JP5810604B2 - Near-infrared cut filter and device using near-infrared cut filter - Google Patents

Description

  The present invention relates to a near-infrared cut filter. More specifically, the present invention relates to a near-infrared cut filter that has a sufficient viewing angle and can be suitably used as a visibility correction filter for a solid-state imaging device such as a CCD or CMOS.

  In recent years, televisions equipped with plasma display panels (PDPs) have been commercialized and have become widespread in ordinary households. This PDP is a display that operates using plasma discharge, but it is known that near infrared rays (wavelength: 800 to 1000 nm) are generated during plasma discharge.

  On the other hand, near-infrared rays are often used in homes for remote control of home appliances such as TVs, stereos or air conditioners, and personal computers in homes. It has always been pointed out that it is likely to cause malfunctions.

  Therefore, many of the commercially available PDPs are provided with a filter function for cutting near infrared rays emitted from the front plate.

  In addition, CCDs and CMOS image sensors, which are solid-state image sensors for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, etc., and these solid-state image sensors are sensitive to near-infrared light at their light receiving parts. Therefore, it is necessary to perform visibility correction, and a near-infrared cut filter is often used.

  As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, a metal such as silver deposited on the surface of a transparent substrate such as glass to reflect near infrared rays, or a transparent resin such as acrylic resin or polycarbonate resin to which a near infrared absorbing dye is added is practical. It is provided.

  However, the near-infrared cut filter in which a metal is vapor-deposited on a glass base material has a problem that not only the manufacturing cost is high, but also a glass piece of the base material is mixed as a foreign substance during cutting. Furthermore, when an inorganic material is used as a base material, there has been a limit to cope with the recent thinning and downsizing of solid-state imaging devices.

  JP-A-6-200113 (Patent Document 1) discloses a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing pigment is contained in the transparent resin.

  However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption capability.

  Further, the present applicant has proposed a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film in JP-A-2005-338395 (Patent Document 2).

JP-A-6-200113 JP 2005-338395 A

  Although the near-infrared cut filter described in Patent Document 2 is excellent in near-infrared cut ability, moisture absorption resistance, and impact resistance, there are cases where a sufficient viewing angle cannot be obtained.

  The present invention has a wide viewing angle, excellent near-infrared cutting ability, low hygroscopicity, no foreign matter and warpage, and can be used preferably for solid-state imaging devices such as CCDs and CMOSs. The purpose is to obtain. Furthermore, it aims at providing the solid-state imaging device which was thin and excellent in impact resistance.

  The near-infrared cut filter according to the present invention has a resin substrate (I) containing a compound (I) having a structure derived from a compound represented by the following formula (I).

[式（Ｉ）中、Ｒ^a、Ｒ^bおよびＹは、下記（ｉ）または（ｉｉ）を満たす。
（ｉ）Ｒ^aはそれぞれ独立に水素原子、炭素数１〜８のアルキル基、−ＮＲ^eＲ^f基（Ｒ^eおよびＲ^fはそれぞれ独立に水素原子または炭素数１〜５のアルキル基を表す。）、またはヒドロキシ基を表し、
Ｒ^bはそれぞれ独立に水素原子、炭素数１〜５のアルキル基、−ＮＲ^gＲ^h基（Ｒ^gおよびＲ^hはそれぞれ独立に水素原子、炭素数１〜５のアルキル基、または−Ｃ（Ｏ）Ｒⁱ基（Ｒⁱは炭素数１〜５のアルキル基を表す。））、またはヒドロキシ基を表し、
Ｙは−ＮＲ^jＲ^k基（Ｒ^jおよびＲ^kはそれぞれ独立に水素原子、炭素数１〜８の脂肪族炭化水素基、任意の水素原子が官能基で置換された炭素数１〜８の置換脂肪族炭化水素基、炭素数６〜１２の芳香族炭化水素基、または任意の水素原子がアルキル基で置換された炭素数６〜１２の置換芳香族炭化水素基を表す。）を表す。
（ｉｉ）１つのベンゼン環上の２つのＲ^aのうちの１つが、同じベンゼン環上のＹと相互に結合して、構成原子数５または６の窒素原子を少なくとも１つ含む複素環を形成し、
Ｒ^bおよび該結合に関与しないＲ^aはそれぞれ独立に前記（ｉ）のＲ^bおよびＲ^aと同義である。]

[In the formula (I), R ^a , R ^b and Y satisfy the following (i) or (ii).
(I) R ^a is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a —NR ^e R ^f group (R ^e and R ^f each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ), Or a hydroxy group,
R ^b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or —C ( O) R ⁱ group (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)), or a hydroxy group,
Y is a —NR ^j R ^k group (R ^j and R ^k are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a 1 to 8 carbon atom in which any hydrogen atom is substituted with a functional group) It represents a substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which an arbitrary hydrogen atom is substituted with an alkyl group.
(Ii) one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing at least one nitrogen atom having 5 or 6 atoms And
R ^b and R ^a not involved in the bond are independently the same as R ^b and R ^a in the above (i). ]

The near-infrared cut filter according to the present invention preferably has a transmittance satisfying the following (A) to (D).
(A) In the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the near infrared cut filter is 75% or more. (B) At the wavelength of 800 to 1000 nm, measured from the vertical direction of the near infrared cut filter. In the wavelength range of 20% or less (C) 800 nm or less, the average value of the transmittance in the case of the longest wavelength (Xa) at which the transmittance when measured from the vertical direction of the near infrared cut filter is 70% and the wavelength In the wavelength region of 580 nm or more, the absolute value of the difference from the shortest wavelength (Xb) at which the transmittance is 30% when measured from the vertical direction of the near-infrared cut filter is less than 75 nm (D) The wavelength range of 560 to 800 nm The wavelength at which the transmittance is 50% when measured from the vertical direction of the near-infrared cut filter (Ya) , The absolute value is less than 15nm the difference between the values of the wavelength in which the transmittance as measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter is 50% (Yb)

The resin substrate (I) preferably satisfies the following (E) and (F).
(E) There is an absorption maximum at a wavelength of 600 to 800 nm. (F) In the wavelength range of 430 to 800 nm, the longest wavelength below the absorption maximum (Za) is 70% when measured from the vertical direction of the substrate. ) And the absolute value of the difference between the shortest wavelength (Zb) at which the transmittance is 30% when measured from the vertical direction of the substrate in the wavelength region of 580 nm or more, is less than 75 nm.

  The compound represented by the formula (I) is preferably a compound represented by the following formula (II).

[式（ＩＩ）中、Ｒ^aおよびＲ^bはそれぞれ独立に、前記式（Ｉ）の（ｉ）と同義であり、Ｒ^cはそれぞれ独立に水素原子、炭素数１〜８の脂肪族炭化水素基、任意の水素原子が官能基で置換された炭素数１〜８の置換脂肪族炭化水素基、炭素数６〜１２の芳香族炭化水素基、または任意の水素原子がアルキル基で置換された炭素数６〜１２の置換芳香族炭化水素基を表す。]

[In the formula (II), R ^a and R ^b each independently have the same meaning as (i) in the formula (I), and R ^c each independently represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 8 carbon atoms. Group, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an arbitrary hydrogen atom is substituted with an alkyl group A substituted aromatic hydrocarbon group having 6 to 12 carbon atoms is represented. ]

  The resin substrate (I) is preferably a substrate comprising a cyclic olefin resin or an aromatic polyether resin.

The cyclic olefin-based resin is a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). It is preferable that

（式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4は、それぞれ独立に下記（ｉ'）〜（ｖｉｉｉ'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xは、それぞれ独立に、０または正の整数を表す。）
（ｉ'）水素原子
（ｉｉ'）ハロゲン原子
（ｉｉｉ'）トリアルキルシリル基
（ｉｖ'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（ｖ'）置換または非置換の炭素数１〜３０の炭化水素基
（ｖｉ'）極性基（但し（ｉｖ'）を除く）
（ｖｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す
（ｖｉｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す

(In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (viii ′), and k ^x , ^mx and p ^x are each independently Represents 0 or a positive integer.)
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bond are each independently the above (i ′ (Vi ') represents a monocyclic or polycyclic hydrocarbon ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other, or R ^{x1 to} R ^x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^x2 and R ^x3 are mutually R ^{x1 to} R ^x4 each representing a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding are independently selected from the atoms or groups selected from the above (i ′) to (vi ′). Express

（式（Ｙ₀）中、Ｒ^y1およびＲ^y2は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、下記（ｉｘ'）を表し、Ｋ ^yおよびＰ ^yは、それぞれ独立に、０または正の整数を表す。）
（ｉｘ'）Ｒ^y1とＲ^y2とが、相互に結合して形成された単環または多環の脂環式炭化水素、芳香族炭化水素または複素環を表す

(In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′) or the following (ix ′), and K ^y and P each ^y independently represents 0 or a positive integer.)
(Ix ′) R ^y1 and R ^y2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other

  The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。）

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

（式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０の時、Ｒ⁷はシアノ基ではない。）

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.)

  The aromatic polyether-based resin may further include at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). preferable.

（式（３）中、Ｒ⁵およびＲ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。）

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

（式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。）

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

  The compound (I) is preferably contained in an amount of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the resin.

The near infrared cut filter according to the present invention can be suitably used for a solid-state imaging device.
A solid-state imaging device and a camera module according to the present invention include the near-infrared cut filter.

According to the present invention, it is possible to produce a near-infrared cut filter having a small incident (transmission) wavelength incident angle dependency, a wide viewing angle, excellent near-infrared cutting ability, low hygroscopicity, and free from foreign matter and warpage. it can.
Further, according to the present invention, the solid-state imaging device, the camera module, and the like can be reduced in thickness and size.

FIG. 1A is a schematic cross-sectional view showing an example of a conventional camera module. FIG. 1B is a schematic cross-sectional view showing an example of a camera module in the case of using the near-infrared cut filter 6 ′ obtained by the present invention. FIG. 2 is a schematic diagram showing a method for measuring the transmittance when measured from the vertical direction of the near-infrared cut filter. FIG. 3 is a schematic diagram showing a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter.

  Hereinafter, the present invention will be specifically described.

[Near-infrared cut filter]
Near infrared cut filter according to the present invention, compounds having a scan Kua Lilium structure represented by the following formula (I) (hereinafter "compound (I ')" also referred to.) A compound having a structure derived from a (I) It has the resin-made board | substrate (I) containing, It is preferable to have the following resin-made board | substrates (I) and the following near-infrared reflective film.
By having such a resin substrate, the near-infrared cut filter becomes a near-infrared cut filter having a particularly small incident angle dependency.

≪Resin substrate (I) ≫
It is preferable that the resin substrate (I) contains the compound (I) and satisfies the following (E) and (F).

(E) It is desirable that the absorption maximum be in the wavelength range of 600 to 800 nm.
If the absorption maximum wavelength of the substrate is within such a range, the substrate can selectively and efficiently cut near infrared rays.

  (F) In the wavelength range of 430 to 800 nm, the transmittance when measured from the vertical direction of the substrate is 70%, the longest wavelength (Za) below the absorption maximum and the wavelength range of 580 nm or more The absolute value (| Za-Zb |) of the difference from the shortest wavelength (Zb) at which the transmittance is 30% when measured from the vertical direction is less than 75 nm, preferably less than 50 nm, more preferably less than 30 nm. It is desirable to take

  When the absorption maximum wavelength of the resin substrate (I) and the absolute value of the difference between (Za) and (Zb) are in the above range, the wavelength (Za) near the near infrared wavelength region when light is incident on the substrate. And (Zb), the transmittance changes suddenly.

  Such a substrate can cut near infrared rays efficiently, and when such a substrate is used for a near infrared cut filter, the absolute value of the difference between (Ya) and (Yb) of the filter. , The incident angle dependence of the absorption wavelength is small, and a near-infrared cut filter with a wide viewing angle can be obtained.

  In addition, when a near-infrared cut filter using such a substrate is used in a lens unit such as a camera module, it is preferable because a low-profile lens unit can be realized.

  Depending on the use such as the front plate for PDP and the camera module, the average transmittance of the substrate when the thickness of the resin substrate containing the compound (I) is 100 μm in the so-called visible light region with a wavelength of 400 to 700 nm is 50%. In some cases, preferably 65% or more is necessary.

  The thickness of the resin substrate (I) can be appropriately selected according to a desired application, and is not particularly limited, but is preferably adjusted so that the substrate satisfies the above (E) and (F), More preferably, it is 250-50 micrometers, More preferably, it is 200-50 micrometers, Most preferably, it is 150-80 micrometers.

  When the thickness of the resin substrate (I) is in the above range, the near infrared cut filter using the substrate can be reduced in size and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when used in a lens unit such as a camera module, it is preferable because a low profile of the lens unit can be realized.

<Compound (I)>
The compound (I) has a structure derived from the compound (I ′). The compound (I) is preferably a dye having a scan Kua beryllium structure.

In formula (I), R ^a , R ^b and Y satisfy the following (i) or (ii).
(I) R ^a is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a —NR ^e R ^f group (R ^e and R ^f each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ), Or a hydroxy group,
R ^b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or —C ( O) R ⁱ group (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)), or a hydroxy group,
Y is a —NR ^j R ^k group (R ^j and R ^k are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a 1 to 8 carbon atom in which any hydrogen atom is substituted with a functional group) It represents a substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which an arbitrary hydrogen atom is substituted with an alkyl group.
(Ii) one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing at least one nitrogen atom having 5 or 6 atoms R ^b and R ^a not involved in the bond are independently the same as R ^b and R ^{a in} (i).

Examples of the alkyl group having 1 to 8 carbon atoms of ^Ra include a methyl group (Me), an ethyl group (Et), an n-propyl group (n-Pr), an i-propyl group (i-Pr), and n-butyl. Group, s-butyl group, t-butyl group (t-Bu), pentyl group, hexyl group and the like, and any hydrogen atom of these groups may be substituted with methyl group, ethyl group or the like good.

Examples of the alkyl group having 1 to 5 carbon atoms of R ^e and R ^f in the —NR ^e R ^f group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an s-butyl group. , T-butyl group and pentyl group.

Examples of the alkyl group having 1 to 5 carbon atoms of R ^b include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, and pentyl group. Can be mentioned.

Examples of the alkyl group having 1 to 5 carbon atoms of R ^g and R ^h in the —NR ^g R ^h group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an s-butyl group. , T-butyl group and pentyl group.

The R ⁱ in the -C (O) R ⁱ groups, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, s- butyl group, a t- butyl group and pentyl group Can be mentioned.

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^j and R ^k in the —NR ^j R ^k group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, s -Chain aliphatic hydrocarbon groups such as butyl group, t-butyl group, pentyl group and hexyl group; Cyclic aliphatic hydrocarbon groups such as cyclopentyl group and cyclohexyl group;

Examples of the substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom of R ^j and R ^k in the —NR ^j R ^k group is substituted with a functional group include any of the chain aliphatic hydrocarbon groups The hydrogen atom of —NR′R ″ group (R ′ and R ″ are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group) And a substituted chain substituted with a functional group such as —CN, —OH, —OR (where R represents a methyl group, an ethyl group, and a propyl group). A cyclic aliphatic hydrocarbon group in which an arbitrary hydrogen atom of the cyclic aliphatic hydrocarbon group is substituted with a methyl group, an ethyl group, or the like.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms of R ^j and R ^k in the —NR ^j R ^k group include a phenyl group.

As the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom of R ^j and R ^k in the —NR ^j R ^k group is substituted with an alkyl group, any hydrogen atom of the phenyl group is a methyl group A substituted phenyl group substituted with a chain aliphatic hydrocarbon group such as ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group and pentyl group; Can be mentioned.

In the formula (I) (ii), at least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring and has at least 5 or 6 constituent atoms. Examples of the heterocyclic ring containing one include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, and pyrazine. Among these heterocyclic rings, a heterocyclic ring that constitutes the heterocyclic ring and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

  Compound (I ′) includes, for example, compound (I-2) having a resonance structure represented by the following formula (I-1). That is, examples of the compound (I ′) include the compound (I-1) and the compound (I-2).

  The compound (I) has a spectral transmittance at an absorption maximum when the transmittance of a solution obtained by dissolving the compound (I) in a good solvent is measured (optical path length: 1 cm). Regardless of the concentration of compound (I), it is desirable that the compound be 30% or less, and the transmittance of a solution obtained by dissolving compound (I) in the good solvent is measured (optical path length 1 cm). The absorption maximum at a wavelength of 600 to 800 nm, and the longest at an absorption maximum of 70% or less in the wavelength region of 430 to 800 nm, regardless of the concentration of the compound (I) in the solution. It is a compound whose absolute value of the difference between the wavelength and the shortest wavelength at which the transmittance is 30% in the wavelength region of 580 nm or more is less than 75 nm, preferably less than 65 nm, more preferably less than 55 nm. Desirable.

  In the conventional near-infrared cut filter, such a compound (I) has a steep slope in the transmittance curve, a narrow absorption region in the near-infrared region, and is mixed with a substrate such as glass. In producing an infrared cut filter, the compound (I) has not been used because it cannot withstand the molding temperature of glass. Therefore, a near-infrared cut filter with a small incident angle dependency was not obtained as in the present invention.

  Since the resin substrate (I) containing such a compound (I) has the characteristics (E) and (F), the near-infrared cut filter of the present invention has the following (A), (C ) And (D). Therefore, a near-infrared cut filter having a small incident angle dependency and a wide viewing angle can be obtained.

  Moreover, when providing the near-infrared reflective film mentioned later on resin-made board | substrates (I) by vapor deposition etc., performances, such as the viewing angle of a near-infrared cut filter becoming narrow, may deteriorate, but the said resin-made board | substrates ( Since I) contains the compound (I), it is possible to prevent the deterioration of the performance of the near-infrared cut filter that can be caused by providing a near-infrared reflective film. Therefore, even when the near-infrared reflective film is provided on the resin substrate (I) by vapor deposition or the like, a near-infrared cut filter having a stable absorption wavelength region that does not depend on the incident angle of incident light can be obtained.

  In the present invention, the compound (I ′) is preferably a compound represented by the following formula (II).

In the formula (II), R ^a and R ^b have the same meanings as (i) in the formula (I), and R ^c each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, A substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an arbitrary hydrogen atom substituted with an alkyl group. Represents a substituted aromatic hydrocarbon group of ˜12.

An aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^c in formula (II), a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, and the number of carbon atoms Examples of the aromatic hydrocarbon group having 6 to 12 and the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which an arbitrary hydrogen atom is substituted with an alkyl group include R ^j and R ^k in the —NR ^j R ^k group. An aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and Examples thereof include the same groups as those described for the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which an arbitrary hydrogen atom is substituted with an alkyl group.

  Further, the compound (II) may be a compound represented by the following formula (II-1) which is the resonance structure.

Examples of the compound represented by the formula (II) include the following (a-1) to (a-19). In the following compounds, “Ac” represents —C (O) —CH ₃ .

  Among these, the compound (a-10) is well dissolved in methylene chloride, and the spectral transmittance measurement (optical path length 1 cm) of a solution in which the compound (a-10) is dissolved in methylene chloride at a concentration of 0.0001 parts by weight. ), There is an absorption maximum at a wavelength of 600 to 800 nm, 0.04 part by weight of the compound (a-10), 100 parts by weight of cyclic olefin resin “Arton G” manufactured by JSR Corporation, and further chlorination. A solution having a resin concentration of 20% by weight obtained by adding methylene was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, peeled off from the glass plate, and further dried at 100 ° C. for 8 hours under reduced pressure. When the spectral transmittance of the obtained substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm is measured, in the wavelength region of a wavelength of 430 to 800 nm, the transmittance is 70% or less where the transmittance is 70% or less. Since the absolute value of the difference between the longest wavelength and the shortest wavelength at which the transmittance is 30% is less than 55 nm in the wavelength region of wavelength 580 nm or more, the incident angle dependency of the absorption (transmission) wavelength is small, and the field of view This is preferable because a near-infrared cut filter having a wide corner can be produced.

  In the present invention, compound (I) may be synthesized by a generally known method, for example, a method described in JP-A-1-228960.

  In the present invention, the amount of the compound (I) used is preferably appropriately selected so that the resin substrate (I) satisfies the above (E) and (F). Specifically, the resin substrate (I) I) Preferably it is 0.01-10.0 weight part with respect to 100 weight part of resin used at the time of manufacture, More preferably, it is 0.01-8.0 weight part, Most preferably, it is 0.01-5.0 weight part. It is.

  When the amount of the compound (I) used is within the above range, the near-infrared ray is less dependent on the incident angle of the absorption wavelength, has a wide viewing angle, has a near-infrared cutting ability, and has excellent transmittance and strength in the range of 430 to 580 nm. A cut filter can be obtained.

  When the amount of compound (I) used is larger than the above range, a near-infrared cut filter in which the properties (properties) of compound (I) are more strongly expressed may be obtained, but the transmittance in the range of 430 to 580 nm is obtained. There is a possibility that the strength of the resin substrate or near-infrared cut filter may decrease, and if the amount of compound (I) used is less than the above range, the transmittance in the range of 430 to 580 nm A high near-infrared cut filter may be obtained, but the properties of compound (I) may be difficult to appear, the incident angle dependency of the absorption wavelength is small, and a resin substrate or a near infrared ray with a wide viewing angle It may be difficult to obtain a cut filter.

<Resin>
The resin substrate (I) used in the present invention only needs to contain the compound (I) and a resin, and the resin is preferably a transparent resin. Such a resin is not particularly limited as long as it does not impair the effects of the present invention. For example, high-temperature deposition performed at a deposition temperature of 100 ° C. or more while ensuring thermal stability and moldability to a film. In order to obtain a film capable of forming a dielectric multilayer film, a resin having a glass transition temperature (Tg) of preferably 110 to 380 ° C., more preferably 110 to 370 ° C., and still more preferably 120 to 360 ° C. may be mentioned. . Further, when the glass transition temperature of the resin is 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher, it is desirable because a film capable of vapor-depositing the dielectric multilayer film can be obtained.

  Further, as the resin, a resin having a total light transmittance at a thickness of 0.1 mm is preferably 75 to 94%, more preferably 78 to 94%, and particularly preferably 80 to 94%. Can be used. When the total light transmittance is within such a range, the resulting substrate exhibits good transparency as an optical film.

  Examples of such resins include cyclic olefin resins, polyether resins, polyarylate resins (PAR), polysulfone resins (PSF), polyethersulfone resins (PES), polyparaphenylene resins (PPP), and polyarylenes. Mention ether phosphine oxide resin (PEPO), polyimide resin (PPI), polyamideimide resin (PAI), (modified) acrylic resin, polycarbonate resin (PC), polyethylene naphthalate (PEN) and organic-inorganic nanohybrid materials Can do.

Among the resins, it is preferable to use a highly transparent cyclic olefin resin or aromatic polyether resin because the transmittance in the visible light region is particularly high, and these resins are low in hygroscopicity and have no warpage. It is preferable because it is difficult to occur.
Further, when a norbornene resin or an aromatic polyether resin is used as the resin, since the dispersibility of the compound (I) in the norbornene resin is good, the optical characteristics are uniform and the molding processability is excellent. A substrate can be obtained.

<Cyclic olefin resin>
Examples of the transparent resin used in the present invention include cyclic olefin resins. The cyclic olefin-based resin is not particularly limited, but for example, at least one selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) A resin obtained by polymerizing monomers, or a resin obtained by hydrogenating the resin obtained above as necessary can be used.

（式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4は、それぞれ独立に下記（ｉ'）〜（ｖｉｉｉ'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xは、それぞれ独立に、０または正の整数を表す。）
（ｉ'）水素原子
（ｉｉ'）ハロゲン原子
（ｉｉｉ'）トリアルキルシリル基
（ｉｖ'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（ｖ'）置換または非置換の炭素数１〜３０の炭化水素基
（ｖｉ'）極性基（但し（ｉｖ'）を除く）
（ｖｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す
（ｖｉｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す

(In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (viii ′), and k ^x , ^mx and p ^x are each independently Represents 0 or a positive integer.)
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bond are each independently the above (i ′ (Vi ') represents a monocyclic or polycyclic hydrocarbon ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other, or R ^{x1 to} R ^x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^x2 and R ^x3 are mutually R ^{x1 to} R ^x4 each representing a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding are independently selected from the atoms or groups selected from the above (i ′) to (vi ′). Express

（式（Ｙ₀）中、Ｒ^y1およびＲ^y2は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、下記（ｉｘ'）を表し、Ｋ ^yおよびＰ ^yは、それぞれ独立に、０または正の整数を表す。）
（ｉｘ'）Ｒ^y1とＲ^y2とが、相互に結合して形成された単環または多環の脂環式炭化水素、芳香族炭化水素または複素環を表す

(In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′) or the following (ix ′), and K ^y and P each ^y independently represents 0 or a positive integer.)
(Ix ′) R ^y1 and R ^y2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other

  Examples of the (ii ′) halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

  Examples of the (iii ′) trialkylsilyl group include a trialkylsilyl group having 1 to 12 carbon atoms, and a trialkylsilyl group having 1 to 6 carbon atoms is preferable. Examples of such a trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group.

Examples of the linking group containing an oxygen atom, sulfur atom, nitrogen atom, or silicon atom include a carbonyl group (—CO—), an oxycarbonyl group (—OCO—), a carbonyloxy group (—COO—), and a sulfonyl group (—SO _2- ), ether bond (—O—), thioether bond (—S—), imino group (—NH—), amide bond (—NHCO—, —CONH—) and siloxane bond (—OSi (R) ₂ — (Wherein R is an alkyl group such as methyl or ethyl)), and the substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms in (iv ′) is a group containing a plurality of these linking groups. It may be.
Point such also excellent in adhesion and adhesion to the near-infrared reflection film Among these, dispersibility and solubility carbonyl group in terms of the compound (I) (* -COO-) and siloxane bond (-OSi (R) _2- ) is preferred. However * it is assumed to be attached to the ring of formula (X _0).

The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms is preferably a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aromatic hydrocarbon groups such as phenyl group, biphenyl group and phenylethyl group; alkenyl groups such as vinyl group, allyl group and propenyl group; Among these groups, a methyl group and an ethyl group are preferable in terms of heat resistance stability.
Examples of the substituent include a hydroxy group and a halogen atom.

  Examples of the (vi ′) polar group include a hydroxy group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a carbonyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; a cyano group; An amino group; an acyl group; a sulfo group; a carboxyl group;

Examples of the alkylidene group formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 with each other include a methylidene group, an ethylidene group, and a propylidene group.

R ^x1 and R ^x2 or R ^x3 and R ^x4 are formed by bonding to each other, monocyclic or polycyclic hydrocarbon ring or heterocyclic ring, and R ^x2 and R ^x3 are bonded to each other. Monocyclic hydrocarbon rings or heterocyclic rings, monocyclic or polycyclic alicyclic hydrocarbons, aromatic hydrocarbons or heterocyclic rings formed by bonding R ^y1 and R ^y2 to each other include cyclo Examples include propylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclobutenylene, cyclopentenylene, cyclohexenylene , phenylene, and naphthylene.

k ^x , m ^x , p ^x , K ^y , and P ^y are each independently preferably an integer of 0 to 3. More preferably k ^x + m ^x + p ^x is 0 to 4 integer, more preferably k ^x + m ^x + p ^x is an integer of 0 to 2, particularly preferably k ^x + m ^x + p ^x is 1. K ^y + P ^y is preferably an integer of 0 to 4, and K ^y + P ^y is more preferably an integer of 0 to 2. m ^x is 0, use of the cyclic olefin monomer k ^x + p ^x is 1, high glass transition temperature, and preferably for mechanical strength also excellent resin is obtained.

Specific examples of the cyclic olefin monomer represented by the formula (X ₀ ) or (Y ₀ ) include, for example, the following compounds, but are not limited to these examples.
Bicyclo [2.2.1] hept-2-ene (norbornene)
5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-propylbicyclo [2.2.1] hepta 2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-t-butylbicyclo [2.2.1] hept-2-ene, 5-isobutylbicyclo [2.2.1] ] Hept-2-ene, 5-pentylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-heptylbicyclo [2.2. 1] Hept-2-ene, 5-octylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, 5-dodecylbicyclo [2.2 .1] hept-2-ene-5-cyclohexyl-bicyclo [2.2.1 Hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyl -Bicyclo [2.2.1] hept-2-ene-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene / 5-phenoxyethylcarbonyl-bicyclo [2.2.1] hepta 2-ene, 5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl -5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene-5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene-5-vinyl-bicycl [2.2.1] hept-2-ene-5-ethylidene-bicyclo [2.2.1] hept-2-ene / 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene 5-Triethoxysilyl-bicyclo [2.2.1] hept-2-ene5,5-dimethyl-bicyclo [2.2.1] hept-2-ene5,6-dimethyl-bicyclo [2 2.1] Hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-chloro-bicyclo [2.2.1] hept-2-ene, 5-bromo -Bicyclo [2.2.1] hept-2-ene.5,6-difluoro-bicyclo [2.2.1] hept-2-ene.5,6-dichloro-bicyclo [2.2.1] hepta 2-ene-5,6-dibromo-bicyclo [2.2.1] hept-2-ene 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hepta 2-ene-5-amino-bicyclo [2.2.1] hept-2-ene

Tricyclo [4.3.0.1 ^2,5 ] dec-3-eneTricyclo [4.4.0.1 ^2,5 ] undec-3-ene7-methyl-tricyclo [4.3.0 .1 ^2,5] dec-3-ene-7-ethyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7-cyclohexyl - tricyclo [4.3.0.1 ^{2, 5} ] dec-3-ene · 7-phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7- (4-biphenyl) -tricyclo [4.3.0.1 ^{2, 5} ] dec-3-ene.7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7,8,9-trimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 8-methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] C Ndeca-3-ene · 7-fluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene · 7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3- Ene-7-bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene 7,8,9-trichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene 7-dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene - hydroxy - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7-cyano - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7-A Roh - tricyclo [4.3.0.1 ^2,5] deca-3-ene

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene-8-methyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-cyclohexyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-phenoxyethyl carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,8-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,9-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-bromo - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene.8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene. 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-cyano - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-amino-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene In addition, these cyclic olefin type monomers may be used individually by 1 type, and may use 2 or more types together.

  The kind and amount of the cyclic olefin monomer used in the present invention are appropriately selected depending on the properties required for the obtained resin.

Among these, when a compound having a structure containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom in the molecule (hereinafter referred to as “polar structure”) is used, There are advantages such as excellent dispersibility of the compound (I) and excellent adhesion and adhesion to other materials (near infrared reflection film and the like). In particular, in the formula (X ₀ ), R ^x1 and R ^x3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and R ^x2 or R ^x4 A resin obtained by polymerizing a compound in which one of the groups has a polar structure and the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because of its low water absorption (wetness). Further, a resin obtained by polymerizing a compound in which either one of R ^y1 or R ^y2 is a group having a polar structure and the other is a hydrogen atom or a C 1-3 hydrocarbon group is preferable because of its low water absorption (wetness). . Furthermore, the cyclic olefin monomer in which the group having the polar structure is a group represented by the following formula (Z ₀ ) is preferable because the heat resistance and water absorption (wet) property of the obtained resin can be easily balanced. Used.

_{- (CH 2) z COOR ...} (Z 0)
(In the formula (Z ₀ ), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10.)

In the above formula (Z ₀ ), the smaller the value of z, the higher the glass transition temperature of the hydrogenated product obtained and the better the heat resistance, so z is preferably an integer of 0 or 1-3, A monomer in which z is 0 is preferable in that its synthesis is easy. Further, R in the above formula (Z ₀ ) tends to decrease the water absorption (wet) property of the hydrogenated polymer obtained as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining heat resistance, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

In the formula (X ₀ ), when an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the formula (Z ₀ ) is bonded, This is preferable because it tends to be a compound having a well-balanced water absorption (wet) property. Furthermore, in the above formula (X ₀ ), a compound in which ^mx is 0 and k ^x + p ^x is 1 has high reactivity, and a polymer can be obtained in high yield. Is preferably used because a polymer hydrogenated product having a high molecular weight can be obtained and it is industrially easily available.

  The cyclic olefin-based resin may be a polymer obtained by copolymerizing the cyclic olefin-based monomer and a monomer copolymerizable with the monomer as long as the effects of the present invention are not impaired.

Examples of these copolymerizable monomers include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene and cyclododecatriene. be able to.
These copolymerizable monomers may be used alone or in combination of two or more.

  The method for polymerizing the cyclic olefin monomer is not particularly limited as long as the monomer can be polymerized. For example, the polymerization can be performed by ring-opening polymerization or addition polymerization.

  The polymer obtained by the ring-opening polymerization reaction has an olefinically unsaturated bond in the molecule. Moreover, also in the said addition polymerization reaction, a polymer may have an olefinically unsaturated bond in the molecule | numerator. Thus, if an olefinically unsaturated bond is present in the polymer molecule, the olefinically unsaturated bond may cause deterioration over time such as coloring or gelation. It is preferable to carry out a hydrogenation reaction to convert to.

  In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a polymer solution having an olefinically unsaturated bond, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to the solution. The reaction can be carried out at -200 ° C, preferably 20-180 ° C.

The hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly the proportion of hydrogen added to the olefinically unsaturated bond measured by 500 MHz and ¹ H-NMR. Preferably it is 98% or more, Most preferably, it is 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and the more preferable it becomes a resin substrate that can maintain stable characteristics over a long period of time.

<Aromatic polyether resin>
Examples of the transparent resin used in the present invention include aromatic polyether resins. The aromatic polyether-based resin is not particularly limited, and for example, a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) and a structural unit represented by the following formula (2): (Hereinafter also referred to as “structural unit (2)”) A resin (hereinafter referred to as “resin (1)”) having at least one structural unit (hereinafter also referred to as “structural unit (1-2)”) selected from the group consisting of It is also preferable. A substrate obtained from such a resin is excellent in excellent heat resistance and mechanical strength, and is further excellent in transparency and surface smoothness.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1.

  The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 1 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. An aromatic hydrocarbon group etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group and the like.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. Preferable examples include organic groups of formulas 1 to 12.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. And an aryloxy group having 1 to 12 carbon atoms and the like. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

  Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

  As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benzine. A triazole group etc. are mentioned.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom. Specifically, an oxazole group, an oxadiazole Group, benzoxazole group, benzoxadiazole group and the like.

As R < ¹ > -R < ⁴ > in said Formula (1), the C1-C12 monovalent hydrocarbon group is preferable from the point of the water absorption (wet) property of resin (1), and C6-C12 aromatic A hydrocarbon group is more preferable, and a phenyl group is more preferable.

In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

The resin (1) has a molar ratio of the structural unit (1) to the structural unit (2) (however, the sum of the structural unit (1) and the structural unit (2) is 100). From the viewpoint of optical properties, heat resistance and mechanical properties, the structural unit (1): structural unit (2) is preferably 50:50 to 100: 0, and the structural unit (1): structural unit (2) = 70:30 to 100: 0 is more preferable, and structural unit (1): structural unit (2) = 80: 20 to 100: 0 is more preferable.
Here, the mechanical characteristics refer to properties such as the tensile strength, breaking elongation, and tensile modulus of the resin.

  The resin (1) further includes at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) (hereinafter referred to as “structural unit (3) -4) "). It is preferable that the resin (1) has such a structural unit (3-4) because the mechanical properties of the substrate containing the resin (1) are improved.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

  The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. And a group substituted with a chlorine atom, a bromine atom or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom or an iodine atom.

  Examples of the organic group having 1 to 12 carbon atoms including at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms and having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one kind of atom selected from the group consisting of oxygen atom and nitrogen atom is specifically selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

Z in the formula (3) is preferably a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms, and water absorption (wet) of the resin (1). From the viewpoint of properties, a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable. .

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f. When m is 0, R ⁷ is not a cyano group.

The resin (1) has a molar ratio of the structural unit (1-2) to the structural unit (3-4) (however, the total of both ((1-2) + (3-4)) is 100. Is preferably (1-2) :( 3-4) = 50: 50 to 100: 0 from the viewpoint of optical properties, heat resistance and mechanical properties, and (1-2) :( 3 -4) = 70: 30 to 100: 0 is more preferable, and (1-2) :( 3-4) = 80: 20 to 100: 0 is more preferable.
Here, the mechanical characteristics refer to properties such as the tensile strength, breaking elongation, and tensile modulus of the resin.

  The resin (1) preferably contains 70 mol% or more of the structural unit (1-2) and the structural unit (3-4) from the viewpoint of optical properties, heat resistance, and mechanical properties, More preferably, it is contained in an amount of 95 mol% or more in all structural units.

  Examples of the resin (1) include a compound represented by the following formula (5) (hereinafter also referred to as “compound (5)”) and a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”). )) Containing at least one compound selected from the group consisting of (hereinafter also referred to as “component (A)”) and a component containing a compound represented by the following formula (6) (hereinafter referred to as “component (B)”) Can be obtained by reaction.

  In said formula (5), X shows a halogen atom independently and a fluorine atom is preferable.

In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently synonymous with X in the formula (5).
However, when m is 0, R ⁷ is not a cyano group.

In the formula (6), each R ^A independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (6), R ¹ to R ⁴ and a~d have the same meanings as R ¹ to R ⁴ and a~d each independently the formula (1).

  Specific examples of the compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2, Mention may be made of 5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and their reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the formula (6) (hereinafter also referred to as “compound (6)”) include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL), 9,9-bis. (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9, Examples include 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  As the compound (7), specifically, 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone (DFDS), 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2′-difluorobenzophenone, 2,2′-difluorodiphenylsulfone, 3,3′-dinitro-4,4′-difluorobenzophenone, 3,3′-dinitro-4,4′-difluorodiphenylsulfone, 4, 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3 , 3′-dinitro-4,4′-dichlorobenzophenone and 3,3′-dinitro-4, 4'-dichlorodiphenyl sulfone and the like can be mentioned. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

It is preferable that at least one compound selected from the group consisting of compound (5) and compound (7) is contained in 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol% to More preferably, it is contained at 100 mol%.
Moreover, it is preferable that (B) component contains the compound represented by following formula (8) as needed. Compound (6) is preferably contained in 100 mol% of component (B) in an amount of 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

In the formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the formula (3), R ^a has the same meaning as R ^a each independently in the formula (6) in.

  Examples of the compound represented by the formula (8) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, and 3,3′-dihydroxy. Diphenylsulfone, 4,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxy) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof Etc. Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

More specifically, the resin (1) can be synthesized by the method (I ′) shown below.
Method (I ′):
The alkali metal salt obtained after reacting the component (B) with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (compound (6) and / or compound (8), etc.) And (A) component are made to react. In addition, the alkali metal salt of (B) component and (A) component can also be made to react by performing reaction with (B) component and an alkali metal compound in presence of (A) component.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^A in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent used in the reaction include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyllactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (carbon number of alkoxy group) 1-4) etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) is 100 mol% in total of component (A) and component (B). More preferably, it is 50 mol% or more and 52 mol% or less, more preferably more than 50 mol% and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 48 mol%. % Or more and 50 mol% or less, more preferably 48 mol% or more and less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60 to 250 degreeC, More preferably, it is the range of 80 to 200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

The resin (1) preferably has a glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min), preferably 230 to 350 ° C., more preferably 240 to 330 ° C., and still more preferably 250 to 300 ° C.
The glass transition temperature of the resin (1) is, for example, Rigaku 8230 type DSC measuring device (temperature increase rate 20 ° C./min) or SII Nano Technologies, Ltd. differential scanning calorimeter (DSC6200) (temperature increase rate). 20 ° C./min) or the like.

  The resin (1) has a polystyrene-equivalent weight average molecular weight (Mw) measured with a TOSOH HLC-8220 GPC apparatus (column: TSKgel α-M, developing solvent: tetrahydrofuran (hereinafter also referred to as “THF”)). , Preferably it is 5,000-500,000, More preferably, it is 15,000-400,000, More preferably, it is 30,000-300,000.

  The resin (1) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C. or higher, more preferably 475 ° C. or higher, and further preferably 490 ° C. or higher.

<Polyimide resin>
An example of the transparent resin that can be used in the present invention is a polyimide resin.
The polyimide resin is not particularly limited as long as it is a polymer containing an imide bond in a repeating unit. For example, the polyimide resin can be synthesized by a method described in JP-A-2008-163107.

  Examples of commercially available transparent resins that can be used in the present invention include the following commercially available products. Examples of commercially available cyclic olefin-based resins include Arton manufactured by JSR Corporation, ZEONOR manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resin include Teijin Limited Pure Ace. Examples of commercially available organic-inorganic nanohybrid materials include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>
Additives such as antioxidants, ultraviolet absorbers, dyes and pigments that absorb near infrared rays, and metal complex compounds are added to the resin substrate (I) as long as the effects of the present invention are not impaired. can do. Moreover, when manufacturing resin-made board | substrate (I) by the solution casting method mentioned later, manufacture of resin-made board | substrate (I) can be made easy by adding a leveling agent and an antifoamer. These other components may be used alone or in combination of two or more.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, and And tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

  These additives may be mixed with the resin or the like when the resin substrate (I) is manufactured, or may be added when the resin is manufactured. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Part.

<Method for Producing Resin Substrate (I) Containing Compound (I)>
The resinous substrate (I) used in the present invention can be formed by, for example, melt molding or cast molding, and if necessary, a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is formed after the molding. It can be produced by a coating method.

(A) Melt molding The resin substrate (I) is a method of melt molding pellets obtained by melt-kneading the resin and the compound (I) and / or the compound (I ′); the resin and the compound A method of melt-molding a resin composition containing (I) and / or compound (I ′); a solvent from compound (I) and / or compound (I ′), the resin, and a resin composition containing the solvent The pellets obtained by removal can be produced by a method such as melt molding. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Casting The resin substrate (I) removes the solvent by casting the resin composition containing the compound (I) and / or the compound (I ′), the resin and the solvent on an appropriate base material. Coating an appropriate substrate with a coating composition such as an antireflective agent, a hard coat agent and / or an antistatic agent, and a resin composition containing compound (I) and / or compound (I ′), A coating composition such as an antireflective agent, a hard coat agent and / or an antistatic agent, and a curable composition containing Compound (I) and / or Compound (I ′) are coated on a suitable substrate and cured and dried. It can also be manufactured by making it.

  For example, a coating film is obtained by applying the above resin composition onto a substrate such as a glass plate, a steel belt, a steel drum or a transparent resin such as a polyester film or a cyclic olefin resin film and drying the solvent. Then, the resin substrate (I) can be obtained by peeling the coating film from the base material. Moreover, unless the effect of this invention is impaired, it is good also considering the laminated body of a base material and a coating film as said resin-made board | substrates (I), without peeling a coating film from a base material. Further, the above resin composition is coated on an optical component such as a glass plate, quartz or transparent plastic and the solvent is dried, or the resin, the coating agent such as a hard coating agent, the solvent and the compound (I) and / or The resinous substrate (I) can be formed directly on the optical component by coating the resin composition containing the compound (I ′), curing and drying.

  The amount of residual solvent in the resin substrate (I) obtained by the above method should be as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. . When the residual solvent amount exceeds 3% by weight, the resin substrate (I) may be deformed over time or the characteristics may be changed, and the desired function may not be exhibited.

≪Near-infrared reflective film≫
The near-infrared reflective film used in the present invention is a film having the ability to reflect near-infrared light. Such a near-infrared reflective film includes an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles mainly containing indium oxide and containing a small amount of tin oxide are dispersed, a high refractive index material layer, and a low refractive index. A dielectric multilayer film in which material layers are alternately stacked can be used.

  Since the near-infrared cut filter of this invention has such a near-infrared reflective film, it has the following characteristic (B). Therefore, a filter capable of sufficiently cutting near infrared rays can be obtained.

  In the present invention, the near-infrared reflective film may be provided on one side of the resin substrate (I) or on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, it is possible to obtain a near-infrared cut filter having high strength and less warpage.

  Among these near-infrared reflective films, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be suitably used.

  As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is usually selected.

  These materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, and indium oxide as main components, and include titanium oxide, tin oxide, and oxide. The thing etc. which contained a small amount (for example, 0-10% with respect to a main component) etc. are mentioned.

  As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected.

  Examples of these materials include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride.

  The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, the high-refractive index material layer and the low-refractive index material layer are alternately formed on the resin substrate (I) directly by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A dielectric multilayer film laminated on the substrate can be formed.

  The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked. When the thickness is within this range, the optical film thickness, the high refractive index material layer, and the low refractive index material layer, where the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4. The thickness of each of the layers becomes almost the same value, and the cutoff / transmission of a specific wavelength tends to be easily controlled from the relationship between the optical characteristics of reflection / refraction.

  The number of laminated layers in the dielectric multilayer film is 5 to 60 layers, preferably 10 to 50 layers.

  In addition, if the substrate is warped when the dielectric multilayer film is formed, the dielectric multilayer film is formed on both surfaces of the substrate or the substrate dielectric multilayer film is formed to solve this problem. A method of irradiating the surface with electromagnetic waves such as ultraviolet rays can be used. In addition, when irradiating electromagnetic waves, you may irradiate during formation of a dielectric multilayer, and you may irradiate separately after formation.

≪Other functional membranes≫
The near-infrared cut filter of the present invention is a near-infrared reflective film on the resin substrate (I) between the resin substrate (I) and the near-infrared reflective film such as a dielectric multilayer film, etc., within a range not impairing the effects of the present invention. The surface hardness of the resin substrate (I) is improved on the surface opposite to the surface on which the resin substrate is provided, or the surface opposite to the surface on which the resin substrate (I) of the near-infrared reflective film is provided, and the chemical resistance is improved. Functional films such as antireflection films, hard coat films, and antistatic films can be provided as appropriate for the purpose of improving the resistance, preventing static electricity, and eliminating scratches. The near-infrared cut filter of the present invention may include one layer composed of the functional film, or may include two or more layers. When the near-infrared cut filter of the present invention includes two or more layers composed of the functional film, two or more similar layers may be included, or two or more different layers may be included.

As a method for laminating the functional film is not particularly limited, antireflective agent, a hard coating agent and / or coating agents, such as antistatic agents, and the like to the resin substrate (I) or near infrared reflection film, as with the Examples thereof include a melt molding method and a casting method. Further, after coating the coating agent resinous substrate a curable composition including a bar coater forming material (I) or near infrared reflection film can also be produced by curing by ultraviolet irradiation or the like .

  Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and examples thereof include urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate resins. . Examples of the curable composition corresponding to these coating agents include urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based curable compositions.

  Examples of the components contained in the urethane-based and urethane acrylate-based curable compositions include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, Although oligourethane (meth) acrylates having two or more (meth) acryloyl groups in the molecule can be exemplified, the invention is not limited to these examples. These components may be used alone or in combination of two or more. Furthermore, oligomers or polymers such as polyurethane (meth) acrylate may be blended.

Although it does not specifically limit as an acrylate type curable composition, The composition etc. which contain (meth) acrylic esters and vinyl compounds can be mentioned.
Specific examples of the (meth) acrylic esters include, for example,
Isobornyl (meth) acrylate,
Bornyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate,
Dicyclopentanyl (meth) acrylate,
Dicyclopentenyl (meth) acrylate,
Cyclohexyl (meth) acrylate,
Benzyl (meth) acrylate,
4-butylcyclohexyl (meth) acrylate,
Acryloylmorpholine,
2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate,
Methyl (meth) acrylate,
Ethyl (meth) acrylate,
Propyl (meth) acrylate,
Isopropyl (meth) acrylate,
Butyl (meth) acrylate,
Amyl (meth) acrylate,
Isobutyl (meth) acrylate,
t-butyl (meth) acrylate,
Pentyl (meth) acrylate,
Isoamyl (meth) acrylate,
Hexyl (meth) acrylate,
Heptyl (meth) acrylate,
Octyl (meth) acrylate,
Isooctyl (meth) acrylate,
2-ethylhexyl (meth) acrylate,
Nonyl (meth) acrylate,
Decyl (meth) acrylate,
Isodecyl (meth) acrylate,
Undecyl (meth) acrylate,
Dodecyl (meth) acrylate,
Lauryl (meth) acrylate,
Stearyl (meth) acrylate,
Isostearyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate,
Butoxyethyl (meth) acrylate,
Ethoxydiethylene glycol (meth) acrylate,
Polyethylene glycol mono (meth) acrylate,
Polypropylene glycol mono (meth) acrylate,
Methoxyethylene glycol (meth) acrylate,
Ethoxyethyl (meth) acrylate,
Methoxy polyethylene glycol (meth) acrylate,
Methoxy polypropylene glycol (meth) acrylate,
Diacetone (meth) acrylamide,
Isobutoxymethyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide,
t-octyl (meth) acrylamide,
Dimethylaminoethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate,
7-amino-3,7-dimethyloctyl (meth) acrylate,
N, N-diethyl (meth) acrylamide,
N, N-dimethylaminopropyl (meth) acrylamide,
Phenoxyethyl (meth) acrylate,
Phenoxy-2-methylethyl (meth) acrylate,
Phenoxyethoxyethyl (meth) acrylate,
3-phenoxy-2-hydroxypropyl (meth) acrylate,
2-phenylphenoxyethyl (meth) acrylate,
4-phenylphenoxyethyl (meth) acrylate,
2-hydroxy-3-phenoxypropyl (meth) acrylate,
p-cumylphenol ethylene oxide modified (meth) acrylate,
2-bromophenoxyethyl (meth) acrylate,
4-bromophenoxyethyl (meth) acrylate,
2,4-dibromophenoxyethyl (meth) acrylate,
2,6-dibromophenoxyethyl (meth) acrylate,
2,4,6-tribromophenoxyethyl (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
Trimethylolpropane trioxyethyl (meth) acrylate,
Ditrimethylolpropane tetra (meth) acrylate,
Pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Glycerin tri (meth) acrylate,
Ethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate,
Tripropylene glycol di (meth) acrylate 1,3-butanediol di (meth) acrylate,
1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate,
Dipropylene glycol di (meth) acrylate ,
Dicyclopentanyloxyethyl (meth) acrylate ,
Application Benefits tricyclodecane dichloride methanol di (meth) acrylate,
Tricyclodecane meth no le (meth) acrylate,
Tricyclodecane dimethanol di (meth) acrylate,
Tetra tricyclodecane Irujime data Nord di (meth) acrylate,
Poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols in the production of these compounds,
Oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, and
Oligoether (meth) acrylates,
However, it is not limited to these examples. These components may be used alone or in combination of two or more. Furthermore, you may mix | blend oligomers or polymers, such as polyester (meth) acrylate.

  Examples of the vinyl compounds include vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. However, the vinyl compounds are not limited to these examples. Absent. These components may be used alone or in combination of two or more.

  Although it does not specifically limit as a component contained in the said epoxy-type, epoxy acrylate-type curable composition, Glycidyl (meth) acrylate, Methyl glycidyl (meth) acrylate, Oligo having two or more (meth) acryloyl groups in a molecule | numerator An epoxy (meth) acrylate etc. can be mentioned. These components may be used alone or in combination of two or more. Furthermore, an oligomer or polymer such as polyepoxy (meth) acrylate may be blended.

  Commercially available products of the coating agent (a curable composition containing a coating agent-forming material) include Toyo Ink Mfg. Co., Ltd. LCH, LAS, Arakawa Chemical Industries Co., Ltd. Beam Set, Daicel Cytec Co., Ltd. EBECRYL, UVACURE , JSR Co., Ltd. Opstar and the like.

Moreover, the said curable composition may contain the polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
Specific examples of the polymerization initiator are not particularly limited,
1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-2-phenylacetophenone,
Xanthone,
Fluorenone,
Benzaldehyde,
Anthraquinone,
Triphenylamine,
Carbazole,
3-methylacetophenone,
4-chlorobenzophenone,
4,4′-dimethoxybenzophenone,
4,4′-diaminobenzophenone,
Michler's ketone,
Benzoinpropyl ether,
Benzoin ethyl ether,
Benzyl dimethyl ketal,
1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
Thioxanthone,
Diethylthioxanthone,
2-isopropylthioxanthone,
2-chlorothioxanthone,
2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one,
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis - (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Gandolfo scan fins oxides.
Among these, 1-hydroxycyclohexyl phenyl ketone is preferable.
These polymerization initiators may be used alone or in combination of two or more.

  As these commercially available products, Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur TPO (manufactured by Ciba Specialty Chemicals), Lucyrin LR8728 (manufactured by BASF), Examples include Darocur 1116, 1173 (manufactured by Merck & Co., Inc.), Ubekrill P36 (manufactured by UCB), and the like.

  In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, further preferably 100% by weight based on the total amount of the curable composition. Is 1 to 5% by weight. When the blending ratio of the polymerization initiator is in the above range, it is possible to obtain a functional film such as an antireflection film, a hard coat film or an antistatic film having excellent curing characteristics and handling properties of the curable composition and having a desired hardness. it can.

  Furthermore, an organic solvent may be added as a solvent to the curable composition, and known ones can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone. These solvents may be used alone or in combination of two or more.

  The thickness of the functional film is preferably 0.1 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.7 μm to 5 μm.

  Further, for the purpose of improving the adhesion between the resin substrate (I) and the functional film and / or the near-infrared reflective film and the adhesion between the functional film and the near-infrared reflective film, the resin substrate (I) and the functional film Surface treatment such as corona treatment or plasma treatment may be applied to the surface.

≪Near-infrared cut filter≫
The near-infrared cut filter of the present invention preferably has a light transmittance satisfying the following (A) to (D).

  (A) In the wavelength range of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction of the near infrared cut filter is 75% or more, preferably 78% or more, more preferably 80% or more. Is desirable. In the present invention, by using a resin having a high total light transmittance at a thickness of 0.1 mm, a compound (I) having no absorption in the wavelength region, and the like, at such a wavelength of 430 to 580 nm, a high transmittance is obtained. The near-infrared cut filter which has can be obtained.

  When the near-infrared cut filter is used for a visibility correction filter or the like in a lens unit such as a solid-state imaging device or a camera module, the average value of transmittance at a wavelength of 430 to 580 nm is the above range, and the transmittance is constant in this wavelength range. It is preferable that

  A higher average value of transmittance in the wavelength range of 430 to 580 nm is preferable. When the average value of the transmittance is high, the intensity of the light passing through the filter is sufficiently secured, and can be suitably used for the above-mentioned use.

  On the other hand, if the average value of the transmittance in the wavelength range of 430 to 580 nm is low, the intensity of the light passing through the filter is not sufficiently secured, and there is a possibility that it cannot be used suitably for the above application.

  (B) In the wavelength range of 800 to 1000 nm, the average transmittance when measured from the vertical direction of the near-infrared cut filter is 20% or less, preferably 15% or less, more preferably 10% or less. Is desirable. In the present invention, a near-infrared cut filter having a sufficiently low transmittance at a wavelength of 800 to 1000 nm is obtained by providing a predetermined near-infrared reflective film having high near-infrared reflectivity on the resin substrate (I). be able to.

  Since the near-infrared cut filter of the present invention selectively reduces the near-infrared wavelength (800 nm or more), it is preferable that the average transmittance in the range of 800 to 1000 nm is low. When the average value of the transmittance is low, the near infrared cut filter can sufficiently cut near infrared rays.

  On the other hand, when the average value of the transmittance in the wavelength range of 800 to 1000 nm is high, the filter cannot sufficiently cut near infrared rays, and when the filter is used for a PDP or the like, It may not be possible to prevent malfunction of electronic equipment in the area.

  (C) In the wavelength region of 800 nm or less, the longest wavelength (Xa) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 70%, and in the wavelength region of wavelength 580 nm or more, The absolute value (| Xa−Xb |) of the difference from the shortest wavelength (Xb) at which the transmittance when measured from the vertical direction is 30% is less than 75 nm, preferably less than 72 nm, more preferably less than 70 nm. It is desirable to take. In the present invention, by using the compound (I), it is possible to obtain a near-infrared cut filter in which the absolute value of the wavelength difference that provides a predetermined transmittance falls within the predetermined range.

  If the absolute value of the difference between (Xa) and (Xb) of the near-infrared cut filter is in the above range, the transmittance changes abruptly between wavelengths (Xa) and (Xb) near the near-infrared wavelength region; Therefore, near infrared rays can be cut efficiently, and the absolute value of the difference between the following (Ya) and (Yb) is reduced, the incident angle dependence of the absorption wavelength is small, and the near infrared ray is cut with a wide viewing angle. A filter can be obtained.

  (D) In the wavelength range of 560 to 800 nm, preferably in the range of 580 to 800 nm, the wavelength value (Ya) at which the transmittance is 50% when measured from the vertical direction of the near infrared cut filter, and the vertical of the near infrared cut filter The absolute value (| Ya−Yb |) of the difference in wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° with respect to the direction is less than 15 nm, preferably less than 13 nm, more preferably It is desirable to take a value of less than 10 nm.

  In the present invention, by using the compound (I), it is possible to obtain a near-infrared cut filter in which the absolute value of the wavelength difference that provides a predetermined transmittance falls within the predetermined range.

  Thus, when the absolute value of the difference between (Ya) and (Yb) is within the above range in the wavelength range of 560 to 800 nm, when such a filter is used for a PDP or the like, the display is viewed from an oblique direction. Also when viewed, it is possible to obtain a near-infrared cut filter that exhibits the same brightness and color tone as viewed from the vertical direction, has a small incident angle dependency of the absorption wavelength, and has a wide viewing angle.

  On the other hand, when a near-infrared cut filter with an absolute value of the difference between (Ya) and (Yb) of 15 nm or more is used for a PDP or the like, the brightness is significantly reduced depending on the viewing angle of the display, the color tone is reversed, There is a possibility that the color may be difficult to see, and there are cases where it cannot be used suitably for the application.

Here, the “viewing angle” is an index indicating how far the screen can be normally viewed when the display is viewed from above, below, left, and right.
In the present invention, it refers to an index indicating how far the screen can be normally viewed when the near-infrared cut filter is viewed from above, below, left, and right.

  In the present invention, as a determination of whether or not normal viewing is possible, in the wavelength range of 560 to 800 nm, the wavelength value (Ya) at which the transmittance when measured from the vertical direction of the filter is 50%, and the filter One criterion is that the absolute value of the difference in wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° with respect to the vertical direction is less than 15 nm.

  The thickness of the near-infrared cut filter is preferably adjusted so that the transmittance of the filter satisfies the above (A) to (D), and is not particularly limited, but is preferably 50 to 250 μm, more preferably 50 to It is 200 micrometers, More preferably, it is 80-150 micrometers.

  When the thickness of the near infrared cut filter is in the above range, the filter can be reduced in size and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when used in a lens unit such as a camera module, it is preferable because a low profile of the lens unit can be realized.

<Uses of near-infrared cut filter>
The near infrared cut filter obtained by the present invention has a wide viewing angle and has excellent near infrared cut ability and the like. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, TVs, car navigation systems, personal digital assistants, personal computers, video games, medical equipment, USB memories, portable game machines, fingerprint authentication Useful for systems, digital music players, toy robots and toys. Furthermore, it is also useful as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

  Here, the case where the near-infrared cut filter obtained by this invention is used for a camera module is demonstrated concretely.

FIG. 1 is a schematic sectional view of the camera module.
FIG. 1 (a) is a schematic cross-sectional view of the structure of a conventional camera module, and FIG. 1 (b) is a camera that can be taken when the near-infrared cut filter 6 ′ obtained in the present invention is used. It is the cross-sectional schematic showing one of the structures of a module.

  In FIG. 1 (b), the near-infrared cut filter 6 ′ obtained by the present invention is used in the upper part of the lens 5, but the near-infrared cut filter 6 ′ obtained by the present invention is as shown in FIG. 1 (a). It can also be used between the lens 5 and the sensor 7.

  In the conventional camera module, light has to be incident on the near infrared cut filter 6 substantially perpendicularly. Therefore, the filter 6 has to be disposed between the lens 5 and the sensor 7.

  Here, since the sensor 7 has high sensitivity and there is a possibility that the sensor 7 may not operate correctly just by touching dust or dust of about 5 μm, the filter 6 used on the upper part of the sensor 7 is one that does not generate dust or dust. There was a need to include no foreign matter. In addition, due to the characteristics of the sensor 7, it is necessary to provide a predetermined distance between the filter 6 and the sensor 7, which is one factor that hinders the reduction in the height of the camera module.

  On the other hand, in the near-infrared cut filter 6 ′ obtained by the present invention, the absolute value of the difference between (Ya) and (Yb) is 15 nm or less. In other words, there is no significant difference between the transmission wavelengths of the light incident from the vertical direction of the filter 6 ′ and the light incident from 30 ° with respect to the vertical direction of the filter 6 ′ (the incident angle dependency of the absorption (transmission) wavelength is (Small), the filter 6 ′ does not need to be disposed between the lens 5 and the sensor 7, and can be disposed on the upper part of the lens.

  For this reason, when the near-infrared cut filter 6 ′ obtained in the present invention is used in a camera module, the camera module is easy to handle, and a predetermined interval is provided between the filter 6 ′ and the sensor 7. Since it is not necessary, the camera module can be reduced in height.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. “Parts” means “parts by weight” unless otherwise specified.

  First, a method for measuring each physical property value and a method for evaluating the physical property will be described.

(1) Molecular weight:
Standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type) manufactured by WATERS, equipped with an H type column manufactured by Tosoh Corporation, under conditions of o-dichlorobenzene solvent and 120 ° C. The converted weight average molecular weight (Mw) and number average molecular weight (Mn) were measured.

(2) Glass transition temperature (Tg):
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

(3) Saturated water absorption:
In accordance with ASTM D570, a test piece having a thickness of 3 mm, a length of 50 mm, and a width of 50 mm was prepared from the resin obtained in the synthesis example, and the obtained test piece was immersed in water at 23 ° C. for 1 week. The water absorption was measured from the weight change.

(4) Spectral transmittance:
Measurement was performed using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

  Here, with respect to the transmittance when measured from the vertical direction of the near-infrared cut filter, light transmitted perpendicularly to the filter was measured as shown in FIG.

  Moreover, the transmittance | permeability at the time of measuring from the angle of 30 degrees with respect to the perpendicular direction of a near-infrared cut filter measured the light which permeate | transmitted at the angle of 30 degrees with respect to the perpendicular direction of a filter like FIG.

  The transmittance is measured using the spectrophotometer under the condition that light is perpendicularly incident on the substrate and the filter, except when measuring (Yb). In the case of measuring (Yb), the measurement is performed using the spectrophotometer under the condition that light is incident at an angle of 30 ° with respect to the vertical direction of the filter.

[Synthesis Example 1]
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter also referred to as “DNM”) 100 parts, 18 parts 1-hexene (molecular weight regulator), 300 parts toluene (solvent for ring-opening polymerization reaction), nitrogen The substituted reaction vessel was charged and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). As for the molecular weight of the resin A, the number average molecular weight (Mn) was 32,000, the weight average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165 ° C.

[Synthesis Example 2]
Fully dried, nitrogen-substituted 1 liter stainless steel autoclave with 6 ppm water dehydrated cyclohexane; 420.4 g, p-xylene; 180.2 g, 5-trimethoxysilyl-bicyclo [2.2.1] hepta -2-ene; 48.75 mmol (10.43 g), and bicyclo [2.2.1] hept-2-ene; 1,425 mmol (134.1 g). It charged so that it might be set to 0.1 MPa. Thereafter, the autoclave was heated to 75 ° C.

  Catalyst component 2-palladium 2-ethylhexanoate (as Pd atom); 0.003 milligram atom and tricyclohexylphosphine; 0.0015 millimole were added to toluene; 10 ml and reacted at 25 ° C. for 1 hour to prepare a solution. Then, the total amount of this solution and triphenylcarbenium pentafluorophenylborate; 0.00315 mmol were added in this order to an autoclave heated to 75 ° C. to initiate polymerization.

Autoclave 5 Torimetoki shish Lil - bicyclo [2.2.1] hept-2-ene, the polymerization initiator 90 minutes after 11.25 mmol (2.41 g), 7.5 mmol thereafter every 30 minutes (1. 61 g), 3.75 mmol (0.80 g), and 3.75 mmol, 4 times in total.

  After performing the polymerization reaction at 75 ° C. for 4 hours, 1 ml of tributylamine was added to terminate the polymerization, and a solution of addition polymer B having a solid content of 19.9% by weight was obtained. A part of the solution of addition polymer B was put in isopropanol, solidified, and further dried to obtain addition polymer B (hereinafter also referred to as “resin B”).

As a result of 270 MHz-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) of this resin B, the proportion of structural units derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in resin B is The number average molecular weight (Mn) is 74,000, the weight average molecular weight (Mw) is 185,000, the glass transition temperature (Tg) is 360 ° C., and the saturated water absorption is 0.35. %Met.

[Synthesis Example 3]
In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube, 10.0 parts by weight of 4,4′-diaminodiphenyl ether under a nitrogen stream ( 0.05 mol) was dissolved in 85 parts by weight of N-methyl-2-pyrrolidone as a solvent, and then 11.2 parts by weight (0.05 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride. ) In a solid state at room temperature over 1 hour, and stirred at room temperature for 2 hours.

  Next, after adding 30.0 parts by weight of xylene as an azeotropic dehydration solvent and raising the temperature to 180 ° C., the reaction is carried out for 3 hours, and xylene is refluxed in a Dean-Stark tube to produce azeotropic product water. separated. After 3 hours, it was confirmed that the distillation of water had ended, xylene was distilled off while raising the temperature to 190 ° C. over 1 hour, and after recovering 29.0 parts by weight, the internal temperature reached 60 ° C. Was cooled to air to obtain 105.4 parts by weight of an N-methyl-2-pyrrolidone solution of polyimide (hereinafter also referred to as “polyimide solution C”).

[Synthesis Example 4]
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, potassium carbonate 41.46 g (0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.
After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 ° C. to obtain white powder D (hereinafter referred to as “resin D”) (yield 95.67 g, yield 95%).

The resulting polymer was subjected to structural analysis. The results show that the characteristic absorption of the infrared absorption spectrum is 3035 cm ⁻¹ (C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O -). The resin D had a number average molecular weight (Mn) of 67,000, a weight average molecular weight (Mw) of 146,000, and a glass transition temperature (Tg) of 275 ° C. The obtained polymer had the structural unit (1).

[Synthesis Example 5]
Instead of 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene was used. Except that, synthesis was performed in the same manner as in Synthesis Example 4 to obtain Resin E. The resin E had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

[Synthesis Example 6]
Instead of 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 78.84 g (0.225 mol) of 9,9-bis (4-hydroxyphenyl) fluorene and 9 , 9-bis (4-hydroxyphenyl) cyclohexane was used in the same manner as in Synthesis Example 4 except that 6.71 g (0.025 mol) was used, and Resin F was obtained. As for the molecular weight of the resin F, the number average molecular weight (Mn) was 36,000, the weight average molecular weight (Mw) was 78,000, and the glass transition temperature (Tg) was 260 ° C.

[Synthesis Example 7]
The synthesis was performed in the same manner as in Synthesis Example 4 except that 78.84 g (0.250 mol) of 4,4-difluorodiphenylsulfone (DFDS) was used instead of 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile. The resin G was obtained. As for the molecular weight of the resin G, the number average molecular weight (Mn) was 37,000, the weight average molecular weight (Mw) was 132,000, and the glass transition temperature (Tg) was 265 ° C.

[Example 1]
The container, the cyclic olefin-based resin "ARTON G" 100 parts by weight of the manufactured by JSR Corporation, scan Kua Lilium compounds "a-10" 0.04 parts by weight, the addition of further methylene chloride, the resin concentration of 20 wt% Solution (ex1) was obtained.
Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

The spectral transmittance of this substrate was measured, and the absorption maximum wavelength and (Za) and (Zb) were determined.
The results are shown in Table 1.

  The absorption maximum wavelength of this substrate was 699 nm. Further, the transmittance is 70% in the wavelength region of 430 to 800 nm, the longest wavelength (Za) below the absorption maximum, and the shortest wavelength (30% in the wavelength region of wavelength 580 nm or more). The absolute value (| Za−Zb |) of the difference from Zb) was 45 nm.

Subsequently, on one side of the substrate, a multilayer deposited film [silica (SiO ₂ : film thickness 83 to 199 nm) layer and titania (TiO ₂ : film thickness 101 to 125 nm) layer that reflects near infrared rays at a deposition temperature of 100 ° C. A multi-layer deposited film (silica (SiO ₂ : film thickness 77 to 189 nm) reflecting near infrared rays at a deposition temperature of 100 ° C. is formed on the other surface of the substrate. Layer and a titania (TiO ₂ : film thickness 84 to 118 nm) layer are alternately laminated, and the number of layers is 26] to obtain a near-infrared cut filter having a thickness of 0.105 mm. The spectral transmittance of the near infrared cut filter was measured, and (Xa), (Xb), (Ya), and (Yb) were obtained. The results are shown in Table 1.

  The average transmittance at a wavelength of 430 to 580 nm was 91%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

  Absolute value of the difference between the longest wavelength (Xa) at which the transmittance is 70% in the wavelength region of wavelength 800 nm or less and the shortest wavelength (Xb) at which the transmittance is 30% in the wavelength region of wavelength 580 nm or more. (| Xa-Xb |) was 39 nm.

  Also, in the wavelength range of 560 to 800 nm, the wavelength value (Ya) at which the transmittance when measured from the vertical direction of the filter is 50% and the case of measuring from an angle of 30 ° with respect to the vertical direction of the filter The absolute value (| Ya−Yb |) of the difference between the wavelength values (Yb) at which the transmittance was 50% was 3 nm.

[Example 2]
A multilayer deposited film that reflects near infrared rays at a deposition temperature of 100 ° C. on one surface of a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm obtained in Example 1 [silica (SiO ₂ : film thickness 120 to 190 nm) Layer and a titania (TiO ₂ : film thickness 70-120 nm) layer are alternately stacked, the number of layers 40] is formed, and a near-infrared cut filter having a thickness of 0.104 mm is obtained. Furthermore, Table 1 shows the results of the same evaluation as in Example 1.

[Example 3]
The container, the cyclic olefin-based resin "ARTON G" 100 parts by weight of the manufactured by JSR Corporation, scan Kua Lilium compounds "a-10" 0.02 part by weight, the addition of further methylene chloride, the resin concentration of 20% A solution was obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
The container, the cyclic olefin-based resin "ARTON G" 100 parts by weight of the manufactured by JSR Corporation, scan Kua Lilium compounds "a-10" 0.04 parts by weight, the addition of further methylene chloride, the resin concentration of 20% A solution was obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

A hard coat agent “Beam Set” manufactured by Arakawa Chemical Industries, Ltd. was applied to both surfaces of this substrate with a bar coater so that the film thickness after curing was 0.002 mm, and then cured by UV irradiation. A substrate having a thickness of 0.104 mm, a length of 60 mm, and a width of 60 mm was obtained.
Further, a near-infrared cut filter having a thickness of 0.109 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 5]
The container, Nippon Zeon cycloolefin resin "ZEONOR 1420R" Co., Ltd. 100 parts by weight, scan Kua Lilium compounds "a-10" 0.40 parts by weight, more cyclohexane and xylene 7: 3 mixed solution adding Thus, a solution having a resin concentration of 20% was obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, and at 80 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 24 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 6]
A container, manufactured by Mitsui Chemicals, Inc. cycloolefin resin "APEL # 6015" 100 parts by weight, scan Kua Lilium compounds "a-10" 0.24 parts by weight, of further cyclohexane and methylene chloride 99: 1 mixed solution By adding, a solution having a resin concentration of 20% was obtained. Then, the solution was cast on a smooth glass plate, dried at 40 ° C. for 4 hours and 60 ° C. for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 7]
A container, a polycarbonate resin "Pureace" 100 parts by weight of Teijin Ltd., scan Kua Lilium compounds "a-10" 0.02 parts by weight, further by adding methylene chloride, the resin concentration of 20% solution Obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 8]
The container, Sumitomo Bakelite polyethersulfone "FS-1300" manufactured by Ltd. 100 parts by weight, scan Kua Lilium compounds "a-10" 0.05 part by weight, the addition of further N- methyl-2-pyrrolidone A solution with a resin concentration of 20% was obtained. Then, the solution was cast on a smooth glass plate, dried at 60 ° C. for 4 hours and at 80 ° C. for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 120 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 9]
In the same manner as in Example 1 except that the resin A obtained in Synthesis Example 1 was used in place of the cyclic olefin resin “Arton G” manufactured by JSR Corporation, the thickness was 0.1 mm, the length was 60 mm, and the width was 60 mm. A substrate was obtained.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 10]
The container, B100 parts by weight of the resin obtained in Synthesis Example 2, scan Kua Lilium compounds "a-10" 0.24 parts by weight, by further addition of toluene, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. A substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm was obtained in the same manner as in Example 1 except that the peeled coating film was further dried at 120 ° C. under reduced pressure for 8 hours.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 11]
The container, the polyimide solution C100 parts obtained in Synthesis Example 3, and to a Kua Lilium based compound "a-10" was added 0.05 parts by weight per 100 parts by weight of the solid content of the polyimide solution C, solid content 18 % Solution was obtained. Then, the solution was cast on a smooth glass plate, dried at 60 ° C. for 4 hours and at 80 ° C. for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 120 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 12]
The container, the resin D100 parts obtained in Synthesis Example 4, scan Kua Lilium compounds "a-10" 0.05 part by weight, the addition of further methylene chloride, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 13]
The container, E100 parts by weight of the resin obtained in Synthesis Example 5, scan Kua Lilium compounds "a-10" 0.05 part by weight, the addition of further methylene chloride, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 14]
The container, F100 parts by weight of the resin obtained in Synthesis Example 6, the scan Kua Lilium compounds "a-10" 0.05 part by weight, the addition of further methylene chloride, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 15]
The container, G100 parts by weight of the resin obtained in Synthesis Example 7, the scan Kua Lilium compounds "a-10" 0.05 part by weight, the addition of further methylene chloride, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 16]
The container, the resin A100 parts obtained in Synthesis Example 1, scan Kua Lilium compounds "a-10" 0.04 parts by weight, the addition of further methylene chloride, the resin concentration was obtained a 20% solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  A composition obtained by mixing tricyclodecane dimethanol diacrylate and methyl ethyl ketone in a ratio of 50:50 on both surfaces of this substrate was applied with a bar coater so that the film thickness after drying was 0.002 mm, and then UV was applied. Irradiated and cured to obtain a substrate having a thickness of 0.104 mm, a length of 60 mm, and a width of 60 mm.

  Further, a near-infrared cut filter having a thickness of 0.109 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Comparative Example 1]
In the same manner as in Example 1 except that a solution having a resin concentration of 20% obtained by dissolving Resin A obtained in Synthesis Example 1 in methylene chloride was used instead of the solution (ex1), a thickness of 0. A substrate having a length of 1 mm, a length of 60 mm, and a width of 60 mm was obtained.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Comparative Example 2]
Scan Kua Lilium compound except using SIR159 (manufactured by Mitsui Chemicals, Inc.) is a nickel complex compound having no scan Kua Lilium structure instead of "a-10" in the same manner as in Example 1, thickness 0 A substrate having a thickness of 1 mm, a length of 60 mm, and a width of 60 mm was obtained.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

[Comparative Example 3]
Scan Kua Lilium compound except for using the scan Kua Lilium structure is cyanine dye having no SDB3535 (H.W.SANDS Co.) in place of "a-10" in the same manner as in Example 1, the thickness A substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm was obtained.
Further, a near-infrared cut filter having a thickness of 0.105 mm was produced from this substrate in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

  The near infrared cut filter of the present invention includes a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a TV, a car navigation system, a portable information terminal, a personal computer, a video game, a medical device, and a USB memory. It can be suitably used for portable game machines, fingerprint authentication systems, digital music players, toy robots, toys and the like.

  Furthermore, it can be suitably used as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

1: Camera module 2: Lens barrel 3: Flexible substrate 4: Hollow package 5: Lens 6: Near-infrared cut filter 6 ': Near-infrared cut filter 7 obtained by the present invention: CCD or CMOS image sensor 8: Near-infrared cut Filter 9: Spectrophotometer

Claims (12)

A resin substrate (I) containing a compound (I) having a structure derived from a compound having an absorption maximum at a wavelength of 600 to 800 nm represented by the following formula (I) and a near-infrared reflective film, A near-infrared cut filter satisfying A) and (D) .
(A) In the wavelength range of 430 to 580 nm, the average value of transmittance when measured from the vertical direction of the near infrared cut filter is 75% or more.
(D) In the wavelength range of 560 to 800 nm, the wavelength value (Ya) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 50% and 30 ° with respect to the vertical direction of the near-infrared cut filter The absolute value of the difference in wavelength value (Yb) at which the transmittance when measured from the angle of 50% is less than 15 nm

[In the formula (I), R ^a , R ^b and Y satisfy the following (i) or (ii).
(I) R ^a is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a —NR ^e R ^f group (R ^e and R ^f each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ), Or a hydroxy group,
R ^b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or —C ( O) R ⁱ group (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)), or a hydroxy group,
Y is a —NR ^j R ^k group (R ^j and R ^k are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a 1 to 8 carbon atom in which any hydrogen atom is substituted with a functional group) It represents a substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which an arbitrary hydrogen atom is substituted with an alkyl group.
(Ii) one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing at least one nitrogen atom having 5 or 6 atoms And
R ^b and R ^a not involved in the bond are independently the same as R ^b and R ^a in the above (i). ] The near-infrared cut filter according to claim 1, wherein the transmittance satisfies the following (B) and (C) .
(B) In the wavelength range of 800 to 1000 nm, the average transmittance when measured from the vertical direction of the near infrared cut filter is 20% or less. The longest wavelength (Xa) at which the transmittance is 70% and the shortest wavelength (Xb) at which the transmittance is 30% when measured from the vertical direction of the near-infrared cut filter in a wavelength region of 580 nm or more. The absolute value of the difference between is less than 75nm The near infrared cut filter according to claim 1 or 2, wherein the resin substrate (I) satisfies the following (E) and (F).
(E) There is an absorption maximum at a wavelength of 600 to 800 nm. (F) In the wavelength range of 430 to 800 nm, the longest wavelength below the absorption maximum (Za) is 70% when measured from the vertical direction of the substrate. ) And the absolute value of the difference between the shortest wavelength (Zb) at which the transmittance is 30% when measured from the vertical direction of the substrate in the wavelength region of 580 nm or more, is less than 75 nm. 4. The near-infrared cut filter according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the following formula (II).

[In the formula (II), R ^a and R ^b each independently have the same meaning as (i) in the formula (I), and R ^c each independently represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 8 carbon atoms. Group, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an arbitrary hydrogen atom is substituted with an alkyl group A substituted aromatic hydrocarbon group having 6 to 12 carbon atoms is represented. ]   The near-infrared cut filter according to any one of claims 1 to 4, wherein the resin substrate (I) is a substrate comprising a cyclic olefin resin or an aromatic polyether resin. A resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) as the cyclic olefin-based resin The near-infrared cut filter according to claim 5, wherein

(In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (viii ′), and k ^x , ^mx and p ^x are each independently Represents 0 or a positive integer.)
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bond are each independently the above (i ′ ) To (vi ′) each representing an atom or group selected from (viiii ′) a monocyclic or polycyclic hydrocarbon ring formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 with each other, or R ^{x1 to} R ^x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^x2 and R ^x3 are mutually R ^{x1 to} R ^x4 each representing a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding are independently selected from the atoms or groups selected from the above (i ′) to (vi ′). Express

(In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′) or the following (ix ′), and K ^y and P each ^y independently represents 0 or a positive integer.)
(Ix ′) R ^y1 and R ^y2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other The aromatic polyether resin has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). The near infrared cut filter according to claim 5.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.) The aromatic polyether-based resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The near-infrared cut filter according to claim 7.

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)   The near-infrared cut filter according to any one of claims 5 to 8, wherein the compound (I) is contained in an amount of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the resin.   The near infrared cut filter according to claim 1, wherein the near infrared cut filter is for a solid-state imaging device.   A solid-state imaging device comprising the near infrared cut filter according to claim 1.   A camera module comprising the near infrared cut filter according to claim 1.

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