TW201211125A

TW201211125A - Near-infrared ray cutting filter and apparatus using near-infrared ray cutting filter

Info

Publication number: TW201211125A
Application number: TW100118291A
Authority: TW
Inventors: Takayuki Asano; Takashi Tsubouchi; Yukie Oohashi; Kouta Taniguchi; Tatsurou Mitsui; Kouji Hatakeyama; Naoki Sugiyama; Katsuya Nagaya
Original assignee: Jsr Corp
Priority date: 2010-05-26
Filing date: 2011-05-25
Publication date: 2012-03-16
Also published as: JP5810604B2; CN102262254B; CN102262254A; KR20110129832A; TWI570174B; KR101578963B1; JP2012008532A

Abstract

The present invention is to obtain a near-infrared ray cutting filter with a broad view angle, an excellent near-infrared ray cutting performance, the low moisture absorption, and no impurities or warpage. The present invention provides a near-infrared ray cutting filter characterized by containing a resin substrate originated from a compound represented by formula (I). In formula (I), Ra, Rb and Y satisfy the condition (i) or (ii): (i) Ra each independently represents hydrogen, C1-8 alkyl, -NReRf (Re and Rf each independently represents hydrogen or C1-5 alkyl) or hydroxyl; Rb each independently represents hydrogen, C1-5 alkyl, or -NRgRh (Rg and Rh each independently represents hydrogen, C1-5 alkyl, or -C(O)Ri, wherein Ri represents C1-5 alkyl) or hydroxyl; Y represents –NRjRk (Rj and Rk each independently represents hydrogen, C1-8 aliphatic hydrocarbonyl, substituted C1-8 aliphatic hydrocarbonyl with any hydrogen substituted by a functional group, C6-12 aromatic hydrocarbonyl or substituted C6-12 aromatic hydrocarbonyl with any hydrogen substituted by a alkyl group); (ii) a 5- or 6-member heterocyclic ring with at least one nitrogen formed by a benzene ring with one of two Ra bonded with Y of the same benzene ring, wherein Rb and Ra not bonded by each other independently have the same definition as Rb and Ra above.

Description

201211125 六、發明說明：【發明所屬之技術領域】本發明係關於近紅外線截止濾波器。更詳言之，係關於具有充分視角，尤其是可使用作爲CCD ' CMOS等固體攝影元件用視感度補正濾波器之近紅外線截止濾波器。【先前技術】近年來，搭載電漿顯示器面板（PDP )之電視已商品化，已廣泛普及於於一般家庭。該PDP係利用電漿放電進行作動之顯示器，但已知電漿放電之際會發生近紅外線（波長：8 00~ 1 0 OOnm )。另一方面，有關家庭內，於電視、收音機或空調等家電製品之遙控器，進而於個人電腦之資料交換利用到近紅外線變多，而經常指出PDP發出之近紅外線成爲該等機器誤動作之原因之可能性高。因此，市售之PDP大多數在其前面板上具備有截止本身發出之近紅外線用之濾波器功能。且，攝影機、數位相機、附加相機功能之行動電話等雖使用照相機畫素之固體攝影元件的CCD或CM0S影像感知器，但該等固體攝影元件由於在其受光部中使用對近紅外線具有感度之矽光二極體，故有必要進行視感度補正’ 且大多使用近紅外線截止濾波器。至於該等近紅外線截止濾波器’自過去以來均使用以各種方法製造者。實用上提供有例如在玻璃等透明基材之 201211125 表面上蒸鍍銀等金屬，而反射近紅外線者，於丙烯酸樹脂或聚碳酸酯樹脂等透明樹脂中添加近紅外線吸收色素者等等。然而，於玻璃基材上蒸鍍金屬之近紅外線截止濾波器不僅增加製造成本，且會有截止時有基材之玻璃片作爲異物而混入之問題。再者，使用無機質材料作爲基材時，爲了對應於近年來的固體攝影裝置之薄型化•小型化而有其界限。又，於特開平6-200 1 1 3號公報（專利文獻1 )中，已知有使用透明樹脂作爲基材，於透明樹脂中含有近紅外線吸收色素之近紅外線截止濾波器。然而，專利文獻1所記載之近紅外線截止濾波器有近紅外線吸收能未必足夠之情況。另外，本申請人在特開200 5 -3 3 8 3 95號公報（專利文獻2 )中提案具有原冰片烯系樹脂製基板與近紅外線反射膜之近紅外線截止濾波器。〔先前技術文獻〕〔專利文獻〕〔專利文獻1〕特開平6-200 1 1 3號公報〔專利文獻2〕特開2005 -3 3 8395號公報【發明內容】〔發明欲解決之課題〕專利文獻2中記載之近紅外線截止濾波器雖近紅外線 -6 - 201211125 截止能、耐吸濕性、耐衝擊性優異，但有無法成爲充分視角値之情況。本發明之目的爲獲得一種視角廣，而且近紅外線截止能優異，吸濕性低，沒有異物或翹曲，尤其可適用於CCD 、CMOS等固體攝影裝置用之近紅外線截止濾波器。另外 ’本發明之目的係提供一種薄型且耐衝擊性優異之固體攝影裝置。〔解決課題之手段〕本發明之近紅外線截止濾波器之特徵爲具有含有具有源自以下述式（π表示之化合物之構造之化合物（I)之樹脂製基板（I )，【化1】201211125 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a near-infrared cut filter. More specifically, it is a near-infrared cut filter having a sufficient viewing angle, in particular, a viscous correction filter for a solid-state imaging device such as a CCD 'CMOS. [Prior Art] In recent years, televisions equipped with plasma display panels (PDPs) have been commercialized and widely used in general households. The PDP is a display that is operated by plasma discharge, but it is known that near-infrared rays (wavelength: 800 to 100 nm) occur when the plasma is discharged. On the other hand, in the home, the remote control of home appliances such as televisions, radios, or air conditioners, and the exchange of data on personal computers, have increased the number of near-infrared rays. It is often pointed out that the near-infrared rays emitted by PDPs are the cause of malfunction of such machines. The possibility is high. Therefore, most of the commercially available PDPs have a filter function for the near-infrared rays emitted from the front panel. Further, a camera, a digital camera, a mobile phone with a camera function, and the like use a CCD or a CMOS image sensor of a solid-state imaging device of a camera pixel, but these solid-state imaging elements have sensitivity to near-infrared rays in their light-receiving portions. For the dimming diode, it is necessary to perform the visual sensitivity correction and most of them use a near-infrared cut filter. As for the near-infrared cut-off filters', various methods have been used since the past. Practically, for example, a metal such as silver is vapor-deposited on the surface of 201211125 of a transparent substrate such as glass, and a near-infrared absorbing pigment is added to a transparent resin such as an acrylic resin or a polycarbonate resin. However, the near-infrared cut-off filter for vapor-depositing a metal on a glass substrate not only increases the manufacturing cost, but also has a problem that the glass piece of the substrate is mixed as a foreign matter at the time of cutting off. In addition, when an inorganic material is used as the substrate, there is a limit in terms of thinning and miniaturization of the solid-state imaging device in recent years. Japanese Patent Publication No. Hei 6-200 1 1 3 (Patent Document 1) discloses a near-infrared cut filter that uses a transparent resin as a substrate and a near-infrared absorbing dye in a transparent resin. However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption energy. In addition, the present applicant proposes a near-infrared cut filter having a base plate made of a base borneol resin and a near-infrared reflecting film, in JP-A-200-323883 (Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-3 3 8395. The near-infrared cut-off filter described in Document 2 is excellent in the cut-off resistance, moisture absorption resistance, and impact resistance of near-infrared -6 - 201211125, but may not be sufficient. SUMMARY OF THE INVENTION The object of the present invention is to obtain a wide viewing angle, excellent near-infrared cutoff performance, low hygroscopicity, and no foreign matter or warpage, and is particularly applicable to a near-infrared cut filter for solid-state imaging devices such as CCD and CMOS. Further, the object of the present invention is to provide a solid-state imaging device which is thin and excellent in impact resistance. [Means for Solving the Problem] The near-infrared cut-off filter of the present invention is characterized in that it has a resin substrate (I) having a compound (I) derived from a structure represented by the following formula (π), [Chem. 1]

(I) 〔式（I)中，Ra、Rb及Y滿足下述（i)或（ii)， (〇 Ra各獨立表示氫原子、碳數1〜8之烷基、-NReRf 基（Re& Rf各獨立表示氫原子或碳數1〜5之烷基）、或羥基， 201211125(I) [In the formula (I), Ra, Rb and Y satisfy the following (i) or (ii), (〇Ra each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a -NReRf group (Re& Rf each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, 201211125

Rb各獨立表示氫原子、碳數1~5之烷基、-NRgRh ( Rg 及Rh各獨立表示氫原子、碳數1〜5之烷基、或-C(O)以基 (1^表示碳數1~5之烷基））、或羥基， Y表示-NRjRk 各獨立表示氫原子、碳數1〜8之脂肪族烴基、任意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數6~1 2之芳香族烴基、或任意之氫原子經烷基取代之碳數6〜12之經取代芳香族烴基， (ii)—個苯環上之兩個1^中之一個與同一苯環上之 Y相互鍵結，形成構成原子數5或6之含有至少一個氮原子之雜環，Rb each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and -NRgRh (wherein Rg and Rh each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or -C(O) as a group (1^ represents carbon) a number of 1 to 5 alkyl groups) or a hydroxyl group, Y represents -NRjRk each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom substituted with a functional group substituted with a carbon number of 1 to 8 An 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 substituted with an alkyl group by any alkyl group, (ii) two 1^ on a benzene ring One of them is bonded to Y on the same benzene ring to form a heterocyclic ring containing at least one nitrogen atom constituting the atomic number 5 or 6.

Rb及未參與該鍵結之Ra各獨立與前述（i)之Rb及Ra 同義〕。本發明之近紅外線截止濾波器之透射率較好滿足下述 (A )〜（D )： (A) 在波長430〜5 80nm之範園內，自近紅外線截止濾波器之垂直方向測定時之透射率平均値爲75 %以上， (B) 在波長800〜lOOOnm內，自近紅外線截止濾波器之垂直方向測定時之透射率平均値爲20%以下， (C )在80 0nm以下之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲70%之最長波長（ Xa)，與在波長5 80nm以上之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲30%之最短波長 (Xb)之差的絕對値未達75nm， (D)在波長5 60〜800nm之範圍內，自近紅外截止濾 201211125 波器之垂直方向測定時之透射率成爲5〇 %之波長之値（Ya )，與自相對於近紅外線截止濾波器之垂直方向爲3 0°之角度測定時之透射率成爲50%之波長之値（Yb )之差的絕對値未達1 5 n m。前述樹脂製基板（I)較好滿足下述（E)及（F): (E) 在波長600〜800nm有吸收極大 (F) 在波長4 3 0〜800nm之波長區域中，自基板之垂直方向測定時之透射率成爲70%之在吸收極大以下之最長波長（Za)，與在波長580 nm以上之波長區域中，自基板之垂直方向測定時之透射率成爲30 %之最短波長（Zb)之差的絕對値未達75nm。以前述式（I)表示之化合物較好爲以下述式（II)表示之化合物：【化2】Rb and Ra which are not involved in the bonding are independently synonymous with Rb and Ra of the above (i). The transmittance of the near-infrared cut filter of the present invention preferably satisfies the following (A) to (D): (A) in the range of the wavelength of 430 to 5 80 nm, measured from the vertical direction of the near-infrared cut filter The average transmittance of transmittance is 75% or more. (B) In the wavelength of 800 to 100 nm, the average transmittance of the transmittance when measured from the vertical direction of the near-infrared cut filter is 20% or less, and (C) is in the wavelength region of 80 nm or less. In the case where the transmittance in the vertical direction of the near-infrared cut filter is measured, the transmittance is 70% of the longest wavelength (Xa), and in the wavelength region of the wavelength of 580 nm or more, the transmittance is measured from the vertical direction of the near-infrared cut filter. The absolute 値 of the difference between the shortest wavelength (Xb) at which the rate becomes 30% is less than 75 nm, and (D) is in the range of wavelength 5 60 to 800 nm, and the transmittance is 5 when measured from the vertical direction of the near-infrared cut filter 201211125. The absolute value of the difference between the 値(Ya) of the wavelength of 〇% and the 値(Yb) of the wavelength at which the transmittance is 50% when measured at an angle of 30° with respect to the vertical direction of the near-infrared cut filter 1 5 nm. The resin substrate (I) preferably satisfies the following (E) and (F): (E) has a maximum absorption at a wavelength of 600 to 800 nm (F) in a wavelength region of a wavelength of 430 to 800 nm, from the vertical of the substrate The transmittance at the time of measurement is 70% of the longest wavelength (Za) below the absorption maximum, and the transmittance at the wavelength of 580 nm or more is the shortest wavelength (Zb) when the transmittance is 30% from the vertical direction of the substrate. The absolute difference between the two is less than 75nm. The compound represented by the above formula (I) is preferably a compound represented by the following formula (II):

〔式（II)中，Ra及Rb各獨立與前述式（I)之（i) 同義，Re各獨立表示氫原子、碳數1~8之脂肪族烴基、任 201211125 意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數6〜12之芳香族烴基、或任意之氫原子經烷基取代之碳數6~ 12之經取代芳香族烴基〕。前述樹脂製基板（I)較好爲含環狀烯烴系樹脂或芳香族聚醚系樹脂而成之基板。前述環狀烯烴系樹脂較好爲由自以下述式（X〇)表示之單體及以下述式（Υ〇)表示之單體所組成群組選出之至少一種單體獲得之樹脂：[In the formula (II), Ra and Rb are each independently synonymous with (i) of the above formula (I), and Re each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom of 201211125; The substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, the aromatic hydrocarbon group having 6 to 12 carbon atoms, or the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted by an alkyl group. The resin substrate (I) is preferably a substrate containing a cyclic olefin resin or an aromatic polyether resin. The cyclic olefin-based resin is preferably a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X〇) and a monomer represented by the following formula (Υ〇):

(式（X。）中，Rxl〜Rx4各獨立表示由下述（i’）〜（ viii’）選出之原子或基，kx、mx及px各獨立表示0或正整數 )， (i’）氫原子， (Π’）鹵素原子， (Hi’）三烷基矽烷基， (iv’）具有含有氧原子、硫原子、氮原子或矽原子之連結基之經取代或未經取代之碳數1〜30之烴基， (ν’）經取代或未經取代之碳數卜30之烴基， (vi’）極性基（但，（iv’）除外）， -10- 201211125 (Vii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之亞烷基，且未參與該鍵結之Rxl〜Rx4各獨立表示自前述（i’）〜 (vi，）選出之原子或基’ (viii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之單環或多環之烴環或雜環’且未參與該鍵結之Rxl〜Rx4各獨立表示自前述（i’）〜（vi，）選出之原子或基，Rx2與Rx3表示相互鍵結形成之單環烴環或雜環，且未參與該鍵結之 RX1〜Rx4各獨立表示自前述（i’）~(vi’）選出之原子或基(In the formula (X.), Rx1 to Rx4 each independently represent an atom or a group selected by the following (i') to (viii'), and kx, mx, and px each independently represent a 0 or a positive integer), (i') a hydrogen atom, a (Π') halogen atom, a (Hi') trialkylsulfanyl group, (iv') a substituted or unsubstituted carbon number having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom a hydrocarbon group of 1 to 30, (ν') a substituted or unsubstituted carbon number of 30, a (vi') polar group (except (iv'), -10- 201211125 (Vii') Rxl and Rx2 or Rx3 and Rx4 represent an alkylene group formed by mutual bonding, and Rx1 to Rx4 not participating in the bonding are each independently represented from the above-mentioned (i') to (vi,) selected atom or base '(viii') Rxl And Rx2 or Rx3 and Rx4 represent a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by mutual bonding, and Rx1 to Rx4 which are not involved in the bonding are independently represented from the above (i') to (vi,). An atom or a group, Rx2 and Rx3 represent a monocyclic hydrocarbon ring or a heterocyclic ring which are bonded to each other, and RX1 to Rx4 which are not involved in the bonding are independently represented from the above (i')~(vi ) Or a group of atoms selected

(式（Y〇)中’ Ryl及Ry2各獨立表示由前述（i’）〜（ vi’）選出之原子或基’或表示下述（ix，），以及？5^各獨立表示0或正整數）， (ix’）Ryl與Ry2表示相互鍵結形成之單環或多環之脂環式烴、芳香族烴或雜環。前述芳香族聚醚系樹脂較好具有由以下述式（1)表示之構造單位及以下述式（2 )表示之構造單位所組成群組選出之至少一種構造單位， -11 - (1) 201211125 【化5】(In the formula (Y〇), 'Ryl and Ry2 each independently represent an atom or a group selected by the above (i') to (vi') or represent the following (ix,), and ?5^ each independently represents 0 or a positive Integer), (ix') Ryl and Ry2 represent a monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring which are bonded to each other. The aromatic polyether-based 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), -11 - (1) 201211125 【化5】

價有機 (式（1)中，RLR4各獨立表示碳數1〜12之一基，a〜d各獨立表示0〜4之整數），【化6】The valence organic (in the formula (1), RLR4 each independently represents a carbon number of 1 to 12, and a to d each independently represents an integer of 0 to 4), [Chem. 6]

(2) (式（2 )中，Ri~R4及a~d各獨立與前述式（1 R1〜R4及a〜d同義，Y表示單鍵、-S02-*>C = 0，R7 獨立表示鹵素原子、碳數1〜12之一價有機基或硝基各獨立表示〇〜4之整數，m表示0或1，但m爲0時，氰基）。前述芳香族聚醚系樹脂較好進而具有由以下51 )表示之構造單位及以'下述式（4)表示之構造單成群組選出之至少一種構造單位 )中之及R8各，层及h R7不爲 ί式（3 位所組 -12- 201211125 【化7】(2) In the formula (2), Ri~R4 and a~d are each independently of the above formula (1 R1 to R4 and a to d are synonymous, Y represents a single bond, -S02-*> C = 0, R7 is independent A halogen atom, a carbon number of 1 to 12, an organic group or a nitro group each independently represent an integer of 〇~4, and m represents 0 or 1, but when m is 0, a cyano group). Further, it has a structural unit represented by the following 51) and at least one structural unit selected by a structural group represented by the following formula (4), and each of R8, the layer and h R7 are not ί (3) Position group -12- 201211125 【化7】

(式（3)中’尺5及尺6各獨立表示碳數1~12之一價有機基，Z表示單鍵、-〇-、-S_、-S〇2-、>c = 0、-CONH-、-COO-或碳數1~12之二價有機基，e及f各獨立表示〇〜4之整數，η表示0或1 ) ’ 【化8】 —-⑷ (式（4)中’ R7、R8、Y、m、g及h各獨立與前述式 (2)中之 R7、R8、Y、m、g及 h 同義，R5、r6、Z、n、e 及f各獨立與前述式Ο )中之R5、R6、Z、η、e及f同義） ο 前述化合物（I)相對於樹脂100重量份含有0.01〜10.0 重量份。本發明之近紅外線截止濾波器可較好地使用於固體攝影裝置。本發明之固體攝影裝置及照相機模組之特徵爲具備前述之近紅外線截止濾波器。 -13- 201211125 〔發明效果〕依據本發明，可製造吸收（透射）波長之入射角依存性小’視角廣，近紅外線截止能優異，吸濕性低，沒有異物或翹曲之近紅外線截止濾波器。且’依據本發明，可使固體攝影裝置及照相機模組等薄型化及小型化》【實施方式】以下針對本發明加以具體說明。〔近紅外線截止濾波器〕本發明之近紅外線截止濾波器之特徵爲具有樹脂製基板（I)，其含有具有源自具有以下述式（I)表示之方酸 (squarylium )構造之化合物（以下亦稱爲「化合物（Γ )」之構造的樹脂基板，且較好具有下述樹脂製基板（I )與下述近紅外線反射膜。近紅外線截止濾波器藉由具有該樹脂製基板，而成爲尤其是入射角依存性小之近紅外線截止濾波器。《樹脂製基板（I )》前述樹脂製基板（I )包含化合物（I )，且較好滿足下述（Ε)及（F)。 (Ε)吸收極大宜落於波長600〜800nm之範圍內。若使基板之吸收極大波長落在該範圍內，則該基板可 -14- 201211125 選擇性且效率良好地截止近紅外線》 (F)在波長4 3 0〜800nm之波長區域中，自基板之垂直方向測定時之透射率成爲70 %之在吸收極大以下之最長波長（Za)，與在波長580nm以上之波長區域中，自基板之垂直方向測定時之透射率成爲30 %之最短波長（Zb)之差之絕對値（|Za-Zb|)宜未達75nm，較好未達50nm，更好未達30nm之値。樹脂製基板（I)之吸收極大波長及（Za)與（Zb) 之差之絕對値在前述範圍時，光入射於該基板時，在近紅外線之波長區域附近之波長（Za )與（Zb )之間之透射率急遽變化。該種基板可有效地截止近紅外線，且，該種基板用於近紅外線截止濾波器時，該濾波器之（Ya )與（Yb )之差之絕對値小，吸收波長之入射角依存性小，可獲得視角廣之近紅外線截止濾波器。又，將使用該種基板之近紅外線截止濾波器使用於照相機模組等透鏡單元時，可實現透鏡單元之薄型化（Low Profile )故較佳。依據PDP用前面板或照相機模組等用途，波長 400〜700nm之所謂可見光區域中，亦有必須使含有化合物 (.1)之樹脂製基板之厚度成爲ΙΟΟμιη時該基板之平均透射率爲50%以上，較好爲65 %以上之情況。前述樹脂製基板（I)之厚度可依據所需用途適宜選擇，並無特別限制，但該基板較好調整至滿足前述（Ε ) -15- 201211125 及（F )，更好爲250〜50μιη，更好爲200〜50μπι ’最好爲 150〜80μηι 〇樹脂製基板（I)之厚度爲前述範圍時，可使利用該基板之近紅外線截止濾波器小型化、輕量化，可適用於固體攝影裝置等各種用途中。尤其使用於照相機模組等透鏡單元時，可實現透鏡單元之薄型化故較佳。〈化合物（I)〉前述化合物（I)具有源自化合物（I’）之構造。又，化合物（I)較好爲具有方酸構造之染料。【化9】 pa 〇b r\- 〇b pa(In the formula (3), the ruler 5 and the ruler 6 each independently represent a carbon number of 1 to 12, and Z represents a single bond, -〇-, -S_, -S〇2-, > c = 0, -CONH-, -COO- or a divalent organic group having a carbon number of 1 to 12, and e and f each independently represent an integer of 〇~4, η represents 0 or 1) '[8] (-) (4) Wherein 'R7, R8, Y, m, g and h are independently synonymous with R7, R8, Y, m, g and h in the above formula (2), and R5, r6, Z, n, e and f are each independently R5, R6, Z, η, e, and f in the above formula 同) are synonymous) ο The compound (I) is contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the resin. The near-infrared cut filter of the present invention can be preferably used in a solid-state imaging device. The solid-state imaging device and camera module of the present invention are characterized by comprising the near-infrared cut filter described above. -13-201211125 [Effect of the Invention] According to the present invention, it is possible to produce an absorption (transmission) wavelength with small incident angle dependency, a wide viewing angle, excellent near-infrared cutoff energy, low hygroscopicity, and no near-infrared cut-off filtering of foreign matter or warpage. Device. Further, according to the present invention, the solid-state imaging device, the camera module, and the like can be made thinner and smaller. [Embodiment] Hereinafter, the present invention will be specifically described. [Near-infrared cut-off filter] The near-infrared cut filter of the present invention is characterized by having a resin substrate (I) containing a compound derived from a squarylium structure represented by the following formula (I) (below The resin substrate having the structure of the compound (Γ) is preferably a resin substrate (I) and a near-infrared reflecting film described below. The near-infrared cut filter has the resin substrate. In particular, a near-infrared cut filter having a small incident angle dependence. "Resin substrate (I)" The resin substrate (I) contains the compound (I), and preferably satisfies the following (Ε) and (F). Ε) The absorption should be within the range of 600~800nm. If the absorption maximum wavelength of the substrate falls within this range, the substrate can be selectively and efficiently cut off near infrared rays. In the wavelength region of 4 3 0 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 region above the wavelength of 580 nm or more. The absolute 値 (|Za-Zb|) of the difference between the shortest wavelength (Zb) at which the transmittance is 30% in the vertical direction is preferably less than 75 nm, preferably less than 50 nm, more preferably less than 30 nm. (I) The absorption maximum wavelength and the absolute difference between (Za) and (Zb) in the above range, when light is incident on the substrate, between wavelengths (Za) and (Zb) near the wavelength region of the near infrared The transmittance is rapidly changed. The substrate can effectively cut off near-infrared rays, and when the substrate is used in a near-infrared cut filter, the difference between (Ya) and (Yb) of the filter is absolutely small, and the absorption wavelength is When the near-infrared cut-off filter using such a substrate is used for a lens unit such as a camera module, the lens unit can be made thinner (Low). In the case of a PDP front panel or a camera module, in the so-called visible light region having a wavelength of 400 to 700 nm, the thickness of the resin substrate containing the compound (.1) must be ΙΟΟμηη. average The thickness of the resin substrate (I) may be appropriately selected depending on the intended use, and is not particularly limited, but the substrate is preferably adjusted to satisfy the above (Ε). -15-201211125 and (F), more preferably 250 to 50 μm, more preferably 200 to 50 μm, preferably 150 to 80 μm, and the thickness of the substrate (I) made of the resin is in the above range, and the substrate can be used in the vicinity. The infrared cut filter is compact and lightweight, and can be applied to various applications such as a solid-state imaging device. In particular, when it is used for a lens unit such as a camera module, it is preferable to reduce the thickness of the lens unit. <Compound (I)> The above compound (I) has a structure derived from the compound (I'). Further, the compound (I) is preferably a dye having a squaric acid structure. [化9] pa 〇b r\- 〇b pa

(i) 式（I)中，Ra、…及Y滿足下述（i)或（ii)。 (i) Ra各獨立表示氫原子、碳數1~8之烷基、-NReRf 基（1^及Rf各獨立表示氫原子或碳數1〜5之烷基）、或羥基，(i) In the formula (I), Ra, ..., and Y satisfy the following (i) or (ii). (i) Ra each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a -NReRf group (wherein 1 and Rf each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), or a hydroxyl group;

Rb各獨立表示氫原子、碳數1〜5之烷基、-NRgRh基（ …及！^各獨立表示氫原子、碳數1〜5之烷基、或-C ( 0) W 基（Ri表示碳數1〜5之烷基））、或羥基， Y表示………基（…及Rk各獨立表示氫原子、碳數1〜8 -16- 201211125 之脂肪族烴基、任意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數6~12之芳香族烴基、或任意之氫原子經烷基取代之碳數6〜1 2之經取代芳香族烴基）’ (ii)—個苯環上之兩個Ra中之一個與同一苯環上之 Y相互鍵結，形成構成原子數5或6之含有至少一個氮原子之雜環，Rb及未參與該鍵結之Ra各獨立與前述（i )之Rb 及1^同義。前述Ra之碳數1~8之烷基可列舉爲甲基（Me)、乙基 (Et)、正丙基（n-Pr)、異丙基（i-Pr)、正丁基、第二丁基、第三丁基（t-Bu )、戊基及己基等’該等基之任意氫原子亦可經甲基及乙基等取代。前述-NReRf基中之11£及Rf之碳數1〜5之烷基可列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等。前述Rb之碳數1〜5之烷基可列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等。前述-NRgRh基中之118及Rh之碳數1〜5之烷基可列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等。前述-C ( 0 ) R1基中之W可列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等。前述-NRjRk基中之。及Rk之碳數1〜8之脂肪族烴基可列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基及己基等之鏈狀脂肪族烴基：環戊基、 -17- 201211125 環己基等環狀脂肪族烴基等。前述-NRjRk基中之…及Rk之任意氫原子經官能基取代之碳數1〜8之經取代之脂肪族烴基可列舉爲前述鏈狀脂肪族烴基之任意氫原子經-NR’R”基（R’及R”表示甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等鏈狀脂肪族烴基）、-CN、-OH、-OR ( R表示甲基、乙基及丙基）等官能基取代之經取代鏈狀脂肪族烴基；前述環狀脂肪族烴基之任意氫原子經甲基及乙基等取代之經取代脂肪族烴基等。前述-NRjRk基中之Rj及妒中之碳數6~12之芳香族烴基可列舉爲苯基等。前述-NRjRk基中之…及Rk中之任意氫原子經烷基取代之碳數6~12之經取代芳香族烴基可列舉爲苯基之任意氫原子經甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基及戊基等鏈狀脂肪族烴基取代之經取代苯基等。前述式（I)之（U)中，一個苯環上之兩個Ra中之一個與同一苯環上之Y相互鍵結而成之構成原子數5或6之含至少一個氮原子之雜環可列舉爲例如吡咯啶、吡咯、咪唑、哌嗤、哌卩定、啦D定、峨曉、塔曝、嘧H定及耻曉等。該等雜環中，較好爲構成該雜環、且相鄰構成苯環之碳原子之 —個原子爲氮原子之雜環’更好爲吡咯啶。化合物（Γ )包含例如以下述式（1-1 )表示之構造之具有共振構造（resonance structure)之化合物（1-2)。亦即，化合物（I’）列舉爲例如化合物（I-1 )及化合物（ -18- 201211125 1-2 )。【化1 0】Rb each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and -NRgRh groups (... and each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a -C(0) W group (Ri represents Alkyl group having a carbon number of 1 to 5), or a hydroxyl group, Y represents a group of (... and Rk each independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 8 -16 to 201211125, and an arbitrary hydrogen atom via a functional group. a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by an alkyl group with any hydrogen atom; Ii) one of the two Ras on the benzene ring and the Y on the same benzene ring are bonded to each other to form a heterocyclic ring containing at least one nitrogen atom constituting the atomic number 5 or 6, Rb and not participating in the bonding Ra is independently synonymous with Rb and 1^ of (i) above. The alkyl group having 1 to 8 carbon atoms of Ra may be exemplified by methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl, and second. Any hydrogen atom of such a group such as a butyl group, a tert-butyl group (t-Bu), a pentyl group or a hexyl group may be substituted with a methyl group, an ethyl group or the like. The alkyl group of the above-mentioned -NReRf group and the carbon number of 1 to 5 of Rf may be exemplified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group and t-butyl group. Amyl and so on. The alkyl group having 1 to 5 carbon atoms of the above Rb may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group or a pentyl group. The alkyl group having a carbon number of 1 to 5 in the above -NRgRh group of 118 and Rh may be exemplified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group and pentane group. Base. The W in the -C(0)R1 group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a tert-butyl group or a pentyl group. The aforementioned -NRjRk base. And the aliphatic hydrocarbon group having 1 to 8 carbon atoms of Rk may be a chain of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group or a hexyl group. The aliphatic hydrocarbon group is a cycloaliphatic group, a cyclic aliphatic hydrocarbon group such as -17-201211125 cyclohexyl group, or the like. The substituted aliphatic hydrocarbon group having a carbon number of 1 to 8 in which the hydrogen atom of any of the above-mentioned -NRjRk groups and Rk is substituted by a functional group may be exemplified by the -NR'R" group of any hydrogen atom of the aforementioned chain aliphatic hydrocarbon group. (R' and R" represent a chain aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl and pentyl), -CN, -OH a substituted chain aliphatic hydrocarbon group substituted with a functional group such as -OR (R represents a methyl group, an ethyl group, and a propyl group); a substituted aliphatic group in which any hydrogen atom of the above cyclic aliphatic hydrocarbon group is substituted with a methyl group or an ethyl group; A hydrocarbon group or the like. The Rj in the -NRjRk group and the aromatic hydrocarbon group having 6 to 12 carbon atoms in the oxime may be exemplified by a phenyl group or the like. The substituted aromatic hydrocarbon group having 6 to 12 carbon atoms which is substituted by an alkyl group in any of the above -NRjRk groups and the hydrogen atom of Rk can be exemplified by any hydrogen atom of a phenyl group via a methyl group, an ethyl group, a n-propyl group, A substituted phenyl group substituted with a chain aliphatic hydrocarbon group such as an isopropyl group, an n-butyl group, a second butyl group, a third butyl group or a pentyl group. In the above (U) of the formula (I), one of the two Ras on one benzene ring and the Y on the same benzene ring are bonded to each other to form a heterocyclic ring containing at least one nitrogen atom having 5 or 6 atoms. For example, pyrrolidine, pyrrole, imidazole, piperidine, piperidine, di Ding, xiaoxiao, tower exposure, pyrimidine and xiaoxiao. Among these heterocyclic rings, a heterocyclic ring constituting the heterocyclic ring and having one atom of a carbon atom constituting the benzene ring adjacent to each other is preferably a pyrrolidine. The compound (?) contains, for example, a compound (1-2) having a resonance structure of a structure represented by the following formula (1-1). That is, the compound (I') is exemplified by, for example, the compound (I-1) and the compound (-18-201211125 1-2). [化1 0]

前述化合物（I)宜爲測定將該化合物（I)溶解於其良溶劑中獲得之溶液之透射率（光路長1cm)時之吸收極大之分光透射率，與該溶液中之化合物（I)之濃度無關地，成爲3 0%以下之化合物，且’較好爲測定將化合物（I )溶解於其良溶劑中獲得之溶液之透射率（光路長1 cm ) 時，與該溶液中之化合物（I)之濃度無關地，於波長 600〜800nm有吸收極大，且在波長430〜800nm之波長區域中之透射率成爲70%之吸收極大以下之最長波長，與波長 580nm以上之波長區域中之透射率成爲30 %之最短波長之差之絕對値未達75nm，較好未達65nm，更好未達55nm之化合物再者，以往之近紅外線截止濾波器，該等化合物（I )基於其透射率曲線具有陡峭傾斜，近紅外線區域之吸收區域狹窄，且在製造於玻璃等基板中混入近紅外線截止濾波器時，該化合物（I)無法耐受玻璃之成形溫度等理由而無法使用。因此，無法獲得尤其如本發明之入射角依存 -19- 201211125 性小之近紅外線截止濾波器。含有該等化合物（I)之樹脂製基板（I)由於具有前述（E)及（F)之特徵，故本發明之近紅外線截止濾波器成爲尤其具有下述（A) 、（ C)及（D)之特徵》因此，可獲得入射角之依存性小、視角廣之近紅外線截止濾波器〇又，利用蒸鍍等而於樹脂製基板（I)上設置後述之近紅外線反射膜時，會有使近紅外線截止濾波器之視角變狹窄等性能變差之情況，但前述樹脂製基板（I )由於含有前述化合物（I)，故可防止因設置近紅外線反射膜產生之近紅外線截止濾波器之性能劣化。據此，即使利用蒸鍍等而於樹脂製基板（I)上設置近紅外線反射膜時，亦可獲得對於入射光之入射角沒有依存性之具有安定吸收波長區域之近紅外線截止濾波器。本發明中之前述化合物（I’）較好爲以下述式（II) 表不之化合物。【化1 1】The compound (I) is preferably a spectral transmittance at which the absorption of the solution obtained by dissolving the compound (I) in a good solvent (the optical path length is 1 cm) is extremely large, and the compound (I) in the solution Regardless of the concentration, it is a compound of 30% or less, and 'it is preferable to measure the transmittance (solution path length of 1 cm) of the solution obtained by dissolving the compound (I) in a good solvent, and the compound in the solution ( Irrespective of the concentration of I), the absorption at the wavelength of 600 to 800 nm is extremely large, and the transmittance in the wavelength region of 430 to 800 nm is the longest wavelength below the absorption maximum of 70%, and the transmission in the wavelength region of the wavelength above 580 nm. The ratio of the shortest wavelength difference of 30% is not more than 75 nm, preferably less than 65 nm, more preferably less than 55 nm. Further, in the conventional near-infrared cut-off filter, the compound (I) is based on its transmittance. The curve has a steep slope, and the absorption region in the near-infrared region is narrow, and when the near-infrared cut filter is mixed in a substrate such as glass, the compound (I) cannot withstand the forming temperature of the glass. It cannot be used. Therefore, it is impossible to obtain a near-infrared cut filter which is particularly small in incident angle dependence of the present invention. Since the resin substrate (I) containing the compound (I) has the characteristics (E) and (F) described above, the near-infrared cut filter of the present invention particularly has the following (A), (C), and (Features of D). Therefore, when a near-infrared reflection filter having a small incident angle and a wide viewing angle is obtained, a near-infrared reflection film to be described later is provided on a resin substrate (I) by vapor deposition or the like. In the case where the viewing angle of the near-infrared cut filter is narrowed, the resin substrate (I) contains the compound (I), so that the near-infrared cut filter formed by the near-infrared reflecting film can be prevented. The performance is degraded. According to this, even when a 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 which is not dependent on the incident angle of incident light can be obtained. The above compound (I') in the present invention is preferably a compound represented by the following formula (II). [1 1]

R。 & (Π) -20- 201211125 式（Π)中，^及妒係與前述式（I)之（i)同義， Rc各獨立表示氫原子、碳數1〜8之脂肪族烴基、任意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數 6〜12之芳香族烴基、或任意氫原子經烷基取代而成之碳數 6〜12之經取代芳香族烴基。式（Π )中之以Re表示之碳數1〜8之脂肪族烴基、任意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數6~ 12之芳香族烴基、及任意氫原子經烷基取代之碳數 6〜12之經取代芳香族烴基可列舉爲與前述-NRjRk基中之Rj 及Rk之碳數1〜8之脂肪族烴基、任意之氫原子經官能基取代之碳數之經取代脂肪族烴基、碳數6~12之芳香族烴基、及任意氫原子經烷基取代之碳數6~ 1 2之經取代芳香族烴基所列舉之基相同之基等。又，化合物（II)亦可爲其共振構造之以下述式（Π-1 )表示之化合物。【化1 2】R. & (Π) -20- 201211125 In the formula (Π), ^ and 妒 are synonymous with (i) of the above formula (I), and Rc each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or any of them. a substituted aliphatic hydrocarbon group having a carbon number of 1 to 8 substituted by a functional group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic having a carbon number of 6 to 12 substituted by an alkyl group; Hydrocarbyl group. An aliphatic hydrocarbon group having a carbon number of 1 to 8 represented by Re in the formula (Π), a substituted aliphatic hydrocarbon group having a carbon number of 1 to 8 substituted with a functional group, and an aromatic hydrocarbon group having 6 to 12 carbon atoms And a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms which are substituted with an alkyl group by any hydrogen atom, and an aliphatic hydrocarbon group having 1 to 8 carbon atoms of Rj and Rk in the above -NRjRk group, and any hydrogen atom The substituted aliphatic hydrocarbon group having a carbon number substituted with a functional group, the aromatic hydrocarbon group having 6 to 12 carbon atoms, and the substituted aromatic hydrocarbon group having an arbitrary alkyl atom substituted with an alkyl group having 6 to 12 carbon atoms are the same Base. Further, the compound (II) may be a compound represented by the following formula (Π-1) which has a resonance structure. [1 2]

至於以前述式（II)表示之化合物可列舉爲下述之（ a-1)〜（a-19)等。再者，下述化合物中，「Ac」表示-C -21 - 201211125 (O ) -CH3。【化1 3】The compound represented by the above formula (II) is exemplified by the following (a-1) to (a-19) and the like. Further, among the following compounds, "Ac" represents -C -21 - 201211125 (O ) -CH3. 【化1 3】

-22- 201211125 【化1 4】-22- 201211125 【化1 4】

-23- 201211125 【化1 5】-23- 201211125 【化1 5】

(曰—19) 該等中’將化合物（a-10)充分溶解於二氯甲烷，且進行使化合物（a-ΙΟ)以〇〇〇〇1重量份之濃度溶解於二氯甲烷中而成之溶液的分光透射率測定（光路長lcm)時，在波長600〜800nm有吸收極大，且將添加化合物（a_1〇) 0.04重量份、JSR股份有限公司製造之環狀烯烴系樹脂「 ARTON G」100重量份以及二氯甲烷所得之樹脂濃度爲20 重量％之溶液澆鑄於平滑玻璃板上，在20°C乾燥8小時後，自玻璃板剝離，接著於減壓下於l〇〇t乾燥8小時獲得之厚度0· 1mm，長度60mm，寬度60mm之基板之分光透射率測定時，在波長43 0~800nm之波長區域中’透射率成爲70% 之吸收極大以下之最長波長’與在波長580nm以上之波長 -24- 201211125 區域中，透射率成爲3 0 %之最短波長之差異之絕對値由於未達55nm，故可製造吸收（透射）波長之入射角依存性小、視角廣的近紅外線截止濾波器因而較佳。本發明中，化合物（I)較好以一般已知方法合成，例如若以特開平1 -22 8 960號公報中所述之方法合成即可。本發明中，化合物（I)之使用量較好以使前述樹脂製基板（I)滿足前述（E)及（F)之方式適當選擇’具體而言，相對於樹脂製基板（〇製造時使用之樹脂1〇〇重量份，較好爲0.01〜10.0重量份，更好爲0.on ·〇重量份，最好爲〇.〇1~5.0重量份。化合物（I)之使用量在前述範圍內時，可獲得吸收波長之入射角依存性小、視角廣、近紅外線截止能、在 4 3 0〜5 8 Onm之範圍內之透射率及強度優異之近紅外線截止濾波器。化合物（I)之使用量多於前述範圍時，亦有可獲得化合物（I )之特性（性質）表現更強之近紅外線截止滬波器之情況，但會有在43〇〜5 80nm之範圍內之透射率比期望値低之虞，或會有樹脂製基板或近紅外線截止濾波器之強度降低之虞’且’化合物（I )之使用量少於前述範圍時，雖有可獲得在43 0〜5 80nm之範圍內之透射率高之近紅外線截止濾波器之情況，但會有不易表現化合物（I )之特性之虞，會有難以獲得吸收波長之入射角依存性小，視角廣之樹脂製基板或近紅外線截止濾波器之情況。 -25- 201211125 〈樹脂〉本發明所使用之樹脂製基板（I)若包含化合物（I) 與樹脂即可，至於該樹脂較好爲透明樹脂。至於該等樹脂只要不損及本發明之效果者即無特別限制，但爲了例如確保熱安定性及成爲薄膜之成形性，且成爲藉由在l〇〇°C以上之蒸鍍溫度下進行高溫蒸鍍而形成介電體多層膜所成之薄膜，列舉爲玻璃轉移溫度（Tg )較好爲1 10〜380°c，更好爲110〜3 70 °C，又更好爲120〜360 °C之樹脂。又，樹脂之玻璃轉移溫度在120°C以上，較好在130°C以上，更好在 1 40 °C以上時，由於可以更高溫蒸鍍形成介電體多層膜而獲得薄膜故而較佳》又，至於前述樹脂，可使用於厚度0.1 mm之全光線透射率較好爲75-94%，更好爲78~94%，最好爲80~94%之樹脂》全光線透射率若在該範爲內，則所得基板顯示作爲光學薄膜之良好透明性。至於該等樹脂之例可列舉爲環狀烯烴系樹脂、聚醚系樹脂、聚芳酯（Polyarylate) (PAR)、聚碾樹脂（PSF) 、聚醚颯樹脂（PES)、聚對伸苯樹脂（PPP)、聚伸芳基醚氧化膦樹脂（PEP0 )、聚醯亞胺樹脂（PPI )、聚醯胺醯亞胺樹脂（PAI )、（改質）丙烯酸系樹脂、聚碳酸酯樹脂（PC)、聚萘二甲酸乙二酯（PEN )及有機-無機奈米混成材料。前述樹脂中，使用透明性高之環狀烯烴系樹脂或芳香族聚醚系樹脂時，在可見光區域之透射率特別高故較佳， -26- 201211125 另外’該等樹脂之吸濕性低，不易產生翹曲故較佳。且，尤其使用原冰片烯系樹脂或芳香族聚醚系樹脂作爲樹脂時’前述化合物（I )對原冰片烯系樹脂之分散性良好’故可獲得光學特性均勻，成形加工性優異之基板。〈環狀烯烴系樹脂〉本發明使用之透明樹脂列舉爲環狀烯烴系樹脂。至於環狀烯烴系樹脂並無特別限制，可使用使由以下述式（χ〇 )表示之單體及以下述式（Yo )表示之單體所組成群組選出之至少一種單體聚合獲得之樹脂’或視需要進一步使前述獲得之樹脂氫化獲得之樹脂。【化1 6】(曰19) In the above, the compound (a-10) was sufficiently dissolved in dichloromethane, and the compound (a-ΙΟ) was dissolved in dichloromethane at a concentration of 1 part by weight of ruthenium. When the spectral transmittance of the solution is measured (the optical path length is 1 cm), the absorption is extremely large at a wavelength of 600 to 800 nm, and the compound (a_1〇) is added in an amount of 0.04 part by weight, and the cyclic olefin resin "ARTON G" manufactured by JSR Co., Ltd. A solution of 100 parts by weight and a resin concentration of 20% by weight of methylene chloride was cast on a smooth glass plate, and after drying at 20 ° C for 8 hours, it was peeled off from the glass plate, followed by drying at 10 ° under reduced pressure. When measuring the spectral transmittance of a substrate having a thickness of 0·1 mm, a length of 60 mm, and a width of 60 mm, the wavelength of 43 0 to 800 nm in the wavelength region of 43 0 to 800 nm is the longest wavelength below the absorption maximum of 70% and the wavelength at 580 nm. In the above-mentioned wavelength -24 - 201211125 region, the absolute difference of the shortest wavelength of the transmittance of 30% is less than 55 nm, so that the near-infrared cutoff with small incident angle dependence and wide viewing angle can be produced for the absorption (transmission) wavelength. filter And preferred. In the present invention, the compound (I) is preferably synthesized by a generally known method, and for example, it can be synthesized by the method described in JP-A No. Hei 1-22 8960. In the present invention, the amount of the compound (I) to be used is preferably selected so that the resin substrate (I) satisfies the above (E) and (F). Specifically, it is used for a resin substrate. The resin is preferably used in an amount of from 0.01 to 10.0 parts by weight, more preferably from 0.01 to 10.0 parts by weight, more preferably from 0.1 to 5% by weight. The compound (I) is used in the above range. In the case of the inside, a near-infrared cut filter having a small incident angle dependence of the absorption wavelength, a wide viewing angle, a near-infrared cutoff energy, and an excellent transmittance and strength in the range of 4 3 0 to 5 8 Onm can be obtained. When the amount used is more than the above range, there is also a case where the near-infrared cut-off wave device having a stronger characteristic (properties) of the compound (I) can be obtained, but there is a transmittance in the range of 43 〇 to 5 80 nm. If the strength of the resin substrate or the near-infrared cut filter is lowered, and the amount of the compound (I) used is less than the above range, it may be obtained at 43 0 to 5 80 nm. Near-infrared cut-off filtering with high transmittance in the range In the case of a device, it may be difficult to express the characteristics of the compound (I), and it may be difficult to obtain a resin substrate or a near-infrared cut filter having a small incident angle dependence of the absorption wavelength and a wide viewing angle. -25- 201211125 <Resin> The resin substrate (I) used in the present invention may contain the compound (I) and the resin, and the resin is preferably a transparent resin. The resin is not particularly harmful as long as the effect of the present invention is not impaired. In order to ensure thermal stability and formability of a film, for example, a film formed by forming a dielectric multilayer film by high-temperature vapor deposition at a vapor deposition temperature of 10 ° C or higher is listed as The glass transition temperature (Tg) is preferably from 1 10 to 380 ° C, more preferably from 110 to 3 70 ° C, and even more preferably from 120 to 360 ° C. Further, the glass transition temperature of the resin is above 120 ° C. Preferably, it is preferably at a temperature of 130 ° C or higher, more preferably at a temperature above 1 40 ° C, since a film can be obtained by forming a dielectric multilayer film at a higher temperature, and preferably, the resin can be used for a thickness of 0.1 mm. The total light transmittance is preferably 7 5-94%, more preferably 78 to 94%, and most preferably 80 to 94% of the resin. If the total light transmittance is within this range, the resulting substrate exhibits good transparency as an optical film. Examples thereof include a cyclic olefin resin, a polyether resin, a polyarylate (PAR), a polyaddition resin (PSF), a polyether oxime resin (PES), and a polyparaphenylene resin (PPP). Poly(aryl ether oxide) phosphine resin (PEP0), polyimide resin (PPI), polyamidimide resin (PAI), (modified) acrylic resin, polycarbonate resin (PC), polynaphthalene Ethylene dicarboxylate (PEN) and organic-inorganic nanocomposite. In the above-mentioned resin, when a cyclic olefin resin or an aromatic polyether resin having high transparency is used, the transmittance in the visible light region is particularly high, and it is preferable that -26-201211125 has a low hygroscopicity of the resins. It is not easy to produce warpage, so it is preferable. In particular, when the original borneol-based resin or the aromatic polyether-based resin is used as the resin, the compound (I) has good dispersibility to the original borneol-based resin. Therefore, a substrate having excellent optical characteristics and excellent moldability can be obtained. <Cyclic olefin resin> The transparent resin used in the present invention is exemplified by a cyclic olefin resin. The cyclic olefin-based resin is not particularly limited, and can be obtained by polymerizing at least one monomer selected from the group consisting of a monomer represented by the following formula (χ〇) and a monomer represented by the following formula (Yo). Resin' or a resin obtained by further hydrogenating the resin obtained as described above. 【化1 6】

(式（Χ〇)中，Rxl~Rx4各獨立表示由下述（Γ)〜（ viii’）選出之原子或基，kx、mx及px各獨立表示〇或正整數 )， (i ’）氫原子， (ii ’）鹵素原子， (iii’）三院基砂院基， (iv’）具有含有氧原子、硫原子、氮原子或砂原子之 -27- 201211125 連結基之經取代或未經取代之碳數1〜30之烴基’ (ν’）經取代或未經取代之碳數1〜30之烴基’ (vi’）極性基（但，（iv’）除外） (vii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之亞烷基，且未參與該鍵結之Rxl〜Rx4各獨立表示自前述（i’）~ (vi’）選出之原子或基， (viii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之單環或多環之烴環或雜環，且未參與該鍵結之Rxl〜Rx4各獨立表示自前述（i’）~(vi’）選出之原子或基，Rx2與Rx3表示相互鍵結形成之單環烴環或雜環，且未參與該鍵結之 Rxl〜Rx4各獨立表示自前述（i，）~(vi’）選出之原子或基【化1 7】(In the formula (Χ〇), Rxl~Rx4 each independently represent an atom or a group selected by (下述)~( viii'), kx, mx and px each independently represent a 〇 or a positive integer), (i ') hydrogen Atom, (ii ') halogen atom, (iii') a three-yard base, (iv') substituted or not containing a -27-201211125 linker containing an oxygen atom, a sulfur atom, a nitrogen atom or a sand atom Substituted hydrocarbon group of 1 to 30 carbon atoms '(ν') substituted or unsubstituted hydrocarbon group 1 to 30' (vi') polar group (except (iv')) (vii') Rxl and Rx2 or Rx3 and Rx4 represent an alkylene group formed by bonding to each other, and Rx1 to Rx4 not participating in the bonding each independently represent an atom or a group selected from the above (i') to (vi'), (viii') Rxl And Rx2 or Rx3 and Rx4 represent a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring which are bonded to each other, and Rx1 to Rx4 which are not involved in the bonding are independently represented from the above (i') to (vi'). An atom or a group, Rx2 and Rx3 represent a monocyclic hydrocarbon ring or a heterocyclic ring formed by mutual bonding, and Rx1 to Rx4 which are not involved in the bonding are independently selected from the above (i,) to (vi'). Atom or base

(丫 0) (式（Y〇)中’ Ryl及RW各獨立表示由前述（i，）〜（ vi’）選出之原子或基’或表示下述（ix，），ky&py各獨立表示0或正整數）， (ix’）RW與RP表示相互鍵結形成之單環或多環之脂環式烴、芳香族烴或雜環。前述（ii’）鹵素原子列舉爲氟原子、氯原子及溴原子 -28- 201211125 前述（iii’）三烷基矽烷基列舉爲碳數1〜12之三烷基矽烷基等，較好爲碳數1~6之三烷基矽烷基。該三烷基矽烷基列舉爲三甲基矽烷基、三乙基矽烷基及三異丙基矽烷基等。前述含有氧原子、硫原子、氮原子及矽原子之連結基列舉爲羰基（-CO-)、氧羰基（-OCO-)、羰氧基（-COO-)、磺醯基（-S02-)、醚鍵（-0-)、硫醚鍵（-S-)、亞胺基（-NH-)、醯胺鍵（-NHCO-、-CONH-)及矽氧烷鍵（-OSi(R) 2-(式中，R爲甲基、乙基等烷基））等，前述（W’）之經取代或未經取代之碳數1〜30之烴基亦可爲含複數個該等連結基之基。該等中就與近紅外線反射膜之接著性或密著性優異方面，化合物（I)之分散性或溶解性方面而言，較好爲羰氧基（*-COO-)及矽氧烷鍵（-OSi(R) 2-)。但*爲鍵結於式（X〇)之環者。前述經取代或未經取代之碳數1〜3 0之烴基較好爲經取代或未經取代之碳數1〜1 5之烴基，列舉爲例如甲基、乙基及丙基等烷基；環戊基及環己基等之環烷基；苯基、聯苯基、苯乙基等芳香族烴基；乙烯基、烯丙基及丙烯基等之烯基等。該等基中，就耐熱安定性方面而言較好爲甲基及乙基。取代基列舉爲羥基、鹵素原子等。至於前述（vi ’）極性基列舉爲例如羥基；甲氧基及乙 -29- 201211125 氧基等碳數1~10之烷氧基；乙醯氧基、丙醯氧基及苯甲醯基氧基等之羰氧基；氰基：胺基；醯基：磺基；羧基等。另外，Rxl與Rx2或Rx3與Rx4相互鍵結形成之亞烷基列舉爲亞甲基、亞乙基、亞丙基等。(丫0) (In the formula (Y〇), 'Ryl and RW each independently represent an atom or a group selected by the above (i,) to (vi') or represent the following (ix,), ky&py independent representations 0 or a positive integer), (ix') RW and RP represent a monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring which are bonded to each other. The above (ii') halogen atom is exemplified by a fluorine atom, a chlorine atom and a bromine atom. -28 - 201211125 The above (iii') trialkylsulfonylalkyl group is exemplified by a trialkylsulfonyl group having 1 to 12 carbon atoms, preferably carbon. A number of 1 to 6 trialkylsulfonyl groups. The trialkylsulfonium alkyl group is exemplified by a trimethyldecyl group, a triethyldecyl group, a triisopropyldecane group or the like. The linking group containing an oxygen atom, a sulfur atom, a nitrogen atom and a ruthenium atom is exemplified by a carbonyl group (-CO-), an oxycarbonyl group (-OCO-), a carbonyloxy group (-COO-), or a sulfonyl group (-S02-). , ether bond (-0-), thioether bond (-S-), imido group (-NH-), guanamine bond (-NHCO-, -CONH-) and decane bond (-OSi(R) 2-(wherein, R is an alkyl group such as a methyl group or an ethyl group) or the like, and the substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms of the above (W') may be a plurality of such linking groups. The basis. Among these, in terms of excellent adhesion or adhesion to the near-infrared reflective film, the dispersibility or solubility of the compound (I) is preferably a carbonyloxy group (*-COO-) and a decane bond. (-OSi(R) 2-). However, * is a ring that is bonded to the formula (X〇). 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, and is exemplified by an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aromatic hydrocarbon group such as a phenyl group, a biphenyl group or a phenethyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; and the like. Among these groups, a methyl group and an ethyl group are preferred in terms of heat stability. The substituent is exemplified by a hydroxyl group, a halogen atom or the like. The above (vi ') polar group is exemplified by, for example, a hydroxyl group; a methoxy group having a carbon number of from 1 to 10 such as a methoxy group and an ethyl group of -29-201211125; an ethoxy group, a propenoxy group, and a benzhydryl group. A carbonyloxy group such as a carbonyl group; a cyano group: an amine group; a fluorenyl group: a sulfo group; a carboxyl group; Further, the alkylene group formed by bonding Rx1 and Rx2 or Rx3 and Rx4 to each other is a methylene group, an ethylene group, a propylene group or the like.

Rxl與Rx2或Rx3與Rx4相互鍵結形成之單環或多環烴環或雜環，rx2與rx3相互鍵結形成之單環烴環或雜環，RW與 Ry2相互鍵結形成之單環或多環之之環式烴、芳香族烴或雜環列舉爲伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸環丁烯基、伸環戊烯基、伸環己烯基、伸苯基、伸萘基等。 kx、mx、px、ky、py較好各獨立爲0〜3之整數。又，較好kx + mx + px爲0〜4之整數，更好爲kx + mx + px爲0〜2之整數，最好kx + mx + px爲1。ky + py較好爲0~4之整數、ky + py更好爲〇〜2之整數。使用mx爲0，kx + px爲1之環狀烯烴系單體時，可獲得玻璃轉移溫度高，且機械強度優異之樹脂故而較佳〇以前述式（X〇)或（Y〇)表示之環狀烯烴系單體之具體例例示爲例如以下所示之化合物，但並不限於該等例示者。 •雙環〔2.2.1〕庚-2-烯（原冰片烯） • 5-甲基-雙環〔2.2.1〕庚-2-烯 • 5-乙基-雙環〔2.2.1〕庚-2-烯 • 5-丙基雙環〔2.2.1〕庚-2-烯 • 5-丁基雙環〔2.2.1〕庚-2-烯 -30- 201211125 • 5_第三丁基雙環〔2.2.1〕庚-2-烯 • 5-異丁基雙環〔2.2.1〕庚-2-烯 • 5-戊基雙環〔2.2.1〕庚-2-烯 • 5-己基雙環〔2.2.1〕庚-2-烯 • 5-庚基雙環〔2.2.1〕庚-2-烯 • 5-辛基雙環〔2.2·1〕庚-2-烯 • 5-癸基雙環〔2.2.1〕庚-2-烯 • 5-十二烷基雙環〔2.2.1〕庚-2-烯 .5-環己基-雙環〔2.2.1〕庚-2-烯 • 5-苯基-雙環〔2.2.1〕庚-2-烯 • 5- ( 4-聯苯基）-雙環〔2.2.1〕庚-2-烯 •5-甲氧基羰基-雙環〔2.2.1〕庚-2-烯 •5-苯氧基羰基-雙環〔2.2.1〕庚-2-烯 •5-苯氧基乙基羰基-雙環〔2.2.1〕庚-2-烯 •5-苯基羰氧基-雙環〔2.2.1〕庚-2-烯 .5-甲基-5-甲氧羰基-雙環〔2.2.1〕庚-2-烯 •5-甲基-5-苯氧基羰基-雙環〔2.2.1〕庚-2-烯 •5-甲基-5·苯氧基乙基羰基-雙環〔2.2.1〕庚-2-烯 • 5-乙烯基-雙環〔2.2.1〕庚-2-烯 • 5-亞乙基-雙環〔2.2.1〕庚-2-烯 •5-三甲氧基矽烷基·雙環〔2.2.1〕庚-2-烯 •5-三乙氧基矽烷基-雙環〔2.2.1〕庚-2-烯 ·5,5-二甲基-雙環〔2.2.1〕庚-2-烯 • 5,6-二甲基-雙環〔2.2.1〕庚-2-烯 -31 - 201211125 • 5-氟-雙環〔2.2.1〕庚-2-烯 • 5-氯-雙環〔2.2.1〕庚-2-烯 • 5-溴-雙環〔2.2.1〕庚-2-烯 • 5,6-二氟-雙環〔2.2. 1〕庚-2-烯 • 5,6-二氯-雙環〔2.2.1〕庚-2-烯 • 5,6-二溴-雙環〔2.2. 1〕庚-2-烯 • 5-羥基·雙環〔2.2.1〕庚-2-烯 • 5-羥基乙基·雙環〔2.2.1〕庚-2-烯 • 5-氰基-雙環〔2.2.1〕庚-2-烯 • 5-胺基-雙環〔2.2.1〕庚-2-烯 •三環〔4.3.0.I2,5〕癸-3-烯 •三環〔4.4.0.12’5〕十一碳-3-烯 • 7-甲基-三環〔4.3.0.12’5〕癸-3-烯 .7-乙基-三環〔4.3.0.12’5〕癸-3-烯 •7-環己基-三環〔4.3.0.12’5〕癸-3-烯 •7-苯基-三環〔4.3.0.12’5〕癸-3-烯 • 7-(4-聯苯基）-三環〔4.3.0.I2’5〕癸-3-烯 •7,8-二甲基-三環〔4.3.0.12’5〕癸-3-烯 •7,8,9-三甲基-三環〔4.3.0.12’5〕癸-3-烯 •8-甲基-三環〔4.4.0.I2’5〕十一碳-3-烯 •8-苯基-三環〔4.4.0.I2’5〕十一碳-3-烯 .7-氟-三環〔4.3.0.I2,5〕癸-3-烯 • 7-氯-三環〔4.3.0.12’5〕癸-3-烯 • 7-溴-三環〔4.3.0.I2’5〕癸-3-烯 -32- 201211125 •7,8-二氯-三環〔4.3.0.I2,5〕癸-3-烯 •7,8,9-三氯-三環〔4.3.0.12,5〕癸-3-烯 •7-氯甲基-三環〔4.3.0.I2,5〕癸-3-烯 •7-二氯甲基-三環〔4.3.0.12,5〕癸-3-烯 •7-三氯甲基-三環〔4.3.0.12’5〕癸-3-烯 •7-羥基-三環〔4.3.0.12’5〕癸-3-烯 • 7-氰基-三環〔4.3.0.I2’5〕癸-3-烯 • 7-胺基-三環〔4.3.0.12’5〕癸-3-烯 •四環〔4.4.0.12’5.17，1()〕十二碳-3-烯 •五環〔7.4·0.12’5·18’"·07’12〕十五碳-3-烯 •8-甲基-四環〔4.4.0.12’5.17，1()〕十二碳-3-烯 • 8 -乙基-四環〔4 _ 4 · 0.1 2 ’5 · 1 7 ’1 G〕十二碳-3 -烯 •8-環己基-四環〔4.4.0.12’5.17’1()〕十二碳-3-烯 •8-苯基-四環〔4.4.0.12’5.17’1Q〕十二碳-3-烯 •8-(4-聯苯基）-四環〔4.4.0.12,5.17’1()〕十二碳-3- 烯 •8-甲氧羰基-四環〔4.4.0.I2’5.17’1Q〕十二碳-3-烯 •8-苯氧羰基-四環〔4.4.0.12’5.17’1()〕十二碳-3-烯 •8-苯氧基乙基羰基-四環〔4.4.0.12’5.17’1()〕十二碳- 3-烯 •8-苯基羰氧基-四環〔4.4.0.12’5.17’1()〕十二碳-3-烯 • 8_甲基·8_甲氧基羰基-四環〔4.4.0.12’5.17’1()〕十二碳-3 -稀 •8-甲基-8-苯氧基羰基-四環〔4.4.0.I2’5.17’1Q〕十二 -33- 201211125 碳-3-烯 •8-甲基-8-苯氧基乙基羰基·四環〔4.4·〇·12,5.17’1()〕十二碳-3-烯 • 8 -乙烯基-四環〔4.4 · 0 · 12 ’5. 1 7 ’1G〕十二碳-3 -嫌 • 8 -亞乙基-四環〔4 · 4 · 0 · 1 2 ’5 · 17 ’1 〇〕十二碳-3 -嫌 • 8，8 -二甲基-四環〔4 ·4.0.12 ’5 · 1 7，丨〇〕十二碳· 3 -烯 • 8，9 -二甲基-四環〔4 ·4.0.12 ’5. 1 7，1 〇〕十二碳-3 -烯 • 8 -氟-四環〔4 · 4 · 0.12 ’5 · 1 7 ’1Q〕十二碳-3 ·嫌 • 8 -氯-四環〔4.4 · 0 · 1 2 ’5 · 1 7 ’1G〕十二碳-3 -嫌 •8-溴四環〔4.4.0.12’5.17’1()〕十二碳-3-烯 • 8，8 -二氯·四環〔4 · 4 · 0 · 12 ’5 · 1 7 ’1Q〕十二碳-3 -烯 • 8，9 -二氯-四環〔4 · 4 · 0.1 2，5.17，丨 G〕十二碳-3 -烯 • 8，8，9，9 -四氯-四環〔4.4.0.1 2 ’5.17 ’1 〇〕十二碳· 3 -嫌 •8-羥基-四環〔4.4.0_12,5.丨7，1。〕十二碳-3-烯 .8 -羥基乙基-四環〔4 · 4 · 0.12 ’5.17 ’1 G〕十二碳-3 -烯 • 8·甲基-8-羥基乙基-四環〔4.4.0.12’5.17’|()〕十二碳- 3-烯 •8-氰基-四環〔4.4.0.12,5.17’1()〕十二碳-3-烯 •8-胺基-四環〔4.4·0·12’5·17’1()〕十二碳-3-烯再者，該等環狀烯烴系單體可單獨使用一種，亦可倂用兩種以上· 本發明使用之環狀烯烴系單體之種類及量係依據所得樹脂所要求之特性適當選擇》該等中，使用具有其分子內含有至少一個由氧原子、 -34- 201211125 硫原子、氮原子及矽原子選出之至少一種原子之構造（以下稱爲「極性構造」）之化合物時，有化合物（I)之分散性優異’且與其他材料（近紅外線反射膜等）之接著性或密著性優異等之優點。尤其，使前述式（XQ)中，Rxl 及Rx3各獨立爲氫原子或碳數1〜3之烴基，較好爲氫原子或甲基，且，Rx2或Rx4之任一者爲具有極性構造之基，其餘爲氫原子或碳數1〜3之烴基之化合物聚合而成之樹脂較好爲吸水（濕）性低。另外，使Ryl或Ry2之任一者爲具有極性構造之基，其他爲氫原子或碳數1〜3之烴基之化合物聚合而成之樹脂，較好吸水（濕）性低。再者，具有前述極性構造之基爲以下述式（ZG)表示之基的環狀烯烴系單體由於所得樹脂之耐熱性與吸水（濕）性之均衡變得容易故可較好地使用。 -(CH2 ) zCOOR ... ( Z〇 ) (式（Z〇 )中，R表示經取代或未經取代之碳原子數 1~15之烴基，z表示0或卜10之整數）。前述式（Zo )中，Z之値愈小則所得之氫化物之玻璃轉移溫度愈高，耐熱性愈優異’故Z較好爲0或1〜3之整數，另外，z爲0之單體就其合成上容易之觀點而言較佳。又，前述式（ZQ )中之R之碳數愈多則有所得聚合物之氫化物之吸水（濕）性下降之傾向，但亦會有玻璃轉移溫度阵低之傾向，故就保持耐熱性之觀點而言’較好爲碳數1〜10 之烴基1最好爲碳數1〜6之烴基。又，前述式（X〇)中，以前述式（Ζ〇)表示之基所鍵 -35- 201211125 結之碳原子上若鍵結碳數1〜3之烷基，尤其是甲基時，有成爲耐熱性與吸水（濕）性之均衡性良好之化合物之傾向故而較佳》另外，前述式（X〇)中，mx爲0，且kx + px爲1 之化合物反應性高，可以高收率獲得聚合物，另外，由於獲得耐熱性高之聚合物氫化物，而且工業上容易取得故可較好地使用。前述環狀烯烴系樹脂亦可爲在不損及本發明效果之範圍內，使前述環狀烯烴系單體與可與該單體共聚合之單體共聚合而成之聚合物。該等可共聚合之單體可列舉爲例如環丁烯、環戊烯、環庚烯、環辛烯、環十二碳烯等環狀烯烴，或1,4-環辛二烯、二環戊二烯、環十二碳三烯等非共軛環狀多烯。該等可共聚合之單體可單獨使用一種亦可倂用兩種以上。前述環狀烯烴系單體之聚合方法只要可使單體聚合即無特別限制，例如可藉由開環聚合、或者加成聚合進行聚合。利用前述開環聚合反應獲得之聚合物於其分子中具有烯烴性不飽和鍵。另外，即使在前述加成聚合反應中，仍有聚合物於其分子中具有烯烴性不飽和鍵之情況。據此，聚合物分子中存在烯烴性不飽和鍵時，相關之烯烴性不飽和鍵會有成爲經時變色或膠凝化等劣化原因之情況，故較好進行將該烯烴性不飽和鍵轉化成飽和鍵之氫化反應。氫化反應可利用慣用方法，亦即於具有烯烴性不飽和 -36- 201211125 鍵之聚合物溶液中添加已知之氫化觸媒，使常壓〜3 00大氣壓，較好3〜200大氣壓之氫氣在0〜200°C，較好20〜180°C下對該等作用而進行。氫化聚合物之氫化率以500MHz、1H-NMR測定之對烯烴性不飽和鍵所加成之氫的比例通常爲50%以.上，較好爲 70%以上，更好爲90%以上，最好爲98%以上，又最好爲 99%以上。氫化率愈高，則成爲對熱或光之安定性優異者，可成爲可維持長期安定特性之樹脂製基板故而較佳。〈芳香族聚醚系樹脂〉本發明所用之透明樹脂列舉爲芳香族聚醚系樹脂。至於芳香族聚醚系樹脂並無特別限制，較好爲例如具有以下述式（1)表示之構造單位（以下亦稱爲「構造單位（1) 」）及以下述式（2)表示之構造單位（以下亦稱爲「構造單位（2 )」）所組成群組選出之至少一種構造單位（以下亦稱爲「構造單位（1 -2 )」之樹脂（以下亦稱爲「樹脂（1)」）。由該樹脂獲得之基板具有優異之耐熱性且力學強度優異’而且透明性及表面平滑性優異。【化18】a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding Rx1 and Rx2 or Rx3 and Rx4 to each other, a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding rx2 and rx3 to each other, and a single ring formed by bonding RW and Ry2 or The cyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring of the polycyclic ring is exemplified by a stretching cyclopropyl group, a cyclopentene butyl group, a cyclopentylene group, a cyclohexylene group, a cycloheptyl group, a cyclobutene group, a cyclopentene group. Base, cyclohexene, phenyl, naphthyl and the like. Preferably, kx, mx, px, ky, and py are each independently an integer of 0 to 3. Further, preferably kx + mx + px is an integer of 0 to 4, more preferably kx + mx + px is an integer of 0 to 2, and preferably kx + mx + px is 1. Ky + py is preferably an integer of 0 to 4, and ky + py is preferably an integer of 〇~2. When a cyclic olefin monomer having mx of 0 and kx + px of 1 is used, a resin having a high glass transition temperature and excellent mechanical strength can be obtained, and it is preferably represented by the above formula (X〇) or (Y〇). Specific examples of the cyclic olefin-based monomer are, for example, the compounds shown below, but are not limited to those exemplified. • Bicyclo [2.2.1] hept-2-ene (formylene) • 5-methyl-bicyclo [2.2.1] hept-2-ene • 5-ethyl-bicyclo [2.2.1] hept-2- Alkene 5-propylbicyclo[2.2.1]hept-2-ene• 5-butylbicyclo[2.2.1]hept-2-ene-30- 201211125 • 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]heptane- 2-ene • 5-heptylbicyclo[2.2.1]hept-2-ene • 5-octylbicyclo[2.2·1]hept-2-ene • 5-decylbicyclo[2.2.1]heptan-2- Alkene 5-dodecylbicyclo[2.2.1]hept-2-ene.5-cyclohexyl-bicyclo[2.2.1]hept-2-ene• 5-phenyl-bicyclo[2.2.1]heptane- 2-ene• 5-(4-biphenyl)-bicyclo[2.2.1]hept-2-ene•5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene•5-phenoxy Carbonyl-bicyclo[2.2.1]hept-2-ene•5-phenoxyethylcarbonyl-bicyclo[2.2.1]hept-2-ene•5-phenylcarbonyloxy-bicyclo[2.2.1]g 2-ene.5-Methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene•5-methyl-5-phenoxycarbonyl-bicyclo[2.2.1]heptan-2- Alkene 5-methyl-5 Phenoxyethylcarbonyl-bicyclo[2.2.1]hept-2-ene•5-vinyl-bicyclo[2.2.1]hept-2-ene• 5-ethylene-bicyclo[2.2.1]g -2-ene•5-trimethoxydecyl-bicyclo[2.2.1]hept-2-ene•5-triethoxydecyl-bicyclo[2.2.1]hept-2-ene·5,5- Dimethyl-bicyclo[2.2.1]hept-2-ene•5,6-dimethyl-bicyclo[2.2.1]hept-2-ene-31 - 201211125 • 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]hept-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]hept-2-ene• 5-amino group -bicyclo[2.2.1]hept-2-ene•tricyclo[4.3.0.I2,5]non-3-ene•tricyclo[4.4.0.12'5]undec-3-ene•7-A Base-tricyclo[4.3.0.12'5]non-3-ene.7-ethyl-tricyclo[4.3.0.12'5]non-3-ene•7-cyclohexyl-tricyclo[4.3.0.12'5 〕癸-3-ene • 7-phenyl-tricyclo[4.3. 0.12'5] indol-3-ene • 7-(4-biphenylyl)-tricyclo[4.3.0.I2'5]non-3-ene•7,8-dimethyl-tricyclo[4.3. 0.12'5]non-3-ene•7,8,9-trimethyl-tricyclo[4.3.0.12'5]non-3-ene•8-methyl-tricyclo[4.4.0.I2'5 ]undec-3-ene•8-phenyl-tricyclo[4.4.0.I2'5]undec-3-ene.7-fluoro-tricyclo[4.3.0.I2,5]癸- 3-ene • 7-chloro-tricyclo[4.3.0.12'5]non-3-ene • 7-bromo-tricyclo[4.3.0.I2'5]indole-3-ene-32- 201211125 •7, 8-Dichloro-tricyclo[4.3.0.I2,5]non-3-ene•7,8,9-trichloro-tricyclo[4.3.0.12,5]indole-3-ene•7-chloromethyl Base-tricyclo[4.3.0.I2,5]non-3-ene•7-dichloromethyl-tricyclo[4.3.0.12,5]non-3-ene•7-trichloromethyl-tricyclic [4.3.0.12'5] indole-3-ene•7-hydroxy-tricyclo[4.3.0.12'5]non-3-ene • 7-cyano-tricyclo[4.3.0.I2'5]癸- 3-ene•7-Amino-tricyclo[4.3.0.12'5]non-3-ene•tetracyclo[4.4.0.12'5.17,1()]dodec-3-ene•pentacyclic [7.4· 0.12'5·18'"·07'12]15-carbon-3-ene•8-methyl-tetracyclo[4.4.0.12'5.17,1()]dodec-3-ene•8-B -tetracyclo[4 _ 4 · 0.1 2 '5 · 1 7 '1 G] dodecyl-3-ene-8-cyclohexyl-tetracyclo[4.4.0.12'5.17'1()] dodeca-3 -ene•8-phenyl-tetracyclo[4.4.0.12'5.17'1Q]dodec-3-ene•8-(4-biphenyl)-tetracyclo[4.4.0.12, 5.17'1()] Dodecyl-3-ene•8-methoxycarbonyl-tetracyclo[4.4.0.I2'5.17'1Q]dodec-3-ene•8-phenoxycarbonyl-tetracyclo[4.4.0.12'5.17' 1()]dodec-3-ene-8-phenoxyethylcarbonyl-tetracyclo[4.4.0.12'5.17'1()]dodecyl-3-ene-8-phenylcarbonyloxy- Tetracycline [4.4.0.12'5.17'1()]dodec-3-ene•8-methyl·8-methoxycarbonyl-tetracyclo[4.4.0.12'5.17'1()]12-carbon- 3--Lessed 8-methyl-8-phenoxycarbonyl-tetracyclo[4.4.0.I2'5.17'1Q]12-33-201211125 Carbon-3-ene•8-methyl-8-phenoxy Ethyl ethyl carbonyl tetracycline [4.4·〇·12,5.17'1()] dodeca-3-ene•8-vinyl-tetracyclo[4.4 · 0 · 12 '5. 1 7 '1G] Dicarbon-3 - sulphate • 8 -ethylidene-tetracycline [4 · 4 · 0 · 1 2 '5 · 17 '1 〇] 12 carbon-3 - suspicion • 8,8-dimethyl-tetracyclic [4 · 4. 0.12 '5 · 1 7,丨〇]dodecyl·3 -ene • 8,9-dimethyl-tetracyclo[4 ·4.0.12 '5. 1 7,1 〇]dodecane-3-ene • 8 -Fluoro-tetracycline [4 · 4 · 0.12 '5 · 1 7 '1Q] 12 carbon-3 · Suspected • 8-Chloro-tetracyclic [4.4 · 0 · 1 2 '5 · 1 7 '1G] Twelve carbon-3 - succinct 8-octane bromide [4.4.0.12'5.17'1()] dodeca-3-ene • 8,8-dichlorotetracycline [4 · 4 · 0 · 12 ' 5 · 1 7 '1Q]Dodecyl-3 -ene • 8,9-Dichloro-tetracyclo[4 · 4 · 0.1 2, 5.17, 丨G] Dodeca-3 - ene • 8,8,9 , 9-tetrachloro-tetracyclo[4.4.0.1 2 '5.17 '1 〇] 12 carbon · 3 - sin • 8-hydroxy-tetracyclic [4.4.0_12, 5. 丨 7,1. ]Dodecyl-3-ene.8-hydroxyethyl-tetracyclo[4 · 4 · 0.12 '5.17 '1 G]dodecano-3 -ene • 8·methyl-8-hydroxyethyl-tetracyclic [4.4.0.12'5.17'|()] Dodecyl-3-ene-8-cyano-tetracyclo[4.4.0.12, 5.17'1()]dodec-3-ene•8-amino- Tetracycline [4.4·0·12'5·17'1()] dodec-3-ene Further, these cyclic olefin monomers may be used singly or in combination of two or more. The type and amount of the cyclic olefin monomer to be used are appropriately selected depending on the properties required for the obtained resin. The use thereof has at least one oxygen atom, -34-201211125 sulfur atom, nitrogen atom and ruthenium in the molecule. When the compound of at least one atom selected from the atom (hereinafter referred to as "polar structure") is excellent in the dispersibility of the compound (I), it is excellent in adhesion or adhesion to other materials (such as a near-infrared reflective film). The advantages of etc. In particular, in the above formula (XQ), Rx1 and Rx3 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 any of Rx2 or Rx4 has a polar structure. The resin obtained by polymerizing a compound having a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferably low in water absorption (wet). Further, a resin obtained by polymerizing a compound having a polar structure or a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, which is one of Ryl or Ry2, preferably has low water absorption (wet) property. Further, the cyclic olefin-based monomer having the above-mentioned polar structure is a group represented by the following formula (ZG). Since the balance between heat resistance and water absorption (wet) of the obtained resin is easy, it can be preferably used. -(CH2) zCOOR ... (Z〇) (In the formula (Z〇), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents an integer of 0 or 10). In the above formula (Zo), the smaller the Z is, the higher the glass transition temperature of the obtained hydride is, and the more excellent the heat resistance is, so Z is preferably an integer of 0 or 1 to 3, and the monomer having z is 0. It is preferable from the viewpoint of its ease of synthesis. Further, as the carbon number of R in the above formula (ZQ) increases, the water absorption (wet) property of the hydride of the obtained polymer tends to decrease, but the glass transition temperature array tends to be low, so that heat resistance is maintained. In view of the above, the hydrocarbon group 1 preferably having a carbon number of 1 to 10 is preferably a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (X〇), when the carbon atom having a carbon number of 1 to 3 is bonded to a carbon atom of the group represented by the above formula (Ζ〇), if it is a methyl group, Further, in the above formula (X〇), a compound having a mx of 0 and a kx + px of 1 is highly reactive, and can be increased in height, and it is preferable to have a tendency to be a compound having a good balance between heat resistance and water absorption (wet). The polymer is obtained at a rate, and since a polymer hydride having high heat resistance is obtained, and it is industrially easy to obtain, it can be preferably used. The cyclic olefin-based resin may be a polymer obtained by copolymerizing the cyclic olefin-based monomer and a monomer copolymerizable with the monomer, without impairing the effects of the present invention. The monomer which can be copolymerized may, for example, be a cyclic olefin such as cyclobutene, cyclopentene, cycloheptene, cyclooctene or cyclododecene, or 1,4-cyclooctadiene or bicyclodene. A non-conjugated cyclic polyene such as pentadiene or cyclododecatriene. These copolymerizable monomers may be used singly or in combination of two or more. The method for polymerizing the above cyclic olefin monomer is not particularly limited as long as it can polymerize the monomer, and for example, it can be polymerized by ring-opening polymerization or addition polymerization. The polymer obtained by the aforementioned ring-opening polymerization has an olefinic unsaturated bond in its molecule. Further, even in the above-mentioned addition polymerization reaction, there are cases where the polymer has an olefinic unsaturated bond in its molecule. Accordingly, when an olefinic unsaturated bond is present in the polymer molecule, the related olefinic unsaturated bond may be a cause of deterioration such as discoloration or gelation over time, so that the conversion of the olefinic unsaturated bond is preferably carried out. Hydrogenation reaction to a saturated bond. The hydrogenation reaction can be carried out by a conventional method, that is, adding a known hydrogenation catalyst to a polymer solution having an olefinic unsaturated-36-201211125 bond, and a hydrogen gas at a normal pressure of 3,000 to 300 atmospheres, preferably 3 to 200 atmospheres. It is carried out at a temperature of from -200 ° C, preferably from 20 to 180 ° C. The hydrogenation ratio of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, as measured by 500 MHz and 1 H-NMR. Good is 98% or more, and preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat or light, and it is preferable to be a resin substrate which can maintain long-term stability characteristics. <Aromatic Polyether Resin> The transparent resin used in the present invention is exemplified by an aromatic polyether resin. The aromatic polyether-based resin is not particularly limited, and is preferably a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)") and a structure represented by the following formula (2). Resin (hereinafter also referred to as "structural unit (1 -2)" resin (hereinafter also referred to as "resin (1)" selected from the group consisting of units (hereinafter also referred to as "structural unit (2)") The substrate obtained from the resin has excellent heat resistance and excellent mechanical strength, and is excellent in transparency and surface smoothness.

-37- 201211125 前述式（1)中，R1〜R4各獨立表示碳數ι~12之—價有機基。a〜d各獨立表示〇〜4之整數，較好爲0或1。碳數1〜12之一價有機基可列舉爲碳數1〜12之一價烴基、及含有由氧原子及氮原子組成之群組選出之至少一種原子之碳數1〜12之一價有機基等。碳數1~12之一價烴基列舉爲碳數12之直鏈狀或分支狀烴基、碳數之脂環式烴基及碳數6〜12之芳香族烴基等。前述碳數1〜12之直鏈狀或分支鏈烴基較好爲碳數1〜8 之直鏈或分支鏈之烴基，更好爲碳數1〜5之直鏈或分支鏈之烴基。前述直鏈或分支鏈之烴基之較佳具體例列舉爲甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基及正庚基等。前述碳數3〜12之脂環式烴基較好爲碳數3~8之脂環式烴基，更好爲碳數3或4之脂環式烴基。碳數3〜12之脂環式烴基之較佳具體例列舉爲環丙基、環丁基、環戊基及環己基等環烷基；環丁烯基、環戊烯基及環己烯基等之環烯基。該脂環式烴基之鍵結部位亦可爲脂環上之任一個碳。前述碳數6〜12之芳香族烴基列舉爲苯基、聯苯基及萘基等。該芳香族烴基之鍵結部位亦可爲芳香族環上之任一個碳。含氧原子之碳數1〜12之有機基列舉爲由氫原子、碳原 -38- 201211125 子及氧原子組成之有機基，其中可列舉較好爲由醚鍵、羰基或酯鍵與烴基所組成之總碳數1〜12之有機基等。具有酯鍵之總碳數1〜12之有機基可列舉爲碳數1〜12之烷氧基、碳數2〜12之烯氧基、碳數2〜12之炔氧基、碳數 6~1 2之芳氧基及碳數1〜12之烷氧基烷基等。具體而言，列舉爲甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、苯氧基、丙烯氧基、環己氧基及甲氧基甲基等。另外，具有羰基之總碳數1~12之有機基可列舉爲碳數 2〜12之醯基等。具體而言，列舉爲乙醯基、丙醯基、異丙醯基及苯甲醯基等。具有酯鍵之總碳數1~12之有機基列舉爲碳數2〜12之醯氧基等。具體而言，列舉爲乙醯氧基、丙醯氧基、異丙醯氧基及異丁醯氧基等。含氮原子之碳數1〜12之有機基列舉爲由氫原子、碳原子及氮原子所組成之有機基。具體而言列舉爲氰基、咪唑基、***基、苯并咪唑基及苯并***基等。含有氧原子及氮原子之碳數1~12之有機基列舉爲由氫原子、碳原子、氧原子及氮原子所組成之有機基，具體而言列舉爲噁唑基、噁二唑基、苯并噁唑基及苯并噁二唑基等。前述式（1 )中之R1〜R4就樹脂（1 )之吸水（濕）性之觀點而言較好爲碳數1〜1 2之一價烴基，更好爲碳數6〜1 2 之芳香族烴基，又更好爲苯基。 -39- 201211125 【化1 9】-37- 201211125 In the above formula (1), R1 to R4 each independently represent a carbon number of ι to 12, and a valence organic group. a to d each independently represent an integer of 〇4, preferably 0 or 1. The one-valent organic group having 1 to 12 carbon atoms may be exemplified by a hydrocarbon group having 1 to 12 carbon atoms and a carbon number of 1 to 12 selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. Base. The one-valent hydrocarbon group having 1 to 12 carbon atoms is exemplified by a linear or branched hydrocarbon group having 12 carbon atoms, an alicyclic hydrocarbon group having a carbon number, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. 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, more preferably a linear or branched hydrocarbon group having 1 to 5 carbon atoms. Preferred specific examples of the straight or branched hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl and Positive heptyl and so on. The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms. Preferred specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms are exemplified by cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group; A cycloalkenyl group. The bonding site of the alicyclic hydrocarbon group may also be any carbon on the alicyclic ring. The aromatic hydrocarbon group having 6 to 12 carbon atoms is exemplified by a phenyl group, a biphenyl group, a naphthyl group and the like. The bonding site of the aromatic hydrocarbon group may also be any carbon on the aromatic ring. The organic group having 1 to 12 carbon atoms of the oxygen atom is exemplified by an organic group consisting of a hydrogen atom, a carbonogen-38-201211125 and an oxygen atom, and preferably an ether bond, a carbonyl group or an ester bond and a hydrocarbon group are used. An organic group having a total carbon number of 1 to 12, and the like. The organic group having a total carbon number of 1 to 12 having an ester bond may, for example, be an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, or a carbon number of 6~. An aryloxy group of 1 2 and an alkoxyalkyl group having 1 to 12 carbon atoms. Specifically, it is methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, propyleneoxy, cyclohexyloxy and methoxymethyl. Further, the organic group having a total carbon number of 1 to 12 of the carbonyl group may, for example, be a fluorenyl group having 2 to 12 carbon atoms. Specifically, it is exemplified by an ethyl group, a propyl group, an isopropyl group, a benzamidine group or the like. The organic group having a total carbon number of 1 to 12 having an ester bond is exemplified by a fluorenyl group having 2 to 12 carbon atoms. Specific examples thereof include an ethenyloxy group, a propenyloxy group, a isopropyloxy group, and an isobutyloxy group. The organic group having 1 to 12 carbon atoms of the nitrogen atom is exemplified by an organic group composed of a hydrogen atom, a carbon atom and a nitrogen atom. Specific examples thereof are a cyano group, an imidazolyl group, a triazolyl group, a benzimidazolyl group, a benzotriazolyl group and the like. The organic group having 1 to 12 carbon atoms containing an oxygen atom and a nitrogen atom is exemplified by an organic group composed of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and specifically exemplified by an oxazolyl group, an oxadiazolyl group, and a benzene group. And oxazolyl and benzooxadiazolyl and the like. R1 to R4 in the above formula (1) are preferably a hydrocarbon having a carbon number of 1 to 12, more preferably a carbon number of 6 to 12, from the viewpoint of water absorption (wet) property of the resin (1). A hydrocarbon group is more preferably a phenyl group. -39- 201211125 【化1 9】

前述式（2 )中’ R1〜R4及a〜d各獨立與前述式（i)中之Ri~R4及a~d同義’ Y表示單鍵、-302-或>〇 = 〇，R7及R8 各獨立表示鹵素原子、碳數1〜12之—價有機基或硝基，m 表示0或1，但111爲0時，r7不爲氰基。g及h各獨立表示〇〜4 之整數，較好爲〇。碳數1~12之一價有機基可列舉爲與前述式（1)中之碳數1〜12之一價有機基相同之有機基。前述樹脂（1)之前述構造單位（1)與前述構造單位 (2)之莫耳比（但’二者（構造單位（1) +構造單位（2 ))之合計爲100) ’就光學特性、耐熱性及力學特性之觀點而言，較好構造單位（1 ):構造單位（2 ) =50 : 50〜100: 〇，更好構造單位（1):構造單位（2) =70: 30〜100: 〇，又更好構造單位（1):構造單位（2) =80: 20〜1 00 : 0 ° 此處，所謂力學特性意指樹脂之拉伸強度、斷裂伸長率及拉伸彈性率等之性質。另外，前述樹脂（1)亦可進一步具有由以下述式（3 )表示之構造單位及以下述式（4 )表示之構造單位所組成群組選出之至少一種構造單位（以下亦稱爲「構造胃 <立 -40- 201211125 (3 _4)」）。前述樹脂（1)具有該等構造單位（3-4)時，由於含有該樹脂（1)之基板之力學特性獲得提高故而較佳。【化2 0】In the above formula (2), 'R1 to R4 and a to d' are each independently synonymous with Ri~R4 and a~d in the above formula (i), and Y represents a single bond, -302- or >〇=〇, R7 and R8 each independently represents a halogen atom, a valence organic group or a nitro group having a carbon number of 1 to 12, and m represents 0 or 1, but when 111 is 0, r7 is not a cyano group. g and h each independently represent an integer of 〇~4, preferably 〇. The one-valent organic group having 1 to 12 carbon atoms is exemplified by the same organic group as the one-valent organic group having 1 to 12 carbon atoms in the above formula (1). The molar ratio of the aforementioned structural unit (1) of the resin (1) to the structural unit (2) (but the sum of the two (structural unit (1) + structural unit (2)) is 100) 'in terms of optical characteristics From the viewpoint of heat resistance and mechanical properties, the preferred structural unit (1): structural unit (2) = 50: 50~100: 〇, better structural unit (1): structural unit (2) = 70: 30 ~100: 〇, and better construction unit (1): structural unit (2) = 80: 20~1 00 : 0 ° Here, the mechanical properties mean the tensile strength, elongation at break and tensile elasticity of the resin. The nature of the rate, etc. In addition, the resin (1) may further have 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 also referred to as "structural" Stomach <立-40- 201211125 (3 _4)"). When the resin (1) has such structural units (3-4), the mechanical properties of the substrate containing the resin (1) are preferably improved. [化2 0]

前述式（3)中’ r5及r6各獨立表示碳數1〜12之—價有機基，Z 表不單鍵、-〇-、-S-、-S〇2· x >C = 0 ' -CONH* 、-COO-或碳數1〜12之二價有機基，n表示0或1，e&f各獨立表示0〜4之整數’較好爲0。碳數卜12之一價有機基可列舉爲與前述式（1)中之碳數1〜12之一價有機基相同之有機基等。碳數卜12之二價有機基可列舉爲碳數1〜12之二價烴基、碳數1 ~ 1 2之二價鹵化烴基、含有由氧原子及氮原子所組成群組選出之至少—種原子之碳數1〜12之二價有機基’及含有由氧原子及氮原子所組成群組選出之至少一種原子之碳數1〜12之二價鹵化有機基等。碳數1〜12之二價烴基列舉爲碳數1~12之直鏈或分支鏈之二價烴基、碳數3~12之二價脂環式烴基及碳數6~1 2之二價芳香族烴基等。碳數1〜12之直鏈狀或分支鏈之二價烴基列舉爲伸甲基、伸乙基、三伸甲基、亞異丙基、五伸甲基、六伸甲基及 -41 - 201211125 七伸甲基等。碳數3〜12之二價脂環式烴基列舉爲伸環丙基、伸環丁基、伸環戊基及伸環己基等伸環烷基；伸環丁烯基、伸環戊烯基及伸環己烯基等伸環烯基等。碳數6〜12之二價芳香族烴基列舉爲伸苯基、伸萘基及伸聯苯基等。碳數1~12之二價鹵化烴基列舉爲碳數1〜12之直鏈或分支鏈二價鹵化烴基，碳數2之二價鹵化脂環式烴基及碳數6~ 12之二價鹵化芳香族烴基等。碳數1~12之直鏈或分支鏈之二價鹵化烴基列舉爲二氟伸甲基、二氯伸甲基、四氟伸乙基、四氯伸乙基、六氟三伸甲基、六氯三伸甲基、六氟亞異丙基及六氯亞異丙基等〇碳數3〜12之二價鹵化脂環式烴基列舉爲前述碳數3〜12 之二價脂環式烴基中所例示之基之至少一部份氫原子經氟原子、氯原子、溴原子或碘原子取代之基等。碳數6〜12之二價鹵化芳香族烴基列舉爲前述碳數6〜12 之二價芳香族烴基中所例示之基之至少一部份氫原子經氟原子、氯原子、溴原子或碘原子取代之基等。含有由氧原子及氮原子所組成群組選出之至少一種原子之碳數1〜12之有機基列舉爲由氫原子及碳原子，與氧原子及/或氮原子所組成之有機基，且具有醚鍵、羰基、酯鍵或醯胺鍵與烴基之總碳數1〜12之二價有機基等。至於含有由氧原子及氮原子所組成群組選出之至少一 -42 - 201211125 種原子之碳數1~12之二價鹵化有機基具由氧原子及氮原子所組成群組選出之至 1〜12之二價有機基中所例示之基之至少原子、氯原子、溴原子或碘原子取代之前述式（3 )中之Z較好爲單鍵、-〇碳數1〜12之二價有機基’就樹脂（1) 觀點而言，更好爲碳數2之二價烴基鹵化烴基或碳數3〜12之二價脂環式烴基【化21】體而言列舉爲含有少一種原子之碳數一部分氫原子經氟基。 -' -so2-、>c=o或之吸水（濕）性之、碳數1〜12之二價In the above formula (3), 'r5 and r6 each independently represent a valence organic group having a carbon number of 1 to 12, and Z represents a single bond, -〇-, -S-, -S〇2·x > C = 0 ' - CONH*, -COO- or a divalent organic group having 1 to 12 carbon atoms, n represents 0 or 1, and e&f each independently represents an integer of 0 to 4', preferably 0. The one-valent organic group of the carbon number 12 is exemplified by the same organic group as the one-valent organic group having 1 to 12 carbon atoms in the above formula (1). The divalent organic group of carbon number 12 can be exemplified by a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, and at least one selected from the group consisting of an oxygen atom and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms of an atom and a divalent halogenated organic group having 1 to 12 carbon atoms and at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The divalent hydrocarbon group having 1 to 12 carbon atoms is exemplified by 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 a divalent aromatic having 6 to 12 carbon atoms. A hydrocarbon group or the like. The divalent hydrocarbon group of a linear or branched chain having 1 to 12 carbon atoms is exemplified by methyl, ethyl, trimethyl, isopropylidene, pentamethyl, hexamethylene and -41 - 201211125 Seven stretches of methyl etc. The divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is exemplified by a cycloalkyl group such as a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group and a cyclohexylene group; a cyclobutenyl group and a cyclopentenyl group; A cyclohexene group such as a cyclohexene group is extended. The divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is exemplified by a stretching phenyl group, a stretching naphthyl group, and a stretching biphenyl group. The divalent halogenated hydrocarbon group having 1 to 12 carbon atoms is exemplified by a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated alicyclic hydrocarbon group having 2 carbon atoms, and a divalent halogenated aromatic having 6 to 12 carbon atoms. A hydrocarbon group or the like. The divalent halogenated hydrocarbon group of a straight or branched chain having 1 to 12 carbon atoms is exemplified by difluoromethyl, dichloromethyl, tetrafluoroethyl, tetrachloroethylene, hexafluorotrimethyl, and A divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, such as chlorotrimethyl, hexafluoroisopropylidene and hexachloroisopropylidene, is exemplified as the aforementioned divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms. A group in which at least a part of hydrogen atoms of the illustrated group are substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms is exemplified by at least a part of hydrogen atoms exemplified in the above-mentioned divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which are through a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Replace the base and so on. The organic group having 1 to 12 carbon atoms of at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom is exemplified by an organic group composed of a hydrogen atom and a carbon atom, and an oxygen atom and/or a nitrogen atom, and has A divalent organic group having an ether bond, a carbonyl group, an ester bond or a guanamine bond and a hydrocarbon group having a total carbon number of from 1 to 12. The divalent halogenated organic base having at least one -42 - 201211125 atoms selected from the group consisting of oxygen atoms and nitrogen atoms is selected from the group consisting of oxygen atoms and nitrogen atoms to 1~ The Z in the above formula (3) substituted with at least an atom, a chlorine atom, a bromine atom or an iodine atom exemplified in the divalent organic group of 12 is preferably a single bond, a divalent organic group having a carbon number of 1 to 12 From the viewpoint of the resin (1), a divalent hydrocarbon group halogenated hydrocarbon group having a carbon number of 2 or a divalent alicyclic hydrocarbon group having a carbon number of 3 to 12 is exemplified as containing one atom less A part of the carbon atoms of the carbon atoms are via a fluorine group. -' -so2-, >c=o or water absorption (wet), carbon number 1~12

前述式（4)中，R7、R·8、γ、m、式（2)中之R7、r8、Y、m、g及h同義 e及f各獨立與前述式（3)中之R5、R6、再者，m爲0時，R7不爲氰基。前述樹脂（1 )之前述構造單位（1 位（3-4 )之莫耳比（但，二者（（1-2 計爲1 0 0 )，就光學特性、耐熱性及力，較好（ 1-2) :( 3-4) = 50:50-100:0, 4) =70:30〜1〇〇:〇，又更好（1-2) :(3-4 此處，所謂力學特性意指樹脂之拉率及拉伸彈性率等性質。 g及h各獨立與前述 ’ R5、 R6、 Ζ、 η、 Ζ、η、e及f同義。 -2 )與前述構造單 )+ ( 3-4 ))之合學特性之觀點而言更好（1 - 2 ) : ( 3 -[)=80:20〜1〇〇:〇 » 伸強度、斷裂伸長 -43- 201211125 前述樹脂（1 )就光學特性、耐熱性及力學特性之觀點而言，較好前述構造單位（1-2)及前述構造單位（3-4 )包含全部構造單位中之70莫耳％以上，更好包含全部構造單位中之9 5莫耳％以上。前述樹脂（1)可藉由例如使含有由以下述式（5)表示之化合物（以下亦稱爲「化合物（5)」）及以下述式 (7)表示之化合物（以下亦稱爲「化合物（？）」）所組成群組選出之至少一種化合物之成分（以下亦稱爲「（A )成分」）與以含有下述式（6)表示之化合物之成分（以下亦稱爲「（B)成分」）反應而獲得。In the above formula (4), R7, R·8, γ, m, R7, r8, Y, m, g and h in the formula (2) are synonymous with e and f, each independently of R5 in the above formula (3), R6. Further, when m is 0, R7 is not a cyano group. The above-mentioned structural unit of the above resin (1) (the molar ratio of the 1-bit (3-4) (but, both ((1-2) is optical property, heat resistance and force, preferably ( 1-2) :( 3-4) = 50:50-100:0, 4) =70:30~1〇〇:〇, and better (1-2) :(3-4 Here, the so-called mechanics The characteristics mean the properties such as the elongation of the resin and the tensile modulus. g and h are each independently synonymous with the above-mentioned 'R5, R6, Ζ, η, Ζ, η, e, and f. -2) and the aforementioned structure single) + ( 3-4)) is better in terms of the characteristics of the school (1 - 2) : ( 3 -[) = 80:20~1〇〇:〇» Extension strength, elongation at break -43- 201211125 The aforementioned resin (1 From the viewpoints of optical properties, heat resistance, and mechanical properties, it is preferred that the structural unit (1-2) and the structural unit (3-4) include 70 mol% or more of all structural units, and more preferably all More than 95% of the structural units. The resin (1) can be, for example, 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 "a compound" (?)") a component of at least one compound selected from the group consisting of (hereinafter also referred to as "(A) component)" and a component containing a compound represented by the following formula (6) (hereinafter also referred to as "(B) ) component)) obtained by reaction.

【化2 2】 CN X【化2 2】 CN X

(5) 前述式（5)中，X獨立表示鹵素原子，且較好爲氟原子。(5) In the above formula (5), X independently represents a halogen atom, and is preferably a fluorine atom.

前述式（7)中’ R7、R8、Y、m、g及h各獨立與前述式（2)中之R7、R8、γ、m、g及h同義，X獨立與前述式 -44 - 201211125 (5 )之X同義。但，m爲0時，R7不爲氰基。【化2 4】In the above formula (7), 'R7, R8, Y, m, g and h are each independently synonymous with R7, R8, γ, m, g and h in the above formula (2), and X is independent from the above formula -44 - 201211125 (5) X is synonymous. However, when m is 0, R7 is not a cyano group. [Chem. 2 4]

前述式（6)中，RA各獨立表示氫原子、甲基、乙基、乙醯基、甲烷磺醯基或三氟甲烷磺醯基，其中以氫原子較佳。又，式（6 )中，R1〜R4及a〜d各獨立與前述式（1 ) 中之R1〜R4及a〜d同義。至於前述化合物（5)，具體而言可列舉爲2,6-二氟苯甲腈（DFBN ) 、2,5-二氟苯甲腈、2,4-二氟苯甲腈、2,6- 二氯苯甲腈、2,5-二氯苯甲腈、2,4-二氯苯甲腈及該等之反應性衍生物。尤其，就反應性及經濟性之觀點而言，較好使用2,6-二氟苯甲腈及2,6-二氯苯甲腈。該等化合物亦可組合兩種以上使用。以前述式（6 )表示之化合物（以下亦稱爲「化合物 (6.)」）具體而言列舉爲9,9-雙（4-羥基苯基）苐（ BPFL) 、9,9-雙（3-苯基-4-羥基苯基）弗、9,9-雙（3,5-二苯基-4-羥基苯基）莽、9,9-雙（4-羥基-3-甲基苯基）莽、9,9-雙（4-羥基- 3,5-二甲基苯基）苐、9,9-雙（4-羥基-3-環己基苯基）苐及該等之反應性衍生物等。上述化合物 -45- 201211125 中，較好使用9,9-雙（4-羥基苯基）苐及9,9-雙（3-苯基-4 -羥基苯基）蕗。該等化合物可組合兩種以上使用。前述化合物（7 )具體而言可列舉爲4,4’-二氟二苯甲酮、4,4’-二氟二苯基颯（DFDS) 、2,4’-二氟二苯甲酮、 2，4’-二氟二苯基颯、2，2’-二氟二苯甲酮、2,2’-二氟二苯基颯、3,3’-二硝基-4,4’-二氟二苯甲酮、3,3，_二硝基·4,4，_ 二氟二苯基颯、4,4’-二氯二苯甲酮、4，4’·二氯二苯基楓、 2,4’-—氯一苯甲酮、2,4’-二氯二苯基颯、2,2，-二氯二苯甲酮、2,2’-二氯二苯基颯、3,3’_二硝基·4,4，_二氯二苯甲酮及3,3’-二硝基-4,4’-二氯二苯基颯等。該等中，較好爲該等該化合物亦 4,4’-二氟二苯甲酮、4,4’-二氟二苯基颯。可組合兩種以上使用。由化合物C 5 )及化合物（7 )所組一種化合物在（A )成分100莫耳％中 7 )所組成群組選出之至少在（A)成分100莫耳％中較好含有8〇莫耳 ’更好含9〇莫耳％〜100莫耳〇/〇。另外，（B)成分較好視需之化合物。化合物在（B 有50莫耳％〜100莫耳％，更好含更好含有90莫耳％〜1〇〇莫耳％。 (B)成分較好視需要含有以下述式 8 )表示在（B)成分100莫耳％中較好含更好含有80莫耳％〜1〇〇莫耳％, 【化2 5】In the above formula (6), RA each independently represents a hydrogen atom, a methyl group, an ethyl group, an ethyl sulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group, and among them, a hydrogen atom is preferred. Further, in the formula (6), R1 to R4 and a to d are each independently the same as R1 to R4 and a to d in the above formula (1). As the above compound (5), specifically, it may be mentioned as 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6- Dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and such reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoint of reactivity and economy. These compounds may also be used in combination of two or more. The compound represented by the above formula (6) (hereinafter also referred to as "compound (6.)") is specifically exemplified as 9,9-bis(4-hydroxyphenyl)fluorene (BPFL), 9,9-bis ( 3-phenyl-4-hydroxyphenyl) sulphate, 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylbenzene ,9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)anthracene and their reactivity Derivatives, etc. Among the above compounds -45 to 201211125, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene are preferably used. These compounds may be used in combination of two or more. Specific examples of the compound (7) include 4,4'-difluorobenzophenone, 4,4'-difluorodiphenylfluorene (DFDS), and 2,4'-difluorobenzophenone. 2,4'-difluorodiphenyl fluorene, 2,2'-difluorobenzophenone, 2,2'-difluorodiphenyl fluorene, 3,3'-dinitro-4,4'- Difluorobenzophenone, 3,3,-dinitro-4,4,-difluorodiphenyl fluorene, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl Maple, 2,4'-chlorobenzophenone, 2,4'-dichlorodiphenyl fluorene, 2,2,-dichlorobenzophenone, 2,2'-dichlorodiphenyl hydrazine, 3,3'-dinitro-4,4,-dichlorobenzophenone and 3,3'-dinitro-4,4'-dichlorodiphenylphosphonium. Among these, it is preferred that the compounds are also 4,4'-difluorobenzophenone or 4,4'-difluorodiphenylfluorene. Two or more types can be used in combination. The compound selected from the group consisting of the compound C 5 ) and the compound (7) is selected from the group consisting of 100 parts by mole of the component (A) and at least 100 mole % of the component (A). 'Better with 9 〇耳 % ~ 100 〇〇 / 〇. Further, the component (B) is preferably a compound as desired. The compound has a content of 50 mol% to 100 mol%, and more preferably contains 90 mol% to 1 mol%. The component (B) preferably contains the following formula 8) as needed ( B) The content of 100% by mole of the component preferably contains 80% by mole to 1% of the molar %, [Chemical 2 5]

-46- 201211125 前述式（8 )中，R5、R6、Z ' η、e及f各獨立式（3)中之R5、R6、Z、n、e及f同義’ RA各獨立式（6)中之RA同義。以前述式（8 )表示之化合物列舉爲氫醌、間酚、2-苯基氫醌、4,4，-聯酚、3,3’-聯酚、4,4’-二羥基颯、3，3’-二羥基二苯基颯、4,4’-二羥基二苯 3,3’-二羥基二苯甲酮、1，1’-聯-2-萘酚、1，1’-聯-4-2，2-雙（4-羥基苯基）丙烷、1，1-雙（4-羥基苯基）、2,2-雙（4-羥基苯基）-1，1，1，3,3,3-六氟丙烷及該應性衍生物等。上述化合物中，較好爲間苯二甲酚聯酚、2,2-雙（4-羥基苯基）丙烷、1，1-雙（4-羥基環己烷、2,2-雙（4-羥基苯基）-1，1，1，3,3,3-六氟丙反應性與力學特性之觀點而言，較好使用4,4’-聯酚化合物亦可組合兩種以上使用。前述樹脂（1)更具體而言可藉以下所示之方法合成。方法（I ’）：使（B)成分在有機溶劑中與鹼金屬化合物反得（B )成分（化合物（6 )及/或化合物（；8 )等）屬鹽之後’使所得鹼金屬鹽與（A)成分反應。又在（A)成分存在下進行（B)成分與鹼金屬化合物，使（B)成分之驗金屬鹽與（A)成分反應。與前述與前述苯二甲基二苯甲酮、萘酚、環己院等之反、4,4，- 苯基）烷，就。該等應，獲之鹼金，亦可之反應 -47- 201211125 反應所使用之鹼金屬化合物可列舉爲鋰、鉀及鈉等之鹼金屬；氫化鋰、氫化鉀及氫化鈉等氫化鹼金屬；氫氧化鋰、氫氧化鉀及氫氧化鈉等氫氧化鹼金屬；碳酸鋰、碳酸鉀及碳酸鈉等鹼金屬碳酸鹽；碳酸氫鋰、碳酸氫鉀及碳酸氫鈉等鹼金屬碳酸氫鹽。該等可使用一種或組合兩種以上使用。鹼金屬化合物相對於前述（B)成分中之全部的-〇-Ra ，鹼金屬化合物中之金屬原子之量通常以成爲1〜3倍當量，較好爲1.1〜2倍當量，更好爲1.2〜1.5倍當量之量使用。又，反應所使用之有機溶劑可使用Ν,Ν-二甲基乙醯胺 (DMAc) 、N，N-二甲基甲醯胺、N-甲基·2·吡咯烷酮、 1，3-二甲基-2-咪唑啶酮、γ-丁內酯、環丁碼、二甲基亞颯、二乙基亞颯、二甲基颯、二乙基颯、二異丙基颯、二苯基颯、二苯基醚、二苯甲酮、二烷氧基苯（烷氧基之碳數爲1〜4)及三烷氧基苯（烷氧基之碳數1〜4)等。該等溶劑中，最好使用Ν-甲基-2-吡咯烷酮、Ν，Ν-二甲基甲醯胺、環丁碼、二苯基楓及二甲基亞颯等之介電率高之極性有機溶劑。該等有機溶劑可單獨使用一種，亦可併用兩種以上〇而且，前述反應時，亦可進一步使用苯、甲苯、二甲本、己院、環己院、辛院、氣本、一卩惡院、四氮咲喃、苯甲醚及苯乙醇等與水共沸之溶劑。 (Α)成分與（Β)成分之使用比例以（Α)成分與（ Β)成分之合計作爲1〇〇莫耳％時，（Α)成分較好爲45莫 -48- 201211125 耳％以上55莫耳％以下，更好爲50莫耳％以上52莫耳％以下，更好超過50莫耳％在52莫耳％以下，（B)成分較好爲45 莫耳％以上55莫耳％以下，更好爲48莫耳％以上50莫耳％以下，又更好爲48莫耳％以上未達50莫耳％。另外，反應溫度較好爲60°C〜25 0°C ，更好爲 80°C〜200°C之範圍。反應時間較好爲15分鐘~100小時，更好爲1小時〜24小時之範圍。前述樹脂（1)以示差掃描熱量測定（DSC，升溫速度20°C/分鐘）之玻璃轉移溫度（Tg )較好爲23 0〜3 5 0°C，更好爲240〜3 3 0 °C，又更好爲25 0~3 00°C。前述樹脂（1 )之玻璃轉移溫度係使用例如Rigaku公司製造之823 0型DSC測定裝置（升溫速度20°C/分鐘）或 SII Nanotechnology股份有限公司製造之示差掃描熱量計 (DSC 62 00)(升溫速度20 °C/分鐘）等測定。前述樹脂（1)係以TOSOH製造之HLC-8220型GPC裝置（管柱：TSKgel α-Μ，展開溶劑：四氫呋喃（以下亦稱爲「THF」））測定，聚苯乙烯換算之重量平均分子量（ 1^%)較好爲 5,000~ 5 00,0〇〇，更好爲 1 5,000〜400,000，又更好爲 3 0,000~300,000。前述樹脂（1 )以熱重量分析法（TGA )測定之熱分解溫度較好爲4 5 0 °C以上，更好爲4 7 5 °C以上，又更好爲 4 9 0 °C以上。〈聚醯亞胺樹脂〉 -49- 201211125 本發明中可使用之透明樹脂可列舉爲聚醯亞胺樹脂。前述聚醯亞胺樹脂並無特別限制，若爲於重複單位中含有醯亞胺鍵之高分子即可，例如可藉特開2008- 1 63 1 07 中列舉之方法合成。本發明中可使用之透明樹脂之市售品可列舉爲以下之市售品等。環狀烯烴系樹脂之市售品可列舉爲例如JSR股份有限公司製造之ARTON，日本ΖΕΟΝ股份有限公司製造之ZEONOR，三井化學股份有限公司製造之APEL、 Polyplastic股份有限公司製造之TOPAS等。聚醚颯樹脂之市售品可列舉爲住友化學股份有限公司製造之 SUMIKAEXCEL PES等。聚醯亞胺樹脂之市售品可列舉爲三菱氣體化學股份有限公司製造之NEOPUR’IMU L等。聚碳酸酯樹脂之市售品可列舉爲帝人股份有限公司製造之 PURE-ACE等。有機·無機奈米混成材料之市售品可列舉爲新日鐵化學股份有限公司製造之SILPLUS等。〈其他成分〉前述樹脂製基板（I)中，在不損及本發明效果之範圍內，可進而添加抗氧化劑、紫外線吸收劑、吸收近紅外線之染料或顏料、及金屬錯合物系化合物等之添加劑。且，藉由後述之溶液澆鑄法製造樹脂製基板（I)時，可添加平流劑或消泡劑，可使樹脂製基板（I )之製造變得容易。該等其他成分可單獨使用一種，亦可倂用兩種以上。前述抗氧化劑列舉爲例如2,6-二第三丁基-4-甲基酚、 -50- 201211125 2,2’-二氧基- 3,3’-二-第三丁基- 5,5’-二甲基二苯基甲烷、及肆〔伸甲基-3- ( 3,5-二第三丁基-4-羥基苯基）丙酸酯〔甲烷等。前述紫外線吸收劑列舉爲例如2,4-二羥基二苯甲酮及 2-羥基-4-甲氧基二苯甲酮等。又，該等添加劑可在製造樹脂製基板（I)時同時混合於樹脂中，亦可在製造樹脂時添加。另外，添加量係依據所需特性適當選擇，但相對於樹脂1 00重量份，通常爲 0.01〜5.0重量份，較好爲〇.〇5〜2.0重量份。〈含有化合物（I)之樹脂製基板（I)之製造方法〉本發明中使用之樹脂製基板（I )可藉由例如熔融成形、澆鑄成形而形成，可視需要，於成形後藉由塗佈抗反射劑、硬質塗佈劑及/或抗靜電劑等塗佈劑之方法製造。 (A)熔融成形前述樹脂製基板（I )可藉由使熔融混練前述樹脂與化合物（I )及/或化合物（Γ )而獲得之顆粒溶融成形之方法；將含有前述樹脂與化合物（I )及/或化合物（Γ ) 之樹脂組成物熔融成形之方法；使自由含有化合物（I) 及./或化合物（Γ )、前述樹脂及溶劑之樹脂組成物去除溶劑獲得之顆粒進行熔融成形之方法等製造。熔融成形方法可列舉爲例如射出成形、熔融擠出成形或吹塑成形等。 -51 - 201211125 (B)澆鑄前述樹脂製基板（I)可藉由將含有化合物（1)及/或化合物（Γ )、前述樹脂及溶劑之樹脂組成物澆鑄於適當基材上並去除溶劑，將含有抗反射劑、硬塗劑及/或抗靜電劑等塗佈劑及化合物（I)及/或化合物（1 ’）之樹脂組成物塗佈於適當基材上，將含有抗反射劑、硬塗劑及/或抗靜電劑等塗佈劑及化合物（I )及/或化合物（I’）之硬化性組成物塗佈於適當基材上並經硬化、乾燥等而製造。例如，可於玻璃板、鋼帶、鋼滾筒或聚酯薄膜、環狀烯烴系樹脂薄膜等透明樹脂等之基材上，塗佈上述之樹脂組成物且將溶劑乾燥獲得塗膜，其後藉由自基材剝離塗膜，可獲得樹脂製基板（I)。另外，只要不損及本發明效果，亦可不自基材剝離塗膜而以基材與塗膜之層合體作爲前述樹脂製基板（I)。另外，亦可將上述樹脂組成物塗佈於玻璃板、石英或透明塑膠製等光學零件上並乾燥溶劑，塗佈含有前述樹脂、硬塗劑等塗佈劑、溶劑及化合物（ I)及/或化合物（Γ )之樹脂組成物並經硬化、乾燥，於光學零件上直接形成樹脂製基板（I)。以前述方法獲得之樹脂製基板（I )中之殘留溶劑量較好儘可能少，通常爲3重量％以下，較好爲1重量％以下，更好爲0 · 5重量％以下。殘留溶劑量超過3重量％時，樹脂製基板（I )經時變形使特性產生變化，而有無法發揮所需功能之虞。 -52- 201211125 〈近紅外線反射膜〉本發明中使用之近紅外線反射膜爲具有反射近紅外線之能力的膜。該等近紅外線反射膜可使用使以鋁蒸鍍膜' 貴金屬薄膜、分散有以氧化銦作爲主成分且含有少量氧化錫之金屬氧化物微粒子之樹脂膜、高折射率材料層與低折射率材料層交互層合而成之介電體多層膜等。本發明之近紅外線截止濾波器由於具有該種近紅外線反射膜，故成爲尤其具有下述（B)之特徵。因此，可獲得可充分截止近紅外線之濾波器。本發明中，近紅外線反射膜可設置於樹脂製基板（I )之單面上，亦可設置於兩面上。設置於單面上時，製造成本或製造之容易性優異，設置於兩面上時，可獲得具有高強度、不易產生翹曲之近紅外線截止濾波器。該等近紅外線反射膜中，亦可較好地使用高折射率材料層與低折射率材料層交叉層合之介電體多層膜。構成高折射率層之材料可使用折射率爲1.7以上之材料，選擇折射率範圍通常爲1.7〜2.5之材料。至於該等材料列舉爲例如以氧化鈦、氧化錐、五氧化鉅、五氧化鈮、氧化鑭、氧化釔、氧化鋅、硫酸鋅及氧化銦等作爲主成分，含有少量（例如，相對於主成分爲 G〜1 〇% ).之氧化鈦、氧化錫及氧化鈽者等。構成低折射率材料層之材料可使用折射率1 · 6以下之材料，且選擇折射率範圍通常爲I.2〜1.6之材料。該等材料列舉爲例如二氧化矽、氧化鋁、氟化鑭、氟 -53 - 201211125 化鎂及六氟化鋁鈉等。層合高折射率材料層與低折射率材料層之方法只要是可層合該等材料層形成介電體多層膜即無特別限制。例如，可在前述樹脂製基板（I)上，直接、藉由CVD法、濺鍍法、真空蒸鍍法、離子輔助蒸鍍法及離子電鍍法等，使高折射率材料層與低折射率材料層交叉層合而形成介電體多層膜。該等高折射率材料層與低折射率材料層之各層厚度，通常將欲截止之近紅外線波長作爲λ(ηΐη)時，較好爲 0.1λ~0.5λ之厚度》若厚度在該範圍內時，則以λ/4算出折射率（η)與膜厚（d)之乘積（nxd)之光學膜厚與高折射率材料層及低折射率材料層之各層厚度成爲大致相同之値，由反射•折射之光學特性之關係，有可容易地控制特定波長之截止•透射之傾向。另外，介電體多層膜中之層合數宜爲5〜60層，較好爲 10〜50層》而且，形成介電體多層膜時在基板產生翹曲之情況，未消除該狀況，可利用於基板兩面上形成介電體多層膜，對基板之形成介電體多層膜之面照射紫外線等電磁波等方法進行。又，照射電磁波時，可在介電體多層膜之形成中照射，亦可於形成後另外照射。《其他之功能膜》本發明之近紅外線截止濾波器在不損及本發明效果之 -54- 201211125 範圍內，可在樹脂製基板（I)與介電體多層膜等之近紅外線反射膜之間，在與樹脂製基板（I )之設置近紅外線反射膜之面相反側之面，或於與近紅外線反射膜之設置樹脂製基板（I)之面相反側之面上適當設置抗反射膜、硬塗膜或抗靜電膜等功能膜，以提高樹脂製基板（I)之表面硬度，改善耐藥品性、抗靜電及消除傷痕等。本發明之近紅外線截止濾波器可含一層由前述功能膜組成之層，亦可含兩層以上。本發明之近紅外線截止濾波器含有兩層以上之由前述功能膜組成之層時，可含兩層以上相同之層，亦可含兩層以上不同之層。層合功能膜之方法並無特別限制，可列舉爲將抗反射劑、硬塗劑及/或抗靜電劑等塗佈劑等，以與前述相同之熔融成形方法及澆鑄等方法塗佈於樹脂製基板（I)或近紅外線反射膜上。另外，亦可以棒塗佈器等將含有前述塗佈劑形成材料等之硬化性組成物塗佈於樹脂製基板（I ) 或近紅外線反射膜上之後，藉由紫外線照射等硬化而製造〇至於前述塗佈劑，列舉爲紫外線（UV ) /電子束（EB )硬化型樹脂或熱硬化型樹脂等，另列舉爲胺基甲酸酯系、胺基甲酸酯丙烯酸酯系、丙烯酸酯系、環氧系及環氧基丙烯酸酯系瓒脂等。對應於該等塗佈劑之前述硬化性組成物列舉爲胺基甲酸酯系、胺基甲酸酯丙烯酸酯系、丙烯酸酯系、環氧系及環氧基丙烯酸酯系硬化性組成物等。前述胺基甲酸酯系、胺基甲酸酯丙烯酸酯系硬化性組 -55- 201211125 成物中所含之成分可列舉爲例如參（2-羥基乙基）異氰脲酸酯三（甲基）丙烯酸酯、雙（2-羥基乙基）異氰脲酸酯二（甲基）丙烯酸酯、分子內具有兩個以上之（甲基）丙烯醯基之寡聚合胺基甲酸酯（甲基）丙烯酸酯類，但並不限於該等例示。該等成分可單獨使用一種，亦可倂用兩種以上。另外亦可調配聚胺基甲酸酯（甲基）丙烯酸酯等寡聚物或聚合物。丙烯酸酯系硬化性組成物並無特別限制，可列舉爲含有（甲基）丙烯酸酯類、乙烯化合物類等之組成物等。前述（甲基）丙烯酸酯類之具體例可列舉爲例如下列者： . (甲基）丙烯酸異冰片酯、 (甲基）丙烯酸冰片酯、 (甲基）丙烯酸三環癸酯、 (甲基）丙烯酸二環戊酯、 (甲基）丙烯酸二環戊烯酯、 (甲基）丙烯酸環己酯、 (甲基）丙烯酸苄酯、 (甲基）丙烯酸4-丁基環己酯、丙烯醯基嗎啉、 (甲基）丙烯酸2-羥基乙酯、 (甲基）丙烯酸2-羥基丙酯、 (甲基）丙烯酸2_羥基丁酯、 (甲基）丙烯酸甲酯、 -56- 201211125 (甲基）丙烯酸乙酯、 (甲基）丙烯酸丙酯、 (甲基）丙烯酸異丙酯、 (甲基）丙烯酸丁酯、 (甲基）丙烯酸戊酯、 (甲基）丙烯酸異丁酯、 (甲基）丙烯酸第三丁酯、 (甲基）丙烯酸戊酯、 (甲基）丙烯酸異戊酯、 (甲基）丙烯酸己酯、 (甲基）丙烯酸庚酯、 (甲基）丙烯酸辛酯、 (甲基）丙烯酸異辛酯、 (甲基）丙烯酸2-乙基己酯、 (甲基）丙烯酸壬酯、 (甲基）丙烯酸癸酯、 (甲基）丙烯酸異癸酯、 (甲基）丙烯酸十一烷酯、 (甲基）丙烯酸十二烷酯、 (甲基）丙烯酸月桂酯、 (甲基）丙烯.酸硬脂酯、 (甲基）丙烯酸異硬脂酯、 (甲基）丙烯酸四氫糠酯、 (甲基）丙烯酸丁氧基乙酯、 -57- 201211125 (甲基）丙烯酸乙氧基二乙二醇酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、甲氧基乙二醇（甲基）丙烯酸酯、 (甲基）丙烯酸乙氧基乙酯、甲氧基聚乙二醇（甲基）丙烯酸酯、甲氧基聚丙二醇（甲基）丙烯酸酯、二丙酮（甲基）丙烯醯胺、異丁氧基甲基（甲基）丙烯醯胺、 N，N-二甲基（甲基）丙烯醯胺、第三辛基（甲基）丙烯醯胺、 (甲基）丙烯酸二甲胺基乙酯、 (甲基）丙烯酸二乙胺基乙酯、 (甲基）丙烯酸7-胺基-3,7-二甲基辛酯、 N，N-二乙基（甲基）丙烯醯胺、 Ν,Ν-二甲基胺基丙基（甲基）丙烯醯胺、 (甲基）丙烯酸苯氧基乙酯、 (甲基）丙烯酸苯氧基-2-甲基乙酯、 (甲基）丙烯酸苯氧基乙氧基乙酯、 (甲基）丙烯酸3-苯氧基-2-羥基丙酯、 (甲基）丙烯酸2-苯基苯氧基乙酯、 (甲基）丙烯酸4-苯基苯氧基乙酯、 (甲基）丙烯酸2-羥基-3-苯氧基丙酯、對-枯基酚環氧乙烷改質之（甲基）丙烯酸酯、 -58- 201211125 (甲基）丙烯酸2-溴苯氧基乙酯、 (甲基）丙烯酸4-溴苯氧基乙酯、 (甲基）丙烯酸2，4-二溴苯氧基乙酯、 (甲基）丙烯酸2,6-二溴苯氧基乙酯、. (甲基）丙烯酸2，4,6-三溴苯氧基乙酯、三羥甲基丙烷三（甲基）丙烯酸酯、 (甲基）丙烯酸三羥甲基丙烷三氧基乙酯、二-三羥甲基丙烷四（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、甘油三（甲基）丙烯酸酯、乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、 1.3- 丁二醇二（甲基）丙烯酸酯、 1.4- 丁二醇二（甲基）丙烯酸酯、 1,6-己二醇二（甲基）丙烯酸酯、 1,9-壬二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸酯、二丙二醇二（甲基）丙烯酸酯、 -59- 201211125 (甲基）丙烯酸環己酯、 (甲基）丙烯酸二環戊烯酯、 (甲基）丙烯酸二環戊酯、 (甲基）丙烯酸二環戊氧基乙酯、 (甲基）丙烯酸異冰片酯、三環癸烷二基二甲醇二（甲基）丙烯酸酯、三環癸烷甲醇（甲基）丙烯酸酯、三環癸烷二甲醇二（甲基）丙烯酸酯、四環癸烷二基二甲醇二（甲基）丙烯酸酯、製造該等化合物時之起始醇類之環氧乙烷或環氧丙烷加成物之聚（甲基）丙烯酸酯類，分子內具有兩個以上之（甲基）丙烯醯基之寡酯（甲基）丙烯酸酯類，及寡醚（甲基）丙烯酸酯類，但並不限於該等。該等成分可單獨使用一種，亦可倂用兩種以上。另外亦可調配聚酯（甲基）丙烯酸酯等寡聚物或聚合物。前述乙烯化合物類可列舉爲例如乙酸乙烯酯、丙酸乙烯酯、二乙烯苯、乙二醇二乙烯醚、二乙二醇二乙烯醚、三乙二醇二乙烯醚等，但並不限於該等。該等成分可單獨使用一種，亦可倂用兩種以上。前述環氧系、環氧基丙烯酸酯系硬化性組成物中所含成分並無特別限制，可列舉爲（甲基；）丙烯酸縮水甘油酯、（甲基）丙烯酸甲基縮水甘油酯、分子內具有兩個以上 (甲基）丙烯醯基之寡聚環氧基（甲基）丙烯酸酯類等。該等成分可單獨使用一種，亦可倂用兩種以上。進而亦可 -60- 201211125 調配聚環氧基（甲基）丙烯酸酯等寡聚物或聚合物。前述塗佈劑（含有塗佈劑形成材料等之硬化性組成物 )之市售品列舉爲東洋油墨製造股份有限公司製造之LCH ' LAS，荒川化學工業股份有限公司製造之BEAMSET， Daicel Scientech股份有限公司製造之EBECRYL、 1；¥八(：1111丑，】811股份有限公司製造之0?3丁八11等。且，前述硬化性組成物亦可包含聚合起始劑。前述聚合起始劑可使用習知之光聚合起始劑或熱聚合起始劑，亦可倂用光聚合起始劑與熱聚合起始劑。聚合起始劑之具體例並無特別限制，列舉爲下.列者： 1-羥基環己基苯基酮， 2,2-二甲氧基-2-苯基苯乙酮，咕噸酮，莽酮，苯甲醛，蒽醌，三苯基胺，卡必醇， 3- 甲基苯乙酮， 4- 氯二苯甲酮， 4,4’-二甲氧基二苯甲酮， 4,4’-二胺基二苯甲酮，米查氏（Michael)酮，苯偶因丙基醚， -61 - 201211125 苯偶因乙基醚，苄基二甲基縮酮， 1- (4-異丙基苯基）-2-羥基-2-甲基丙-1-酮， 2- 羥基-2-甲基-1-苯基丙-1-酮，噻噸酮，二乙基噻噸酮， 2-異丙基噻噸酮， 2-氯噻噸酮， 2-甲基-1-〔4-(甲硫基）苯基〕-2-嗎啉基-丙-1-酮， 2,4,6·三甲基苯甲醯基二苯基氧化膦，雙-(2,6-二甲氧基苯甲醯基）-2,4,4-三甲基戊基氧化膦。該等中，較好爲1-羥基環己基苯基酮。該等聚合起始劑可單獨使用一種，亦可倂用兩種以上〇該等之市售品列舉爲Irgacure 184、369、651、500、 907、CGI 1 700 ' CGI 1 75 0、CGI 1 8 5 0、CG24-61、Darocure TPO (以上爲汽巴•特用化學品公司製造）、lucirin LR8728 ’（ BASF 製造）、D arocure 1 1 1 6、1 1 73 (以上爲 Merck公司製造）、UBECRYL P36 ( UCB公司製造）等。前述硬化性組成物中，聚合起始劑之調配比例以@化性組成物之總量作爲1 0 〇重量％，較好爲〇 . 1〜1 〇重量％，更好爲0.5〜10重量％，又更好爲^重量％。聚合起始劑之調配比例在前述範圍內時，硬化性組成物之硬化特性及操作 -62- 201211125 性優異，可獲得具有所需硬度之抗反射膜、硬塗膜或抗靜電膜等功能膜。另外，前述硬化性組成物中亦可添加有機溶劑作爲溶劑，且可使用習知者。有機溶劑之具體例可列舉爲甲醇、乙醇、異丙醇、丁醇、辛醇等醇類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；乙酸乙酯、乙酸丁酯、乳酸乙酯、γ-丁內酯、丙二醇單甲基醚乙酸酯、丙二醇單乙 '基醚乙酸酯等酯類；乙二醇單甲基醚、二乙二醇單丁基醚等醚類；苯、甲苯、二甲苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、Ν-甲基吡咯烷酮等醯胺類。該等溶劑可單獨使用一種，亦可倂用兩種以上。前述功能膜之厚度較好爲Ο.ίμιη〜20μιη，更好爲 0.5μιη~10μηι，最好爲 0.7μηι〜5μπι。又，爲提高樹脂製基板（I )與功能膜及/或近紅外線反射膜之密著性，或功能膜與近紅外線反射膜之密著性，樹脂製基板（I)或功能膜之表面亦可經電暈處理或電漿處理等表面處理。《近紅外線截止濾波器》本發明之近紅外線截止濾波器之光線透射率較好滿足下述（Α)〜（D)。 (Α)在波長430〜580nm之範圍內’自近紅外線截止濾波器之垂直方向測定時之透射率平均値宜爲7 5 %以上’ 較好爲78%以上，更好爲80%以上之値。本發明中藉由使 -63- 201211125 用於厚度0.1 mm之全光線透射率高之樹脂，且於該波長區域中不具有吸收之化合物（I)等，可獲得於該波長 430〜5 8 0nm具有高透射率之近紅外線截止濾波器。將近紅外線截止濾波器使用於固體攝影裝置或照相機模組等透鏡單元中之視感度補正用濾波器等時，較好於波長430〜5 80nm之透射率之平均値在前述範圍，且在該波長範圍內之透射率爲固定。於波長43 0〜5 80 nm之範圍內之透射率之平均値較高較佳。透射率之平均値若高，則可充分確保通過濾波器之光的強度，可較好地使用於前述用途。另一方面，於波長43 0~5 80nm之範圍內之透射率平均値若低，則無法充分確保通過濾波器之光的強度，故有無法適用於前述用途之虞。 (B)在波長8 00〜lOOOnm範圍內，自近紅外線截止濾波器之垂直方向測定時之透射率平均値宜成爲20%以下，較好爲1 5 %以下，更好爲1 0%以下之値。本發明藉由在樹脂製基板（I )上設置具有高的近紅外線反射能之特定近紅外線反射膜，可獲得該種於波長800~1 000nm之透射率充分低之近紅外線截止濾波器。本發明之近紅外線截止濾波器係爲了選擇性地減低近紅外線之波長（800nm以上）者，故於800〜1 OOOnm範圍內之透射率平均値較低者較佳。透射率之平均値低時，近紅外線截止濾波器可充分截止近紅外線。 ’ 另一方面，在波長800~ 1 000nm範圍內之透射率平均値 -64- 201211125 若高，則濾波器無法充分截止近紅外線，於該濾波器用於 PDP等時，會有無法防止家庭內之PDP週邊之電子設備誤作動之虞。 (C )在800nm以下之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲70%之最長波長（ Xa)，與在波長5 80nm以上之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲30%之最短波長 (Xb )之差的絕對値（|Xa_Xb| )宜未達75nm，較好未達 72nm，更好未達70nm之値。本發明中，藉由使用前述化合物（I)，可獲得成爲特定透射率之波長之差的絕對値在前述特定範圍之近紅外線截止濾波器。近紅外線截止濾波器之（Xa)與（Xb)之差之絕對値若在前述範圍內，則近紅外線之波長區域附近之波長（Xa )與（Xb)之間之透射率急遽變化，故可有效地截止近紅外線，且，可獲得下述（Ya )與（Yb )之差之絕對値小、吸收波長之入射角之依存性小、視角廣之近紅外線截止濾波器。 (D)在波長560〜800nm之範圍內，較好在5 80〜800nm 之範圍內，自近紅外截止濾波器之垂直方向測定時之透射率成爲50%之波長之値（Ya)，與自相對於近紅外線截止濾波器之垂直方向爲3 0。之角度測定時之透射率成爲50%之波長之値（Yb )之差的絕對値（|Ya-Yb| )宜未達15nm ’ 較好未達13nm，更好未達10nm之値。本發明中藉由使用前述化合物（I)，可獲得成爲特 -65- 201211125 定透射率之波長之差的絕對値在前述特定範圍內之近紅外線截止濾波器。如此’波長560〜800nm之範圍內，（Ya)與（γ”之差的絕對値在前述範圍內時，該濾波器用於PDP等時，自斜方向觀看顯示器時’亦顯示與自垂直方向觀看之情況相同之明亮度與色調’可獲得吸收波長之入射角依存性小、視角廣之近紅外線截止濾波器。另一方面’將（Ya )與（Yb )之差的絕對値爲i5nm 以上之近紅外線截止濾波器用於PDP等時，會有隨著觀看顯示器之角度而顯著減低明亮度，使色調反轉，不易看見特定顏色之虞’故有不適用於前述用途之情況。此處，所謂「視角」爲由上下左右觀看顯示器時，顯示可正常看見畫面之某位置角度之指標。本發明中，亦指自上下左右觀看近紅外線截止濾波器時，顯示可正常觀看畫面之某位置角度之指標。是否可正常觀看之判斷，在本發明中係以在波長560〜 800nm之範圍內，自濾波器之垂直方向測定時之透射率成爲50%之波長之値（Ya)，與自相對於濾波器之垂直方向成30°角度時之透射率成爲50%之波長之値（Yb)之差的絕對値成爲未達15nm作爲一個基準。前述近紅外線截止濾波器之厚度較好調整至使該濾波器之透射率滿足前述（A ) ~ ( D)，雖無特別限制，但較好爲50〜250nm，更好爲50〜200nm，又更好爲80〜150nm。近紅外線截止濾波器·之厚度若在前述範圍，則可使濾 -66- 201211125 波器小型化、輕量化，可較好地使用於固體攝影裝置等各種用途中。尤其使用於照相機模組等之透鏡單元時，可實現透鏡單元之薄型化故而較佳。〈近紅外線截止濾波器之用途〉本發明中獲得之近紅外線截止濾波器具有廣視角、優異近紅外線截止能等。因此可使用作爲照相機模組之CCD 或CMOS等之固體攝影元件之視感度補償用。尤其，可使用於數位相機、行動電話用之相機、數位錄影機、PC相機、監控照相機、汽車用照相機、電視、汽車導航、行動資料終端機、個人電腦、影像遊戲機、醫療設備、USB記億體、攜帶式遊戲機、指紋辨識系統、數位音樂播放器、玩具機器人及玩具等之中。另外，於作爲安裝於汽車或建築物等之玻璃等之熱線截止濾波器等亦有用。此處，針對於照相機模組中使用本發明中獲得之近紅外線截止濾波器之情況加以具體說明。圖1顯示照相機模組之剖面槪略圖。圖1 ( a )爲以往之照相機模組之構造的剖面槪略圖，圖1 ( b )爲表示使用於本發明獲得之近紅外線截止濾波器 6 ’之情況下可確實獲得之照相機模組之構造之一之剖面槪略圖。圖1 (b)中，在透鏡5之上部使用於本發明獲得之近紅外線截止濾波器6’，但於本發明獲得之近紅外線截止濾波器6’亦可使用於如圖1(a)中所示之透鏡5與感知器7之 -67- 201211125 間。以往之照相機模組光必須以對近紅外線截止濾波器6 幾乎垂直地入射。因此，濾波器6必須配置在透鏡5與感知器7之間。此處，由於感知器7爲高感度，而有僅與於5 μ左右之灰塵或塵埃接觸即無法正確作動之虞，故於感知器7之上部使用之濾波器6爲無灰塵或塵埃者，有必要爲不含異物者。且，由前述感知器7之特性，濾波器6與感知器7之間有必要設有特定間隔，以將成爲阻礙照相機模組薄型化之 —原因。相對於此，於本發明獲得之近紅外線截止濾波器6’之 (Ya )與（Yb )之差的絕對値爲15nm以下。亦即，自濾波器6’之垂直方向入射之光，與自相對於濾波器6’之垂直方向成3 0°入射之光之透射波長並無太大差異（吸收（透射）波長之入射角依存性小），故濾波器6 ’不需要配置在透鏡5與感知器7之間，亦可配置在透鏡上部。因此，將本發明獲得之近紅外線截止濾波器6’用於照相機模組時，該照相機模組之操作性變容易，且，在濾波器6’與感知器7之間不需設置特定間隔，故使照相機模組之薄型化成爲可能。〔實施例〕以下以實施例說明本發明，但本發明並不受該等實施例之任何限制。又，「份」若無特別說明則意指「重量份 -68- 201211125 首先，針對各物性値之測定方法及物性之評價加以說明。 (1 )分子量：使用安裝有TOSOH製造之Η型管柱之WATERS公司製造之凝膠滲透層析儀（GPC)裝置（150C型），以鄰-二氯苯溶劑、1 20°C之條件下測定標準聚苯乙烯換算之重量平均分子量（Mw)及數平均分子量（Μη)。 (2 )玻璃轉移溫度（Tg ): 使用SII Nanotechnology股份有限公司製造之示差掃描熱量計（DSC6200)，升溫速度：每分鐘20°C，在氮氣流下測定。 (3 )飽和吸水率：以ASTM D570爲準，自於合成例獲得之樹脂製作厚度 3mm，長度50mm，寬度50mm之試驗片，將所得試驗片浸漬於23 °C水中一週後，由試驗片之重量變化測定吸水率。 (4 )分光透射率：使用日立高科技股份有限公司製造之分光光度計（U-4 100 )測定。此處，自近紅外線截止濾波器之垂直方向測定時之透射率係如圖2般，測定對於濾波器垂直透射之光。又，自相對於近紅外線截止濾波器之垂直方向成30° 之角度測定時之透射率係如圖3所示，測定以相對於近紅外線截止濾波器之垂直方向成3 0°之角度透射之光。 -69- 201211125 又，該透射率除測定（Yb )之情況以外，係在使光相對於基板、濾波器成垂直入射之條件下，使用該分光光度計測定者。測定（Yb )之情況爲以使光相對於濾波器之垂直方向成3 0 °之角度入射之條件下，使用該分光光度計測定者。〔合成例1〕將以下述式（a)表示之8-甲基-8-甲氧基羰基四環〔 4.4.0.12’5.17’1Q〕十二碳-3-烯（以下亦稱爲「DNM」）100 份，1-己烯（分子量調節劑）18份及甲苯（開環聚合反應用溶劑）300份饋入經氮氣置換之反應容器中，將該溶液加熱至80°C。接著，於反應容器內之溶液中添加作爲聚合觸媒之三乙基鋁之甲苯溶液（〇.6111〇1/升）0.2份，及甲醇改質之六氯化鎢之甲苯溶液（濃度〇.〇25mol/升）0.9份，該溶液於80°C加熱攪拌3小時獲得經開環聚合反應之開環聚合物溶液。該聚合反應中之聚合轉化率爲97%。【化2 6】-46- 201211125 In the above formula (8), R5, R6, Z' η, e, and f are independent of each of the formula (3), and R5, R6, Z, n, e, and f are synonymous 'RA each independent formula (6) The RA in the synonym. The compound represented by the above formula (8) is exemplified by hydroquinone, m-phenol, 2-phenylhydroquinone, 4,4,-biphenol, 3,3'-biphenol, 4,4'-dihydroxyindole, 3 , 3'-dihydroxydiphenylanthracene, 4,4'-dihydroxydiphenyl 3,3'-dihydroxybenzophenone, 1,1'-bi-2-naphthol, 1,1'-linked -4-2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl), 2,2-bis(4-hydroxyphenyl)-1,1,1,3 , 3,3-hexafluoropropane and the like. Among the above compounds, preferred are metaxyl phenol phenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxycyclohexane, 2,2-bis(4- From the viewpoint of reactivity of hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropyl and mechanical properties, it is preferred to use a 4,4'-biphenol compound in combination of two or more. The resin (1) can be more specifically synthesized by the method shown below. Method (I '): The component (B) is reacted with an alkali metal compound in an organic solvent to obtain a component (B) (compound (6) and/or After the compound (;8) or the like is a salt, the obtained alkali metal salt is reacted with the component (A), and the component (B) and the alkali metal compound are further reacted in the presence of the component (A) to make the metal salt of the component (B). The reaction with the component (A) is the same as the above-mentioned benzoic benzophenone, naphthol, cyclohexyl or the like, and 4,4,-phenyl) alkane. The alkali metal compound used in the reaction may be exemplified by an alkali metal such as lithium, potassium or sodium; or a hydrogenated alkali metal such as lithium hydride, potassium hydride or sodium hydride; An alkali metal hydroxide such as lithium hydroxide, potassium hydroxide or sodium hydroxide; an alkali metal carbonate such as lithium carbonate, potassium carbonate or sodium carbonate; or an alkali metal hydrogencarbonate such as lithium hydrogencarbonate, potassium hydrogencarbonate or sodium hydrogencarbonate. These may be used alone or in combination of two or more. The amount of the metal atom in the alkali metal compound is usually from 1 to 3 equivalents, preferably from 1. 1 to 2 times the equivalent, more preferably 1. 2~1. Use in 5 equivalents. Further, as the organic solvent used in the reaction, hydrazine, hydrazine-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl can be used. Base-2-imidazolidinone, γ-butyrolactone, cyclobutyl, dimethyl hydrazine, diethyl hydrazine, dimethyl hydrazine, diethyl hydrazine, diisopropyl hydrazine, diphenyl hydrazine And diphenyl ether, benzophenone, dialkoxybenzene (the alkoxy group has a carbon number of 1 to 4), and a trialkoxybenzene (the alkoxy group has a carbon number of 1 to 4). Among these solvents, it is preferred to use a high dielectric constant of Ν-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, cyclobutyl hydride, diphenyl maple, and dimethyl fluorene. Organic solvents. These organic solvents may be used singly or in combination of two or more kinds. In the above reaction, benzene, toluene, dimethyl meth, hexa, hexaxy, xinyuan, qi, abdomen may be further used. A solvent that azeotropes with water, such as a hospital, tetrazolium, anisole, and phenylethyl alcohol. When the ratio of the (Α) component to the (Β) component is 1% by mole based on the total of the (Α) component and the (Β) component, the (Α) component is preferably 45%-48-201211125% by volume or more. Mol% or less, more preferably 50 mol% or more and 52 mol% or less, more preferably 50 mol% or less and 52 mol% or less, and (B) component is preferably 45 mol% or more and 55 mol% or less. More preferably, it is 48 mol% or more and 50 mol% or less, and more preferably 48 mol% or more and less than 50 mol%. Further, the reaction temperature is preferably from 60 ° C to 25 ° C, more preferably from 80 ° C to 200 ° C. The reaction time is preferably from 15 minutes to 100 hours, more preferably from 1 hour to 24 hours. The glass transition temperature (Tg) of the resin (1) by differential scanning calorimetry (DSC, heating rate 20 ° C / min) is preferably 23 0 to 3 50 ° C, more preferably 240 to 3 30 ° C. , and better is 25 0~3 00 °C. The glass transition temperature of the resin (1) is, for example, a 823 0 type DSC measuring device (temperature rising rate: 20 ° C/min) manufactured by Rigaku Co., Ltd. or a differential scanning calorimeter (DSC 62 00) manufactured by SII Nanotechnology Co., Ltd. (heating) The measurement was performed at a speed of 20 ° C / min). The resin (1) is measured by a HLC-8220 type GPC apparatus (column: TSKgel α-Μ, development solvent: tetrahydrofuran (hereinafter also referred to as "THF")) manufactured by TOSOH, and has a weight average molecular weight in terms of polystyrene ( 1^%) is preferably 5,000 to 50,000, 0 Torr, more preferably 1 5,000 to 400,000, still more preferably 3 0,000 to 300,000. The thermal decomposition temperature of the resin (1) measured by thermogravimetric analysis (TGA) is preferably 450 ° C or higher, more preferably 4 7 5 ° C or higher, and still more preferably 4 90 ° C or higher. <Polyimide Resin Resin> -49- 201211125 The transparent resin which can be used in the present invention is exemplified by a polyimide resin. The polyimine resin is not particularly limited, and may be a polymer having a quinone bond in a repeating unit, and may be synthesized, for example, by the method described in JP-A-2008-1631 07. Commercial products of the transparent resin which can be used in the present invention are exemplified by the following commercially available products. The commercially available product of the cyclic olefin resin is, for example, ARTON manufactured by JSR Co., Ltd., ZEONOR manufactured by Nippon Co., Ltd., APEL manufactured by Mitsui Chemicals Co., Ltd., TOPAS manufactured by Polyplastic Co., Ltd., and the like. A commercially available product of polyether oxime resin is SUMIKAEXCEL PES manufactured by Sumitomo Chemical Co., Ltd., and the like. A commercially available product of a polyimide resin is NEOPUR'IMU L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. A commercially available product of a polycarbonate resin is exemplified by PURE-ACE manufactured by Teijin Co., Ltd. Commercially available products of the organic-inorganic nano-mixed material are SILPLUS manufactured by Nippon Steel Chemical Co., Ltd., and the like. <Other components> In the resin substrate (I), an antioxidant, an ultraviolet absorber, a near-infrared absorbing dye or pigment, a metal complex compound, or the like may be further added to the extent that the effects of the present invention are not impaired. Additives. Further, when the resin substrate (I) is produced by the solution casting method described later, a flow agent or an antifoaming agent can be added, and the production of the resin substrate (I) can be facilitated. These other components may be used alone or in combination of two or more. The aforementioned antioxidants are exemplified by, for example, 2,6-di-t-butyl-4-methylphenol, -50-201211125 2,2'-dioxy-3,3'-di-t-butyl- 5,5 '-Dimethyldiphenylmethane, and hydrazine [methyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate [methane, etc.). Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Further, these additives may be simultaneously mixed in the resin when the resin substrate (I) is produced, or may be added at the time of resin production. Further, the amount of addition is appropriately selected depending on the desired characteristics, but is usually 0% with respect to 100 parts by weight of the resin. 01~5. 0 parts by weight, preferably 〇. 〇5~2. 0 parts by weight. <Method for Producing Resin-Based Substrate (I) Containing Compound (I)> The resin-made substrate (I) used in the present invention can be formed, for example, by melt molding or cast molding, and may be coated after molding as needed. A method of applying a coating agent such as an antireflective agent, a hard coating agent, and/or an antistatic agent. (A) a method of melt-molding the resin-made substrate (I) by melt-kneading the resin obtained by melt-blending the resin and the compound (I) and/or the compound (Γ); the resin and the compound (I) are contained. And/or a method for melt-forming a resin composition of the compound (Γ); to freely contain the compound (I) and Or a compound (Γ), a resin composition of the above resin and a solvent, and a method of melt-forming the pellet obtained by removing the solvent. The melt molding method is, for example, injection molding, melt extrusion molding, or blow molding. -51 - 201211125 (B) Casting the resin substrate (I) by casting a resin composition containing the compound (1) and/or the compound (Γ), the resin, and a solvent onto a suitable substrate and removing the solvent. Applying a coating agent containing an antireflective agent, a hard coating agent, and/or an antistatic agent, and a resin composition of the compound (I) and/or the compound (1 ') to an appropriate substrate, and containing an antireflective agent, A coating agent such as a hard coating agent and/or an antistatic agent, and a curable composition of the compound (I) and/or the compound (I') are applied onto a suitable substrate and cured by curing or drying. For example, the above resin composition can be applied to a substrate such as a transparent resin such as a glass plate, a steel strip, a steel roll, a polyester film or a cyclic olefin resin film, and the solvent can be dried to obtain a coating film, and then borrowed. The resin substrate (I) can be obtained by peeling off the coating film from the substrate. Further, as long as the effect of the present invention is not impaired, the coating film of the substrate and the coating film may be used as the resin substrate (I) without peeling off the coating film from the substrate. Further, the resin composition may be applied to an optical component such as a glass plate, quartz or a transparent plastic, and the solvent may be dried, and the coating agent, the solvent, and the compound (I) and/or the resin, the hard coating agent, and the like may be applied. Or the resin composition of the compound (Γ) is hardened and dried to form a resin substrate (I) directly on the optical component. The amount of the residual solvent in the resin substrate (I) obtained by the above method is preferably 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 amount of the residual solvent exceeds 3% by weight, the resin substrate (I) is deformed over time to change the characteristics, and the desired function cannot be exhibited. -52-201211125 <Near-infrared reflecting film> The near-infrared reflecting film used in the present invention is a film having the ability to reflect near-infrared rays. As the near-infrared reflective film, a resin film, a high refractive index material layer, and a low refractive index material layer in which a noble metal film is deposited as a noble metal film, a metal oxide fine particle containing a small amount of tin oxide as a main component, and a small amount of tin oxide are dispersed can be used. A dielectric multilayer film or the like which is laminated in an alternating manner. Since the near-infrared cut filter of the present invention has such a near-infrared reflecting film, it is characterized in particular by the following (B). Therefore, a filter which can sufficiently cut off near infrared rays can be obtained. In the present invention, the near-infrared reflective film may be provided on one surface of the resin substrate (I) or may be provided on both surfaces. When it is provided on one surface, it is excellent in manufacturing cost or ease of manufacture, and when it is provided on both surfaces, a near-infrared cut filter having high strength and being less likely to cause warpage can be obtained. In the near-infrared reflecting film, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are laminated in a cross layer can also be preferably used. The material constituting the high refractive index layer can be used with a refractive index of 1. For materials above 7 or more, the refractive index range is usually 1. 7~2. 5 materials. The materials are exemplified by, for example, titanium oxide, oxidized cone, pentoxide pentoxide, cerium pentoxide, cerium oxide, cerium oxide, zinc oxide, zinc sulfate, and indium oxide as a main component, and contain a small amount (for example, relative to the main component). For G~1 〇%). Titanium oxide, tin oxide and antimony oxide. The material constituting the low refractive index material layer may be a material having a refractive index of 1.6 or less, and the selected refractive index range is usually I. 2~1. 6 materials. These materials are exemplified by, for example, cerium oxide, aluminum oxide, cerium fluoride, fluorine-53 - 201211125 magnesium, 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 it can laminate the material layers to form a dielectric multilayer film. For example, the high refractive index material layer and the low refractive index can be directly formed on the resin substrate (I) by a CVD method, a sputtering method, a vacuum deposition method, an ion assisted vapor deposition method, an ion plating method, or the like. The material layers are laminated to form a dielectric multilayer film. The thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0 when the near infrared wavelength to be cut off is λ(ηΐη). 1λ~0. Thickness of 5λ" When the thickness is within this range, the optical film thickness and the high refractive index material layer and the low refractive index material layer of the product (nxd) of the refractive index (η) and the film thickness (d) are calculated as λ/4 The thickness of each layer is substantially the same, and the relationship between the optical characteristics of reflection and refraction makes it possible to easily control the cutoff and transmission of a specific wavelength. Further, the number of laminations in the dielectric multilayer film is preferably 5 to 60 layers, preferably 10 to 50 layers. Further, when the dielectric multilayer film is formed, warpage occurs on the substrate, and the state is not eliminated. A dielectric multilayer film is formed on both surfaces of the substrate, and the surface of the dielectric multilayer film on which the substrate is formed is irradiated with electromagnetic waves such as ultraviolet rays. Further, when electromagnetic waves are irradiated, they may be irradiated during formation of the dielectric multilayer film, or may be irradiated separately after formation. <<Other Functional Films>> The near-infrared cut-off filter of the present invention can be used in a near-infrared reflective film such as a resin substrate (I) and a dielectric multilayer film in the range of -54 to 201211125 which does not impair the effects of the present invention. An anti-reflection film is provided on the surface opposite to the surface on which the near-infrared reflecting film of the resin substrate (I) is provided, or on the surface opposite to the surface on which the resin-made substrate (I) is placed on the near-infrared reflecting film. A functional film such as a hard coat film or an antistatic film to improve the surface hardness of the resin substrate (I), to improve chemical resistance, antistatic properties, and to eliminate scratches. The near-infrared cut filter of the present invention may comprise a layer composed of the aforementioned functional film, or may have two or more layers. When the near-infrared cut filter of the present invention comprises a layer composed of two or more layers of the above functional film, it may contain two or more layers, or may have two or more layers. The method of laminating the functional film is not particularly limited, and a coating agent such as an antireflective agent, a hard coating agent, and/or an antistatic agent may be applied to the resin by a method such as the melt molding method and casting described above. On the substrate (I) or near-infrared reflective film. In addition, a curable composition containing the coating agent forming material or the like may be applied to a resin substrate (I) or a near-infrared reflective film by a bar coater or the like, and then cured by ultraviolet irradiation or the like to produce a crucible. The coating agent is exemplified by an ultraviolet (UV) / electron beam (EB) curing resin or a thermosetting resin, and is exemplified by an urethane type, an urethane acrylate type, or an acrylate type. Epoxy and epoxy acrylate rouge. The curable composition corresponding to the coating agent is exemplified by an urethane type, an urethane acrylate type, an acrylate type, an epoxy type, and an epoxy acrylate type hardening composition. . The component contained in the above-mentioned urethane-based or urethane-acrylate-curable group -55-201211125 can be exemplified by ginseng (2-hydroxyethyl) isocyanurate three (A) Acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, an oligomeric urethane having more than two (meth)acryloyl groups in the molecule (A) Acrylates, but are not limited to these examples. These components may be used alone or in combination of two or more. Further, an oligomer or a polymer such as a polyurethane (meth) acrylate may be blended. The acrylate-based curable composition is not particularly limited, and examples thereof include a composition containing a (meth) acrylate or a vinyl compound. Specific examples of the above (meth) acrylates include, for example, the following: Isobornyl (meth)acrylate, borneol (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (A) Cyclohexyl acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2-hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, -56- 201211125 ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylic acid Isopropyl ester, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (methyl) ) isoamyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (meth) methacrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Alkyl ester, dodecyl (meth)acrylate, lauryl (meth)acrylate, (meth) propylene. Acid stearyl ester, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, -57- 201211125 ethoxylated ethylene (meth) acrylate Glycol ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene 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, third octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , 7-Amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl(meth)acrylamide, hydrazine, hydrazine-dimethylaminopropyl (methyl) ) acrylamide, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, (methyl) Propylene 3-phenoxy-2-hydroxypropyl ester, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 2-hydroxyl (meth)acrylate -3-phenoxypropyl ester, p-cumylphenol ethylene oxide modified (meth) acrylate, -58- 201211125 2-bromophenoxyethyl (meth) acrylate, (methyl) 4-bromophenoxyethyl 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, di- Trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , triglyceride (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(a) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, -59- 201211125 (meth)acrylic acid cyclohexane Ester, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecane Dimethanol di(meth)acrylate, tricyclodecanemethanol (meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, tetracyclodecane diyl dimethanol di(methyl) An acrylate, a poly(meth) acrylate of an ethylene oxide or a propylene oxide adduct of a starting alcohol in the production of the compounds, having two or more (meth) acrylonitrile groups in the molecule. Oligoester (meth) acrylates and oligoether (meth) acrylates, but are not limited thereto. These components may be used alone or in combination of two or more. Further, an oligomer or a polymer such as polyester (meth) acrylate may be blended. Examples of the vinyl compound include, but are not limited to, vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Wait. These components may be used alone or in combination of two or more. The component contained in the epoxy-based or epoxy acrylate-based curable composition is not particularly limited, and examples thereof include (methyl) glycidyl acrylate, methyl glycidyl (meth)acrylate, and intramolecular. An oligomeric epoxy (meth) acrylate having two or more (meth) acrylonitrile groups. These components may be used alone or in combination of two or more. Further, an oligomer or a polymer such as polyepoxy (meth) acrylate may be blended at -60 to 201211125. Commercial products of the above-mentioned coating agent (containing a curable composition such as a coating agent forming material) are listed as LCH 'LAS manufactured by Toyo Ink Manufacturing Co., Ltd., BEAMSET manufactured by Arakawa Chemical Industries Co., Ltd., and limited by Daicel Scientech EBECRYL, 1; ¥8 (:1111 ugly, 811 811, Manufactured by the company 811 股份有限公司丁 11 11 11 11 11 。。。。。。。。。。。。。。。。。。。。。。。。。。。。 The photopolymerization initiator and the thermal polymerization initiator may be used in a conventional photopolymerization initiator or a thermal polymerization initiator. Specific examples of the polymerization initiator are not particularly limited and are listed below. Lister: 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, anthrone, benzaldehyde, hydrazine, triphenylamine, carbitol , 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Mickey (Michael) Ketone, benzoin propyl ether, -61 - 201211125 Benzene ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl)-2-hydroxy-2-methyl propyl 1-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, Bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide. Among these, 1-hydroxycyclohexyl phenyl ketone is preferred. These polymerization initiators may be used alone or in combination of two or more. Commercially available products are listed as Irgacure 184, 369, 651, 500, 907, CGI 1 700 'CGI 1 75 0, CGI 1 8 50, CG24-61, Darocure TPO (above is produced by Ciba Specialty Chemicals), lucirin LR8728 ' (made by BASF), Darocure 1 1 16 6, 1 1 73 (above is manufactured by Merck), UBECRYL P36 (manufactured by UCB Corporation). In the above curable composition, the blending ratio of the polymerization initiator is 10% by weight based on the total amount of the @chemical composition, preferably 〇. 1 to 1 〇% by weight, preferably 0. 5 to 10% by weight, more preferably ^% by weight. When the blending ratio of the polymerization initiator is within the above range, the hardening property of the curable composition and the handling property are excellent, and a functional film such as an antireflection film, a hard coating film or an antistatic film having a desired hardness can be obtained. . Further, an organic solvent may be added as a solvent to the curable composition, and a conventional one may be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ethyl acetate; , butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other esters; ethylene glycol monomethyl ether, diethylene glycol single An ether such as butyl ether; an aromatic hydrocarbon such as benzene, toluene or xylene; or a guanamine such as dimethylformamide, dimethylacetamide or hydrazine-methylpyrrolidone. These solvents may be used singly or in combination of two or more. The thickness of the aforementioned functional film is preferably Ο. Μμηη~20μιη, preferably 0. 5μιη~10μηι, preferably 0. 7μηι~5μπι. Further, in order to improve the adhesion between the resin substrate (I) and the functional film and/or the near-infrared reflective film, or the adhesion between the functional film and the near-infrared reflective film, the surface of the resin substrate (I) or the functional film is also Surface treatment such as corona treatment or plasma treatment. <<Near-infrared cut filter>> The light transmittance of the near-infrared cut filter of the present invention satisfies the following (Α) to (D). (Α) In the range of wavelength 430 to 580 nm, the transmittance at the time of measurement from the vertical direction of the near-infrared cut filter is preferably at least 75% or more, preferably 78% or more, more preferably 80% or more. . In the present invention, by using -63-201211125 for thickness 0. A resin having a high total light transmittance of 1 mm and having no absorption compound (I) or the like in the wavelength region can be obtained as a near-infrared cut filter having a high transmittance at a wavelength of 430 to 580 nm. When the near-infrared cut-off filter is used for a luminosity correction filter or the like in a lens unit such as a solid-state imaging device or a camera module, it is preferable that the average transmittance of the transmittance at a wavelength of 430 to 580 nm is within the aforementioned range, and at the wavelength The transmittance in the range is fixed. The average 値 of the transmittance in the wavelength range of 43 0 to 5 80 nm is preferably higher. If the average value of the transmittance is high, the intensity of light passing through the filter can be sufficiently ensured, and it can be preferably used for the above-mentioned use. On the other hand, if the average transmittance of the light in the range of the wavelength of 43 0 to 500 nm is low, the intensity of the light passing through the filter cannot be sufficiently ensured, and therefore it is not suitable for the above-mentioned use. (B) In the range of wavelengths of 00 to 100 nm, the transmittance at the time of measurement from the vertical direction of the near-infrared cut filter is preferably 20% or less, preferably 15% or less, more preferably 10% or less. value. In the present invention, by providing a specific near-infrared reflecting film having high near-infrared reflection energy on the resin substrate (I), it is possible to obtain a near-infrared cut filter having a sufficiently low transmittance at a wavelength of 800 to 1 000 nm. In the near-infrared cut filter of the present invention, in order to selectively reduce the wavelength of near-infrared rays (800 nm or more), the average transmittance of light in the range of 800 to 1 OOO nm is preferably lower. When the average transmittance is low, the near-infrared cut-off filter can sufficiently cut off near-infrared rays. On the other hand, if the transmittance of the wavelength in the range of 800 to 1 000 nm is 値-64-201211125, if the filter is high, the filter cannot sufficiently cut off the near-infrared rays. When the filter is used for a PDP or the like, it may not be prevented in the home. The electronic equipment around the PDP is mistaken. (C) In the wavelength region of 800 nm or less, the transmittance at the time of measurement from the vertical direction of the near-infrared cut filter becomes the longest wavelength (Xa) of 70%, and in the wavelength region of the wavelength of 580 nm or more, the near-infrared ray is cut off. The absolute 値(|Xa_Xb|) of the difference between the shortest wavelength (Xb) at which the transmittance is 30% in the vertical direction of the filter is preferably less than 75 nm, preferably less than 72 nm, more preferably less than 70 nm. In the present invention, by using the above compound (I), a near-infrared cut filter having an absolute 差 which is a difference in wavelength of a specific transmittance in the above specific range can be obtained. If the absolute value of the difference between (Xa) and (Xb) of the near-infrared cut filter is within the above range, the transmittance between the wavelengths (Xa) and (Xb) near the wavelength region of the near-infrared rays changes rapidly, so The near-infrared rays are effectively cut off, and a near-infrared cut filter having a small absolute difference between (Ya) and (Yb), a small dependence of an incident angle of an absorption wavelength, and a wide viewing angle can be obtained. (D) In the range of wavelength 560 to 800 nm, preferably in the range of 580 to 800 nm, the transmittance at the time of measurement from the vertical direction of the near-infrared cut filter becomes 50% (Ya), and The vertical direction with respect to the near-infrared cut filter is 30. The absolute 値(|Ya-Yb|) of the difference between the wavelengths (Yb) at which the transmittance is 50% is preferably less than 15 nm', preferably less than 13 nm, more preferably less than 10 nm. In the present invention, by using the above-mentioned compound (I), a near-infrared-line cut filter which is an absolute enthalpy of the difference in wavelength between the wavelengths of the specific wavelength of -65 - 201211125 can be obtained within the above specific range. When the absolute value of the difference between (Ya) and (γ) is within the above range in the range of 560 to 800 nm, when the filter is used for a PDP or the like, when viewing the display from an oblique direction, it is also displayed and viewed from the vertical direction. In the case of the same brightness and color tone, a near-infrared cut filter having a small incident angle dependence of the absorption wavelength and a wide viewing angle can be obtained. On the other hand, the absolute value of the difference between (Ya) and (Yb) is i5 nm or more. When the near-infrared cut-off filter is used for a PDP or the like, there is a case where the brightness is remarkably reduced as the angle of the display is viewed, the color tone is reversed, and the specific color is not easily seen, so that it is not suitable for the above-mentioned use. When the "viewing angle" is viewed from the top, bottom, left, and right, the display shows an angle at which a certain position of the screen can be normally seen. In the present invention, when the near-infrared cut filter is viewed from the top, bottom, left, and right, the position angle of the normal viewing screen is displayed. The judgment of whether or not the normal viewing is possible in the present invention is the transmission in the vertical direction of the filter in the range of the wavelength of 560 to 800 nm.値 (Ya) which is 50% of the wavelength, and the absolute 値 of the difference (Yb) between the wavelengths at which the transmittance becomes 50% from the direction perpendicular to the vertical direction of the filter becomes less than 15 nm as a reference. 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 nm, more preferably 50 to 200 nm. Further, it is preferably 80 to 150 nm. When the thickness of the near-infrared cut filter is within the above range, the filter can be reduced in size and weight, and can be preferably used in various applications such as a solid-state imaging device. In particular, when a lens unit such as a camera module is used, it is preferable to reduce the thickness of the lens unit. <Application of Near Infrared Cut Filter> The near-infrared cut filter obtained in the present invention has a wide viewing angle and excellent near infrared rays. It can be used for the visual sensitivity compensation of a solid-state imaging device such as a CCD or a CMOS of a camera module. In particular, it can be used for a digital camera, a camera for a mobile phone, and a digital video recorder. , PC cameras, surveillance cameras, automotive cameras, televisions, car navigation, mobile data terminals, personal computers, video game consoles, medical devices, USB devices, portable game consoles, fingerprint recognition systems, digital music players, It is also useful as a hot wire cut-off filter or the like for mounting on a glass such as a car or a building, etc. Here, the near-infrared cut filter obtained by the present invention is used for a camera module. Fig. 1 shows a schematic cross-sectional view of a camera module. Fig. 1 (a) is a schematic cross-sectional view showing the structure of a conventional camera module, and Fig. 1 (b) is a view showing the use of the present invention. In the case of the infrared cut filter 6', a schematic cross-sectional view of one of the configurations of the camera module can be obtained. In Fig. 1(b), the near-infrared cut filter 6' obtained by the present invention is used in the upper portion of the lens 5, but the near-infrared cut filter 6' obtained in the present invention can also be used in Fig. 1(a). The lens 5 shown is between -67 and 201211125 of the sensor 7. In the past, the camera module light had to be incident almost perpendicularly to the near-infrared cut filter 6. Therefore, the filter 6 must be disposed between the lens 5 and the sensor 7. Here, since the sensor 7 is highly sensitive and has no contact with dust or dust of about 5 μ, the filter 6 used in the upper portion of the sensor 7 is dust-free or dust-free. It is necessary to be free of foreign objects. Further, due to the characteristics of the above-described sensor 7, it is necessary to provide a specific interval between the filter 6 and the sensor 7, so as to hinder the thinning of the camera module. On the other hand, the absolute 差 of the difference between (Ya) and (Yb) of the near-infrared cut filter 6' obtained by the present invention is 15 nm or less. That is, the light incident from the vertical direction of the filter 6' is not much different from the transmission wavelength of light incident at 30° from the vertical direction of the filter 6' (incidence angle of absorption (transmission) wavelength) Since the dependency is small, the filter 6' does not need to be disposed between the lens 5 and the sensor 7, and may be disposed on the upper portion of the lens. Therefore, when the near-infrared cut filter 6' obtained by the present invention is used for a camera module, the operability of the camera module becomes easy, and a specific interval is not required between the filter 6' and the sensor 7. Therefore, the thinning of the camera module is made possible. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited by the Examples. In addition, "parts" means "parts by weight - 68 - 201211125. First, the measurement method and physical properties of each physical property are described. (1) Molecular weight: Η-type pipe column manufactured by using TOSOH A gel permeation chromatography (GPC) device (Model 150C) manufactured by WATERS, measuring the weight average molecular weight (Mw) and the number of standard polystyrene in an o-dichlorobenzene solvent at 10 °C Average molecular weight (Μη) (2) Glass transition temperature (Tg): Using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnology Co., Ltd., heating rate: 20 ° C per minute, measured under a nitrogen stream. (3) Saturated Water absorption rate: According to 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 one week, and the water absorption was measured from the weight change of the test piece. (4) Spectral transmittance: measured by a spectrophotometer (U-4 100) manufactured by Hitachi High-Technologies Co., Ltd. Here, the measurement from the vertical direction of the near-infrared cut filter The transmittance is measured as the light transmitted vertically to the filter as shown in Fig. 2. Further, the transmittance when measured at an angle of 30° with respect to the vertical direction of the near-infrared cut filter is as shown in Fig. 3, and the measurement is relative to The light transmitted at an angle of 30° in the vertical direction of the near-infrared cut filter. -69- 201211125 In addition, the transmittance is made to make the light perpendicular to the substrate and the filter, except for the case of the measurement (Yb). The measurement was carried out using the spectrophotometer. The measurement (Yb) was carried out using the spectrophotometer under the condition that the light was incident at an angle of 30° with respect to the vertical direction of the filter. Example 1] 8-methyl-8-methoxycarbonyltetracyclohexane represented by the following formula (a) [4] 4. 0. 12’5. 17'1Q] 100 parts of dodeca-3-ene (hereinafter also referred to as "DNM"), 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization) are fed through nitrogen In the replacement reaction vessel, the solution was heated to 80 °C. Next, a toluene solution of triethylaluminum as a polymerization catalyst is added to the solution in the reaction vessel (〇. 6111〇1/liter)0. 2 parts, and methanol modified toluene solution of tungsten hexachloride (concentration 〇. 〇25mol/L)0. 9 parts, the solution was heated and stirred at 80 ° C for 3 hours to obtain a ring-opening polymer solution by ring-opening polymerization. The polymerization conversion ratio in this polymerization reaction was 97%. [Chem. 2 6]

將如此獲得之開環聚合物溶液1，000份饋入高壓釜中，於該開環聚合物溶液中添加0.12份之RuHCl ( CO ) 〔 P -70- 201211125 (C6H5 ) 3〕3，在氫氣壓l〇〇kg/Cm2，反應溫度165°c之條件下，加熱攪拌3小時進行氫化反應。使所得反應溶液（氫化聚合物容易）冷卻後，將氫氣釋壓。將該反應溶液注入大量甲醇中且分離回收凝固物，並使之乾燥，獲得氫化聚合物（以下亦稱爲「樹脂A」）。樹脂A之分子量係數平均分子量（Μη)爲32,0 00，重量平均分子量（Mw )爲1 37,000，玻璃轉移溫度（Tg )爲 165°C » 〔合成例2〕於經充分乾燥、經氮氣置換之1升不銹鋼製高壓釜中饋入水份6ppm之經脫水環己烷420.4g;對-二甲苯180.2g; 5-三甲氧基矽烷基-雙環〔2.2.1〕庚-2-烯48.75mmol ( 10.43呂）及雙環〔2.2.1〕庚-2-烯 1.425111111〇1(134.4)，以使高壓釜之內壓成爲0.1 MPa之方式饋入氣體狀乙烯。隨後，將高壓釜加溫至7 5 t。將觸媒成分之2-乙基己酸鈀（以Pd原子計）：0.003 mg 原子與三環己基膦：0.0015mmol添加於甲苯：l〇ml中，在 2 5°C反應1小時調製溶液，以該溶液總量，及三苯基碳鑰五氟苯基硼酸鹽：〇.〇〇315mmol之順序添加於加溫至75°C之高壓釜中開始聚合。在聚合開始90分鐘後，將5-三甲氧基矽烷基-雙環〔 2.2.1〕庚-2 -稀 11.25mmol(2.41g)，隨後每 30 分鐘添加 7 · 5 mm ο 1 ( 1 · 6 1 g ) 、3.7 5 mmo 1 ( 0.8 0 g ) ·、3.7 5 mmo 1 )共 -71 - 201211125 計四次添加於高壓釜中。在75 °C進行聚合反應4小時後，添加三丁基胺：1ml終止聚合，獲得固體成分19.9重量％之加成聚合物B之溶液。將加成聚合物B之溶液之一部分倒入異丙醇中，經凝固，再經乾燥，獲得加成聚合物B (以下亦稱爲「樹脂B」）。該樹脂B之270MHz-核磁共振分析（1H-NMR分析）之結果，樹脂B中之源自5-三甲氧基矽烷-雙環〔2.2.1〕庚-2-烯之構造單位之比例爲4.8莫耳％，分子量係數平均分子量（Μη)爲74,000，重量平均分子量（Mw)爲1 85,000，玻璃轉移溫度（T g )爲3 6 0 °C，飽和吸水率爲0.3 5 %。〔合成例3〕 , 在氮氣流下’於備置溫度計、攪拌器、氮氣導入管、附有側管之滴加漏斗、Dean-Stark管、冷卻管之5 00mL五頸燒瓶中’將4,4’-二胺基二苯基醚10.0重量份（0.05莫耳 )溶解於作爲溶劑之N -甲基-2-吡咯烷酮85重量份中之後 ’在室溫下，於1小時內直接以固體分批投入丨，2,4,5-環己烷四羧酸二酐11.2重量份（〇.〇5莫耳），在室溫下攪拌2小時。接著’添加作爲共沸脫水溶劑之二甲苯3 〇 . 0重量份且升溫至180°C後，進行反應3小時，以Dean-Stark使二甲苯回流’分離共沸之生成水。3小時後，確認水之餾出終止 ’於1小時內升溫至190 °C同時餾除二甲苯，回收29.0重量份以後，使內溫空氣冷卻至6 0。(：，獲得聚醯亞胺的n -甲基· -72- 201211125 2-吡咯烷酮溶液（以下亦稱爲「聚醯亞胺溶液C」）105.4 重量份。〔合成例4〕於3升之四頸燒瓶中添加2，6-二氟苯甲腈35.12g ( 0.253mol) 、9,9-雙（3-苯基-4-羥基苯基）蕗 125.65g ( 0.250mol )、碳酸鉀 41.46g( 0.30 0mol) 、N，N-二甲基乙醯胺（以下亦稱爲「DMAc」）443g及甲苯lllg。接著，於四頸燒瓶上裝置溫度計、攪拌機、附加氮氣導入管之三向旁通栓、Dean-Stark管及冷卻管。接著，燒瓶內經氮氣置換後，使所得溶液在140°C反應3小時，且自Dean-St ark管隨時去除生成之水。未確認到水生成之後，使溫度緩慢上升至1 6(TC，在該溫度反應6小時。冷卻至室溫（25t )後，以濾紙去除生成之鹽，將濾液倒入甲醇中再沉澱，藉過濾單離過濾物（殘留物）。所得過濾物在60°C真空乾燥隔夜，獲得白色粉末D(以下稱爲樹脂I))(收量9 5.6 7 g，收率9 5 % )。進行所得聚合物之構造分析。結果，紅外線吸收光譜之特性吸收爲 3 03 5 cm·1 ( C-H伸縮）、2229cm·1 ( CN )、 1574CHT1、1499cm·1 (芳香環骨架吸收）、1240cm·1 ( -〇· )。樹脂D之分子量係數平均分子量（Μη)爲67,000，重量平均分子量（Mw)爲146,000，玻璃轉移溫度（Tg)爲 275C。所得聚合物具有則述構造（1)。 -73- 201211125 〔合成例5〕除使用9,9-雙（4-羥基苯基）莽87.60g( 0.250mol) 代替 9,9-雙（3-苯基-4·羥基苯基）^^5.658( 0.250^101) 以外’餘與合成例4同樣進行合成，獲得樹脂e。樹脂E之分子量係數平均分子量（Μη)爲75,000，重量平均分子量 (Mw)爲1 88,000，玻璃轉移溫度（Tg)爲285 〇c。〔合成例6〕除使用9,9·雙（4-羥基苯基）蒹78 84g ( 〇 225m〇i ) 及9,9-雙（4-羥基苯基）環己烷6.71g( 0.025mol)代替 9,9-雙（3-苯基-4-羥基苯基）苐i 25.65g( 0.250mol)以外，餘與合成例4同樣進行合成，獲得樹脂ρ。樹脂F之分子量係數平均分子量（Μη)爲36,000，重量平均分子量（ Mw)爲78,000’玻璃轉移溫度（Tg)爲260。(3。〔合成例7〕除使用 4,4-一氟—苯基楓（dfdS) 78.84g( 0.250mol )代替2,6-—氟本甲腈35.12g(〇253mol)以外，餘與合成例4同樣進行合成，獲得樹脂樹脂α之分子量係數平均分子量（Μη)爲37, 〇〇〇，重量平均分子量（Mw)爲 1 3 2,000，玻璃轉移溫度（Tg)爲265 t。〔實施例1〕 • 74 - 201211125 將JSR股份有限公司製造之環狀烯烴系樹脂「ART0N Gj 100重量份、方酸（squarylium)系化合物「a-10」 0.04重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度 20重量％之溶液（exl )。接著，將該溶液澆鑄於平滑玻璃板上，在20 °C乾燥8 小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於 1 00 °C乾燥8小時，獲得厚度0.1 mm，長度60mm，寬度 60mm之基板。測定該基板之分光透射率，求得吸收極大波長及（Za )、（Zb)。其結果示於表1。該基板之吸收極大波長爲699 nm。且，波長 43 0~800nm之波長區域中，透射率成爲70%之吸收極大以下之最長波長（Za )，與波長5 80nm以上之波長區域中，透射率成爲30%之最短波長（Zb)之差的絕對値（丨Za-Zb| )爲 45nm。接著，於該基板之單面上，在蒸鑛溫度1〇〇 °C形成反射近紅外線之多層蒸鍍膜〔使二氧化矽（Si02 :膜厚 83~199nm)層與二氧化鈦（Ti02:膜厚101〜125nm)層交互層合而成者，層合數20〕。再於基板另一面上以蒸鍍溫度1 〇〇°C形成反射近紅外線之多層蒸鍍膜〔使二氧化矽（ Si02 :膜厚77〜189nm )層與二氧化鈦（Ti02 :膜厚 84~118nm)層交互層合而成者，層合數26〕，獲得厚度 0.1 0 5 mm之近紅外線截止濾波器。測定該近紅外線截止濾波器之分光透射率，求得（Xa) 、（Xb)與（Ya)、（ -75- 2012111251,000 parts of the thus obtained ring-opening polymer solution was fed into the autoclave, and 0.12 parts of RuHCl (CO) [P-70-201211125 (C6H5)3]3 was added to the ring-opening polymer solution in hydrogen. The pressure was 10 kg/cm 2 and the reaction temperature was 165 ° C, and the mixture was heated and stirred for 3 hours to carry out a hydrogenation reaction. After the obtained reaction solution (hydrogenated polymer was easily used) was cooled, hydrogen gas was released. The reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The molecular weight coefficient of the resin A has an average molecular weight (?η) of 32,00, a weight average molecular weight (Mw) of 1 37,000, and a glass transition temperature (Tg) of 165 ° C » [Synthesis Example 2] After being sufficiently dried and replaced with nitrogen In a 1 liter stainless steel autoclave, 420.4 g of dehydrated cyclohexane having a water content of 6 ppm was fed; 180.2 g of p-xylene; 5-trimethoxydecyl-bicyclo[2.2.1]hept-2-ene 48.75 mmol (10.43 lv) and bicyclo [2.2.1]hept-2-ene 1.425111111 〇 1 (134.4) were fed with gaseous ethylene so that the internal pressure of the autoclave became 0.1 MPa. Thereafter, the autoclave was warmed to 75 t. Palladium 2-ethylhexanoate (calculated as Pd atom) of the catalyst component: 0.003 mg atom and tricyclohexylphosphine: 0.0015 mmol was added to toluene: 10 ml, and the solution was prepared by reacting at 25 ° C for 1 hour. The polymerization was started by adding the total amount of the solution and triphenylcarbo-pentafluorophenylborate: 〇〇.〇〇 315 mmol to an autoclave heated to 75 ° C. After 90 minutes from the start of the polymerization, 5-trimethoxydecyl-bicyclo[2.2.1]heptane-2-diluted 11.25 mmol (2.41 g), followed by addition of 7 · 5 mm ο 1 (1 · 6 1) every 30 minutes g ) , 3.7 5 mmo 1 (0.8 0 g ) ·, 3.7 5 mmo 1 ) Total -71 - 201211125 Four times added to the autoclave. After the polymerization reaction was carried out at 75 ° C for 4 hours, tributylamine was added: 1 ml of the polymerization was terminated to obtain a solution of the addition polymer B having a solid content of 19.9% by weight. One part of the solution of the addition polymer B is poured into isopropyl alcohol, solidified, and dried to obtain an addition polymer B (hereinafter also referred to as "resin B"). As a result of 270 MHz-NMR analysis (1H-NMR analysis) of the resin B, the ratio of the structural unit derived from 5-trimethoxynonane-bicyclo[2.2.1]hept-2-ene in the resin B was 4.8 mol. The ear %, the molecular weight coefficient average molecular weight (?n) was 74,000, the weight average molecular weight (Mw) was 185,000, the glass transition temperature (Tg) was 360 ° C, and the saturated water absorption was 0.35%. [Synthesis Example 3], under a nitrogen flow, '4,4' in a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube. -1 parts by weight (0.05 mol) of diaminodiphenyl ether was dissolved in 85 parts by weight of N-methyl-2-pyrrolidone as a solvent, and then directly injected in solid portions in one hour at room temperature.丨, 11.2 parts by weight of 2,4,5-cyclohexanetetracarboxylic dianhydride (〇.〇5 mol), and stirred at room temperature for 2 hours. Then, 3 parts by weight of xylene as an azeotropic dehydrating solvent was added and the temperature was raised to 180 ° C, and then the reaction was carried out for 3 hours, and xylene was refluxed by Dean-Stark to separate the azeotropically formed water. After 3 hours, it was confirmed that the water distillation was terminated. The temperature was raised to 190 °C in 1 hour while distilling off xylene, and 29.0 parts by weight was recovered, and then the inner air was cooled to 60. (:, 105.4 parts by weight of a solution of n-methyl-72-201211125 2-pyrrolidone (hereinafter also referred to as "polyimine solution C") of polyimine. [Synthesis Example 4] In the 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, and 41.46 g of potassium carbonate ( 0.30 0 mol), N,N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene llg. Next, a three-way bypass plug of a thermometer, a stirrer, and an additional nitrogen introduction tube was placed on a four-necked flask. Then, the Dean-Stark tube and the cooling tube. After the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. After the formation of water was not confirmed, the temperature was slow. The temperature was raised to 16 (TC, and reacted at this temperature for 6 hours. After cooling to room temperature (25 t), the formed salt was removed with a filter paper, and the filtrate was poured into methanol to reprecipitate, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60 ° C overnight to obtain a white powder D (hereinafter referred to as Resin I)) (received 9 5.6 7 g, collected The rate was 9 5 %. The structural analysis of the obtained polymer was carried out. As a result, the characteristic absorption of the infrared absorption spectrum was 3 03 5 cm·1 (CH stretching), 2229 cm·1 (CN), 1574 CHT1, 1499 cm·1 (aromatic ring skeleton) Absorption), 1240 cm·1 (-〇·). The molecular weight coefficient of the resin D has an average molecular weight (?η) of 67,000, a weight average molecular weight (Mw) of 146,000, and a glass transition temperature (Tg) of 275 C. The obtained polymer has the structure described above. (1) -73- 201211125 [Synthesis Example 5] In addition to using 9,9-bis(4-hydroxyphenyl)phosphonium 87.60 g (0.250 mol) instead of 9,9-bis(3-phenyl-4.hydroxybenzene) In the same manner as in Synthesis Example 4, the resin was obtained in the same manner as in Synthesis Example 4. The average molecular weight (Μη) of the molecular weight coefficient of the resin E was 75,000, and the weight average molecular weight (Mw) was 188,000. The temperature (Tg) was 285 〇c. [Synthesis Example 6] Except that 9,9·bis(4-hydroxyphenyl)fluorene 78 84g (〇225m〇i) and 9,9-bis(4-hydroxyphenyl) were used. 6.71 g (0.025 mol) of cyclohexane was used in the same manner as in Synthesis Example 4 except that 9,9-bis(3-phenyl-4-hydroxyphenyl)oxime 25.65 g (0.250 mol) was used. The resin ρ was obtained. The molecular weight coefficient of the resin F was 36,000, and the weight average molecular weight (Mw) was 78,000'. The glass transition temperature (Tg) was 260. (3) [Synthesis Example 7] Except for the use of 4,4-fluoro-phenyl maple (dfdS) 78.84 g (0.250 mol) instead of 2,6--fluorobenzonitrile 35.12 g (〇253 mol), In the same manner as in Example 4, the molecular weight coefficient average molecular weight (??) of the resin resin ? was 37, 〇〇〇, the weight average molecular weight (Mw) was 132,000, and the glass transition temperature (Tg) was 265 t. [Example 1 】 - 74 - 201211125 0.04 parts by weight of a cyclic olefin resin "ART0N Gj, squarylium compound "a-10" manufactured by JSR Co., Ltd., and further dichloromethane are added to a container. A solution (exl) having a resin concentration of 20% by weight. Next, the solution was cast on a smooth glass plate, and dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° After drying at ° C for 8 hours, a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm was obtained. The spectral transmittance of the substrate was measured, and the absorption maximum wavelengths and (Za) and (Zb) were determined. The results are shown in Table 1. The absorption maximum wavelength is 699 nm, and the wavelength region of wavelength 43 0 to 800 nm Among them, the transmittance is 70%, the longest wavelength (Za) below the absorption maximum, and the absolute 値 (丨Za-Zb|) of the difference between the shortest wavelength (Zb) at which the transmittance becomes 30% in the wavelength region of the wavelength of 580 nm or more. Then, it is 45 nm. Next, a multilayer vapor-deposited film that reflects near-infrared rays is formed on one side of the substrate at a vaporization temperature of 1 ° C (a layer of cerium oxide (SiO 2 : film thickness: 83 to 199 nm) and titanium dioxide (Ti02) : film thickness: 101~125nm), the layers are alternately laminated, the number of laminations is 20]. Then, on the other side of the substrate, a multi-layer vapor-deposited film that reflects near-infrared rays is formed at a vapor deposition temperature of 1 ° C. Si02: film thickness: 77 to 189 nm) The layer of titanium dioxide (Ti02: film thickness: 84 to 118 nm) was laminated and laminated, and the number of layers was 26], and a near-infrared cut filter having a thickness of 0.105 mm was obtained. The spectral transmittance of the infrared cut-off filter is obtained by (Xa), (Xb) and (Ya), (-75- 201211125

Yb)。其結果示於表1。於波長43 0〜5 80nm之透射率之平均値爲91%，於波長 800~ lOOOnm之透射率之平均値爲1%以下。於波長800nm以下之波長區域中，透射率成爲70%之最長波長（Xa)，與波長580nm以上之波長區域中，透射率成爲30%之最短波長（Xb)之差的絕對値（|Xa-Xb|)爲 3 9 n m ° 且，於波長5 60〜SOOnm之範圍內，自濾波器之垂直方向測定時之透射率成爲50%之波長之値（Ya )，與自相對於濾波器之垂直方向成30°角度測定時之透射率成爲50%之波長之値（Yb )之差的絕對値（|Ya-Yb| )爲3nm。〔實施例2〕於實施例1中獲得之厚度O.lmm，長度60mm，寬度 60mm之基板之單面上，在蒸鍍溫度1〇〇 °C下形成反射近紅外線之多層蒸鍍膜〔使二氧化矽（Si02:膜厚120〜190 nm )層與二氧化鈦（Ti02:膜厚70〜120nm)層交互層合而成者’層合數40〕，獲得厚度0.1 04mm之近紅外線截止濾波器。接著，與實施例1同樣進行評價，結果示於表1。〔實施例3〕將JSR股份有限公司製造之環狀烯烴系樹脂「ARt〇N G」100重量份、方酸系化合物「a-i〇」〇.〇2重量份進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著， -76- 201211125 將該溶液澆鑄於平滑玻璃板上，在2 (TC乾燥8小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於1 OOt乾燥8小時，獲得厚度0.1mm，長度60mm，寬度60mm之基板。接著，與實施例1同樣，由該基板製造厚度0.1 〇5mm之近紅外線截止濾波器。結果示於表1。〔實施例4〕將JSR股份有限公司製造之環狀烯烴系樹脂「ARTON G」10 0重量份、方酸系化合物「a-10」0.04重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在2 0 °C乾燥8小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於1 0 0 °C乾燥8小時，獲得厚度0.1mm’長度60mm，寬度60mm之基板。於該基板之兩面上，以使硬化後之膜厚各成爲 0.0 02 mm之方式，利用棒塗佈器讀塗佈荒川化學工業股份有限公司製造之硬質塗劑「BEAMSET」後照射UV使之硬化，獲得厚度〇.l〇4mm，長度60mm，寬度60mm之基板。接著’與實施例1同樣，由該基板製造厚度〇.l〇9rnm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例5〕將曰本ΖΕΟΝ股份有限公司製造之環狀烯烴系樹脂「 ZEONOR 1420R」100重量份、方酸系化合物「a_1〇」〇 4〇 -77- 201211125 重量份、進而環己烷及二甲苯之7:3混合溶液添加於容器中，獲得樹脂濃度爲20%之溶液。接著’將該溶液澆鑄於平滑玻璃板上，在6(TC乾燥8小時’ 80°C下乾燥8小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於l〇〇°C,乾燥24 小時，獲得厚度0.1mm，長度60mm，寬度60mm之基板。接著，與實施例1同樣，由該基板製造厚度0.1 〇5 mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1 8 〔實施例6〕將三井化學股份有限公司製造之環狀烯烴系樹脂「 APEL #6015」100重量份、方酸系化合物「a-10」0.24重量份、進而環己烷與二氯甲烷之99:1混合溶液添加於容器中，獲得樹脂濃度爲20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在40°C乾燥4小時，在60°C乾燥4小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於1 00°C乾燥8小時，獲得厚度〇_lmm，長度60mm，寬度60mm之基板。接著，與實施例1同樣，由該基板製造厚度0.105 mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例7〕將帝人股份有限公司製造之聚碳酸酯樹脂「PURE-ACE」100重量份、方酸系化合物ra-10」〇.〇2重量份，進 -78- 201211125 而二氯甲烷添加於容器中，獲得樹脂濃度爲20%之溶液。接著’將該溶液澆鑄於平滑玻璃板上，在20。(：乾燥8小時後’自玻璃板剝離。使剝離之塗膜再於減壓下於1 0 0 °C乾燥8小時，獲得厚度〇.imm，長度6〇mm，寬度60mm之基板〇接著，與實施例1同樣，由該基板製造厚度0.105mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例8〕將住友Backlight股份有限公司製造之聚醚楓「FS-1 3 00」1〇〇重量份、方酸系化合物「a_i〇」〇.05重量份，進而N_甲基-2-吡咯烷酮添加於容器中，獲得樹脂濃度爲20% 之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在601：乾燥4小時’在80°C乾燥4小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於120 °C乾燥8小時，獲得厚度0.1 mm，長度60mm，寬度60mm之基板。接著，與實施例1同樣，由該基板製造厚度0.1 05 mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果不於表1。〔實施例9〕除使用合成例1中獲得之樹脂A代替JSR股份有限公司製造之環狀烯烴系樹脂「ARTON G」以外，餘與實施例1 -79- 201211125 同樣’獲得厚度0.1mm’長度60mm，寬度60mm之基板。接著’與實施例1同樣’由該基板製造厚度0.105mm之近紅外線截止漉波器》進行與實施例1同樣之評價，結果示於表1 * 〔實施例1 0〕將合成例2中獲得之樹脂B 100重量份、方酸系化合物「a-ΙΟ」0·24重量份、進而甲苯添加於容器中，獲得樹脂濃度爲20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在2 0 °C乾燥8小時後，自玻璃板剝離。除使剝離之塗膜再於減壓下於1 20°C乾燥8小時以外，餘與實施例1同樣，獲得厚度長度60mm，寬度60mm之基板》接著，與實施例1同樣，由該基板製造厚度0.1 05 mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例1 1〕於容器中，添加合成例3中獲得之聚醯亞胺溶液C 100 重量份、及相對於聚醯亞胺溶液c之固體成分1〇〇重量份爲 0.05重量份之方酸系化合物「a-ΙΟ」，獲得固體成分18% 之溶液。接著，將該溶液澆鑄於平滑玻璃板上’在60°C乾燥4小時，在8 0 t乾燥4小時後，自玻璃板剝離。使剝離之塗膜再於減壓下於120°C乾燥8小時’獲得厚度〇. 1 mm，長度60mm，寬度60mm之基板。 -80- 201211125 接著，與實施例1同樣，由該基板製造厚度〇.l〇5mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例1 2〕將合成例4中獲得之樹脂D 100重量份、方酸系化合物「a-10」0.05重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在20°C乾燥8 小時後，自玻璃板剝離。使剝離之樹脂再於減壓下於 100 °c乾燥8小時’獲得厚度0.1mm，長度60mm，寬度 6 0 m m之基板。接著，與實施例1同樣，由該基板製造厚度0.105mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表I。〔實施例1 3〕將合成例5中獲得之樹脂E 100重量份、方酸系化合物「a-10」0.05重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在20°C乾燥8 小時後，自玻璃板剝離。使剝離之樹脂再於減壓下於 1 〇〇 °C乾燥8小時’獲得厚度0.1 mm，長度60mm，寬度 60mm之基板。 -81 - 201211125 接著，與實施例1同樣，由該基板製造厚度0.105min之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例1 4〕將合成例6中獲得之樹脂F 100重量份、方酸系化合物「a-10」0.05重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在20 °C乾燥8 小時後，自玻璃板剝離。使剝離之樹脂再於減壓下於 100 °C乾燥8小時，獲得厚度0.1mm，長度60mm，寬度 60mm之基板。接著，與實施例1同樣，由該基板製造厚度0」05mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例】5〕將合成例7中獲得之樹脂G 100重量份、方酸系化合物「a-10」0.05重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上’在20°C乾燥8 小時後，自玻璃板剝離。使剝離之樹脂再於減壓下於 loot：乾燥8小時，獲得厚度0.1mm，長度60mm’寬度 60mm之基板。 -82- 201211125 接著，與實施例1同樣，由該基板製造厚度0.105mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔實施例1 6〕將合成例1中獲得之樹脂A 100重量份、方酸系化合物「a-10」0.04重量份、進而二氯甲烷添加於容器中，獲得樹脂濃度20%之溶液。接著，將該溶液澆鑄於平滑玻璃板上，在20°C乾燥8 小時後，自玻璃板剝離。使剝離之樹脂再於減壓下於 1 0 0 °C乾燥8小時，獲得厚度0 · 1 m m，長度6 0 m m，寬度 60mm之基板。於該基板之兩面上，以使乾燥後之膜厚各成爲 0.002mm之方式，利用棒塗佈器塗佈以50:50之比例混合三環癸烷二甲醇二丙烯酸酯與甲基乙基酮而成之組成物後，照射UV使之硬化’獲得厚度0.104mm，長度60mm，寬度 60mm之基板。接著，與實施例1同樣，由該基板製造厚度〇.l〇9mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔比較例1〕除使用將合成例1中獲得之樹脂A溶解於二氯甲烷中獲得之樹脂濃度20%之溶液代替溶液（exl )以外，餘與實施 -83- 201211125 例1同樣，獲得厚度0.1mm，長度60mm，寬度60mm之基板〇接著，與實施例1同樣，由該基板製造厚度0.1 05mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。〔比較例2〕除使用不具有方酸構造之鎳錯合物化合物之SIR159 ( 三井化學股份有限公司製造）代替方酸系化合物「a-10j 以外，餘與實施例1同樣，獲得厚度0.1mm，長度60mm，寬度60mm之基板。接著’與實施例1同樣，由該基板製造厚度0.105 mm之近紅外線截止濾波器》進行與實施例1同樣之評價，結果示於表1。〔比較例3〕除使用不具有方酸構造之花菁系色素之SDB3535 ( H.W.SANDS公司製造）代替方酸系化合物「ado」以外，餘與實施例1同樣’獲得厚度〇lmm，長度6〇mm，寬度 60mm之基板》接著’與實施例1同樣，由該基板製造厚度〇· i 05mm之近紅外線截止濾波器。進行與實施例1同樣之評價，結果示於表1。 -84- 201211125 【表1】透明樹脂型墓板沂紅外線截止濾波盛 ___ 1 吸收極大波長 IZa-Zbl 波長430nm ~580nm 之诱射率之率均値波長800nm~ lOOOnm之诱射率之平均値 IXa-Xbl lYa-Ybl 實施例1 699nm 45nm 91% 1%以下 39nm 3nm 管施例2 699nm 45nm 8Q% 1%以下 40nm 5nm 實施例3 700nm 40nm 91% 1%以下 28nm 5nm 實施例4 699nm 47nm 90% 1%以下 4»Onm 3nm 實施例5 6Q6nm 47nm 91% 1%以下 40nm 5nm f麵is 697nm 41 nm BQ% 1%以下 38nm 6nm 啻施例7 707nm 53nm B5% 1%以下 nm Bnm 窗施例8 714nm 60nm 85% 1兴以下 50nm 8nm 窨施例9 699nm 45nm 91% 1%以下 39nm 3nm 實施 697nm 41 nm 89% 1%以下 38nm 6nm 實施#[ill 710nm 53nm 85% 1%以下 46nm Bnm 啻施例12 705nm 54nm 65% 以下 47nm 6nm Wiii3 7〇4nm 52nm 85% 1%以下 46nm 5nm 實施例14 706nm 53nm 85% 1H以下 4βηηι 6nm 眚施例15 708nm 54nm 8596 1%以T 48nm 7nm 實施钿16 €99nm 47nm 9G% 1%以下 40nm 3nm 比較例1 無班 dm I 1%以下 10nm 25nm hh較例2 828nm I 60nm B591> 10nm 25nm 比較例3 1030nm I 86nm 85% 1%以下 10nm 25nm 〔產業上利用之可能性〕本發明之近紅外線截止濾波器可較好地使用於數位相機、行動電話用相機、數位錄影機、PC相機、監控照相機、汽車用照相機、電視、汽車導航、行動資料終端機、個人電腦、影像遊戲機、醫療設備、USB記憶體、攜帶式遊戲機、指紋辨識系統、數位音樂播放器、玩具機器人及玩具等。另外，亦可使用作爲安裝於汽車或建築物等之玻璃等之熱線截止濾波器等。【圖式簡單說明】圖1 ( a )爲顯示以往之照相機模組之一例的剖面槪略圖。圖1 ( b )爲顯示使用本發明所得之近紅外線截止濾波器6 ’時之照相機模組之一例之剖面槪略圖。圖2爲顯示測定自近紅外線截止濾波器之垂直方向測 -85- 201211125 定時之透射率之方法的模式圖。圖3爲顯示測定自相對於近紅外線截止濾波器之垂直方向30°之角度測定時之透射率之方法的模式圖。【主要元件符號說明】 1 :照相機模組 2 :透鏡鏡筒 3 :可撓性基板 4 :中空封裝 5 :透鏡 6 :近紅外線截止濾波器 6’ ：本發明中獲得之近紅外線截止濾波器 7 : CCD或CMOS影像感知器 8 :近紅外線截止濾波器 9 :分光光度計 -86-Yb). The results are shown in Table 1. The average 値 of the transmittance at a wavelength of 43 0 to 5 80 nm is 91%, and the average 値 of the transmittance at a wavelength of 800 to 100 nm is 1% or less. In the wavelength region of the wavelength of 800 nm or less, the transmittance becomes the longest wavelength (Xa) of 70%, and in the wavelength region of the wavelength of 580 nm or more, the absolute 値 (|Xa-) of the difference between the shortest wavelength (Xb) at which the transmittance becomes 30%. Xb|) is 3 9 nm ° and in the range of wavelength 5 60 to SOOnm, the transmittance when measured from the vertical direction of the filter becomes 50% of the wavelength (Ya), and is perpendicular to the filter The absolute enthalpy (|Ya-Yb|) of the difference of the ytterbium (Yb) at which the transmittance was 50% in the direction measured at an angle of 30° was 3 nm. [Example 2] A multilayer vapor-deposited film reflecting near-infrared rays was formed 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 at a vapor deposition temperature of 1 ° C. A layer of yttrium oxide (SiO 2 : film thickness: 120 to 190 nm) and a layer of titanium dioxide (Ti02: film thickness: 70 to 120 nm) were laminated to form a 'layer number of 40', and a near-infrared cut filter having a thickness of 0.104 mm was obtained. Subsequently, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. [Example 3] 100 parts by weight of a cyclic olefin resin "ARt〇NG" manufactured by JSR Co., Ltd., and 2 parts by weight of a squaraine-based compound "ai〇", and further dichloromethane were added to a container. A solution with a resin concentration of 20%. Then, the solution was cast on a smooth glass plate at -76-201211125, and peeled off from the glass plate after drying for 2 hours at TC. The peeled coating film was further dried at 100 Torr for 8 hours under reduced pressure to obtain a thickness of 0.1. Next, a substrate having a length of 60 mm and a width of 60 mm was produced. Next, a near-infrared cut filter having a thickness of 0.1 〇 5 mm was produced from the substrate in the same manner as in Example 1. The results are shown in Table 1. [Example 4] Manufactured by JSR Co., Ltd. 10 parts by weight of a cyclic olefin resin "ARTON G" and 0.04 parts by weight of a squaraine-based compound "a-10", and further dichloromethane was added to a container to obtain a solution having a resin concentration of 20%. After casting on a smooth glass plate and drying at 20 ° C for 8 hours, it was peeled off from the glass plate. The peeled coating film was further dried at 100 ° C for 8 hours under reduced pressure to obtain a thickness of 0.1 mm 'length 60 mm. A substrate having a width of 60 mm. The hard coating agent "BEAMSET" manufactured by Arakawa Chemical Industries Co., Ltd. was applied by a bar coater so that the film thickness after hardening was 0.002 mm on both sides of the substrate. Irradiate UV to harden it A substrate having a thickness of 〇4〇4 mm, a length of 60 mm, and a width of 60 mm. Next, a near-infrared cut filter having a thickness of 〇.10 〇9 rnm was produced from the substrate in the same manner as in Example 1. The same evaluation as in Example 1 was carried out. [Table 5] [Example 5] 100 parts by weight of a cyclic olefin resin "ZEONOR 1420R" manufactured by Sakamoto Co., Ltd., and a squaraine-based compound "a_1〇" 〇4〇-77-201211125 parts by weight, Further, a 7:3 mixed solution of cyclohexane and xylene was added to the vessel to obtain a solution having a resin concentration of 20%. Then, the solution was cast on a smooth glass plate at 6 (TC drying for 8 hours '80 ° C). After drying for 8 hours, it was peeled off from the glass plate, and the peeled coating film was further dried at 10 ° C for 24 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. In the same manner, a near-infrared cut filter having a thickness of 0.1 〇 5 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 18. [Example 6] A cyclic olefin manufactured by Mitsui Chemicals Co., Ltd. Resin "APEL #6015" 100 parts by weight of 0.24 parts by weight of a squaraine-based compound "a-10" and a 99:1 mixed solution of cyclohexane and dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. It was cast on a smooth glass plate, dried at 40 ° C for 4 hours, and dried at 60 ° C for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C for 8 hours under reduced pressure to obtain a thickness. 〇_lmm, 60mm in length and 60mm in width. Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 7] 100 parts by weight of a polycarbonate resin "PURE-ACE" manufactured by Teijin Co., Ltd., and a squaraine-based compound ra-10"〇.〇2 parts by weight, and added to -78-201211125, and added with dichloromethane In the container, a solution having a resin concentration of 20% was obtained. The solution was then cast onto a smooth glass plate at 20. (: After drying for 8 hours, ' peeling from the glass plate. The peeled coating film was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of im.imm, a length of 6 mm, and a width of 60 mm. Next, A near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate in the same manner as in Example 1. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 8] Polyether produced by Sumitomo Backlight Co., Ltd. Maple "FS-1 3 00" 1 part by weight, squaraine-based compound "a_i〇" 〇.05 parts by weight, and further N-methyl-2-pyrrolidone is added to the container to obtain a solution having a resin concentration of 20%. Then, the solution was cast on a smooth glass plate, and dried at 60 ° C for 4 hours at 601: dried for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 120 ° C under reduced pressure. A substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm was obtained in an hour. Then, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate in the same manner as in Example 1. The same evaluation as in Example 1 was carried out, and the result was not Table 1. [Example 9] Except for the use of Synthesis Example 1 In addition to the cyclic olefin resin "ARTON G" manufactured by JSR Co., Ltd., the obtained resin A was obtained in the same manner as in Example 1-79-201211125 to obtain a substrate having a thickness of 0.1 mm and a length of 60 mm and a width of 60 mm. In the same manner as in Example 1, the same procedure as in Example 1 was carried out in the same manner as in Example 1. The results are shown in Table 1 * [Example 10] The resin B 100 obtained in Synthesis Example 2 0 parts by weight of the squaraine-based compound "a-ΙΟ", and further toluene was added to the container to obtain a solution having a resin concentration of 20%. Then, the solution was cast on a smooth glass plate at 20 ° After drying for 8 hours, the film was peeled off from the glass plate, and the substrate having a thickness of 60 mm and a width of 60 mm was obtained in the same manner as in Example 1 except that the peeled film was dried at 1200 ° C for 8 hours under reduced pressure. A near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate in the same manner as in Example 1. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 1 1] In the container, a synthesis example was added. The gathering in 3 100 parts by weight of the imine solution C and 0.05 parts by weight of the squaraine-based compound "a- ΙΟ" with respect to 1 part by weight of the solid content of the polyimine solution c, and a solution having a solid content of 18% was obtained. The solution was cast on a smooth glass plate to dry at 60 ° C for 4 hours, and after drying at 80 t for 4 hours, it was peeled off from the glass plate. The peeled coating film was further dried at 120 ° C for 8 hours under reduced pressure. A substrate having a thickness of 1 mm, a length of 60 mm, and a width of 60 mm was obtained. -80-201211125 Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 〇5 〇 5 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 1 2] 100 parts by weight of the resin D obtained in Synthesis Example 4, 0.05 parts by weight of the squaraine-based compound "a-10", and further dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. Next, the solution was cast on a smooth glass plate, and after drying at 20 ° C for 8 hours, it was peeled off from the glass plate. The peeled resin was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 m. Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 1 3] 100 parts by weight of the resin E obtained in Synthesis Example 5, 0.05 parts by weight of the squaraine-based compound "a-10", and further dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. Next, the solution was cast on a smooth glass plate, and after drying at 20 ° C for 8 hours, it was peeled off from the glass plate. The peeled resin was further dried at 1 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. -81 - 201211125 Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 0.105 min was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 1 4] 100 parts by weight of the resin F obtained in Synthesis Example 6, 0.05 parts by weight of the squaraine-based compound "a-10", and further dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. Next, the solution was cast on a smooth glass plate, and after drying at 20 ° C for 8 hours, it was peeled off from the glass plate. The peeled resin was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 0 mm to 05 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Examples] 5] 100 parts by weight of the resin G obtained in Synthesis Example 7, 0.05 parts by weight of the squaraine-based compound "a-10", and further dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. Next, the solution was cast on a smooth glass plate and dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm and a length of 60 mm' width of 60 mm. -82-201211125 Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Example 1 6] 100 parts by weight of the resin A obtained in Synthesis Example 1 and 0.04 parts by weight of the squaraine-based compound "a-10" and further dichloromethane were added to a container to obtain a solution having a resin concentration of 20%. Next, the solution was cast on a smooth glass plate, and after drying at 20 ° C for 8 hours, it was peeled off from the glass plate. The peeled resin was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0 · 1 m m, a length of 60 m, and a width of 60 mm. On both sides of the substrate, tricyclodecane dimethanol diacrylate and methyl ethyl ketone were mixed at a ratio of 50:50 by a bar coater so that the film thickness after drying was 0.002 mm. After the composition was formed, it was cured by irradiation with UV to obtain a substrate having a thickness of 0.104 mm, a length of 60 mm, and a width of 60 mm. Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 〇.10 〇 9 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Comparative Example 1] A thickness was obtained in the same manner as in Example 1 of Example-83-201211125 except that a solution having a resin concentration of 20% obtained by dissolving the resin A obtained in Synthesis Example 1 in dichloromethane was used instead of the solution (exl). Substrate of 0.1 mm, length 60 mm, and width 60 mm Next, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. [Comparative Example 2] A thickness of 0.1 mm was obtained in the same manner as in Example 1 except that SIR159 (manufactured by Mitsui Chemicals, Inc.) of a nickel complex compound having no squaraine structure was used instead of the squaraine-based compound "a-10j". A substrate having a length of 60 mm and a width of 60 mm. Then, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced from the substrate, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1. [Comparative Example 3 In the same manner as in Example 1, except that SDB3535 (manufactured by HWSANDS Co., Ltd.) which does not have a squaraine-based coloring matter, was used in the same manner as in Example 1, a thickness of 〇lmm, a length of 6 mm, and a width of 60 mm were obtained. Substrate>> Next, in the same manner as in the first embodiment, a near-infrared cut filter having a thickness of 〇·i 05 mm was produced from the substrate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. -84- 201211125 [Table 1] Transparent resin type tomb board 沂 Infrared cut-off filter ___ 1 Absorption maximum wavelength IZa-Zbl The wavelength of the 430nm ~ 580nm rate is the average of the exposure rate of the wavelength 800nm ~ lOOOnm IXa-Xbl lYa-Ybl Example 1 699 nm 45 nm 91% 1% or less 39 nm 3 nm Tube Example 2 699 nm 45 nm 8Q% 1% or less 40 nm 5 nm Example 3 700 nm 40 nm 91% 1% or less 28 nm 5 nm Example 4 699 nm 47 nm 90% 1% or less 4»Onm 3nm Example 5 6Q6nm 47nm 91% 1% or less 40 nm 5 nm f plane is 697 nm 41 nm BQ% 1% or less 38 nm 6 nm 啻 Example 7 707 nm 53 nm B5% 1% or less nm Bnm window Example 8 714 nm 60 nm 85% 1 Hz 50 nm 8 nm 窨 Example 9 699 nm 45 nm 91% 1% or less 39 nm 3 nm 697 nm 41 nm 89% 1% or less 38 nm 6 nm Implementation #[ill 710 nm 53 nm 85% 1% or less 46 nm Bnm 啻 Example 12 705 nm 54 nm 65% or less 47 nm 6 nm Wiii 3 7 〇 4 nm 52 nm 85% 1% or less 46 nm 5 nm Example 14 706 nm 53 nm 85% 1H or less 4βηηι 6 nm 眚 Example 15 708 nm 54 nm 8596 1% at T 48 nm 7 nm 钿16 €99 nm 47 nm 9G% 1% or less 40 nm 3 nm Comparative Example 1 No shift dm I 1% or less 10 nm 25 nm hh Comparative Example 2 828 nm I 60 nm B591> 10 nm 25 nm Comparative Example 3 1030 nm I 86 nm 85% 1% or less 10 nm 25 nm [Industrial Applicability] The near-infrared cut filter of the present invention can be preferably used for a digital camera, a camera for a mobile phone, and a digital device. Video recorders, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation, mobile data terminals, personal computers, video game consoles, medical devices, USB memory, portable game consoles, fingerprint recognition systems, digital music players , toy robots and toys. Further, a hot wire cut filter or the like which is attached to a glass such as an automobile or a building can be used. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) is a schematic cross-sectional view showing an example of a conventional camera module. Fig. 1(b) is a schematic cross-sectional view showing an example of a camera module when the near-infrared cut filter 6' obtained by the present invention is used. Fig. 2 is a schematic view showing a method of measuring the transmittance from the vertical direction of the near-infrared cut filter at -85 - 201211125. Fig. 3 is a schematic view showing a method of measuring transmittance at an angle of 30° with respect to the vertical direction of the near-infrared cut filter. [Description of main component symbols] 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 in the present invention : CCD or CMOS image sensor 8 : Near-infrared cut-off filter 9 : Spectrophotometer -86-

Claims

201211125 七、申請專利範園： 1.一種近紅外線截止濾波器，其特徵爲具有含有化合物（I)之樹脂製基板（I )，該化合物（I)具有源自以下述式（I)表示之化合物的構造，【化1】201211125 VII. Patent application: 1. A near-infrared cut filter characterized in that it has a resin substrate (I) containing a compound (I) having a compound represented by the following formula (I). Structure of the compound, [Chemical 1]

(I) 〔式（I )中，Ra、Rb及Y滿足下述（i )或（ii )， (i) Ra各獨立表示氫原子、碳數1〜8之烷基、-NReRf 基（Re&Rf各獨立表示氫原子或碳數1〜5之烷基）或羥基 > Rb各獨立表示氫原子、碳數1~5之烷基、-NRgRh ( R6 及Rh各獨立表示氫原子、碳數1〜5之烷基或-C (0)…基（ 1^表示碳數1~5之烷基））或羥基， Υ表示-NRjRk (R^Rk各獨立表示氫原子、碳數1〜8之脂肪族烴基、任意之氫原子經官能基取代之碳數1 ~ 8之經取代脂肪族烴基、碳數6~12之芳香族烴基或任意之氫原子經烷基取代之碳數6〜1 2之經取代芳香族烴基）， (Π) —個苯環上之兩個Ra中之一個與同一苯環上之 -87- 201211125 Y相互鍵結，形成構成原子數5或6之含有至少一個氮原子之雜環， Rb及與未參與該鍵結之Ra各獨立與前述（i)之Rb及尺3同義〕。 2.如申請專利範圍第1項之近紅外線截止濾波器，其透射率滿足下述（A)〜（D)： (A) 在波長430〜5 80nm之範圍內，自近紅外線截止濾波器之垂直方向測定時之透射率平均値爲75 %以上， (B) 在波長800〜lOOOnm內，自近紅外線截止濾波器之垂直方向測定時之透射率平均値爲20%以下， (C) 在波長800nm以下之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲70%之最長波長（Xa)，與在波長580 nm以上之波長區域中，自近紅外線截止濾波器之垂直方向測定時之透射率成爲3 0%之最短波長（Xb)之差的絕對値未達75nm， (D) 在波長560〜800nm之範圍內，自近紅外截止濾波器之垂直方向測定時之透射率成爲50%之波長之値（Ya )，與自相對於近紅外線截止濾波器之垂直方向爲30°之角度測定時之透射率成爲50%之波長之値（Yb)之差的絕對値未達15nm。 3 .如申請專利範圍第1或2項之近紅外線截止濾波器，其中前述樹脂製基板（I)滿足下述（E)及（F)： (E) 在波長600~800nm有吸收極大 (F) 在波長4 3 0〜800nm之波長區域中’自基板之垂直 -88- 201211125 方向測定時之透射率成爲7 0%之在吸收極大以下之最長波長（Za )，與在波長5 80nm以上之波長區域中，自基板之垂直方向測定時之透射率成爲30%之最短波長（Zb)之差的絕對値未達75nm。 4.如申請專利範圍第1至3項中任一項之近紅外線截止濾波器，其中以前述式（I)表示之化合物爲以下述式（II )表示之化合物：【化2】(I) [In the formula (I), Ra, Rb and Y satisfy the following (i) or (ii), and (i) Ra each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a -NReRf group (Re& Rf each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. Rb each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and -NRgRh (R6 and Rh each independently represent a hydrogen atom or carbon. a number of 1 to 5 alkyl groups or -C (0) ... groups (1^ represents an alkyl group having 1 to 5 carbon atoms) or a hydroxyl group, and Υ represents -NRjRk (R^Rk each independently represents a hydrogen atom, a carbon number of 1~ 8 aliphatic hydrocarbon group, any hydrogen atom substituted by a functional group, substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, aromatic hydrocarbon group having 6 to 12 carbon atoms or carbon atom of any hydrogen atom substituted by alkyl group 6~ 1 2 substituted aromatic hydrocarbon group), (Π) - one of the two Ras on the benzene ring is bonded to -87-201211125 Y on the same benzene ring to form at least 5 or 6 of the constituent atoms. A heterocyclic ring of a nitrogen atom, Rb and Ra which are not involved in the bonding are independently synonymous with Rb and Rule 3 of the above (i). 2. The near-infrared cut filter according to item 1 of the patent application, the transmittance of which satisfies the following (A) to (D): (A) in the range of wavelength 430 to 5 80 nm, from the near-infrared cut filter The average transmittance of the transmittance when measured in the vertical direction is 75% or more. (B) In the wavelength of 800 to 100 nm, the average transmittance of the transmittance when measured from the vertical direction of the near-infrared cut filter is 20% or less, (C) at the wavelength. In the wavelength region below 800 nm, the transmittance at the time of measurement from the vertical direction of the near-infrared cut filter becomes the longest wavelength (Xa) of 70%, and the wavelength from the near-infrared cut filter in the wavelength region of the wavelength of 580 nm or more The absolute 値 of the difference between the shortest wavelength (Xb) at which the transmittance is 30% is less than 75 nm, and (D) the transmittance at the wavelength of 560 to 800 nm measured from the vertical direction of the near-infrared cut filter. The ratio of the ratio (Ya) at a wavelength of 50% to the wavelength (Yb) at which the transmittance is 50% when measured at an angle of 30° with respect to the vertical direction of the near-infrared cut filter is not Up to 15nm. 3. The near-infrared cut filter according to claim 1 or 2, wherein the resin substrate (I) satisfies the following (E) and (F): (E) has a large absorption at a wavelength of 600 to 800 nm (F) In the wavelength region of 4 3 0 to 800 nm, the transmittance when measured from the vertical -88 - 201211125 direction of the substrate becomes 70% of the longest wavelength (Za) below the absorption maximum, and the wavelength above 580 nm. In the wavelength region, the absolute 差 of the difference between the shortest wavelength (Zb) at which the transmittance is 30% measured from the vertical direction of the substrate is less than 75 nm. 4. The near-infrared cut-off filter according to any one of claims 1 to 3, wherein the compound represented by the above formula (I) is a compound represented by the following formula (II):

〔式（II)中，Ra及Rb各獨立與前述式（I)之（i) 同義，Re各獨立表示氫原子、碳數1~8之脂肪族烴基、任意之氫原子經官能基取代之碳數1〜8之經取代脂肪族烴基、碳數6~1 2之芳香族烴基、或任意之氫原子經烷基取代之碳數6~ 12之經取代芳香族烴基〕。 5.如申請專利範圍第1至4項中任一項之近紅外線截止濾波器，其中前述樹脂製基板（I)爲含環狀烯烴系樹脂或芳香族聚醚系樹脂而成之基板。 -89- 201211125 6.如申請專利範圍第5項之近紅外線截止濾波器’其中前述環狀烯烴系樹脂爲由自以下述式（Xg)表示之單體及以下述式（Yo )表示之單體所組成群組選出之至少—種單體獲得之樹脂：[In the formula (II), Ra and Rb are each independently synonymous with (i) of the above formula (I), and Re each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and an arbitrary hydrogen atom substituted by a functional group. a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by an alkyl group. 5. The near-infrared cut filter according to any one of the first to fourth aspect, wherein the resin substrate (I) is a substrate containing a cyclic olefin resin or an aromatic polyether resin. -89-201211125 6. The near-infrared cut filter of the fifth aspect of the invention, wherein the cyclic olefin-based resin is a monomer represented by the following formula (Xg) and a single formula represented by the following formula (Yo) At least one monomer selected from the group consisting of:

(式（Χ〇 )中，Rxl~Rx4各獨立表示由下述（丨’）~( viii’）選出之原子或基，kx、mx及px各獨立表示〇或正整數 )， (i’）氫原子， (ii’）鹵素原子， (iii’）三烷基矽烷基， (iv，）具有含有氧原子、硫原子、氮原子或矽原子之連結基之經取代或未經取代之碳數1〜30之烴基， (ν’）經取代或未經取代之碳數1~30之烴基， (vi’）極性基（但，（iv’）除外）， (vii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之亞烷基，且未參與該鍵結之Rxl〜Rx4各獨立表示自前述（i’）〜 (vi’）選出之原子或基， (viii’）Rxl與Rx2或Rx3與Rx4表示相互鍵結形成之單 90- 201211125 環或多環之烴環或雜環，且未參與該鍵結之Rxl~Rx4各獨立表示自前述（i’）〜（vi’）選出之原子或基，Rx2與Rx3表示相互鍵結形成之單環烴環或雜環，且未參與該鍵結之 Rxl〜Rx4各獨立表示自前述（Γ)〜（vi’）選出之原子或基(In the formula (Χ〇), Rxl~Rx4 each independently represent an atom or a group selected by (丨')~( viii'), and kx, mx, and px each independently represent a 〇 or a positive integer), (i') a hydrogen atom, (ii') a halogen atom, (iii') a trialkylsulfanyl group, (iv,) a substituted or unsubstituted carbon number having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom a hydrocarbon group of 1 to 30, (ν') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, (vi') a polar group (except (iv'), (vii') Rxl and Rx2 or Rx3 And Rx4 represent an alkylene group which is bonded to each other, and Rx1 to Rx4 which are not involved in the bonding each independently represent an atom or a group selected from the above (i') to (vi'), (viii') Rxl and Rx2 or Rx3 and Rx4 represent a single 90-201211125 ring or polycyclic hydrocarbon ring or heterocyclic ring formed by mutual bonding, and Rxl~Rx4 not participating in the bonding are independently represented from the above (i') to (vi'). Atom or a group, Rx2 and Rx3 represent a monocyclic hydrocarbon ring or a heterocyclic ring which are bonded to each other, and Rx1 to Rx4 which are not involved in the bonding are independently represented from the above (Γ)~ vi ') or group of atoms selected

(式（Yo )中，Ryl及Ry2各獨立表示由前述（i，）〜（ vi’）選出之原子或基，或表示下述（ix’），Ky&Py各獨立表示〇或正整數）， (ix’）表示相互鍵結形成之單環或多環之脂環式烴、芳香族烴或雜環。 7.如申請專利範圍第5項之近紅外線截止濾波器，其中前述芳香族聚醚系樹脂具有由以下述式（1)表示之構造單位及以下述式（2 )表示之構造單位所組成群組選出之至少一種構造單位’ -91 - 201211125 【化5】(In the formula (Yo), Ryl and Ry2 each independently represent an atom or a group selected by the above (i,) to (vi'), or represent the following (ix'), and Ky & Py each independently represent a 〇 or a positive integer) (ix') represents a monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring which are bonded to each other. 7. The near-infrared cut-off filter according to the fifth aspect of the invention, wherein the aromatic polyether-based resin has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) At least one structural unit selected by the group ' -91 - 201211125 【化5】

價有機 (式（1 )中，RLR4各獨立表示碳數1〜12之基，a~d各獨立表示〇~4之整數），The organic value (in the formula (1), RLR4 each independently represents a carbon number of 1 to 12, and a~d each independently represents an integer of 〇~4),

(2) (式（2 )中，R1〜R4及a~d各獨立與前述式（ 111~114及3〜£1同義，丫表示單鍵、-3〇2-或>〇 = 〇’ R 獨立表示鹵素原子、碳數1〜12之一價有機基或硝各獨立表示〇〜4之整數，m表示0或1，但111爲〇時氰基）。 8.如申請專利範圍第7項之近紅外線截止濾丨中前述芳香族聚醚系樹脂進而具有由以下述式（之構造單位及以下述式（4)表示之構造單位所；選出之至少一種構造單位， 1 )中之 7及R8各 S，g及 h R7不爲 ί器，其 3 )表示 i成群組 -92- 201211125 【化7】(2) In the formula (2), R1 to R4 and a~d are each independently of the above formula (111 to 114 and 3 to £1, and 丫 represents a single bond, -3〇2- or >〇=〇' R independently represents a halogen atom, a carbon number of 1 to 12, an organic group or a nitrate, each independently representing an integer of 〇~4, and m represents 0 or 1, but 111 is a cerium group when 〇). In the near-infrared cut-off filter, the aromatic polyether-based resin further has at least one structural unit selected from the following structural formulas and structural units represented by the following formula (4); And R8 each S, g and h R7 is not ί, 3) means i is group -92- 201211125 【化7】

(式（3)中’ R5及R6各獨立表示碳數1〜丨2之一價有機基，Z 表示單鍵、-〇-、-S-、-S〇2-' >C = 0、-CONH-、-COO-或碳數1~12之二價有機基，e及f各獨立表示〇〜4之整數，η表示0或1 ) ’(In the formula (3), 'R5 and R6 each independently represent a carbon number of 1 to 2, a one-valent organic group, and Z represents a single bond, -〇-, -S-, -S〇2-' > C = 0, -CONH-, -COO- or a divalent organic group having a carbon number of 1 to 12, and e and f each independently represent an integer of 〇~4, η represents 0 or 1) '

(式（4)中，R7、R8、Υ、m、g及h各獨立與前述式 (2 )中之 R7、R8、Y、m、g及 h同義，R5、R6、Z、η、e 及f各獨立與前述式（3 )中之R5、R6、z、η、e及f同義） ο 9.如申請專利範圍第5至8項中任一項之近紅外線截止濾波器’其中相對於樹脂100重量份含有0.01〜10.0重量份之前述化合物（I )。 1〇·如申請專利範圍第1至9項中任一項之近紅外線截止濾波器’其中前述近紅外線截止濾波器爲固體攝影裝置用。 -93- 201211125 11. 一種固體攝影裝置，其特徵爲具備如申請專利範圍第1至10項中任一項之近紅外線截止濾波器。 1 2. —種照相機模組，其特徵爲具備如申請專利範圍第1至1 〇項中任一項之近紅外線截止濾波器。(In the formula (4), R7, R8, Υ, m, g and h are each independently synonymous with R7, R8, Y, m, g and h in the above formula (2), R5, R6, Z, η, e And f are each independently synonymous with R5, R6, z, η, e, and f in the above formula (3). 9.2 The near-infrared cut filter of any one of claims 5 to 8 The compound (I) is contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the resin. The near infrared ray cut filter of any one of claims 1 to 9, wherein the near-infrared cut filter is used for a solid-state imaging device. A solid-state imaging device characterized by having a near-infrared cut filter according to any one of items 1 to 10 of the patent application. A camera module comprising a near-infrared cut filter according to any one of claims 1 to 1.