JP6358114B2 - Optical filter and device using optical filter - Google Patents
Optical filter and device using optical filter Download PDFInfo
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- JP6358114B2 JP6358114B2 JP2015018246A JP2015018246A JP6358114B2 JP 6358114 B2 JP6358114 B2 JP 6358114B2 JP 2015018246 A JP2015018246 A JP 2015018246A JP 2015018246 A JP2015018246 A JP 2015018246A JP 6358114 B2 JP6358114 B2 JP 6358114B2
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Images
Landscapes
- Optical Filters (AREA)
Description
本発明は、光学フィルターおよび光学フィルターを用いた装置に関する。詳しくは、特定の吸収を有する化合物を含む、可視光線と一部の近赤外線を選択的に透過させる光学フィルター(2波長バンドパスフィルター)、ならびに該光学フィルターを用いた固体撮像装置およびカメラモジュールに関する。 The present invention relates to an optical filter and an apparatus using the optical filter. Specifically, the present invention relates to an optical filter (two-wavelength bandpass filter) that selectively transmits visible light and part of near-infrared light, including a compound having specific absorption, and a solid-state imaging device and camera module using the optical filter. .
ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話、スマートフォンなどの固体撮像装置にはカラー画像の固体撮像素子であるCCDやCMOSイメージセンサーが使用されているが、これら固体撮像素子は、その受光部において人間の目では感知できない近赤外線に感度を有するシリコンフォトダイオードが使用されている。これらの固体撮像素子では、人間の目で見て自然な色合いにさせる視感度補正を行うことが必要であり、特定の波長領域の光線を選択的に透過もしくはカットする光学フィルター(例えば近赤外線カットフィルター)を用いることが多い。 A solid-state imaging device such as a video camera, a digital still camera, a mobile phone with a camera function, or a smartphone uses a CCD or CMOS image sensor, which is a solid-state imaging device for color images. However, silicon photodiodes having sensitivity to near infrared rays that cannot be detected by human eyes are used. These solid-state image sensors need to be corrected for visibility so that they appear natural to the human eye. Optical filters that selectively transmit or cut light in a specific wavelength region (for example, near-infrared cut) Filter) is often used.
このような近赤外線カットフィルターとしては、従来から、各種方法で製造されたものが使用されている。例えば、特許文献1には、透明樹脂からなる基板を用い、透明樹脂中に近赤外線吸収剤を含有させた近赤外線カットフィルターが記載されており、特許文献2には、銅イオンを含有するガラス基板を用いた近赤外線カットフィルターが記載されている。
As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example,
一方、近年、近赤外光線を利用したモーションキャプチャーや距離認識(空間認識)などのセンシング機能をカメラモジュールに付与する試みが行われている。このような用途では、可視光線と一部の近赤外光線を選択的に透過させることが必要となるため、従来のような近赤外線を一律に遮蔽する近赤外線カットフィルターを用いることはできない。 On the other hand, in recent years, an attempt has been made to provide a camera module with a sensing function such as motion capture using near infrared rays or distance recognition (space recognition). In such applications, it is necessary to selectively transmit visible light and part of near-infrared light. Therefore, it is impossible to use a near-infrared cut filter that uniformly blocks near-infrared light as in the prior art.
可視光線と一部の近赤外線を選択的に透過させる光学フィルターとして、(株)東亜理化学研究所やセラテックジャパン(株)などがガラス基板上に誘電体多層膜を製膜したフィルターを販売している。 As an optical filter that selectively transmits visible light and some near-infrared rays, Toa Riken Laboratories Co., Ltd. and Ceratech Japan Co., Ltd. sell filters with a dielectric multilayer film on a glass substrate. Yes.
前記可視光線と一部の近赤外線を選択的に透過させる光学フィルターとして市販されている光学フィルターでは、光線が斜めから入射した際に分光特性が大きく変わってしまう。特に、近赤外選択透過帯域の短波長側で光学フィルターの入射角依存が大きいと、斜め入射時にセンシング機能に用いる近赤外光線のシグナルノイズ比(S/N比)が悪化するほか、カメラ画質や特に画像端部における色再現性に悪影響が出るなどといった問題が有る。図1は従来の2波長バンドパスフィルターの分光透過スペクトル例を示しているが、入射角度が30度となると近赤外選択透過帯域が大幅に短波長シフトしてしまい、本来光線カットすべき波長領域(この図の例では750〜800nm付近)の透過率が高くなってしまうことが確認される。このため、特に近赤外選択透過帯域の短波長側の入射角依存性が少なく、良好な近赤外光線S/N比、カメラ画質、可視光線および一部の近赤外光線の選択的透過の全てを満足する光学フィルターの出現が望まれていた。 In an optical filter that is commercially available as an optical filter that selectively transmits visible light and part of near infrared light, the spectral characteristics change greatly when the light is incident obliquely. In particular, if the incident angle dependence of the optical filter is large on the short wavelength side of the near-infrared selective transmission band, the signal-to-noise ratio (S / N ratio) of near-infrared rays used for the sensing function during oblique incidence deteriorates, and the camera There is a problem that the image quality and particularly the color reproducibility at the edge of the image are adversely affected. FIG. 1 shows an example of a spectral transmission spectrum of a conventional two-wavelength bandpass filter. However, when the incident angle is 30 degrees, the near-infrared selective transmission band is significantly shifted by a short wavelength, and the wavelength that should originally be cut by light rays. It is confirmed that the transmittance in the region (near 750 to 800 nm in the example of this figure) becomes high. Therefore, the near-infrared selective transmission band has little dependency on the incident angle on the short wavelength side, and good near-infrared ray S / N ratio, camera image quality, selective transmission of visible rays and some near-infrared rays. The appearance of an optical filter that satisfies all of the above has been desired.
本発明の目的は、可視光線と一部の近赤外線とを選択的に透過させる機能を有し、かつ、近赤外選択透過帯域の短波長側で入射角依存の少ない光学フィルターおよび該光学フィルターを用いた装置を提供することにある。 An object of the present invention is to provide an optical filter having a function of selectively transmitting visible light and part of near-infrared light and having little incident angle dependence on the short wavelength side of the near-infrared selective transmission band, and the optical filter It is providing the apparatus using this.
本発明者らは、前記課題を達成するために鋭意検討した結果、光学フィルターの基材が、特定の構造を有する化合物を含む透明樹脂層と誘電体多層膜とを有することにより、可視光線と一部の近赤外光線の透過特性に優れ、かつ、近赤外選択透過帯域の短波長側で入射角依存の少ない光学フィルターが得られることを見出し、本発明を完成するに至った。本発明の態様例を以下に示す。 As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that the substrate of the optical filter has a transparent resin layer containing a compound having a specific structure and a dielectric multilayer film, so that visible light and The present inventors have found that an optical filter having excellent near-infrared ray transmission characteristics and having a small incident angle dependency on the short wavelength side of the near-infrared selective transmission band can be obtained, and the present invention has been completed. Examples of embodiments of the present invention are shown below.
[1] 基材と該基材の少なくとも一方の面に誘電体多層膜とを有し、該基材が、下記式(S1)で表される化合物(S)を含む透明樹脂層を有することを特徴とする、可視光線と一部の近赤外線を選択的に透過させる光学フィルター。 [1] A substrate and a dielectric multilayer film on at least one surface of the substrate, and the substrate has a transparent resin layer containing a compound (S) represented by the following formula (S1) An optical filter that selectively transmits visible light and some near infrared rays.
R1〜R8は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−NRgRh基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、RgおよびRhは、それぞれ独立に水素原子、−C(O)Ri基または下記La〜Leのいずれかを表し、Riは下記La〜Leのいずれかを表し、
(La)炭素数1〜12の脂肪族炭化水素基
(Lb)炭素数1〜12のハロゲン置換アルキル基
(Lc)炭素数3〜14の脂環式炭化水素基
(Ld)炭素数6〜14の芳香族炭化水素基
(Le)炭素数3〜14の複素環基
(Lf)炭素数1〜12のアルコキシ基
(Lg)置換基Lを有してもよい炭素数1〜12のアシル基、
(Lh)置換基Lを有してもよい炭素数1〜12のアルコキシカルボニル基
置換基Lは、炭素数1〜12の脂肪族炭化水素基、炭素数1〜12のハロゲン置換アルキル基、炭素数3〜14の脂環式炭化水素基、炭素数6〜14の芳香族炭化水素基および炭素数3〜14の複素環基からなる群より選ばれる少なくとも1種である。
R 1 to R 8 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR g R h group, a —SO 2 R i group, or —OSO. It represents either 2 R i group or a group represented by L a ~L h, R g and R h each independently represents a hydrogen atom, one of the -C (O) R i groups or the following L a ~L e , R i represents any of the following L a ~L e,
(L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L d ) carbon the number 6 to 14 aromatic hydrocarbon group (L e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L f) an alkoxy group having 1 to 12 carbon atoms (L g)
(L h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms.
[2] 前記化合物(S)が、波長750nm以上850nm以下に吸収極大を有することを特徴とする項[1]に記載の光学フィルター。 [2] The optical filter according to item [1], wherein the compound (S) has an absorption maximum at a wavelength of 750 nm to 850 nm.
[3] 前記透明樹脂層が、前記化合物(S)の他に波長600nm以上750nm未満に吸収極大を有する化合物(A)を含むことを特徴とする項[1]または[2]に記載の光学フィルター。 [3] The optical according to item [1] or [2], wherein the transparent resin layer contains, in addition to the compound (S), a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm. filter.
[4] 前記透明樹脂が、環状(ポリ)オレフィン系樹脂、芳香族ポリエーテル系樹脂、ポリイミド系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリアリレート系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート系樹脂、フッ素化芳香族ポリマー系樹脂、(変性)アクリル系樹脂、エポキシ系樹脂、アリルエステル系硬化型樹脂、シルセスキオキサン系紫外線硬化型樹脂、アクリル系紫外線硬化型樹脂およびビニル系紫外線硬化型樹脂からなる群より選ばれる少なくとも1種の樹脂である、項[1]〜[3]のいずれか1項に記載の光学フィルター。 [4] The transparent resin is a cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin Item [1] to [3], which is at least one resin selected from the group consisting of a curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin. The optical filter according to any one of the above.
[5] 前記基材が、化合物(S)を含む透明樹脂製基板を含有することを特徴とする項[1]〜[4]のいずれか1項に記載の光学フィルター。
[6] 固体撮像装置用である項[1]〜[5]のいずれか1項に記載の光学フィルター。
[7] 項[1]〜[5]のいずれか1項に記載の光学フィルターを具備する固体撮像装置。
[8] 項[1]〜[5]のいずれか1項に記載の光学フィルターを具備するカメラモジュール。
[5] The optical filter according to any one of [1] to [4], wherein the base material includes a transparent resin substrate containing the compound (S).
[6] The optical filter according to any one of items [1] to [5], which is for a solid-state imaging device.
[7] A solid-state imaging device comprising the optical filter according to any one of items [1] to [5].
[8] A camera module comprising the optical filter according to any one of items [1] to [5].
本発明によれば、可視光線と一部の近赤外光線の透過特性に優れ、かつ、近赤外選択透過帯域の短波長側で入射角依存の少ない光学フィルターを提供することができる。 According to the present invention, it is possible to provide an optical filter that is excellent in transmission characteristics of visible light and part of near-infrared light and has little incident angle dependency on the short wavelength side of the near-infrared selective transmission band.
以下、本発明について具体的に説明する。
[光学フィルター]
本発明の光学フィルターは、後述する特定の化合物(S)を含む透明樹脂層を有する基材(i)と、誘電体多層膜とを有し、可視光線と一部の近赤外線を選択的に透過させるフィルターである。このように、本発明の光学フィルターは、化合物(S)を含む透明樹脂層と誘電体多層膜とを併用するため、透過率特性に優れ、さらに近赤外選択透過帯域の短波長側で入射角依存性の少ない光学フィルターである。
Hereinafter, the present invention will be specifically described.
[Optical filter]
The optical filter of the present invention has a base material (i) having a transparent resin layer containing a specific compound (S) described later, and a dielectric multilayer film, and selectively transmits visible light and some near infrared rays. It is a filter that allows transmission. Thus, since the optical filter of the present invention uses the transparent resin layer containing the compound (S) and the dielectric multilayer film in combination, it has excellent transmittance characteristics and is incident on the short wavelength side of the near-infrared selective transmission band. It is an optical filter with little angular dependence.
本発明の光学フィルターを固体撮像素子などに使用する場合、可視光透過率が高い方が好ましい。具体的には、波長430〜580nmの領域において、光学フィルターの垂直方向から測定した場合の平均透過率が好ましくは75%以上、より好ましくは80%以上、さらに好ましくは83%以上、特に好ましくは85%以上である。この波長域において平均透過率がこの範囲にあると、本発明の光学フィルターを固体撮像素子用途として使用した場合、優れた撮像感度を達成することができる。 When the optical filter of the present invention is used for a solid-state imaging device or the like, it is preferable that the visible light transmittance is high. Specifically, in the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is preferably 75% or more, more preferably 80% or more, still more preferably 83% or more, particularly preferably. 85% or more. When the average transmittance is within this range in this wavelength region, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used as a solid-state imaging device.
本発明の光学フィルターは、波長650nm以上の領域に光線阻止帯Za、光線透過帯Zb、光線阻止帯Zcを有する。ただし、それぞれの帯域の波長はZa<Zb<Zcである。なお、前記「Za<Zb<Zc」は、各帯域の中心波長がこの式を満たす。 The optical filter of the present invention has a light blocking band Za, a light transmitting band Zb, and a light blocking band Zc in a region having a wavelength of 650 nm or more. However, the wavelength of each band is Za <Zb <Zc. In “Za <Zb <Zc”, the center wavelength of each band satisfies this equation.
Zaは、波長650nm以上900nm以下において、光学フィルターの垂直方向から測定した場合の透過率が、20%超から20%以下になる最も短い波長Za1から、20%未満から20%以上となる最も長い波長Za2までの波長帯域を指す。 Za is the longest, with the transmittance measured from the vertical direction of the optical filter at a wavelength of 650 nm or more and 900 nm or less, from the shortest wavelength Za1 that is more than 20% to 20% or less, and from less than 20% to 20% or more. It refers to the wavelength band up to the wavelength Za2.
Zbは、波長750nm以上1050nm以下において、光学フィルターの垂直方向から測定した場合の透過率が、40%以下から40%超になる最も短い波の長Zb1から、40%超から40%以下となる最も長い波長Zb2までの波長帯域を指す。 Zb is from 40% to 40% from the shortest wave length Zb1 at which the transmittance when measured from the vertical direction of the optical filter at wavelengths of 750 nm to 1050 nm is from 40% to 40%. It refers to the wavelength band up to the longest wavelength Zb2.
Zcは、波長820nm以上において、光学フィルターの垂直方向から測定した場合の透過率が、20%超から20%以下になる最も短い波長Zc1から、Zc1+200nmである波長Zc2までの波長帯域を指す。 Zc refers to the wavelength band from the shortest wavelength Zc1 at which the transmittance when measured from the vertical direction of the optical filter at a wavelength of 820 nm or more is more than 20% to 20% or less to the wavelength Zc2 that is Zc1 + 200 nm.
本発明の光学フィルターを、近赤外センシング機能を併せ持つ固体撮像素子などに使用する場合、光線(近赤外線)透過帯域Zbの最大透過率は高い方が好ましく、光線阻止帯域ZaおよびZcの最小透過率は低い方が好ましい。このような場合、優れた近赤外センシング性能を達成可能であるとともに、不要な波長の光線を効果的にカットすることができ、カメラ画像の色再現性を向上させることができる。 When the optical filter of the present invention is used for a solid-state imaging device having a near-infrared sensing function, the maximum transmittance of the light ray (near-infrared) transmission band Zb is preferably higher, and the minimum transmission of the light-rejection bands Za and Zc. A lower rate is preferred. In such a case, it is possible to achieve excellent near-infrared sensing performance, and it is possible to effectively cut off light beams having unnecessary wavelengths, and to improve the color reproducibility of the camera image.
光線透過帯域Zbにおける光学フィルターの垂直方向から測定した場合の最大透過率は、好ましくは55%以上、より好ましくは57%以上、さらに好ましくは60%以上、特に好ましくは63%以上である。光線阻止帯域ZaおよびZcにおける光学フィルターの垂直方向から測定した場合の最小透過率は、好ましくは15%以下、より好ましくは10%以下、さらに好ましくは8%以下、特に好ましくは5%以下である。Zbにおける最大透過率やZaおよびZcにおける最小透過率が上記範囲にあると、高い近赤外センシング性能を達成しつつノイズが少なく色再現性に優れたカメラ画像を得ることができる。 The maximum transmittance when measured from the vertical direction of the optical filter in the light transmission band Zb is preferably 55% or more, more preferably 57% or more, still more preferably 60% or more, and particularly preferably 63% or more. The minimum transmittance when measured from the vertical direction of the optical filter in the light blocking zones Za and Zc is preferably 15% or less, more preferably 10% or less, still more preferably 8% or less, and particularly preferably 5% or less. . When the maximum transmittance in Zb and the minimum transmittance in Za and Zc are in the above ranges, a camera image with low noise and excellent color reproducibility can be obtained while achieving high near-infrared sensing performance.
前記Zbのうち、透過率50%となる、最も短波長側の波長の値(Xa)と最も長波長側の波長の値(Xb)との差Xb−Xaで光線透過帯Zbの幅を定義することができ、Xb−Xaの値は好ましくは5〜150nm、さらに好ましくは10〜140nm、特に好ましくは15〜130nmである。また、Y=(Xa+Xb)/2で表されるZbの中心波長Yの値は、好ましくは750〜950nm、より好ましくは760〜940nm、さらに好ましくは770〜930nm、特に好ましくは780〜920nmである。Xb−XaやYの値がこの範囲にあると、近赤外センシング感度とカメラ画像の色再現性とにより優れる光学フィルターを得ることができる。 The width of the light transmission band Zb is defined by the difference Xb−Xa between the wavelength value (Xa) on the shortest wavelength side and the wavelength value (Xb) on the longest wavelength side that has a transmittance of 50% among the Zb. The value of Xb-Xa is preferably 5 to 150 nm, more preferably 10 to 140 nm, and particularly preferably 15 to 130 nm. The value of the central wavelength Y of Zb represented by Y = (Xa + Xb) / 2 is preferably 750 to 950 nm, more preferably 760 to 940 nm, still more preferably 770 to 930 nm, and particularly preferably 780 to 920 nm. . If the values of Xb-Xa and Y are in this range, an optical filter that is superior in near-infrared sensing sensitivity and color reproducibility of the camera image can be obtained.
本発明の光学フィルターは、該光学フィルターの垂直方向に対して30°の角度から測定した透過率曲線のうち前記Zbに相当する帯域において透過率が50%となる最も短波長側の波長の値(Xa')と前記Xaとの差の絶対値|Xa−Xa'|が、好ましくは30nm未満、さらに好ましくは25nm未満、特に好ましくは20nm未満である。|Xa−Xa'|の値がこの範囲にあると、分光特性の入射角依存性が小さい光学フィルターを得ることができ、該光学フィルターを特にセンシング機能を有するカメラモジュールなどの用途に使用した場合、光を該フィルターに斜めから入射させても良好な近赤外線S/N比とカメラ画質を同時に達成することができる。このような光学フィルターは、可視光線と一部の近赤外線を選択的に透過させるように、前記基材(i)上に誘電体多層膜を形成することで得ることができる。 The optical filter of the present invention is the wavelength value on the shortest wavelength side where the transmittance is 50% in the band corresponding to Zb in the transmittance curve measured from an angle of 30 ° with respect to the vertical direction of the optical filter. The absolute value | Xa−Xa ′ | of the difference between (Xa ′) and Xa is preferably less than 30 nm, more preferably less than 25 nm, and particularly preferably less than 20 nm. When the value of | Xa−Xa ′ | is within this range, it is possible to obtain an optical filter having a small incident angle dependency of spectral characteristics, and when the optical filter is used for a camera module having a sensing function. Even when light is incident on the filter obliquely, a good near infrared S / N ratio and camera image quality can be achieved at the same time. Such an optical filter can be obtained by forming a dielectric multilayer film on the substrate (i) so as to selectively transmit visible light and part of near infrared light.
本発明の光学フィルターは、前記Yに関し、Y−10nm〜Y+10nmの波長域における垂直方向から測定した場合の平均透過率が、好ましくは60%以上、より好ましくは65%以上、特に好ましくは70%以上である。このような透過特性を有するフィルターは、可視域と目的とする近赤外域において高い光線透過特性を達成でき、カメラ機能と近赤外センシング機能を良好なレベルで両立することができる。 The optical filter of the present invention has an average transmittance of 60% or more, more preferably 65% or more, and particularly preferably 70% when measured from the vertical direction in the wavelength range of Y-10 nm to Y + 10 nm. That's it. A filter having such transmission characteristics can achieve high light transmission characteristics in the visible region and the target near-infrared region, and can achieve both a camera function and a near-infrared sensing function at a good level.
本発明の光学フィルターは、波長560〜800nmの範囲において、光学フィルターの垂直方向から測定した時の透過率が50%となる最も短い波長の値(Xd)と、光学フィルターの垂直方向に対して30°の角度から測定した時の透過率が50%となる波長の値(Xe)との差の絶対値が小さい方が好ましい。(Xd)と(Xe)との差の絶対値は、好ましくは25nm未満、より好ましくは15nm未満、特に好ましくは10nm未満である。このような光学フィルターは、可視光線と一部の近赤外光線を選択的に透過させるように、前記基材(i)上に誘電体多層膜を形成することで得られる。 The optical filter of the present invention has the shortest wavelength value (Xd) at which the transmittance when measured from the vertical direction of the optical filter is 50% in the wavelength range of 560 to 800 nm and the vertical direction of the optical filter. It is preferable that the absolute value of the difference from the wavelength value (Xe) at which the transmittance when measured from an angle of 30 ° is 50% is small. The absolute value of the difference between (Xd) and (Xe) is preferably less than 25 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm. Such an optical filter can be obtained by forming a dielectric multilayer film on the substrate (i) so as to selectively transmit visible light and part of near infrared light.
本発明の光学フィルターの厚みは、所望の用途に応じて適宜選択すればよいが、近年の固体撮像装置の薄型化、軽量化等の流れによれば、本発明の光学フィルターの厚みも薄いことが好ましい。本発明の光学フィルターは、前記基材を含むため、薄型化が可能である。 The thickness of the optical filter of the present invention may be appropriately selected according to the desired application. However, according to the recent trend of thinning and weight reduction of solid-state imaging devices, the thickness of the optical filter of the present invention is also thin. Is preferred. Since the optical filter of the present invention includes the substrate, it can be thinned.
本発明の光学フィルターの厚みは、例えば、好ましくは200μm以下、より好ましくは180μm以下、さらに好ましくは150μm以下、特に好ましくは120μm以下であることが望ましく、下限は特に制限されないが、例えば、20μmであることが望ましい。 The thickness of the optical filter of the present invention is preferably, for example, preferably 200 μm or less, more preferably 180 μm or less, further preferably 150 μm or less, particularly preferably 120 μm or less, and the lower limit is not particularly limited, but for example, 20 μm It is desirable to be.
[基材(i)]
前記基材(i)は、単層であっても多層であってもよく、近赤外線吸収剤として少なくとも化合物(S)を1種以上含有する透明樹脂層を有すればよい。基材(i)が単層の場合は、例えば、化合物(S)を含む透明樹脂製基板(ii)からなる基材を挙げることができ、この透明樹脂製基板(ii)が前記透明樹脂層となる。多層の場合は、例えば、ガラス支持体やベースとなる樹脂製支持体などの支持体または透明樹脂製基板(ii)上に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材や、化合物(S)を含む透明樹脂製基板(ii)上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を挙げることができる。製造コストや光学特性調整の容易性、さらに、樹脂製支持体や透明樹脂製基板(ii)の傷消し効果を達成できることや基材(i)の耐傷つき性向上等の点から、化合物(S)を含有する透明樹脂製基板(ii)上に硬化性樹脂からなるオーバーコート層などの樹脂層が積層された基材が特に好ましい。
[Base material (i)]
The base material (i) may be a single layer or a multilayer, and may have a transparent resin layer containing at least one compound (S) as a near infrared absorber. When the base material (i) is a single layer, for example, a base material made of a transparent resin substrate (ii) containing the compound (S) can be mentioned, and this transparent resin substrate (ii) is the transparent resin layer. It becomes. In the case of a multilayer, for example, a support such as a glass support or a base resin support or an overcoat layer made of a curable resin containing the compound (S) on the transparent resin substrate (ii) Examples include a substrate on which a transparent resin layer is laminated, and a substrate on which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing the compound (S). . From the standpoints of manufacturing cost and ease of optical property adjustment, and further the achievement of scratch-removing effect of the resin support and the transparent resin substrate (ii) and the improvement of scratch resistance of the substrate (i), the compound (S A substrate in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing) is particularly preferable.
以下、化合物(S)および透明樹脂を含有する層を「透明樹脂層」ともいい、それ以外の樹脂層を単に「樹脂層」ともいう。
波長750nm以上の領域において、前記基材(i)の垂直方向から測定した最も低い透過率(Tb)は、好ましくは40%以下、さらに好ましくは25%以下、特に好ましくは10%以下である。
Hereinafter, the layer containing the compound (S) and the transparent resin is also referred to as “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.
In the region of a wavelength of 750 nm or more, the lowest transmittance (Tb) measured from the vertical direction of the substrate (i) is preferably 40% or less, more preferably 25% or less, and particularly preferably 10% or less.
波長750nm以上の領域における前記基材(i)の垂直方向から測定した透過率が50%未満から50%以上となる最も短い波長(Xf)は、好ましくは770〜900nm、さらに好ましくは775〜890nm、特に好ましくは780〜880nmである。 The shortest wavelength (Xf) at which the transmittance measured from the vertical direction of the substrate (i) in the region of a wavelength of 750 nm or more is less than 50% to 50% or more is preferably 770 to 900 nm, more preferably 775 to 890 nm. Especially preferably, it is 780-880 nm.
基材(i)の(Tb)および(Xf)がこのような範囲にあれば、近赤外線選択透過帯域付近の不要な近赤外線を選択的に効率よくカットすることができ、センシング用近赤外線S/N比を向上できるとともに、基材(i)上に誘電体多層膜を製膜した際、近赤外線選択透過帯域の短波長側の光学特性の入射角依存性を低減することができる。 If (Tb) and (Xf) of the base material (i) are in such a range, unnecessary near infrared rays near the near infrared selective transmission band can be selectively and efficiently cut, and the sensing near infrared S S The / N ratio can be improved, and when the dielectric multilayer film is formed on the substrate (i), the incident angle dependency of the optical characteristics on the short wavelength side of the near infrared selective transmission band can be reduced.
波長600nm以上750nm未満の領域において、前記基材(i)の垂直方向から測定した最も低い透過率(Ta)は、好ましくは40%以下、さらに好ましくは25%以下、特に好ましくは10%以下である。
In the region of
波長600nm以上の領域における前記基材(i)の垂直方向から測定した透過率が50%超から50%以下となる最も短い波長(Xc)は、好ましくは610〜670nm、さらに好ましくは620〜665nm、特に好ましくは630〜660nmである。 The shortest wavelength (Xc) at which the transmittance measured from the vertical direction of the substrate (i) in the wavelength region of 600 nm or more is from 50% to 50% is preferably 610 to 670 nm, more preferably 620 to 665 nm. Especially preferably, it is 630-660 nm.
基材(i)の(Ta)および(Xc)がこのような範囲にあれば、不要な近赤外線を選択的に効率よくカットすることができるとともに、基材(i)上に誘電体多層膜を製膜した際、可視波長〜近赤外波長域付近の光学特性の入射角依存性を低減することができる。 If (Ta) and (Xc) of the substrate (i) are in such a range, unnecessary near infrared rays can be selectively and efficiently cut, and a dielectric multilayer film is formed on the substrate (i). When the film is formed, it is possible to reduce the incident angle dependency of the optical characteristics in the vicinity of the visible wavelength to the near infrared wavelength region.
基材(i)の波長430〜580nmにおける平均透過率は、好ましくは75%以上、さらに好ましくは78%以上、特に好ましくは80%以上である。このような透過特性を有する基材を用いると、可視域および目的とする近赤外域において高い光線透過特性を達成でき、カメラ機能と近赤外センシング機能を良好なレベルで両立することができる。 The average transmittance of the substrate (i) at a wavelength of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. When a substrate having such transmission characteristics is used, high light transmission characteristics can be achieved in the visible range and the target near-infrared range, and both the camera function and the near-infrared sensing function can be achieved at a good level.
前記基材(i)の厚みは、所望の用途に応じて適宜選択することができ、特に制限されないが、得られる光学フィルターの入射角依存性を低減するように適宜選択することが望ましく、好ましくは10〜200μm、さらに好ましくは20〜180μm、特に好ましくは30〜150μmである。 The thickness of the base material (i) can be appropriately selected according to a desired application, and is not particularly limited. However, it is desirable and preferably selected appropriately so as to reduce the incident angle dependency of the obtained optical filter. Is 10 to 200 μm, more preferably 20 to 180 μm, and particularly preferably 30 to 150 μm.
基材(i)の厚みが前記範囲にあると、該基材(i)を用いた光学フィルターを薄型化および軽量化することができ、固体撮像装置等の様々な用途に好適に用いることができる。特に、前記透明樹脂製基板(ii)からなる基材(i)をカメラモジュール等のレンズユニットに用いた場合には、レンズユニットの低背化、軽量化を実現することができるため好ましい。 When the thickness of the substrate (i) is in the above range, the optical filter using the substrate (i) can be thinned and reduced in weight, and can be suitably used for various applications such as a solid-state imaging device. it can. In particular, when the base material (i) made of the transparent resin substrate (ii) is used in a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.
前記基材(i)は、化合物(S)に加え、さらに、波長600nm以上750nm未満に吸収極大を有する化合物(A)を含有してもよい。
前記化合物(A)と前記化合物(S)とを併用する場合、これらの化合物は、同一の層に含まれていても別々の層に含まれていてもよい。同一の層に含まれる場合は、例えば、化合物(A)と化合物(S)とがともに同一の透明樹脂製基板(ii)中に含まれる基材や、ガラス支持体等の支持体上に化合物(A)と化合物(S)とが含まれる透明樹脂層が積層されている基材を挙げることができ、別々の層に含まれる場合は、例えば、化合物(A)が含まれる透明樹脂製基板(ii)上に化合物(S)が含まれる透明樹脂層が積層されている基材や、化合物(S)が含まれる透明樹脂製基板(ii)上に化合物(A)が含まれる透明樹脂層が積層されている基材を挙げることができる。
In addition to the compound (S), the substrate (i) may further contain a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm.
When the compound (A) and the compound (S) are used in combination, these compounds may be contained in the same layer or in different layers. When they are contained in the same layer, for example, the compound (A) and the compound (S) are both contained in the same transparent resin substrate (ii) and on a support such as a glass support. (A) and the base material with which the transparent resin layer containing compound (S) is laminated | stacked can be mentioned, When it is contained in a separate layer, for example, the substrate made of transparent resin containing compound (A) (Ii) A base material on which a transparent resin layer containing the compound (S) is laminated, or a transparent resin layer containing the compound (A) on the transparent resin substrate (ii) containing the compound (S) Can be mentioned.
化合物(A)と化合物(S)とは、同一の層に含まれている方がより好ましく、このような場合、別々の層に含まれる場合よりも化合物(A)と化合物(S)との含有量比率を制御することがより容易となる。 The compound (A) and the compound (S) are more preferably contained in the same layer. In such a case, the compound (A) and the compound (S) are more contained than in the case where they are contained in separate layers. It becomes easier to control the content ratio.
<化合物(S)>
化合物(S)は、下記式(S1)で表されるスクアリリウム系化合物である。このような化合物(S)を用いることにより、吸収極大付近でのシャープな吸収と高い可視光透過率を同時に達成することができる。さらに、有機色素は、通常、蛍光を発生させるものが多いが、出願人が鋭意検討した結果、化合物(S)は蛍光強度を著しく低く抑えることができることを見出した。そのため、化合物(S)を含む透明樹脂層を有する本願発明の光学フィルターを、近赤外センシング機能を有するカメラモジュールに使用した際、色素蛍光によるセンシング機能の誤作動を防止することができる。
<Compound (S)>
The compound (S) is a squarylium compound represented by the following formula (S1). By using such a compound (S), sharp absorption near the absorption maximum and high visible light transmittance can be achieved simultaneously. Furthermore, many organic dyes usually generate fluorescence. However, as a result of extensive studies by the applicant, it has been found that the compound (S) can suppress the fluorescence intensity extremely low. Therefore, when the optical filter of the present invention having a transparent resin layer containing the compound (S) is used in a camera module having a near-infrared sensing function, malfunction of the sensing function due to dye fluorescence can be prevented.
R1〜R8は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−NRgRh基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、RgおよびRhは、それぞれ独立に水素原子、−C(O)Ri基または下記La〜Leのいずれかを表し、Riは下記La〜Leのいずれかを表す。
(La)炭素数1〜12の脂肪族炭化水素基
(Lb)炭素数1〜12のハロゲン置換アルキル基
(Lc)炭素数3〜14の脂環式炭化水素基
(Ld)炭素数6〜14の芳香族炭化水素基
(Le)炭素数3〜14の複素環基
(Lf)炭素数1〜12のアルコキシ基
(Lg)置換基Lを有してもよい炭素数1〜12のアシル基、
(Lh)置換基Lを有してもよい炭素数1〜12のアルコキシカルボニル基
置換基Lは、炭素数1〜12の脂肪族炭化水素基、炭素数1〜12のハロゲン置換アルキル基、炭素数3〜14の脂環式炭化水素基、炭素数6〜14の芳香族炭化水素基および炭素数3〜14の複素環基からなる群より選ばれる少なくとも1種である。
R 1 to R 8 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR g R h group, a —SO 2 R i group, or —OSO. It represents either 2 R i group or a group represented by L a ~L h, R g and R h each independently represents a hydrogen atom, one of the -C (O) R i groups or the following L a ~L e , R i represents any of the following L a ~L e.
(L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L d ) carbon the number 6 to 14 aromatic hydrocarbon group (L e) carbon atoms, which may have a
(L h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms.
前記R1としては、好ましくは水素原子、塩素原子、フッ素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、シクロヘキシル基、フェニル基、水酸基、アミノ基、ジメチルアミノ基、ニトロ基であり、より好ましくは水素原子、塩素原子、フッ素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、水酸基である。 R 1 is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group. Group, hydroxyl group, amino group, dimethylamino group and nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group.
前記R2〜R7としては、好ましくはそれぞれ独立に水素原子、塩素原子、フッ素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、シクロヘキシル基、フェニル基、水酸基、アミノ基、ジメチルアミノ基、シアノ基、ニトロ基、アセチルアミノ基、プロピオニルアミノ基、N−メチルアセチルアミノ基、トリフルオロメタノイルアミノ基、ペンタフルオロエタノイルアミノ基、t−ブタノイルアミノ基、シクロヘキシノイルアミノ基、n−ブチルスルホニル基であり、より好ましくは水素原子、塩素原子、フッ素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、tert−ブチル基、水酸基、ジメチルアミノ基、ニトロ基、アセチルアミノ基、プロピオニルアミノ基、トリフルオロメタノイルアミノ基、ペンタフルオロエタノイルアミノ基、t−ブタノイルアミノ基、シクロヘキシノイルアミノ基である。 R 2 to R 7 are preferably each independently a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino Group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert group -Butyl group, hydroxyl group, dimethylamino group, nitro group, acetylamino group, propio Arylamino group, trifluoromethyl meth alkanoylamino group, pentafluoro ethanoyl group, t-butanoyl group, a cyclohexylene Sino-yl-amino group.
前記R8としては、好ましくは水素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、シクロヘキシル基、フェニル基であり、より好ましくは水素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、tert−ブチル基である。 R 8 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, or a phenyl group, and more preferably Are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group.
前記Xとしては、好ましくは酸素原子、硫黄原子であり、特に好ましくは酸素原子である。
化合物(S)は、下記式(S1)のような記載方法に加え、下記式(S2)のように共鳴構造を取るような記載方法でも構造を表すことができる。つまり、下記式(S1)と下記式(S2)との違いは構造の記載方法のみであり、どちらも同一の化合物を表す。本発明中では特に断りのない限り、下記式(S1)のような記載方法にてスクアリリウム系化合物の構造を表すものとする。
X is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
The compound (S) can also represent the structure by a description method such as the following formula (S2), in addition to a description method such as the following formula (S1). That is, the difference between the following formula (S1) and the following formula (S2) is only the structure description method, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium compound is represented by a description method such as the following formula (S1).
化合物(S)の吸収極大波長は、好ましくは波長750nm以上850nm以下、より好ましくは755nm以上845nm以下、さらに好ましくは760nm以上840nm以下、特に好ましくは765nm以上835nm以下である。化合物(S)の吸収極大波長がこのような範囲にあると、近赤外選択透過帯域付近の不要な近赤外線を選択的に効率よくカットすることができる。 The absorption maximum wavelength of the compound (S) is preferably from 750 nm to 850 nm, more preferably from 755 nm to 845 nm, still more preferably from 760 nm to 840 nm, particularly preferably from 765 nm to 835 nm. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near infrared rays in the vicinity of the near infrared selective transmission band can be selectively and efficiently cut.
化合物(S)は、一般的に知られている方法で合成すればよく、例えば、特開平1−228960号公報、特開2001−40234号公報、特許第3094037号公報、特許第3196383号公報等に記載されている方法などを参照して合成することができる。 The compound (S) may be synthesized by a generally known method. For example, JP-A-1-228960, JP-A-2001-40234, JP-A-3094037, JP-A-3196383, etc. Can be synthesized with reference to the method described in the above.
化合物(S)の含有量は、前記基材(i)として、例えば、化合物(S)を含有する透明樹脂製基板(ii)からなる基材や、化合物(S)を含有する透明樹脂製基板(ii)上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を用いる場合には、透明樹脂100重量部に対して、好ましくは0.01〜2.0重量部、より好ましくは0.02〜1.5重量部、特に好ましくは0.03〜1.0重量部であり、前記基材(i)として、ガラス支持体やベースとなる樹脂製支持体に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材を用いる場合には、化合物(S)を含む透明樹脂層を形成する樹脂100重量部に対して、好ましくは0.1〜5.0重量部、より好ましくは0.2〜4.0重量部、特に好ましくは0.3〜3.0重量部である。化合物(S)の含有量が前記範囲内にあると、良好な近赤外線吸収、透過特性と高い可視光透過率とを両立した光学フィルターを得ることができる。 The content of the compound (S) is, for example, a substrate made of a transparent resin substrate (ii) containing the compound (S) or a transparent resin substrate containing the compound (S) as the substrate (i). (Ii) When using a substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the transparent resin. , More preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. As the base material (i), a compound is used as a glass support or a resin support as a base. In the case of using a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing (S) is used, with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (S) And preferably 0.1 to 5.0 parts by weight, more preferably 0. To 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near-infrared absorption and transmission characteristics and high visible light transmittance can be obtained.
<化合物(A)>
化合物(A)は、波長600nm以上750nm未満に吸収極大を有すれば特に制限されないが、溶剤可溶型の色素化合物であることが好ましく、スクアリリウム系化合物、フタロシアニン系化合物およびシアニン系化合物からなる群より選ばれる少なくとも1種であることがより好ましく、スクアリリウム系化合物を含むことがさらに好ましく、スクアリリウム系化合物とその他の化合物(A)をそれぞれ1種以上含むことがさらに好ましく、その他の化合物(A)としてはフタロシアニン系化合物およびシアニン系化合物が特に好ましい。
<Compound (A)>
The compound (A) is not particularly limited as long as it has an absorption maximum at a wavelength of 600 nm or more and less than 750 nm, but is preferably a solvent-soluble dye compound, and is a group consisting of a squarylium compound, a phthalocyanine compound, and a cyanine compound. More preferably, it is at least one selected from the above, more preferably contains a squarylium compound, more preferably contains at least one squarylium compound and another compound (A), and other compound (A). Particularly preferred are phthalocyanine compounds and cyanine compounds.
スクアリリウム系化合物は、優れた可視光透過性、急峻な吸収特性および高いモル吸光係数を有するが、光線吸収時に散乱光の原因となる蛍光を発生させる場合がある。そのような場合、スクアリリウム系化合物とその他の化合物(A)とを組み合わせて使用することにより、散乱光が少なくカメラ画質がより良好な光学フィルターを得ることができる。 The squarylium-based compound has excellent visible light permeability, steep absorption characteristics, and a high molar extinction coefficient, but may generate fluorescence that causes scattered light upon light absorption. In such a case, an optical filter with less scattered light and better camera image quality can be obtained by using a combination of the squarylium compound and the other compound (A).
化合物(A)の吸収極大波長は、好ましくは620nm以上748nm以下、さらに好ましくは650nm以上745nm以下、特に好ましくは660nm以上740nm以下である。基材(i)が化合物(S)に加えて化合物(A)を含有することにより、光学フィルターとした際に近赤外選択透過帯域の短波長側に加え可視域の入射角依存性も低減でき、前記の(Xd)と(Xe)との差の絶対値を小さくすることがより容易となる。 The absorption maximum wavelength of the compound (A) is preferably 620 nm to 748 nm, more preferably 650 nm to 745 nm, and particularly preferably 660 nm to 740 nm. When the base material (i) contains the compound (A) in addition to the compound (S), the dependence on the incident angle in the visible region is reduced in addition to the short wavelength side of the near-infrared selective transmission band when an optical filter is used. This makes it easier to reduce the absolute value of the difference between the above (Xd) and (Xe).
化合物(A)の含有量は、前記基材(i)として、例えば、化合物(A)を含有する透明樹脂製基板(ii)からなる基材や、化合物(S)を含有する透明樹脂製基板(ii)上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を用いる場合には、透明樹脂100重量部に対して、好ましくは0.01〜2.0重量部、より好ましくは0.02〜1.5重量部、特に好ましくは0.03〜1.0重量部であり、前記基材(i)として、ガラス支持体やベースとなる樹脂製支持体に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材を用いる場合には、化合物(A)を含む透明樹脂層を形成する樹脂100重量部に対して、好ましくは0.1〜5.0重量部、より好ましくは0.2〜4.0重量部、特に好ましくは0.3〜3.0重量部である。 The content of the compound (A) is, for example, a substrate made of a transparent resin substrate (ii) containing the compound (A) or a transparent resin substrate containing the compound (S) as the substrate (i). (Ii) When using a substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the transparent resin. , More preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. As the base material (i), a compound is used as a glass support or a resin support as a base. In the case of using a substrate on which a transparent resin layer such as an overcoat layer made of a curable resin containing (S) is used, with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A) And preferably 0.1 to 5.0 parts by weight, more preferably 0. To 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight.
<その他の色素(X)>
前記基材(i)には、さらに、化合物(S)および化合物(A)に該当しない、その他の色素(X)が含まれていてもよい。
<Other dye (X)>
The base material (i) may further contain other dye (X) that does not correspond to the compound (S) and the compound (A).
その他の色素(X)としては、吸収極大波長が650nm未満もしくは850nm超のものであれば特に制限されないが、例えば、スクアリリウム系化合物、フタロシアニン系化合物、シアニン系化合物、ナフタロシアニン系化合物、クロコニウム系化合物、ポルフィリン系化合物および金属ジチオラート系化合物からなる群より選ばれる少なくとも1種の化合物が挙げられる。化合物(S)の吸収特性や目的とする近赤外透過波長によっては、化合物(S)とその他の色素(X)とを併用することで、可視波長域に加え近赤外透過帯域の長波長側においても入射角依存性を低減することができ、良好な赤外センシング性能を達成することができる。 Other dyes (X) are not particularly limited as long as the absorption maximum wavelength is less than 650 nm or more than 850 nm. For example, squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds And at least one compound selected from the group consisting of a porphyrin compound and a metal dithiolate compound. Depending on the absorption characteristics of the compound (S) and the target near-infrared transmission wavelength, the long wavelength of the near-infrared transmission band in addition to the visible wavelength range can be obtained by using the compound (S) in combination with the other dye (X). Also on the side, the dependency on the incident angle can be reduced, and good infrared sensing performance can be achieved.
その他の色素(X)の含有量は、前記基材(i)として、例えば、その他の色素(X)を含有する透明樹脂製基板(ii)からなる基材や、その他の色素(X)を含有する透明樹脂製基板(ii)上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を用いる場合には、透明樹脂100重量部に対して、好ましくは0.01〜1.5重量部、より好ましくは0.02〜1.0重量部、特に好ましくは0.03〜0.7重量部であり、前記基材(i)として、ガラス支持体やベースとなる樹脂製支持体上にその他の色素(X)および硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材を用いる場合には、その他の色素(X)を含む透明樹脂層を形成する樹脂100重量部に対して、好ましくは0.1〜4.0重量部、より好ましくは0.2〜3.0重量部、特に好ましくは0.3〜2.0重量部である。その他の色素(X)の含有量が前記範囲内にあると、良好な近赤外線吸収特性と高い可視光透過率とを両立させることができる。 The content of the other dye (X) is, for example, a base material made of a transparent resin substrate (ii) containing the other dye (X) or the other dye (X) as the base material (i). In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the transparent resin substrate (ii) to be contained, it is preferably 0.01 to 100 parts by weight of the transparent resin To 1.5 parts by weight, more preferably 0.02 to 1.0 parts by weight, particularly preferably 0.03 to 0.7 parts by weight, and serves as a glass support or base as the substrate (i). When using a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin or the like is laminated on a resin support, a transparent resin layer containing the other dye (X) Is preferably 0.1-4. Parts by weight, more preferably 0.2 to 3.0 parts by weight, particularly preferably 0.3 to 2.0 parts by weight. When the content of the other dye (X) is within the above range, both good near-infrared absorption characteristics and high visible light transmittance can be achieved.
<透明樹脂>
樹脂製支持体やガラス支持体などに積層する透明樹脂層および透明樹脂製基板(ii)は、透明樹脂を用いて形成することができる。前記基材(i)に用いる透明樹脂としては、1種単独でもよいし、2種以上でもよい。
<Transparent resin>
The transparent resin layer and the transparent resin substrate (ii) to be laminated on a resin support or glass support can be formed using a transparent resin. As transparent resin used for the said base material (i), 1 type may be individual and 2 or more types may be sufficient.
透明樹脂としては、本発明の効果を損なわないものである限り特に制限されないが、例えば、熱安定性やフィルムへの成形性を確保し、かつ、100℃以上の蒸着温度で行う高温蒸着により誘電体多層膜を形成しうる基材とするため、ガラス転移温度(Tg)が、好ましくは110〜380℃、より好ましくは110〜370℃、さらに好ましくは120〜360℃である樹脂が挙げられる。また、前記樹脂のガラス転移温度が140℃以上であると、誘電体多層膜をより高温で蒸着形成し得るフィルム(透明樹脂層および透明樹脂製基板(ii))が得られるため、特に好ましい。Tgは、具体的には、下記実施例に記載の方法で測定することができる。 The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it ensures thermal stability and moldability to a film, and dielectrics are formed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. In order to use as a base material which can form a body multilayer film, the resin whose glass transition temperature (Tg) becomes like this. Preferably it is 110-380 degreeC, More preferably, it is 110-370 degreeC, More preferably, it is 120-360 degreeC. Moreover, it is especially preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film (transparent resin layer and transparent resin substrate (ii)) on which the dielectric multilayer film can be deposited at a higher temperature can be obtained. Specifically, Tg can be measured by the method described in the Examples below.
透明樹脂としては、当該樹脂からなる厚さ0.1mmの樹脂製支持体を形成した場合に、この樹脂製支持体の全光線透過率(JIS K7375)が、好ましくは75%以上、さらに好ましくは78%以上、特に好ましくは80%以上となる樹脂を用いることができる。全光線透過率がこのような範囲となる樹脂を用いれば、得られる基材(i)は光学フィルムとして良好な透明性を示す。 As the transparent resin, when a resin support made of the resin and having a thickness of 0.1 mm is formed, the total light transmittance (JIS K7375) of the resin support is preferably 75% or more, more preferably Resins that can be 78% or more, particularly preferably 80% or more can be used. If a resin having a total light transmittance in such a range is used, the obtained base material (i) exhibits good transparency as an optical film.
透明樹脂として、溶媒可溶性の樹脂を用いる場合、該透明樹脂のゲルパーミエーションクロマトグラフィー(GPC)法により測定される、ポリスチレン換算の重量平均分子量(Mw)は、通常15,000〜350,000、好ましくは30,000〜250,000であり、数平均分子量(Mn)は、通常10,000〜150,000、好ましくは20,000〜100,000である。MwおよびMnは、具体的には、下記実施例に記載の方法で測定することができる。 When a solvent-soluble resin is used as the transparent resin, the polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, Preferably it is 30,000-250,000, and a number average molecular weight (Mn) is 10,000-150,000 normally, Preferably it is 20,000-100,000. Specifically, Mw and Mn can be measured by the methods described in the following examples.
透明樹脂としては、例えば、環状(ポリ)オレフィン系樹脂、芳香族ポリエーテル系樹脂、ポリイミド系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド(アラミド)系樹脂、ポリアリレート系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート(PEN)系樹脂、フッ素化芳香族ポリマー系樹脂、(変性)アクリル系樹脂、エポキシ系樹脂、アリルエステル系硬化型樹脂、シルセスキオキサン系紫外線硬化型樹脂、アクリル系紫外線硬化型樹脂およびビニル系紫外線硬化型樹脂を挙げることができる。 Examples of transparent resins include cyclic (poly) olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins. Resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins Examples thereof include resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins.
≪環状(ポリ)オレフィン系樹脂≫
環状(ポリ)オレフィン系樹脂としては、下記式(X0)で表される単量体および下記式(Y0)で表される単量体からなる群より選ばれる少なくとも1種の単量体から得られる樹脂、および当該樹脂を水素添加することで得られる樹脂が好ましい。
≪Cyclic (poly) olefin resin≫
The cyclic (poly) olefin resin is at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ) And a resin obtained by hydrogenating the resin are preferred.
(i')水素原子
(ii')ハロゲン原子
(iii')トリアルキルシリル基
(iv')酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、
置換または非置換の炭素数1〜30の炭化水素基
(v')置換または非置換の炭素数1〜30の炭化水素基
(vi')極性基(但し、(iv')を除く。)
(vii')Rx1とRx2またはRx3とRx4とが、相互に結合して形成されたアルキリデン基
(但し、前記結合に関与しないRx1〜Rx4は、それぞれ独立に前記(i')〜(vi')より選ばれる原子または基を表す。)
(viii')Rx1とRx2またはRx3とRx4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環(但し、前記結合に関与しないRx1〜Rx4は、それぞれ独立に前記(i')〜(vi')より選ばれる原子または基を表す。)
(ix')Rx2とRx3とが、相互に結合して形成された単環の炭化水素環または複素環(但し、前記結合に関与しないRx1とRx4は、それぞれ独立に前記(i')〜(vi')より選ばれる原子または基を表す。)
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (v ′) A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi ′) polar group (excluding (iv ′))
(Vii ′) an alkylidene group formed by bonding R x1 and R x2 or R x3 and R x4 to each other (provided that R x1 to R x4 not involved in the bonding are independently the above (i ′ )-(Vi ′) represents an atom or group selected from.
(Viii ′) R x1 and R x2 or R x3 and R x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R x1 to R not involved in the bonding) x4 each independently represents an atom or group selected from the above (i ′) to (vi ′).
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by bonding R x2 and R x3 to each other (provided that R x1 and R x4 not involved in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').
≪芳香族ポリエーテル系樹脂≫
芳香族ポリエーテル系樹脂は、下記式(1)で表される構造単位および下記式(2)で表される構造単位からなる群より選ばれる少なくとも1種の構造単位を有することが好ましい。
≪Aromatic polyether resin≫
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).
また、前記芳香族ポリエーテル系樹脂は、さらに下記式(3)で表される構造単位および下記式(4)で表される構造単位からなる群より選ばれる少なくとも1種の構造単位を有することが好ましい。 The aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.
≪ポリイミド系樹脂≫
ポリイミド系樹脂としては、特に制限されず、繰り返し単位にイミド結合を含む高分子化合物であればよく、例えば、特開2006−199945号公報や特開2008−163107号公報に記載されている方法で合成することができる。
≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a high molecular compound containing an imide bond in a repeating unit. For example, the method described in JP-A-2006-199945 and JP-A-2008-163107 is used. Can be synthesized.
≪フルオレンポリカーボネート系樹脂≫
フルオレンポリカーボネート系樹脂としては、特に制限されず、フルオレン部位を含むポリカーボネート樹脂であればよく、例えば、特開2008−163194号公報に記載されている方法で合成することができる。
≪Fluorene polycarbonate resin≫
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety. For example, the fluorene polycarbonate resin can be synthesized by a method described in JP-A-2008-163194.
≪フルオレンポリエステル系樹脂≫
フルオレンポリエステル系樹脂としては、特に制限されず、フルオレン部位を含むポリエステル樹脂であればよく、例えば、特開2010−285505号公報や特開2011−197450号公報に記載されている方法で合成することができる。
≪Fluorene polyester resin≫
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, the fluorene polyester resin is synthesized by a method described in JP 2010-285505 A or JP 2011-197450 A. Can do.
≪フッ素化芳香族ポリマー系樹脂≫
フッ素化芳香族ポリマー系樹脂としては、特に制限されないが、フッ素原子を少なくとも1つ有する芳香族環と、エーテル結合、ケトン結合、スルホン結合、アミド結合、イミド結合およびエステル結合からなる群より選ばれる少なくとも1つの結合を含む繰り返し単位とを含有するポリマーであることが好ましく、例えば特開2008−181121号公報に記載されている方法で合成することができる。
≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. The polymer preferably contains a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.
≪アクリル系紫外線硬化型樹脂≫
アクリル系紫外線硬化型樹脂としては、特に制限されないが、分子内に一つ以上のアクリル基もしくはメタクリル基を有する化合物と、紫外線によって分解して活性ラジカルを発生させる化合物を含有する樹脂組成物から合成されるものを挙げることができる。アクリル系紫外線硬化型樹脂は、前記基材(i)として、ガラス支持体上やベースとなる樹脂製支持体上に化合物(S)および硬化性樹脂を含む透明樹脂層が積層された基材や、化合物(S)を含有する透明樹脂製基板(ii)上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を用いる場合、該硬化性樹脂として特に好適に使用することができる。
≪Acrylic UV curable resin≫
The acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned. The acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing a compound (S) and a curable resin is laminated on a glass support or a base resin support as the base (i) In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the transparent resin substrate (ii) containing the compound (S), it is particularly preferably used as the curable resin. be able to.
≪市販品≫
透明樹脂の市販品としては、以下の市販品等を挙げることができる。環状(ポリ)オレフィン系樹脂の市販品としては、JSR(株)製アートン、日本ゼオン(株)製ゼオノア、三井化学(株)製APEL、ポリプラスチックス(株)製TOPASなどを挙げることができる。ポリエーテルサルホン系樹脂の市販品としては、住友化学(株)製スミカエクセルPESなどを挙げることができる。ポリイミド系樹脂の市販品としては、三菱ガス化学(株)製ネオプリムLなどを挙げることができる。ポリカーボネート系樹脂の市販品としては、帝人(株)製ピュアエースなどを挙げることができる。フルオレンポリカーボネート系樹脂の市販品としては、三菱ガス化学(株)製ユピゼータEP−5000などを挙げることができる。フルオレンポリエステル系樹脂の市販品としては、大阪ガスケミカル(株)製OKP4HTなどを挙げることができる。アクリル系樹脂の市販品としては、(株)日本触媒製アクリビュアなどを挙げることができる。シルセスキオキサン系紫外線硬化型樹脂の市販品としては、新日鐵化学(株)製シルプラスなどを挙げることができる。
≪Commercial product≫
The following commercial products etc. can be mentioned as a commercial item of transparent resin. Examples of commercially available cyclic (poly) olefin-based resins include Arton manufactured by JSR Co., Ltd., ZEONOR manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. . Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include NIPPON CATALYST ACRYVIEWER. Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.
<その他成分>
前記基材(i)は、本発明の効果を損なわない範囲において、さらに酸化防止剤、近紫外線吸収剤、蛍光消光剤および金属錯体系化合物等の添加剤を含有してもよい。また、後述するキャスト成形により基材(i)を製造する場合には、レベリング剤や消泡剤を添加することで基材(i)の製造を容易にすることができる。これらその他成分は、1種単独で用いてもよいし、2種以上を併用してもよい。
<Other ingredients>
The base material (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and a metal complex compound as long as the effects of the present invention are not impaired. Moreover, when manufacturing base material (i) by the cast molding mentioned later, manufacture of base material (i) can be made easy by adding a leveling agent and an antifoamer. These other components may be used alone or in combination of two or more.
前記近紫外線吸収剤としては、例えばアゾメチン系化合物、インドール系化合物、ベンゾトリアゾール系化合物、トリアジン系化合物などが挙げられる。
前記酸化防止剤としては、例えば2,6−ジ−t−ブチル−4−メチルフェノール、2,2'−ジオキシ−3,3'−ジ−t−ブチル−5,5'−ジメチルジフェニルメタン、およびテトラキス[メチレン−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]メタンなどが挙げられる。
Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, and And tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane.
なお、これら添加剤は、基材(i)を製造する際に、樹脂などとともに混合してもよいし、樹脂を合成する際に添加してもよい。また、添加量は、所望の特性に応じて適宜選択されるものであるが、樹脂100重量部に対して、通常0.01〜5.0重量部、好ましくは0.05〜2.0重量部である。 These additives may be mixed together with a resin or the like when producing the substrate (i), or may be added when a resin is synthesized. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Part.
<基材(i)の製造方法>
前記基材(i)が、化合物(S)を含有する透明樹脂製基板(ii)を含む基材である場合、該透明樹脂製基板(ii)は、例えば、溶融成形またはキャスト成形により形成することができ、さらに、必要により、成形後に、反射防止剤、ハードコート剤および/または帯電防止剤等のコーティング剤をコーティングすることで、オーバーコート層が積層された基材を製造することができる。
<Method for producing substrate (i)>
When the base material (i) is a base material including a transparent resin substrate (ii) containing the compound (S), the transparent resin substrate (ii) is formed by, for example, melt molding or cast molding. In addition, if necessary, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. .
前記基材(i)が、ガラス支持体やベースとなる樹脂製支持体または透明樹脂製基板(ii)上に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材である場合、例えば、ガラス支持体やベースとなる樹脂製支持体または透明樹脂製基板(ii)に化合物(S)を含む樹脂溶液を溶融成形またはキャスト成形することで、好ましくはスピンコート、スリットコート、インクジェットなどの方法にて塗工した後に溶媒を乾燥除去し、必要に応じてさらに光照射や加熱を行うことで、ガラス支持体やベースとなる樹脂製支持体または透明樹脂製基板(ii)上に透明樹脂層が形成された基材を製造することができる。 Transparent resin layer such as an overcoat layer in which the base material (i) is a glass support, a resin support as a base, or a curable resin containing the compound (S) on a transparent resin substrate (ii) Is a laminated substrate, for example, by melt-molding or cast-molding a resin solution containing the compound (S) on a glass support or base resin support or transparent resin substrate (ii), Preferably, the solvent is dried and removed after coating by a method such as spin coating, slit coating, and ink jet, and if necessary, further irradiation with light or heating is performed, whereby a glass support or a resin support as a base or A base material having a transparent resin layer formed on a transparent resin substrate (ii) can be produced.
≪溶融成形≫
前記溶融成形としては、具体的には、樹脂と化合物(S)等とを溶融混練りして得られたペレットを溶融成形する方法;樹脂と化合物(S)とを含有する樹脂組成物を溶融成形する方法;または、化合物(S)、樹脂および溶剤を含む樹脂組成物から溶剤を除去して得られたペレットを溶融成形する方法などが挙げられる。溶融成形方法としては、射出成形、溶融押出成形またはブロー成形などを挙げることができる。
≪Melt molding≫
Specifically, the melt molding is a method of melt-molding pellets obtained by melt-kneading a resin and a compound (S) or the like; melting a resin composition containing the resin and the compound (S) A method of molding; or a method of melt-molding pellets obtained by removing the solvent from the resin composition containing the compound (S), the resin and the solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.
≪キャスト成形≫
前記キャスト成形としては、化合物(S)、樹脂および溶剤を含む樹脂組成物を適当な支持体の上にキャスティングして溶剤を除去する方法;または化合物(S)と、光硬化性樹脂および/または熱硬化性樹脂とを含む硬化性組成物を適当な支持体の上にキャスティングして溶媒を除去した後、紫外線照射や加熱などの適切な手法により硬化させる方法などにより製造することもできる。
≪Cast molding≫
As the cast molding, a method of removing a solvent by casting a resin composition containing the compound (S), a resin and a solvent on an appropriate support; or the compound (S) and a photocurable resin and / or It can also be produced by a method in which a curable composition containing a thermosetting resin is cast on an appropriate support to remove the solvent and then cured by an appropriate method such as ultraviolet irradiation or heating.
前記基材(i)が、化合物(S)を含有する透明樹脂製基板(ii)からなる基材である場合には、該基材(i)は、キャスト成形後、支持体から塗膜を剥離することにより得ることができ、また、前記基材(i)が、ガラス支持体やベースとなる樹脂製支持体等の支持体または透明樹脂製基板(ii)上に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材である場合には、該基材(i)は、キャスト成形後、塗膜を剥離しないことで得ることができる。 When the base material (i) is a base material made of a transparent resin substrate (ii) containing the compound (S), the base material (i) is coated with a coating film from the support after cast molding. The base material (i) contains the compound (S) on a support such as a glass support or a base resin support or a transparent resin substrate (ii). In the case of a base material on which a transparent resin layer such as an overcoat layer made of a curable resin is laminated, the base material (i) can be obtained by not peeling the coating film after cast molding. .
前記支持体としては、例えば、ガラス板、スチールベルト、スチールドラムおよび透明樹脂(例えば、ポリエステルフィルム、環状オレフィン系樹脂フィルム)製支持体が挙げられる。 As said support body, the support body made from a glass plate, a steel belt, a steel drum, and transparent resin (for example, a polyester film, a cyclic olefin resin film) is mentioned, for example.
さらに、ガラス板、石英または透明プラスチック製等の光学部品に、前記樹脂組成物をコーティングして溶剤を乾燥させる方法、または、前記硬化性組成物をコーティングして硬化および乾燥させる方法などにより、光学部品上に透明樹脂層を形成することもできる。 Further, the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried. A transparent resin layer can also be formed on the component.
前記方法で得られた透明樹脂層(透明樹脂製基板(ii))中の残留溶剤量は可能な限り少ない方がよい。具体的には、前記残留溶剤量は、透明樹脂層(透明樹脂製基板(ii))の重さに対して、好ましくは3重量%以下、より好ましくは1重量%以下、さらに好ましくは0.5重量%以下である。残留溶剤量が前記範囲にあると、変形や特性が変化しにくい、所望の機能を容易に発揮できる透明樹脂層(透明樹脂製基板(ii))が得られる。 The amount of residual solvent in the transparent resin layer (transparent resin substrate (ii)) obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.8% by weight with respect to the weight of the transparent resin layer (transparent resin substrate (ii)). 5% by weight or less. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate (ii)) that can easily exhibit a desired function is obtained, in which deformation and characteristics are hardly changed.
[誘電体多層膜]
本発明の光学フィルターを構成する誘電体多層膜は、不要な近赤外線を反射によりカットするとともに必要となる近赤外線を透過させる能力を有する膜である。本発明では、誘電体多層膜は基材(i)の片面に設けてもよいし、両面に設けてもよい。片面に設ける場合、製造コストや製造容易性に優れ、両面に設ける場合、高い強度を有し、反りの生じにくい光学フィルターを得ることができる。
[Dielectric multilayer film]
The dielectric multilayer film constituting the optical filter of the present invention is a film having the ability to cut unnecessary near infrared rays by reflection and transmit the necessary near infrared rays. In the present invention, the dielectric multilayer film may be provided on one side of the substrate (i) or on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, an optical filter having high strength and less warpage can be obtained.
本発明の光学フィルターを固体撮像素子などの用途に適用する場合、光学フィルターの反りが小さい方が好ましいことから、誘電体多層膜を基材(i)の両面に設けることが好ましく、両面に設けた誘電体多層膜は分光特性が同じでも異なっていてもよい。両面に設けた誘電体多層膜の分光特性が同じ場合では近赤外波長域において光線阻止帯域ZaおよびZcの透過率を効率よく低減することができ、両面に設けた誘電体多層膜の分光特性が異なる場合では光線阻止帯域Zcをより長波長側まで広げることが容易になる傾向がある。 When the optical filter of the present invention is applied to uses such as a solid-state imaging device, it is preferable that the warp of the optical filter is smaller. Therefore, it is preferable to provide the dielectric multilayer film on both surfaces of the substrate (i). The dielectric multilayer films may have the same or different spectral characteristics. When the spectral characteristics of the dielectric multilayer films provided on both surfaces are the same, the transmittance of the light blocking zones Za and Zc can be efficiently reduced in the near-infrared wavelength region, and the spectral characteristics of the dielectric multilayer films provided on both surfaces. When the values are different, there is a tendency that the light blocking band Zc can be easily extended to the longer wavelength side.
誘電体多層膜としては、高屈折率材料層と低屈折率材料層とを交互に積層したものが挙げられる。高屈折率材料層を構成する材料としては、屈折率が1.7以上の材料を用いることができ、屈折率が通常は1.7〜2.5の材料が選択される。このような材料としては、例えば、酸化チタン、酸化ジルコニウム、五酸化タンタル、五酸化ニオブ、酸化ランタン、酸化イットリウム、酸化亜鉛、硫化亜鉛または酸化インジウム等を主成分とし、酸化チタン、酸化錫および/または酸化セリウム等を少量(例えば、主成分に対して0〜10重量%)含有させたものが挙げられる。 Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately stacked. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main components, and titanium oxide, tin oxide, and / or Or what contains a small amount (for example, 0-10 weight% with respect to a main component) of cerium oxide etc. is mentioned.
低屈折率材料層を構成する材料としては、屈折率が1.6以下の材料を用いることができ、屈折率が通常は1.2〜1.6の材料が選択される。このような材料としては、例えば、シリカ、アルミナ、フッ化ランタン、フッ化マグネシウムおよび六フッ化アルミニウムナトリウムが挙げられる。 As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of usually 1.2 to 1.6 is selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.
高屈折率材料層と低屈折率材料層とを積層する方法については、これらの材料層を積層した誘電体多層膜が形成される限り特に制限はない。例えば、基材(i)上に、直接、CVD法、スパッタ法、真空蒸着法、イオンアシスト蒸着法またはイオンプレーティング法等により、高屈折率材料層と低屈折率材料層とを交互に積層した誘電体多層膜を形成することができる。 The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a high-refractive index material layer and a low-refractive index material layer are alternately laminated directly on the substrate (i) by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A dielectric multilayer film can be formed.
高屈折率材料層および低屈折率材料層の各層の物理膜厚は、それぞれ層の屈折率にもよるが、通常、5〜500nmであることが好ましく、誘電体多層膜の物理膜厚の合計値は光学フィルター全体として1.0〜8.0μmであることが好ましい。 The physical film thickness of each of the high-refractive index material layer and the low-refractive index material layer is preferably 5 to 500 nm, although it depends on the refractive index of each layer, and is the total physical film thickness of the dielectric multilayer film. The value is preferably 1.0 to 8.0 μm for the entire optical filter.
誘電体多層膜における高屈折率材料層と低屈折率材料層との合計の積層数は、光学フィルター全体として16〜70層であることが好ましく、20〜60層であることがより好ましい。各層の厚み、光学フィルター全体としての誘電体多層膜の厚みや合計の積層数が前記範囲にあると、十分な製造マージンを確保できる上に、光学フィルターの反りや誘電体多層膜のクラックを低減することができる。 The total number of stacked high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 16 to 70 layers, and more preferably 20 to 60 layers as a whole. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.
本発明では、高屈折率材料層および低屈折率材料層を構成する材料種、高屈折率材料層および低屈折率材料層の各層の厚さ、積層の順番、積層数を適切に選択することで、可視域に十分な透過率を確保した上で近赤外波長域に所望の波長の光線阻止帯域や光線透過帯域を有する光学フィルターを得ることができる。 In the present invention, the material type constituting the high-refractive index material layer and the low-refractive index material layer, the thickness of each layer of the high-refractive index material layer and the low-refractive index material layer, the order of stacking, and the number of stacks are appropriately selected. Thus, it is possible to obtain an optical filter having a light blocking band and a light transmission band of a desired wavelength in the near infrared wavelength range while ensuring a sufficient transmittance in the visible range.
ここで、前記条件を最適化するには、例えば、光学薄膜設計ソフト(例えば、Essential Macleod、Thin Film Center社製)を用い、近赤外波長域において光線の透過を抑制したい波長域の透過率を低くするともに、光線を透過させたい波長域の透過率を高くするようにパラメーターを設定すればよい。例えば、両面に形成された誘電体多層膜によって800nm付近に光線透過帯域を設ける場合、前記ソフトを使用し、一方の誘電体多層膜の波長720〜760nmの目標透過率を0%、780〜820nmの目標透過率を100%とした上でそれぞれの波長域のTarget Toleranceの値を0.5以下などとし、もう一方の誘電体多層膜の波長780〜820nmの目標透過率を100%とした上で850〜1100nmの目標透過率を0%とした上でそれぞれの波長域のTarget Toleranceの値を0.5以下などとするパラメーター設定方法が挙げられる。 Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used, and the transmittance in the wavelength range where light transmission is desired to be suppressed in the near-infrared wavelength range. The parameter may be set so as to increase the transmittance in the wavelength region where light is to be transmitted. For example, when a light transmission band is provided in the vicinity of 800 nm by a dielectric multilayer film formed on both surfaces, the above-described software is used, and the target transmittance of one dielectric multilayer film at a wavelength of 720 to 760 nm is 0%, 780 to 820 nm. The target transmittance of each wavelength region is set to 100%, the Target Tolerance value of each wavelength region is set to 0.5 or less, and the target transmittance of the other dielectric multilayer film at wavelengths of 780 to 820 nm is set to 100%. And a parameter setting method in which the target transmittance at 850 to 1100 nm is set to 0% and the Target Tolerance value of each wavelength region is set to 0.5 or less.
[その他の機能膜]
本発明の光学フィルターは、本発明の効果を損なわない範囲において、基材(i)と誘電体多層膜との間、基材(i)の誘電体多層膜が設けられた面と反対側の面、または誘電体多層膜の基材(i)が設けられた面と反対側の面に、基材(i)や誘電体多層膜の表面硬度の向上、耐薬品性の向上、帯電防止および傷消しなどの目的で、反射防止膜、ハードコート膜や帯電防止膜などの機能膜を適宜設けることができる。
[Other functional membranes]
As long as the optical filter of the present invention does not impair the effects of the present invention, the optical filter between the substrate (i) and the dielectric multilayer film is on the side opposite to the surface on which the dielectric multilayer film of the substrate (i) is provided. On the surface or the surface opposite to the surface on which the substrate (i) of the dielectric multilayer film is provided, the surface hardness of the substrate (i) or the dielectric multilayer film is improved, the chemical resistance is improved, the antistatic A functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided for the purpose of scratch removal.
本発明の光学フィルターは、前記機能膜からなる層を1層含んでもよく、2層以上含んでもよい。本発明の光学フィルターが前記機能膜からなる層を2層以上含む場合には、同様の層を2層以上含んでもよいし、異なる層を2層以上含んでもよい。 The optical filter of the present invention may include one layer composed of the functional film, or may include two or more layers. When the optical filter of the present invention includes two or more layers made of the functional film, it may include two or more similar layers or two or more different layers.
機能膜を積層する方法としては、特に制限されないが、反射防止剤、ハードコート剤および/または帯電防止剤等のコーティング剤などを基材(i)または誘電体多層膜に、前記と同様に溶融成形またはキャスト成形する方法等を挙げることができる。 The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted in the base material (i) or the dielectric multilayer film as described above. Examples of the method include molding or cast molding.
また、前記コーティング剤などを含む硬化性組成物をバーコーター等で基材(i)または誘電体多層膜上に塗布した後、紫外線照射等により硬化することによっても製造することができる。 Further, the composition can also be produced by applying a curable composition containing the coating agent or the like on the substrate (i) or the dielectric multilayer film with a bar coater or the like and then curing the composition by ultraviolet irradiation or the like.
前記コーティング剤としては、紫外線(UV)/電子線(EB)硬化型樹脂や熱硬化型樹脂などが挙げられ、具体的には、ビニル化合物類や、ウレタン系、ウレタンアクリレート系、アクリレート系、エポキシ系およびエポキシアクリレート系樹脂などが挙げられる。これらのコーティング剤を含む前記硬化性組成物としては、ビニル系、ウレタン系、ウレタンアクリレート系、アクリレート系、エポキシ系およびエポキシアクリレート系硬化性組成物などが挙げられる。 Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.
また、前記硬化性組成物は、重合開始剤を含んでいてもよい。前記重合開始剤としては、公知の光重合開始剤または熱重合開始剤を用いることができ、光重合開始剤と熱重合開始剤を併用してもよい。重合開始剤は、1種単独で用いてもよいし、2種以上を併用してもよい。 Moreover, the said curable composition may contain the polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
前記硬化性組成物中、重合開始剤の配合割合は、硬化性組成物の全量を100重量%とした場合、好ましくは0.1〜10重量%、より好ましくは0.5〜10重量%、さらに好ましくは1〜5重量%である。重合開始剤の配合割合が前記範囲にあると、硬化性組成物の硬化特性および取り扱い性が優れ、所望の硬度を有する反射防止膜、ハードコート膜や帯電防止膜などの機能膜を得ることができる。 In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the curable composition is 100% by weight. More preferably, it is 1 to 5% by weight. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.
さらに、前記硬化性組成物には溶剤として有機溶剤を加えてもよく、有機溶剤としては、公知のものを使用することができる。有機溶剤の具体例としては、メタノール、エタノール、イソプロパノール、ブタノール、オクタノール等のアルコール類;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル類;エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル等のエーテル類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類;ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等のアミド類を挙げることができる。 Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone.
これら溶剤は、1種単独で用いてもよいし、2種以上を併用してもよい。
前記機能膜の厚さは、好ましくは0.1〜20μm、さらに好ましくは0.5〜10μm、特に好ましくは0.7〜5μmである。
These solvents may be used alone or in combination of two or more.
The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.
また、基材(i)と機能膜および/または誘電体多層膜との密着性や、機能膜と誘電体多層膜との密着性を上げる目的で、基材(i)、機能膜または誘電体多層膜の表面にコロナ処理やプラズマ処理等の表面処理をしてもよい。 Further, for the purpose of improving the adhesion between the base material (i) and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the base material (i), the functional film or the dielectric Surface treatment such as corona treatment or plasma treatment may be applied to the surface of the multilayer film.
[光学フィルターの用途]
本発明の光学フィルターは、視野角が広く、可視光と一部の近赤外線を選択的に透過させることができる。したがって、カメラ機能と近赤外センシング機能を併せ持つCCDやCMOSイメージセンサーなどの固体撮像素子の視感度補正用として有用である。特に、デジタルスチルカメラ、スマートフォン用カメラ、携帯電話用カメラ、デジタルビデオカメラ、ウェアラブルデバイス用カメラ、PCカメラ、監視カメラ、自動車用カメラ、暗視カメラ、モーションキャプチャー、レーザー距離計、バーチャル試着、ナンバープレート認識装置、テレビ、カーナビゲーション、携帯情報端末、ビデオゲーム機、携帯ゲーム機、指紋認証システム、デジタルミュージックプレーヤー等に有用である。
[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and can selectively transmit visible light and some near infrared rays. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS image sensor having both a camera function and a near-infrared sensing function. Especially digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, night vision cameras, motion capture, laser rangefinders, virtual fittings, license plates It is useful for recognition devices, televisions, car navigation systems, portable information terminals, video game machines, portable game machines, fingerprint authentication systems, digital music players, and the like.
[固体撮像装置]
本発明の固体撮像装置は、本発明の光学フィルターを具備する。ここで、固体撮像装置とは、カメラ機能と近赤外センシング機能を併せ持つCCDやCMOSイメージセンサー等といった固体撮像素子を備えたイメージセンサーであり、具体的にはデジタルスチルカメラ、スマートフォン用カメラ、携帯電話用カメラ、ウェアラブルデバイス用カメラ、デジタルビデオカメラ等の用途に用いることができる。例えば、本発明のカメラモジュールは、本発明の光学フィルターを具備する。
[Solid-state imaging device]
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor having both a camera function and a near-infrared sensing function. Specifically, a digital still camera, a smartphone camera, a mobile phone It can be used for applications such as telephone cameras, wearable device cameras, and digital video cameras. For example, the camera module of the present invention includes the optical filter of the present invention.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。なお、「部」は、特に断りのない限り「重量部」を意味する。また、各物性値の測定方法および物性の評価方法は以下のとおりである。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. “Parts” means “parts by weight” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of the physical property are as follows.
<分子量>
樹脂の分子量は、各樹脂の溶剤への溶解性等を考慮し、下記の(a)または(b)の方法にて測定を行った。
<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(a)ウオターズ(WATERS)社製のゲルパーミエ−ションクロマトグラフィー(GPC)装置(150C型、カラム:東ソー(株)製Hタイプカラム、展開溶剤:o−ジクロロベンゼン)を用い、標準ポリスチレン換算の重量平均分子量(Mw)および数平均分子量(Mn)を測定した。 (A) Weight of standard polystyrene conversion using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS Average molecular weight (Mw) and number average molecular weight (Mn) were measured.
(b)東ソー(株)製GPC装置(HLC−8220型、カラム:TSKgelα‐M、展開溶剤:テトラヒドロフラン)を用い、標準ポリスチレン換算の重量平均分子量(Mw)および数平均分子量(Mn)を測定した。
なお、後述する樹脂合成例3で合成した樹脂については、上記方法による分子量の測定ではなく、下記方法(c)による対数粘度の測定を行った。
(B) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: tetrahydrofuran) manufactured by Tosoh Corporation. .
In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(c)ポリイミド樹脂溶液の一部を無水メタノールに投入してポリイミド樹脂を析出させ、ろ過して未反応単量体を分離した。80℃で12時間真空乾燥して得られたポリイミド0.1gをN−メチル−2−ピロリドン20mLに溶解し、キャノン−フェンスケ粘度計を使用して30℃における対数粘度(μ)を下記式により求めた。
μ={ln(ts/t0)}/C
t0:溶媒の流下時間
ts:希薄高分子溶液の流下時間
C:0.5g/dL
(C) A part of the polyimide resin solution was put into anhydrous methanol to precipitate a polyimide resin, and filtered to separate unreacted monomers. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
μ = {ln (t s / t 0)} / C
t 0 : Flowing time of solvent t s : Flowing time of dilute polymer solution C: 0.5 g / dL
<ガラス転移温度(Tg)>
エスアイアイ・ナノテクノロジーズ(株)製の示差走査熱量計(DSC6200)を用いて、昇温速度:毎分20℃、窒素気流下で測定した。
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.
<分光透過率>
基材の(Ta)、(Xc)、(Tb)および(Xf)、ならびに、光学フィルターの各波長領域における透過率、(Xa)、(Xb)、(Xd)、(Xe)および(Xa')は、(株)日立ハイテクノロジーズ製の分光光度計(U−4100)を用いて測定した。
<Spectral transmittance>
(Ta), (Xc), (Tb) and (Xf) of the substrate, and transmittance in each wavelength region of the optical filter, (Xa), (Xb), (Xd), (Xe) and (Xa ′) ) Was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
ここで、光学フィルターの垂直方向から測定した場合の透過率では、図2(a)のようにフィルターに対して垂直に透過した光を測定した。また、光学フィルターの垂直方向に対して30°の角度から測定した場合の透過率では、図2(b)のようにフィルターの垂直方向に対して30°の角度で透過した光を測定した。 Here, with respect to the transmittance when measured from the vertical direction of the optical filter, the light transmitted perpendicularly to the filter was measured as shown in FIG. In addition, with respect to the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter, light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured as shown in FIG.
なお、この透過率は、(Xa’)および(Xe)を測定する場合を除き、光が基板およびフィルターに対して垂直に入射する条件で、該分光光度計を使用して測定したものである。(Xa’)および(Xe)を測定する場合には、光がフィルターの垂直方向に対して30°の角度で入射する条件で該分光光度計を使用して測定したものである。 This transmittance is measured using the spectrophotometer under the condition that light is perpendicularly incident on the substrate and the filter, except when measuring (Xa ′) and (Xe). . In the case of measuring (Xa ') and (Xe), the measurement is performed using the spectrophotometer under the condition that light is incident at an angle of 30 ° with respect to the vertical direction of the filter.
[合成例]
下記実施例で用いた化合物(S)および化合物(A)は、一般的に知られている方法で合成することができ、例えば、特許第3366697号公報、特許第2846091号公報、特許第2864475号公報、特許第3094037号公報、特許第3703869号公報、特開昭60−228448号公報、特開平1−146846号公報、特開平1−228960号公報、特許第4081149号公報、特開昭63−124054号公報、「フタロシアニン −化学と機能―」(アイピーシー、1997年)、特開2007−169315号公報、特開2009−108267号公報、特開2010−241873号公報、特許第3699464号公報、特許第4740631号公報などに記載されている方法を参照して合成することができる。
[Synthesis example]
The compound (S) and the compound (A) used in the following examples can be synthesized by a generally known method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475. Publication, Japanese Patent No. 3094037, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-281960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. Sho 63- No. 124054, “Phthalocyanine -Chemistry and Function” (IPC, 1997), JP 2007-169315, JP 2009-108267, JP 2010-241873, JP 3699464, It can be synthesized by referring to the method described in Japanese Patent No. 4740631. Yes.
<樹脂合成例1>
下記式(a)で表される8−メチル−8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン100部、1−ヘキセン(分子量調節剤)18部およびトルエン(開環重合反応用溶媒)300部を、窒素置換した反応容器に仕込み、この溶液を80℃に加熱した。次いで、反応容器内の溶液に、重合触媒として、トリエチルアルミニウムのトルエン溶液(濃度0.6mol/リットル)0.2部と、メタノール変性の六塩化タングステンのトルエン溶液(濃度0.025mol/リットル)0.9部とを添加し、この溶液を80℃で3時間加熱攪拌することにより開環重合反応させて開環重合体溶液を得た。この重合反応における重合転化率は97%であった。
<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 2,5 . 1 7,10 ] 100 parts of dodec-3-ene, 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 80 ° C. Heated. Next, 0.2 parts of a toluene solution of triethylaluminum (concentration 0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) 0 as a polymerization catalyst were added to the solution in the reaction vessel. .9 parts was added and the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.
<樹脂合成例2>
3Lの4つ口フラスコに2,6−ジフルオロベンゾニトリル35.12g(0.253mol)、9,9−ビス(4−ヒドロキシフェニル)フルオレン87.60g(0.250mol)、炭酸カリウム41.46g(0.300mol)、N,N−ジメチルアセトアミド(以下「DMAc」ともいう。)443gおよびトルエン111gを添加した。続いて、4つ口フラスコに温度計、撹拌機、窒素導入管付き三方コック、ディーンスターク管および冷却管を取り付けた。次いで、フラスコ内を窒素置換した後、得られた溶液を140℃で3時間反応させ、生成する水をディーンスターク管から随時取り除いた。水の生成が認められなくなったところで、徐々に温度を160℃まで上昇させ、そのままの温度で6時間反応させた。室温(25℃)まで冷却後、生成した塩をろ紙で除去し、ろ液をメタノールに投じて再沈殿させ、ろ別によりろ物(残渣)を単離した。得られたろ物を60℃で一晩真空乾燥し、白色粉末(以下「樹脂B」ともいう。)を得た(収率95%)。得られた樹脂Bは、数平均分子量(Mn)が75,000、重量平均分子量(Mw)が188,000であり、ガラス転移温度(Tg)が285℃であった。
<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 ° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.
<樹脂合成例3>
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク管および冷却管を備えた500mLの5つ口フラスコに、窒素気流下、1,4−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン27.66g(0.08モル)および4,4'−ビス(4−アミノフェノキシ)ビフェニル7.38g(0.02モル)を入れて、γ−ブチロラクトン68.65gおよびN,N−ジメチルアセトアミド17.16gに溶解させた。得られた溶液を、氷水バスを用いて5℃に冷却し、同温に保ちながら1,2,4,5−シクロヘキサンテトラカルボン酸二無水物22.62g(0.1モル)およびイミド化触媒としてトリエチルアミン0.50g(0.005モル)を一括添加した。添加終了後、180℃に昇温し、随時留出液を留去させながら6時間還流させた。6時間の還流後、内温が100℃になるまで空冷し、DMAc143.6gを加えて希釈し、攪拌しながら冷却することで、固形分濃度20重量%のポリイミド樹脂溶液264.16gを得た。このポリイミド樹脂溶液の一部を1Lのメタノール中に注ぎ入れてポリイミドを沈殿させた。濾別したポリイミドをメタノールで洗浄した後、100℃の真空乾燥機中で24時間乾燥させて白色粉末(以下「樹脂C」ともいう。)を得た。
<Resin synthesis example 3>
To a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube and a condenser tube, was added 1,4-bis (4-amino-α, α under a nitrogen stream. -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After refluxing for 6 hours, it was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of DMAc, and cooled with stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. . A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”).
得られた樹脂CのIRスペクトルを測定したところ、イミド基に特有の1704cm-1、1770cm-1の吸収が見られた。樹脂Cはガラス転移温度(Tg)が310℃であり、対数粘度を測定したところ、0.87であった。 The IR spectrum of the obtained resin C was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.
[実施例1]
実施例1では、透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作成した。
[Example 1]
In Example 1, an optical filter having a base material made of a transparent resin substrate was prepared according to the following procedure and conditions.
容器に、樹脂合成例1で得られた樹脂A 100部、化合物(S)として上記表1に記載の化合物(s−5)(ジクロロメタン中での吸収極大波長770nm)0.03部および塩化メチレンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、20℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、縦60mm、横60mmの透明樹脂製基板からなる基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を図3および表7に示す。 In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, 0.03 part of compound (s-5) (absorption maximum wavelength in dichloromethane of 770 nm) described in Table 1 above as compound (S), and methylene chloride Was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in FIG.
続いて、得られた基材の片面に誘電体多層膜(I)を形成し、さらに基材のもう一方の面に誘電体多層膜(II)を形成し、厚さ約0.104mmの光学フィルターを得た。
誘電体多層膜(I)は、蒸着温度100℃でシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)。誘電体多層膜(II)は、蒸着温度100℃でシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)。誘電体多層膜(I)および(II)のいずれにおいても、シリカ層およびチタニア層は、基材側からチタニア層、シリカ層、チタニア層、・・・シリカ層、チタニア層、シリカ層の順で交互に積層されており、光学フィルターの最外層をシリカ層とした。
Subsequently, the dielectric multilayer film (I) is formed on one surface of the obtained base material, and the dielectric multilayer film (II) is further formed on the other surface of the base material, so that the optical thickness is about 0.104 mm. A filter was obtained.
The dielectric multilayer film (I) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (a total of 24 layers). The dielectric multilayer film (II) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (18 layers in total). In both of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are in order of the titania layer, the silica layer, the titania layer,..., The silica layer, the titania layer, and the silica layer from the substrate side. The outermost layer of the optical filter was a silica layer.
誘電体多層膜(I)および(II)の設計は、以下のようにして行った。
各層の厚さと層数については、可視域の反射防止効果と近赤外域の選択的な透過・反射性能を達成できるよう基材屈折率の波長依存特性や、適用した化合物(S)の吸収特性に合わせて光学薄膜設計ソフト(Essential Macleod、Thin Film Center社製)を用いて最適化を行った。最適化を行う際、本実施例においてはソフトへの入力パラメーター(Target値)を下記表2の通りとした。
The dielectric multilayer films (I) and (II) were designed as follows.
Regarding the thickness and the number of layers, the wavelength dependence characteristics of the refractive index of the base material and the absorption characteristics of the applied compound (S) so as to achieve an antireflection effect in the visible range and selective transmission / reflection performance in the near infrared range. Was optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 2 below.
膜構成最適化の結果、実施例1では、誘電体多層膜(I)は、膜厚13〜174nmのシリカ層と膜厚9〜200nmのチタニア層とが交互に積層されてなる、積層数24の多層蒸着膜となり、誘電体多層膜(II)は、膜厚41〜198nmのシリカ層と膜厚12〜122nmのチタニア層とが交互に積層されてなる、積層数18の多層蒸着膜となった。最適化を行った膜構成の一例を表3に示す。 As a result of the optimization of the film configuration, in Example 1, the dielectric multilayer film (I) was formed by alternately laminating a silica layer having a film thickness of 13 to 174 nm and a titania layer having a film thickness of 9 to 200 nm. The dielectric multi-layer film (II) is a multi-layer vapor-deposited film having 18 layers, in which a silica layer having a film thickness of 41 to 198 nm and a titania layer having a film thickness of 12 to 122 nm are alternately stacked. It was. Table 3 shows an example of the optimized film configuration.
得られた光学フィルターの垂直方向および垂直方向から30°の角度から測定した分光透過率を測定し、各波長領域における光学特性を評価した。結果を図4および表7に示す。波長430〜580nmにおける透過率の平均値は90%、Xaは826nm、Xbは902nm、Yは864nm、波長Y−10nm〜Y+10nmの波長域における平均透過率は89%、絶対値|Xa−Xa’|は20nm、絶対値|Xd−Xe|は25nmであった。 The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. The average transmittance at wavelengths of 430 to 580 nm is 90%, Xa is 826 nm, Xb is 902 nm, Y is 864 nm, the average transmittance is 89% in the wavelength range of wavelengths Y-10 nm to Y + 10 nm, and the absolute value | Xa−Xa ′ | Was 20 nm, and the absolute value | Xd−Xe | was 25 nm.
[実施例2]
実施例1において、化合物(s−5)0.03部の代わりに上記表1に記載の化合物(s−11)(ジクロロメタン中での吸収極大波長776nm)0.03部を用いたこと、ならびに、化合物(A)として、下記式(a−1)で表わされる化合物(a−1)(ジクロロメタン中での吸収極大波長698nm)0.03部および下記式(a−2)で表わされる化合物(a−2)(ジクロロメタン中での吸収極大波長733nm)0.03部を用いたこと以外は、実施例1と同様の手順および条件で化合物(S)および化合物(A)を含む透明樹脂製基板からなる基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を図5および表7に示す。
[Example 2]
In Example 1, 0.03 part of compound (s-11) (absorption maximum wavelength 776 nm in dichloromethane) described in Table 1 above was used instead of 0.03 part of compound (s-5), and As a compound (A), 0.03 part of a compound (a-1) represented by the following formula (a-1) (absorption maximum wavelength 698 nm in dichloromethane) and a compound represented by the following formula (a-2) ( a-2) Transparent resin substrate containing compound (S) and compound (A) under the same procedure and conditions as in Example 1 except that 0.03 part (absorption maximum wavelength in dichloromethane: 733 nm) was used A substrate consisting of The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in FIG.
膜構成最適化の結果、実施例2では、誘電体多層膜(III)は、膜厚27〜198nmのシリカ層と膜厚10〜121nmのチタニア層とが交互に積層されてなる、積層数24の多層蒸着膜となり、誘電体多層膜(IV)は、膜厚41〜198nmのシリカ層と膜厚12〜122nmのチタニア層とが交互に積層されてなる、積層数18の多層蒸着膜となった。最適化を行った膜構成の一例を表5に示す。 As a result of the optimization of the film configuration, in Example 2, the dielectric multilayer film (III) is formed by alternately laminating a silica layer having a film thickness of 27 to 198 nm and a titania layer having a film thickness of 10 to 121 nm. The dielectric multilayer film (IV) is a multilayer deposited film having 18 layers, in which a silica layer having a film thickness of 41 to 198 nm and a titania layer having a film thickness of 12 to 122 nm are alternately stacked. It was. Table 5 shows an example of the optimized film configuration.
得られた光学フィルターの分光透過率を測定し、各波長領域における光学特性を評価した。結果を図6および表7に示す。 The spectral transmittance of the obtained optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.
[実施例3]
実施例3では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作成した。
[Example 3]
In Example 3, an optical filter having a base material composed of a transparent resin substrate having a resin layer on both sides was prepared according to the following procedure and conditions.
実施例1において、化合物(s−5)0.03部の代わりに上記表1に記載の化合物(s−14)(ジクロロメタン中での吸収極大波長795nm)0.03部を用いたこと以外は、実施例1と同様の手順および条件で化合物(S)を含む透明樹脂製基板を得た。 In Example 1, 0.03 part of compound (s-14) (absorption maximum wavelength 795 nm in dichloromethane) described in Table 1 above was used instead of 0.03 part of compound (s-5). A transparent resin substrate containing the compound (S) was obtained by the same procedure and conditions as in Example 1.
得られた透明樹脂製基板の片面に、下記組成の樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(1)からなる樹脂層を形成し、化合物(S)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。 A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (S) was obtained. . The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
樹脂組成物(1):トリシクロデカンジメタノールアクリレート 60重量部、ジペンタエリスリトールヘキサアクリレート 40重量部、1−ヒドロキシシクロヘキシルフェニルケトン 5重量部、メチルエチルケトン(溶剤、固形分濃度(TSC):30%)
続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(V)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(VI)を形成し、厚さ約0.108mmの光学フィルターを得た。誘電体多層膜の設計は、実施例1と同様に基材屈折率の波長依存性等を考慮した上で、実施例1と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。
Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)
Subsequently, in the same manner as in Example 1, a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (VI) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.108 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[実施例4]
実施例3において、化合物(s−14)0.03部の代わりに上記表1に記載の化合物(s−5)0.01部および上記表1に記載の化合物(s−21)(ジクロロメタン中での吸収極大波長782nm)0.02部を用いたこと以外は、実施例3と同様の手順および条件で化合物(S)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。
[Example 4]
In Example 3, in place of 0.03 part of compound (s-14), 0.01 part of compound (s-5) described in Table 1 above and compound (s-21) described in Table 1 above (in dichloromethane) The base material which has a resin layer on both surfaces of the transparent resin board | substrate containing a compound (S) in the same procedure and conditions as Example 3 except having used 0.02 part of absorption maximum wavelength in 782 nm. . The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(VII)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(VIII)を形成し、厚さ約0.108mmの光学フィルターを得た。誘電体多層膜の設計は、実施例1と同様に基材屈折率の波長依存性等を考慮した上で、実施例1と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。 Subsequently, in the same manner as in Example 1, a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (VIII) formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers (18 layers in total) on the other surface of the substrate. An optical filter having a thickness of about 0.108 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[実施例5]
実施例3において、化合物(s−14)0.03部の代わりに、上記表1に記載の化合物(s−11)0.04部を用いたこと、ならびに、化合物(A)として、下記式(a−3)で表わされる化合物(a−3)(ジクロロメタン中での吸収極大波長703nm)0.02部および下記式(a−4)で表わされる化合物(a−4)(ジクロロメタン中での吸収極大波長736nm)0.06部を用いたこと以外は、実施例3と同様の手順および条件で化合物(S)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。
[Example 5]
In Example 3, 0.04 part of the compound (s-11) described in Table 1 above was used instead of 0.03 part of the compound (s-14), and the following formula was used as the compound (A). 0.02 part of compound (a-3) represented by (a-3) (maximum absorption wavelength 703 nm in dichloromethane) and compound (a-4) represented by the following formula (a-4) (in dichloromethane) Except that 0.06 part of absorption maximum wavelength (736 nm) was used, a base material having resin layers on both surfaces of a transparent resin substrate containing the compound (S) was obtained in the same procedure and conditions as in Example 3. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
[実施例6]
実施例6では、両面に化合物(S)を含む透明樹脂層を有する樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作成した。
[Example 6]
In Example 6, an optical filter having a base material composed of a resin substrate having a transparent resin layer containing the compound (S) on both surfaces was prepared according to the following procedure and conditions.
容器に、樹脂合成例1で得られた樹脂Aおよび塩化メチレンを加えて樹脂濃度が20重量%の溶液を調製し、得られた溶液を用いたこと以外は、実施例1と同様にして樹脂製基板を作成した。 Resin A and methylene chloride obtained in Resin Synthesis Example 1 were added to a container to prepare a solution having a resin concentration of 20% by weight, and the resin was used in the same manner as in Example 1 except that the obtained solution was used. A substrate was made.
得られた樹脂製基板の両面に、実施例2と同様に下記組成の樹脂組成物(2)からなる樹脂層を形成し、両面に化合物(S)を含む透明樹脂層を有する樹脂製基板からなる基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。
樹脂組成物(2):トリシクロデカンジメタノールアクリレート 100重量部、1−ヒドロキシシクロヘキシルフェニルケトン 4重量部、化合物(s−5)0.75重量部、化合物(a−2)0.75重量部、化合物(a−3)0.75重量部、メチルエチルケトン(溶剤、TSC:25%)
A resin layer made of the resin composition (2) having the following composition is formed on both surfaces of the obtained resin substrate in the same manner as in Example 2, and the resin substrate having a transparent resin layer containing the compound (S) on both surfaces. A base material was obtained. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
Resin composition (2): 100 parts by weight of tricyclodecane dimethanol acrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.75 part by weight of compound (s-5), 0.75 part by weight of compound (a-2) , 0.75 parts by weight of compound (a-3), methyl ethyl ketone (solvent, TSC: 25%)
続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(XI)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(XII)を形成し、厚さ約0.110mmの光学フィルターを得た。誘電体多層膜の設計は、実施例1と同様に基材屈折率の波長依存性等を考慮した上で、実施例2と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。 Subsequently, in the same manner as in Example 1, a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XII) in which silica (SiO 2 ) layers and titania (TiO 2 ) layers are alternately laminated (18 layers in total) on the other surface of the substrate. An optical filter having a thickness of about 0.110 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[実施例7]
実施例7では、片面に化合物(S)を含む透明樹脂層を有する透明ガラス基板からなる基材を有する光学フィルターを以下の手順および条件で作成した。
[Example 7]
In Example 7, an optical filter having a base material composed of a transparent glass substrate having a transparent resin layer containing the compound (S) on one side was prepared by the following procedure and conditions.
縦60mm、横60mmの大きさにカットした透明ガラス基板「OA−10G(厚み200um)」(日本電気硝子(株)製)上に下記組成の樹脂組成物(3)をスピンコーターで塗布し、ホットプレート上80℃で2分間加熱し溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、スピンコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、化合物(S)を含む透明樹脂層を有する透明ガラス基板からなる基材を得た。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。
On a transparent glass substrate “OA-10G (
樹脂組成物(3):トリシクロデカンジメタノールアクリレート 20重量部、ジペンタエリスリトールヘキサアクリレート 80重量部、1−ヒドロキシシクロヘキシルフェニルケトン 4重量部、化合物(s−5)1.5重量部、化合物(a−2)1.5重量部、化合物(a−3)1.5重量部、メチルエチルケトン(溶剤、TSC:35%)
続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(XIII)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(XIV)を形成し、厚さ約0.110mmの光学フィルターを得た。誘電体多層膜の設計は、実施例1と同様に基材屈折率の波長依存性を考慮した上で、実施例2と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。
Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts by weight of compound (s-5), compound ( a-2) 1.5 parts by weight, compound (a-3) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, similarly to Example 1, a dielectric multilayer film (XIII) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XIV) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.110 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the base material refractive index as in Example 1. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[比較例1]
実施例1において、化合物(S)を用いなかったこと以外は、実施例1と同様にして基材を作成した。続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(XV)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(XVI)を形成し、厚さ約0.106mmの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性を考慮した上で、実施例1と同様の設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を図7および表7に示す。
[Comparative Example 1]
In Example 1, a substrate was prepared in the same manner as in Example 1 except that the compound (S) was not used. Subsequently, as in Example 1, a dielectric multilayer film (XV) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XVI) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.106 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.
[比較例2]
基材として近赤外線吸収ガラス基板「BS−6(厚み210μm)」(松浪硝子工業(株)製)を用いたこと以外は、実施例1と同様にして、基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(XVII)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(XVIII)を形成し、厚さ約0.216mmの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性を考慮した上で、下記表6のような設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を図8および表7に示す。
[Comparative Example 2]
In the same manner as in Example 1 except that near-infrared absorbing glass substrate “BS-6 (thickness 210 μm)” (manufactured by Matsunami Glass Industry Co., Ltd.) was used as the base material, silica (SiO 2 ) Layer and titania (TiO 2 ) layer are alternately laminated (24 layers in total) to form a dielectric multilayer film (XVII), and further, a silica (SiO 2 ) layer and titania on the other surface of the substrate A dielectric multilayer film (XVIII) formed by alternately laminating (TiO 2 ) layers (18 layers in total) was formed, and an optical filter having a thickness of about 0.216 mm was obtained. The dielectric multilayer film was designed using design parameters as shown in Table 6 below in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.
[比較例3]
実施例1において、化合物(S)の代わりに上記化合物(a−2)0.03部および上記化合物(a−3)0.03部を用いたこと以外は、実施例1と同様にして基材を作成した。この基材の分光透過率を測定し、(Ta)、(Tb)、(Xc)および(Xf)を求めた。結果を表7に示す。
[Comparative Example 3]
In Example 1, 0.03 part of the compound (a-2) and 0.03 part of the compound (a-3) were used instead of the compound (S). Made the material. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
続いて、実施例1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24)誘電体多層膜(XIX)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計18層)誘電体多層膜(XXX)を形成し、厚さ約0.106mmの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性等を考慮した上で、実施例2と同様の設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。 Subsequently, in the same manner as in Example 1, a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material (24 in total). Dielectric multilayer film (XIX) Further, a dielectric multilayer film (XXX) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers on the other surface of the substrate (18 layers in total), An optical filter having a thickness of about 0.106 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the refractive index of the substrate. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[比較例4]
基材として透明ガラス基板「OA−10G(厚み200um)」(日本電気硝子(株)製)を用いたこと以外は、実施例1と同様にして、基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計24層)誘電体多層膜(XXI)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる(合計20層)誘電体多層膜(XXII)を形成し、厚さ約0.206mmの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性を考慮した上で、実施例1と同様の設計パラメーターを用いて行った。この光学フィルターの分光透過率および反射率を測定し、各波長領域における光学特性を評価した。結果を表7に示す。
[Comparative Example 4]
A silica (SiO 2 ) layer on one side of the base material in the same manner as in Example 1 except that a transparent glass substrate “OA-10G (thickness: 200 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) was used as the base material. And a titania (TiO 2 ) layer are alternately laminated (a total of 24 layers) to form a dielectric multilayer film (XXI), and a silica (SiO 2 ) layer and a titania (TiO 2 ) are formed on the other surface of the substrate. 2 ) Dielectric multilayer film (XXII) was formed by alternately laminating layers (total 20 layers), and an optical filter having a thickness of about 0.206 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.
[実施例8〜13]
樹脂、溶媒、樹脂製基板の乾燥条件、化合物(S)および化合物(A)を表7に示すように変更したこと以外は、実施例5と同様にして、基材および光学フィルターを作成した。得られた基材および光学フィルターの光学特性を表7に示す。
[Examples 8 to 13]
A substrate and an optical filter were prepared in the same manner as in Example 5 except that the resin, the solvent, the drying conditions for the resin substrate, the compound (S), and the compound (A) were changed as shown in Table 7. Table 7 shows the optical properties of the obtained substrate and optical filter.
実施例および比較例で適用した基材の構成、各種化合物などは下記の通りである。
<基材の形態>
形態(1):化合物(S)を含む透明樹脂製基板
形態(2):化合物(S)を含む透明樹脂製基板の両面に樹脂層を有する
形態(3):樹脂製基板の両面に化合物(S)を含む透明樹脂層を有する
形態(4):ガラス基板の片方の面に化合物(S)を含む透明樹脂層を有する
形態(5):化合物(S)を含まない透明樹脂製基板(比較例)
形態(6):近赤外線吸収ガラス基板(比較例)
形態(7):ガラス基板(比較例)
<透明樹脂>
樹脂A:環状オレフィン系樹脂(樹脂合成例1)
樹脂B:芳香族ポリエーテル系樹脂(樹脂合成例2)
樹脂C:ポリイミド系樹脂(樹脂合成例3)
樹脂D:環状オレフィン系樹脂「ゼオノア 1420R」(日本ゼオン(株)製)
<ガラス基板>
ガラス基板(1): 縦60mm、横60mmの大きさにカットした透明ガラス基板「OA−10G(厚み200μm)」(日本電気硝子(株)製)
ガラス基板(2): 縦60mm、横60mmの大きさにカットした近赤外線吸収ガラス基板「BS−6(厚み210μm)」(松浪硝子工業(株)製)
<化合物(S)>
化合物(s−5):上記表1に記載の化合物(s−5)(ジクロロメタン中での吸収極大波長770nm)
化合物(s−11):上記表1に記載の化合物(s−11)(ジクロロメタン中での吸収極大波長776nm)
化合物(s−14):上記表1に記載の化合物(s−14)(ジクロロメタン中での吸収極大波長795nm)
化合物(s−21):上記表1に記載の化合物(s−21)(ジクロロメタン中での吸収極大波長782nm)
化合物(s−23):上記表1に記載の化合物(s−23)(ジクロロメタン中での吸収極大波長784nm)
<化合物(A)>
化合物(a−1):上記の化合物(a−1)(ジクロロメタン中での吸収極大波長698nm)
化合物(a−2):上記の化合物(a−2)(ジクロロメタン中での吸収極大波長733nm)
化合物(a−3):上記の化合物(a−3)(ジクロロメタン中での吸収極大波長703nm)
化合物(a−4):上記の化合物(a−4)(ジクロロメタン中での吸収極大波長736nm)
<溶媒>
溶媒(1):塩化メチレン
溶媒(2):N,N−ジメチルアセトアミド
溶媒(3):シクロヘキサン/キシレン(重量比:7/3)
The configurations of the base materials and various compounds applied in the examples and comparative examples are as follows.
<Form of substrate>
Form (1): Transparent resin substrate containing compound (S) Form (2): Having resin layers on both sides of transparent resin substrate containing compound (S) Form (3): Compound (on both sides of resin substrate) Form (4): having a transparent resin layer containing compound (S) on one side of a glass substrate Form (5): transparent resin substrate containing no compound (S) (Comparison) Example)
Form (6): Near-infrared absorbing glass substrate (comparative example)
Form (7): Glass substrate (comparative example)
<Transparent resin>
Resin A: Cyclic olefin resin (resin synthesis example 1)
Resin B: Aromatic polyether resin (resin synthesis example 2)
Resin C: Polyimide resin (resin synthesis example 3)
Resin D: Cyclic olefin resin “Zeonor 1420R” (manufactured by Nippon Zeon Co., Ltd.)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness: 200 μm)” cut to 60 mm length and 60 mm width (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): Near-infrared absorbing glass substrate “BS-6 (thickness 210 μm)” cut to a size of 60 mm length and 60 mm width (manufactured by Matsunami Glass Industry Co., Ltd.)
<Compound (S)>
Compound (s-5): Compound (s-5) described in Table 1 above (absorption maximum wavelength in dichloromethane: 770 nm)
Compound (s-11): Compound (s-11) described in Table 1 above (absorption maximum wavelength in dichloromethane: 776 nm)
Compound (s-14): Compound (s-14) described in Table 1 above (absorption maximum wavelength in dichloromethane of 795 nm)
Compound (s-21): Compound (s-21) described in Table 1 above (absorption maximum wavelength in dichloromethane: 782 nm)
Compound (s-23): Compound (s-23) described in Table 1 above (absorption maximum wavelength in dichloromethane of 784 nm)
<Compound (A)>
Compound (a-1): The above compound (a-1) (maximum absorption wavelength 698 nm in dichloromethane)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 733 nm)
Compound (a-3): Compound (a-3) above (absorption maximum wavelength in dichloromethane: 703 nm)
Compound (a-4): Compound (a-4) above (absorption maximum wavelength 736 nm in dichloromethane)
<Solvent>
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Cyclohexane / xylene (weight ratio: 7/3)
<樹脂製基板乾燥条件>
表7における、実施例および比較例の(透明)樹脂製基板乾燥条件は以下の通りである。なお、減圧乾燥前に、塗膜をガラス板から剥離した。
条件(1):20℃/8hr→減圧下 100℃/8hr
条件(2):60℃/8hr→80℃/8hr→減圧下 140℃/8hr
条件(3):60℃/8hr→80℃/8hr→減圧下 100℃/24hr
<Resin substrate drying conditions>
In Table 7, the (transparent) resin substrate drying conditions of Examples and Comparative Examples are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.
Condition (1): 20 ° C./8 hr → under reduced
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced
<樹脂層形成用組成物>
表7の実施例における、樹脂層を形成する樹脂組成物は、以下の通りである。
樹脂組成物(1):トリシクロデカンジメタノールアクリレート 60重量部、ジペンタエリスリトールヘキサアクリレート 40重量部、1−ヒドロキシシクロヘキシルフェニルケトン 5重量部、メチルエチルケトン(溶剤、TSC:30%)
樹脂組成物(2):トリシクロデカンジメタノールアクリレート 100重量部、1−ヒドロキシシクロヘキシルフェニルケトン 4重量部、(s−5)0.75重量部、化合物(a−2)0.75重量部、化合物(a−3)0.75重量部、メチルエチルケトン(溶剤、TSC:25%)
樹脂組成物(3):トリシクロデカンジメタノールアクリレート 20重量部、ジペンタエリスリトールヘキサアクリレート 80重量部、1−ヒドロキシシクロヘキシルフェニルケトン 4重量部、(s−5)1.5重量部、化合物(a−2)1.5重量部、化合物(a−3)1.5重量部、メチルエチルケトン(溶剤、TSC:35%)
<Composition for resin layer formation>
The resin composition for forming the resin layer in the examples of Table 7 is as follows.
Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, TSC: 30%)
Resin composition (2): Tricyclodecane dimethanol acrylate 100 parts by weight, 1-hydroxycyclohexyl phenyl ketone 4 parts by weight, (s-5) 0.75 parts by weight, compound (a-2) 0.75 parts by weight, 0.75 part by weight of compound (a-3), methyl ethyl ketone (solvent, TSC: 25%)
Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts by weight of (s-5), compound (a -2) 1.5 parts by weight, compound (a-3) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)
本発明の光学フィルターは、デジタルスチルカメラ、スマートフォン用カメラ、携帯電話用カメラ、デジタルビデオカメラ、ウェアラブルデバイス用カメラ、PCカメラ、監視カメラ、自動車用カメラ、暗視カメラ、モーションキャプチャー、レーザー距離計、バーチャル試着、ナンバープレート認識装置、テレビ、カーナビ、携帯情報端末、パソコン、ビデオゲーム機、携帯ゲーム機、指紋認証システム、デジタルミュージックプレーヤー等に好適に用いることができる。 The optical filter of the present invention includes a digital still camera, a smartphone camera, a mobile phone camera, a digital video camera, a wearable device camera, a PC camera, a surveillance camera, an automobile camera, a night vision camera, a motion capture, a laser rangefinder, It can be suitably used for virtual try-on, license plate recognition device, television, car navigation, portable information terminal, personal computer, video game machine, portable game machine, fingerprint authentication system, digital music player, and the like.
1:光学フィルター
2:分光光度計
3:光
1: Optical filter 2: Spectrophotometer 3: Light
Claims (8)
該基材が、下記式(S1)で表される化合物(S)を含む透明樹脂層を有することを特徴とする、可視光線と一部の近赤外線を選択的に透過させる光学フィルター。
R1〜R8は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−NRgRh基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、RgおよびRhは、それぞれ独立に水素原子、−C(O)Ri基または下記La〜Leのいずれかを表し、Riは下記La〜Leのいずれかを表し、
(La)炭素数1〜12の脂肪族炭化水素基
(Lb)炭素数1〜12のハロゲン置換アルキル基
(Lc)炭素数3〜14の脂環式炭化水素基
(Ld)炭素数6〜14の芳香族炭化水素基
(Le)炭素数3〜14の複素環基
(Lf)炭素数1〜12のアルコキシ基
(Lg)置換基Lを有してもよい炭素数1〜12のアシル基、
(Lh)置換基Lを有してもよい炭素数1〜12のアルコキシカルボニル基
置換基Lは、炭素数1〜12の脂肪族炭化水素基、炭素数1〜12のハロゲン置換アルキル基、炭素数3〜14の脂環式炭化水素基、炭素数6〜14の芳香族炭化水素基および炭素数3〜14の複素環基からなる群より選ばれる少なくとも1種である。] A dielectric multilayer film on at least one surface of the substrate and the substrate;
An optical filter that selectively transmits visible light and part of near infrared light, wherein the substrate has a transparent resin layer containing a compound (S) represented by the following formula (S1).
R 1 to R 8 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR g R h group, a —SO 2 R i group, or —OSO. It represents either 2 R i group or a group represented by L a ~L h, R g and R h each independently represents a hydrogen atom, one of the -C (O) R i groups or the following L a ~L e , R i represents any of the following L a ~L e,
(L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L d ) carbon the number 6 to 14 aromatic hydrocarbon group (L e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L f) an alkoxy group having 1 to 12 carbon atoms (L g) substituents L carbon 1 to 12 acyl groups,
(L h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms. ]
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