JP2017067863A - Resin composition for optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for optical material capable of producing a near-infrared ray absorbing material which can more sharply shield a wavelength region to be shielded and exhibits high transmittance in a wavelength region to be transmitted, and can steeply separate necessary waves and unnecessary waves.SOLUTION: A resin composition for optical material contains (A) a near-infrared light absorbing dye and an inorganic compound, (B) a thermosetting and/or photocurable resin and (C) a curing agent, and a transmittance of arbitrary one wavelength W in a visible light region and a near-infrared region when the resin composition is cured by heat and/or light is 50% or more, and a transmittance of a wavelength that is the wavelength W+50nm is 30% or less. The near-infrared light absorbing dye is preferably a phthalocyanine dye and/or oxocarbon dye. The inorganic compound is preferably at least one selected from the group consisting of a copper complex of a phosphate compound and/or phosphonic acid compound, and a cesium composite tungsten oxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition for optical materials, a near-infrared light absorbing material, a near-infrared cut filter including the near-infrared light absorbing material, a sealing material, a light receiving element, a light emitting / receiving composite element, and an image sensor. About.

  In addition to optical members and optical device members, selective optical transmission filters that selectively reduce the transmittance of light of a specific wavelength are used as optical filters for display device parts, mechanical parts, electrical / electronic parts, etc. . In recent years, digital camera modules are being mounted on mobile phones and the like, and the miniaturization is progressing. Accordingly, there is an increasing demand for thinning the light selective transmission filter. The light selective transmission filter mainly uses an inorganic multilayer film by depositing metal or the like on a base material, and the refractive index of each wavelength is controlled. Conventionally, a glass plate has been used as the base material. However, in response to the growing demand for thinning, technologies based on resins are being studied.

  In Patent Document 1, a resin layer having a characteristic of cutting a long wavelength by mixing a dye that absorbs light having a wavelength longer than a desired wavelength, and a light having a wavelength shorter than the desired wavelength. A light receiving device is described in which a light receiving element is sealed by laminating a resin layer having a characteristic of cutting short wavelengths by mixing a dye that absorbs light. Specifically, in this light receiving device, a dye that absorbs light having a wavelength of about 840 nm or less and light having a wavelength of about 1050 nm or more is used for light of 940 nm. Patent Document 2 describes a semiconductor light receiving device using a sealing resin in which an inorganic infrared absorber and an organic infrared absorber are used in combination. However, specific light selective transmission performance is not described.

  A light selective transmission filter is required to be easy to manufacture and handle, and to be able to cut off the wavelength range to be blocked more sharply and to have high light selective transmission that shows high transmittance in the wavelength range to be transmitted. Yes.

JP-A-4-305981 JP 2007-12947 A

Therefore, an object of the present invention is to provide a near-infrared absorbing material capable of sharply separating a necessary wavelength and an unnecessary wavelength, which can sharply block a wavelength region to be blocked and exhibit high transmittance in a wavelength region to be transmitted. It is providing the resin composition for optical materials which can be manufactured.
Another object of the present invention is to provide a near-infrared absorption capable of sharply separating a necessary wavelength from an unnecessary wavelength, which can sharply block a wavelength region to be blocked and exhibit high transmittance in a wavelength region to be transmitted. To provide materials.
Another object of the present invention is to provide a near-infrared cut filter or a sealing material that does not require a vapor deposition film such as metal and has high light selective transmission even in a single layer, and further, a manufacturing process in the case of a single layer. An object of the present invention is to provide a near-infrared cut filter or encapsulant with improved productivity that can be processed easily at the same time.
Furthermore, another object of the present invention includes a near-infrared light cut filter or a sealing material having high light selective transmission even with a single layer, the manufacturing process is shortened, and the productivity is improved, and the optical performance is further improved. An object of the present invention is to provide an improved light receiving element, a light emitting / receiving composite element, and an image sensor.

  By including a near-infrared light-absorbing dye and an inorganic compound, the present inventors can sharply block the wavelength range desired to be blocked, and exhibit a high transmittance in the wavelength range desired to be transmitted. It has been found that a resin composition for optical materials capable of producing a near-infrared absorbing material excellent in light selective transmission capable of sharply separating the light and a near-infrared absorbing material excellent in light selective transmission can be obtained. The invention has been completed.

  That is, the resin composition for an optical material of the present invention comprises (A) a near infrared light absorbing dye and an inorganic compound, (B) a heat and / or photocurable resin, and (C) a curing agent, And / or when cured by light, the transmittance of any one wavelength W from the visible light region to the near infrared light region is 50% or more, and the transmittance of the wavelength W + 50 nm is 30% or less. is there.

  Moreover, the near-infrared absorbing material of the present invention includes a layer having (A) a near-infrared light-absorbing dye and an inorganic compound, and (R) a resin, and includes any layer from the visible light region to the near-infrared light region. The transmittance of one wavelength W is 50% or more, and the transmittance of the wavelength W + 50 nm is 30% or less.

  The near infrared light absorbing dye is preferably a phthalocyanine dye and / or an oxocarbon dye.

  The inorganic compound is preferably at least one selected from the group consisting of a phosphate complex and / or a phosphonic acid compound copper complex and a cesium composite tungsten oxide.

The near-infrared cut filter or sealing material of the present invention includes any one of the above near-infrared absorbing materials.
Moreover, the light receiving element, the light emitting / receiving composite element, or the image sensor of the present invention includes the near infrared cut filter or the sealing material.

According to the present invention, it is possible to manufacture a near-infrared absorbing material capable of sharply separating a necessary wavelength and an unnecessary wavelength, which can cut off a wavelength range to be blocked more sharply and exhibit high transmittance in a wavelength range to be transmitted. A resin composition for optical materials can be provided.
Further, according to the present invention, there is provided a near-infrared absorbing material capable of sharply separating a necessary wavelength and an unnecessary wavelength, which can cut off a wavelength range desired to be cut off sharply and exhibit high transmittance in a wavelength range desired to be transmitted. Can be provided.
In addition, according to the present invention, a near-infrared cut filter or sealing material having high light selective transmission even with a single layer, and further, when it is a single layer, the manufacturing process can be shortened and processing can be easily performed. A near-infrared cut filter or a sealing material with improved productivity can be provided.
Furthermore, according to the present invention, a light-receiving element that includes a near-infrared light cut filter or a sealing material having high light selective transmission even in a single layer, the manufacturing process is shortened, and productivity and light performance are improved. A light receiving composite element and an image sensor can be provided.

It is a graph which made the horizontal axis the wavelength and the vertical axis | shaft the transmittance | permeability with respect to the near-infrared absorber which hardened | cured the resin composition for optical materials of an Example.

1. Optical Material Resin Composition The optical material resin composition of the present invention comprises (A) a near-infrared light absorbing dye and an inorganic compound, (B) a heat and / or photocurable resin, and (C) a curing agent. Including. The resin composition for an optical material according to the present invention includes (A) a near infrared light absorbing dye and an inorganic compound, so that when cured by heat and / or light, from the visible light region to the near infrared light region. The transmittance of any one of the wavelengths W is 50% or more, and the transmittance of the wavelength W + 50 nm is 30% or less. The transmittance of the wavelength W is preferably 50% or more, and the transmittance of the wavelength W + 50 nm is preferably 25% or less. When the transmittance satisfies such conditions, the resin composition for optical materials can cut off the wavelength range to be blocked more sharply, and shows high transmittance in the wavelength range to be transmitted. Have As wavelength W, 500-1000 nm is preferable and 550-800 nm is more preferable.

  The resin composition for optical materials of the present invention can be cured by heat and / or light by a known method. Although a specific curing method will be described in detail later, as a curing condition at the time of measuring the transmittance, a plate-like body having a thickness of about 0.3 mm can be mentioned. In the case of curing by heat, for example, heating at 25 ° C. to 250 ° C. for 15 minutes to 48 hours can be mentioned. In the case of curing with light, for example, the acceleration voltage is set to 10 kV to 500 kV, the irradiation amount of the electron beam is set to 2 kGy to 500 kGy or less, and the irradiation time of ultraviolet light or visible light with a wavelength of 180 to 500 nm is set to 0.1 micron. Second to 30 minutes may be mentioned.

1-1 (A) Near-infrared light-absorbing dye and inorganic compound (A) The near-infrared light-absorbing dye and inorganic compound used in the resin composition for an optical material of the present invention can be exemplified as follows. .

1-1-1 Near Infrared Light Absorbing Dye The near infrared light absorbing dye used in the present invention is preferably a dye having an absorption maximum in a wavelength region of 600 nm to 900 nm, such as a phthalocyanine dye or an oxocarbon dye. Porphyrin dyes, cyanine dyes, quaterylene dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like. Of these, phthalocyanine dyes and oxocarbon dyes are preferred. Near infrared light absorbing dyes may be used alone or in combination of two or more.

<Phthalocyanine dye>
As the phthalocyanine-based dye, a metal phthalocyanine complex is suitable. For example, a metal element such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead is a central metal. A metal phthalocyanine complex is mentioned. Among these metal elements, those having one or more of copper, vanadium, and zinc as a central metal are preferable because they are more excellent in solubility or dispersibility in a resin component, visible light transmittance, and light resistance. The central metal is more preferably copper, zinc or vanadium, and further preferably copper or zinc. The phthalocyanine-based dye using copper does not deteriorate by light even when dispersed in any resin component (binder resin), and has very excellent light resistance. A phthalocyanine complex (phthalocyanine dye) containing zinc as a metal element is preferable because it has excellent solubility in a resin component.

  Among the phthalocyanine dyes, a compound represented by the following general formula (I) is particularly preferable.

In the formula, M represents a metal atom, a metal oxide, or a metal halide. R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 are the same or different and are a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), or a bromine atom. (Br), an iodine atom (I), an OR ⁱ group which may have a substituent, or an NHR ^j group which may have a substituent. R ⁱ and R ^j represent an alkyl group, an aryl group, or an aralkyl group. However, all of R ^{a1 to} R ^a4 and R ^{d1 to} R ^d4 do not represent a hydrogen atom (H) or a fluorine atom (F).

R ⁱ and R ^j are an alkyl group, an aryl group, or an aralkyl group, and may have a substituent. As an alkyl group, a C1-C20 alkyl group is preferable, for example, More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Most preferably, it is C1-C4. It is an alkyl group. Among R ⁱ and R ^j , a phenyl group or a phenyl group having a substituent is preferable.

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

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

R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 are preferably such that at least one of them represents an OR ⁱ group. Thereby, it will become more excellent in light resistance. Here, the carbon to which the OR ⁱ group is bonded represents the α-position carbons in the four aromatic rings of the phthalocyanine skeleton (Cα: carbons at positions 1, 4, 8, 11, 15, 18, 22, 25 of the phthalocyanine ring). Or β-position carbon (Cβ: represents carbons at positions 2, 3, 9, 10, 16, 17, 23, and 24 of the phthalocyanine ring), but is preferably at least the α-position carbon. It is. Among them, a form in which an OR ⁱ group is bonded to two or more carbons on average among α-position carbons (Cα) is preferable, and more preferably, one or more α-position carbons (Cα) have an OR ⁱ group on each aromatic ring. It is a combined form. Moreover, it is also preferable that a hydrogen atom or a fluorine atom is bonded to an average of 4 or more carbons in the β-position carbon (Cβ). More preferably, it is a form in which hydrogen atoms or fluorine atoms are bonded to an average of 6 or more carbons among β-position carbons (Cβ), and more preferably, hydrogen atoms or fluorine atoms are bonded to all carbons of β-position carbons (Cβ). It is a form in which atoms are bonded. By setting it as such a form, since it becomes a phthalocyanine-type pigment | dye which fully satisfy | fills the absorption characteristic mentioned above, it becomes possible to fully exhibit the effect of this invention.

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

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

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

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

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

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

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

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

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

  Among the phthalocyanine dyes described above, a compound represented by the following general formula (II) is more preferable.

Wherein, M ² represents a metal atom, a metal oxide or a metal halide. Of these, α-position atoms (Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ ) and β-position atoms (Z ² , Z ³ , Z ⁶ , Z ¹⁶ ) ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ , Z ¹⁵ ) are substituted with a substituent represented by the following formula (ii-a), (ii-b) or (ii-c), or a halogen atom or the like. It may be a hydrogen atom.

In formula (ii-a), X ¹ represents an oxygen atom or a sulfur atom. R ¹ may be the same or different and may have a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkoxy group having 1 to 20 carbon atoms or —COOR ² is represented. R ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ¹ is an integer from 0 to 5. In formula (ii-b), X ² represents an oxygen atom or a sulfur atom. R ³ may be the same or different and each may have a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkoxy group having 1 to 20 carbon atoms or —COOR ⁴ is represented. R ⁴ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ² is an integer of 0-7. In formula (ii-c), X ³ represents an oxygen atom or a sulfur atom. R ⁵ represents an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

<Oxocarbon compounds (oxocarbon dyes)>
The oxocarbon-based compound preferably contains at least one of a squarylium-based compound and a croconium-based compound.
The structure of the squarylium-based compound is not particularly limited, and examples thereof include a compound represented by the following formula (9).

[In Formula (9), at least one of R ^A1 and R ^A2 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent. ]
The structure of the croconium-based compound is not particularly limited, and examples thereof include a compound represented by the following formula (10).

[In Formula (10), at least one of R ^A3 and R ^A4 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent. ]

Examples of the heterocyclic ring include an aromatic heterocyclic ring and an alicyclic heterocyclic ring.
Examples of the aromatic heterocycle include a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and a condensed 2- to 8-membered ring. And a condensed aromatic heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyridine ring, a pyrazine ring, a pyrimidine ring, Pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, furan ring, thiazole ring, oxazole ring , Indole ring, isoindole ring, indazole ring, benzimidazole ring, benztriazole ring, Zochiazoru ring, benzoxazole ring, purine ring, carbazole ring.
The alicyclic heterocycle includes, for example, a 5-membered or 6-membered monocyclic alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring. And a condensed alicyclic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyrrolidine ring, a piperidine, etc. Ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydropyran ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, etc. .
As an aromatic ring, a C6-C14 thing is mentioned, For example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned.
The substituent of the heterocyclic ring or aromatic ring may be the same or different and may be 1 to 5 substituents such as hydroxyl group, carboxyl group, nitro group, alkoxy group, alkyloxycarbonyl group, amide group, sulfonamide group, alkyl Group, aralkyl group, cyano group, halogen atom, -R = R'-Ar (R and R 'are the same and represent N or CH, Ar represents a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, a halogen atom, And an aryl group which may be substituted with a substituent selected from the group consisting of an alkyl group optionally substituted with a group, a cyano group and a halogen atom). Examples of the substituent of the alkyl group or the alkoxy group include the same or different 1 to 3 substituents such as a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an aryl group, and a halogen atom.
Among them, a 5-membered or 6-membered heterocyclic ring which may have a substituent or a 5-membered or 6-membered aromatic ring which may have a substituent is preferable.

  The oxocarbon-based compound preferably includes at least one of a squarylium-based compound having the structure of the above formula (9) and a croconium-based compound having the structure of the above formula (10), and has the structure of the above formula (9). It is more preferable to include a squarylium-based compound, and it is more preferable to include a squarylium-based compound having the structure of the above formula (9).

<Squarylium compound (squarylium dye)>
In the squarylium compound, R ^A1 and R ^A2 in the formula (9) are each independently a specific structural unit represented by the following formula (11) or a specific structural unit represented by the following formula (12). It is particularly preferred. By having such a structure, shoulder peaks that may appear on the lower wavelength side than the maximum absorption wavelength can be reduced, so that the required wavelength and the unnecessary wavelength can be more sharply separated. R ^A1 and R ^A2 may be the same or different.

[In Formula (11), Ring A is a 4- to 12-membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 9, and m or less (where m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Ys are the same. It may be different or different.
Ring B is an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures.
In addition, * represents the coupling | bond part with a 4-membered ring in Formula (9). ]

[In Formula (12), R ^e1 , R ^e2 , R ^e4 , R ^e5 are each independently an organic group, a polar functional group, or a hydrogen atom, and R ^e3 is an organic group or a polar functional group containing a nitrogen atom. And at least one of R ^e1 and R ^e5 is an organic group or a polar functional group containing a nitrogen atom or an oxygen atom.
In addition, * represents the coupling | bond part with a 4-membered ring in Formula (9). ]

Hereinafter, the details of Expression (11) and Expression (12) will be described.
In formula (11), * represents a binding site to the squarylium skeleton represented by formula (9), and the carbon atom [carbon atom indicated by an arrow in the above formula (11)] is a hydrocarbon bonded to the squarylium skeleton. It is characterized in that it forms a ring (ring A).
In formula (11), ring A is an unsaturated hydrocarbon ring having 4 to 12 members. Ring A is an unsaturated hydrocarbon having at least one double bond between the carbon atom bonded to the squarylium skeleton (in the above formula (11), the carbon atom indicated by the arrow) and the carbon atom constituting the pyrrole ring. The ring may be a ring and may have an unsaturated bond (preferably a double bond) in addition to the double bond, but preferably the ring A has one double bond. . Ring A is preferably a 5- to 12-membered ring, more preferably a 6- to 8-membered ring.
Examples of the structure of ring A include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, Examples include cycloalkene structures such as cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

In formula (11), for example, n is an integer of 0 to 9 and is not more than m (where m is a value obtained by subtracting 3 from the number of members of ring A). n is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2. When n is 1 or more, the hydrogen atom bonded to the carbon atom constituting the ring A is substituted with Y.
In formula (11), X and Y are organic groups or polar functional groups. Examples of the organic group as X and Y include, for example, alkyl group, alkoxy group, alkylthiooxy group (alkylthio group), alkyloxycarbonyl group, alkylsulfonyl group, aryl group, aralkyl group, aryloxy group, arylthiooxy Examples include a group (arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an amide group (—NHCOR), a sulfonamide group (—NHSO ₂ R), a carboxy group (carboxylic acid group), and a cyano group. Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).

As an organic group or polar functional group which is an example of X, an alkyl group, an alkyloxycarbonyl group or an aryl group is preferable, and an alkyl group or an aryl group is more preferable. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 6 if it is a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 if it is an alicyclic alkyl group. Preferably, it is 5-6. 6-10 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-8. Specifically, preferred examples of the organic group or polar functional group of X include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.
As the organic group or polar functional group as an example of Y, among the above, an alkyl group, an alkoxy group, a halogeno group, a phenyl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group, and a hydroxyl group are preferable. An alkyl group or a hydroxyl group is preferable. In this case, 1-5 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-3, More preferably, it is 1-2. Specifically, preferred examples of the organic group or polar functional group as Y include a methyl group, an ethyl group, and a hydroxyl group.
When n is 2 or more and a plurality of Y are present, each Y may be the same or different. When n is 2 or more, a plurality of Ys may be bonded to different carbon atoms, or two Ys may be bonded to one carbon atom.

  In formula (11), ring B is an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring containing these ring structures, which may have a substituent. Examples of the ring B include rings having the structures of the following formulas (A-1) to (A-12), and rings in which one or more hydrogen atoms of these rings are substituted with an arbitrary substituent. Among these, a benzene ring (A-1), a naphthalene ring (A-2, A-3), or a ring substituted with the following substituents is preferable, and a benzene ring (A-1) or a benzene ring (A- A ring in which the following substituent is substituted in 1) is more preferable. Here, examples of the substituent include the groups described above as the organic group or polar functional group as examples of X and Y, and among them, an alkyl group (particularly preferably a linear or straight chain having 1 to 4 carbon atoms) Branched alkyl group), aryl group, alkoxy group; alkylthio group (particularly preferably 1 to 2 carbon atoms), electron donating group such as amino group, amide group, sulfonamide group, halogeno group (particularly preferred is chloro Group, a bromo group, etc.), an alkoxycarbonyl group (ester group), a carboxy group (carboxylic acid group), a sulfo group (sulfonic acid group), a nitro group and the like are preferable, and an electron attractive group is particularly preferable. The number of substituents in ring B may be one or two or more.

The above formulas (A-1) to (A-12) represent the ring B including a part of the pyrrole ring. For example, the formula (A-1) is indicated by an arrow a in the figure below. The carbon atom at the β-position of the pyrrole ring and the carbon atom at the α-position of the pyrrole ring indicated by the arrow b in the figure below are shown.

In addition, R ^A1 and R ^A2 which are specific structural units in the compound (9) having a squarylium skeleton may be the same or different.

  A particularly preferred squarylium-based compound has a squarylium skeleton of formula (9), and in the structural unit of formula (11), ring A is cyclohexene, cycloheptene, or cyclooctene, and X is an alkyl having 1 to 4 carbon atoms. A compound in which ring B is a benzene ring (A-1) or a naphthalene ring (A-2, A-3). In this particularly preferred oxocarbon compound, when ring B has a substituent, the substituent is preferably an alkyl group, a trihalogenomethyl group, a phenyl group, an alkoxy group, a cyano group, a carboxyl group, or a halogeno group.

  Although the manufacturing method of the squarylium type compound which has a specific structural unit shown by the said Formula (11) which is one of the suitable squarylium type compounds used for this invention is not specifically limited, For example, following formula (13):

[In formula (13), ring A, ring B, X, Y, and n are the same as those in formula (11)]. A pyrrole ring-containing compound represented by the formula is used as an intermediate raw material, and this is reacted with squaric acid. be able to.

The pyrrole ring-containing compound used as an intermediate raw material can be synthesized by appropriately adopting known synthetic techniques. For example, a pyrrole ring-containing compound can be synthesized by a synthesis method described in the following paper.
SAJJADIFAR ET AL: 'New 3H-Indole Synthesis by Fischer's Method. Part I.' Molecules 2010, no. 15, April 2010, pages 2491-2498
In addition, the squarylium compound having the specific structural unit represented by the above formula (11) can be synthesized by appropriately adopting a known synthesis method in which a pyrrole ring-containing compound and squaric acid are reacted. For example, a squarylium compound is synthesized by a synthesis method described in a paper such as Serguei Miltsov et al. (“New Cyanine Dyes: Norindosquarocyanines”, Tetrahedron Letters, Volume 40, Issue 21, May 21, 1999, p. 4067-4068). can do.
The obtained squarylium-based compound can be appropriately purified by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization, and crystallization as necessary.

  In Formula (12), * represents a binding site to the squarylium skeleton represented by Formula (9), and the carbon atom (carbon atom indicated by an arrow in Formula (12)) bound to the squarylium skeleton is It is characterized in that it forms an aromatic ring.

In formula (12), at least one of R ^e1 and R ^e5 is an organic group or a polar functional group containing a nitrogen atom or an oxygen atom. Preferably, one of R ^e1 and R ^e5 is —NHR ^f1 or a hydroxyl group, and the other is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, —NR ^f2 R ^f3 , Or -NR ^f4 . R ^{f1 to} R ^f3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, —S (═O) ₂ —R ^f5 , or —C (═O) —R ^f6 (R ^f5 , R ^f6 is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group or araryl group having 6 to 11 carbon atoms. R ^f4 is a cycloalkyl group having 3 to 9 members, or a part of —CH ₂ — in the cycloalkyl group is —O—, —S—, —Se—, —S (═O) _2. —, —C (═O) —, or —NR ^f7 — (R ^f7 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 11 carbon atoms, or A cycloalkyl group having 3 to 9 members and substituted with an (araryl group). R ^e1 and R ^e5 are preferably either —NHR ^f1 or a hydroxyl group.

In formula (12), R ^e2 and R ^e4 are each independently an organic group, a polar functional group, or a hydrogen atom. Examples of the organic group as examples of R ^e2 and R ^e4 include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and an aryl group. Examples include a ruthiooxy group (arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an amide group (—NHCOR), a sulfonamide group (—NHSO ₂ R), a carboxy group (carboxylic acid group), and a cyano group. Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).
In Formula (12), R ^e3 is an organic group or a polar functional group containing a nitrogen atom, and R ^e3 is preferably NR ^f8 R ^f9 or NR ^f10 . R ^f8 and R ^f9 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C (═O) —R ^f11 (R ^f11 may have a hydrogen atom or a substituent. A good alkyl group having 1 to 20 carbon atoms, or an aryl group or araryl group having 6 to 11 carbon atoms). R ^f10 is a cycloalkyl group having 3 to 9 members, or a part of —CH ₂ — in the cycloalkyl group is —O—, —S—, —Se—, —S (═O) _2. -, - C (= O) -, - CHR f12 - or ^{-CR f13 R f14 - (R f12} ~R f14 each alkyl group of 1 to 5 carbon atoms) configurations number is 3 to 9-membered substituted with A cycloalkyl group; When R ^e3 is NR ^f10 , R ^e3 may be bonded to R ^e2 or R ^e4 to form a ring.

  In addition, in Formula (12), although the structure of the squarylium type compound which has a benzene ring which has a substituent is shown, the squarylium type compound which has polycyclic aromatic hydrocarbons, such as a naphthalene ring, may be sufficient. A squarylium-based compound having a polycyclic aromatic hydrocarbon can be a dye having an absorption maximum in a relatively large wavelength region (around 800 nm).

  The method for producing a squarylium compound having a specific structural unit represented by the above formula (12), which is one of the preferred squarylium compounds used in the present invention, is not particularly limited, and a known synthesis method is appropriately employed. Can be synthesized.

<Croconium-based compounds (croconium-based dyes)>
The structure of the croconium-based compound is not particularly limited, and examples thereof include a compound represented by the above formula (10). In formula (10), R ^a3 and R ^a4 are more preferably each independently a structural unit represented by the following formula (21). R ^a3 and R ^a4 may be the same or different.

[In formula (21), A, B, X, Y, n, and m are the same as those in formula (11). * Represents the binding site with the 5-membered ring in formula (10). ]

  The content of the near-infrared light absorbing dye is preferably 1 mass ppm to 20 mass%, more preferably 10 mass ppm to 10 mass%, in 100 mass% of the resin composition for optical materials. In particular, from the viewpoint of curability of the optical material resin composition, the content of the oxocarbon dye is preferably 5 mass ppm to 10 mass%, preferably 10 mass ppm to 1 mass, in 100 mass% of the optical material resin composition. The mass% is more preferable.

1-1-2 Inorganic Compound Examples of the inorganic compound used in the present invention include copper complexes of phosphate ester compounds and copper complexes of phosphonic acid compounds; alkali metal composite tungsten oxides such as cesium composite tungsten oxides; Zinc, titanium oxide, tin oxide, indium oxide, indium tin oxide, antimony oxide, antimony composite tin oxide, and zinc antimonate. Among these, a copper complex of a phosphate ester compound and / or a phosphonic acid compound and a cesium composite tungsten oxide are preferable. An inorganic compound may be used independently or may be used 2 or more types.

  As the cesium composite tungsten oxide, for example, compounds described in JP 2010-168430 A can be preferably used. As a copper complex of a phosphonic acid compound, for example, compounds described in WO2009 / 12306 can be preferably used.

0.1 mass%-50 mass% are preferable in 100 mass% of resin compositions for optical materials, and, as for content of an inorganic compound, 1 mass%-30 mass% are more preferable.
The metal oxide is in the form of fine particles, and the average dispersed particle size is 0.001 to 0.2 μm. Preferably it is 0.005-0.15 micrometer. Such a range is preferable because transparency is not impaired.

  (A) The near-infrared light-absorbing dye and the inorganic compound are any one wavelength selected from the visible light region to the near-infrared light region when the resin composition for optical materials is cured by heat and / or light. Selection is made so that the transmittance of W is 50% or more and the transmittance of the wavelength W + 50 nm is 30% or less. The combination of the near infrared light absorbing dye and the inorganic compound can be determined by the wavelength W. Further, the combination of the near-infrared light absorbing dye and the inorganic compound is selected in consideration of the respective stability and (B) influence on heat and / or curing of the photocurable resin.

  Preferred combinations of near infrared light absorbing dyes and inorganic compounds include, for example, phthalocyanine dyes and / or oxocarbon dyes as near infrared light absorbing dyes, and phosphate ester compounds and / or phosphonic acid compound coppers as inorganic compounds. Examples thereof include at least one selected from the group consisting of a complex and a cesium composite tungsten oxide.

1-2 (B) Heat and / or photo-curable resin (B) The heat and / or photo-curable resin is at least one type selected from the group consisting of acrylic curable resins and epoxy curable resins. Preferably, it is a functional resin. These curable resins are preferably the main components of the optical material resin composition. For example, in 100% by mass of the optical material resin composition, the total amount thereof is preferably 30% by mass or more. . More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more.

  The acrylic curable resin is a resin containing a (meth) acrylate (acrylate or methacrylate) compound, and includes, for example, one or more of aliphatic (meth) acrylate and aromatic (meth) acrylate. Those are preferred. In particular, aliphatic (meth) acrylate is preferable in terms of excellent light resistance. As the aliphatic (meth) acrylate, an aliphatic (meth) acrylate compound having two or more organic skeleton units containing an aliphatic hydrocarbon in the molecule (that is, 2 organic skeleton units containing an aliphatic hydrocarbon in the molecule). A compound having at least one and having a (meth) acryloyl group at at least one molecular terminal), and the resulting cured product can be further excellent in light resistance. Furthermore, it is preferable that one or more other (meth) acrylate monomers are included. As a result, the viscosity and cure shrinkage of the resin composition for optical materials can be made more suitable, and the resin composition for optical materials can be further useful.

  A particularly preferred form of the acrylic curable resin is an aliphatic (meth) acrylate compound (hereinafter simply referred to as “aliphatic (meth) acrylate compound”) having two or more organic skeleton units containing an aliphatic hydrocarbon in the molecule. And at least one selected from the group consisting of fluorene-based (meth) acrylates and other (meth) acrylate monomers. Each of these components can be used alone or in combination of two or more.

The aliphatic (meth) acrylate compound is a compound having two or more organic skeleton units containing an aliphatic hydrocarbon in one molecule and a (meth) acryloyl group at at least one molecular terminal. The organic skeleton units having two or more in the molecule may be of the same type or of different types. In addition, a compound having a (meth) acryloyl group at both ends is more preferable.
In addition, the said aliphatic (meth) acrylate compound may contain the aromatic ring in the structure in the range which does not impair the light resistance and heat resistance of hardened | cured material. For example, when the entire aliphatic (meth) acrylate compound is 100% by mass, the mass ratio of the aromatic ring contained in the structure is preferably 20% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass%, Most preferably, it is 0 mass%, ie, it does not contain an aromatic ring.

  Examples of the organic skeleton containing the aliphatic hydrocarbon include a urethane skeleton (—O—C (═O) —N (H) —R—) having an aliphatic hydrocarbon (R) and a urethane bond; An ester skeleton having a hydrocarbon (R) and an ester bond (—O—C (═O) —R—); an ether skeleton having an aliphatic hydrocarbon (R) and an ether bond (—O—R—); Carbonate skeleton having an aliphatic hydrocarbon (R) and a carbonate bond (—O—C (═O) —O—R—); an oxyalkylene skeleton composed of oxyalkylene groups (—RO—); a (meth) acrylate monomer One or more of (meth) acrylate-based (co) polymer skeletons composed of (co) polymers of the above are suitable, and those having such skeletons are from the resin composition for optical materials. The resulting cured product (molded product) is resistant to The more excellent as the sex and heat resistance. Thus, the organic skeleton containing the aliphatic hydrocarbon is selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton, a carbonate skeleton, an oxyalkylene skeleton, and a (meth) acrylate (co) polymer skeleton. The form which is at least one kind of skeleton is also a preferred form of the present invention.

Among the organic skeletons, it is particularly preferable to have at least one skeleton selected from the group consisting of a urethane skeleton, an ester skeleton, and an ether skeleton. That is, the aliphatic (meth) acrylate compound is particularly preferably an organic skeleton having one urethane skeleton in the molecule and further containing a urethane skeleton and / or other aliphatic hydrocarbon (for example, ester skeleton, ether). (Meth) acrylate compound having one or more skeletons, carbonate skeletons, oxyalkylene skeletons, (meth) acrylate (co) polymer skeletons, etc.) in the molecule [hereinafter also referred to as “urethane (meth) acrylate compounds”. ] An organic skeleton having two or more ester skeletons in the molecule and containing an aliphatic hydrocarbon other than the urethane skeleton in some cases (for example, ether skeleton, carbonate skeleton, oxyalkylene skeleton, (meth) acrylate (co)) (Meth) acrylate compound further having a polymer skeleton etc. [hereinafter also referred to as “polyester (meth) acrylate compound”. ] An organic skeleton having two or more ether skeletons in the molecule and optionally containing an aliphatic hydrocarbon other than the urethane skeleton (eg, ester skeleton, carbonate skeleton, oxyalkylene skeleton, (meth) acrylate (co)) (Meth) acrylate compound [hereinafter also referred to as “polyether (meth) acrylate compound”]. ]. Among these, from the viewpoint of further improving the heat resistance, a urethane (meth) acrylate compound or a polyester (meth) acrylate compound is preferable, more preferably a urethane (meth) acrylate compound, and further preferably a urethane skeleton in the molecule. It is a urethane (meth) acrylate compound having at least one ester skeleton.
In the present specification, in addition to the urethane skeleton, for example, all aliphatic (meth) acrylate compounds having an organic skeleton containing other aliphatic hydrocarbons such as an ester skeleton and an ether skeleton are all urethane (meth). It shall be classified as an acrylate compound. That is, for example, even if it has an ester skeleton or an ether skeleton in the molecule, it is included in the urethane (meth) acrylate compound as long as it further has a urethane skeleton.

The urethane (meth) acrylate compound can be obtained, for example, as a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and a (meth) acrylate monomer having a hydroxyl group. In addition, the reaction conditions normally used can be employ | adopted for this reaction.
Examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. When polyester polyol is used as the polyol, a urethane (meth) acrylate compound having a urethane skeleton and an ester skeleton in the structure is obtained. Similarly, when a polyether polyol is used as the polyol, a urethane (meth) acrylate compound having a urethane skeleton and an ether skeleton in the structure is obtained, and when a polycarbonate diol is used as the polyol, the urethane skeleton and the carbonate skeleton are included in the structure. A urethane (meth) acrylate-based compound having

  The method for producing the polyester polyol is not particularly limited, and for example, a polycondensation reaction between a diol and a dicarboxylic acid or a dicarboxylic acid chloride may be performed, or a diol or a dicarboxylic acid may be esterified to undergo an ester exchange reaction. For this reaction, reaction conditions that are usually used can be employed. Examples of the diol include one or more of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and tetrapropylene glycol. Can be used. As the dicarboxylic acid, one or more of adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid and the like can be used.

  As said polyether polyol, 1 type (s) or 2 or more types, such as a polyethylene oxide, a polypropylene oxide, ethylene oxide propylene oxide random copolymerization, can be used.

  The polycarbonate diol is produced by a transesterification reaction between a low-molecular carbonate compound and a diol, and dimethyl carbonate can be used as the low-molecular carbonate compound. Examples of the diol include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 2- Use of one or more of ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, polyoxyethylene glycol, etc. it can.

  As the diisocyanate, a linear or cyclic aliphatic diisocyanate can be used. Typical examples include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate, and one or more of these can be used.

  Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, pentaerythritol triacrylate, and dipentaerythritol penta. An acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  Specific examples of the urethane (meth) acrylate compound include, for example, EBECRYL230, 270, 9260, 8296 (manufactured by Daicel Cytec); CN 9893, 9788, 983, 980, 981, 991, 9006, 9010, 9178 (manufactured by Sartomer) ); UF-8001G (manufactured by Kyoeisha); UV-7550B, 6100B, 3310B, 3200B, 3000B (manufactured by Nippon Synthetic Chemical Co., Ltd.) and the like.

  Among the aliphatic (meth) acrylate compounds, as the polyester (meth) acrylate compound and the polyether (meth) acrylate compound, in addition to the ester skeleton and the ether skeleton, other skeletons other than the urethane skeleton are included in the structure. It may have a (meth) acryloxy group at the end of the structure or in the side chain. Specific examples of the polyester (meth) acrylate compound include CN294, CN2280, CN2270, CN2297, CN2470 (manufactured by Sartomer) and the like.

  Of the organic skeletons containing the aliphatic hydrocarbons, the oxyalkylene skeleton (oxyalkylene chain) is not particularly limited. For example, an oxyalkylene chain having 1 to 30 carbon atoms is preferable.

  Moreover, as said (meth) acrylate type | system | group (co) polymer frame | skeleton, what is necessary is just a structure formed by (co) polymerizing arbitrary (meth) acrylate monomers, for example, an aliphatic (meth) acrylate compound and a fluorene type | system | group ( In addition to (meth) acrylate, a structure formed by (co) polymerizing one or more of (meth) acrylate monomers and the like to be described later can be used.

  The molecular weight of the aliphatic (meth) acrylate compound varies depending on the number of organic skeletons containing aliphatic hydrocarbons, but preferably has a weight average molecular weight of 500 to 20000. When the weight average molecular weight is in such a range, the resin composition for optical materials is excellent in mold followability, and the entrapment of bubbles during injection into the mold and the shrinkage during curing are further suppressed. It becomes a resin composition. More preferably, it is 1000-15000, More preferably, it is 1500-10000. In the present specification, the weight average molecular weight can be measured by gel permeation chromatography (column: 4 TSKELSUPER HZM-N 6.0 * 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard). .

  As said other (meth) acrylate monomer, when using together with the said aliphatic (meth) acrylate compound, (meth) acrylate monomers other than the said aliphatic (meth) acrylate compound are said fluorene type | system | group (meth) acrylate and When using together, it is suitable to use (meth) acrylate monomers other than the said fluorene type (meth) acrylate, respectively. In addition, the (meth) acrylate monomer used as a raw material of the said aliphatic (meth) acrylate compound can also be used as said other (meth) acrylate monomer. That is, since the (meth) acrylate monomer used as a raw material does not correspond to the aliphatic (meth) acrylate compound itself, it corresponds to “a (meth) acrylate monomer other than an aliphatic (meth) acrylate compound”.

  As said other (meth) acrylate monomer, it is preferable to have an aliphatic cyclic structure, an aromatic cyclic structure, a heterocyclic structure, a neopentyl structure, and / or an alkylene glycol structure (oxyalkylene chain). The (meth) acrylate having such a structure is a monomer that is excellent in light resistance and heat resistance, has a high glass transition temperature (Tg), and gives a hard cured product. If the resin composition for optical material contains such a monomer, the light resistance and heat resistance of the molded product obtained from the resin composition for optical material are further improved, and the resulting molded product is harder, Shape retention can be further improved.

  The other (meth) acrylate monomer may be either a polyfunctional monomer or a monofunctional monomer, but the monofunctional monomer has a small shrinkage when cured, but the obtained cured product has a high hardness. On the other hand, the polyfunctional monomer, the cured product obtained has a high hardness, but the shrinkage when cured is larger than the monofunctional monomer, warping occurs after curing, surface Smoothness may be impaired. Therefore, it is preferable that the polyfunctional monomer and the monofunctional monomer are properly used according to the properties required for the molded product.

  Among the other (meth) acrylate monomers, as the aliphatic cyclic structure in the (meth) acrylate monomer having an aliphatic cyclic structure, for example, a cyclohexyl structure, an isobornyl structure, a dicyclopentanyl structure, an adamantyl structure, and the like are preferable. is there. Thereby, it can be made further excellent in light resistance, heat resistance, and shape retainability. Among these, more preferred are a cyclohexyl structure and an isobornyl structure.

  Specific examples of the (meth) acrylate monomer having an aliphatic cyclic structure include, for example, cyclohexyl structures such as cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and cyclohexanedimethanol di (meth) acrylate. (Meth) acrylate having (meth) acrylate having isobornyl structure such as isobornyl (meth) acrylate and isobornyl di (meth) acrylate; (meth) acrylate having adamantyl structure such as adamantyl (meth) acrylate and adamantyl di (meth) acrylate Dicyclopentanyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, tricyclodecane methanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate. Among these, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate are preferable. More preferred are cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.

In the (meth) acrylate monomer having the aromatic cyclic structure, as the aromatic cyclic structure, for example, a bisphenol A, S, F structure, a fluorene structure, or the like is preferable.
Specific examples of the (meth) acrylate monomer having such an aromatic cyclic structure include, for example, bisphenol A such as ethylene oxide adduct di (meth) acrylate and bisphenol A diglycidyl ether (meth) acrylic acid adduct of bisphenol A. (Meth) acrylate etc. which have a structure are mentioned.

  Specific examples of the (meth) acrylate monomer having a heterocyclic structure include PT810 manufactured by Ciba Specialty Chemicals; ERL4234, 4299, 4221 and 4206 manufactured by UCC; FA-731A (triazine manufactured by Hitachi Chemical Co., Ltd.) A compound having a ring; tris (2-acryloyloxyethyl) isocyanurate) and the like.

  Specific examples of the (meth) acrylate monomer having the neopentyl structure and the (meth) acrylate monomer having a neopentyl structure and an alkylene glycol structure include, for example, neopentyl (meth) acrylate, neopentyl di (meth) acrylate, neopentyl glycol (meta ) Acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, and the like. Among these, neopentyl glycol di (meth) acrylate and ethoxylated neopentyl glycol di (meth) acrylate are preferable. More preferred is neopentyl glycol di (meth) acrylate.

  Specific examples of the (meth) acrylate monomer having an alkylene glycol structure include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3 -Alkylene glycols such as butylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, (meth) of diol Examples include acrylate and di (meth) acrylate. More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butane Examples include diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,12-dodecanediol di (meth) acrylate.

Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol glycol (meth) acrylate and di (meth) acrylate are preferable. When the alkylene glycol is long, the shape retention of the cured product (molded product) obtained by curing the resin composition for optical materials may not be sufficient, and the hygroscopicity may not be sufficiently reduced. If the chain is short, the shrinkage of the cured product may not be sufficiently reduced. More preferred are di (meth) acrylates of any of these glycols. Specific examples of such di (meth) acrylates of glycol include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). Preferred are acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and the like. More preferred are diethylene glycol di (meth) acrylate and dipropylene glycol di (meth) acrylate. Among these, more preferred are dimethacrylates of any of these glycols. Di (meth) acrylate is more preferable than mono (meth) acrylate because the moisture resistance of the cured product is higher, and dimethacrylate is more preferable than diacrylate because the moisture resistance of the cured product is further increased.
Of the (meth) acrylate monomers having an alkylene glycol structure, those having a repeating structure of an oxyalkylene chain are structurally equivalent to the aliphatic (meth) acrylate compound.

  When the acrylic curable resin is a resin containing an aliphatic (meth) acrylate compound and another (meth) acrylate monomer, these blending mass ratios (aliphatic (meth) acrylate compound / other (meth) The acrylate monomer is preferably, for example, 30 to 99/1 to 70. If the blending mass ratio is within this range, the viscosity of the resin composition for optical materials can be set to a more suitable range for molding processing, and curing shrinkage can be further reduced. More preferably, it is 50-95 / 5-50, More preferably, it is 60-90 / 10-40.

The epoxy-based curable resin is a resin including an epoxy group-containing compound (epoxy compound), and includes, for example, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, and a hydrogenated epoxy compound. Is preferred. Among these, from the viewpoint of the strength of the molded product, an aromatic epoxy compound, an alicyclic epoxy compound, and a hydrogenated epoxy compound are preferable, and the epoxy curable resin is an aromatic epoxy compound, an alicyclic epoxy compound, and a hydrogenated epoxy. A form containing at least one epoxy compound selected from the group consisting of compounds is also a preferred form of the present invention.
In the present specification, the epoxy group includes an oxirane ring which is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to an epoxy group in a narrow sense. It is a waste.

  The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule, for example, glycidyl having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a benzene ring, a naphthalene ring, or an anthracene ring. A compound is preferred. Among these, in order to realize a higher refractive index, a compound having a bisphenol skeleton and / or a fluorene skeleton is preferable. More preferably, it is a compound having a fluorene skeleton, whereby the refractive index can be remarkably increased, and heat discoloration can be further suppressed. Moreover, higher refractive index can also be achieved by using a brominated compound of an aromatic epoxy compound, and it is preferable to use it appropriately depending on the application.

  As the aromatic epoxy compound, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, an aromatic epoxy compound having a bromo substituent, and the like are preferable. A fluorene epoxy compound is preferred. Specifically, bisphenol A type epoxy compound (Japan Epoxy Resin, 828EL, 1003 or 1007), bisphenol F type epoxy compound, fluorene type epoxy compound (Osaka Gas Chemical Co., Ltd., Ogsol PG-100) and the like are preferably used. It is done. More preferably, it is a bisphenol A type epoxy compound.

As the aromatic epoxy compound, an aromatic glycidyl ether compound is also suitable, but as the aromatic glycidyl ether compound, for example, an epibis type glycidyl ether type epoxy resin, a high molecular weight epibis type glycidyl ether type epoxy resin, In addition to novolak aralkyl type glycidyl ether type epoxy resins, glycidyl ether compounds having a benzene ring (epoxy compounds having a benzene ring) and the like can be mentioned.
As said epibis type glycidyl ether type epoxy resin, what is obtained by condensation reaction of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and epihalohydrin, for example is suitable.
The high molecular weight epibis type glycidyl ether type epoxy resin can be obtained, for example, by subjecting the epibis type glycidyl ether type epoxy resin to an addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol. Are preferred.

  Examples of the novolak aralkyl type glycidyl ether type epoxy resin include phenols, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and other phenols, formaldehyde, acetoaldehyde, propion Polyhydric phenols obtained by condensation reaction of aldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and epihalohydrin What is obtained by performing a condensation reaction is suitable.

  Examples of the glycidyl ether compound having a benzene ring include phenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, and the like. Specific examples include EX-141, 145, 146, 147, 201 manufactured by Nagase ChemteX Corporation.

  Examples of the aromatic epoxy compound further include, for example, an aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, and the like with epihalohydrin, and the bisphenols and tetramethyl. High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc .; obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin The glycidyl ester type epoxy resin etc. which are used can also be used.

  The said aliphatic epoxy compound is a compound which has an aliphatic epoxy group, and an aliphatic glycidyl ether type epoxy resin is suitable. Examples of the aliphatic glycidyl ether type epoxy resin include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol ( PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose, maltose, etc., and epihalohydrin Preferred are those obtained, those having a propylene glycol skeleton, an alkylene skeleton, an oxyalkylene skeleton, etc. A. 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 preferable.

  The alicyclic epoxy compound is a compound having an alicyclic epoxy group, and as the alicyclic epoxy group, for example, an epoxycyclohexane group (epoxycyclohexane skeleton), a cyclic aliphatic hydrocarbon directly or a hydrocarbon. And an epoxy group added through the intermediate. Among these, a compound having an epoxycyclohexane group is preferable. 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.

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

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

  As the epoxy-based curable resin, a tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin can also be used.

  A particularly preferred form of the (B) heat and / or photocurable resin is to make at least an epoxy curable resin essential. Thereby, shrinkage (curing shrinkage) after curing due to the curing reaction can be more sufficiently suppressed, and molding is further facilitated.

The epoxy-based curable resin includes the following average composition formula (4):
R ⁸ _r (OR ⁹ ) _s SiO _{(4-rs) / 2} (4)
[In the above average composition formula (4), R ⁸ is the same or different and is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 to 7 carbon atoms. 22 represents an alkyl-substituted aryl group, a C 7-22 aralkyl group, a monovalent organic group having an epoxy group, or a monovalent organic group having an oxetanyl group. R ⁹ is the same or different and is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl-substituted aryl group having 7 to 22 carbon atoms, Alternatively, it represents an aralkyl group having 7 to 22 carbon atoms. r and s are numbers of 1.0 ≦ r ≦ 1.7 and 0.05 ≦ s ≦ 1.0, and satisfy 1.05 ≦ r + s ≦ 2.0. ] May be contained. When the epoxy-based curable resin contains the polysiloxane compound represented by the average composition formula (4), the molded body obtained from the epoxy-based curable resin is excellent in heat resistance and crack resistance, Excellent light resistance.

In the average composition formula (4), the groups represented by R ⁸ and R ⁹ may have a substituent or may be an unsubstituted product having no substituent. Specific examples of the alkyl group having 1 to 22 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, and n-decyl. Group and the like. Specific examples of the alkenyl group having 2 to 22 carbon atoms include vinyl group, allyl group, cyclohexenyl group, norbornyl group and the like. Specific examples of the aryl group having 6 to 14 carbon atoms include phenyl group, tolyl group, p-hydroxyphenyl group, naphthyl group and the like. Specific examples of the alkyl-substituted aryl group having 7 to 22 carbon atoms include a methylphenyl group, an ethylphenyl group, a t-butylphenyl group, and an n-octylphenyl group. Specific examples of the aralkyl group having 7 to 22 carbon atoms include 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, and benzyl group. Specific examples of the monovalent organic group having an epoxy group include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4 -An epoxy cyclohexyl) propyl group etc. are mentioned. Specific examples of the monovalent organic group having an oxetanyl group include 3-methyl-3-n-propoxymethyloxetanyl group, 3-ethyl-3-n-propoxymethyloxetanyl group, and 3-methyl-3-n-butoxy. Examples thereof include a methyl oxetanyl group.

The polysiloxane compound preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 20,000. When the weight average molecular weight of the polysiloxane compound is within the above range, the viscosity of the curable resin composition can be prevented from becoming too high, and handling becomes easy. Furthermore, when sealing is performed, bubbles can be prevented from occurring in the sealing material or at the interface between the sealing material and the adherend, and the light transmittance and heat resistance of the sealing material obtained from the curable resin composition can be prevented. Property, crack resistance and sealing performance can be made sufficiently high.
As a weight average molecular weight of the said polysiloxane compound, More preferably, it is 1,500-15,000, More preferably, it is 2,000-10,000. The weight average molecular weight of the polysiloxane compound can be measured by the same method as the weight average molecular weight of the alicyclic epoxy resin described above.

  The polysiloxane compound preferably has a viscosity at 25 ° C. of 1 to 8,000 Pa · s. When the viscosity is such, it is possible to prevent the viscosity of the curable resin composition from becoming too high and handling becomes easy. The viscosity at 25 ° C. is more preferably 5 to 5,000 Pa · s, and still more preferably 10 to 3,000 Pa · s. The viscosity of the polysiloxane compound can be measured by an R / S rheometer (manufactured by Brookfield).

The content of the polysiloxane compound with respect to the epoxy curable resin depends on the amount of OR ⁹ contained in the polysiloxane compound and the ratio of the epoxy group contained in the epoxy curable resin. When the total amount of the conductive resin is 100 parts by mass, it is 10 to 900 parts by mass. When the content of the polysiloxane compound is within the above range, the polysiloxane compound reacts with the epoxy curable resin in addition to the function as a curing accelerator (catalyst) of the epoxy curable resin, and reacts with the epoxy curable resin. The function as a curing agent for curing can also be exhibited well. Moreover, the formed body formed from the resin composition containing an epoxy-based curable resin is excellent in heat resistance, light resistance, and crack resistance.

1-3 (C) Curing Agent (C) The curing agent includes a polymerization initiator in the present invention, and examples thereof include radical polymerization initiators, cationic curing agents, acid anhydrides, amines, and phenol resins. 1 type (s) or 2 or more types can be used. Among these, when the resin composition for optical materials requires an acrylic curable resin, it is preferable that the resin composition for optical materials further contains a radical polymerization initiator, and the resin composition for optical materials When the product essentially requires an epoxy curable resin, it is preferable that the resin composition for an optical material further contains an acid anhydride, an amine, a phenol resin, or a cationic curing agent. More preferably, when the epoxy curable resin is essential, the resin composition for an optical material further contains an acid anhydride or a cationic curing agent.

  What is necessary is just to select suitably as content of the said hardening | curing agent according to a hardening system, the kind of hardening agent to be used, curable resin, etc. For example, when an acrylic curable resin is essential and a radical polymerization initiator is used, the content of the radical polymerization initiator is 0.01 to 10 parts by mass with respect to 100 parts by mass of the acrylic curable resin. Is preferred. More preferably, it is 0.1-5 mass parts, More preferably, it is 0.2-3 mass parts, Most preferably, it is 0.2-2 mass parts.

  Further, when an epoxy curable resin is essential and a cationic curing agent is used, the content of the cationic curing agent is 100 mass of the epoxy curable resin as a solid content converted amount as an active ingredient amount not including a solvent or the like. It is preferable to set it as 0.01-10 mass parts with respect to a part. If it is 0.01 mass part or more, a cure rate will be improved more and it will become possible to harden | cure and shape | mold more fully in a short time. More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more. Moreover, if it is 10 mass parts or less, the coloring at the time of hardening can be suppressed more fully and it is suitable. More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it is 2 mass parts or less.

When acid anhydrides, amines, or phenol resins are used as the curing agent, the content of the curing agent (total amount of acid anhydrides, amines, and phenol resins) is 100% by mass of the resin composition for optical materials. On the other hand, it is suitable that it is 25-150 mass%. More preferably, it is 35-130 mass%. Moreover, when using together the said epoxy-type curable resin and an acid anhydride, amines, or a phenol resin, the mixing ratio is an acid anhydride, amines, or a phenol resin with respect to 1 chemical equivalent of an epoxy-type curable resin. Are preferably mixed so that the total amount is 0.5 to 1.6 equivalents. More preferably, the mixing is performed at a ratio of 0.7 to 1.4 equivalents, more preferably 0.9 to 1.2 equivalents.
Among acid anhydrides, amines, and phenol resins, it is particularly preferable to use acid anhydrides as described above.

Below, each hardening | curing agent is further demonstrated.
The radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals and initiating the polymerization. For example, 1,1′-azobis (cyclohexane-1-carbonitrile), 1,1 '-Azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, phenylazotriphenylmethane, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azo Bisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), methyl 2,2′-azobis-2-methylpropionate, dimethyl 2,2′-azobisisobutyrate, 2,2′azobis Azo initiators such as 2-methylvaleronitrile; benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauro peroxide Tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, such as t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-amylperisononanoate, t-amylperoxyacetate, t-amylperoxybenzoate, etc. Oxide-based initiators; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propyl Pan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4 Alkylphenone-based initiators such as -methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,4 acylphosphine oxide-based initiators such as 6-trimethyl benzoyl) phenyl phosphine oxide, bis (eta ^{5-2,4-cyclopentadienyl} -1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and other titanocene initiators; 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), etc. Examples include oxime ester initiators.

  The cationic curing agent is a compound that generates cationic active species, and is also called a cationic curing catalyst (thermal latent cationic curing catalyst, photolatent cationic curing catalyst). When a cationic curing agent is used, a compound containing a cationic species is excited by heating or light irradiation to cause heat or photolysis reaction, and curing proceeds. The curing / molding reaction can be suitably advanced. Further, the cationic curing agent is different from acid anhydrides, amines, phenol resins and the like that are generally used as a curing agent, and even if it is contained in the resin composition for optical material, the resin composition for optical material It is a one-part liquid that has excellent handling properties and does not cause an increase in viscosity or gelation over time at room temperature, and as a function of a cationic curing agent, it can sufficiently promote the curing reaction and exhibit an excellent effect. Resin composition (one-component material) can be provided.

Examples of the cationic curing agent include the following formula (5):
_{^{(R 21 a R 22 b R}} 23 c R 24 d Z) + m21 (A 1 X 21 n1) -m21 (5)
[In the above formula (5), 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 ²¹ , R ²² , R ²³ and R ²⁴ are the same or different and represent an organic group. a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. Cation _{^{(R 21 a R 22 b R}} 23 c R 24 d Z) + m21 represents an onium salt. A ¹ represents a metal element or a metalloid element (metalloid) which is a central atom of a halide complex, and is selected from B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. And at least one selected from the group consisting of X ²¹ represents a halogen element. m21 is the net charge of the halide complex ion. n1 is the number of halogen elements in the halide complex ion. ] The compound represented by this is suitable.

Specific examples of the anion (A ¹ X ²¹ _n1 ) ^-m21 of the above formula (5) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ). , Hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
Furthermore, an anion represented by the formula A ¹ X ²¹ _n1 (OH) ⁻ can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

  Among the above cationic curing agents, specific products of the heat-latent cationic curing catalyst include, for example, AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries). Diazonium salt types such as: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhône-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries, Ltd.) ) Iodonium salt type; CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), Optomer SP series Optomer CP Sulfonium salts such as Aze (manufactured by Adeka), Sun Aid SI series (manufactured by Sanshin Chemical Industry), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.) Type.

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

  When the photolatent cationic curing catalyst is used, it is preferable to use a photosensitizer in combination. Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethyl). Amines such as amino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like are preferable.

  It is preferable that the compounding quantity of the said photosensitizer is 0.1-20 mass% with respect to 100 mass% of said resin compositions for optical materials. Thereby, photopolymerization can proceed more efficiently and the curing reaction can be sufficiently performed. More preferably, it is 0.5-10 mass%.

  Various Lewis acids can also be used as the thermal cation curing catalyst. Examples of Lewis acids include transition metal elements, rare earth elements, Mg, Zn, P, As, Sb, Sn, B, Al halides, organic salts, and organometallic compounds. Specifically, iron chloride, copper chloride, palladium chloride, scandium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, europium trifluoromethanesulfonate, magnesium acetate, magnesium trifluoromethanesulfonate, zinc chloride, zinc acetate, trifluoromethanesulfone Zinc acid, phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, tin chloride, boron trifluoride, tributylborane, triphenylborane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) phenylborane, Pentafluorophenyldiphenylborane, tris (4-fluorophenyl) borane, aluminum chloride, trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylalumina Miniumu, triphenyl aluminum, tris (pentafluorophenyl) aluminum, and the like. Among them, boron compounds such as boron trifluoride, tributylborane, triphenylborane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) phenylborane, pentafluorophenyldiphenylborane, tris (4-fluorophenyl) borane, Aluminum compounds such as aluminum chloride, trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triphenylaluminum, and tris (pentafluorophenyl) aluminum are preferred.

  Moreover, a metal chelate compound or a metal alkoxide can also be suitably used as the thermal cation curing catalyst. As a metal chelate compound or a metal alkoxide, the following general formula (6):

(In the formula, M represents any of Al, Mg, Ti or Zr. R ¹⁰ is the same or different and represents an alkyl group or alkoxyl group having 1 to 6 carbon atoms. R ¹¹ is the same or different. Represents an alkyl group having 1 to 12 carbon atoms, g represents a valence of an ion of a metal atom represented by M, and h represents a number of 0 to 3. In the formula, A dotted line between them indicates that an oxygen atom is coordinated to M. A structural portion formed by two oxygen atoms coordinated to M and three carbon atoms between the two oxygen atoms. The dotted arc indicates that at least one pair of atoms in the structure portion is connected by a double bond, and the double bond may be conjugated with the ring structure forming the dotted arc portion. ) Can be suitably used.
Incidentally, "R ¹⁰ are the same or different and each represents an alkyl group or an alkoxyl group having 1 to 6 carbon atoms" and, if the structural part in marked with h () there is a plurality, the plurality of structural parts It means that the structures of R ¹⁰ in may be the same or different. The same is true for R ^11.

  Specific examples of the metal chelate compound represented by the general formula (6) include aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), Plenact AL-M (trade name, manufactured by Kawaken Fine Chemical Co., Ltd.) ), Aluminum chelating compounds such as aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), aluminum tris (ethyl acetylacetonate); magnesium ethyl acetoacetate monoisopropylate, magnesium bis (ethyl acetoacetate) Magnesium chelate compounds such as magnesium acetoacetate monoisopropylate and magnesium bis (acetylacetonate); zirconium tris (acetylacetate) Toneto), such as titanium bis (acetoacetate) dibutyrate and the like.

  Among the compounds represented by the general formula (6), the metal alkoxide is represented by the following general formula (7):

(Wherein R ¹² represents an alkyl group). That is, it is a compound represented by h = 0 in the general formula (6).

In the general formula (7), R ¹² represents an alkyl group, and specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n -Hexyl group, cyclohexyl group, n-decyl group, etc. are mentioned. R ¹² is preferably an alkyl group having 1 to 22 carbon atoms.

  Specific examples of the metal alkoxide represented by the general formula (7) include aluminum alkoxides such as aluminum triethoxide, aluminum triisopropoxide, aluminum trisec-butoxide, aluminum tritert-butoxide; magnesium diethoxide, Examples thereof include aluminum alkoxides such as magnesium diisopropoxide and magnesium ditert-butoxide; titanium tetraisopropoxide and the like.

  When a metal chelate compound or metal alkoxide is used as the thermal cation curing catalyst in the present invention, among the metal chelate compound or metal alkoxide represented by the general formula (6), an aluminum chelate compound or aluminum alkoxide in which M is Al is preferable. Of these, aluminum chelate compounds are more preferred. By using such an aluminum chelate compound as the thermal cation curing catalyst, the encapsulant obtained from the composition of the present invention is more excellent in heat resistance and light resistance.

  In addition, compounds such as amine compounds, phosphine compounds, polyalcohols, and polyethers can also be used as the curing regulator. Specific examples of the compound include triethylamine, tributylamine, diisopropylamine, diethanolamine, triethanolamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, bis ( 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), bis ( Amine compounds such as 2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate; Phosphine, trimethylphosphine, preparative Little yl phosphine, phosphine compounds such as methyl diphenyl phosphine, ethylene glycol, propylene glycol, glycerin, diethylene glycol, polyalcohols such as triethylene glycol, polyethylene glycol, and a polyether such as polypropylene glycol.

  When acid anhydrides, amines, or phenol resins are used as the curing agent, those usually used may be used as these curing agents. Specifically, examples of acid anhydrides (acid anhydride curing agents) include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Phthalic anhydride, nadic anhydride, methyl nadic anhydride, het anhydride, hymic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Alicyclic carboxylic acid anhydrides such as dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, chlorendic acid, methylendomethylenetetrahydrophthalic anhydride, etc .; dodecenyl succinic anhydride, polyazeline acid anhydride, polysebacin Aliphatic anhydrides such as acid anhydrides and polydodecanedioic anhydrides; Tal anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, aromatic carboxylic acid anhydrides such as biphenyltetracarboxylic acid anhydride.

  As said amines (amine type hardening | curing agent), an aromatic amine is preferable, for example, 1,3-diamino-2,4-diethyltoluene, bis (3-ethyl-4-aminophenyl) methane, phenylenediamine, diamino Examples thereof include diphenylmethane, 2,2′-bis- (aminophenyl) propane, diaminodiphenylsulfone, toluenediamine, diethyltoluenediamine, and derivatives thereof.

  Examples of the phenol resins (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; fluorenes such as 1,1-di-4-hydroxyphenylfluorene Phenols having a skeleton; phenolic poly Polyphenolic compounds such as tadiene, novolak resins made from various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols: xylylene skeleton Various novolak resins such as a phenol novolac resin containing a phenol, a novolak resin containing a dicyclopentadiene skeleton, and a phenol novolak resin containing a fluorene skeleton may be mentioned.

  Among the acid anhydrides, amines or phenol resins, preferably acid anhydrides, more preferably alicyclic carboxylic acid anhydrides, and still more preferably methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride. Methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, more preferably methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

1-4 Curing accelerator The resin composition for optical materials may also contain a curing accelerator. In particular, when an acid anhydride, an amine, or a phenol resin is used as the curing agent, it is preferable to use a curing accelerator in combination. Curing accelerators include tertiary amines, diazabicycloalkenes, imidazoles, organophosphorus compounds, and their organic acid salts, quaternary ammonium salts, quaternary phosphonium salts, organometallic compounds, boron compounds. And metal halides.

Examples of tertiary amines include benzyldimethylamine, dimethylcyclohexylamine, and triethanolamine.
Examples of diazabicycloalkenes include 1,8-diazabicyclo (5,4,0) undecene-7.
Examples of imidazoles include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Undecylimidazolyl- ( ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-ethylimidazolyl- (1')]-ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole and the like.

Examples of the organic phosphorus compounds include triphenylphosphine, tri (p-methoxy) phenylphosphine, and triphenyl phosphite.
Examples of the quaternary ammonium salts include tetraoctyl ammonium bromide, tetrabutyl ammonium bromide, tetraethyl ammonium bromide and the like.
Examples of quaternary phosphonium salts include tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetrabutylphosphonium laurate, tetrabutylphosphonium acetate, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium benzotriazolate. , Tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium o, o-diethyl phosphorodityroate and the like.
Examples of the organometallic compounds include zinc octylate, zinc stearate, tin octylate, and aluminum tris (acetylacetonate).
Examples of boron compounds include boron trifluoride and triphenylborane.
Examples of metal halides include zinc chloride and tin chloride.

  Of these, imidazoles, organophosphorus compounds, and quaternary phosphonium salts are preferred from the viewpoint of heat resistance and transparency of the cured product. The said hardening accelerator can be used 1 type or in combination of 2 or more types. It is preferable that the usage-amount of a hardening accelerator shall be 0.01-10 mass% with respect to 100 mass% of total amounts of the said resin composition for optical materials, More preferably, it is 0.03-5 mass%.

1-5 Additives The resin composition for optical materials of the present invention is not limited to the above-described essential components and suitable components, but may be pigments, dyes other than those described above, and reactive dilution as long as the effects of the present invention are not impaired. Agent, saturated compound having no unsaturated bond, antioxidant, ultraviolet absorber, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization initiator, polymerization inhibitor, Adhesion improvers such as inorganic and organic fillers, coupling agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, anti-settling agents Contains thickeners, anti-sagging agents, anti-coloring agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, desiccants, antifouling agents, antistatic agents, conductive agents (electrostatic aids), etc. It may be.

2. Near-infrared absorbing material The near-infrared absorbing material of the present invention includes (A) a near-infrared light absorbing dye and an inorganic compound, and (R) a layer having a resin. (A) Preferred embodiments of the near-infrared light absorbing dye and the inorganic compound are the same as those of the resin composition for optical materials. (A) The near-infrared light absorbing dye and the inorganic compound have a transmittance of 50% or more for any one wavelength W from the visible light region to the near-infrared light region, and a transmittance of 30% for the wavelength W + 50 nm. The type and content are adjusted to be as follows. The transmittance of the wavelength W is preferably 50% or more, and the transmittance of the wavelength W + 50 nm is preferably 25% or less. The preferable aspect of the wavelength W is the same as the description in description of the resin composition for optical materials.

  The (R) resin contained in the near-infrared absorbing material of the present invention is obtained by curing the (B) heat and / or photocurable resin. (B) As a curing method for the heat and / or photocurable resin and the resin composition for optical materials containing the same (hereinafter, these may be collectively referred to as a resin composition), a normal method is adopted. For example, it can be carried out by heating or irradiation with active energy rays.

  For example, in the case of curing by heating, the curing temperature and curing time may be appropriately set according to the curing agent and the like, for example, preferably 25 to 250 ° C, more preferably 60 to 200 ° C, and still more preferably 80 to 180 ° C. Particularly preferred is 100 to 180 ° C, most preferred 110 to 150 ° C.

  The thermosetting can also be performed in air and / or under an atmosphere of an inert gas such as nitrogen under reduced pressure or under pressure. Further, the curing temperature may be changed stepwise. For example, from the viewpoint of improving productivity, etc., the resin composition is held in the mold at a predetermined temperature and time, and then taken out of the mold and left in an inert gas atmosphere such as air and / or nitrogen for heat treatment. It is also possible to do. Moreover, you may combine hardening by active energy ray irradiation.

In the case of curing by irradiation with active energy rays, any active energy rays may be used as long as they can generate active species such as radicals and cations, for example, ultraviolet rays, visible rays, electron beams, α rays, β rays. Ionizing radiation such as γ-ray, microwave, high frequency, infrared ray, laser beam and the like are suitable, and may be appropriately selected in consideration of the absorption wavelength of the compound that generates the active species. Among these, ultraviolet rays or visible rays having a wavelength of 180 to 500 nm are preferable because they can be easily handled, and light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is particularly effective for curing.
The curing by irradiation with active energy rays can be performed in air and / or in an inert gas, under any atmosphere under reduced pressure or under pressure.

  Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, Short arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, sunlight and the like are suitable. In addition to these light sources, thermal energy may be applied using infrared rays, far infrared rays, hot air, high-frequency heating, or the like.

  In the case of curing using an electron beam, the lower limit of the acceleration voltage is set to 10 kV or higher, preferably 20 kV or higher, more preferably 30 kV or higher, and the upper limit is set to 500 kV or lower, preferably 300 kV or lower, more preferably 200 kV or lower. It is mentioned to use the set electron beam. In addition, the lower limit of the electron beam irradiation dose is set to 2 kGy or more, preferably 3 kGy or more, more preferably 5 kGy or more, and the upper limit is set to 500 kGy or less, preferably 300 kGy or less, more preferably 200 kGy or less. . Furthermore, you may provide a thermal energy simultaneously using the said electron beam using infrared rays, far infrared rays, a hot air, high frequency heating, etc.

  What is necessary is just to set suitably the irradiation time of the said active energy ray irradiation, ie, the hardening time in hardening by an active energy ray, according to the kind, irradiation amount, etc. of an active energy ray. For example, the irradiation time of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is preferably 0.1 microseconds to 30 minutes, and more preferably 0.1 milliseconds to 1 minute.

3. Near-infrared light cut filter or sealing material The near-infrared light cut filter or sealing material of this invention contains the said near-infrared absorber. For this reason, even a single layer has high light selective transmission, and an expensive inorganic vapor deposition filter is unnecessary. In the case of a single layer, the manufacturing process can be shortened, and at the same time, processing can be easily performed, and productivity can be improved.
The near infrared light cut filter or sealing material of the present invention may have a multilayer structure of two or more layers.

4). Light-receiving element, light-emitting / light-receiving composite element, or image sensor The light-receiving element, light-emitting / light-receiving composite element, or image sensor of the present invention includes the near infrared light cut filter or the sealing material. Since a single layer includes a near-infrared light cut filter or a sealing material having high light selective transmission, the manufacturing process can be shortened, productivity can be improved, and optical performance can be further improved.

  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. In addition, evaluation of the Example was performed as follows. Moreover, below, a part shall mean a mass part and% shall mean the mass%.

[Evaluation method]
(1) Transmittance The resin composition was injected between two glass plates with a 0.3 mm spacer in between and cured in an oven at 150 ° C. for 1 hour to produce a plate-like sample having a thickness of 0.3 mm. . About the obtained sample, the transmittance | permeability was measured using UV-VIS spectrophotometer (Agilent 8453, product made by Agilent Technologies).
(2) Viscosity Viscosity was measured using an R / S rheometer (manufactured by Brookfield, USA) under the conditions of 40 ° C. and rotation speed D = 1 / s. An RC25-1 measuring jig was used at a viscosity of 20 Pa · s or more, and an RC50-1 jig was used at a viscosity of less than 20 Pa · s. Moreover, about the thing whose viscosity at the rotational speed D = 1 / s cannot be measured, the value of rotational speed D = 5-100 / s was extrapolated and evaluated as a viscosity.

Preparation Example 1
<Preparation of resin composition>
A reactor equipped with a thermometer, a reflux condenser, and a stirrer was charged with 208 g of methyltrimethoxysilane (Toray Dow Corning, Z-6366), 57.4 g of methyl isobutyl ketone, and 21.1 g of formic acid. While stirring at an internal temperature of 35 ° C., 44.2 g of water was added and stirred for 10 minutes. Thereafter, using a 90 ° C. oil bath, the temperature inside the reaction system was raised while stirring, and refluxing was started. After 1 hour from the start of reflux, the reflux condenser was removed from the separable flask, and the mixture was heated and stirred again to distill off the solvent at normal pressure. When the amount of distillate reached 117.4 g, the oil bath was removed and the temperature was lowered to stop the distillation. After reaching the internal temperature of 53 ° C., the solvent was distilled off under reduced pressure at 10 kPa for 1 hour while stirring in an oil bath at 53 ° C., and then the solvent was distilled off under reduced pressure at 53 ° C. and 1 kPa for 30 minutes while stirring. did. Further, while raising the temperature and stirring, the solvent was distilled off under reduced pressure for 30 minutes at 80 ° C. and 1 kPa, thereby obtaining 115.7 g of a polysiloxane compound (1). The resulting polysiloxane compound (1) had a weight average molecular weight of 4,101 and a viscosity at 25 ° C. of 1630 Pa · s.

  274.3 mg of diisopropoxyaluminum ethyl acetoacetate (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) and tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate ( LA57, manufactured by ADEKA) 257.1 mg was weighed, and 4.78 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) was added as a solvent, heated to 60 ° C., mixed for 30 minutes, and cured. Catalyst (1) was prepared.

  In a reactor equipped with a thermometer and a stirrer, 30 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) and 30 g of YX-8040 (manufactured by Mitsubishi Chemical Corporation, solid hydrogenated bisphenol A type epoxy resin) are added. Weighed and heated to 140 ° C. in a nitrogen atmosphere and mixed for 1 hour. After cooling to 70 ° C., 40 g of polysiloxane compound (1) was added and mixed for 30 minutes. After cooling to room temperature, 0.3 g of the curing catalyst (1) was added and mixed for 30 minutes to obtain a resin composition (1).

Preparation Example 2
<Production of phthalocyanine G>
In a 1000 ml three-necked reaction vessel, 100 g (0.58 mol) of 3-nitrophthalonitrile, 159.7 g (1.16 mol) of potassium carbonate, 104.6 g (0.64 mol) of 2,6-dichlorophenol, and 400 g of acetonitrile are added. Prepared. After stirring and reacting at 60 ° C. overnight, the reaction solution was filtered, acetonitrile was distilled off from the filtrate by a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 100.9 g of Intermediate F (yield 60.2%).
The reaction in the production process of this intermediate F is simplified and shown in the following chemical formula (16).

  A 300 ml four-necked flask was charged with 60.0 g (0.21 mol) of the intermediate F, 5.65 g (0.057 mol) of copper (I) chloride, and 140.0 g of diethylene glycol monomethyl ether while stirring at 160 ° C. After reacting for 24 hours, 100.0 g of methyl cellosolve was added to prepare a reaction solution. This reaction solution was dropped into a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again stirred and washed with a mixed solution of methanol and water, suction filtered, and then dried at 90 ° C. for 24 hours using a vacuum dryer, to obtain 51.48 g of the target phthalocyanine G ( Yield 80.4%). The reaction in the production process of phthalocyanine G is simplified and shown in the following chemical formula (17).

  In the structure, phthalocyanine G is substituted with the substituent I shown on the right side in four of the parts indicated by “*” in the main skeleton (total 8) and the substituents shown on the lower side in the remaining four ( That is, the hydrogen atoms are each substituted or bonded. Further, phthalocyanine G has absorption maximums at 630 nm and 701 nm, and the wavelength having the largest absorbance (absorption maximum wavelength) was 701 nm.

[Example 1]
To 100 parts of the resin composition (1) obtained in Preparation Example 1, 0.01 part of phthalocyanine G obtained in Preparation Example 2, 0.025 part of squarylium 1 (the following formula), YMF-02A (Sumitomo Metal) 2.43 parts (0.45 parts in terms of solid content) of Cesium Tungsten Oxide Dispersion (Min Co., Ltd., solid content: 18.5%) was added and mixed, and the dye-containing resin composition (resin composition for optical material) was mixed. Obtained. The squarylium 1 was produced by the synthesis method described in the paper mentioned in the specification.

  Using the obtained dye-containing resin composition, a transmittance evaluation sample (near infrared absorbing material) was prepared by the above method, and the transmittance was measured. Table 1 shows the formulation of the dye-containing resin composition and the transmittance at 650 nm and 700 nm. Moreover, the graph which made the horizontal axis the wavelength and used the vertical axis | shaft for the near-infrared absorber manufactured from the pigment | dye containing resin composition created in Example 1 in FIG. 1 is shown.

As shown in Table 1 and FIG. 1, the transmittance for a wavelength of 650 nm is 53% and the transmittance for a wavelength of 700 nm is 19%, so that a necessary wavelength and an unnecessary wavelength can be sharply separated without a reflective vapor deposition film or the like. It was.

Claims (8)

(A) a near infrared light absorbing dye and an inorganic compound,
(B) a heat and / or photocurable resin, and (C) a curing agent,
When cured by heat and / or light, the transmittance of any one wavelength W from the visible light region to the near infrared light region is 50% or more, and the transmittance of the wavelength W + 50 nm is 30%. The resin composition for optical materials which is the following. The resin composition for an optical material according to claim 1, wherein the near-infrared light absorbing dye is a phthalocyanine dye and / or an oxocarbon dye. The resin for optical materials according to claim 1 or 2, wherein the inorganic compound is at least one selected from the group consisting of a copper complex of a phosphate ester compound and / or a phosphonic acid compound and a cesium composite tungsten oxide. Composition. (A) a layer having a near infrared light absorbing dye and an inorganic compound, and (R) a resin,
A near-infrared absorbing material in which the transmittance of any one wavelength W from the visible light region to the near-infrared light region is 50% or more, and the transmittance of the wavelength W + 50 nm is 30% or less. The near-infrared absorbing material according to claim 4, wherein the near-infrared light absorbing dye is a phthalocyanine dye and / or an oxocarbon dye. The near-infrared absorption according to claim 4 or 5, wherein the inorganic compound is at least one selected from the group consisting of a copper complex of a phosphate ester compound and / or a phosphonic acid compound and a cesium composite tungsten oxide. Wood. The near-infrared light cut filter or sealing material containing the near-infrared absorber of any one of Claims 4-6. A light-receiving element, a light-emitting / light-receiving composite element, or an image sensor comprising the near-infrared light cut filter or the sealing material according to claim 7.