JP6356429B2 - LAMINATED RESIN COMPOSITION AND USE THEREOF - Google Patents

Description

The present invention relates to a lamination resin composition and its use. More specifically, the present invention relates to a resin composition used as a material for forming a layer on a substrate, a laminate using the same, a light selective transmission filter, and an imaging device.

In recent years, in various fields such as the field of optical devices such as display elements and image sensors, members / materials having a laminated structure in which various layers are formed on a substrate made of glass or the like (a laminated body or a material) (Also referred to as a laminate) has been widely used. For example, conventionally, reduction of optical noise in an image pickup device is provided with an absorption glass such as blue glass doped with copper ions, a resin filter having a light absorption function and a reflection function for reducing optical noise, and the like on a resin component. Although the absorption glass is extremely excellent in heat resistance, there is a problem that cracking and chipping are likely to occur and the workability is not sufficient, while the resin filter is cracked. In addition to being able to suppress the occurrence of chipping and excellent workability, on the other hand, heat resistance is not sufficient compared to glass, and there has been a problem that warpage due to linear expansion cannot be denied. Development of an optical filter having a laminated structure in which a layer having a light absorption function and a reflection function is formed on a substrate such as glass is underway.
Conventional optical filters having a laminated structure are disclosed in Patent Documents 1 to 5 and the like.

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

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

By the way, when forming a layer such as an IR cut layer on a substrate, a method of vapor deposition at a high temperature is desired from the viewpoint of forming a dense layer. Therefore, high heat resistance is required for the material of the layer (laminate material) formed on the substrate. In addition, since members constituting the imaging element are often reflow-mounted, the layering material is also required to have heat resistance that can withstand the reflow process. Furthermore, a lamination material that is expected to be applied to various uses including an image pickup device is required to have excellent storage stability before being subjected to a lamination process and excellent film formability. However, at present, no conventional material for lamination has been developed that can sufficiently meet these requirements.

The present invention has been made in view of the above situation, and has a heat resistance that is excellent as a material for forming a layer on a substrate, and can achieve both storage stability and film formability. An object is to provide a composition. Another object of the present invention is to provide a laminate excellent in surface appearance and heat resistance obtained from such a laminate resin composition, a light selective transmission filter using the laminate, and an imaging device.

The inventors of the present invention have studied various materials for forming a layer on a substrate. As a result, a resin composition containing an oxirane compound having one or more oxirane rings in a molecule, a solvent, and a cation curing catalyst is used in a high-temperature deposition or reflow process. In addition to being excellent in heat resistance so that it can sufficiently cope with the above, it has been found that it is excellent in chemical resistance, moisture resistance, and curing shrinkage reduction, and a cured film can be formed on a substrate in a short time. In order to further enhance the appearance of the cured film obtained from such a resin composition, it is conceivable to increase the crosslink density in the resin composition to improve the film formability. However, in order to improve the storage stability, it is conceivable to reduce the crosslinking density. However, in this case, the film formability is not sufficient, and a cured product having a high appearance cannot be obtained. We found that there is a trade-off between storage stability and film formability.

Therefore, if the resin composition further contains a nitrogen-containing compound having a predetermined boiling point, the resin composition is excellent in storage stability due to the presence of the nitrogen-containing compound during storage (storage) or transfer, while at the time of curing. It has been found that a cured product having excellent film formability and high appearance can be easily obtained due to volatilization of part or all of the nitrogen-containing compound. Furthermore, the resin composition having such a configuration efficiently provides a cured product having a sufficiently excellent appearance even without undergoing a photocuring step as preliminary curing, that is, only a thermal curing step as main curing. It has been found that it is useful from the viewpoint of productivity and workability of cured products. And the light selective transmission filter and image pick-up element containing the laminated body using such a resin composition are found to be extremely useful in the optical field and the optical device field, and can solve the above-mentioned problems wonderfully. I came up with the present invention.

That is, the present invention is a resin composition used as a material for forming a layer on a substrate, the resin composition comprising a compound having one or more oxirane rings in a molecule, a solvent, a cationic curing catalyst, and The nitrogen-containing compound is a resin composition for lamination having a boiling point of 120 ° C. or lower.

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

[Laminating resin composition]
The laminating resin composition of the present invention (also simply referred to as a resin composition) includes a compound having one or more oxirane rings in the molecule, a solvent, a cationic curing catalyst, and a nitrogen-containing compound. You may use 1 type (s) or 2 or more types, respectively. Moreover, you may contain 1 type, or 2 or more types of another component as needed.

-Oxirane compounds-
The compound having one or more oxirane rings in the molecule (also simply referred to as oxirane compound) is a compound (cation curable compound) that has a cationic curable group called an oxirane ring and is cured (polymerized) by heat or light. . When the resin composition contains an oxirane compound, the amount of shrinkage of the cured product can be sufficiently reduced, and the cured film (resin layer) can be obtained by shortening the time until curing to increase productivity. Also, it is excellent in heat resistance (heat decomposition resistance and coloration resistance) and chemical resistance.

In the present specification, compounds that are cured (polymerized) by heat or light are collectively referred to as “curable compounds”, and among them, curable compounds having a cationic curable group are collectively referred to as “cationic curable compounds”.
A group containing an oxirane ring which is a three-membered ether is referred to as an “epoxy group”. “Epoxy group” includes, in addition to a narrowly defined epoxy group, a group in which an oxirane ring is bonded to carbon such as a glycidyl group, a group containing an ether or ester bond such as a glycidyl ether group and a glycidyl ester group, epoxy A cyclohexane ring etc. shall be included.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the said resin composition, it is preferable that content of an oxirane compound is 5 mass% or more with respect to 100 mass% of total amounts of the curable compound in a resin composition from a viewpoint of improving adhesiveness more. More preferably, it is 10 mass% or more, More preferably, it is 30 mass% or more, Most preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 100 mass%.

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

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

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

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

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

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

As content of the said solvent, it is suitable that it is 30 mass% or more with respect to 100 mass% of total amounts of the said resin composition. Thereby, the said resin composition can exhibit the fluidity | liquidity more excellent as a material which forms a layer on a board | substrate (preferably transparent inorganic material layer). More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 60 mass% or more. Further, considering the work efficiency at the time of curing and fully exhibiting the effects of other components, it is preferably 95% by mass or less. More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less, Most preferably, it is 80 mass% or less.

The content of the solvent is preferably 30 parts by mass or more with respect to 100 parts by mass of the total amount of the curable compound. More preferably, it is 50 mass parts or more, More preferably, it is 100 mass parts or more, Most preferably, it is 200 mass parts or more. Moreover, it is preferable that it is 5000 mass parts or less, More preferably, it is 1000 mass parts or less, More preferably, it is 500 mass parts or less.

The resin composition also preferably does not contain a large amount of water in order to exhibit the effect of the nitrogen-containing compound more sufficiently. Specifically, the water content is preferably 5% by mass or less with respect to 100% by mass of the total amount of the resin composition. More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less, Most preferably, it is 0 mass%, that is, it is substantially free of water.

-Cationic curing catalyst-
The resin composition also includes a cationic curing catalyst.
The cationic curing catalyst is a catalyst that accelerates the cationic curing reaction, and functions, for example, differently from the curing accelerator in the acid anhydride curing reaction. Specific examples include a heat latent cationic curing catalyst and a photolatent cationic curing catalyst.

When the said resin composition contains a cationic curing catalyst, the shrinkage amount of hardened | cured material can fully be reduced. Moreover, since a hardening reaction can be suitably advanced in a short time and a hardened | cured material can be formed rapidly, manufacturing efficiency will be improved more. In addition, a cured product having high heat resistance and releasability can be obtained, and the resin composition can stably exist as a one-component composition (one-component property) excellent in handling properties. Furthermore, compared with the case where addition type curing such as acid anhydride curing is employed, the obtained cured product is superior in characteristics required for optical applications such as heat resistance, chemical stability, and moisture resistance. Become. Among the cationic curing catalysts, it is preferable to include at least a heat latent cationic curing catalyst.

Unlike the acid anhydrides, amines, phenol resins, etc., which are generally used as curing agents, the heat-latent cationic curing catalyst may be contained in the resin composition even if it is contained in the resin composition at room temperature. Without causing viscosity increase or gelation over time, and as an action of the heat latent cationic curing catalyst, it can fully accelerate the curing reaction and exert an excellent effect, and it is excellent in handling properties. A resin composition (one-component material) can be provided.

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

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

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

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

The photolatent cationic curing catalyst is also called a photocationic polymerization initiator, and exhibits a substantial function as a curing agent when irradiated with light. By using a photolatent cationic curing catalyst, a compound containing a cationic species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds.

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

More preferred as the cationic curing catalyst is a boron compound, and an aromatic fluorine compound is even more preferred.
The cation curing catalyst is particularly preferably the following general formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. A is an integer equal to or greater than 1, b is an integer equal to or greater than 0, and a + b = 3 is satisfied.) And a Lewis base (organic borane). . Thus, the form in which the said cation curing catalyst contains the compound which consists of a Lewis' acid and a Lewis base represented by General formula (1) is one of the suitable forms of this invention. When such a compound is used, coloring due to heat (during curing, film formation, use environment) is reduced, and moisture and heat resistance is reduced, compared to the case of using a conventional cationic curing catalyst such as an antimony sulfonium salt. And a cured product superior in durability such as resistance to thermal shock.
The presence / absence or degree of coloring of the cured product based on the curing catalyst to be used can usually be confirmed from the change in transmittance at 400 nm. That is, by measuring the 400 nm transmittance of the cured product, the presence / absence or degree of coloring of the cured product can be evaluated.

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

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

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

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

Examples of the compound having a nitrogen atom include amines (monoamine, polyamine), ammonia and the like. Specifically, for example, an amine having a hindered amine structure, a low boiling point amine, ammonia and the like can be mentioned. In the present invention, in particular, the nitrogen-containing compound of the present invention described later (that is, a nitrogen-containing compound having a boiling point in a predetermined range). Is preferably used. Thus, it is also suitable that the nitrogen-containing compound of the present invention is contained in the resin composition as part of forming the cationic curing catalyst.

When an amine having a hindered amine structure is used as the Lewis base, the cured product can be prevented from oxidation due to the radical scavenging effect, and the resulting cured product is more excellent in heat resistance (wet heat resistance). On the other hand, when the nitrogen-containing compound of the present invention is used as the Lewis base, the resulting cured product is excellent in low water absorption and UV radiation resistance. When the nitrogen-containing compound of the present invention volatilizes in the curing step, the salt structure derived from the nitrogen-containing compound in the final molded body (cured product) is reduced, so that the water absorption rate of the cured product can be reduced. Presumed to be possible. In particular, ammonia is preferable because of its excellent effects.

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

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

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

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

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

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

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

Specific examples of the cationic curing catalyst comprising a Lewis acid and a Lewis base represented by the general formula (1) include, for example, TPB / monoalkylamine complexes, TPB / dialkylamine complexes, TPB / trialkylamine complexes, and the like. TPB alkylamine complex; organic borane / amine complex such as TPB / hindered amine complex; organic borane / ammonia complex such as TPB / NH ₃ complex; TPB / triarylphosphine complex, TPB / diarylphosphine complex, TPB / monoarylphosphine complex, etc. And organic borane / phosphine complexes such as TPB / alkyl thiol complexes; organic borane / sulfide complexes such as TPB / diaryl sulfide complexes and TPB / dialkyl sulfide complexes. Among these, as the complex of TPB and the nitrogen-containing compound of the present invention, a TPB / NH ₃ complex is preferable.

In the resin composition, the content of the cation curing catalyst is an amount of an active ingredient not containing a solvent or the like (meaning a solid content equivalent amount. A cation composed of a Lewis acid and a Lewis base represented by the general formula (1). When a curing catalyst is used, the total amount of the Lewis acid and Lewis base is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the cationic curable compound. . As a result, the curing rate can be further increased, productivity can be further improved, and the possibility of coloring during curing, heating, use, or the like can be further suppressed. In addition, for example, when reflow mounting a laminate obtained using the above resin composition, heat resistance of 200 ° C. or higher is necessary, so that it should be 10 parts by mass or less from the viewpoint of colorlessness and transparency. Is preferred. More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it is 2 mass parts or less.

From the viewpoint of storage stability, the cationic curing catalyst preferably has a pH of 4 or more, more preferably 7 or more, as evaluated by a pH measuring device (Horiba, D-51). In consideration of stability at room temperature, the pH is preferably 8 or more, more preferably 8.5 or more. On the other hand, considering the film formability during curing, the pH is preferably 13 or less, more preferably 11 or less.

Similarly, the pH of the resin composition using the cation curing catalyst is preferably 3.5 or more as evaluated by a pH measuring machine (Horiba, D-51). More preferably, the pH is 4 or more, and further preferably pH 4.5 or more. On the other hand, from the viewpoint of film formability, the pH is preferably 13 or less, more preferably 11 or less. Furthermore, if the viewpoint of a curing rate is added, pH 10 or less is preferable, More preferably, it is pH 8 or less, More preferably, it is pH 7 or less.

-Nitrogen-containing compounds-
The resin composition also includes a nitrogen-containing compound having a boiling point of 120 ° C. or lower (also simply referred to as “nitrogen-containing compound”). Thereby, at the time of storage (storage) and transfer, while the resin composition is excellent in storage stability due to the presence of the nitrogen-containing compound, at the time of curing, due to volatilization of a part or all of the nitrogen-containing compound, It becomes possible to easily obtain a cured product having excellent film formability and high appearance.

The boiling point of the nitrogen-containing compound is preferably 100 ° C. or less, more preferably 80 ° C. or less, still more preferably 50 ° C. or less, particularly preferably 30 ° C. or less, and most preferably 5 ° C. from the viewpoint of further manifesting the above effects. It is as follows.

The boiling point of the nitrogen-containing compound is also the temperature at which the resin layer is formed from the resin composition on the substrate (for example, the temperature at which the resin layer is formed by a solution coating method described later such as a spin coating method). Is A (° C.), it is preferably (A + 80) ° C. or lower. That is, for example, when A = room temperature (25 ° C.), the boiling point of the nitrogen-containing compound is preferably 105 ° C. or less. Thereby, it becomes possible to fully exhibit the effect of this invention. More preferably, it is (A + 60) ° C. or less, further preferably (A + 30) ° C. or less, and particularly preferably (A + 10) ° C. or less.

Specific examples of the nitrogen-containing compound include ammonia (boiling point: −33.34 ° C.); monomethylamine (boiling point: −6 ° C.), monoethylamine (boiling point: 16.6 ° C.), monopropylamine (boiling point: 48 ° C), primary amines such as monobutylamine (boiling point: 78 ° C), monopentylamine (boiling point: 104 ° C), ethylenediamine (boiling point: 117 ° C); dimethylamine (boiling point: 6.9 ° C), diethylamine ( Boiling point: 55.5 ° C), dipropylamine, methylethylamine (boiling point: 36-37 ° C), methylpropylamine (boiling point: 78 ° C), methylbutylamine (boiling point: 90-92 ° C), ethylpropylamine (boiling point: 80-85 ° C), secondary amines such as piperidine (boiling point: 106 ° C); trimethylamine (boiling point: 2.9 ° C), triethylamine ( Point: 89.7 ° C.) tertiary amines such as; the like. Among these, ammonia is particularly preferable because it can exhibit the above-described effects. Thus, the form in which the nitrogen-containing compound is ammonia is one of the preferred forms of the present invention.

In the resin composition, the content of the nitrogen-containing compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the curable compound. More preferably, it is 0.01-5 mass parts. In the present invention, it is also preferable to use a cationic curing catalyst comprising a Lewis acid represented by the general formula (1) and a nitrogen-containing compound as a Lewis base. In this case, the content ratio of the nitrogen-containing compound is preferably set as appropriate so as to be within the preferable range of the ratio n (b) / n (a) described above.

-Other ingredients-
In addition to the essential components described above, the resin composition is a pigment, a curable compound other than the oxirane compound (also referred to as another curable compound), and other than the cationic curing catalyst, as long as the effects of the present invention are not impaired. Curing agents (also called other curing agents), photosensitizers, curing accelerators, flexible components, reactive diluents, saturated compounds without unsaturated bonds, pigments, dyes, antioxidants, ultraviolet rays Absorber, IR cut agent, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, anaerobic polymerization initiator, polymerization inhibitor, inorganic filler, organic filler, coupling agent, etc., adhesion improver, heat Stabilizer, antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, emulsifier, slip Anti-scratch agent, anti-skinning agent, desiccant, antifouling agent, Antistatic agents, may contain such conductive agent (electrostatic aid). These can use 1 type (s) or 2 or more types.

-Dye-
When the resin composition contains a pigment, the pigment is preferably dispersed or dissolved in the resin composition. More preferably, it is a form in which a pigment is dissolved and contained in a resin composition. That is, the dye is preferably one that dissolves in a curable compound (also referred to as a resin component) that constitutes the resin composition, a solvent, or the like.

What is necessary is just to select the said pigment | dye suitably according to a desired absorption characteristic, and can use 1 type (s) or 2 or more types. For example, phthalocyanine dyes, porphyrin dyes, chlorin dyes, choline dyes, cyanine dyes, quaterylene dyes, squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes and the like are preferable. . Among these, phthalocyanine dyes are preferable from the viewpoint of light resistance and heat resistance.

As the phthalocyanine dye, a metal phthalocyanine complex is suitable. For example, a metal element such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead is used as a central metal. Metal phthalocyanine complexes. Among these metal elements, one or more of copper, vanadium, and zinc is used as a central metal because it is more soluble or dispersible in a curable compound (also referred to as a resin component), visible light transmittance, and light resistance. Those that do are preferred. The central metal is more preferably copper, zinc or vanadium, and further preferably copper or zinc. The phthalocyanine-based dye using copper is not deteriorated by light even when dispersed in any resin component (binder resin, curable compound), and has very excellent light resistance. A phthalocyanine complex (phthalocyanine dye) containing zinc as a metal element is preferable because it has excellent solubility in a resin component.

The phthalocyanine dye is preferably a compound represented by the following general formula (I). By using such a dye, when the resin composition or laminate of the present invention is applied to an imaging device, generation of flare and ghost can be sufficiently suppressed, and it can be a problem when combined with a reflective film. Incident angle dependency can also be sufficiently reduced. In addition, for example, when used in combination with a reflective film or an interference film, it becomes possible to exhibit light selective transparency close to the sensitivity of the human eye.

In the formula, M represents a metal atom, a metal oxide, or a metal halide. R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 are the same or different and are a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), or 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. However, 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. As an alkyl group, a C1-C20 alkyl group is preferable, for example, More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Most preferably, it is C1-C4. It is an alkyl group. Among R ⁱ , a phenyl group or a phenyl group having a substituent is preferable.

Examples of the substituent that the OR ⁱ group may have include electrons such as an alkoxycarbonyl group (—COOR), a halogen group (halogen atom), a cyano group (—CN), and a nitro group (—NO ₂ ). An attractive group; an electron donating group such as an alkyl group (—R) and an alkoxy group (—OR); and the like, and may include one or more of these. The electron withdrawing group is preferably an alkoxycarbonyl group, a chloro group (chlorine atom) or a cyano group, and more preferably a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group or a cyano group.
Note that R constituting the alkoxycarbonyl group (—COOR) is preferably an alkyl group having 1 to 4 carbon atoms, and R constituting the alkyl group (—R) is alkyl having 1 to 4 carbon atoms. A group is preferred. The alkoxycarbonyl group is preferably a methoxycarbonyl group or a methoxyethoxycarbonyl group, and the alkyl group is preferably a methyl group or a dimethyl group.

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

R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 are preferably such that at least one of them represents an OR ⁱ group. Thereby, it will become more excellent in light resistance.
Here, the carbon to which the OR ⁱ group is bonded is the α-position carbon in the four aromatic rings of the phthalocyanine skeleton (C _α : the carbon at the 1,4,8,11,15,18,22,25-position of the phthalocyanine ring. Or β-position carbon (C _β : represents the 2,3,9,10,16,17,23,24-position carbon of the phthalocyanine ring), but at least the α-position carbon. Is preferred. Among them, form OR ⁱ group is attached to an average of 2 or more carbons of the alpha-position carbon (C _alpha), and more preferably, OR ⁱ to one or more alpha-position carbon (C _alpha) on each aromatic ring This is a form in which groups are bonded. Moreover, it is also preferable that a hydrogen atom or a fluorine atom is bonded to an average of 4 or more carbons in the β-position carbon (C _β ). More preferably, a hydrogen atom or a fluorine atom is bonded to an average of 6 or more carbons among β-position carbon (C _β ), and still more preferably, hydrogen atoms are bonded to all carbons of β-position carbon (C _β ). Or it is the form which the fluorine atom couple | bonded.

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

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

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

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

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

In the above reaction, two or more compounds different from each other in R ^{a to} R ^d may be used in combination as the phthalonitrile derivative represented by the general formula (i).

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

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

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

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

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

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

The dye preferably has an absorption maximum of 1 or more in a wavelength range of 600 to 750 nm when the absorbance property is evaluated by a resin film evaluation method.

Further, the dye preferably has a transmittance at a wavelength of 550 nm of 80% or more when the absorbance property is evaluated by a resin film evaluation method. More preferably, it is 83% or more, still more preferably 85% or more, particularly preferably 87% or more, and most preferably 89% or more.

The resin film evaluation method is a method for evaluating absorbance characteristics in a film state in which a dye is dispersed or dissolved in a measurement resin.
“A film in which a dye is dispersed or dissolved in a measurement resin” is a film composed of a dye to be measured and a measurement resin, and the conditions under which the absorbance at the absorption maximum wavelength can be evaluated (the absorbance at the absorption maximum wavelength is spectroscopic). Any film may be used as long as the content of the dye and the thickness of the film are selected so as to satisfy the conditions under which the absorbance can be measured without exceeding the measurement limit of the photometer.

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

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

In the resin composition, the total amount of the pigment (total concentration of all pigments) is, for example, 0.0001% by mass or more and 15% by mass or less with respect to 100% by mass of the total amount of the curable compound (resin component). Is preferred. Thereby, it is possible to obtain a laminate having a high visible light transmittance and excellent in blocking characteristics in the near infrared region. More preferably, it is 0.001 mass% or more, More preferably, it is 0.1 mass% or more, Especially preferably, it is 1 mass% or more, More preferably, it is 10 mass% or less, More preferably, it is 7 mass% or less, Especially Preferably it is 5 mass% or less.
The content of the phthalocyanine dye represented by the general formula (I) in the total amount of the dye of 100% by mass is preferably 10 to 100% by mass. More preferably, it is 15-100 mass%.

The dye may also contain a dye that does not correspond to the phthalocyanine dye represented by the general formula (I) described above, and the content of such a dye is 50% by mass with respect to 100% by mass of the total amount of the dye. % Or less is preferable. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Especially preferably, it is substantially free of the pigment | dye which does not correspond to the phthalocyanine type pigment | dye represented by the general formula (I) mentioned above.

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

-Other curable compounds-
The other curable compound is an organic compound having a curable functional group and may be a compound other than the oxirane compound essential in the present invention. The curable functional group means a functional group that undergoes a curing reaction by heat or light (a group that causes a curing reaction of the resin composition). For example, in addition to an oxirane group (oxirane ring) or an epoxy group, an oxetane group (oxetane ring). Cation curable groups such as ethylene sulfide group, dioxolane group, trioxolane group, vinyl ether group and styryl group; radical curable groups such as acrylic group, methacryl group and vinyl group; Therefore, as said other curable compound, it is a compound (cation curable compound) which has cation curable groups other than the oxirane compound mentioned above, and / or a compound (radical curable compound) which has a radical curable group. It is preferable.

Specific examples of the other curable compounds include compounds having one or more oxetane groups (oxetane rings) in the molecule (referred to as oxetane compounds). When the said resin composition contains an oxetane compound, it is preferable to use together with an alicyclic epoxy compound and / or a hydrogenated epoxy compound from a viewpoint of a cure rate.

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

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

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

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

-Other curing agents-
Examples of the other curing agent include a radical curing catalyst such as a thermal latent radical curing catalyst and a photolatent radical curing catalyst; a commonly used curing agent such as an acid anhydride type, a phenol type or an amine type; Can be mentioned.

Preferred examples of the thermal latent radical curing catalyst include organic peroxides and azo compounds exemplified in JP2013-138158A [0059].

Preferred examples of the photolatent radical curing catalyst include compounds exemplified in JP2013-138158A [0062]. Among them, acetophenones, benzophenones, and acylphosphine oxides are preferably used, and in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-thiomethyl) Phenyl) propan-1-one is preferably used.

When using the said radical curing catalyst, the compounding quantity is 0.01- with respect to 100 mass parts of total amounts of a radical curable compound, respectively as an active ingredient amount (meaning solid content conversion amount) which does not contain a solvent etc. It is suitable to be 10 parts by mass. More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it is 2 mass parts or less.

Examples of the usually used curing agents such as acid anhydrides, phenols and amines include compounds described in JP 2013-138158 A [0064] to [0065]. Among them, preferred are acid anhydride curing agents, and more preferred are methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrophthalic anhydride. More preferred are methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

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

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

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

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

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

Examples of the curing accelerator include organic base acid salts or aromatic compounds having tertiary nitrogen. Examples of organic base acid salts include, for example, JP 2013-138158 A [0089] to [0092]. The organic phosphonium salts, organic onium salts such as organic ammonium salts, and acid salts of organic bases having tertiary nitrogen are preferably used. Moreover, as an aromatic compound which has tertiary nitrogen, the phenyl group substituted imidazole and tertiary amino group substituted phenol which were illustrated by Unexamined-Japanese-Patent No. 2013-138158 [0093] are used preferably, for example. Among them, particularly preferred curing accelerators include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8-diazabicyclo (5,4,0) undecene-7 octylate, , 4,6-tri (dimethylaminomethyl) -phenol, tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, trimellitic acid salt of 1-benzyl-2-phenylimidazole, tetraphenylphospho Nitrobromide, triphenylphosphine / toluene bromide.

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

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

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

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

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

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

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

In the resin composition, the number of foreign matters having a particle diameter of 10 μm or more contained per 1 cm ^{3 of} the resin composition is preferably 1000 or less, more preferably 100 or less, and still more preferably 10 or less.
In addition, the foreign material contained in the said resin composition can be removed by filtering, when preparing a resin composition.

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

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

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

-Curing method-
It does not specifically limit as a hardening method of the said resin composition, For example, various methods, such as thermosetting and photocuring (curing by active energy ray irradiation), can be used suitably. Curing may be performed in one step, or may be performed in two steps such as primary curing (preliminary curing) and secondary curing (main curing), but the resin composition of the present invention has curability. Since it is high, a cured product having a sufficiently excellent appearance can be efficiently provided even at one stage. Therefore, for example, compared with the case of performing two-stage curing of photocuring and thermal curing, the process can be shortened by omitting the photocuring process, and thus the cured product is excellent in productivity and workability.

The curing method is particularly preferably a thermosetting method. The heat curing is preferably performed at about 30 to 400 ° C., and may be changed stepwise within this temperature range.

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

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

The resin composition for lamination of the present invention has a high heat resistance and can give a cured product that is remarkably excellent in film properties. Therefore, when a resin layer made of the resin composition of the present invention is formed on a base material, the resin layer has high heat resistance, excellent surface appearance, and reduction in visible light transmittance and coloring are sufficiently suppressed. Therefore, the resin composition of the present invention and the laminate obtained using the resin composition are members of various elements for forming a film (for example, optical materials such as a light selective transmission filter typified by an IR cut filter). Useful as. In addition, various devices such as mobile phones, televisions, personal computers, and in-vehicle applications are in the process of adopting a solder reflow process for reasons such as simplification of manufacturing processes and cost reduction. Since the resin composition of the present invention and a laminate obtained using the resin composition are sufficiently subjected to a solder reflow process, the deterioration of optical properties is sufficiently suppressed. Therefore, members of various elements that employ the solder reflow process (for example, It is particularly useful as an optical material such as a light selective transmission filter typified by an IR cut filter. Among these, when a transparent inorganic material layer is used as a base material, it is preferable because a laminate that can suppress generation of cracks, chipping, and warpage and has excellent heat resistance can be obtained. Thus, the laminated body obtained by forming the resin layer which consists of the said resin composition on a base material is also one of this invention.

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

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

Here, “having a resin layer on a base material” means not only a form in which the resin layer is in direct contact with the base material, but also a form having a resin layer via another constituent member existing on the base material. To include. The same applies to “forming a resin layer on a substrate”, and not only when forming a resin layer directly on a substrate, but also forming a resin layer via another component existing on the substrate. Including cases. The same applies to “applying a resin composition onto a substrate”, and not only when the resin composition is applied directly onto a substrate, but also through other constituent members present on the substrate. It also includes the case of applying.

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

A solution coating method is suitable as a method of forming a coating film made of the resin composition on the substrate (or other constituent member). Specifically, it is as described later.

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

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

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

In this specification, the absorption characteristics and transmittance of the laminate, the resin layer, and the transparent inorganic material layer are measured using, for example, an absorptiometer (also referred to as a spectrophotometer, manufactured by Shimadzu Corporation, spectrophotometer UV-3100). It can be determined by measuring the absorption spectrum or transmittance spectrum.
It is preferable that the resin layer also has the same characteristics as the absorption characteristics and transmission characteristics of the laminate described above. Especially, it is preferable that the said resin layer is a form whose absorbance is so high that it is a long wavelength side in the wavelength range of 600-680 nm.

The thickness of the laminate is preferably 1 mm or less, for example. Thereby, the request | requirement for size reduction of the apparatus etc. (for example, image pick-up element etc.) which have a laminated body can fully be met. More preferably, it is 500 micrometers or less, More preferably, it is 300 micrometers or less. Moreover, it is preferable that it is 30.1 micrometers or more. More preferably, it is 50 μm or more.

<Base material>
In the above laminate, the base material is not particularly limited, but for example, 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 organic materials or organic-inorganic composite materials include resin films made of these materials. Examples of the inorganic material include glass, crystal, and metal oxide.
The material of the base material is preferably a material having reflow resistance.

Among the above-mentioned base materials, those made of a transparent inorganic material are suitable. That is, the substrate is preferably a layer made of a transparent inorganic material (referred to as a transparent inorganic material layer). Thereby, as described above, cracks, chipping and warpage can be suppressed, and a laminate having excellent heat resistance can be obtained. Thus, the laminated body obtained by forming the resin layer which consists of the said resin composition on a transparent inorganic material layer is one of the suitable forms of this invention.

Examples of the transparent inorganic material include glass and crystal.
The transparent inorganic material may also be obtained by including transition metal ions in a material that forms glass, crystal, or the like. As the transition metal ion, one or more kinds which are usually used as those having light absorption ability may be used. For example, Ag ⁺ , Fe ⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2+ and the} like may be used. Can be mentioned.
In addition, the form whose said base material is glass or a quartz substrate is one of the suitable forms of this invention.

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

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

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

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

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

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

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

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

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

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

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

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

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

In the embodiment in which the light selective transmission filter of the present invention is an infrared cut filter, it is preferable to selectively reduce the infrared transmittance of 750 to 1000 nm to 5% or less. The transmittance in other wavelength regions is preferably 70% or more, and more preferably 75% or more, but only the transmittance in a specific wavelength region is high depending on the use of the filter. Good. For example, when the infrared cut filter is used as a camera module, it is preferable that the transmittance of infrared light is 5% or less and the transmittance of 450 to 600 nm in visible light is 70% or more. More preferably, it is 80% or more. Moreover, it is preferable that the transmittance | permeability of the light of the wavelength range of 480-550 nm is 85% or more among visible light, and it is more preferable that it is 90% or more. In the infrared cut filter, the transmittance of other wavelengths (other than the infrared region) is more preferably 85% or more, and still more preferably 90% or more. That is, the light selective transmission filter is preferably an infrared cut filter having a light transmittance of 85% or more at a wavelength of 480 to 550 nm and a transmittance of 5% or less at 750 to 1000 nm.
The transmittance can be measured using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The light selective transmission filter of the present invention is not only useful as, for example, a heat ray cut filter mounted on a glass of an automobile or a building, but also blocks light noise in a camera module (also referred to as a solid-state imaging device) application. It is also useful as a filter for correcting visibility. Among these, the light selective transmission filter of the present invention is useful as a filter used in camera modules such as digital still cameras and mobile phone cameras. That is, the light selective transmission filter is preferably a light selective transmission filter for an image sensor. Thus, an image sensor provided with the light selective transmission filter is also one preferred embodiment of the present invention.

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

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

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

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

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

Since the laminating resin composition of the present invention has the above-described configuration, it has excellent heat resistance as a material for forming a layer on a substrate, and can achieve both storage stability and film formability. It can be done. In addition, if such a resin composition is used, a cured product having an excellent appearance and exhibiting high heat resistance can be provided, which is extremely useful for imaging device applications. In addition, a laminate obtained by forming a resin layer made of such a resin composition on a substrate can be suitably applied as a member constituting an image sensor, particularly a light selective transmission filter, particularly (near) infrared cut. It is effective as a constituent member of a filter (IRCF).

It is the transmittance | permeability spectrum in each step in Example 1. FIG.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Example 2 and Comparative Examples 1 to 4
A curable resin composition (2) and comparative resin compositions (1) to (4) were obtained in the same manner as in Example 1 except that the type and amount of the dye were changed as shown in Table 1.
About the obtained resin composition, the storage stability was evaluated by the method described later.
Moreover, using the obtained resin composition, it formed into a film and hardened | cured similarly to Example 1, and evaluated film forming property, each transmittance | permeability, and heat resistance (reflow heat resistance). The results are shown in Table 2.

<Storage stability of resin composition>
Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured under the condition of 25 ° C. The viscosity before and after being allowed to stand for 1 week at 40 ° C. was measured and evaluated according to the following criteria.
A: The amount of change from the initial viscosity was less than 30%.
X: The amount of change from the initial viscosity was 30% or more, or gelled.

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

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

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

<Film forming properties>
The cured product after final curing (that is, the cured product obtained by the above <curing method>) was confirmed with a 20-fold stereo microscope and evaluated according to the following criteria.
X: A defect with a length or diameter of 2 mm or more occurred.
Δ: A defect with a length or diameter of 1 mm or more and less than 2 mm occurred.
A: A defect having a length or diameter of 0.03 mm or more and less than 1 mm occurred.
A: Only defects of less than 0.03 mm occurred.

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

<Heat resistance (Reflow heat resistance)>
The cured product after final curing (that is, the cured product obtained in the above <curing method>) was dried in the atmosphere at 260 ° C. for 20 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd., DH611), and then the wavelength The transmittance of the cured product at 430 nm, 550 nm and 650 nm was measured using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). Moreover, the crack and peeling were confirmed visually. The evaluation of cracks and peeling was performed according to the following criteria for five evaluation samples.
○: No cracks or peeling occurred.
X: Cracks or peeling occurred even with one sheet.

Abbreviations and the like in Table 1 are as follows.
CEL-2021P: Liquid alicyclic epoxy resin “Celoxide CEL-2021P”, epoxy equivalent 131, weight average molecular weight 120, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd .: Alicyclic epoxy resin, weight average molecular weight 2900, Daicel Chemical Industries, Ltd. PGMEA: Propylene glycol monomethyl ether acetate (also known as 1,2-propanediol monomethyl ether acetate)
THF: tetrahydrofuran phthalocyanine (1): phthalocyanine dye phthalocyanine obtained in Synthesis Example 1 (2): phthalocyanine dye phthalocyanine obtained in Synthesis Example 2 (3): phthalocyanine dye antimony catalyst obtained in Synthesis Example 3 SI- 60L: Trade name “Sun-Aid SI-60L”, Sanshin Chemical Co., Ltd. curing catalyst A: Cationic curing catalyst A obtained in Preparation Example 2
Curing catalyst B: Cationic curing catalyst B obtained in Preparation Example 3

From the examples and comparative examples, the following was found.
The resin compositions obtained in Examples 1 and 2 contain ammonia as the nitrogen-containing compound of the present invention by using curing catalyst B as the cationic curing catalyst. It was found that such a resin composition was excellent in storage stability and extremely excellent in film formability, and the cured product had high transparency and heat resistance. In contrast, the resin compositions obtained in Comparative Examples 1 to 4 do not contain the nitrogen-containing compound of the present invention, but the film formability is inferior to Examples 1 and 2, and among them Comparative Examples 1 to 2 It was found that the resin composition obtained in 2 has insufficient storage stability.

Claims (11)

A resin composition used as a material for forming a layer on a substrate by a solution coating method ,
The resin composition includes a curable compound, a solvent, a cationic curing catalyst, and a nitrogen-containing compound,
The curable compound contains 5% by mass or more of a compound having one or more oxirane rings in the molecule with respect to 100% by mass of the total amount of the curable compound,
The nitrogen-containing compound is ammonia or a primary amine, secondary amine, or tertiary amine having a boiling point of 120 ° C. or lower,
The resin composition for lamination, wherein the content of the solvent is 30% by mass or more with respect to 100% by mass of the total amount of the resin composition . The said resin composition contains a pigment | dye further, and the total amount of this pigment | dye is 1 mass% or more and 10 mass% or less with respect to 100 mass% of total amounts of a sclerosing | hardenable compound. Laminating resin composition. The resin composition for lamination according to claim 1 or 2, wherein the nitrogen-containing compound is ammonia. Content of the said nitrogen-containing compound is 0.01-10 mass parts with respect to 100 mass parts of total amounts of a sclerosing | hardenable compound, The resin composition for lamination | stacking in any one of Claims 1-3 characterized by the above-mentioned. . The cationic curing catalyst has the following general formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine bonded to an aromatic ring. It represents the number of atoms, a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. The resin composition for lamination according to any one of claims 1 to 4. In the cationic curing catalyst, the ratio (n (b) / n (a)) of the number of atoms n (b) of the Lewis base to the number of boron atoms n (a) which is the Lewis acid point is 1.5. It is the above, The resin composition for lamination | stacking of Claim 5 characterized by the above-mentioned. 7. The resin composition for lamination according to claim 5, wherein the content of the cationic curing catalyst is 0.2 to 10 parts by mass with respect to 100 parts by mass of the total amount of the curable compound. A laminate obtained by forming a resin layer comprising the resin composition for lamination according to any one of claims 1 to 7 on a substrate. The laminate according to claim 8 , wherein the base material is glass or a quartz substrate. Light selective transmission filter which comprises a laminate according to claim 8 or 9. Imaging device characterized in that it comprises a laminate according to claim 8 or 9.

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