JP2016027400A - Resin composition for lamination and intended purposes thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lamination resin composition exhibiting excellent heat resistance as a material for forming a layer on a substrate, and a laminated material obtained by forming a layer formed of the lamination resin composition on a base material and exhibiting excellent heat resistance, and particularly a lamination resin composition capable of maintaining high adhesiveness to the substrate in a case of work for coating the substrate without being primed with a resin composition solution (first solution).SOLUTION: Provided is a lamination resin composition used as a material for forming a layer on a base material, the resin composition containing an oxirane compound having one or more oxirane rings in molecules, a silane coupling agent, and a coloring agent, the oxirane compound including an oxirane compound having a hydroxyl group and/or an ester group, and the silane coupling agent including a silane coupling agent having an amino group.SELECTED DRAWING: None

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 obtained by forming a layer made of the resin composition on a substrate, a light selective transmission filter, and an imaging element.

  In recent years, in various fields such as optical devices such as display elements and image sensors, members and materials having a laminated structure in which various layers are formed on a substrate made of glass or the like (laminate or laminate) Are also widely used. As a layer formed on the substrate, for example, an ITO (indium-tin composite oxide) transparent conductive layer used for a touch panel, an infrared (IR) cut layer for reducing optical noise in an image sensor, and light on the substrate surface Examples thereof include an antireflection (AR) layer that reduces reflection.

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

  Conventionally, optical noise reduction in an image sensor is performed by providing an absorption glass such as blue glass doped with copper ions, a resin filter having a light absorption function or a reflection function for reducing optical noise on a resin component, and the like. I have been. However, although the absorbing glass is very excellent in heat resistance, cracks and chipping are likely to occur, and the processability is not sufficient. On the other hand, the resin filter can suppress the occurrence of cracks and chipping and is excellent in workability. On the other hand, the heat resistance is not sufficient as compared with glass, and the occurrence of warpage due to linear expansion cannot be denied. Therefore, in recent years, development of an optical filter 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 has been advanced.

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

JP 2008-51985 A JP 2006-106570 A JP 2012-167145 A JP 2013-50593 A JP 2012-103340 A JP 2012-189632 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, for example, since an image pickup device such as a digital camera module is mounted on a mobile phone or the like, downsizing and cost reduction are also required. Therefore, instead of a conventional inorganic glass as an image pickup lens, a resin lens is used. Adoption is progressing. In such a member mounting process, in order to realize cost reduction, it is a mainstream to adopt a solder reflow method. Therefore, the material of the layer formed on the surface of the lens or the like is required to have heat resistance that the cured product (molded product) can withstand the reflow process.

  As described above, Patent Documents 1 to 6 propose an IR cut filter having a multilayer structure. However, the conventional technology has room for further study on a resin composition that gives a molded article excellent in characteristics such as heat resistance when performing high-temperature vapor deposition as described above and heat resistance in a reflow process.

  Further, in Patent Document 3, it is described that an undercoat layer may be provided on a substrate for improving adhesion with an upper layer, preventing diffusion of a substance, or planarizing a surface, if necessary. In order to increase the adhesion, it is described that a device such as undercoating is devised. Therefore, there is room for study on a resin composition that can improve the adhesion without providing such an undercoat layer.

  This invention is made | formed in view of the said present condition, and consists of the resin composition for lamination which has the outstanding heat resistance and adhesiveness as a material which forms a layer on a base material, and this resin composition for lamination | stacking It aims at providing the laminated body which has the outstanding heat resistance and adhesiveness obtained by forming a layer on a base material. In particular, an object of the present invention is to provide a resin composition for laminating (especially for an imaging device) that can maintain high adhesion to a substrate even if the substrate is coated with a resin composition solution (one solution) without undercoating. To do. Another object of the present invention is to provide a light selective transmission filter and an image sensor using such a laminate.

  The inventors of the present invention have studied variously about the resin composition for lamination as a material for forming a layer on a base material (also referred to as a substrate), and the resin composition has one or more oxirane rings in the molecule, The resin composition further comprises an oxirane compound having a hydroxyl group and / or an ester group, a silane coupling agent having an amino group, and a dye (preferably a dye having an absorption maximum in a wavelength range of 600 to 900 nm). Has been found to be excellent in heat resistance and adhesion, and can be suitably used as a material for forming a layer on a substrate by high temperature vapor deposition. Furthermore, it has been found that it is suitable for an image sensor. Also, it has been found that a cured product (also referred to as a laminate or a laminate) having a laminated structure obtained by laminating such a resin composition on a substrate has heat resistance that can withstand a reflow process. It was. The inventors have found that a light selective transmission filter and an image sensor including such a laminate are extremely useful in the optical field and the optical device field, and have conceived that the above problems can be solved brilliantly. Reached.

  That is, the present invention is a resin composition used as a material for forming a layer on a substrate, the resin composition comprising an oxirane compound having one or more oxirane rings in a molecule, a silane coupling agent, and The oxirane compound includes a dye, the oxirane compound includes an oxirane compound having a hydroxyl group and / or an ester group, and the silane coupling agent is a resin composition for lamination including a silane coupling agent having an amino group.

  This invention is also a laminated body obtained by forming the 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.

  Since the laminating resin composition of the present invention has the above-described configuration, it can provide a cured product (laminate) excellent in film formability, adhesion, heat resistance, moist heat resistance, and temperature shock resistance. Is. In particular, even if the resin composition solution (one liquid) is coated on the substrate without undercoating, the adhesiveness with the substrate can be maintained high, so that the workability can be improved. Such a laminate can be suitably applied to various uses such as optical materials, and is particularly useful as a material constituting an IR cut filter.

The present invention is described in detail below. In addition, what combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.
In this specification, “absorption maximum” means the relationship between wavelength and absorbance expressed as a two-dimensional graph of the X axis and Y axis (where the X axis is the wavelength and the Y axis is the absorbance). In addition, it means the apex at which the absorbance changes from increasing to decreasing, and the wavelength of this apex is called “absorption maximum wavelength”. Further, among the absorption maximum wavelengths (also referred to as absorption peak wavelengths), those having the maximum absorbance are referred to as “maximum absorption wavelength” or “maximum absorption peak wavelength”.
“Absorption width (also referred to as absorption band width)” is a wavelength width at an arbitrary transmission intensity. When the absorption width is wide (large), the light selective transparency is excellent, and the design conditions of the reflective film are widened, so that it becomes easy to manufacture a light selective transmission filter (such as an infrared cut filter).

“A to B” representing a range means “A or more and B or less”.
[Laminating resin composition]
The resin composition for lamination of the present invention (also simply referred to as “resin composition”) contains a specific oxirane compound having one or more oxirane rings in the molecule, a specific silane coupling agent, and a dye as essential components. However, you may contain another component in the range which does not prevent the effect of this invention, and these components can use 1 type (s) or 2 or more types, respectively. It is preferably for coating (1 liquid type), preferably for (solid) imaging device, and preferably a resin composition for laminating on a glass substrate.
-Dye-
In the laminating resin composition of the present invention, as the dye, a dye having an absorption maximum in an arbitrary wavelength region can be selected. For example, it is preferable to include a dye having an absorption maximum in the wavelength region of 600 to 900 nm (hereinafter also referred to as a specific dye). By including such a pigment, infrared rays of 780 nm to 10 μm in particular can be reduced, and optical noise caused by this can be removed. In the present invention, it is preferable to include a dye having an absorption maximum on the short wavelength side among conventional near-infrared absorbers having an absorption maximum of 600 to 900 nm. As a result, a suitable performance for reducing optical noise, such as high visible light transmittance and excellent blocking performance in the near infrared region, can be obtained. The specific dye is more preferably a dye having an absorption maximum in a wavelength range of 600 to 800 nm, and more preferably a dye having an absorption maximum in a wavelength range of 650 to 750 nm.

  The specific dye may have a plurality of absorption maxima in the wavelength region of 600 to 900 nm. Of the absorption maximums in the wavelength range of 600 to 900 nm, the absorption maximum on the shortest wavelength side is preferably in the wavelength range of 650 to 750 nm. The specific dye is also preferably one having substantially no absorption maximum in a wavelength region of 400 nm or more and less than 600 nm.

In the resin composition, 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, it is preferable that the pigment is dissolved in a resin component or a solvent contained in the resin composition.
1 type (s) or 2 or more types can be used for a pigment | dye.

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

  In addition, it is especially preferable that the pigment | dye which has (pi) electron bond in the said molecule | numerator is what has an absorption maximum in the wavelength range mentioned above, ie, a specific pigment | dye.

  Examples of the dye having a π electron bond in the molecule include phthalocyanine dyes, porphyrin dyes, cyanine dyes, quaterylene dyes, squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like. These can be used, and one or more of these can be used. From the viewpoint of heat resistance, weather resistance, permeability, and compatibility of the resin composition of the present invention, phthalocyanine compounds and / or squarylium compounds are particularly preferable.

  From the viewpoint of heat resistance, a phthalocyanine compound (phthalocyanine dye) is more preferable.

  As the phthalocyanine compound, 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, lead and the like as a central metal. Metal phthalocyanine complexes. Among these metal elements, the solubility or dispersibility (for example, the solubility or dispersibility in the resin component), the visible light transmission, and the light resistance are more excellent, so that at least one of copper, vanadium and zinc is mainly used. A metal is preferable. That is, copper, zinc or vanadium is preferable as the central metal, and copper and zinc are more preferable. The phthalocyanine using copper is not deteriorated by light even when dispersed in any resin component (binder resin), and has very excellent light resistance. In addition, phthalocyanine complexes (phthalocyanine dyes) having zinc as a central metal are preferable because they are excellent in solubility in resin components and can easily obtain a laminate (particularly, a near infrared cut filter) having higher light selective permeability. is there.

  Among the phthalocyanine compounds, a compound represented by the following general formula (I) is particularly preferable. When a resin composition containing such a compound is used, it is possible to obtain a laminate in which generation of cracks, chipping and warpage is further suppressed, and which can sufficiently withstand high temperature deposition. In addition, when such a laminate is applied to an imaging device, the occurrence of flare and ghost can be sufficiently suppressed, and the incidence angle dependency that can be a problem when combined with a reflective film can be sufficiently reduced. it can. Furthermore, when the laminate is used in combination with, for example, a reflective film or an interference film, it becomes possible to exhibit light selective transparency close to the sensitivity of the human eye. Moreover, when the phthalocyanine dye represented by the following general formula (I) is used, the laminate (particularly, the near infrared cut filter) obtained using the resin composition of the present invention has an absorption maximum in the wavelength range of 650 to 680 nm. It becomes easy to have.

式中Ｍは、金属原子、金属酸化物又は金属ハロゲン化物を表す。Ｒ^ａ１〜Ｒ^ａ４、Ｒ^ｂ１〜^ｂ４、Ｒ^ｃ１〜Ｒ^ｃ４及びＲ^ｄ１〜Ｒ^ｄ４は、同一又は異なって、水素原子（Ｈ）、フッ素原子（Ｆ）、塩素原子（Ｃｌ）、臭素原子（Ｂｒ）、ヨウ素原子（Ｉ）、又は、置換基を有していてもよいＯＲ^ｉ基を表す。ＯＲ^ｉ基は、アルコキシ基、フェノキシ基又はナフトキシ基を表す。
上記フタロシアニン系化合物の合成後は、従来公知の方法に従って、晶析、濾過、洗浄、及び／又は、乾燥を行ってもよい。

In the formula, M represents a metal atom, a metal oxide, or a metal halide. R ^{a1 to} R ^a4 , R ^b1 to ^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), 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.
After the synthesis of the phthalocyanine compound, crystallization, filtration, washing, and / or drying may be performed according to a conventionally known method.

  The resin composition of the present invention may also contain two or more dyes. Among these, the two or more kinds of dyes include at least a dye α and a dye β having different absorption characteristics, and the dye α is a phthalocyanine-based dye and has an absorption spectrum of a resin layer composed of the dye α and a measurement resin. When measured, the absorption maximum in the wavelength range of 600 to 650 nm and 680 to 750 nm, respectively, the dye β, when measuring the absorption spectrum of the resin layer consisting of the dye β and the measurement resin, It is preferable that the absorption maximum is exhibited in a wavelength range of 650 to 680 nm. Thereby, when the resin composition or laminated body (especially near infrared cut filter) of this invention is applied to an image pick-up element use, sufficient light absorption width can be ensured and generation | occurrence | production of a flare and a ghost can fully be suppressed. In addition, it is possible to sufficiently reduce the incident angle dependency that can be a problem when combined with a reflective film. 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.

  The dye α is a phthalocyanine dye, but the dye β is also preferably a phthalocyanine dye. It is preferable that the pigment α and the pigment β are phthalocyanine compounds represented by the general formula (I) described above.

  In the resin composition, the total amount of all the pigments is preferably 0.0001% by mass or more and 20% by mass or less with respect to 100% by mass of the total amount of the resin composition, for example. Thereby, it becomes possible to obtain a cured product (resin layer) having higher visible light transmittance and superior in blocking performance in the near infrared region. The lower limit of the pigment content is more preferably 0.001% by mass or more, further preferably 0.005% by mass or more, particularly preferably 0.1% by mass or more, and most preferably 1% by mass or more. Moreover, as an upper limit, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

  It is preferable that the said resin composition contains the pigment | dye (specific pigment | dye) which has an absorption maximum in the wavelength range of 600-900 nm, and may contain the other pigment | dye. For example, a dye having a characteristic absorption at a specific wavelength in each of the near-infrared, infrared, ultraviolet, and visible light bands other than the wavelength range of 600 to 900 nm may be appropriately selected according to the intended use, and for various uses of optical materials. Can be applied.

  The content of the other pigment is preferably 50% by mass or less with respect to 100% by mass of the total amount of the pigment. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less. In other words, the amount of the dye having an absorption maximum in the wavelength range of 600 to 900 nm is preferably 50% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight with respect to 100% by weight of the total amount of the dye. % Or more.

As for content of the pigment | dye in a resin composition, 0.05-30 mass% is mentioned preferably with respect to 100 mass% of resin compositions (resin layer corresponded to solid content), and 0.05-20 mass% is further. Preferably, 0.5-10 mass% is mentioned more preferably.
-Oxirane compounds-
The curable compound in the laminating resin composition of the present invention includes an oxirane compound having one or more oxirane rings in the molecule (also simply referred to as an oxirane compound). The proportion of the oxirane compound in the total amount of 100% by mass of the curable compound used in the present invention is preferably 5% by mass or more from the viewpoint of further improving heat resistance and film strength. 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%. Moreover, as a ratio of the oxirane compound with respect to the resin composition for lamination (total amount 100% by mass) of the present invention, 5 to 50% by mass is preferable, 10 to 40% by mass is more preferable, and 15 to 35% by mass. Is more preferable. In addition, it is preferable to have the said oxirane ring in the range of 1-1000 in a molecule | numerator.

  The resin composition for lamination according to the present invention includes an oxirane compound having one or more oxirane rings in the molecule (also simply referred to as an oxirane compound), and the oxirane compound includes an oxirane compound having a hydroxyl group and / or an ester group. That is, the laminating resin composition of the present invention contains an oxirane compound having a hydroxyl group and / or an ester group, and does not contain a hydroxyl group or an ester group in addition to the oxirane compound having a hydroxyl group and / or an ester group. Other oxirane compounds may be included.

  The 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. Moreover, since the said oxirane compound has a hydroxyl group and / or ester group, the said resin composition becomes what was excellent in adhesiveness.

  In the present specification, compounds that are cured (polymerized) by heat or light are collectively referred to as “curable compound” or “resin component”, and curable compounds having a cationic curable group are collectively referred to as “cationic curable”. Compound ".

A group containing an oxirane ring which is a three-membered ether is referred to as an “epoxy group”. In the “epoxy group”, in addition to an epoxy group in a narrow sense, a group in which an oxirane ring is bonded to carbon such as a glycidyl group, a group including an ether bond or an ester bond such as a glycidyl ether group and a glycidyl ester group, An epoxy cyclohexane ring and the like are included.
As the oxirane compound having a hydroxyl group and / or an ester group, an epoxy compound having a hydroxyl group and / or an ester group is suitable. 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 epoxy cyclohexane group (also referred to as an epoxy cyclohexane 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 an epoxycyclohexane group include 2,2-bis (hydroxymethyl)-
1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol,
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 compound, hydrogenated bisphenol S
Type epoxy compounds and hydrogenated bisphenol F type epoxy compounds are preferred. 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. In the aromatic epoxy compound, a compound in which the epoxy group is a glycidyl group is preferable, but a compound having a glycidyl ether group (also referred to as an aromatic glycidyl ether compound) 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 828EL and 1003.
, 1007 (above, Japan Epoxy Resin Co., Ltd.) and other bisphenol A type compounds; Compound; and the like, and among them, ogsol EG-210 is preferable.
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,
Preferable examples include those obtained by condensation reaction of polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, mono / polysaccharides such as glucose, fructose, lactose and maltose) and epihalohydrin. 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 total amount is 100% by mass of the oxirane compound.
It is suitable that it is 50 mass% or more with respect to. Thereby, it becomes possible to exhibit the effect by an alicyclic epoxy compound or a hydrogenated epoxy compound more. More preferably 6
It is 0 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.
In the resin composition, it is essential that the oxirane compound contains an oxirane compound having a hydroxyl group and / or an ester group, but may contain other oxirane compounds. As other oxirane compounds, novolak / aralkyl type glycidyl ether type epoxy resins and the like can be used.
In the 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-forming property at the time of forming a resin layer on a base material (it is also called a board | substrate). In this way, the oxirane compound is a compound having a weight average molecular weight of 2000 or more with respect to 100% by mass of the entire oxirane compound.
The form containing 100% by mass is one of the preferred forms of the present invention. More preferably 30 to 10
It is 0 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 2
It is preferable that it is 200 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 columns: TSK-GEL GMHXL-L and TSK-GELG5000HXL (
(Each eluent: Tetrahydrofuran (THF))
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

The resin composition for lamination of the present invention may contain one or more organic compounds having a curable functional group (referred to as other curable compounds) in addition to the oxirane compound described above.
The curable functional group refers to a functional group that undergoes a curing reaction by heat or light (that is, a group that causes a curing reaction of a resin composition). A cation curable group such as a group (oxetane ring), an ethylene sulfide group, a dioxolane group, a trioxolane group, a vinyl ether group, and a styryl group; a radical curable group such as an acryl group, a methacryl group, and a vinyl group; Therefore, as the other curable compound, a compound having a cationic curable group (also referred to as “cationic curable compound” or “cationic curable resin”) and / or a compound having a radical curable group (“
It is preferably also referred to as “radical curable resin” or “radical curable compound”.
As a result, the time until curing is shortened and the productivity is further increased, and the obtained cured product is also more excellent in heat resistance (heat decomposition resistance, heat resistance coloring property). Among them, it is more preferable to include a cationic curable compound in that the shape shrinkage with a mold or the like is easily performed due to a low curing shrinkage rate. In addition, the oxirane compound mentioned above is contained in a cationic curable compound.
The cationic curable compounds (oxirane compounds and other cationic curable compounds) are also
It is preferable to include a compound having two or more cationically polymerizable groups in one molecule, that is, a polyfunctional cationic curable compound. Thereby, sclerosis | hardenability is improved more and the hardened | cured material which is excellent with various characteristics can be obtained. The compound having two or more cationic polymerizable groups in one molecule may be a compound having two or more identical cationic polymerizable groups, or a compound having two or more different cationic polymerizable groups. May be. In the present invention, the polyfunctional cation curable compound is particularly preferably a polyfunctional alicyclic epoxy compound or a polyfunctional hydrogenated epoxy compound. By using these, a cured product can be obtained in a shorter time.
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, 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-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (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 and the like are preferable.
Specific examples of the oxetane compound include ETERNACOLL (R) EHO,
ETERRNACOLL (R) OXBP, ETERRNACOLL (R) OXMA, ETER
NACOLL (R) HBOX, ETERNCOLL (R) OXIPA (above, manufactured by Ube Industries); OXT-101, OXT-121, OXT-211, OXT-221, OXT-
212, OXT-610 (above, manufactured by Toa Gosei Co., Ltd.) and the like are suitable.

  Further, the laminating resin composition of the present invention preferably contains a compound that can shorten the curing time and serves as a diluent for the purpose of adjusting the resin viscosity. Examples thereof include vinyl ether monomers and aromatic monomers having 1 to 2 vinyl groups.

  Examples of vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, (1-ethylpropyl) vinyl ether, neopentyl. Vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, cyclohexane methanol vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, norbornyl vinyl ether, norbornenyl vinyl ether, norbornyl methyl vinyl ether, norbornenyl methyl vinyl ether, 2-acetoxyethyl Vinyl ether, 4-acetoxy-butyl vinyl ether, acetoxy cyclohexanemethanol vinyl ether, acetoxy diethylene vinyl ether, but acetoxy triethylene glycol vinyl ether, but is not limited thereto.

  Cationic polymerization catalysts suitable for vinyl ether monomers include protonic acids, metal oxides, halogens, and the like described in "Lecture Polymerization Reaction Vol. 3 (Toshinobu Higashimura, Kagaku Dojin, 1974)". Metal halides, organometallic compounds, stable cations and the like can be used. In addition, as the living cationic polymerization catalyst, initiators, Lewis acids, bases, salts, and the like described in "Experimental Chemistry Course Vol. 26 (5th edition, Maruzen, 2005)" can be used. That is, vinyl ether-hydrogen chloride adduct, vinyl ether-trifluoroacetic acid adduct, vinyl ether-acetic acid adduct as initiator, zinc chloride, tin tetrachloride, iron chloride, titanium tetrachloride as Lewis acid, ethyl acetate, diethyl as base Ether, tetrahydrofuran, 1,4-dioxane, quaternary ammonium salts and the like can be used as the salt, but are not limited thereto. Among these, vinyl ether-hydrogen chloride adduct, vinyl ether-trifluoroacetic acid adduct as initiator, zinc chloride as Lewis acid, ethyl acetate, diethyl ether, tetrahydrofuran, 1,4-dioxane as iron chloride base should be used. Is preferred.

  As a combination of initiator, Lewis acid, added base, and added salt, an initiator system that combines a relatively weak Lewis acid with an initiator, and a Lewis base that is added to an initiator system that combines a relatively strong Lewis acid with an initiator And a system in which a salt of a nucleophilic anion is added to an initiator system in which a relatively strong Lewis acid is combined with the initiator. Any of these may be used.

  The aromatic monomer having 1 to 2 vinyl groups is preferably a compound that can be cured by a cationic curing agent and has a double bond (vinyl group) in the skeleton and is liquid at 25 ° C. .

  For example, styrene, vinyl toluene, divinylbenzene and the like are exemplified, and styrene and divinylbenzene are preferable, and divinylbenzene is particularly preferable. This monomer plays a role as a diluent for the purpose of adjusting the resin viscosity required in the molding process without impairing the heat resistance, and further from the viewpoint of the crosslinking effect, a vinyl group is added. An aromatic monomer having two is preferable. In particular, divinylbenzene does not have a so-called polar component such as an oxygen atom in the compound, functions as a bifunctional crosslinking monomer, and serves as a viscosity modifier for a resin composition necessary for maintaining good molding processability. Not only is it useful for solvent resistance. The above aromatic monomers may be used alone or in combination of two or more.

  In a generally known cationic polymerization resin, a vinyl ether compound having no aromatic skeleton may be used as a diluent, but from the viewpoint of heat resistance, an aromatic having 1 to 2 vinyl groups. It is preferable to use a system monomer. The vinyl ether monomer and / or the aromatic monomer is preferably contained in an amount of 1 to 40 parts by weight, more preferably 1 to 30 parts by weight with respect to the resin composition (100 parts by weight in total) of the present invention. Part, particularly preferably 1 to 20 parts by mass. Moreover, the other monomer which melt | dissolves the said oxirane compound can be used together in the range which does not impair the effect of this invention.

As a cationic curing agent suitable for aromatic monomers having 1 to 2 vinyl groups, Bronsted acid is generated by heat or ultraviolet irradiation, and epoxy compounds and vinyl group-containing aromatic monomers are polymerized. Any known and commonly used ones can be used. For example, an onium salt in which the cation moiety is any selected from the group consisting of aromatic sulfonium and aromatic iodonium, and the anion moiety is composed of BF4-, PF6-, SbF6-, and the like.
-Coupling agent-
The resin composition of the present invention contains a specific coupling agent as an essential component. By containing a specific coupling agent, the heat-and-moisture resistance of the resin composition and the cured product (laminate) can be greatly improved, and the adhesiveness (particularly adhesion to a glass substrate) can be improved.

  The specific coupling agent used in the present invention is a silane coupling agent having an amino group. By including the silane coupling agent in the resin composition, there is an effect of improving adhesion to the glass substrate and an effect of suppressing water intrusion into the resin composition by a water repellent effect, as a result, A near-infrared cut filter excellent in heat resistance and heat-and-moisture resistance can be obtained. Specifically, peeling or the like can be suppressed during use in a solder reflow process or in a humid heat environment. Moreover, when an inorganic layer is formed on the cured product of the resin composition as an optical filter, the adhesion between the inorganic layer and the cured product is improved, and the heat and moisture resistance can be greatly improved, and adhesion (particularly adhesion to a glass substrate) is improved. Property) can be improved.

  Examples of the silane coupling agent include silicon as a central metal. By using a silane coupling agent, it becomes possible to further improve the heat and moisture resistance. The silane coupling agent is also preferably a coupling agent having, for example, a vinyl group, a (meth) acryl group, an oxirane group (oxirane ring), an amino group, a mercapto group, an isocyanate as a reactive group. Among them, an amino group is essential as a reactive group. Moreover, it is preferable to have an alkoxy group.

  As the amino group-containing silane coupling agent, those in which an amino group and an organic group are directly bonded to a silicon atom, and partial hydrolysis condensates thereof are generally used.

  Specific examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. Methyldiethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- ( 2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminopropyltriisopropoxysilane, 3- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino)- 2-methylpropyltri Toxisilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-amino Propyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, bis (3-tri Methoxysilylpropyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, γ- (N-phenylamino) propyltrimethoxysilane, γ- (N-phenylamino) propylmethyl Methoxysilane, γ- (N-methylamino) propyltrimethoxysilane, γ- (N-methylaminopropyl) methyldimethoxysilane, γ- (N-ethylamino) propyltrimethoxysilane, γ- (N-ethylamino) Propylmethyldimethoxysilane, γ- (N-ethylamino) propylmethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethylsilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxy Silane, γ- (N, N-dimethylamino) propyl Examples include propyltrimethoxysilane. Among these, a primary amine (a silane coupling agent having a primary amino group) is preferable because of good adhesion to a glass substrate. An amino group-containing silane coupling agent having a methoxy group is more preferred, and an amino group-containing silane coupling agent having a chain shape (preferably a straight chain having no ring structure) is particularly preferred. Among them, 3-aminopropyltrimethoxysilane and 3- (2-aminoethyl) aminopropyltrimethoxysilane are easily available, have high compatibility with the resin composition, and exhibit high adhesion to the glass substrate. Therefore, it is preferable. A silane coupling agent having both a primary amino group and a secondary amino group can also be used.

  Specific examples of the silane coupling agent include silane coupling agents such as Z-6610, Z-6020, Z-6011, Z-6094, and Z-6023 manufactured by Toray Dow Corning.

  In the present invention, a mercapto group-containing silane coupling agent may be contained in combination with an amino group-containing silane coupling agent.

As the mercapto group-containing silane coupling agent, those in which a mercapto group and an organic group are directly bonded to a silicon atom, and partial hydrolysis condensates thereof are generally used. Examples of the mercapto group-containing silane coupling agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and the like. As the organic group in the silane coupling agent, a hydrocarbon group substituted with a nitrogen atom, an oxygen atom, a halogen atom, a sulfur atom or the like is used.
Other specific examples of silane coupling agents that can be used in combination include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ- (2,3-epoxycyclohexyl) propyltrimethoxy. Examples include silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. Among them, those having an oxirane group as a reactive group are preferable.

  In addition, it is suitable that content of the amino group containing silane coupling agent which occupies for 100 mass% of total amounts of a silane coupling agent is 50-100 mass%. More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%, Most preferably, it is 100 mass%.

  The blending ratio of the amino group-containing silane coupling agent is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to 100% by mass of the oxirane compound, so that heat resistance and adhesion are achieved. Performance and light selective transmission filter performance can be improved.

  The content of the amino group-containing silane coupling agent in the resin composition is preferably 0.00001 to 20% by mass with respect to 100% by mass of the resin composition (resin layer corresponding to the solid content). 10 mass% is mentioned more preferably, and 0.00005-5 mass% is mentioned especially preferably.

By setting it as the said content, the laminated body (especially near-infrared cut filter) excellent in adhesiveness with a glass substrate and having high heat resistance excellent in adhesiveness with an inorganic multilayer film can be obtained. Moreover, the light resistance (sunlight resistance or UV resistance) of the coating film after forming the inorganic multilayer film can be improved by using a phthalocyanine dye as a resin.
-Curing agent-
It is preferable that the resin composition further contains a curing agent. One or more kinds of curing agents can be used in combination.

  What is necessary is just to select the said hardening | curing agent suitably according to hardening reaction, the kind of curable compound (it is also called curable resin), etc. For example, when heat curing is performed, a commonly used curing agent such as a heat latent radical curing catalyst, an acid anhydride system, a phenol system, or an amine system can be used in addition to the heat latent cationic curing catalyst. Among them, it is preferable to use a heat latent cationic curing catalyst and a heat latent radical curing catalyst, and it is particularly preferable to use a heat latent cationic curing catalyst for the purpose of reducing the shrinkage of the cured product. Moreover, when hardening by active energy ray irradiation, a photoinitiator can be used as a hardening | curing agent. Among them, it is preferable to use a photolatent cationic curing catalyst and a photolatent radical curing catalyst, and it is particularly preferable to use a photolatent cationic curing catalyst for the purpose of reducing the shrinkage of the cured product. Thus, a cationic curing catalyst is particularly preferable as the curing agent.

In the present specification, a catalyst that promotes a cationic curing reaction, such as a heat latent cationic curing catalyst or a photolatent cationic curing catalyst, is also referred to as a “cation curing catalyst”. The cationic curing catalyst functions differently from, for example, a curing accelerator in an acid anhydride curing reaction.
Among the curing agents, the heat-latent cationic curing catalyst is different from acid anhydrides, amines, phenol resins, etc. that are generally used as curing agents, and even if contained in the resin composition, the resin composition Without causing an increase in viscosity or gelation over time at room temperature, and as an action of the heat latent cationic curing catalyst, it can sufficiently promote the curing reaction and exert an excellent effect,
It is possible to provide a one-component resin composition (also referred to as “one-component material”) that is superior in handling properties.
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 (AX n) -m (1)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements. R ¹ , R ² , R ³ and R ⁴ is the same or different and represents an organic group, a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^{+ m} represents an onium salt, A is a metal element or a metalloid element (meta) that is a central atom of a halide complex
lloid), B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr,
It is at least one selected from the group consisting of Mn and Co. X represents a halogen element.
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 (AX _n ) ^-m of the general formula (1) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexa Examples include fluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), and the like. An anion represented by the general formula AX _n (OH) — can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ).
, Trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (F
SO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate ion and the like.
Specific examples of the thermal latent cationic curing catalyst include AMERICURE series (American Can), ULTRASET series (Adeka), WPA, and the like.
Diazonium salt type such as G series (manufactured by Wako Pure Chemical Industries); UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (Rhone-Poulenc (currently Rhodia), WPI series (Wako Pure Chemical Industries) and other iodonium salt types; CYRAC
URE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), Optomer S
P series / Optomer CP series (manufactured by Adeka), Sun Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.)
And sulfonium salt types such as CPI series (manufactured by San Apro).
Examples of the thermal latent radical curing catalyst include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate,
organic peroxides such as t-butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1
Azo compounds such as' -azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate);

As the photopolymerization initiator, it is preferable to use a photolatent cationic curing catalyst or a photolatent radical curing catalyst as described above. The photolatent cationic curing catalyst is also called a photocationic polymerization initiator, and exhibits a substantial function as a curing agent when irradiated with light. By using a photolatent cationic curing catalyst, a compound containing a cationic species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds.
Examples of the photolatent cationic curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl]
Sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio)
Phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate, diallyl iodonium hexafluoroantimonate and the like are preferable. 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); Among these, it is preferable to use an onium salt. Moreover, as an onium salt, it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.
Examples of the photolatent radical curing catalyst include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl]
Propanone oligomers, acetophenones such as 1,1-dichloroacetophenone; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone 4-benzoyl-4′-methyl-
Diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,
Benzophenones such as N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 , 4-Dimethyl-9H-
Thioxanthones such as thioxanthone-9-one mesochloride; xanthones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; acetophenone dimethyl ketal, benzyldimethyl ketal, etc. Ketals; 2-methyl-1- [4- (methylthio) phenyl]-
2-morpholino-propan-1-one or 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) -butanone-1; acylphosphine oxides;
Among these, acetophenones, benzophenones, and acylphosphine oxides are preferably used, and in particular, 2-hydroxy-2-methyl-1-phenylpropane-1-
On, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one is preferably used.
When a cationic curing catalyst or a radical curing catalyst is used as the curing agent, the blending amount means an amount of an active ingredient that does not contain a solvent or the like (solid content conversion amount). When a cationic curing catalyst composed of a Lewis acid and a Lewis base represented by the general formula (2) described later is used, the total amount of the Lewis acid and the Lewis base is used. ) Is preferably 0.01 to 25 parts by mass with respect to 100 parts by mass of the total amount of the cationic curable compound or the radical curable compound. As a result, the curing rate can be further increased, productivity and solvent resistance can be further improved, and the possibility of coloring during curing, heating, use, or the like can be further suppressed. Further, for example, when reflow mounting a cured product or a laminate obtained using the resin composition, heat resistance of 200 ° C. or higher is necessary, and from the viewpoint of colorlessness and transparency, 20 parts by mass or less. Is preferable. More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 3 mass parts or less.
In the case of using a commonly used curing agent such as an acid anhydride, phenol, or amine as the curing agent, those usually used may be used as these curing agents.
For example, as the acid anhydride-based curing agent, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthal, acid anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, Methyl nadic acid anhydride, het acid anhydride, hymic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-
Cycloaliphatic carboxylic acid anhydrides such as methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, chlorendic acid, methylendomethylenetetrahydrophthalic anhydride; dodecenyl anhydride Aliphatic carboxylic acid anhydrides such as succinic acid, polyazeline acid anhydride, polysebacic acid anhydride, polydodecanedioic acid anhydride; phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid And aromatic carboxylic anhydrides such as anhydride, ethylene glycol trimellitic anhydride, and biphenyltetracarboxylic anhydride.
Examples of the phenolic curing agent include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4′-butylene-bis (3-methyl) -6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton; 1,1 -Di-4
-Phenols having a fluorene skeleton such as hydroxyphenylfluorene; polyphenol compounds such as phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, Various novolak resins such as novolak resins made from various phenols such as naphthols: xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolac resins, fluorene skeleton-containing phenol novolak resins, and the like.
Of the commonly used curing agents such as acid anhydrides, phenols or amines, acid anhydrides are preferred, more preferably methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydro. Phthalic anhydride, hexahydrophthalic anhydride. More preferred are methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.
When 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, the mixing ratio of the said curable compound (it is also called curable resin) 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 curable resin. It is preferable. More preferably 0.7-1.
Mixing at a ratio of 4 equivalents, more preferably 0.9 to 1.2 equivalents.
The curing agent is preferably a cationic curing catalyst such as a thermal latent cationic curing catalyst or a photolatent cationic curing catalyst as described above. Thereby, since a hardening reaction can be suitably advanced in a short time and a hardened | cured material can be formed rapidly, manufacturing efficiency will be improved more. Moreover, in addition to obtaining a cured product with higher heat resistance and releasability,
The resin composition can exist stably as a one-component composition (one-component property) excellent in handling properties. Thus, the form in which the resin composition further contains a cationic curing catalyst is also a preferred form of the present invention. Among these, it is preferable to use at least a heat latent cationic curing catalyst.
The cationic curing catalyst is a catalyst that accelerates the cationic curing reaction, and functions differently from, for example, a curing accelerator in an acid anhydride curing reaction.
The cationic curing catalyst preferably contains a boron compound, and more preferably contains an aromatic fluorine compound.
As the cation curing catalyst, the following general formula (2):

（式中、Ｒは、同一又は異なって、置換基を有してもよい炭化水素基を表す。ｘは１〜５
の整数であり、同一又は異なって、芳香環に結合しているフッ素原子の数を表す。ａは１
以上の整数であり、ｂは０以上の整数であり、ａ＋ｂ＝３を満たす。）で表されるルイス
酸（有機ボラン）と、ルイス塩基とからなる形態である。
これにより、硬化方法としてカチオン硬化を採用することができるため、例えば酸無水物
硬化のような付加型硬化を採用する場合と比較して、得られる硬化物が耐熱性、化学的安
定性、耐湿性等の光学用途で求められる特性により優れたものとなる。また、アンチモン
系スルホニウム塩等の従来のカチオン硬化触媒を用いた場合と比較して、熱（硬化時、成
膜時、使用環境）による着色が低減され、耐湿熱性や耐温度衝撃性等の耐久性により優れ
た硬化物が得られる。
なお、用いる触媒に基づく硬化物の着色の有無・程度は、通常、４００ｎｍにおける透過
率の変化からも確認することができる。つまり、硬化物の４００ｎｍの透過率を測定する
ことによって、硬化物の着色の有無・程度を評価することができる。
上記一般式（２）におけるＲは、同一又は異なって、置換基を有してもよい炭化水素基を
表す。上記炭化水素基は特に限定されないが、炭素原子数１〜２０の炭化水素基であるこ
とが好ましい。炭素原子数１〜２０の炭化水素基は、全体として炭素原子数が１〜２０で
あれば限定されないが、アルキル基、アリール基、アルケニル基であることが好ましい。
当該アルキル基、アリール基、アルケニル基は、無置換の基であっても、水素原子の１又
は２以上が他の有機基又はハロゲン原子によって置換された基であってもよい。この場合
の他の有機基としては、アルキル基（Ｒで表される炭化水素基がアルキル基である場合に
は、置換後の炭化水素基は全体として無置換のアルキル基に該当する。）、アリール基、
アルケニル基、アルコキシ基、水酸基等が挙げられる。
上記一般式（２）におけるｘは１〜５の整数であり、同一又は異なって、芳香環に結合し
ているフッ素原子の数を表す。芳香環におけるフッ素原子の結合位置は特に限定されない
。ｘとして好ましくは２〜５であり、より好ましくは３〜５であり、最も好ましくは５で
ある。
またａは１以上の整数であり、ｂは０以上の整数であり、ａ＋ｂ＝３を満たす。すなわち
、上記ルイス酸は、フッ素原子が結合した芳香環が少なくとも１つ、ホウ素原子に結合し
たものである。ａとしてより好ましくは２以上であり、特に好ましくは３、すなわち、フ
ッ素原子が結合した芳香環がホウ素原子に３つ結合している形態である。
上記ルイス酸として具体的には、例えば、トリス（ペンタフルオロフェニル）ボラン（「
ＴＰＢ」と称す）、ビス（ペンタフルオロフェニル）フェニルボラン、ペンタフルオロフ
ェニル−ジフェニルボラン、トリス（４−フルオロフェニル）ボラン等が好ましい。これ
らの中でも、硬化物の耐熱性、耐湿熱性、耐温度衝撃性等を向上できる点で、ＴＰＢがよ
り好ましい。なお、カチオン硬化触媒のうち、ルイス酸としてＴＰＢを含むものを、「Ｔ
ＰＢ系触媒」とも称す。
上記ルイス塩基は、上記ルイス酸に配位することができるもの、すなわち、上記ルイス酸
が有するホウ素原子と配位結合を形成できるものであれば限定されず、ルイス塩基として
通常用いられるものを用いることができるが、非共有電子対を有する原子を有する化合物
が好適である。具体的には、窒素原子、リン原子又は硫黄原子を有する化合物であること
が好適である。この場合、ルイス塩基は、窒素原子、リン原子又は硫黄原子が有する非共
有電子対を、上記ルイス酸のホウ素原子に供与することにより、配位結合を形成すること
となる。また、上記ルイス塩基は、窒素原子又はリン原子を有する化合物がより好ましい
。上記窒素原子を有する化合物として好ましくは、アミン類（モノアミン、ポリアミン）、アンモニア等が挙げられる。より好ましくは、ヒンダードアミン構造を有するアミン、低沸点のアミン、アンモニアであり、更に好ましくは、ヒンダードアミン構造を有するポリアミン、アンモニアである。上記ルイス塩基としてヒンダードアミン構造を有するポリアミンを用いると、ラジカル捕捉効果により硬化物の酸化防止が可能となり、得られる硬化物がより耐熱性（耐湿熱性）に優れたものとなる。一方、上記ルイス塩基としてアンモニア又は低沸点のアミンを用いると、得られる硬化物が低吸水性、耐ＵＶ照射性に優れたものとなる。硬化工程でアンモニア又は低沸点のアミンが揮発することにより、最終の成形体（硬化物）中の、アンモニア又は低沸点のアミンに由来する塩構造が少なくなるため、硬化物の吸水率を低減することができると推測される。特にアンモニアは上述の効果に優れるため好ましい。
ここで、後述するように、本発明では１２０℃以下の沸点を有する窒素含有化合物を含む
ことが好ましいため、上記ルイス塩基として１２０℃以下の沸点を有する窒素含有化合物
を用いることも好適である。すなわち１２０℃以下の沸点を有する窒素含有化合物は、上
記カチオン硬化触媒を形成する一部として、樹脂組成物中に含有されることも好適である
。

(In formula, R is the same or different and represents the hydrocarbon group which may have a substituent. X is 1-5.
And is the same or different and represents the number of fluorine atoms bonded to the aromatic ring. a is 1
It is an integer above, b is an integer greater than or equal to 0, and satisfies a + b = 3. ) Represented by a Lewis acid (organic borane) and a Lewis base.
As a result, cationic curing can be employed as a curing method. Therefore, compared to the case where addition-type curing such as acid anhydride curing is employed, the resulting cured product has heat resistance, chemical stability, and moisture resistance. The properties required for optical applications such as properties are superior. In addition, compared to the case of using a conventional cationic curing catalyst such as antimony sulfonium salt, coloring due to heat (during curing, film formation, environment of use) is reduced, and durability such as moisture and heat resistance and temperature impact resistance is reduced. A cured product superior in properties can be obtained.
The presence / absence or degree of coloring of the cured product based on the catalyst to be used can be confirmed from the change in transmittance at 400 nm. That is, by measuring the 400 nm transmittance of the cured product, the presence / absence or degree of coloring of the cured product can be evaluated.
R in the said General formula (2) is the same or different, and represents the hydrocarbon group which may have a substituent. Although the said hydrocarbon group is not specifically limited, It is preferable that it is a C1-C20 hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group.
The alkyl group, aryl group, and alkenyl group may be an unsubstituted group, or may be a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom. Other organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group corresponds to an unsubstituted alkyl group as a whole), An aryl group,
An alkenyl group, an alkoxy group, a hydroxyl group, etc. are mentioned.
X in the said General formula (2) is an integer of 1-5, and is the same or different and represents the number of the fluorine atoms couple | bonded with the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. x is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.
A is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom. a is more preferably 2 or more, and particularly preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.
Specific examples of the Lewis acid include tris (pentafluorophenyl) borane (“
TPB ”), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, tris (4-fluorophenyl) borane and the like are preferable. 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. Among the cationic curing catalysts, those containing TPB as a Lewis acid are referred to as “T
Also referred to as “PB catalyst”.
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 the unshared electron pair of the nitrogen atom, phosphorus atom or sulfur atom to the boron atom of the Lewis acid. The Lewis base is more preferably a compound having a nitrogen atom or a phosphorus atom. Preferred examples of the compound having a nitrogen atom include amines (monoamines and polyamines) and ammonia. More preferred are amines having a hindered amine structure, amines having a low boiling point, and ammonia, and still more preferred are polyamines having a hindered amine structure and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, the cured product can be prevented from oxidation due to the radical scavenging effect, and the resulting cured product is more excellent in heat resistance (moisture heat resistance). On the other hand, when ammonia or a low-boiling amine is used as the Lewis base, the resulting cured product is excellent in low water absorption and UV irradiation resistance. As ammonia or low boiling point amine volatilizes in the curing process, the salt structure derived from ammonia or low boiling point amine in the final molded product (cured product) is reduced, so the water absorption of the cured product is reduced. It is speculated that it can. In particular, ammonia is preferable because of its excellent effects.
Here, as described later, since it is preferable to include a nitrogen-containing compound having a boiling point of 120 ° C. or less in the present invention, it is also preferable to use a nitrogen-containing compound having a boiling point of 120 ° C. or less as the Lewis base. That is, it is also preferable that the nitrogen-containing compound having a boiling point of 120 ° C. or less is contained in the resin composition as part of forming the cationic curing catalyst.

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; TIN
UVIN770, TINUVIN765, TINUVIN144, TINUVIN123
, TINUVIN744, CHIMASSORB2020FDL (above, manufactured by BASF)
; Adekastab LA52, Adekastab LA57 (above, manufactured by ADEKA) and the like. Among them, TINUVIN770 having two or more hindered amine structures per molecule, T
INUVIN765, ADK STAB LA52, and ADK STAB LA57 are suitable.
As the low boiling point amine, an amine having a boiling point of 120 ° C. or lower is preferably used, more preferably 80 ° C. or lower, still more preferably 50 ° C. or lower, and still more preferably 30
C. or lower, particularly preferably 5 ° C. or lower. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine, piperidine; And tertiary amines such as trimethylamine and triethylamine.
The compound having a phosphorus atom is preferably a phosphine. Specific examples include triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and diphenylphosphine.
Preferred examples of the compound having a sulfur atom include thiols and sulfides. As thiols, specifically, methyl thiol, ethyl thiol, propyl thiol,
Examples include hexyl thiol, decane thiol, and phenyl thiol. Specific examples of the sulfides include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide and the like.
In the cationic curing catalyst composed of the Lewis acid and the Lewis base represented by the general formula (2), the mixing ratio of the Lewis acid and the Lewis base is not necessarily a stoichiometric ratio. That is, any one of Lewis acid and Lewis base (converted to the base point amount) may be contained in excess of the theoretical amount (equivalent). Specifically, the mixing ratio of the Lewis acid and the Lewis base in the cation curing catalyst is such that the atomic number n (b) of the atom serving as the Lewis base point with respect to the atomic number n (a) of boron serving as the Lewis acid point. Expressed as a ratio (n (b) / n (a)), even if it is not 1 (stoichiometric ratio), it acts as a cationic curing catalyst. Here, the ratio n (b) / n (a) in the cationic curing catalyst
Affects the storage stability and cationic curing properties (curing speed, degree of curing of the cured product, etc.) of the resin composition.
When the Lewis base has two Lewis base points in the molecule, such as diamines,
When the mixing molar ratio of Lewis base to Lewis acid constituting the cationic curing catalyst is 0.5, the ratio n (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.
The ratio 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.
In addition, when the Lewis base is a nitrogen-containing compound having a boiling point of 120 ° C. or less (particularly ammonia or a low-boiling amine having a small steric hindrance), especially when it is ammonia, the ratio n (
b) / n (a) is preferably greater than 1. More preferably, it is 1.001 or more, More preferably, it is 1.01 or more, Especially preferably, it is 1.1 or more, Most preferably, it is 1.5 or more.
The presence form of the Lewis acid and the Lewis base constituting the cation curing catalyst is not particularly limited, but it is preferable that the Lewis base is present in an electronic interaction with the Lewis acid. More preferably, at least a part of the Lewis base is coordinated to the Lewis acid, and more preferably at least a Lewis base equivalent to an equivalent amount to the Lewis acid present is coordinated to the Lewis acid. It is a form. When the abundance ratio of Lewis base to Lewis acid is equivalent or less than equivalent, that is, when the ratio n (b) / n (a) is 1 or less, almost all of the Lewis base present is coordinated to the Lewis acid. The form formed is preferable. On the other hand, in the form in which the Lewis base is contained in excess (more than equivalent), it is preferable that the Lewis base is coordinated with the Lewis acid in an equivalent amount, and the excess Lewis base is present in the vicinity of the complex.
Specific examples of the cationic curing catalyst comprising a Lewis acid and a Lewis base represented by the general formula (2) include, for example, a TPB / monoalkylamine complex, a TPB / dialkylamine complex,
TPB alkylamine complexes such as TPB / trialkylamine complexes, organic borane / amine complexes such as TPB / hindered amine complexes; organic borane / ammonia complexes such as TPB / NH ₃ complexes; TPB / triarylphosphine complexes, TPB / diarylphosphine complexes , TP
Organic borane / phosphine complex such as B / monoarylphosphine complex; Organic borane / thiol complex such as TPB / alkylthiol complex; TPB / diaryl sulfide complex, TPB
/ Organic borane / sulfide complexes such as dialkyl sulfide complexes. Above all,
TPB / alkylamine complex, TPB / hindered amine complex, TPB / NH ₃ complex, T
PB / phosphine complexes are preferred.
In the above resin composition, the content of the cation curing catalyst is the amount of the active ingredient that does not include a solvent or the like (
Solid content equivalent amount). Cations contained in the resin composition as a cation curing catalyst composed of a Lewis acid and a Lewis base represented by the general formula (2) are the total amount of the Lewis acid and the Lewis base) It is suitable to set it as 0.01-25 mass parts with respect to 100 mass parts of total amounts of a sclerosing | hardenable compound. As a result, the curing rate can be further increased, productivity and solvent resistance 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 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, Particularly preferably, it is 6 parts by mass or less.

-Nitrogen-containing compounds-
The resin composition preferably also contains a nitrogen-containing compound having a boiling point of 120 ° C. or lower (also simply referred to as “nitrogen-containing compound”). As a result, the resin composition is excellent in storage stability due to the presence of the nitrogen-containing compound at the time of storage (storage) or transfer, while part or all of the nitrogen-containing compound is volatilized at the time of curing. It is possible to easily obtain a cured product having excellent film formability and high appearance. Thus, the form in which the resin composition further contains a nitrogen-containing compound having a boiling point of 120 ° C. or less is also a preferred form of the present invention.
The boiling point of the nitrogen-containing compound is preferably 10 from the viewpoint of further manifesting the above effects.
0 ° C. or less, more preferably 80 ° C. or less, further preferably 50 ° C. or less, particularly preferably 30
° C or lower, most preferably 5 ° C or lower.
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. For example, A
When the room temperature is 25 ° C., the boiling point of the nitrogen-containing compound is preferably 105 ° C. or less. Thereby, it becomes possible to exhibit the effect by using the nitrogen-containing compound mentioned above more fully. More preferably (A + 60) ° C. or lower, still more preferably (A + 30) ° C. or lower,
Particularly preferably, it is (A + 10) ° C. or lower.
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), monobutylamine (boiling point: 78 ° C), monopentylamine, ethylenediamine (boiling point: 117 ° C) Primary amines such as 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.), piperidine (
Secondary amines such as boiling point: 106 ° C .; tertiary amines such as trimethylamine (boiling point: 2.9 ° C.) and triethylamine (boiling point: 89.7 ° C.); 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 0.01-5
Part by mass.
In the present invention, it is also preferable to use a cationic curing catalyst comprising a Lewis acid represented by the general formula (2) 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.
-Solvent-
It is preferable that 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.
When it contains the said solvent, it is preferable that it is 10 mass parts or more as the content with respect to 100 mass parts of total amounts of a sclerosing | hardenable compound (resin component). Thereby, the said resin composition can exhibit the fluidity | liquidity more excellent as a material which forms a layer on a base material (preferably transparent inorganic material layer). 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. On the other hand, the content of the solvent is preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less, and still more preferably 1000 parts by mass or less.
By the way, for example, other components (for example, curable compounds and pigments) can be sufficiently dissolved in the solvent; there is little film thickness unevenness when the solution is coated on a substrate; No surface roughness due to bumping or the like even when heated to a temperature; it does not reduce the strength of the film as a hardening inhibiting factor; it does not induce changes in physical properties such as thickening even when the solution is stored for a long period of time Based on such conditions, an appropriate solvent should be selected according to the type of components (for example, curable compound, dye, curing catalyst, etc.) in the resin composition to be used. Is preferred.
Then, when the present inventors advanced examination, as a solvent, acetone, (gamma) -butyllactone, diethyl diglycol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), It has been found that when tetrahydrofuran (THF) or the like is used, a good film is formed. Especially, PGMEA has a boiling point of 145 ° C.
Despite being relatively high, the volatility is high, so when PGMEA is used as the main component of the solvent, there is little film thickness unevenness, no surface roughness due to bumping, and little inhibition of curing, A resin composition (resin solution) containing PGMEA found to have good storage stability
Found that the quality of the coating film using it was high and the solution could be stably produced. It has been found that a solvent having a relatively large molecular structure other than PGMEA having a dielectric constant of less than 10 and a molecular weight of more than 100 exhibits substantially the same effect. Thus, the resin composition further contains a solvent, and the solvent includes a solvent having a dielectric constant of less than 10 and a molecular weight of more than 100 (“a solvent having a dielectric constant of less than 10 and a molecular weight of more than 100”). Moreover, it is one of the suitable forms of this invention.
The resin composition having the above-described form is suitable as, for example, an ink solution for a light selective transmission filter (for example, an infrared absorption filter).

-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 the photosensitizer is included, the content is 10 as the total amount of the curable resin (curable compound).
It is preferable to set it as 0.1-20 mass parts with respect to 0 mass parts. More preferably 0.5-1
0 parts by mass.
-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, and organic base acid salts include organic onium salts such as organic phosphonium salts and organic ammonium salts, and tertiary nitrogen. Organic base acid salts having Examples of organic phosphonium salts include phosphonium bromides having four phenyl rings such as tetraphenyl phosphonium bromide and triphenyl phosphine / toluene bromide. Examples of organic ammonium salts include tetraoctyl ammonium bromide, tetra Examples include tetra (C1-C8) alkylammonium bromides such as butylammonium bromide and tetraethylammonium bromide. Examples of acid salts of organic bases having tertiary nitrogen include alicyclic bases having tertiary nitrogen in the ring. Examples include acid salts and organic acid salts of various imidazoles.
Examples of the organic acid salt of an alicyclic base having tertiary nitrogen in the ring include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8-diazabicyclo (5,4).
, 0) Diaza compounds such as octylate of undecene-7 and salts of phenols, the following polyvalent carboxylic acids or phosphinic acids.
Examples of the organic acid salts of the various imidazoles include salts of imidazoles with organic acids such as polycarboxylic acids. Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. Examples include 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, and the like. Preferred imidazoles include, for example, 3 described later.
Examples thereof include the same imidazoles as phenyl group-substituted imidazoles in aromatic compounds having secondary nitrogen.
Examples of the polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as maleic acid and oxalic acid. Examples of preferred polyvalent carboxylic acids include acids.
For example, aromatic polycarboxylic acids such as terephthalic acid, trimellitic acid and pyromellitic acid can be mentioned. Examples of preferable salts of imidazoles with organic acids such as polyvalent carboxylic acids include polyvalent carboxylates of imidazoles having a substituent at the 1-position. More preferred is, for example, trimellitic acid salt of 1-benzyl-2-phenylimidazole.
Examples of the aromatic compound having tertiary nitrogen include phenyl group-substituted imidazoles and 3
Examples include secondary amino group-substituted phenols. Examples of phenyl group-substituted imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Examples include 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like. Preferably, for example, imidazoles having an aromatic substituent at the 1-position, more preferably
For example, 1-benzyl-2-phenylimidazole. Examples of tertiary amino group-substituted phenols include di (C1) such as 2,4,6-tri (dimethylaminomethyl) -phenol.
-C4) Phenols having 1 to 3 alkylamino (C1-C4) alkyl groups.
Among the above-mentioned curing accelerators, particularly preferred curing accelerators include 1,8-diazabicyclo (5
, 4,0) Undecene-7 phenol salt, 1,8-diazabicyclo (5,4,0) undecene-7 octylate, 2,4,6-tri (dimethylaminomethyl) -phenol,
Tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, trimellitic acid salt of 1-benzyl-2-phenylimidazole, tetraphenylphosphonium bromide, triphenylphosphine / toluene bromide.
When the said hardening accelerator is included, it is preferable that the content shall be 0.01-5 mass parts with respect to 100 mass parts of total amounts of curable resin (curable compound). More preferably, it is 0.03-3 mass parts.
-Flexible component-
The resin composition preferably also includes a component having flexibility (referred to as “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.
The flexible component may be a compound different from the curable resin, or at least one of the curable resins may be a flexible component.
Examples of the flexible component include compounds having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] m— (n is an integer of 2 or more, and m is an integer of 1 or more. In the formula, n is 2 to 12, m is an integer of 1 to 1000, and more preferably, n is 3 to 6 and m is 1 to 20.
Is an integer. ), For example, an epoxy compound containing an oxybutylene group (manufactured by Japan Epoxy Resin, YL-7217, epoxy equivalent 437, liquid epoxy compound (
10 ° C or higher)) is preferred. As other suitable flexible components, liquid rubber such as liquid nitrile rubber, polymer rubber such as polybutadiene, fine particle rubber having a particle diameter of 100 nm or less, and the like are preferable.
Among these, the flexible component is preferably a compound containing an epoxy group, more preferably an oxybutylene group (— [— (CH ₂ ) ₄ —O—] _m — (m is the same as above)). It is a compound which has this.
When the flexible component is included, the content thereof is preferably 40% by mass or less with respect to 100% by mass of the total amount of the curable compound and the flexible component. More preferably 30
It is at most 20% by mass, more preferably at most 20% by mass. Moreover, 0.01 mass% or more is preferable, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.
-Other ingredients-
In addition to the above-mentioned essential components and suitable components, the above-mentioned resin composition for lamination is not saturated with a curing accelerator, a reactive diluent, and an unsaturated bond as long as the effects of the present invention are not impaired. Compound, Pigment, Dye, Antioxidant, UV absorber, IR cut agent, Light stabilizer, Plasticizer, Non-reactive compound, Chain transfer agent, Anaerobic polymerization initiator, Polymerization inhibitor, Inorganic filler, Organic filler Adhesion improvers other than coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners and sagging prevention Agents, color separation preventing agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic aids) and the like.
When the 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 zirconia having a particle size of 40 nm or less are preferable. For example, MEK-ST manufactured by Nissan Chemical Industries, Ltd. is preferably used.
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.
The resin composition may cause defects such as striations and dents in the coating film during coating and curing, and it is preferable to add a leveling agent or a surfactant as necessary. As the additive, a silicone-based additive or an acrylic additive is preferable. For example, BYK-378, BYK-392, BYK-337, BYK-355, BYK-354, BYK-306, BYK-330 manufactured by BYK Chemie are preferable. As addition amount, 0.001 part-10 parts are preferable with respect to resin, More preferably, 0.01-5 parts are preferable. If it is excessive, precipitation or turbidity may occur in the coating film, and if it is too small, defects in the coating film cannot be suppressed.
In addition, the foreign material contained in the said resin composition can be removed by filtering, when preparing a resin composition.
-Preparation method-
The method for preparing the laminating resin composition of the present invention is not particularly limited, and can be obtained by mixing the components by a usual 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 below the decomposition temperature of the curable resin (curable compound) or below the reaction temperature, but preferably 140 to 20 ° C. before the addition of the curing agent (catalyst). Preferably 12
0-40 ° C.

  As a mixing method, it can prepare by mixing and dispersing using various mixers and dispersers. A dispersion process and a mixing process are not specifically limited, What is necessary is just to perform by a normal method. Further, it may further include other steps that are normally performed.

In the preparation of the resin composition of the present invention, the order of adding and mixing the respective components can be appropriately selected. However, after adding and mixing the pigment to the resin curing component, a form in which a silane coupling agent is further added and mixed, or the resin curing component After adding and mixing a silane coupling agent, a form in which a dye is further added is preferable. In particular, a form in which a resin component, a solvent, and a dye are mixed and then a silane coupling agent and a curing agent are mixed is most preferable.
-Viscosity-
The resin composition preferably has a viscosity of 10,000 Pa · s or less. This makes it possible to obtain a film having excellent processing characteristics, for example, a smooth surface during coating.
More preferably, it is 1000 Pa · s or less, More preferably, it is 200 Pa · s or less, More preferably, it is 10000 mPa · s or less, Most preferably, it is 100 mPa · s or less, Most preferably, it is 50 mPa · s or less. Moreover, it is preferable that it is 0.01 mPa * s or more, More preferably, it is 0.1 mPa * s or more.
The measurement of the viscosity can be evaluated for the resin composition using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The numerical value of the viscosity is preferably a value evaluated under the condition of 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. As thermosetting, it is preferable to cure at about 30 to 400 ° C., and as photocuring, 10 to 10000 mJ /
It is preferred to cure in cm ^2. Curing may be performed in one stage, or may be performed in two stages such as primary curing (preliminary curing) and secondary curing (main curing).
Hereinafter, the case of performing the two-stage curing will be described in detail.
As a two-step curing method, the resin composition is 10 to 100 as the first step corresponding to the primary curing.
Equivalent to secondary curing in which photocuring is performed at 000 mJ / cm ² or thermosetting at 80 to 200 ° C., and the cured product obtained in the first step is thermosetting at over 200 ° C. and below 500 ° C. It is preferable to employ a method including the second step.
In the first step, in the case of thermosetting, the curing temperature is preferably 80 to 200 ° C. More preferably, it is 100 degreeC or more and 160 degrees C or less. The curing temperature is 80-2.
You may change in steps within the range of 00 degreeC.
The curing time in the thermosetting step is preferably, for example, within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.
The thermosetting step can also be performed in air or in an atmosphere of an inert gas such as nitrogen, under reduced pressure, or under pressure. Moreover, you may combine photocuring (curing by active energy ray irradiation).
In the curing method, in the second step, the cured product obtained in the first step exceeds 150 ° C.,
It is preferable to heat cure at 500 ° C. or lower. The lower limit of the curing temperature is more preferably 200.
Or higher, more preferably 230 ° C. or higher, even more preferably 250 ° C. or higher, more preferably 300 ° C. or higher, particularly preferably 330 ° C. or higher, and most preferably 350 ° C. or higher. The upper limit is more preferably 400 ° C. or lower. Also, the curing temperature exceeds 150 ° C. and 500
You may change in steps within the temperature range below ℃.
The curing time in the second step is not particularly limited as long as the curing rate of the cured product to be obtained is sufficient, but considering the production efficiency, for example, 10 minutes to 30 hours is preferable. . More preferably, it is 30 minutes to 10 hours.
The second step can also be performed in any atmosphere such as air or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0
. 5% by volume or less, most preferably 0.3% by volume or less.
By carrying out the first step, it is possible to suppress the aggregation and repellency of the coating liquid with respect to the coated substrate. Moreover, it becomes possible to improve the heat resistance with respect to a reflow process and a vapor deposition process by implementing the said 2nd process.
The curing method preferably includes the first step and the second step, but before and after that,
A curing treatment may be included in the middle. For example, after the first step is performed by photocuring, thermal curing is performed at 150 ° C. for 60 minutes under nitrogen, and the second step is performed by thermal curing. By performing such treatment, it is possible to further improve the film formability and heat resistance.
As another curing method, one-step curing is also preferable. In particular, when the laminating resin composition of the present invention contains a nitrogen-containing compound having a boiling point of 120 ° C. or lower, the curability is particularly excellent. Only by the heat curing step as curing, a cured product exhibiting a sufficiently excellent appearance can be efficiently provided. Therefore, in this case, for example, compared with the case where two-stage curing of photocuring and thermal curing is performed, the process can be shortened by omitting the photocuring process, so that the productivity and workability of the cured product are excellent. become.
As the curing method by the one-step curing, a thermosetting method is particularly preferable. The thermosetting is preferably performed at about 80 to 400 ° C., and may be changed stepwise within this temperature range. The temperature for the one-step curing is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, and most preferably 150 ° C. or higher from the viewpoint of increasing the curability of the resin. On the other hand, from the viewpoint of suppressing the deterioration of the dye and the coupling agent, the temperature is preferably less than 300 ° C, more preferably less than 250 ° C, and most preferably less than 200 ° C.
The curing time in the one-step curing process is not particularly limited as long as the curing rate of the cured product to be obtained is sufficient, but considering the production efficiency, for example, it is preferably 1 minute to 30 hours. is there. More preferably, it is 10 minutes to 10 hours.
The one-step curing process 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 from the viewpoint of suppressing deterioration of the pigment and the resin. 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. From the viewpoint of improving the simplicity and productivity of the apparatus, curing in an atmospheric atmosphere is preferable. In addition, from the viewpoint of improving the transmittance in the visible region around 500 nm of the resin of the present application, a form in which curing in the air is essential is also a preferred form.
In the curing, from the viewpoint of improving the production amount, it is preferable to directly dry by a flat plate heating apparatus such as a hot plate or an oven that is at a predetermined temperature after coating.
As described above, the lamination resin composition of the present invention can give a cured product excellent in heat resistance, adhesion (adhesiveness), moist heat resistance, temperature impact resistance, light resistance and the like. Therefore, when a resin layer made of the resin composition of the present invention is formed on a substrate, the resin layer has high heat resistance and the like, excellent surface appearance, and sufficiently suppresses the reduction of visible light transmittance and coloring. 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 elements such as a light selective transmission filter typified by an IR cut filter). Material). In addition, various elements such as mobile phones, televisions, personal computers, and in-vehicle applications are in a process of adopting a solder reflow process for reasons such as simplification of manufacturing process and cost reduction. Since the laminated body obtained by using the solder reflow process sufficiently suppresses the deterioration of the optical characteristics, the members of various elements adopting the solder reflow process (for example, light represented by an IR cut filter) It is particularly useful as an optical material such as a selective transmission 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 hardened | cured material (laminated body) obtained by forming the layer which consists of the said resin composition for lamination | stacking on a base material is also one of this invention.

[Laminate]
The laminate (also referred to as “laminate”) of the present invention has a layer (also referred to as “resin layer”) made of the above-described resin composition for lamination on a substrate. That is, the laminating resin composition of the present invention can be used as a material for forming a 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 (preferably for coating on a glass substrate).
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 resin layer via another constituent member existing on the base material. The form is also included.
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 further improving the adhesiveness, for example, the surface treatment of the constituent member with a liquid material containing a metal oxide precursor such as a silane coupling agent is performed. The resin composition can also be applied after applying the above. Thereby, for example, in use in a solder reflow process or a wet heat environment, it is possible to further suppress peeling and the like. As the silane coupling agent, a compound having an amino group, a mercapto group, or an oxirane group as a reactive group is preferable.
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). 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 a coating film is formed by spin coating, a transparent inorganic material layer (or other constituent member) is placed at around room temperature (25 ° C.).
It is preferable to dry the solvent while rotating at 0 to 4000 rpm for about 10 to 60 seconds. In addition, it is also preferable to perform the inkjet method from the viewpoint of reducing the deviation while obtaining a sample other than a round shape that is difficult to obtain by spin coating. Moreover, it is preferable to perform photocuring and / or thermosetting as needed after spin coating or inkjet.
As one of the preferable forms of the said laminated body, the form which has an absorption maximum in the wavelength range of 650-680 nm, and has only one absorption maximum in the wavelength range of 400-680 nm is mentioned. Specifically, such a laminate has an absorption maximum in a wavelength region of 650 to 680 nm, and 4
The form which makes the phthalocyanine type pigment | dye which shows the absorption characteristic of having only one absorption maximum in the wavelength range of 00-680 nm essential is mentioned. This form makes it possible to create a laminate with high heat resistance, and 400 to 68 depending on the combination with an inorganic reflective film or an inorganic interference film.
A spectrum having no absorption maximum at 0 nm can be obtained. Thereby, since the said laminated body can exhibit the light selective permeability close | similar to the sensitivity of human eyes, it becomes a very useful laminated body for an image pick-up element use. In addition, when the laminate is applied to an imaging device, generation of flare and ghost can be sufficiently suppressed, and incident angle dependency that can be a problem when combined with a reflective film can be sufficiently reduced. More preferably, the laminate is 650-
It has an absorption maximum in the wavelength region of 680 nm, and 1 absorption maximum in the wavelength region of 400 to 750 nm.
Have only one. Thereby, the said effect can be exhibited further.
Here, “having only one absorption maximum in the wavelength region of 400 to 680 nm” means 400 to 6
It means that only one apex (absorption maximum) at which the absorbance changes from increase to decrease is observed in the wavelength region of 80 nm. The peak having the peak at the absorption maximum 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.
The laminate preferably has a transmittance at a wavelength of 550 nm of 80% or more. Wavelength 5
If the transmittance is 50% or more at 50 nm, more excellent light selective transparency can be exhibited. The transmittance is more preferably 83% or more, further preferably 85% or more, particularly preferably 87% or more, and most preferably 89% or more.
The laminate preferably has a transmittance of 60% or less at an absorption maximum wavelength or a maximum absorption wavelength existing in a wavelength range of 650 to 680 nm. More preferably, it is 50% or less, More preferably, it is 40% or less, More preferably, it is 30% or less.
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 in the longer wavelength side in the wavelength range of 600 to 680 nm. For example, when the transmittance is measured every 1 nm in the wavelength range of 600 to 680 nm, It is preferable that the transmittance does not exceed the transmittance at longer wavelengths. Thereby, since the transmittance spectrum becomes a smoother curve, more excellent light selective transparency 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, it is possible to sufficiently meet the demand for downsizing of the image sensor. More preferably, it is 500 μm or less, more preferably 300 μm or less, particularly preferably 150 μm or less, and most preferably 100 μm or less.
It is below μm. Moreover, it is preferable that it is 30 micrometers or more. More preferably, it is 50 μm or more.
As described above, the laminate has an absorption maximum in the wavelength range of 650 to 680 nm, and 4
The form having only one absorption maximum in the wavelength range of 00 to 680 nm is one of the preferred forms of the present invention.
One.

<Base material>
In the above laminate, the substrate is not particularly limited, but examples thereof include organic materials, inorganic materials,
It is preferable to use one or more of organic-inorganic composite materials, metal materials, and the like as materials. Examples of organic materials or organic-inorganic composite materials include resin films made of these materials. Examples of organic materials include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as triacetyl cellulose (TAC) and methyl methacrylate copolymers, styrene resins, polysulfone resins, and polyethers. Examples include sulfone resins, polycarbonate resins, vinyl chloride resins, and polymethacrylimide resins.
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 base material is
A layer made of a transparent inorganic material (referred to as a transparent inorganic material layer) is preferable. This
It is preferable because a laminate that can further suppress the occurrence of cracks, chipping, and warpage, and is superior in 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 80%.
The above is preferable. 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, 30-1
000 μm is preferable. More preferably, it is 50 μm or more.
The resin composition of the present invention can form a cured product having high adhesion to a glass substrate, for example, without undercoating with a coupling agent to the substrate, but the substrate is previously treated with the coupling agent. It is one of the preferred embodiments of the present invention. Thereby, the adhesiveness is further improved, and for example, in the use in a solder reflow process or a wet heat environment, peeling or the like can be further suppressed.
In addition, it is preferable that the base material processed with the coupling agent is a base material surface-treated with the coupling agent.

A suitable form of the coupling agent preferably contains silicon, zirconia, titanium and / or aluminum as a central metal. Among these, those having silicon as a central metal are preferable. More preferred is a silane coupling agent.
A form in which the substrate is treated with a coupling agent as described above and the coupling agent contains silicon, zirconia, titanium and / or aluminum as a central metal is also one of preferred forms of the present invention. One.
<Resin layer>
Although the thickness of the layer (resin layer) made of the above resin composition for lamination is not particularly limited, from the viewpoint of heat resistance and transparency during film formation and reflow, and from the viewpoint of preventing peeling and cracking at the interface due to thermal expansion. , 50 μm or less, more preferably 30 μm or less, still more preferably 1
It is 0 μm or less, particularly preferably 5 μm or less, and most preferably 2 μm or less. Further, 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
The thickness is preferably μm or more, and more preferably 0.5 μm or more.
<UV cut layer>
It is also preferred that the laminate further has a UV (ultraviolet) cut layer. Thereby, since deterioration due to ultraviolet rays can be sufficiently suppressed, the weather resistance of the laminate can be greatly improved. Thus, the form which the said laminated body further has a UV cut layer is one of the suitable forms of this invention.
The UV cut layer is preferably disposed on the light incident side in the laminate. In the laminate, the UV cut layer may be one layer or two or more layers.
The UV cut layer can be formed of, for example, a resin composition containing at least a resin component and an ultraviolet absorber. As the ultraviolet absorber, for example, a compound having an absorptivity in a wavelength region of 350 to 400 nm is preferable. Specifically, it is preferable to use a phthalocyanine dye having an absorption ability in a wavelength region of 350 to 400 nm. For example, TINUV
IN P, TINUVIN 234, TINUVIN 329, TINUVIN 213
, TINUVIN 571, TINUVIN 326 (manufactured by BASF) or the like can also be used.

[Use of laminate]
The laminate of the present invention is particularly suitable for imaging device applications. The laminating resin composition 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 laminate is also one aspect of the present invention, and an image pickup device including the laminate is also included in the present invention. In addition, it is particularly preferable that the image pickup device includes a light selective transmission filter including the laminate.
However, the resin composition for lamination and the laminate are not limited to the above-mentioned applications. For example, optical materials (members), mechanical component materials, electrical / electronic component materials, automobile component materials, civil engineering and building materials, In addition to molding materials, it is also useful for various applications such as paints and adhesive materials.
Hereinafter, the light selective transmission filter and the image sensor will be described.
<Light selective transmission filter>
The light selective transmission filter of the present invention includes one or more of the above laminates, but may further include one or more other layers as necessary. In the light selective transmission filter, it is preferable to use a transparent inorganic material layer of the laminate as a base material and a resin layer formed from the resin composition as an absorption layer.
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. For example, a layer that blocks ultraviolet rays is applied with a liquid resin composition containing an ultraviolet absorber on an absorption layer formed on a substrate (for example, a glass substrate) as a countermeasure against deterioration of the absorption layer to light. It is also preferable to form a resin layer containing an ultraviolet absorber by drying or curing.
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 the light to be reduced, an infrared cut filter, an ultraviolet cut filter, an infrared / ultraviolet cut filter, etc. can be used.
1000 nm infrared light (more preferably 650 nm to 1000 nm infrared light) and 200 to
It is preferable to reduce the ultraviolet light of 350 nm and transmit other light. 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 range of wavelengths to be selectively reduced is 650 nm to 2500 nm, 650
It is preferable that it is nm-1000 nm or 800 nm-1000 nm. A filter that selectively reduces at least one of wavelengths in these ranges is also included in the infrared cut filter. The wavelength range to be selectively reduced is 650 n in the near infrared region.
m to 1000 nm is more preferable.
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, 750
Those which selectively reduce the transmittance of infrared light of ˜1000 nm to 5% or less are preferable. 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, 480-55 also in visible light.
The transmittance of light in the 0 nm wavelength region is preferably 85% or more, and more preferably 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, 200
Those that selectively reduce the transmittance of ultraviolet light of ˜350 nm to 5% or less are preferable.
In the form in which the light selective transmission filter of the present invention is an infrared / ultraviolet cut filter,
What selectively reduces 650 nm-1 micrometer infrared light and 200-350 nm ultraviolet light to 5% or less is preferable.
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.
Examples of the material include silica, alumina, lanthanum fluoride, magnesium fluoride,
Aluminum 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.
The thickness of each of the dielectric layer A and the dielectric layer B is usually determined by λ (
nm), a thickness of 0.1λ to 0.5λ is preferable. 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 2-8μ
m. In addition, as the total thickness of the reflective film that the light selective transmission filter and the image sensor have,
It is suitable to be in the above range.
From the viewpoint of obtaining a smooth transmittance spectrum as an optical filter with respect to the absorption maximum wavelength of the absorption layer in the infrared region (650 to 750 nm) as a preferable form of the reflection film and the absorption layer, the transmittance is higher than that of the absorption layer. It is preferable that the wavelength of the reflective film to be reduced is present at +30 nm or less, more preferably +20 nm or less, still more preferably +10 nm or less, and particularly preferably 0 nm or less. On the other hand, from the viewpoint of reducing the angle dependency as an optical filter, it is preferably −10 nm or more, more preferably 0 nm or more, further preferably 10 nm or more, and particularly preferably 20 nm or more. preferable.
Here, when the resin layer which is a part of the laminate of the present invention is used as the absorption layer of the reflection type light selective transmission filter and a reflection film is formed on at least one surface of the laminate, It is preferable to form a multilayer film of 10 layers or more. Moreover, it is also suitable to form the resin layer formed from the said resin composition after forming a reflecting film.
The reflective film is preferably present on the base material 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 a transparent inorganic material layer or a resin layer. This
The possibility of the light selective transmission filter being deformed and curled or cracked by the vapor deposition can be reduced. In this case, an adhesive layer is preferably formed on the transparent inorganic material layer or the 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 substrate is excellent in light blocking performance, but has an incident angle dependency (“viewing angle dependency”) in which reflection characteristics change depending on the incident angle of light. In other words, the spectral transmittance curve varies depending on the incident angle, and therefore, improvement thereof is a problem.
The incident angle dependency of the light blocking characteristic is, for example, a spectrophotometer (Shimadzu UV-3100).
, Manufactured by Shimadzu Corporation) with different incident angles (for example, 0 °, 20 °, 25 °, 3 °
0 ° etc. The transmittance at an incident angle of 0 ° is a transmittance measured so that light enters from the thickness direction of the light selective transmission filter, and the transmittance at an incident angle of 20 ° is the thickness direction of the light selective transmission filter. It is a transmittance measured as light is incident from a direction inclined by 20 ° with respect to the angle. ) Can be measured and evaluated by the amount of change in the 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 2 °
Even if it is changed to 5 °, it is preferable that the transmittance spectrum does not change in the region where the transmittance is 80% or more, and more preferably, the transmittance spectrum does not change in the region where the transmittance is 70% or more. 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 particularly excellent in light resistance, heat resistance and light selective transmission, and can sufficiently reduce the incident angle dependency of the light blocking characteristics. In addition to being useful as a heat ray cut filter or the like that is mounted on the camera, it is also useful as a filter for blocking light noise and correcting visibility in camera module (also referred to as a solid-state imaging device) application. Among these, the light selective transmission filter of the present invention is useful as a filter used in camera modules such as digital still cameras and mobile phone cameras. In other words, the light selective transmission filter is preferably a light selective transmission filter for an image sensor. Thus, an image sensor provided with the light selective transmission filter is also one preferred embodiment of the present invention.

<Image sensor>
The image pickup device of the present invention includes one or more of the laminates, but may further include one or more other members as necessary. Usually, the imaging device has a detection element (sensor) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) and a lens, but further includes an optical filter, an adhesive for fixing the member, and the like. Can be mentioned.
Preferably, the imaging element has a form in which a reflective film is formed on at least one surface of the laminate. That is, it is preferable that the imaging device includes the laminate and the reflective film. With such a configuration, the incident angle dependency of the light blocking characteristic can be more sufficiently reduced. In this case, the arrangement form (configuration) of the reflective film in the image sensor is not particularly limited. For example, by forming a reflective film directly on the lens, the lens and the reflective film are integrated with each other (also referred to as form (a)); the imaging element includes an optical filter including the reflective film. And the like (form (b)) having a reflective film as an independent component.
The reflective film is as described above.
In the form (a), when the imaging element has two or more lenses, the number of lenses on which the reflective film is formed is not particularly limited.
In the form (b), the optical filter including the reflective film may have only a function of reflecting (near) infrared light, or may have a function of absorbing (near) infrared light. May be.
The optical filter including the reflective film may be a light selective transmission filter including the laminate of the present invention and the reflective film, or may be an optical filter other than the light selective transmission filter. Moreover, you may have 1 or 2 or more of optical filters containing a reflecting film, and an arrangement | positioning form is not specifically limited, either. For example, when the image sensor has two or more lenses, the filter having the reflective film may be disposed between the lenses.
The reflective film is preferably formed on one surface or both surfaces of the lens and / or one surface or both surfaces of the substrate.

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 of cationic curing catalyst>
Preparation Example 1 (Synthesis of TPB-containing powder B)
According to the synthesis method described in International Publication No. 1997/031924, 255 g of 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 then white crystals of TPB / water complex (TPB-containing powder B)
18.7 g was obtained. This complex has a water content of 9.2% (Karl Fischer moisture meter) and T
The PB content was 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the dried complex, but no peaks other than TPB were detected.
The measurement result of ¹⁹ F-NMR is shown below.
¹⁹ F-NMR (CDCl ₃ ) ppm (standard substance: CFCl ₃ 0 ppm)
δ = −135.6 (6F, m)
δ = -156.5 (3F, dd)
δ = −163.5 (6F, d)
Preparation Example 2 (Preparation of cationic curing catalyst 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
In a 1000 ml four-necked separable flask, 54 g of tetrafluorophthalonitrile (0.
27 mol), potassium fluoride 34.5 g (0.59 mol), and acetone 126 g
In addition, 127 g (0.55 mol) of 3-chloro-4-hydroxybenzoic acid methoxyethyl ester and 216 g of acetone were added to a dropping funnel. 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）工程２
２００ｍｌの四つ口フラスコに、工程１で得られた中間体（１）を２０．０ｇ（０．０３
２ｍｏｌ）、ヨウ化亜鉛（ＩＩ）２．５７ｇ（０．００８１ｍｏｌ）、及び、ベンゾニト
リル３０．０ｇを仕込み、１６０℃で撹拌しながら２４時間反応させた。反応終了後、メ
チルセロソルブ５２．７ｇを反応液に加えた後、メタノールと水の混合溶液に滴下して結
晶を析出させ、吸引ろ過後ウェットケーキを得た。得られたケーキを再度、メタノールと
水の混合溶液で撹拌洗浄し、吸引ろ過した。得られたケーキを、真空乾燥機を用いて９０
℃で２４時間乾燥後、目的物であるフタロシアニン（１）を１７．７８ｇ（収率８７．１
％）得た。
この工程２の反応を、以下に簡略して示す。

(2) Step 2
In a 200 ml four-necked flask, 20.0 g (0.03) of the intermediate (1) obtained in Step 1 was added.
2 mol), 2.57 g (0.0081 mol) of zinc (II) iodide and 30.0 g of benzonitrile were charged and reacted at 160 ° C. for 24 hours with stirring. 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 subjected to 90% using a vacuum dryer.
After drying at 24 ° C. for 24 hours, 17.78 g (yield: 87.1) of the target phthalocyanine (1) was obtained.
%)Obtained.
The reaction of Step 2 is simply shown below.

合成例１で得たフタロシアニン（１）は、上記構造中、主骨格中に「＊」で示す部分（合
計８個）のそれぞれに、右側に示す置換基が置換した構造からなる。
合成例２（フタロシアニン（２）の合成）
（１）工程１
１０００ｍｌの四つ口セパラブルフラスコにテトラフルオロフタロニトリル７５ｇ（０．
３７ｍｏｌ）、フッ化カリウム５２．３ｇ（０．９０ｍｏｌ）、及び、アセトニトリル１
６７ｇを仕込み、更に滴下ロートに２，６−ジクロロフェノール１２３．４ｇ（０．７６
ｍｏｌ）及びアセトニトリル１３３ｇを仕込んだ。攪拌しながら、滴下ロートより２，６
−ジクロロフェノール溶液を約２時間かけて滴下した後、更に２時間攪拌を続けた。その
後、一晩攪拌し反応させた。反応液をろ過し、ロータリーエバポレーターでろ液からアセ
トニトリルを留去し、メタノールを加えて再結晶を行った。得られた結晶をろ過し、真空
乾燥により、中間体（２）を１４８．１ｇ（収率８０．２％）を得た。
この工程１の反応を、以下に簡略して示す。

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
In a 1000 ml four-necked separable flask, 75 g of tetrafluorophthalonitrile (0.
37 mol), 52.3 g (0.90 mol) of potassium fluoride, and acetonitrile 1
67 g is charged, and 123.4 g (0.76 g) of 2,6-dichlorophenol is further added to the dropping funnel.
mol) and 133 g of acetonitrile were charged. While stirring, from the dropping funnel 2,6
-The dichlorophenol solution was added dropwise over about 2 hours, and 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）工程２
５００ｍｌの四つ口セパラブルフラスコに、中間体（２）を１４０ｇ（０．２９ｍｏｌ）
、炭酸カリウム１０７．８ｇ（０．７８ｍｏｌ）、ｐ−ヒドロキシ安息香酸メチル９２．
１ｇ（０．６１ｍｏｌ）及びアセトン２８０ｇを仕込んだ。反応液を６０℃で一晩攪拌し
反応させた後、反応液をろ過し、ロータリーエバポレーターでろ液からアセトンを留去し
、メタノールとメタノールの混合液を加えて再結晶を行った。得られた結晶をろ過し、真
空乾燥により、中間体（３）を２０２．３ｇ（収率９３．１％）を得た。
この工程２の反応を、以下に簡略して示す。

(2) Step 2
In a 500 ml four-necked separable flask, 140 g (0.29 mol) of intermediate (2)
Potassium carbonate 107.8 g (0.78 mol), methyl p-hydroxybenzoate 92.
1 g (0.61 mol) and 280 g of acetone were charged. The reaction solution was stirred and reacted overnight at 60 ° C., then the reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and recrystallization was performed by adding a mixed solution of methanol and methanol. The obtained crystals were filtered and vacuum-dried to obtain 202.3 g (yield 93.1%) of intermediate (3).
The reaction of Step 2 is simply shown below.

（３）工程３
２００ｍｌの四つ口フラスコに工程２で得られた中間体（３）を２２．５ｇ（０．０３０
ｍｏｌ）、ヨウ化亜鉛（ＩＩ）２．３７ｇ（０．００７４ｍｏｌ）、ベンゾニトリル５２
．５ｇを仕込み、１６０℃で撹拌しながら２４時間反応させた。反応終了後、メチルセロ
ソルブ３０．３ｇを反応液に加えた後、メタノールと水の混合溶液に滴下して結晶を析出
させ、吸引ろ過後ウェットケーキを得た。得られたケーキを再度、メタノールと水の混合
溶液で撹拌洗浄し、吸引ろ過した。得られたケーキを、真空乾燥機を用いて９０℃で２４
時間乾燥後、目的物であるフタロシアニン（２）を１７．８３ｇ（収率８６．１％）得た
。
この工程３の反応を、以下に簡略して示す。

(3) Process 3
In a 200 ml four-necked flask, 22.5 g (0.030) of the intermediate (3) obtained in Step 2 was added.
mol), zinc iodide (II) 2.37 g (0.0074 mol), benzonitrile 52
. 5 g was charged and reacted at 160 ° C. with stirring for 24 hours. 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 cake obtained was heated at 90 ° C. for 24 hours using a vacuum dryer.
After drying for a period of time, 17.83 g (yield: 86.1%) of the target phthalocyanine (2) was obtained.
The reaction of this step 3 is simply shown below.

合成例２で得たフタロシアニン（２）は、上記構造中、主骨格中に「＊」で示す部分（合
計１６個）のうち８個に右側の上に示す置換基が、残り８個に右側の下に示す置換基が、
それぞれ置換（又は結合）した構造からなる。
合成例３（フタロシアニン（３）の合成）
（１）工程１
１０００ｍｌの三つ口反応容器に３−ニトロフタロニトリル１００ｇ（０．５８ｍｏｌ）
、炭酸カリウム１５９．７ｇ（１．１６ｍｏｌ）、２，６−ジクロロフェノール１０４．
６ｇ（０．６４ｍｏｌ）及びアセトニトリル４００ｇを仕込んだ。６０℃で一晩攪拌し反
応させた後に、反応液をろ過し、ロータリーエバポレーターでろ液からアセトニトリルを
留去し、メタノールを加えて再結晶を行った。得られた結晶をろ過し、真空乾燥により、
中間体（４）を１００．９ｇ（収率６０．２％）を得た。
この工程１の反応を、以下に簡略して示す。

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. The substituent shown below is
Each consists of a substituted (or bonded) structure.
Synthesis Example 3 (Synthesis of phthalocyanine (3))
(1) Step 1
In a 1000 ml three-necked reaction vessel, 100 g (0.58 mol) of 3-nitrophthalonitrile
Potassium carbonate 159.7 g (1.16 mol), 2,6-dichlorophenol 104.
6 g (0.64 mol) and 400 g of acetonitrile were charged. 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 are filtered and vacuum dried.
100.9 g (yield 60.2%) of intermediate (4) was obtained.
The reaction of this step 1 is simply shown below.

（２）工程２
３００ｍｌの四つ口フラスコに、工程１で得られた中間体（４）を６０．０ｇ（０．２１
ｍｏｌ）、塩化銅（Ｉ）５．６５ｇ（０．０５７ｍｏｌ）、ジエチレングリコールモノメ
チルエーテル１４０．０ｇを仕込み、１６０℃で撹拌しながら２４時間反応させた。反応
終了後、メチルセロソルブ１００．０ｇを反応液に加えた後、メタノールと水の混合溶液
に滴下して結晶を析出させ、吸引ろ過後ウェットケーキを得た。得られたケーキを再度、
メタノールと水の混合溶液で撹拌洗浄し、吸引ろ過した。得られたケーキを、真空乾燥機
を用いて９０℃で２４時間乾燥後、目的物であるフタロシアニン（３）を５１．４８ｇ（
収率８０．４％）得た。
この工程２の反応を、以下に簡略して示す。

(2) Step 2
In a 300 ml four-necked flask, 60.0 g (0.21) of the intermediate (4) obtained in Step 1 was added.
mol), 5.65 g (0.057 mol) of copper (I) chloride, and 140.0 g of diethylene glycol monomethyl ether were added and reacted at 160 ° C. for 24 hours with stirring. 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 cake obtained again
The mixture was stirred and washed 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 then 51.48 g of the target phthalocyanine (3) (
Yield 80.4%).
The reaction of Step 2 is simply shown below.

合成例３で得たフタロシアニン（３）は、上記構造中、主骨格中に「＊」で示す部分（合
計８個）のうち４個に右側の上に示す置換基が、残り４個に右側の下に示す置換基（すな
わち水素原子）が、それぞれ置換（又は結合）した構造からなる。
＜樹脂組成物及び硬化物（積層体）の調製＞
実施例１
セロキサイドＣＥＬ−２０２１Ｐを１５部、ＥＨＰＥ−３１５０を８５部、プロピレング
リコールモノメチルエーテルアセテート（ＰＧＭＥＡ）２４０部、テトラヒドロフラン（
ＴＨＦ）４０部、及び、合成例１で得たフタロシアニン（１）を８部、８０℃にて均一混
合した。その後、４０℃に降温し、シランカップリング剤としてＫＢＭ−９０３（信越シリコーン社製）を１部、硬化剤としてカチオン硬化触媒Ｂを５．６部均一に混合し、
異物を０．４５μｍフィルター（ＧＬサイエンス社製、非水系１３Ｎ）にてろ過した。以
上により、樹脂組成物（１）を得た。
得られた樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、成膜性、各透過率
や耐熱性、接着性を評価した。結果を表３に示す。
実施例２〜５
樹脂組成物を構成するシランカップリング剤の量、並びに、硬化剤の量を表１に示すとおりに変更したこと以外は、実施例１と同様にして樹脂組成物（２）〜（５）を得た。当該樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、硬化物（積層物）を得た。
実施例６
セロキサイドＣＥＬ−２０２１Ｐを１５部、ＥＨＰＥ−３１５０を８５部、ＥＨＶＥを８０部、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）２４０部、テトラヒドロフラン（ＴＨＦ）４０部、及び、合成例１で得たフタロシアニン（１）を８部、８０℃にて均一混合した。その後、４０℃に降温し、シランカップリング剤としてＫＢＭ−９０３（信越シリコーン社製）を１部、硬化剤としてカチオン硬化触媒Ｂを２０部均一に混合し、異物を０．４５μｍフィルター（ＧＬサイエンス社製、非水系１３Ｎ）にてろ過した。以上により、樹脂組成物（６）を得た。
得られた樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、成膜性、各透過率
や耐熱性、接着性を評価した。結果を表３に示す。
実施例７
セロキサイドＣＥＬ−２０２１Ｐを１５部、ＥＨＰＥ−３１５０を８５部、プロピレング
リコールモノメチルエーテルアセテート（ＰＧＭＥＡ）２４０部、テトラヒドロフラン（
ＴＨＦ）４０部、及び、合成例１で得たフタロシアニン（１）を３部、合成例３で得たフタロシアニン（３）を１０部、合成例２で得たフタロシアニン（２）を２部、８０℃にて均一混合した。その後、４０℃に降温し、シランカップリング剤としてＫＢＭ−９０３（信越シリコーン社製）を１部、硬化剤としてカチオン硬化触媒Ｂを５．６部均一に混合し、異物を０．４５μｍフィルター（ＧＬサイエンス社製、非水系１３Ｎ）にてろ過した。以上により、樹脂組成物（７）を得た。
得られた樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、成膜性、各透過率
や耐熱性、接着性を評価した。結果を表３に示す。
実施例８〜１０
セロキサイドＣＥＬ−２０２１Ｐを１５部、ＥＨＰＥ−３１５０を８５部、プロピレング
リコールモノメチルエーテルアセテート（ＰＧＭＥＡ）２４０部、テトラヒドロフラン（
ＴＨＦ）４０部、及び、合成例１で得たフタロシアニン（１）を９部、８０℃にて均一混
合した。その後、２５℃に降温し、シランカップリング剤としてＫＢＭ−９０３（信越シリコーン社製）を２部、硬化剤としてカチオン硬化触媒Ｂを１０部均一に混合し、異物を０．４５μｍフィルター（ＧＬサイエンス社製、非水系１３Ｎ）にてろ過した。以上により、樹脂組成物（１２）を得た。
得られた樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、成膜性、各透過率
や耐熱性、接着性を評価した。結果を表４に示す。
実施例１１
セロキサイドＣＥＬ−２０２１Ｐを１５部、ＥＨＰＥ−３１５０を８５部、プロピレング
リコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１４０部、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）１１０部、及び、合成例１で得たフタロシアニン（１）を９部、８０℃にて均一混合した。その後、２５℃に降温し、シランカップリング剤としてＫＢＭ−９０３（信越シリコーン社製）を２部、硬化剤としてカチオン硬化触媒Ｂを１０部均一に混合し、異物を０．４５μｍフィルター（ＧＬサイエンス社製、非水系１３Ｎ）にてろ過した。以上により、樹脂組成物（１３）を得た。
得られた樹脂組成物を用いて、後述の方法により成膜及び硬化を行い、成膜性、各透過率
や耐熱性、接着性を評価した。結果を表４に示す。

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 resin composition and cured product (laminate)>
Example 1
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
(THF) 40 parts and phthalocyanine (1) obtained in Synthesis Example 1 were uniformly mixed at 80 ° C. at 80 ° C. Thereafter, the temperature was lowered to 40 ° C., 1 part of KBM-903 (manufactured by Shin-Etsu Silicone) as a silane coupling agent, and 5.6 parts of cationic curing catalyst B as a curing agent were uniformly mixed.
The foreign matter was filtered with a 0.45 μm filter (GL Science, non-aqueous 13N). Thus, a resin composition (1) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 3.
Examples 2-5
Resin compositions (2) to (5) were prepared in the same manner as in Example 1 except that the amount of the silane coupling agent constituting the resin composition and the amount of the curing agent were changed as shown in Table 1. Obtained. Using the resin composition, film formation and curing were performed by the method described later to obtain a cured product (laminate).
Example 6
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 80 parts of EHVE, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), 40 parts of tetrahydrofuran (THF), and the phthalocyanine (1) obtained in Synthesis Example 1 Was uniformly mixed at 80 ° C. Thereafter, the temperature is lowered to 40 ° C., 1 part of KBM-903 (manufactured by Shin-Etsu Silicone) as a silane coupling agent, and 20 parts of a cationic curing catalyst B as a curing agent are uniformly mixed, and a 0.45 μm filter (GL Science) The product was filtered through a non-aqueous system (13N). Thus, a resin composition (6) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 3.
Example 7
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
THF) 40 parts, 3 parts of the phthalocyanine (1) obtained in Synthesis Example 1, 10 parts of the phthalocyanine (3) obtained in Synthesis Example 3, 2 parts of the phthalocyanine (2) obtained in Synthesis Example 2 Uniform mixing at 0 ° C. Thereafter, the temperature was lowered to 40 ° C., 1 part of KBM-903 (manufactured by Shin-Etsu Silicone) as a silane coupling agent, 5.6 parts of cationic curing catalyst B as a curing agent were uniformly mixed, and foreign matter was filtered with a 0.45 μm filter ( It filtered with the GL Science company make, non-aqueous type | system | group 13N). Thus, a resin composition (7) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 3.
Examples 8-10
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
(THF) 40 parts and 9 parts of the phthalocyanine (1) obtained in Synthesis Example 1 were uniformly mixed at 80 ° C. Thereafter, the temperature was lowered to 25 ° C., 2 parts of KBM-903 (manufactured by Shin-Etsu Silicone) as a silane coupling agent and 10 parts of a cation curing catalyst B as a curing agent were uniformly mixed, and a 0.45 μm filter (GL Science) The product was filtered through a non-aqueous system (13N). Thus, a resin composition (12) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 4.
Example 11
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 140 parts of propylene glycol monomethyl ether acetate (PGMEA), 110 parts of propylene glycol monomethyl ether (PGME), and 9 of the phthalocyanine (1) obtained in Synthesis Example 1 Partly mixed at 80 ° C. Thereafter, the temperature was lowered to 25 ° C., 2 parts of KBM-903 (manufactured by Shin-Etsu Silicone) as a silane coupling agent and 10 parts of a cation curing catalyst B as a curing agent were uniformly mixed, and a 0.45 μm filter (GL Science) The product was filtered through a non-aqueous system (13N). Thus, a resin composition (13) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 4.

Example 12
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 140 parts of propylene glycol monomethyl ether acetate (PGMEA), 110 parts of propylene glycol monomethyl ether (PGME), and 9 of the phthalocyanine (1) obtained in Synthesis Example 1 Partly mixed at 80 ° C. Thereafter, the temperature was lowered to 25 ° C., 2 parts of Z-6094 (manufactured by Toray Dow Corning) as a silane coupling agent, and 20 parts of a cationic curing catalyst B as a curing agent were uniformly mixed, and foreign matter was filtered with a 0.45 μm filter (GL It filtered with the science company make, nonaqueous 13N). Thus, a resin composition (14) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 4.
Example 13
100 parts of EHPE-3150 and 100 parts of dichlorobenzene were uniformly mixed at 80 ° C. Thereafter, the temperature was lowered to 25 ° C., and 200 parts of chloroform and 4 parts of squarylium dye (manufactured by Tokyo Chemical Industry Co., Ltd., product number: B4649, squarylium dye, CAS: 358727-55-6) were uniformly mixed. Thereafter, 1 part of Z-6094 (manufactured by Toray Dow Corning) as a silane coupling agent and 10 parts of a cationic curing catalyst B as a curing agent are uniformly mixed, and a foreign matter is 0.45 μm filter (manufactured by GL Sciences, non-aqueous). 13N). Thus, a resin composition (15) was obtained.
Using the obtained resin composition, a film was formed and cured by the method described later, and film forming properties, transmittances, heat resistance, and adhesiveness were evaluated. The results are shown in Table 4.
Comparative Example 1
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
(THF) 40 parts and phthalocyanine (1) obtained in Synthesis Example 1 were uniformly mixed at 80 ° C. 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 resin composition (8) was obtained.
Comparative Example 2
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
THF) 40 parts, 3 parts of the phthalocyanine (1) obtained in Synthesis Example 1, 10 parts of the phthalocyanine (3) obtained in Synthesis Example 3, 2 parts of the phthalocyanine (2) obtained in Synthesis Example 2 Uniform mixing at 0 ° 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 resin composition (9) was obtained.
Comparative Example 3
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
THF) 40 parts, 3 parts of the phthalocyanine (1) obtained in Synthesis Example 1, 10 parts of the phthalocyanine (3) obtained in Synthesis Example 3, 2 parts of the phthalocyanine (2) obtained in Synthesis Example 2 Uniform mixing at 0 ° C. Thereafter, the temperature was lowered to 40 ° C., 10 parts of Z-6043 (manufactured by Toray Dow Corning Co., Ltd.) as a silane coupling agent, 5.6 parts of a cationic curing catalyst B as a curing agent were uniformly mixed, and a 0.45 μm filter for foreign matters. It filtered with (GL Science company make, non-aqueous type | system | group 13N). Thus, a resin composition (10) was obtained.
Comparative Example 4
15 parts of Celoxide CEL-2021P, 85 parts of EHPE-3150, 240 parts of propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (
THF) 40 parts, 3 parts of the phthalocyanine (1) obtained in Synthesis Example 1, 10 parts of the phthalocyanine (3) obtained in Synthesis Example 3, 2 parts of the phthalocyanine (2) obtained in Synthesis Example 2 Uniform mixing at 0 ° C. Thereafter, the temperature was lowered to 40 ° C., 10 parts of Z-6040 (manufactured by Toray Dow Corning) as the silane coupling agent, 5.6 parts of the cationic curing catalyst B as the curing agent were uniformly mixed, and the foreign matter was filtered with a 0.45 μm filter. It filtered with (GL Science company make, non-aqueous type | system | group 13N). Thus, a resin composition (11) was obtained.

  Using the resin compositions obtained in the above Examples and Comparative Examples, film formation and curing were performed by the methods described later, and film forming properties, transmittances, heat resistance, and adhesive properties were evaluated. The results are shown in Table 3.

A method for obtaining a cured product (laminate) by forming a film and curing using each resin composition will be described below.
<Film formation and curing (thermosetting) method>
1. Film formation method (1) Coating of resin composition Glass substrate washed with isopropanol solvent (manufactured by SCHOTT, glass, D263, 8
Inch round shape), each resin composition is hung on a spin coater (Mikasa 1H-
DX2), a predetermined rotation speed (2500 rpm, 2000 rpm, or 1500 rpm) was obtained over 3 seconds, a predetermined time was maintained, and the rotation speed was returned to 0 rpm over 3 seconds to form a film (that is, coating was performed). ).
2. Curing method (thermosetting)
The film obtained by the film forming method of 1 was cured. Specifically, it is as follows.
For curing of Examples 1 to 9 and Comparative Examples 1 to 4, using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo Systems Co., Ltd.), under an N ₂ atmosphere (oxygen concentration of 30 ppm or less), 30 ° C. Then, the temperature was raised by a program that reached 250 ° C. in 1 hour, held at 250 ° C. for 1 hour, and then lowered to 30 ° C.
Regarding the curing of Examples 10 to 12, the coated glass was put into an oven adjusted to 180 ° C. in an air atmosphere using an oven (manufactured by ESPEC, PV-211) for 1 hour. After holding, the coated glass was removed from the oven.
Regarding the curing of Example 13, using an inert gas oven (INL-45N1-S, manufactured by Koyo Thermo Systems Co., Ltd.), reaching 200 ° C. in one hour from 30 ° C. in an N ₂ atmosphere (oxygen concentration of 30 ppm or less). The temperature was raised with a program to keep the temperature at 200 ° C. for 1 hour, and then the temperature was lowered to 30 ° C.
3. Vapor deposition film formation method An alternate vapor deposition layer (infrared reflective layer) of 20 titanium oxide layers / 20 silica layers is formed on the opposite surface of the coating layer obtained by the curing method 2 above, and titanium oxide 3 An alternating vapor deposition layer (antireflection layer) of 3 layers / silica was formed.
<Evaluation methods for physical properties>
1. Center of cured product after film-forming final curing (that is, cured product obtained by the above-described curing method 2) 3 cm × 3 cm
The square range was confirmed with a 20 × stereomicroscope and evaluated according to the following criteria.
A: Only defects of less than 0.03 mm occurred.
A: A defect having a length or diameter of 0.03 mm or more and less than 1 mm occurred.
Δ: A defect with a length or diameter of 1 mm or more and less than 2 mm occurred.
X: A defect with a length or diameter of 2 mm or more occurred.
2. The transmittance spectrum in each stage was measured using a transmittance spectrophotometer (manufactured by Shimadzu Corporation, UV-3100). Tables 3 and 4 show the transmittance 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.
In addition, the transmittance | permeability after vapor deposition film formation measured the laminated body from the incident light source side so that it might become an infrared reflective layer / glass / coating layer / antireflection layer in order. In addition, when the laminate is installed so as to be perpendicular to the incident light (the transmittance spectrum measured in this way is also referred to as a 0 degree spectrum. Light enters from the thickness direction (vertical direction) of the laminate. And when the laminate is installed so that light is incident from a direction inclined by 30 degrees with respect to the thickness direction (vertical direction) of the laminate (the transmittance measured in this manner). Spectra were referred to as 30 degree spectra).
3. Heat resistance (Reflow heat resistance)
The cured product after the final curing (that is, the cured product obtained by the above-described curing method 2) is dried at 260 ° C. for 20 minutes in the air using a dryer (manufactured by Yamato Kagaku Co., Ltd., DH611). 430
The transmittance of the cured product at 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.

4. Adhesiveness (boiling test)
The cured product after final curing was allowed to stand in a boiling environment for 5 hours using a boiling bath. After that, on this cured product, using a cutter (made by OLFA, NT cutter, A300), cut,
Eleven cross-cut lines were produced in the vertical and horizontal rows at 1 mm intervals, respectively, and 100 squares of 1 mm ² squares were produced. On the cured product, a tape (manufactured by 3M, mending tape 810) was affixed at room temperature to prevent air from entering, and left for 30 seconds. Then, the sample for evaluation was produced by performing peeling operation within 1 second so that peeling force might become fixed to hardened | cured material. Evaluation samples were evaluated according to the following criteria.
○: No peeling occurred in one square out of 100 squares produced.
Δ: Peeling occurred in 1 to 10 squares out of 100 squares produced.
X: Peeling occurred in 11 to 100 squares out of the 100 squares produced.
5. Adhesiveness (pressure cooker (PCT) test)
The cured product after final curing is set to 120 ° C./2 atm / humidity 100% using a PCT tester.
After standing for 0 hour, the adhesiveness was evaluated in the same manner as 4 above.

略号等は、下記のとおりである。
ＣＥＬ−２０２１Ｐ：液状脂環式エポキシ樹脂「セロキサイドＣＥＬ−２０２１Ｐ」、エ
ポキシ当量１３１、重量平均分子量１２０、ダイセル化学工業社製
ＥＨＰＥ−３１５０：脂環式エポキシ樹脂、重量平均分子量２９００、ダイセル化学工業
社製
ＥＨＶＥ：日本カーバイド社製、２−エチルヘキシルビニルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（別名：１，２−プロ
パンジオールモノメチルエーテルアセタート）
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＴＨＦ：テトラヒドロフラン
フタロシアニン（１）：合成例１で得たフタロシアニン系色素
フタロシアニン（２）：合成例２で得たフタロシアニン系色素
フタロシアニン（３）：合成例３で得たフタロシアニン系色素
ＴＣ−ＳＱ−１：東京化成工業社製、商品番号：Ｂ４６４９、スクアリリウム色素、ＣＡＳ：３５８７２７−５５−６
ＫＢＭ−９０３：シランカップリング剤、信越シリコーン社製、3−アミノプロピルトリメトキシシラン
Ｚ−６０９４：シランカップリング剤、商品名「Ｚ−６０９４」、東レダウコーニング社製、３−（２−アミノエチル）アミノプロピルトリメトキシシラン
Ｚ−６０４３：シランカップリング剤、商品名「Ｚ−６０４３」、東レダウコーニング社
製
Ｚ−６０４０：シランカップリング剤、商品名「Ｚ−６０４０」、東レダウコーニング社
製

Abbreviations and the like 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. EHVE manufactured by Nippon Carbide, 2-ethylhexyl vinyl ether PGMEA: propylene glycol monomethyl ether acetate (also known as 1,2-propanediol monomethyl ether acetate)
PGME: propylene glycol monomethyl ether THF: tetrahydrofuran phthalocyanine (1): phthalocyanine dye phthalocyanine obtained in Synthesis Example 1 (2): phthalocyanine dye phthalocyanine obtained in Synthesis Example 2 (3): phthalocyanine system obtained in Synthesis Example 3 Dye TC-SQ-1: manufactured by Tokyo Chemical Industry Co., Ltd., product number: B4649, squarylium dye, CAS: 358727-55-6
KBM-903: Silane coupling agent, manufactured by Shin-Etsu Silicone, 3-aminopropyltrimethoxysilane Z-6094: Silane coupling agent, trade name “Z-6094”, manufactured by Toray Dow Corning, 3- (2-amino Ethyl) aminopropyltrimethoxysilane Z-6043: Silane coupling agent, trade name “Z-6043”, manufactured by Toray Dow Corning Z-6040: Silane coupling agent, trade name “Z-6040”, Toray Dow Corning Made

表１〜４より、以下のことがわかった。

From Tables 1 to 4, the following was found.

  In the above-mentioned examples, by using a resin composition containing a specific oxirane compound and an amino group-containing silane coupling agent, a cured product having excellent adhesion and heat resistance (reflow heat resistance) can be provided. It was found that such a resin composition can be suitably used as a lamination material (in particular, an optical material such as an IR cut filter) for forming a layer on a substrate.

  In particular, in Examples 1 to 7 using KBM-903 in which the functional group of the silane coupling agent is an amino group, from Comparative Examples 3 and 4 using Z-6040 and Z-6043 in which the functional group is an epoxy group It was confirmed that the adhesion (after the PCT test) was improved.

  Even if pretreatment coating is not performed using a silane coupling agent on the base material, it is exposed to a moist heat environment by using an amino group-containing silane coupling agent as one of the components of the resin composition forming the resin layer. It was found that peeling and the like are sufficiently suppressed even after the treatment.

  In addition, about the composition and mixture ratio which were prepared in the said Example, it has proved that there exists an advantageous effect within the preferable range described in this specification.

  Since the resin composition of the present invention and the near-infrared cut filter using the resin composition are excellent in heat resistance and adhesiveness, they can be used in various fields such as optical devices such as display elements and imaging elements. For example, it can be used for electronic parts such as a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, and a display element (LED or the like).

Claims (8)

A resin composition used as a material for forming a layer on a substrate,
The resin composition includes an oxirane compound having one or more oxirane rings in the molecule, a silane coupling agent, and a dye. The oxirane compound includes an oxirane compound having a hydroxyl group and / or an ester group, and the silane The coupling resin composition includes a silane coupling agent having an amino group. Content of the said silane coupling agent is 0.1-20 mass% with respect to 100 mass% of said oxirane compounds, The resin composition for lamination | stacking of Claim 1 characterized by the above-mentioned. The said resin composition for lamination | stacking contains a cationic curing catalyst further, The resin composition for lamination | stacking of Claim 1 or 2 characterized by the above-mentioned. The resin composition for lamination according to any one of claims 1 to 3, wherein the silane coupling agent having an amino group is a silane coupling agent having a primary amino group. The resin composition for lamination according to any one of claims 1 to 4, wherein the resin composition for lamination is for coating. A layered product obtained by forming a layer comprising the resin composition for lamination according to any one of claims 1 to 5 on a substrate. A light selective transmission filter comprising the laminate according to claim 6. An image pickup device comprising the laminate according to claim 6.