contain a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, a colorant, a colorant, a colorant, An antioxidant, an ultraviolet absorber, an IR cutter, a light stabilizer, a plasticizer, a nonreactive compound, a chain transfer agent, an anaerobic polymerization initiator, a polymerization inhibitor, an inorganic filler, an organic filler, Antifogging agents, antifogging agents, anti-fogging agents, anti-fouling agents, antistatic agents, antistatic agents, anti-fogging agents, antistatic agents, antistatic agents, antifoaming agents, antifoaming agents, leveling agents, wetting and dispersing agents, (Electrostatic assistant), and the like.

Since the resin composition contains an inorganic filler, it is possible to reduce the coefficient of thermal expansion, and it is possible to suppress the expansion due to heat in the solder reflow step, the inorganic oxide deposition step, and the like. As the inorganic filler, it is preferable to blend nanoparticles from the viewpoint that transparency is not impaired, and it is preferable to contain silica, titanium oxide, zinc oxide, and zirconia having a particle diameter of 40 nm or less. For example, MEK-ST manufactured by Nissan Chemical Industries, Ltd. and the like are preferably used.

In the resin composition, the number of foreign matters having a particle diameter of 10 占 퐉 or more contained in 1 cm3 of the resin composition is preferably 1,000 or less, more preferably 100 or less, and still more preferably 10 or less.

The foreign matters contained in the resin composition can be removed by filtration when preparing the resin composition.

- Preparation method -

The method of preparing the resin composition for lamination of the present invention is not particularly limited and can be obtained by mixing the components in a usual manner. When the component-containing components are mixed, the respective components or the mixture may be heated and mixed so as to have a uniform composition, if necessary. The heating temperature is not particularly limited as long as it is not more than the decomposition temperature of the curable resin (curable compound) or not more than the reaction temperature, but is preferably 140 to 20 占 폚, more preferably 120 to 40 占 폚 to be.

-Viscosity-

The resin composition preferably has a viscosity of 10000 Pa 占 퐏 or less. This makes it possible to obtain a film having excellent processing characteristics and having a smooth surface at the time of coating, for example. More preferably 1000 Pa 占 퐏 or less, even more preferably 200 Pa 占 퐏 or less, still more preferably 10000 mpa 占 퐏 or less, particularly preferably 100 mpa 占 퐏 or less, and most preferably 50 mpa 占 퐏 s or less. Further, it is preferably 0.01 mPa s or more, more preferably 0.1 mPa s or more.

The viscosity can be evaluated by using an E-type viscometer (manufactured by Toray Industries, Inc.) for the resin composition. The value of the viscosity is preferably a value evaluated under the condition of 25 캜.

- Curing method -

The curing method of the resin composition is not particularly limited, and various methods such as heat curing and photo curing (curing by irradiation with active energy ray) can be preferably used. The heat curing furnace is preferably cured at about 30 to 400 DEG C, and the photocuring furnace is preferably cured at 10 to 10,000 mJ / cm &lt; 2 &gt;. The curing may be carried out in one step or in two steps such as primary curing (pre-curing) and secondary curing (final curing).

Hereinafter, the case of performing the two-step curing will be described in detail.

As the two-step curing method, the first step corresponding to the first curing is a step of photo-curing the resin composition at 10 to 100,000 mJ / cm 2 or thermally curing at 80 to 200 ° C, And a second step corresponding to secondary curing which thermally cures the obtained cured product at a temperature higher than 200 ° C and lower than 500 ° C.

In the first step, in the case of thermal curing, the curing temperature is preferably 80 to 200 캜. And more preferably 100 ° C or more and 160 ° C or less. The curing temperature may be changed stepwise within a range of 80 to 200 占 폚.

The curing time in the heat curing step is preferably, for example, 10 minutes or less, more preferably 5 minutes or less, and still more preferably 3 minutes or less. It is preferably at least 10 seconds, more preferably at least 30 seconds.

The thermosetting step may also be carried out under an atmosphere of air or an inert gas such as nitrogen, under a reduced pressure, or under a pressurized atmosphere. It is also possible to combine photo-curing (curing by irradiation with active energy rays).

In the curing method, in the second step, it is preferable that the cured product obtained in the first step is thermally cured at a temperature higher than 150 ° C and lower than 500 ° C. The lower limit of the curing temperature is more preferably 200 DEG C or higher, more preferably 230 DEG C or higher, still more preferably 250 DEG C or higher, still more preferably 300 DEG C or higher, particularly preferably 330 DEG C or higher, 350 ° C or higher. The upper limit is more preferably 400 DEG C or less. The curing temperature may be changed stepwise within a temperature range of 150 ° C to 500 ° C.

The curing time in the second step is not particularly limited and may be a time for which the curing rate of the resulting cured product becomes sufficient, but is preferably 10 minutes to 30 hours, for example, considering the production efficiency. More preferably from 30 minutes to 10 hours.

The second step may also be carried out under any atmosphere of air or an inert gas atmosphere such as nitrogen. In particular, it is preferable to carry out the second step under an atmosphere having a low oxygen concentration. For example, it is preferable to carry out the reaction in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably not more than 3% by volume, even more preferably not more than 1% by volume, particularly preferably not more than 0.5% by volume, most preferably not more than 0.3% by volume.

By carrying out the first step, cohesion, cratering, etc. of the coating on the coated substrate can be suppressed. Further, by carrying out the second step, the heat resistance to the reflow step and the deposition step can be improved.

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

As another curing method, it is also preferable to use one-step curing. In particular, when the resin composition for laminating according to the present invention contains a nitrogen-containing compound having a boiling point of 120 캜 or less, since the curing property is particularly excellent, the curing process as a preliminary curing is not required, It is possible to efficiently give a cured product having a sufficiently excellent appearance. Therefore, in this case, the process can be shortened by omitting the photo-curing step, as compared with, for example, the two-step curing of photo-curing and thermosetting, so that the productivity and workability of the cured product are excellent.

As the curing method by the one-step curing, the heat curing method is particularly preferable. The thermosetting is preferably performed at a temperature of about 20 to 400 DEG C, and may be changed stepwise within this temperature range.

The curing time in the one-stage curing process is not particularly limited, but may be a time period during which the curing rate of the resulting cured product becomes sufficient. However, considering the production efficiency, the curing time is preferably 10 minutes to 30 hours, for example. More preferably from 30 minutes to 10 hours.

The one-stage curing process can be carried out in any atmosphere of air or an inert gas atmosphere such as nitrogen. Particularly, it is preferable to conduct it in an atmosphere having a low oxygen concentration. For example, in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably not more than 3% by volume, even more preferably not more than 1% by volume, particularly preferably not more than 0.5% by volume, most preferably not more than 0.3% by volume.

As described above, the resin composition for lamination of the present invention can impart a cured product excellent in heat resistance, heat and humidity resistance, resistance to thermal shock, and light resistance. Therefore, when 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, reduced visible light transmittance and sufficiently suppressed coloring, The resin composition of the present invention and the laminate obtained by using the resin composition of the present invention are useful as members of various elements (for example, optical materials such as optical selective permeation filters typified by IR cut filters). In addition, various devices such as a mobile phone, a television, a PC, and a vehicle application have a flow of adopting a solder reflow process for reasons such as simplification of production process and cost reduction. As a result, The resultant laminate is excellent in the optical characteristics such as the optical characteristics of members of various elements employing a solder reflow process (for example, optical components such as a light-selective filter typified by an IR cut filter, etc.) Materials). In particular, when a transparent inorganic material layer is used as the substrate, cracks, chipping and warping can be suppressed, and a laminate having excellent heat resistance can be obtained. Thus, a cured product (laminate) obtained by forming a layer made of the 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 a &quot; laminate &quot;) has a layer (also referred to as a &quot; resin layer &quot;) composed of the 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 be provided on only one side of the base material or on both sides of the base material. The base material and the resin layer may each be a single layer structure or a multilayer structure.

The laminate is obtained by forming a resin layer on a substrate. As a method of forming the laminate, a method of forming the resin composition on a substrate and curing it is preferable. That is, a method of forming a coating film on a substrate is preferable. The resin composition for lamination used in the laminate of the present invention is preferably for coating.

Here, the term &quot; having a resin layer on a substrate &quot; includes not only a form in which a resin layer is in direct contact with a substrate but also a form having a resin layer via other constituent members present on the substrate. The same is true for "forming a resin layer on a substrate", and includes not only a case where a resin layer is directly formed on a substrate but also a case where a resin layer is formed through another constituent member existing on the substrate . The same is applied to "coating a resin composition on a substrate", and includes not only a case where the resin composition is applied directly to a substrate but also a case where the resin composition is applied through other constituent members present on the substrate .

In the case of applying the resin composition through the other constituent members, the surface treatment of the constituent member is performed by a liquid material containing a metal oxide precursor such as a silane coupling agent, for example, , It is preferable to apply the resin composition. This makes it possible to further suppress, for example, peeling and the like in use in the solder reflow process and the wet heat environment. As the silane coupling agent, a compound having an oxirane ring is preferable, and Z-6040 and Z-6043 manufactured by Toray Dow Corning Inc. are preferably used.

As a method of forming a coating film composed of a resin composition on the substrate (or other constituent member), a solution coating method is preferable. Specifically, conventionally used methods such as a spin coating method, a casting method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a screen printing method, a flexographic printing method and an inkjet method can be mentioned. Among them, the spin coating method is preferable from the viewpoint of reducing the deviation of the coat layer on the substrate. When a coating film is formed by the spin coating method, it is preferable to dry the solvent while rotating the transparent inorganic material layer (or another constituent member) at about room temperature (25 캜) for about 10 to 60 seconds at 500 to 4000 rpm. It is also preferable to carry out by the ink jet method from the viewpoint of reducing the deviation while obtaining a sample other than an annular sample which is difficult to obtain in a spin coat. It is preferable to perform photo-curing and / or thermosetting after spin coating or after ink-jetting, if necessary.

One of the preferable forms of the laminate is a form having 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. Specific examples of such a laminated body include a phthalocyanine-based dye having an absorption maximum in a wavelength range of 650 to 680 nm and an absorption characteristic of having only one absorption maximum in a wavelength range of 400 to 680 nm . With this configuration, it is possible to produce a laminate having high heat resistance, and it becomes possible to obtain a spectrum having an absorption maximum at 400 to 680 nm by combining with an inorganic reflective film or an inorganic interference film. As a result, the laminate can exhibit light selectivity close to that of human eyes, resulting in a laminate which is very useful for image pickup device applications. In addition, when the above-described laminate is applied to an image pickup device application, generation of flare and ghost can be sufficiently suppressed, and the incident angle dependency which can be a problem in combination with a reflection film can be sufficiently reduced. The laminate preferably 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. Thus, the above effects can be further exerted.

Here, "having only one absorption peak at a wavelength range of 400 to 680 nm" means that only one peak (absorption maximum) at which the absorbance changes from increasing to decreasing at a wavelength range of 400 to 680 nm is observed . The peak having the peak of the absorption peak may be sharp or broad. In the latter case, a broad absorption peak may be formed by superimposing two or more sharp absorption peaks so that the absorbance changes from increasing to decreasing at a peak (absorption maximum).

It is preferable that the 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, excellent optical selectivity can be exhibited. The transmittance is more preferably not less than 83%, more preferably not less than 85%, particularly preferably not less than 87%, and most preferably not less than 89%.

It is preferable that the laminate further has a transmittance at a maximum absorption wavelength or a maximum absorption wavelength present in a wavelength range of 650 to 680 nm of 60% or less. , More preferably not more than 50%, further preferably not more than 40%, further preferably not more than 30%.

It is preferable that the laminate further has a higher absorbance at a longer wavelength side in a wavelength range of 600 to 680 nm. In other words, it is preferable that the transmittance is lower in the wavelength region of 600 to 680 nm and longer in the longer wavelength side. For example, when the transmittance is measured every 1 nm in the wavelength region of 600 to 680 nm, It is preferable not to exceed the transmittance at a wavelength longer than that. Thereby, since the transmittance spectrum becomes a smoother curve, it is possible to exhibit better optical selectivity.

In the present specification, the absorption characteristics and the transmittance of the laminate, the resin layer and the transparent inorganic material layer are measured using, for example, an absorbance meter (also referred to as a spectrophotometer, manufactured by Shimadzu Corporation, spectrophotometer UV-3100) Or by measuring the transmittance spectrum.

It is also preferable that the resin layer has the same characteristics as those of the above-described laminated body. In particular, it is preferable that the resin layer has a higher absorbance in a wavelength range of 600 to 680 nm and a longer wavelength side.

The thickness of the laminate is preferably 1 mm or less, for example. This makes it possible to fully meet the demand for downsizing of the image pickup device. More preferably 500 mu m or less, further preferably 300 mu m or less, particularly preferably 150 mu m or less, and most preferably 100 mu m or less. Further, it is preferably 30 m or more. More preferably at least 50 mu m.

As described above, 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.

<Description>

The base material of the laminate is not particularly limited, but it is preferable to use one or more materials such as an organic material, an inorganic material, an organic-inorganic composite material, and a metal material. Examples of the organic material or the organic-inorganic composite material include resin films made of these materials. Examples of the inorganic material include glass, quartz, and metal oxides.

It is preferable that the material of the substrate is a material having a flowability.

Of the above-described substrates, a transparent inorganic material is preferably used. That is, the substrate is preferably a layer made of a transparent inorganic material (referred to as a transparent inorganic material layer). As a result, cracks, chipping, and warpage can be further suppressed, and a laminate excellent in heat resistance can be obtained. A laminate obtained by forming a resin layer made of the resin composition on the transparent inorganic material layer as described above is one of the preferred embodiments of the present invention.

Examples of the transparent inorganic material include glass, quartz, and the like.

The transparent inorganic material may also be obtained by incorporating transition metal ions in a material for forming glass or quartz. The transition metal ions, as having a light absorption capacity is when normally used more than one or two or to be used as, for example, Ag ^+, Fe ^+, Co ^{2 +,} Ni ^{2 +,} Cu ^{2 +,} Zn ^{2 +} And the like. Further, the form in which the substrate is a glass or a quartz substrate is one of the preferred forms 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. , More preferably 85% or more, and even 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 占 퐉, for example. More preferably at least 50 mu m.

The substrate is also preferably treated with a coupling agent. As a result, the adhesiveness is further improved and it becomes possible to further suppress the peeling or the like in the use in the solder reflow process or the wet heat environment, for example.

Further, it is preferable that the reference column treated with the coupling agent and the substrate treated with the coupling agent.

Preferred examples of the coupling agent and the like are as described above, and it is preferable that the coupling agent contains silicon, zirconia, titanium and / or aluminum as the central metal. Among them, it is preferable to have silicon as a center metal. More preferred is a silane coupling agent.

As described above, the substrate is treated with a coupling agent, and the coupling agent containing silicon, zirconia, titanium and / or aluminum as a central metal is also a preferred embodiment of the present invention.

<Resin Layer>

The thickness of the layer (resin layer) composed of the resin composition for lamination is not particularly limited, but from the viewpoints of heat resistance and transparency at the time of film formation or reflow, and prevention of peeling and cracking at the interface due to thermal expansion, More preferably not more than 30 占 퐉, further preferably not more than 10 占 퐉, particularly preferably not more than 5 占 퐉, and most preferably not more than 2 占 퐉. From the viewpoint of preventing defects by making the film thickness sufficiently thicker than the general foreign body size, the concentration of the coloring matter dissolved in the resin composition is reduced, and from the viewpoint of suppressing the association or precipitation of the coloring matter, it is preferably 0.1 탆 or more, Is 0.5 m or more.

&Lt; UV cut layer >

It is also preferable that the laminate further has a UV (ultraviolet) cut layer. As a result, deterioration due to ultraviolet rays can be sufficiently suppressed, so that the weather resistance of the laminate can be remarkably improved. The form in which the laminate further has the UV cut layer is one of the preferred embodiments of the present invention.

It is preferable that the UV cut layer is disposed on the light incidence side of the laminate. In the laminate, the UV cut layer may be a single layer or two or more layers.

The UV-cut layer may be formed of, 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 region of 350 to 400 nm is preferable. Specifically, it is preferable to use a phthalocyanine dye having an absorption ability in a wavelength range of 350 to 400 nm. One or more of TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571 and TINUVIN 326 (manufactured by BASF) may be used, for example.

[Use of laminate]

The laminate of the present invention is particularly preferable for use in an imaging element. The resin composition for lamination of the present invention is also particularly preferable for use as an imaging element. Among them, it is preferable to use the above-mentioned laminate as a constituent material of the optical selective transmission filter. In this case, it is more preferable that the resin layer formed by the resin composition is used as a (near) infrared absorbing layer (also simply referred to as an absorbing layer) in the optically selective permeation filter. Such a photo-selective transmission filter including the laminate is also one of the present invention, and an image pickup device including the laminate is also included in the present invention. It is particularly preferable that the image pickup device includes a photo-selective transmission filter including the above-described laminate.

However, the resin composition for lamination and the laminate are not limited to the above-mentioned applications, and examples thereof include optical materials (members), mechanical parts materials, electric / electronic parts materials, automobile parts materials, But also for various uses such as a coating material and an adhesive material.

Hereinafter, the optical selective transmission filter and the imaging device will be described.

<Optical selective permeation filter>

The optically selective transmission filter of the present invention includes one or more of the above-described laminate, but may have one or more other layers as required. In the optically selective transmission filter, it is preferable to use the transparent inorganic material layer of the laminate as a substrate and the resin layer formed of the resin composition as an absorbing layer, respectively.

The optical selective transmission filter may have various other functions besides the function of selectively reducing the transmittance of a desired light. For example, in the case of the infrared cut filter, which is one of the preferred forms of the optical selective transmission filter, it is possible to improve the properties of the infrared cut filter such as the form having various functions other than the infrared cut such as the function of shielding ultraviolet rays, And the like.

In the case where the optical 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 may be formed directly on the laminate by, for example, CVD, sputtering, or vacuum evaporation, or may be obtained by bonding a functional material layer formed on the temporary substrate subjected to the release treatment to the laminate with an adhesive . Alternatively, a liquid composition containing a raw material may be applied to the laminate and dried to form a film. For example, as a countermeasure against deterioration of light in the absorbing layer, for example, the ultraviolet blocking layer may be formed by coating a liquid resin composition containing an ultraviolet absorbing agent on an absorbing layer formed on a substrate (for example, a glass substrate) It is also preferable to form a resin layer containing a polyolefin.

The optical selective transmission filter selectively reduces the transmittance of light. The light to be reduced should be between 10 nm and 1000 nm, and may be selected according to the application to be used. An ultraviolet ray cut filter, an infrared ray / ultraviolet ray cut filter or the like can be used depending on the wavelength of the light to be reduced. Among them, the infrared ray light of 750 to 1000 nm (more preferably, the infrared ray of 650 to 1000 nm) And ultraviolet light having a wavelength of 200 to 350 nm, and transmits the other light. That is, the optical selective transmission filter of the present invention is preferably an infrared / ultraviolet cut filter.

The infrared cut filter may be a filter having a function of selectively reducing light having a wavelength (range) out of light having a wavelength of 650 nm to 10,000 nm which is an infrared region. The range of the selectively reduced wavelength is preferably 650 nm to 2500 nm, 650 nm to 1000 nm, or 800 nm to 1000 nm. Filters for selectively reducing at least one of the wavelengths in these ranges are also included in the infrared cut filter. It is more preferable that the range of the wavelength selectively reduced is from 650 nm to 1000 nm in the near infrared region.

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

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

In the mode in which the optical 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. It is also preferable that the transmittance of the light in the wavelength range of 480 to 550 nm in the visible light is 85% or more, more preferably 90% or more. Further, in the infrared cut filter, the transmittance of the other wavelengths (other than the infrared region) is more preferably 85% or more, and still more preferably 90% or more. That is, the optical selective transmission filter is preferably an infrared cut filter having a light transmittance of 85% or more at a wavelength of 480 to 550 nm and a transmittance of 5% or less at 750 to 1000 nm.

The transmittance can be measured using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation).

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

In the mode in which the optical 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 optical selective transmission filter, a reflection film (preferably a (near) infrared reflective film) is preferably formed on at least one surface of the laminate. That is, it is preferable that the filter is a photo-selective transmission filter including the laminate and the reflective film. With such a configuration, the dependence of the incident angle on the light blocking property can be sufficiently reduced. In this case, the arrangement (configuration) of the reflective film in the optical selective transmission filter is not particularly limited.

The reflective film is preferably an inorganic multilayer film capable of controlling the refractive index of each wavelength from the viewpoint of excellent heat resistance. The inorganic multilayer film is preferably a refractive index control multilayer film formed by alternately laminating a low refractive index material and a high refractive index material on a surface of a substrate, an absorbing layer, and other constituent members by a vacuum evaporation method, a sputtering method, or the like. The reflective film is also preferably a transparent conductive film. As the transparent conductive film, a transparent conductive film as a film for reflecting 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 obtained by alternately laminating a dielectric layer A and a dielectric layer B having a refractive index higher than that of the dielectric layer A.

As the material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be usually used. Preferably, the material has a refractive index in the range of 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 the 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, tin oxide, cerium oxide, and the like in a small amount, such as titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, And the like.

The thickness of each of the layers of the dielectric layer A and the dielectric layer B is preferably 0.1 to 0.5 [lambda] when the wavelength of the light to be blocked is lambda (nm). When the thickness is out of the above range, the product (nxd) of the refractive index (n) and the film thickness (d) greatly differs from the optical film thickness calculated by? / 4, There is a possibility that control for blocking and transmission of a specific wavelength can not be performed.

The dielectric layer A and the dielectric layer B are laminated by a CVD method, a sputtering method, a vacuum deposition method, or the like without any particular limitation as long as the dielectric multilayered film obtained by laminating these material layers is formed. The dielectric multilayered film can be formed by alternately laminating.

It is preferable that the reflective film is a multilayer film as described above, but the number of the laminated films is preferably in the range of 10 to 80 layers as a total of the number of laminated reflective films of the imaging element. More preferably in the range of 25 to 50 layers.

The thickness of the reflective film is preferably 0.5 to 10 mu m. More preferably 2 to 8 占 퐉. It is also preferable that the total thickness of the optical selective transmission filter and the reflective film of the image pickup device is within the above range.

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

Here, when a resin layer which is a part of the laminate of the present invention is used as an absorbing layer of a reflection type optical selective transmission filter and a reflective film is formed on at least one surface of the laminate, it is preferable to form a multi- desirable. It is also preferable to form a resin layer formed of the resin composition after forming the reflective film.

It is preferable that the reflective film exists directly on the substrate or the resin layer constituting the laminate, or via another constituent member. For example, it is preferable to form a reflective film on these surfaces by using a CVD method, a sputtering method, a vacuum deposition method, or the like. Among them, it is preferable to use a vacuum deposition method. More preferably, a vapor deposition layer is formed on a temporary substrate such as a glass subjected to a release treatment, and the vapor deposition layer is transferred to a transparent inorganic material layer or a resin layer to form a reflective film. This makes it possible to reduce the possibility that the optical selective transmission filter is deformed and curled or cracked by vapor deposition. In this case, it is preferable to form an adhesive layer on the transparent inorganic material layer or the resin layer to which the vapor deposition layer is to be transferred.

As described above, the evaporation method is preferably used for forming the reflective film (preferably, the inorganic multilayer film), but the deposition temperature is preferably 100 ° C or higher. More preferably 120 ° C or higher, and even more preferably 150 ° C or higher. The deposition at such a high temperature has an advantage such that the inorganic film (inorganic film constituting the inorganic multilayer film) becomes dense and hardened, various resistance is improved, and the yield is improved. Therefore, it is very meaningful to use a transparent inorganic material layer, a resin component and a coloring matter resistant to such a deposition temperature. The use of the laminate of the present invention not only enables deposition at a high temperature but also a difference in coefficient of linear expansion from an inorganic film is small even when vapor deposition is performed at a low temperature. For example, in a heating environment in a manufacturing process such as a reflow process, The inorganic layer crack due to the difference in linear expansion coefficient does not occur in the use environment.

In general, a reflection type filter having a reflective film on one side or both sides of a substrate is excellent in blocking ability of light, but has an incident angle dependency (also referred to as a "viewing angle dependency") in which a reflection characteristic is changed by an incident angle of light Since the spectral transmittance curve is different, the improvement is a problem.

The incident angle dependency of the light shielding property can be measured by using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation), for example, with a transmittance (for example, 0 deg., 20 deg., 25 deg. The transmittance at an incident angle of 0 DEG is a transmittance measured by allowing light to enter from the thickness direction of the optical selective transmission filter and the transmittance at an incident angle of 20 DEG is a direction in which the optical selective transmission filter is inclined by 20 (The light transmittance is measured by allowing light to enter from the light source), and it can be evaluated by the amount of spectrum change.

The incident angle dependency of the light blocking property is required to be sufficiently reduced by absorption of the absorption layer, and it is preferable that the transmittance spectrum does not change or the degree of the change is small relative to the change of the incident angle. More specifically, it is preferable that the spectrum of the transmittance does not change in the region where the transmittance is 80% or more even when the incident angle of 0 DEG is changed to 20 DEG (more preferably, it is changed to 25 DEG), more preferably the transmittance 70 The spectrum of the transmittance does not change in the region where the transmittance is 60% or more, and more preferably the spectrum of the transmittance does not change in the region where the transmittance is 60% or more. Most preferably, the spectrum does not change in any transmittance region.

The optical selective transmission filter of the present invention is particularly excellent in light resistance, heat resistance and optical selectivity and can sufficiently reduce the dependence of the incident angle on the light blocking property. Therefore, for example, a heat ray cut filter And is also useful as a filter for correcting the visual sensitivity by blocking the light noise in the use of a camera module (also referred to as a solid-state image pickup device). Among them, the optically-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 cellular phone. That is, it is preferable that the optical selective transmission filter is an optical selective transmission filter for an imaging element. The imaging element including the optical selective transmission filter is also one of the preferred embodiments of the present invention.

<Image pickup device>

The imaging element of the present invention includes one or more of the above-described laminate, but may have one or more other members as required, as well. Normally, the image pickup element has a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) and a lens, and further includes an optical filter and an adhesive for fixing the member.

Preferably, the imaging element is a reflective film formed on at least one surface of the laminate. That is, it is preferable that the imaging element includes the laminate and the reflective film. With such a configuration, the dependence of the incident angle on the light blocking property can be sufficiently reduced. In this case, the arrangement (configuration) of the reflective film in the imaging device is not particularly limited. For example, a form in which a reflection film is directly formed on a lens, whereby the lens and the reflection film are integrated (also referred to as a form (a)); (Form (b)) having a reflective film as a constituent member independent of the lens by providing the imaging element with the optical filter including the reflective film.

The reflective film is as described above.

In the above mode (a), when the imaging element has two or more lenses, the number of lenses in which the reflection film is formed is not particularly limited.

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

The optical filter including the reflective film may be a light selective transmission filter having a laminate of the present invention and a reflective film, or may be an optical filter other than the optical selective transmission filter. In addition, the optical filter may have one or more optical filters including a reflection film, and the arrangement thereof is not particularly limited. For example, when the image pickup element has two or more lenses, the filter having the reflection film may be disposed between the lenses.

It is preferable that the reflective film is formed on one surface or both surfaces of the lens and / or one surface or both surfaces of the substrate.

Since the resin composition for lamination of the present invention has the above-described constitution, it is possible to provide a cured product (laminate) excellent in film-forming property, adhesive property, heat resistance, moisture resistance and thermal 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.

Fig. 1 shows a transmittance spectrum at each step in Example 7. Fig.
Fig. 2 shows the transmittance spectra at each step in Example 8. Fig.

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 specified, "part" means "part by mass" and "%" means "% by mass".

&Lt; Preparation of cationic curing catalyst >

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

According to the synthesis method described in WO 1997/031924, 255 g of isopara E solution having a content of TPB (tris (pentafluorophenyl) borane) of 7% was prepared. Water was added dropwise to this solution at 60 占 폚. White crystals precipitated from the middle of the dropwise addition. After the reaction solution was cooled to room temperature, the obtained slurry was suction filtered and washed with n-heptane. The obtained cake was dried under reduced pressure at 60 캜 to obtain 18.7 g of a white crystal, TPB-water complex (TPB-containing powder B). The complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were carried out on the complex after drying, but peaks other than TPB were not detected.

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

Preparation Example 2 (Preparation of cationic curing catalyst A)

2.1 g of? -Butyrolactone was added to 2 g of the TPB-containing powder B obtained in Preparation Example 1 (1.816 g (3.547 mmol) of TPB pure water and 0.184 g (10.211 mmol) of water) And mixed for 10 minutes. Thereafter, 0.778 g (0.984 mmol, molar number of N group: 3.934 mol) of Adecastab LA-57 (hindered amine, manufactured by ADEKA) was added and mixed at room temperature for 10 minutes. Minute to prepare a homogeneous solution of a cationic curing catalyst (TPB catalyst). This was used as a cationic curing catalyst A.

Preparation Example 3 (Preparation of cationic curing catalyst B)

1.6 g of? -Butyrolactone was added to 2 g of the TPB-containing powder B obtained in Preparation Example 1 (1.816 g (3.547 mmol) of TPB pure water and 0.184 g (10.211 mmol) of water) And mixed for 10 minutes. Thereafter, 2.1 g of a 2 mol / l ammonia-ethanol solution was added and mixed at room temperature for 60 minutes to obtain a homogeneous solution of a cationic curing catalyst (TPB catalyst). This was used as the cationic curing catalyst B.

&Lt; Preparation of resin composition and cured product (laminate) >

Example 1

15 parts of EHPE-3150 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) as the oxirane compound, 15 parts of CELOXIDE CEL-2021P (liquid phase alicyclic epoxy resin, epoxy equivalent 131, manufactured by Daicel Chemical Industries, Ltd.) 330 parts of hexanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 6 parts of TX-EX-609K (phthalocyanine dye, absorption maximum wavelength: 715 nm, manufactured by Nippon Catalysts Co., Ltd.) as a coloring agent were uniformly mixed at 80 占 폚. Thereafter, the temperature was lowered to 40 占 폚, and 1 part of the cation curing catalyst A was uniformly mixed as a curing agent, and the foreign matters were filtered with a 0.45 占 퐉 filter (GL Science, nonaqueous 13N). Thus, a resin composition (1) was obtained. Using the resin composition, film formation and curing were carried out by the method described later to obtain a cured product (laminate).

Examples 2 to 6

(2) to (6) were obtained in the same manner as in Example 1 except that the amounts of the coloring matters 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 carried out by the method described later to obtain a cured product (laminate).

Comparative Example 1

100 parts of DPE-6A (Kyowa Chemical Co., Ltd.) as an acrylic curing resin, 330 parts of cyclohexanone (Wako Pure Chemical Industries, Ltd.) as a solvent, TX-EX-609K (phthalocyanine dye, absorption maximum wavelength: 715 nm , Manufactured by Nippon Catalyst Co., Ltd.) were uniformly mixed. Thereafter, the temperature was lowered to 40 占 폚, and 1 part of perhexyl I (manufactured by NIHIKI CORPORATION) as a curing agent was uniformly mixed and the foreign matter was filtered through a 0.45 占 퐉 filter (GL Science, nonaqueous 13N). Thus, a resin composition for comparison (Comparative Example 1) was obtained. Using the resin composition, film formation and curing were carried out by the method described later to obtain a cured product (laminate).

Comparative Example 2

100 parts of UN-904 (Negami Kogyo Co.) as a urethane acrylic curing resin, 330 parts of cyclohexanone (Wako Pure Chemical Industries, Ltd.) as a solvent, TX-EX-609K (phthalocyanine dye, absorption maximum wavelength: 715 nm , Manufactured by Nippon Catalyst Co., Ltd.) were uniformly mixed. Thereafter, the temperature was lowered to 40 占 폚, and 1 part of perhexyl I (manufactured by NIHIKI CORPORATION) as a curing agent was uniformly mixed and the foreign matter was filtered through a 0.45 占 퐉 filter (GL Science, nonaqueous 13N). Thus, a comparative resin composition (Comparative Example 2) was obtained. Using the resin composition, film formation and curing were carried out by the method described later to obtain a cured product (laminate).

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

<Film Formation and Curing Methods of Examples 1 to 6 and Comparative Examples 1 and 2>

1, film forming method

Each resin composition was dropped on a glass substrate (S9213, 76 mm x 52 mm x 1.2 mm-1.5 mm, manufactured by Matsunami Glass Industries, Ltd., water glass polished glass) washed with an isopropanol solvent, 1H-DX2, manufactured by Mikasa Co., Ltd.) for 3 seconds at a predetermined number of revolutions for a predetermined time, and the number of revolutions was returned to 0 rpm over 3 seconds to form a film. Table 2 shows specific film forming conditions.

2, hardening method

(1) Photocuring (UV curing)

(Basic constituent unit "ML-251B / D", irradiation optical unit "PM25C-135", manufactured by Ushio Inc.) equipped with a 250 W high-pressure mercury lamp (USH-250BY, ) Was used. The illuminance of the surface of the substrate on the irradiation side was set to 33 mW / cm 2 at a wavelength of 365 nm, and the total amount of light was irradiated so as to be 2 J / cm 2.

(2) Thermal curing

Using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised in a program of reaching 250 占 폚 at 30 占 폚 under an N2 atmosphere (oxygen concentration of 30 ppm or less) For 1 hour, and then the temperature was reduced to 30 占 폚.

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 thermoset Respectively.

(3) After the final curing, the outer peripheral portion of the glass was removed by using a diamond cutter so as to equalize, and six samples of 15 mm x 15 mm evaluation sample were taken out from one glass substrate.

Film properties, adhesiveness, transmittance of a cured product, heat resistance (film formation heat resistance and reflow heat resistance), resistance to humidity and humidity, and the like were measured for the resin composition or cured product (laminate) obtained in the above Examples and Comparative Examples. The thermal shock resistance was evaluated by the following method. The results are shown in Table 2.

&Lt; Evaluation methods of properties of each of Examples 1 to 6 and Comparative Examples 1 and 2 >

1, coat film thickness

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

2, film forming property

Five samples for evaluation of the cured product after the final curing (i.e., the cured product obtained by the curing method of the above-mentioned 2) were confirmed by naked eyes and 20 times of a stereomicroscope and evaluated according to the following criteria.

&Amp; cir &amp;: Only defects less than 0.1 mm did not occur.

?: Defects having a length (diameter) of 0.1 mm or more and less than 1 mm occurred.

DELTA: Defects having a length (diameter) of 1 mm or more and less than 2 mm occurred.

X: Defects having a length (diameter) of 2 mm or more occurred.

3, Adhesiveness

The cured product after the final curing was cut into cured products by using a cutter (manufactured by OLFA, NT cutter, A300), and 11 cross-cut lines were prepared in 1-mm intervals in a row and in a row, 100 squares were prepared. A tape (Mending Tape 810 manufactured by 3M Co., Ltd.) was pasted on the cured product at room temperature to prevent air from entering the cured product, and left for 30 seconds. Thereafter, a peeling operation was carried out within one second so that the peeling force became constant on the cured product, thereby preparing an evaluation sample.

Evaluation samples were evaluated according to the following criteria.

?: No peeling occurred in one square of the 100 mass produced.

?: Peeling occurred in 1 to 10 masses out of the square of 100 masses produced.

X: Peeling occurred in 11 to 100 mass out of a square of 100 mass produced.

4, transmittance of the cured product (presence or absence of coloring)

Using a spectrophotometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100), the transmittance of the cured product at 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, , And the presence or absence of coloration was evaluated.

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

After curing the final cured product, the cured product was dried in the air at 300 ° C for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and the transmittance of the cured product at wavelengths of 400 nm and 550 nm was measured with an absorbance meter , Spectrophotometer UV-3100). In addition, cracks and peeling were visually observed.

6, Heat resistance test (Reflow heat resistance test)

After curing the final cured product, the cured product was dried in air at 260 占 폚 for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and the transmittance of the cured product at wavelengths of 400 nm and 550 nm was measured with an absorbance meter , Spectrophotometer UV-3100). In addition, cracks and peeling were visually observed.

7, Humidity Resistance Test

After curing the final cured product, the cured product was stopped for 100 hours under a temperature of 85 캜 and a relative humidity of 85% using a thermo-hygrostat (manufactured by ESPEC, SH-211) 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 visually observed.

8, Thermal shock test

The cured product after the final curing was placed in a cold / hot cycle in which the temperature cycle was performed at 115 ° C for 30 minutes and -40 ° C for 30 minutes, and the transmittance of the cured product at 400 nm and 550 nm at 100 cycles was measured with an absorbance meter Manufactured by Shimadzu Corporation, spectrophotometer UV-3100). In addition, cracks and peeling were visually observed.

9, Evaluation of cracking and peeling

Five evaluation samples were evaluated according to the following criteria.

?: No cracking or peeling occurred at all.

X: Cracks or peeling occurred even in one sheet.

The abbreviations in Table 1 are as follows.

CEL-2021P: liquid phase alicyclic epoxy resin "Celloxide CEL-2021P", epoxy equivalent: 131, weight average molecular weight: 120, manufactured by Daicel Chemical Industries,

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 Co., Ltd.

CPI-101A: a light-curable cationic curing catalyst (antimony-based sulfonium salt (SbF ₆ salt)),

SI-100L: a thermal latent cationic curing catalyst &quot; SANEADE SI-100L &quot; (antimony sulfonium salt (SbF ₆ salt)) manufactured by Sanshin Chemical Industry Co.,

DPE-6A: acrylic curing resin "Light Acrylate DPE-6A" manufactured by Kyowa Chemical Co., Ltd.

UN-904: urethane acrylic curing resin "Art Resin UN-904" manufactured by Negami Industrial Co., Ltd.

Perhexyl I: radical polymerization initiator, Nichi-like production

The results are shown in Table 2 below.

1, film-forming property and adhesive property

It was found that Examples 1 to 6 containing an oxirane compound were superior in film formability and adhesiveness to Comparative Examples 1 and 2 containing no oxirane compound.

In Examples 1 to 6, film formation was observed more than in the case of using the cationic curing catalysts different from those in the case of using the light-potential cationic curing catalyst (Examples 2, 3 and 5) as curing agents (Examples 1, 4 and 6) And it was found that the property was excellent.

2, the transmittance after final curing

In Examples 1 to 6, it was found that the transmittance after final curing (in particular, the transmittance at 550 nm) was high. This indicates that in Examples 1 to 6, the coloration upon final curing can be reduced. In Examples 4 to 6 in which the content of pigment is large, the transmittance of 400 nm is lower than that of Examples 1 to 3 in which the content of pigment is small, but the transmittance of 550 nm is about the same.

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 those in the case of using different cationic curing catalysts (Examples 2, 5 and 6) , Indicating that the effect of reducing coloring is high.

3, film forming heat resistance, reflow heat resistance, resistance to humid heat, temperature shock resistance

In Examples 1 to 6, cracking and peeling did not occur at all after each test, and the transmittance did not change before and after the test. Thus, it was found that the film formation heat resistance, reflow heat resistance, wet heat resistance, I could.

Among Examples 1 to 6, the film forming heat resistance, the heat resistance, and the heat resistance were superior to those in the case of using a TPB-based catalyst (Examples 1, 3, and 4) Low heat resistance, heat resistance, and thermal shock resistance.

In the above-mentioned embodiment, by using a resin composition containing a specific oxirane compound and a dye, it is possible to obtain a cured product having excellent film-forming properties, adhesiveness, heat resistance (film formation heat resistance, reflow heat resistance) , And that such a resin composition can be preferably used as a material for lamination (particularly, an optical material such as an IR cut filter) for forming a layer on a substrate. It is also believed that the functional groups as in the above examples are all expressed in the same manner in the resin composition of the present invention.

Therefore, from the results of the above-described embodiments, it can be said that the present invention can be applied to various aspects disclosed in this specification throughout the technical scope of the present invention, thereby exerting an advantageous effect.

Synthesis Example 1 (Synthesis of phthalocyanine (1)

(1) Step 1

54 g (0.27 mol) of tetrafluorophthalonitrile, 34.5 g (0.59 mol) of potassium fluoride and 126 g of acetone were placed in a 1000 ml four-necked separable flask, and 3-chloro-4-hydroxy Benzoic acid methoxyethyl ester (127 g, 0.55 mol) and acetone (216 g). While stirring the reaction vessel under ice-cooling, 3-chloro-4-hydroxybenzoic acid methoxyethyl ester solution was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Thereafter, the reaction temperature was slowly raised to room temperature and stirred overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to effect recrystallization. The obtained crystals were filtered and vacuum dried to obtain 108.7 g (yield: 64.8%) of intermediate (1).

The reaction of this Step 1 is briefly described below.

[Chemical formula 10]

(2) Step 2

20.0 g (0.032 mol) of the intermediate (1) obtained in Step 1, 2.57 g (0.0081 mol) of zinc iodide (II) and 30.0 g of benzonitrile were charged into a 200 ml four-necked flask, Lt; / RTI &gt; After completion of the reaction, 52.7 g of methylcellosolve was added to the reaction solution, and the solution 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 again washed with a mixed solution of methanol and water with stirring, and subjected to suction filtration. The obtained cake was dried at 90 캜 for 24 hours using a vacuum drier to obtain 17.78 g (yield: 87.1%) of the desired phthalocyanine (1).

The reaction of Step 2 is briefly described below.

(11)

The phthalocyanine (1) obtained in Synthesis Example 1 has a structure in which the substituents shown on the right are substituted for each of the moieties shown by "*" in the main skeleton (total of 8).

Synthesis Example 2 (Synthesis of phthalocyanine (2)

(1) Step 1

75 g (0.37 mol) of tetrafluorophthalonitrile, 52.3 g (0.90 mol) of potassium fluoride and 167 g of acetonitrile were introduced into a 1000 ml four-neck separable flask, and 2,6-dichlorophenol 123.4 g (0.76 mol) of acetonitrile and 133 g of acetonitrile. While stirring, a 2,6-dichlorophenol solution was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Thereafter, the reaction was carried out overnight with stirring. The reaction solution was filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, and methanol was added to carry out recrystallization. The obtained crystals were filtered and vacuum dried to obtain 148.1 g (yield: 80.2%) of intermediate (2).

The reaction of this Step 1 is briefly described below.

[Chemical Formula 12]

(2) Step 2

140 g (0.29 mol) of intermediate (2), 107.8 g (0.78 mol) of potassium carbonate, 92.1 g (0.61 mol) of methyl p-hydroxybenzoate and 280 g of acetone were introduced into a 500 ml four-necked separable flask. The reaction solution was stirred at 60 ° C overnight for reaction. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and a mixed solution of methanol and methanol was added to carry out recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 202.3 g (yield: 93.1%) of intermediate (3).

The reaction of Step 2 is briefly described below.

[Chemical Formula 13]

(3) Step 3

22.5 g (0.030 mol) of intermediate (3) obtained in Step 2, 2.37 g (0.0074 mol) of zinc iodide (II) and 52.5 g of benzonitrile were charged into a 200 ml four-necked flask and stirred at 160 ° C for 24 hours Lt; / RTI &gt; After the completion of the reaction, 30.3 g of methylcellosolve was added to the reaction solution, and the solution 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 again washed with a mixed solution of methanol and water with stirring, and subjected to suction filtration. The obtained cake was dried at 90 캜 for 24 hours using a vacuum drier to obtain 17.83 g (yield: 86.1%) of the desired phthalocyanine (2).

The reaction of this Step 3 is briefly described below.

[Chemical Formula 14]

The phthalocyanine (2) obtained in Synthesis Example 2 had the substituents shown on the right side in eight of the moieties shown by "*" in the main skeleton (total of 16) and the substituents shown on the right side in the remaining eight Substituted (or bonded) structure.

Synthesis Example 3 (Synthesis of phthalocyanine (3)

(1) Step 1

100 g (0.58 mol) of 3-nitropthalonitrile, 159.7 g (1.16 mol) of potassium carbonate, 104.6 g (0.64 mol) of 2,6-dichlorophenol and 400 g of acetonitrile were introduced into a three- . After the reaction was allowed to proceed at 60 DEG C overnight, the reaction solution was filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, and methanol was added to perform recrystallization. The obtained crystals were filtered and vacuum dried to obtain 100.9 g (yield: 60.2%) of Intermediate (4).

The reaction of this Step 1 is briefly described below.

[Chemical Formula 15]

(2) Step 2

60.0 g (0.21 mol) of Intermediate (4) obtained in Step 1, 5.65 g (0.057 mol) of copper (I) chloride and 140.0 g of diethylene glycol monomethyl ether were introduced into a 300 ml four-necked flask. And reacted for 24 hours while stirring. After completion of the reaction, 100.0 g of methylcellosolve was added to the reaction solution, which was then 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 again washed with a mixed solution of methanol and water with stirring, and subjected to suction filtration. The obtained cake was dried at 90 캜 for 24 hours using a vacuum drier to obtain 51.48 g (yield: 80.4%) of the desired phthalocyanine (3).

The reaction of Step 2 is briefly described below.

[Chemical Formula 16]

In the phthalocyanine (3) obtained in Synthesis Example 3, the substituents shown on the right side are attached to four of the moieties shown by "*" in the main skeleton (total of 8), and the substituents shown on the right side Hydrogen atoms) are substituted (or bonded), respectively.

&Lt; Preparation of resin composition and cured product (laminate) >

Example 7

15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), 40 parts of tetrahydrofuran (THF) and 8 parts of phthalocyanine (1) obtained in Synthesis Example 1 , And uniformly mixed at 80 ° C. Thereafter, the temperature was lowered to 40 占 폚, 5.6 parts of the cationic curing catalyst B was uniformly mixed as a curing agent, and the foreign matters were filtered through a 0.45 占 퐉 filter (GL Science, nonaqueous 13N). Thus, a resin composition (7) was obtained. The resin composition thus obtained was evaluated for storage stability by the following method.

The obtained resin composition was subjected to film formation and curing by a method to be described later to evaluate film formability, transmittance and heat resistance (reflow heat resistance). The results are shown in Fig. 1 and Table 4.

Example 8 and Reference Examples 1 to 4

The resin composition (8) and the reference resin compositions (1) to (4) were obtained in the same manner as in Example 7 except that the kinds and amounts of the pigments were changed as shown in Table 3.

The resin composition thus obtained was evaluated for storage stability by the following method.

Using the obtained resin composition, film formation and curing were carried out in the same manner as in Example 7 to evaluate the film formability, the respective transmittance and heat resistance (reflow heat resistance). The results are shown in Fig. 2 (Example 8 only) and Table 4.

&Lt; Storage stability of resin composition >

Viscosity was measured at 25 占 폚 using an E-type viscometer (manufactured by Toki Industries Co., Ltd.). The viscosity before and after standing for one week at 40 占 폚 was measured and evaluated according to the following criteria.

?: 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 gelation.

&Lt; Film formation, curing (thermal curing) and deposition film forming methods of Examples 7 to 8 and Reference Examples 1 to 4 >

1, film forming method

Each resin composition was dropped on a glass substrate (glass, D263, 8-inch ring made by SCHOTT) washed with an isopropanol solvent, and then the resin composition was dropped on a glass substrate (1H-DX2 manufactured by Mikasa Co., And the number of revolutions was returned to 0 rpm over 3 seconds to form a film (that is, coated). The specific film forming conditions are shown in Table 4 (2500 rpm). Further, a transmittance spectrum after the film formation (coating) was obtained.

2, curing method (thermosetting)

The film obtained by the above-mentioned film formation method 1 was cured. Concretely, using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo System Co., Ltd.), a program of reaching 250 ° C for 1 hour from 30 ° C under an N ₂ atmosphere After the temperature was raised, the temperature was maintained at 250 ° C for 1 hour, and then the temperature was decreased to 30 ° C. Further, the transmittance spectrum after the curing was obtained.

3, Deposition film formation method

An alternate deposition layer (infrared reflection layer) of 20 titanium oxide / 20 silica layer was formed on the opposite surface of the coating layer obtained by the curing method of 2, and an alternate vapor deposition layer (three layers of titanium oxide / ).

<Evaluation methods of physical properties and the like of Examples 7 to 9 and Reference Examples 1 to 4>

1, film forming property

The range of the square of 3 cm x 3 cm in the center of the cured product after the final curing (i.e., the cured product obtained by the curing method of the above 2) was confirmed by a 20-times stereomicroscope and evaluated according to the following criteria.

&Amp; cir &amp;: Only defects less than 0.03 mm did not occur.

?: Defects having a length or diameter of 0.03 mm or more and less than 1 mm occurred.

DELTA: Defects having a length or a diameter of 1 mm or more and less than 2 mm occurred.

X: Defects of length or diameter of 2 mm or more occurred.

2, transmittance

The transmittance spectrum at each step was measured using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). The spectra are shown in Figs. 1 and 2 (Examples 7 and 8). Table 4 shows the transmittance at 430 nm as a short wavelength region of visible light, 550 nm as a central region of visible light, and 650 nm as an absorption wavelength of a dye in each step.

The transmittance after formation of the vapor deposition film was measured by arranging a laminate so that the order of the infrared reflection layer / glass / coating layer / antireflection layer was from the incident light source side. When the laminate is arranged so as to be perpendicular to the incident light (the transmittance spectrum measured in this manner is also referred to as a 0 degree spectrum, which is measured by making light incident from the thickness direction (vertical direction) of the laminate) (Transmittance spectrum measured in this manner is referred to as a 30-degree spectrum) in such a manner that light enters from a direction tilted by 30 degrees with respect to the thickness direction (vertical direction) of the laminate.

3, Heat resistance (Reflow heat resistance)

After the final cured cured product (i.e., the cured product obtained by the curing method of the above 2) was dried in the air at 260 占 폚 for 20 minutes using a drier (DH611, manufactured by Yamato Scientific Co., Ltd.) The transmittance of the cured product at 650 nm was measured using an absorbance meter (Spectrophotometer UV-3100, manufactured by Shimadzu Corporation). In addition, cracks and peeling were visually observed. Cracks and delamination were evaluated for the five evaluation samples by the following criteria.

?: No cracking or peeling occurred at all.

X: Cracks or peeling occurred even in one sheet.

Of the abbreviations in Table 3, those not listed in Table 1 are as follows.

PGMEA: Propylene glycol monomethyl ether acetate (also known as 1,2-propanediol monomethyl ether acetate)

THF: tetrahydrofuran

Phthalocyanine (1): The phthalocyanine dye obtained in Synthesis Example 1

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

Phthalocyanine (3): The phthalocyanine dye obtained in Synthesis Example 3

Antimony catalyst SI-60L: trade name "SANEID SI-60L", manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.

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

Curing catalyst B: The cationic curing catalyst B obtained in Preparation Example 3

From Table 4, the following can be found.

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

Example 9

15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), 40 parts of tetrahydrofuran (THF) and 8 parts of phthalocyanine (1) obtained in Synthesis Example 1 , And uniformly mixed at 80 ° C. Then, 20 parts of Z-6043 (manufactured by Toray Dow Corning) as a silane coupling agent and 5.6 parts of a cationic curing catalyst B as a curing agent were uniformly mixed, and the foreign matters were filtered through a 0.45 mu m filter Gt; N, &lt; / RTI &gt; nonaqueous 13 N). Thus, a resin composition (9) was obtained.

Using the obtained resin composition, film formation and curing were carried out by a method described later to evaluate the film formability, the respective transmittance, the heat resistance and the adhesion. The results are shown in Table 6.

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

(10) and reference resin compositions (5) to (6) were obtained 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 Example 10 and Reference Examples 5 to 6 ). 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 carried out in the same manner as in Example 9 to evaluate the film formability, the respective transmittance, the heat resistance and the adhesion. The results are shown in Table 6.

&Lt; Examples 7 ', 8 ', 9, 10 and Reference Examples 5 to 6 >

1, film forming method

 (1) Pretreatment coating

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

40 parts of Z-6043 (manufactured by Toray Industries, Inc.) as a silane coupling agent, 40 parts of ethanol, 10.3 parts of water and 4 parts of formic acid were uniformly mixed at 25 占 폚 for 1 hour. Next, 1 part of the mixed solution and 99 parts of ethanol were uniformly mixed at 25 占 폚, and the foreign matters were filtered with a 0.45 占 퐉 filter (non-aqueous 13N, manufactured by GL Science). Thus, a pretreatment coating solution was obtained.

b) In the same manner as the coating of the resin composition described later, the above-mentioned pretreatment coating solution was dropped on a glass substrate (made by SCHOTT, glass, D263, 8-inch ring) washed with isopropanol solvent, (I.e., coated) at a predetermined number of revolutions (2500 rpm) over 3 seconds, and the number of revolutions was returned to 0 rpm over 3 seconds by using a pressure gauge (-DX2).

In addition, only the pretreatment coatings were conducted in Examples 7 'and 8'.

(2) Coating of Resin Composition

Each resin composition was dropped on a glass substrate (glass, D263, 8-inch ring made by SCHOTT) washed with an isopropanol solvent, and then the resin composition was dropped on a glass substrate (1H-DX2 manufactured by Mikasa Co., (2500 rpm) for a predetermined time, and the number of revolutions was returned to 0 rpm over 3 seconds (i.e., coated).

2, curing method (thermosetting)

The film obtained by the above-mentioned film formation method 1 was cured. Concretely, using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo System Co., Ltd.), a program of reaching 250 ° C for 1 hour from 30 ° C under an N ₂ atmosphere After the temperature was raised, the temperature was maintained at 250 ° C for 1 hour, and then the temperature was decreased to 30 ° C.

3, Deposition film formation method

An alternate deposition layer (infrared reflection layer) of 20 titanium oxide / 20 silica layer was formed on the opposite surface of the coating layer obtained by the curing method of 2, and an alternate vapor deposition layer (three layers of titanium oxide / ).

<Evaluation methods of physical properties and the like of Examples 7 ', 8', 9 and 10 and Reference Examples 5 to 6>

The film formability, the transmittance and the heat resistance (reflow heat resistance) were evaluated in the same manner as in Example 7.

1, Adhesiveness (self-examination)

The final cured cured product was quenched for 5 hours in a boiling environment using a boiling bath. Thereafter, cuttings were cut on the cured product by using a cutter (NT cutter, A300, manufactured by OLFA), and 11 cross-cut lines were formed at intervals of 1 mm each in a row and a row, and a square of 1 mm &lt; 2 & Mass. A tape (Mending Tape 810, manufactured by 3M Company) was attached to the cured product at room temperature so as to prevent air from entering the cured product, and left for 30 seconds. Thereafter, a peeling operation was performed within one second so that the peeling force became constant on the cured product, thereby preparing a sample for evaluation. Evaluation samples were evaluated according to the following criteria.

?: No peeling occurred in one square of the 100 mass produced.

?: Peeling occurred in 1 to 10 masses out of the square of 100 masses produced.

X: Peeling occurred in 11 to 100 mass out of a square of 100 mass produced.

2, Adhesion (pressure cooker (PCT) test)

After curing the final cured product, the cured product was stopped at 120 ° C / 2 atm / 100% humidity for 50 hours using a PCT tester.

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

Z-6043: Silane coupling agent, trade name "Z-6043", manufactured by Toray Dow Corning Co.

Z-6040: Silane coupling agent, trade name &quot; Z-6040 &quot;, manufactured by Toray Dow Corning Incorporated

Table 6 shows the following.

It can be seen that the pretreatment coating is performed using a silane coupling agent on the base material or the use of a silane coupling agent as one of the components contained in the resin composition forming the resin layer sufficiently suppresses peeling and the like even after exposure to a humid environment there was.

Claims (13)

1. A resin composition for use as a material for forming a layer on a substrate,
The resin composition contains an oxirane compound having at least one oxirane ring in the molecule, and a colorant,
The oxirane compound contains a compound having a hydroxyl group and / or an ester group,
Wherein the coloring matter contains a dye having an absorption maximum in a wavelength range of 600 to 900 nm. The method according to claim 1,
Wherein the oxirane compound contains 10 to 100 mass% of a compound having a weight average molecular weight of 2000 or more based on 100 mass% of the entire oxirane compound. 3. The method according to claim 1 or 2,
Wherein the resin composition for laminating further contains a cationic curing catalyst. 4. The method according to any one of claims 1 to 3,
Wherein the resin composition for lamination is for coating. 5. The method according to any one of claims 1 to 4,
Wherein the resin composition for lamination contains two or more coloring matters,
The two or more kinds of coloring matter contain at least the coloring matter alpha and the coloring matter beta having different absorption characteristics,
The dye alpha is a phthalocyanine dye, and when the absorption spectrum of the cured product of the dye alpha and the measurement resin is measured, the absorption maximum is shown in the wavelength range of 600 to 650 nm and 680 to 750 nm, respectively,
And the dye beta has an absorption maximum in a wavelength range of 650 to 680 nm when the absorption spectrum of the cured product of the dye beta and the measurement resin is measured. 6. The method according to any one of claims 1 to 5,
Wherein the resin composition for lamination further contains a silane coupling agent. 7. The method according to any one of claims 1 to 6,
Wherein the resin composition for laminating further contains a solvent,
Wherein the solvent has a solvent having a dielectric constant of 10 or more and / or a solvent having a dielectric constant of 5 or more and less than 10 and a molecular weight of 100 or less. 8. The method according to any one of claims 1 to 7,
Wherein the resin composition for laminating further contains a nitrogen-containing compound having a boiling point of 120 占 폚 or less. A laminate obtained by forming a layer comprising the resin composition for lamination according to any one of claims 1 to 8 on a substrate. 10. The method of claim 9,
The substrate is treated with a coupling agent,
Wherein the coupling agent contains silicon, zirconia, titanium and / or aluminum as a central metal. 11. The method according to claim 9 or 10,
Wherein 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. A photo-selective transmission filter comprising the laminate according to any one of claims 9 to 11. An imaging device comprising the laminate according to any one of claims 9 to 11.

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