JPWO2019167876A1 - Optical filter and equipment using optical filter - Google Patents
Optical filter and equipment using optical filter Download PDFInfo
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- JPWO2019167876A1 JPWO2019167876A1 JP2020503489A JP2020503489A JPWO2019167876A1 JP WO2019167876 A1 JPWO2019167876 A1 JP WO2019167876A1 JP 2020503489 A JP2020503489 A JP 2020503489A JP 2020503489 A JP2020503489 A JP 2020503489A JP WO2019167876 A1 JPWO2019167876 A1 JP WO2019167876A1
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- optical filter
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B11/00—Filters or other obturators specially adapted for photographic purposes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/50—Constructional details
- H04N23/55—Optical parts specially adapted for electronic image sensors; Mounting thereof
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Signal Processing (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Multimedia (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Optical Filters (AREA)
- Blocking Light For Cameras (AREA)
- Solid State Image Pick-Up Elements (AREA)
Abstract
本発明の課題は、カメラ画像の色シェーディング抑制およびゴースト抑制と可視光波長領域での透過率特性とを高いレベルで両立し、かつ、高温に長時間晒された場合においても光学特性を維持可能な良好な耐熱性を有する光学フィルターを提供することにある。本発明の光学フィルターは、要件(a)を満たす基材を有し、かつ、前記基材の少なくとも一方の面に誘電体多層膜が形成されていることを特徴とする:(a)波長900nm以上1200nm以下の領域に吸収極大を有する有機顔料(S)を含む層を有する。An object of the present invention is to achieve both color shading suppression and ghost suppression of a camera image and transmittance characteristics in the visible light wavelength region at a high level, and to maintain optical characteristics even when exposed to a high temperature for a long time. It is an object of the present invention to provide an optical filter having good heat resistance. The optical filter of the present invention is characterized by having a base material satisfying the requirement (a) and having a dielectric multilayer film formed on at least one surface of the base material: (a) wavelength 900 nm. It has a layer containing an organic pigment (S) having an absorption maximum in the region of 1200 nm or less.
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、特定の波長領域に吸収を有する有機顔料を含む光学フィルター、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. More specifically, the present invention relates to an optical filter containing an organic pigment having absorption in a specific wavelength region, and a solid-state image sensor and a 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。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 CCD or CMOS image sensor, which is a solid-state image sensor for color images, is used in a solid-state image sensor such as a video camera, a digital still camera, or a mobile phone with a camera function. In these solid-state image sensors, a silicon photodiode having sensitivity to near infrared rays, which cannot be perceived by the human eye, is used in the light receiving portion thereof. In these solid-state image sensors, it is necessary to perform luminosity factor correction that makes the color tone natural to the human eye, and an optical filter (for example, near-infrared ray cut) that selectively transmits or cuts light in a specific wavelength region is required. 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、基材として透明樹脂を用い、透明樹脂中に近赤外線吸収色素を含有させた近赤外線カットフィルターが知られている(例えば特許文献1参照)。しかしながら、特許文献1に記載された近赤外線カットフィルターは、近赤外線吸収特性が必ずしも充分ではない場合があった。 As such a near-infrared cut filter, those manufactured by various methods have been conventionally used. For example, a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin is known (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.
本出願人は、特許文献2において、特定の波長領域に吸収極大がある近赤外線吸収色素を含有する透明樹脂製基板を用いることで、入射角度を変化させても光学特性の変化が少なく、かつ、高い可視光透過率を有する近赤外線カットフィルターを提案している。また、特許文献3には、特定の構造を有するフタロシアニン系色素を用いることで、従来の課題であった優れた可視光透過率と吸収極大波長の長波長化とを高いレベルで両立した近赤外線カットフィルターを得ることができる旨が記載されている。 In Patent Document 2, the applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that the optical characteristics do not change much even if the incident angle is changed. , Proposes a near-infrared cut filter with high visible light transmittance. Further, in Patent Document 3, by using a phthalocyanine dye having a specific structure, near-infrared rays that achieve both excellent visible light transmittance and long absorption maximum wavelength, which have been problems in the past, at a high level. It is stated that a cut filter can be obtained.
しかし、特許文献2および3に記載の近赤外線カットフィルターでは、適用されている基材が、700nm付近には十分な強度の吸収帯を持っているものの、例えば900〜1200nmといった近赤外線波長領域にはほぼ吸収を持たない。そのため、近赤外線波長領域の光線は、ほぼ誘電体多層膜の反射でのみカットしているが、このような構成では光学フィルター中の内部反射や、光学フィルターとレンズ間の反射によるわずかな迷光が、暗い環境下で撮影を行う際にゴーストやフレアの原因となる場合があった。特に、近年はスマートフォンなどのモバイル機器であってもカメラの高画質化が強く求められており、従来の光学フィルターでは好適に使用できない場合があった。 However, in the near-infrared cut filter described in Patent Documents 2 and 3, although the applied base material has an absorption band having sufficient strength in the vicinity of 700 nm, it is in the near-infrared wavelength region such as 900 to 1200 nm. Has almost no absorption. Therefore, the light rays in the near-infrared wavelength region are cut almost only by the reflection of the dielectric multilayer film, but in such a configuration, the internal reflection in the optical filter and the slight stray light due to the reflection between the optical filter and the lens are generated. , May cause ghosts and flares when shooting in a dark environment. In particular, in recent years, there has been a strong demand for higher image quality of cameras even in mobile devices such as smartphones, and there have been cases where conventional optical filters cannot be used suitably.
一方、近赤外線波長領域に幅広い吸収をもつ基材を用いた光学フィルターとして、特許文献4のような赤外線遮蔽フィルターが提案されている。特許文献4では、主にジチオレン構造を有する化合物を適用することで近赤外線波長領域の幅広い吸収を達成しているが、700nm付近の吸収強度は十分ではない。特に、近年のカメラモジュール低背化に伴う高入射角条件(例えば45度入射)での使用では、色シェーディングによる画像劣化が起こる場合があった。 On the other hand, as an optical filter using a base material having a wide absorption in the near infrared wavelength region, an infrared shielding filter as in Patent Document 4 has been proposed. In Patent Document 4, a wide absorption in the near-infrared wavelength region is achieved by mainly applying a compound having a dithiolene structure, but the absorption intensity near 700 nm is not sufficient. In particular, in recent years, when the camera module is used under a high incident angle condition (for example, 45 degree incident) due to the reduction in height of the camera module, image deterioration due to color shading may occur.
また、特許文献5には、近赤外線吸収ガラス基材と近赤外線吸収色素を含有する層とを有する近赤外線カットフィルターが開示されているが、特許文献5に記載の構成でも色シェーディングを十分改良することができない場合があった。例えば、特許文献5の図5には、0度入射時と30度入射時の光学特性グラフが示されているが、30度入射時においても可視光透過帯の裾部分の領域(630〜700nm)で大きな波長シフトが観測されている。 Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass base material and a layer containing a near-infrared absorbing dye, but the configuration described in Patent Document 5 also sufficiently improves color shading. Sometimes I couldn't. For example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0-degree incident and 30-degree incident, but even at 30-degree incident, the region of the hem of the visible light transmission band (630 to 700 nm). ), A large wavelength shift is observed.
本発明者らは、上述した課題を解決するために、900〜1200nmといった近赤外線波長領域に吸収極大を持つ色素を光学フィルターに用いることを検討した。しかしながら、このような色素は、前記近赤外線波長領域とともに430〜580nmの可視光領域にも吸収を持つ場合が多いため、ゴーストの改善と可視光透過率の両立が課題であった。さらに、上記色素は耐熱性や耐UV性が低いことに起因する光学特性の低下が問題となることがあった。具体的には、溶剤を揮発させるための乾燥工程や硬化性樹脂を硬化させるためのUV照射工程において、色素が劣化することにより、900〜1200nm波長領域の近赤外線吸収率および430〜580nm波長領域の透過率が低下し、所望の分光特性が得られないという問題があった。それゆえ、900〜1200nmに吸収極大を持つ色素は耐熱性や耐UV性を高めることが重要である。 In order to solve the above-mentioned problems, the present inventors have studied the use of a dye having an absorption maximum in the near-infrared wavelength region such as 900 to 1200 nm for an optical filter. However, since such dyes often have absorption in the visible light region of 430 to 580 nm as well as the near infrared wavelength region, it has been a problem to improve ghost and to achieve both visible light transmittance. Further, the dye has a problem of deterioration of optical characteristics due to low heat resistance and UV resistance. Specifically, in the drying step for volatilizing the solvent and the UV irradiation step for curing the curable resin, the dye deteriorates, so that the near-infrared transmittance in the 900 to 1200 nm wavelength range and the 430 to 580 nm wavelength range There is a problem that the transmittance of the infrared ray is lowered and the desired spectral characteristics cannot be obtained. Therefore, it is important that the dye having the maximum absorption at 900 to 1200 nm enhances heat resistance and UV resistance.
また、上記課題に加えて、近年では車載用途などへの展開に鑑み、耐熱性に対する要求も益々厳しくなっている。すなわち、高温に長時間さらされた場合においても、分光特性の変化を極力抑制できることが求められている。 In addition to the above problems, in recent years, the demand for heat resistance has become more and more strict in view of the development in in-vehicle applications and the like. That is, it is required that changes in spectral characteristics can be suppressed as much as possible even when exposed to high temperatures for a long time.
上述した色素の耐熱性や耐UV性を向上させる方法として、例えば色素を染料(溶解状態)としてではなく、顔料(粒子分散状態)として用いる方法が知られている(例えば特許文献6,7)。特許文献7では、耐熱性に課題のあるジイモニウム系色素を用いた近赤外線カットフィルターに関して、色素を分散媒(トルエン)に分散させた後、樹脂中に分散させることで、溶解して使用(染料として使用)した場合に対して耐熱性や耐UV性が向上することが示されている。しかしながら、上記先行文献の技術を用いても、近赤外線領域の吸収は十分なものではないばかりか、ヘイズ値が極めて高いフィルムしか得ることができず、上記課題を解決できるものではなかった。 As a method for improving the heat resistance and UV resistance of the dye described above, for example, a method of using the dye not as a dye (dissolved state) but as a pigment (particle dispersion state) is known (for example, Patent Documents 6 and 7). .. In Patent Document 7, regarding a near-infrared cut filter using a diimonium-based dye, which has a problem in heat resistance, the dye is dispersed in a dispersion medium (toluene) and then dissolved in a resin to be used (dye). It has been shown that heat resistance and UV resistance are improved when used as a. However, even if the technique of the above-mentioned prior literature is used, not only the absorption in the near-infrared region is not sufficient, but only a film having an extremely high haze value can be obtained, and the above-mentioned problems cannot be solved.
本発明は、従来の光学フィルターでは十分になし得なかった、カメラ画像の色シェーディング抑制およびゴースト抑制と可視光波長領域での透過率特性とを高いレベルで両立し、かつ、高温に長時間晒された場合においても光学特性を維持可能な良好な耐熱性を有する光学フィルターを提供することを課題とする。 The present invention achieves both color shading suppression and ghost suppression of camera images and transmittance characteristics in the visible light wavelength region at a high level, which cannot be sufficiently achieved by conventional optical filters, and is exposed to high temperatures for a long time. An object of the present invention is to provide an optical filter having good heat resistance that can maintain optical characteristics even when the optical filter is used.
本発明者らは、前記課題を解決するために鋭意検討した結果、基材が特定の波長領域に吸収極大を有する有機顔料を含む層を有すること、かつ、前記基材の少なくとも一方の面に誘電体多層膜を形成することにより、可視光領域の透過率を維持しつつ、近赤外線カット特性、可視光透過率、色シェーディング抑制効果およびゴースト抑制効果を達成可能な光学フィルターが得られることを見出した。 As a result of diligent studies to solve the above problems, the present inventors have made sure that the base material has a layer containing an organic pigment having an absorption maximum in a specific wavelength region, and that the base material has at least one surface of the base material. By forming the dielectric multilayer film, it is possible to obtain an optical filter capable of achieving near-infrared cut characteristics, visible light transmittance, color shading suppressing effect and ghost suppressing effect while maintaining the transmittance in the visible light region. I found it.
また、本発明者らは、前記有機顔料を微粒子化させて平均粒子径を特定の範囲にすることで、ヘイズ値を極めて低いレベルに維持し、かつ耐熱性に優れた光学フィルターが得られることを見出した。
これらの知見に基づいて完成させた本発明の態様の例を以下に示す。Further, the present inventors can obtain an optical filter having an extremely low haze value and excellent heat resistance by making the organic pigment into fine particles and setting the average particle size within a specific range. I found.
An example of the embodiment of the present invention completed based on these findings is shown below.
[1] 下記要件(a)を満たす基材を有し、かつ、前記基材の少なくとも一方の面に誘電体多層膜を有することを特徴とする光学フィルター:
(a)波長900nm以上1200nm以下の領域に吸収極大を有する有機顔料(S)を含む層を有する。[1] An optical filter having a base material satisfying the following requirement (a) and having a dielectric multilayer film on at least one surface of the base material:
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a region having a wavelength of 900 nm or more and 1200 nm or less.
[2] 前記基材が、さらに下記要件(b)を満たすことを特徴とする、項[1]に記載の光学フィルター:
(b)波長650nm以上760nm以下の領域に吸収極大を有する化合物(A)を含む層を有する。[2] The optical filter according to item [1], wherein the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength of 650 nm or more and 760 nm or less.
[3] 前記化合物(A)が、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種の化合物であることを特徴とする項[2]に記載の光学フィルター。 [3] The optical filter according to Item [2], wherein the compound (A) is at least one compound selected from the group consisting of a squarylium compound, a phthalocyanine compound and a cyanine compound.
[4] 前記有機顔料(S)が、下記式(I)で表されるジイモニウム系化合物を含むことを特徴とする、項[1]〜[3]のいずれか1項に記載の光学フィルター。 [4] The optical filter according to any one of Items [1] to [3], wherein the organic pigment (S) contains a diimonium-based compound represented by the following formula (I).
R1は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、−SRi基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、R2は、独立にハロゲン原子、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、−SRi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2〜14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種であり、
nは0〜4の整数を表し、
Xは電荷を中和させるのに必要なアニオンを表す。
R 1 is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphoric acid group, -SR i group, -SO 2 R i groups, -OSO 2 R i group or a group represented by L a ~ Represents any of L h , R 2 is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR g R h group, -SR i group, -SO 2 It represents any of R i group, -OSO 2 R i group or L a to L h below, and R g and R h are independently hydrogen atom, -C (O) R i group or L a to L below, respectively. represents either e, R i represents any of the following L a ~L e,
(L a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L d) carbon Aromatic hydrocarbon group of number 6 to 14 (L e ) Heterocyclic group having 2 to 14 carbon atoms (L f ) An alkoxy group having 1 to 12 carbon atoms (L g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, 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. Yes,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge.
[5] 前記有機顔料(S)の平均粒子径が200nm以下であ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。 [5] The optical filter according to any one of Items [1] to [4], wherein the organic pigment (S) has an average particle size of 200 nm or less.
[6] 前記有機顔料(S)を含む層が透明樹脂層であることを特徴とする、項[1]〜[5]のいずれか1項に記載の光学フィルター。 [6] The optical filter according to any one of Items [1] to [5], wherein the layer containing the organic pigment (S) is a transparent resin layer.
[7] 前記透明樹脂層を構成する透明樹脂が、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種の樹脂であることを特徴とする項[6]に記載の光学フィルター。 [7] The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate. Based resin, polysulfone based resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, A term characterized by being at least one resin selected from the group consisting of an allyl ester-based curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet curable resin, and a vinyl-based ultraviolet curable resin [ 6] The optical filter according to.
[8] 前記基材が、酸性官能基を有する分散剤を含有し、かつ、その含有量が前記有機顔料(S)100質量部に対して5〜300質量部であることを特徴とする項[1]〜[7]のいずれか1項に記載の光学フィルター。 [8] The item is characterized in that the base material contains a dispersant having an acidic functional group, and the content thereof is 5 to 300 parts by mass with respect to 100 parts by mass of the organic pigment (S). The optical filter according to any one of [1] to [7].
[9] 固体撮像装置用である項[1]〜[8]のいずれか1項に記載の光学フィルター。 [9] The optical filter according to any one of items [1] to [8] for a solid-state image sensor.
[10] 項[1]〜[9]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。
[11] 項[1]〜[9]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。[10] A solid-state image sensor including the optical filter according to any one of items [1] to [9].
[11] A camera module including the optical filter according to any one of items [1] to [9].
本発明によれば、近赤外線カット特性に優れ、入射角依存性が少なく、可視光波長域での透過率特性、色シェーディング抑制効果、ゴースト抑制効果および耐熱性に優れた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 having excellent near-infrared cut characteristics, less dependence on incident angle, transmittance characteristics in the visible light wavelength range, color shading suppression effect, ghost suppression effect and heat resistance. Can be done.
以下、本発明に係る光学フィルターおよび該光学フィルターを用いた装置について詳細に説明する。 Hereinafter, the optical filter according to the present invention and the device using the optical filter will be described in detail.
本発明の光学フィルターは、後述する要件(a)を満たす基材を有し、かつ、前記基材の少なくとも一方の面に誘電体多層膜を有することを特徴とする。
本発明の光学フィルターの厚みは、近年の固体撮像装置の薄型化、軽量化等の流れを考慮すると、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 optical filter of the present invention is characterized by having a base material satisfying the requirement (a) described later and having a dielectric multilayer film on at least one surface of the base material.
The thickness of the optical filter of the present invention is preferably thin in consideration of the recent trend toward thinner and lighter solid-state image sensors. Since the optical filter of the present invention contains the base material, it can be made thinner.
本発明の光学フィルターの厚みは、好ましくは210μm以下、より好ましくは190μm以下、さらに好ましくは160μm以下、特に好ましくは130μm以下であり、下限は特に限定されないが、20μm以上であることが好ましい。 The thickness of the optical filter of the present invention is preferably 210 μm or less, more preferably 190 μm or less, further preferably 160 μm or less, particularly preferably 130 μm or less, and the lower limit is not particularly limited, but is preferably 20 μm or more.
[基材]
本発明で用いられる基材は、下記要件(a)を満たす。
(a)波長900nm以上1200nm以下の領域に吸収極大を有する有機顔料(S)を含む層を有する。
また、前記基材は、さらに下記要件(b)を満たすことが好ましい。
(b)波長650nm以上760nm以下の領域に吸収極大を有する化合物(A)を含む層を有する。
以下、各要件について説明する。[Base material]
The base material used in the present invention satisfies the following requirement (a).
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a region having a wavelength of 900 nm or more and 1200 nm or less.
Further, it is preferable that the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength of 650 nm or more and 760 nm or less.
Each requirement will be described below.
<要件(a)>
要件(a)において、有機顔料(S)を含む層を構成する成分は特に限定されず、例えば、透明樹脂、ゾルゲル材料、低温硬化ガラス材料などが挙げられるが、取扱いが容易であること等の観点から透明樹脂であることが好ましい。<Requirement (a)>
In the requirement (a), the components constituting the layer containing the organic pigment (S) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, and low-temperature cured glass materials, but they are easy to handle. From the viewpoint, it is preferably a transparent resin.
≪有機顔料(S)≫
有機顔料(S)は、波長900nm以上1200nm以下の領域に吸収極大を有している有機顔料であれば特に限定されず、例えば、波長900nm以上1200nm以下の領域に吸収極大を有する化合物(S)を、分散媒および必要に応じて分散剤やその他の添加剤とともに、公知の方法で分散させることにより、有機顔料(S)の分散体として得ることができる。≪Organic pigment (S) ≫
The organic pigment (S) is not particularly limited as long as it is an organic pigment having an absorption maximum in the wavelength region of 900 nm or more and 1200 nm or less, and for example, the compound (S) having an absorption maximum in the wavelength region of 900 nm or more and 1200 nm or less. Can be obtained as a dispersion of the organic pigment (S) by dispersing the above with a dispersion medium and, if necessary, a dispersant and other additives by a known method.
(1) 化合物(S)
前記化合物(S)は、波長900nm以上1200nm以下の領域に吸収極大を有している化合物であれば特に限定されないが、好ましくはジイモニウム系化合物、金属ジチオラート錯体系化合物、ピロロピロール系化合物、シアニン系化合物、クロコニウム系化合物およびナフタロ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種の化合物であり、さらに好ましくはジイモニウム系化合物および金属ジチオラート錯体系化合物からなる群より選ばれる少なくとも1種の化合物であり、特に好ましくは下記式(I)で表されるジイモニ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、良好な近赤外線吸収特性と優れた可視光透過率を付与することができる。(1) Compound (S)
The compound (S) is not particularly limited as long as it is a compound having an absorption maximum in the region of a wavelength of 900 nm or more and 1200 nm or less, but is preferably a diimonium-based compound, a metal dithiolate complex-based compound, a pyrolopyrrole-based compound, or a cyanine-based compound. It is at least one compound selected from the group consisting of compounds, croconium compounds and naphthalocyanine compounds, and more preferably at least one compound selected from the group consisting of diimonium compounds and metal dithiolate complex compounds. Particularly preferably, it is a diimonium-based compound represented by the following formula (I). By using such a compound (S), good near-infrared absorption characteristics and excellent visible light transmittance can be imparted.
R1は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、−SRi基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、R2は、独立にハロゲン原子、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、−SRi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2〜14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種であり、
nは0〜4の整数を表し、
Xは電荷を中和させるのに必要なアニオンを表す。
R 1 is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphoric acid group, -SR i group, -SO 2 R i groups, -OSO 2 R i group or a group represented by L a ~ Represents any of L h , R 2 is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR g R h group, -SR i group, -SO 2 It represents any of R i group, -OSO 2 R i group or L a to L h below, and R g and R h are independently hydrogen atom, -C (O) R i group or L a to L below, respectively. represents either e, R i represents any of the following L a ~L e,
(L a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L d) carbon Aromatic hydrocarbon group of number 6 to 14 (L e ) Heterocyclic group having 2 to 14 carbon atoms (L f ) An alkoxy group having 1 to 12 carbon atoms (L g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, 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. Yes,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge.
前記R1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、アダマンチル基、トリフルオロメチル基、ペンタフルオロエチル基、3−ピリジニル基、エポキシ基、フェニル基、ベンジル基、フルオレニル基であり、より好ましくはイソプロピル基、sec−ブチル基、tert−ブチル基、ベンジル基である。The R 1 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, an adamantyl group, or a trifluoromethyl group. , Pentafluoroethyl group, 3-pyridinyl group, epoxy group, phenyl group, benzyl group, fluorenyl group, more preferably isopropyl group, sec-butyl group, tert-butyl group, benzyl group.
前記R2としては、好ましくは塩素原子、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、メトキシ基、エトキシ基、n−プロポキシ基、n−ブトキシ基、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、tert−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、メチルチオ基、エチルチオ基、n−プロピルチオ基、n−ブチルチオ基であり、より好ましくは塩素原子、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、メトキシ基、エトキシ基、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、tert−ブタノイルアミノ基、シクロヘキシノイルアミノ基であり、特に好ましくは、メチル基、エチル基、n−プロピル基、イソプロピル基である。同じ芳香環に結合しているR2の数(nの値)は、0〜4であれば特に限定されないが、0もしくは1であることが好ましい。The R 2 is preferably a chlorine atom, a fluorine 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, a phenyl group, or a hydroxyl group. , Amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino Group, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably chlorine. Atomic, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group , Pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, particularly preferably methyl group, ethyl group, n-propyl group, isopropyl group. The number (value of n) of R 2 bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but it is preferably 0 or 1.
前記Xは電荷を中和するのに必要なアニオンであり、Xが2価のアニオンである場合にはXは1つであり、Xが1価のアニオンである場合にはXは2つである。後者の場合は2つのアニオンが同一であっても異なっていてもよいが、合成上の観点から同一である方が好ましい。Xはこのようなアニオンであれば特に限定されないが、一例として、下記表1に記載のものを挙げることができる。 The X is an anion required to neutralize the charge, X is one when X is a divalent anion, and two X when X is a monovalent anion. is there. In the latter case, the two anions may be the same or different, but they are preferably the same from a synthetic point of view. X is not particularly limited as long as it is such an anion, but as an example, those listed in Table 1 below can be mentioned.
上記式(I)で表されるジイモニウム系化合物としては、例えば、下記表2−1〜2−4に記載のものを挙げることができる。 Examples of the diimonium-based compound represented by the above formula (I) include those listed in Tables 2-1 to 2-4 below.
前記化合物(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、特許第4168031号公報、特許第4252961号公報、特表2010−516823号公報、特開昭63−165392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, Japanese Patent No. 4168031, Japanese Patent No. 4252961, Japanese Patent Application Laid-Open No. 2010-516823, Japanese Patent Application Laid-Open No. 63-165392. It can be synthesized by referring to the methods described in the publications and the like.
前記化合物(S)の吸収極大波長は、好ましくは920nm以上1195nm以下、より好ましくは950nm以上1190nm以下、さらに好ましくは980nm以上1180nm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、不要な近赤外線を効率よくカットすることができ、優れたゴースト抑制効果を得ることができる。 The absorption maximum wavelength of the compound (S) is preferably 920 nm or more and 1195 nm or less, more preferably 950 nm or more and 1190 nm or less, and further preferably 980 nm or more and 1180 nm or less. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near infrared rays can be efficiently cut, and an excellent ghost suppressing effect can be obtained.
(2) 分散媒
有機顔料(S)は、一般的に知られている方法、例えば公知の分散機を用いる方法で前記化合物(S)を分散媒に分散させて使用することが好ましい。本発明において、化合物(S)に対して溶解性が著しく高い分散媒を選択した場合、化合物(S)が分散媒中に溶解し染料化してしまう。この場合、所望の分光特性が得られなくなるばかりか、耐熱性や耐UV性を著しく低下させてしまう。従って、化合物(S)に対して溶解性が低く、染料化しない分散媒を選択する必要がある。分散媒が化合物(S)を染料化するか否かは、化合物(S)の濃度が0.1質量%となるように、化合物(S)に分散媒を加えて、ガラス板状に滴下して乾燥後、走査型電子顕微鏡にて観察することで確認することができる。化合物(S)が粒子状に存在している場合は顔料化するものと判断でき、粒子状の物質が確認されない場合は染料化するものと判断できる。(2) Dispersion Medium The organic pigment (S) is preferably used by dispersing the compound (S) in a dispersion medium by a generally known method, for example, a method using a known disperser. In the present invention, when a dispersion medium having extremely high solubility in the compound (S) is selected, the compound (S) dissolves in the dispersion medium and becomes a dye. In this case, not only the desired spectral characteristics cannot be obtained, but also the heat resistance and UV resistance are significantly lowered. Therefore, it is necessary to select a dispersion medium that has low solubility in compound (S) and does not dye. Whether or not the dispersion medium dyes the compound (S) is determined by adding the dispersion medium to the compound (S) and dropping it in the form of a glass plate so that the concentration of the compound (S) is 0.1% by mass. After drying, it can be confirmed by observing with a scanning electron microscope. When the compound (S) is present in the form of particles, it can be determined that it is pigmented, and when the particulate substance is not confirmed, it can be determined that it is dyed.
分散媒としては、化合物(S)を染料化してしまうもの以外であれば特に限定されないが、分散プロセスでの安全性の点から比較的極性の高い溶媒が好ましく、例えばイソプロパノール、エタノール等のアルコール類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸ブチル、酢酸エチル等のエステル類、プロピレングリコールモノメチルエーテル等のエーテル類が挙げられる。 The dispersion medium is not particularly limited as long as it does not dye the compound (S), but a solvent having a relatively high polarity is preferable from the viewpoint of safety in the dispersion process, and alcohols such as isopropanol and ethanol are preferable. , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, and ethers such as propylene glycol monomethyl ether.
化合物(S)がジイモニウム系化合物の場合は、分散液の保存安定性の点から、イソプロパノール、エタノール等のアルコール類が特に好ましい。なお、塩化メチレンなどのハロゲン溶媒を用いた場合には化合物(S)が染料化してしまうため好ましくない。 When the compound (S) is a diimonium-based compound, alcohols such as isopropanol and ethanol are particularly preferable from the viewpoint of storage stability of the dispersion. When a halogen solvent such as methylene chloride is used, the compound (S) is dyed, which is not preferable.
(3) 分散機
前記化合物(S)を分散媒に分散させる際に用いられる分散機としては、例えば、ビーズミル、ボールミル、振動ボールミル、遊星ボールミル、サンドミル、コロイドミル、ジェットミル及びローラミルなどが挙げられる。
また、いわゆるソルトミリングにより、化合物(S)の一次粒子を微細化して有機顔料(S)を調製してもよい。ソルトミリングの方法としては、例えば、特開平8−179111号公報に開示されている方法を採用することができる。(3) Disperser Examples of the disperser used to disperse the compound (S) in a dispersion medium include bead mills, ball mills, vibrating ball mills, planetary ball mills, sand mills, colloid mills, jet mills and roller mills. ..
Further, the organic pigment (S) may be prepared by refining the primary particles of the compound (S) by so-called salt milling. As the salt milling method, for example, the method disclosed in JP-A-8-179111 can be adopted.
(4) 分散剤
分散安定性向上を目的として、公知の分散剤を用いて化合物(S)を分散させてもよい。分散剤としては、例えば、ウレタン系分散剤、ポリエチレンイミン系分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンアルキルフェニルエーテル系分散剤、ポリエチレングリコールジエステル系分散剤、ソルビタン脂肪酸エステル系分散剤、ポリエステル系分散剤、(メタ)アクリル系分散剤等が挙げられる。市販品として、例えば、Disperbyk−2000、Disperbyk−2001、BYK−LPN6919、BYK−LPN21116、BYK−LPN22102(以上、ビックケミー(BYK)社製)等の(メタ)アクリル系分散剤、Disperbyk−161、Disperbyk−162、Disperbyk−165、Disperbyk−167、Disperbyk−170、Disperbyk−182(以上、ビックケミー(BYK)社製)、ソルスパース76500(ルーブリゾール(株)社製)等のウレタン系分散剤、ソルスパース24000(ルーブリゾール(株)社製)等のポリエチレンイミン系分散剤、アジスパーPB821、アジスパーPB822、アジスパーPB880、アジスパーPB881(以上、味の素ファインテクノ(株)社製)等のポリエステル系分散剤の他、BYK−LPN21324(ビックケミー(BYK)社製)、マリアリムSCシリーズ、エスリームADシリーズ、エスリームC2093I(以上、日油(株)社製)などを使用することができる。また、(メタ)アクリル系分散剤として、例えば、特開2011−232735号公報、特開2011−237769号公報、特開2012−32767号公報、国際公開第2011/129078号パンフレット、国際公開第2012/001945号パンフレット等に開示されている共重合体も使用することもできる。分散剤は、1種又は2種以上を組み合わせて使用することができる。(4) Dispersant For the purpose of improving dispersion stability, the compound (S) may be dispersed using a known dispersant. Examples of the dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, and sorbitan fatty acid ester dispersants. , Polyester-based dispersant, (meth) acrylic-based dispersant, and the like. As commercially available products, for example, (meth) acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (all manufactured by Big Chemie (BYK)), Disperbyk-161, Disperbyk. Urethane-based dispersants such as -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (BYK)), Solspers 76500 (manufactured by Lubrizol Co., Ltd.), Solspers 24000 ( In addition to polyethyleneimine dispersants such as Lubrizol Co., Ltd.), polyester dispersants such as Ajispar PB821, Ajispar PB822, Ajispar PB880, and Ajispar PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) LPN21324 (manufactured by Big Chemie (BYK)), Marialim SC series, Esleem AD series, Esleam C2093I (all manufactured by Nichiyu Co., Ltd.) and the like can be used. Further, as the (meth) acrylic dispersant, for example, Japanese Patent Application Laid-Open No. 2011-232735, Japanese Patent Application Laid-Open No. 2011-237769, Japanese Patent Application Laid-Open No. 2012-32767, International Publication No. 2011/129078 Pamphlet, International Publication No. 2012 The copolymer disclosed in Pamphlet No. / 001945 and the like can also be used. The dispersant can be used alone or in combination of two or more.
本発明では、酸性官能基を有する分散剤を用いることが、分散安定性が良好な点、および化合物(S)に対する化学的な作用が小さい点で好ましい。前記酸性官能基を有する分散剤としては、カルボン酸、スルホン酸、フェノール系水酸基またはこれらの塩を有する分散剤であれば特に限定されないが、例えば、酸性官能基を有するエチレン性不飽和単量体と他の共重合可能なエチレン性不飽和単量体との共重合体などが挙げられる。また、市販品としては、上述したマリアリムSCシリーズ、DISPERBYK−103、DISPERBYK−110、DISPERBYK−118などが挙げられる。 In the present invention, it is preferable to use a dispersant having an acidic functional group because the dispersion stability is good and the chemical action on the compound (S) is small. The dispersant having an acidic functional group is not particularly limited as long as it is a dispersant having a carboxylic acid, a sulfonic acid, a phenolic hydroxyl group or a salt thereof, and for example, an ethylenically unsaturated monomer having an acidic functional group. And other copolymers with copolymerizable ethylenically unsaturated monomers. In addition, examples of commercially available products include the above-mentioned Marialim SC series, DISPERBYK-103, DISPERBYK-110, DISPERBYK-118 and the like.
分散剤の含有量は、分散剤の種類により適宜選択可能であるが、前記有機顔料(S)100質量部に対して、好ましくは5〜300質量部、より好ましくは10〜200質量部、更に好ましくは20〜150質量部である。分散剤の含有量が前記範囲内であることにより、分散液の分散安定性が良好であり、かつ基材や光学フィルターの耐熱性、耐水性および密着性が優れるため好ましい。 The content of the dispersant can be appropriately selected depending on the type of the dispersant, but is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and further, with respect to 100 parts by mass of the organic pigment (S). It is preferably 20 to 150 parts by mass. When the content of the dispersant is within the above range, the dispersion stability of the dispersion is good, and the heat resistance, water resistance and adhesion of the base material and the optical filter are excellent, which is preferable.
本発明では、分散工程に続いて遠心分離処理を行うことが好ましい。遠心分離処理により、分散が不十分な粗大な有機顔料粒子を除去し、有機顔料の平均粒子径を低減させることができ、結果として光学フィルターのヘイズを低減することができる。 In the present invention, it is preferable to perform the centrifugation treatment after the dispersion step. By the centrifugation treatment, coarse organic pigment particles having insufficient dispersion can be removed, the average particle size of the organic pigment can be reduced, and as a result, the haze of the optical filter can be reduced.
遠心分離処理の時間としては、特に限定されないが、例えば1分以上60分以下とすることができる。また、 遠心分離を行う際の遠心分離機の遠心加速度としては特に限定されないが、例えば10G以上50,000G以下とすることができる。 The time of the centrifugation is not particularly limited, but may be, for example, 1 minute or more and 60 minutes or less. The centrifugal acceleration of the centrifuge when performing centrifugation is not particularly limited, but can be, for example, 10 G or more and 50,000 G or less.
(5) 有機顔料(S)の平均粒子径
有機顔料(S)の平均粒子径は、好ましくは200nm以下、より好ましくは5〜190nm、さらに好ましくは10〜180nm、特に好ましくは15〜150nmである。ここで、本発明における有機顔料(S)の平均粒子径は、後述する実施例に記載の測定方法で求めた値である。有機顔料(S)の平均粒子径が前記範囲にあると、ヘイズ値を極めて低いレベルに維持し、かつ耐熱性に優れた光学フィルターを得ることができる。(5) Average Particle Size of Organic Pigment (S) The average particle size of the organic pigment (S) is preferably 200 nm or less, more preferably 5 to 190 nm, still more preferably 10 to 180 nm, and particularly preferably 15 to 150 nm. .. Here, the average particle size of the organic pigment (S) in the present invention is a value obtained by the measuring method described in Examples described later. When the average particle size of the organic pigment (S) is in the above range, an optical filter having an extremely low haze value and excellent heat resistance can be obtained.
(6) 有機顔料(S)の含有量
有機顔料(S)全体の含有量は、前記基材として、例えば、有機顔料(S)を含有する透明樹脂製基板からなる基材や、有機顔料(S)を含有する透明樹脂製基板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質量部に対して、好ましくは0.01〜2.0質量部、より好ましくは0.02〜1.5質量部、特に好ましくは0.03〜1.0質量部であり、前記基材として、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上に有機顔料(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、有機顔料(S)を含む透明樹脂層を形成する樹脂100質量部に対して、好ましくは0.1〜5.0質量部、より好ましくは0.2〜4.0質量部、特に好ましくは0.3〜3.0質量部である。有機顔料(S)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した光学フィルターを得ることができる。なお、本発明では、基材として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上に有機顔料(S)を含有する硬化性樹脂等からなるオーバーコート層を設けることが望ましい。(6) Content of Organic Pigment (S) The content of the entire organic pigment (S) is, for example, a base material made of a transparent resin substrate containing the organic pigment (S) or an organic pigment (S). When a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing S) is used, it is preferably 0.01 with respect to 100 parts by mass of the transparent resin. ~ 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, particularly preferably 0.03 to 1.0 parts by mass, and the base material is a glass support or a resin support as a base. When a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a support such as a body is used, the transparent resin containing the organic pigment (S) is used. With respect to 100 parts by mass of the resin forming the layer, preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, and particularly preferably 0.3 to 3.0 parts by mass. is there. When the content of the organic pigment (S) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained. In the present invention, it is desirable to provide an overcoat layer made of a curable resin containing an organic pigment (S) on a support such as a glass support or a resin support as a base as a base material.
<要件(b)>
要件(b)において、化合物(A)を含む層を構成する成分は特に限定されず、例えば、透明樹脂、ゾルゲル材料、低温硬化ガラス材料などが挙げられるが、取扱いが容易であることや化合物(A)との相溶性の観点から透明樹脂であることが好ましい。<Requirement (b)>
In the requirement (b), the components constituting the layer containing the compound (A) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, low-temperature cured glass materials, etc., but they are easy to handle and the compounds ( From the viewpoint of compatibility with A), a transparent resin is preferable.
≪化合物(A)≫
化合物(A)は、波長650nm以上760nm以下の領域に吸収極大を有する化合物であれば特に限定されないが、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を含む2種以上であることが特に好ましい。化合物(A)がスクアリリウム系化合物を含む2種以上である場合、構造の異なるスクアリリウム系化合物が2種以上でもよく、スクアリリウム系化合物とその他の化合物(A)との組み合わせでもよい。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 is a compound having an absorption maximum in the region of 650 nm or more and 760 nm or less, but is preferably a solvent-soluble dye compound, and is a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound. It is more preferably at least one selected from the group consisting of compounds, further preferably containing a squarylium-based compound, and particularly preferably two or more kinds containing a squarylium-based compound. When the compound (A) is two or more kinds including a squarylium-based compound, two or more kinds of squarylium-based compounds having different structures may be used, or a combination of the squarylium-based compound and another compound (A) may be used. As the other compound (A), a phthalocyanine compound and a cyanine compound are particularly preferable.
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。 Squalylium compounds have excellent visible light transmittance, steep absorption characteristics, and high molar absorption coefficient, but may generate fluorescence that causes scattered light when absorbing light. In such a case, by using the squarylium compound and the other compound (A) in combination, it is possible to obtain an optical filter with less scattered light and better camera image quality.
化合物(A)の吸収極大波長は、好ましくは660nm以上755nm以下、より好ましくは670nm以上750nm以下、さらに好ましくは680nm以上745nm以下である。 The absorption maximum wavelength of compound (A) is preferably 660 nm or more and 755 nm or less, more preferably 670 nm or more and 750 nm or less, and further preferably 680 nm or more and 745 nm or less.
化合物(A)が2種以上の化合物の組み合わせである場合、適用する化合物(A)のうち最も吸収極大波長が短いものと最も吸収極大波長の長いものの吸収極大波長の差は、好ましくは10〜60nm、より好ましくは15〜55nm、さらに好ましくは20〜50nmである。吸収極大波長の差が上記範囲にあると、蛍光による散乱光を十分低減できるとともに、700nm付近の幅広い吸収帯と優れた可視光透過率を両立できるため好ましい。 When the compound (A) is a combination of two or more kinds of compounds, the difference between the absorption maximum wavelengths of the compound (A) to be applied having the shortest absorption maximum wavelength and the longest absorption maximum wavelength is preferably 10 to 10. It is 60 nm, more preferably 15 to 55 nm, and even more preferably 20 to 50 nm. When the difference in absorption maximum wavelength is within the above range, scattered light due to fluorescence can be sufficiently reduced, and a wide absorption band around 700 nm and excellent visible light transmittance can be compatible with each other, which is preferable.
化合物(A)全体の含有量は、前記基材として、例えば、有機顔料(S)および化合物(A)を含有する透明樹脂製基板からなる基材や、化合物(A)を含有する透明樹脂製基板上に有機顔料(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樹脂層が積層された基材を用いる場合には、透明樹脂100質量部に対して、好ましくは0.04〜2.0質量部、より好ましくは0.06〜1.5質量部、さらに好ましくは0.08〜1.0質量部であり、前記基材として、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上に有機顔料(S)および化合物(A)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質量部に対して、好ましくは0.4〜5.0質量部、より好ましくは0.6〜4.0質量部、さらに好ましくは0.8〜3.5質量部である。 The content of the entire compound (A) is, as the base material, for example, a base material made of a transparent resin substrate containing the organic pigment (S) and the compound (A), or a transparent resin containing the compound (A). When a base material in which a resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a substrate is used, it is preferably 0.04 with respect to 100 parts by mass of the transparent resin. ~ 2.0 parts by mass, more preferably 0.06 to 1.5 parts by mass, still more preferably 0.08 to 1.0 parts by mass, and the base material is a glass support or a resin support as a base. When a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) and a compound (A) is laminated on a support such as a body is used, the compound (A) is used. With respect to 100 parts by mass of the resin forming the transparent resin layer containing the above, preferably 0.4 to 5.0 parts by mass, more preferably 0.6 to 4.0 parts by mass, still more preferably 0.8 to 3. 5 parts by mass.
前記基材は、有機顔料(S)を含む層を有していれば、単層であっても多層であってもよい。また、化合物(A)は有機顔料(S)と同一の層に含まれていても異なる層に含まれていてもよい。 The base material may be a single layer or a multilayer as long as it has a layer containing the organic pigment (S). Further, the compound (A) may be contained in the same layer as the organic pigment (S) or may be contained in a different layer.
有機顔料(S)を含む層と化合物(A)を含む層とが同一である場合、例えば、有機顔料(S)および化合物(A)を含む透明樹脂製基板からなる基材、有機顔料(S)および化合物(A)を含む透明樹脂製基板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、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上に有機顔料(S)および化合物(A)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挙げることができる。 When the layer containing the organic pigment (S) and the layer containing the compound (A) are the same, for example, a substrate composed of a transparent resin substrate containing the organic pigment (S) and the compound (A), an organic pigment (S). ) And compound (A) on a transparent resin substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, on a support such as a glass support or a base resin support. Examples thereof include a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) and a compound (A) is laminated.
有機顔料(S)を含む層と化合物(A)を含む層とが異なる場合、例えば、有機顔料(S)を含む透明樹脂製基板上に化合物(A)を含む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、化合物(A)を含む透明樹脂製基板上に有機顔料(S)を含む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、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上に有機顔料(S)を含む硬化性樹脂等からなるオーバーコート層と化合物(A)を含む硬化性樹脂等からなるオーバーコート層とが積層された基材などを挙げることができる。なお、本発明では、化合物(A)を含む透明樹脂製基板上に有機顔料(S)を含有する硬化性樹脂等からなるオーバーコート層を設けることが好ましく、この場合において、有機顔料(S)の平均粒子径が150nm以下であることが更に好ましく、100nm以下であることが特に好ましい。 When the layer containing the organic pigment (S) and the layer containing the compound (A) are different, for example, an overcoat made of a curable resin containing the compound (A) or the like on a transparent resin substrate containing the organic pigment (S). A base material on which a resin layer such as a layer is laminated, or a base material on which a resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a transparent resin substrate containing the compound (A). , An overcoat layer made of a curable resin containing an organic pigment (S) and an overcoat layer made of a curable resin containing a compound (A) on a support such as a glass support or a resin support as a base. Examples thereof include a base material on which and is laminated. In the present invention, it is preferable to provide an overcoat layer made of a curable resin or the like containing an organic pigment (S) on a transparent resin substrate containing the compound (A). In this case, the organic pigment (S) The average particle size of the above is more preferably 150 nm or less, and particularly preferably 100 nm or less.
<その他の特性および物性>
波長430〜580nmの領域における基材の平均透過率は、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、可視光領域において高い光線透過特性を達成でき、高感度なカメラ機能を達成することができる。<Other characteristics and physical characteristics>
The average transmittance of the substrate in the wavelength region of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. By using a base material having such a transmission characteristic, a high light transmission characteristic can be achieved in the visible light region, and a highly sensitive camera function can be achieved.
基材の厚みは、所望の用途に応じて適宜選択することができ、特に限定されないが、好ましくは10〜200μm、より好ましくは20〜180μm、さらに好ましくは25〜150μmである。基材の厚みが前記範囲にあると、該基材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からなる基材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。 The thickness of the base material can be appropriately selected depending on the desired application, and is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 180 μm, and even more preferably 25 to 150 μm. When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and can be suitably used for various applications such as a solid-state image sensor. In particular, when the base material made of the transparent resin substrate is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.
<透明樹脂>
前記基材を構成する透明樹脂層、透明樹脂製基板および樹脂製支持体に用いられる透明樹脂としては、本発明の効果を損なわないものである限り特に限定されないが、例えば、熱安定性および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フィルムとするため、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えるフィルムが得られるため、特に好ましい。<Transparent resin>
The transparent resin used for the transparent resin layer, the transparent resin substrate, and the resin support constituting the base material is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, thermal stability and a film. The glass transition temperature (Tg) is preferably 110 to 380 ° C., in order to obtain a film capable of forming a dielectric multilayer film by high temperature vapor deposition performed at a vapor deposition temperature of 100 ° C. or higher while ensuring moldability to the resin. Examples thereof include resins having a temperature of 110 to 370 ° C, more preferably 120 to 360 ° C. Further, when the glass transition temperature of the resin is 140 ° C. or higher, a film capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained, which is particularly preferable.
透明樹脂としては、当該樹脂からなる厚さ0.1mmの樹脂板を形成した場合に、この樹脂板の全光線透過率(JIS K7105)が、好ましくは75〜95%、より好ましくは78〜95%、さらに好ましくは80〜95%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、得られる基板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 plate having a thickness of 0.1 mm made of the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, More preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the obtained substrate exhibits good transparency as an optical film.
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。 The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of a transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000, and is a number. The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
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 the transparent resin include cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, and polysalphon. Based resin, polyether sulfone based resin, polyparaphenylene based resin, polyamideimide based resin, polyethylene naphthalate (PEN) based resin, fluorinated aromatic polymer based resin, (modified) acrylic resin, epoxy resin, allyl Examples thereof include ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic-based UV-curable resins, and vinyl-based UV-curable resins.
透明樹脂は、1種単独で用いても、2種以上を組み合わせて用いてもよい。 The transparent resin may be used alone or in combination of two or more.
≪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 polyolefin resin≫
The cyclic polyolefin resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0). A resin and a resin obtained by hydrogenating the resin are preferable.
(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、(ii')および(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') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. ~ 30 hydrocarbon groups (v') substituted or unsubstituted hydrocarbon groups (vi') polar groups with 1 to 30 carbon atoms (excluding (ii') and (iv'))
(Vii') Alkylidene groups formed by mutual bonding of R x1 and R x2 or R x3 and R x4 (however, R x1 to R x4 not involved in the bond are independently described in (i'). ) ~ (Vi') represents an atom or group selected.)
(Viii') A monocyclic or polycyclic hydrocarbon ring or heterocycle formed by mutually bonding R x1 and R x2 or R x3 and R x4 (however, R x1 to R not involved in the bond). x4 represents an atom or group independently 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 (however, R x1 and R x4 that are not involved in the bond are independently described in (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 resin preferably has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (1) and the 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。 Further, the aromatic polyether resin further has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4). Is preferable.
≪ポリイミド系樹脂≫
ポリイミド系樹脂としては、特に限定されず、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 polymer compound containing an imide bond in the repeating unit. For example, the methods described in JP-A-2006-199945 and JP-A-2008-163107 can be 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、特に限定されず、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-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized by, for example, the 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、特に限定されず、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, it is synthesized by the method described in JP-A-2010-285505 and JP-A-2011-197450. Can be done.
≪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、特に限定されないが、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 and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is preferably a polymer containing 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、特に限定されないが、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(A)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(A)を含有する透明樹脂製基板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 groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. What is done can be mentioned. The acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing the compound (A) and a curable resin is laminated on a glass support or a resin support as a base, or a compound ( When a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing A) is used, it can be particularly preferably used as the curable resin.
≪エポキシ系樹脂≫
エポキシ系樹脂としては、特に限定されないが、紫外線硬化型と熱硬化型に大別することができる。紫外線硬化型エポキシ系樹脂としては、例えば、分子内に一つ以上のエポキシ基を有する化合物と、紫外線によって酸を発生させる化合物(以下「光酸発生剤」ともいう)を含有する組成物から合成されるものを挙げることができ、熱硬化型エポキシ系樹脂としては、例えば、分子内に一つ以上のエポキシ基を有する化合物と、酸無水物を含有する組成物から合成されるものを挙げることができる。エポキシ系紫外線硬化型樹脂は、前記基材として、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(A)を含む透明樹脂層が積層された基材や、化合物(A)を含有する透明樹脂製基板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。≪Epoxy resin≫
The epoxy resin is not particularly limited, but can be roughly classified into an ultraviolet curable type and a thermosetting type. The ultraviolet curable epoxy resin is synthesized from, for example, a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates acid by ultraviolet rays (hereinafter, also referred to as "photoacid generator"). Examples of the thermosetting epoxy resin include those synthesized from a compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. Can be done. The epoxy-based ultraviolet curable resin contains, as the base material, a base material in which a transparent resin layer containing the compound (A) is laminated on a glass support or a resin support as a base, or a compound (A). When a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate is used, it can be particularly preferably used as the curable resin.
≪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≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd.
<その他の色素(X)>
前記基材には、さらに、有機顔料(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 pigments (X)>
The base material may further contain an organic pigment (S) and another dye (X) that does not correspond to the compound (A).
その他の色素(X)としては、吸収極大波長が波長650nm未満もしくは波長760nm超900nm未満の領域にある色素であれば特に限定されないが、吸収極大波長が760nm超900nm未満の領域にある色素が好ましい。このような色素としては、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、オクタフィリン系化合物、ジイモニウム系化合物、ピロロピロール系化合物、ボロンジピロメテン(BODIPY)系化合物、ペリレ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。 The other dye (X) is not particularly limited as long as it has a maximum absorption wavelength in the region of less than 650 nm or a wavelength of more than 760 nm and less than 900 nm, but a dye having a maximum absorption wavelength in the region of more than 760 nm and less than 900 nm is preferable. .. Examples of such dyes include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyllin compounds, diimonium compounds, pyrolopyrrole compounds, and borondipyrromethene (BODIPY). Examples thereof include at least one compound selected from the group consisting of a system compound, a perylene system compound and a metal dithiolate system compound.
その他の色素(X)の含有量は、前記基材として、例えば、その他の色素(X)を含有する透明樹脂製基板からなる基材を用いる場合には、透明樹脂100質量部に対して、好ましくは0.005〜1.0質量部、より好ましくは0.01〜0.9質量部、特に好ましくは0.02〜0.8質量部であり、前記基材として、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上にその他の色素(X)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、有機顔料(S)を含有する透明樹脂製基板上にその他の色素(X)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質量部に対して、好ましくは0.05〜4.0質量部、より好ましくは0.1〜3.0質量部、特に好ましくは0.2〜2.0質量部である。 The content of the other dye (X) is adjusted with respect to 100 parts by mass of the transparent resin when, for example, a base material made of a transparent resin substrate containing the other dye (X) is used as the base material. It is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.9 part by mass, and particularly preferably 0.02 to 0.8 part by mass, and the base material is a glass support or a base. Contains a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing another dye (X) is laminated on a support such as a resin support, or an organic pigment (S). When a base material in which a resin layer such as an overcoat layer made of a curable resin containing another dye (X) is laminated on a transparent resin substrate is used, the transparent resin containing the other dye (X) is contained. With respect to 100 parts by mass of the resin forming the resin layer, preferably 0.05 to 4.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, and particularly preferably 0.2 to 2.0 parts by mass. Is.
<その他成分>
前記基材は、本発明の効果を損なわない範囲において、その他成分として、さらに酸化防止剤、近紫外線吸収剤および蛍光消光剤などを含有してもよい。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 may further contain an antioxidant, a near-ultraviolet absorber, a fluorescent quencher and the like as other components as long as the effects of the present invention are not impaired. 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。 Examples of the near-ultraviolet absorber include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.
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、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、およびトリス(2,4−ジ−t−ブチルフェニル)ホスファイトなどが挙げられる。 Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis. [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite and the like can be mentioned.
なお、これらその他成分は、基材を製造する際に、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質量部に対して、通常0.01〜5.0質量部、好ましくは0.05〜2.0質量部である。 These other components may be mixed with a resin or the like when the base material is produced, or may be added when the resin is synthesized. The amount to be added is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. It is a department.
<基材の製造方法>
前記基材が、有機顔料(S)を含有する透明樹脂製基板を含む基材である場合、該透明樹脂製基板は、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。<Manufacturing method of base material>
When the base material is a base material containing a transparent resin substrate containing an organic pigment (S), the transparent resin substrate can be formed by, for example, melt molding or cast molding, and further, if necessary. By coating with a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding, a base material on which an overcoat layer is laminated can be produced.
前記基材が、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上または有機顔料(S)を含有しない透明樹脂製基板上に有機顔料(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、前記支持体または前記透明樹脂製基板上に化合物(A)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、前記支持体または前記透明樹脂製基板上に有機顔料(S)を含む透明樹脂層が形成された基材を製造することができる。 The base material is made of a curable resin containing an organic pigment (S) on a support such as a glass support or a resin support as a base, or a transparent resin substrate containing no organic pigment (S). In the case of a base material on which a transparent resin layer such as an overcoat layer is laminated, for example, it is preferable to melt-mold or cast-mold a resin solution containing the compound (A) on the support or the transparent resin substrate. After coating by a method such as spin coating, slit coating, or inkjet, the solvent is dried and removed, and if necessary, further light irradiation or heating is performed to obtain an organic pigment on the support or the transparent resin substrate. A base material on which a transparent resin layer containing (S) is formed can be produced.
≪溶融成形≫
前記溶融成形としては、具体的には、樹脂と有機顔料(S)と必要に応じて他の成分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;樹脂と有機顔料(S)と必要応じて他の成分とを含有する樹脂組成物を溶融成形する方法;または、有機顔料(S)、樹脂、溶剤および必要に応じて他の成分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。≪Melting molding≫
Specifically, the melt molding is a method of melt-molding a pellet obtained by melt-kneading a resin, an organic pigment (S) and, if necessary, other components; a resin and an organic pigment (S). A method of melt-molding a resin composition containing and, if necessary, other components; or removing the solvent from the organic pigment (S), resin, solvent and, if necessary, the resin composition containing other components. Examples thereof include a method of melt-molding the obtained pellets. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding and the like.
≪キャスト成形≫
前記キャスト成形としては、有機顔料(S)、樹脂、溶剤および必要に応じて他の成分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;または有機顔料(S)と、光硬化性樹脂および/または熱硬化性樹脂と、必要に応じて他の成分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≫
The cast molding is a method of casting a resin composition containing an organic pigment (S), a resin, a solvent and, if necessary, other components on a suitable support to remove the solvent; or an organic pigment (S). ), A photocurable resin and / or a thermosetting resin, and if necessary, a curable composition containing other components is cast on a suitable support to remove the solvent, and then irradiated with ultraviolet rays. It can also be produced by a method of curing by an appropriate method such as heating.
前記基材が、有機顔料(S)を含有する透明樹脂製基板からなる基材である場合には、該基材は、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、前記基材が、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上または有機顔料(S)を含有しない透明樹脂製基板上に有機顔料(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 is a base material made of a transparent resin substrate containing an organic pigment (S), the base material can be obtained by peeling the coating film from the support after cast molding. Further, the base material is a curable resin containing an organic pigment (S) on a support such as a glass support or a resin support as a base, or on a transparent resin substrate containing no organic pigment (S). In the case of a base material on which a transparent resin layer such as an overcoat layer made of the above is laminated, the base material can be obtained by not peeling off the coating film after cast molding.
前記支持体としては、例えば、近赤外線吸収ガラス板(例えば、松浪硝子工業社製「BS−11」やAGC テクノグラス社製「NF−50T」などのような銅成分を含有するリン酸塩系ガラス板)、透明ガラス板(例えば、日本電気硝子社製「OA−10G」や旭硝子社製「AN100」などのような無アルカリガラス板)、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。 The support includes a phosphate-based support containing a copper component such as a near-infrared absorbing glass plate (for example, "BS-11" manufactured by Matsunami Glass Industry Co., Ltd. or "NF-50T" manufactured by AGC Techno Glass Co., Ltd.). Glass plate), transparent glass plate (for example, non-alkali glass plate such as "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. and "AN100" manufactured by Asahi Glass Co., Ltd.), steel belt, steel drum and transparent resin (for example, polyester film). , Cyclic olefin resin film) support.
前記方法で得られた透明樹脂層(透明樹脂製基板)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)100質量部に対して、好ましくは3質量部以下、より好ましくは1質量部以下、さらに好ましくは0.5質量部以下である。残留溶剤量が前記範囲にあると、基材の変形や光学特性の変化が起こりにくい、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)が得られる。 The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 part by mass with respect to 100 parts by mass of the transparent resin layer (transparent resin substrate). It is as follows. When the amount of the residual solvent is within the above range, a transparent resin layer (transparent resin substrate) capable of easily exhibiting a desired function can be obtained, in which deformation of the base material and change in optical characteristics are unlikely to occur.
[誘電体多層膜]
本発明の光学フィルターは、前記基材の少なくとも一方の面に誘電体多層膜を有する。本発明における誘電体多層膜とは、近赤外線を反射する能力を有する膜または可視光領域における反射防止効果を有する膜であり、誘電体多層膜を有することでより優れた可視光透過率と近赤外線カット特性を達成することができる。[Dielectric multilayer film]
The optical filter of the present invention has a dielectric multilayer film on at least one surface of the substrate. The dielectric multilayer film in the present invention is a film having an ability to reflect near infrared rays or a film having an antireflection effect in the visible light region, and having a dielectric multilayer film has a more excellent visible light transmittance. Infrared cut characteristics can be achieved.
本発明では、誘電体多層膜は前記基材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、反りやねじれが生じにくい光学フィルターを得ることができる。光学フィルターを固体撮像素子用途に適用する場合、光学フィルターの反りやねじれが小さい方が好ましいことから、誘電体多層膜を樹脂製基板の両面に設けることが好ましい。 In the present invention, the dielectric multilayer film may be provided on one side of the base material or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter which has high strength and is less likely to warp or twist. When the optical filter is applied to a solid-state image sensor application, it is preferable that the optical filter has a small warp or twist. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the resin substrate.
前記誘電体多層膜は、好ましくは波長700〜1100nm、より好ましくは波長700〜1150nm、さらに好ましくは700〜1200nmの範囲全体にわたって反射特性を有することが望ましい。 It is desirable that the dielectric multilayer film preferably has a reflection property over a wavelength range of 700 to 1100 nm, more preferably a wavelength of 700 to 1150 nm, and even more preferably 700 to 1200 nm.
基材の両面に誘電体多層膜を有する形態として、光学フィルターの垂直方向に対して5°の角度から測定した場合に、主に波長700〜950nm付近に反射特性を有する第一光学層を基材の片面に有し、主に900nm〜1150nm付近に反射特性を有する第二光学層を基材の他方の面上に有する形態(図1(a)参照)や、光学フィルターの垂直方向に対して5°の角度から測定した場合に、主に波長700〜1150nm付近に反射特性を有する第三光学層を基材の片面に有し、可視光領域の反射防止特性を有する第四光学層を基材の他方の面上に有する形態(図1(b)参照)などが挙げられる。 As a form having dielectric multilayer films on both sides of the base material, it is based on the first optical layer having reflection characteristics mainly in the vicinity of a wavelength of 700 to 950 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter. With respect to the form in which the second optical layer having one side of the material and having the reflection characteristics mainly in the vicinity of 900 nm to 1150 nm is provided on the other side of the base material (see FIG. 1A) and the vertical direction of the optical filter. When measured from an angle of 5 °, a third optical layer having reflection characteristics mainly in the vicinity of a wavelength of 700 to 1150 nm is provided on one side of the base material, and a fourth optical layer having antireflection characteristics in the visible light region is provided. Examples thereof include a form having the base material on the other surface (see FIG. 1B).
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100質量部に対して0〜10質量部)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 laminated. 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 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10 parts by mass with respect to 100 parts by mass of the main component) can be 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 the 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 1.2 to 1.6 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride.
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限定はない。例えば、基材上に、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 dielectric in which high refractive index material layers and low refractive index material layers are alternately laminated directly on a base material by a CVD method, a sputtering method, a vacuum vapor deposition method, an ion-assisted vapor deposition method, an ion plating method, or the like. A 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厚さは、通常、遮断しようとする近赤外線波長をλ(nm)とすると、0.1λ〜0.5λの厚さが好ましい。λ(nm)の値としては、例えば700〜1400nm、好ましくは750〜1300nmである。厚さがこの範囲であると、屈折率(n)と膜厚(d)との積(n×d)がλ/4で算出される光学的膜厚と、高屈折率材料層および低屈折率材料層の各層の厚さとがほぼ同じ値となって、反射・屈折の光学的特性の関係から、特定波長の遮断・透過を容易にコントロールできる傾向にある。 The thickness of each of the high refractive index material layer and the low refractive index material layer is usually preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is in this range, the optical film thickness in which the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4, the high refractive index material layer, and the low refraction The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking / transmitting of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction.
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く、24〜50層であることが特に好ましい。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 layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers as a whole, more preferably 20 to 60 layers, and 24. It is particularly preferable to have ~ 50 layers. When 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 warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.
本発明では、化合物(A)や有機顔料(S)などの近赤外線吸収剤の吸収特性に合わせて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、可視光領域に十分な透過率を確保した上で近赤外線波長域に十分な光線カット特性を有し、且つ、斜め方向から近赤外線が入射した際の反射率を低減することができる。 In the present invention, the material species, the high refractive index material layer and the low refractive index material layer constituting the high refractive index material layer and the low refractive index material layer according to the absorption characteristics of the near infrared absorber such as the compound (A) and the organic pigment (S). By appropriately selecting the thickness of each layer of the refractive index material layer, the order of lamination, and the number of laminations, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible light region. Moreover, the reflectance when near-infrared light is incident from an oblique direction can be reduced.
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、可視光領域の反射防止効果と近赤外線領域の光線カット効果を両立できるようにパラメーターを設定すればよい。上記ソフトの場合、例えば第一光学層の設計にあたっては、波長400〜700nmの目標透過率を100%、Target Toleranceの値を1とした上で、波長705〜950nmの目標透過率を0%、Target Toleranceの値を0.5にするなどのパラメーター設定方法が挙げられる。これらのパラメーターは基材(i)の各種特性などに合わせて波長範囲をさらに細かく区切ってTarget Toleranceの値を変えることもできる。 Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Ethential Macleod, manufactured by Thin Film Center) is used to achieve both an antireflection effect in the visible light region and a light ray cutting effect in the near infrared region. You can set the parameters so that you can. In the case of the above software, for example, when designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the value of Target Tolerance is set to 1, and the target transmittance at a wavelength of 705 to 950 nm is set to 0%. Parameter setting methods such as setting the value of Target Tolerance to 0.5 can be mentioned. These parameters can also change the value of Target Tolerance by further dividing the wavelength range according to various characteristics of the base material (i) and the like.
[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、基材と誘電体多層膜との間、基材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が設けられた面と反対側の面に、基材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]
The optical filter of the present invention has a surface between the base material and the dielectric multilayer film, a surface opposite to the surface on which the dielectric multilayer film is provided, or a dielectric multilayer film, as long as the effects of the present invention are not impaired. Antireflection film, hard, for the purpose of improving the surface hardness of the base material and the dielectric multilayer film, improving chemical resistance, antistatic and scratch erasing on the surface opposite to the surface on which the base material of the film is provided. A functional film such as a coat film or an antistatic film can be appropriately provided.
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 contain one layer made of the functional film, or may contain two or more layers. When the optical filter of the present invention contains two or more layers made of the functional film, it may contain 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、特に限定されないが、反射防止剤、ハードコート剤および/または帯電防止剤等を含むコーティング剤を基材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 for laminating the functional film is not particularly limited, but a coating agent containing an antireflection agent, a hard coating agent and / or an antistatic agent and the like is melt-molded or cast on a base material or a dielectric multilayer film in the same manner as described above. Examples thereof include a molding method.
また、前記コーティング剤をバーコーター等で基材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。 It can also be produced by applying the coating agent on a base material or a dielectric multilayer film with a bar coater or the like and then curing the coating agent by irradiation with ultraviolet rays 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を含む硬化性組成物などが挙げられる。前記硬化性組成物に含まれる硬化性樹脂としては、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。 Examples of the coating agent include a curable composition containing an ultraviolet (UV) / electron beam (EB) curable resin and a thermosetting resin. Specific examples of the curable resin contained in the curable composition include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based resins.
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。 In addition, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.
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質量部とした場合、好ましくは0.1〜10質量部、より好ましくは0.5〜10質量部、さらに好ましくは1〜5質量部である。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。 The proportion of the polymerization initiator in the curable composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, when the total amount of the curable composition is 100 parts by mass. More preferably, it is 1 to 5 parts by mass. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflection film, a hard coat film or an antistatic film which has excellent curing properties and handleability of the curable composition and has 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。 Further, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone and 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 thereof 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。 These solvents may be used alone or in combination of two or more.
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。 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、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 and the functional film and / or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, a corona is formed on the surface of the base material, the functional film or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment may be performed.
[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、優れた近赤外線カット能等を有する。したがって、カメラモジュールのCCDやCMOSイメージセンサー等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、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。さらに、自動車や建物等のガラス板等に装着される熱線カットフィルターなどとしても有用である。[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and has excellent near-infrared ray cutting ability. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor such as a CCD or CMOS image sensor of a camera module. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, televisions, car navigation systems, mobile information terminals, video game machines, portable game machines. , Fingerprint authentication system, digital music player, etc. Further, it is also useful as a heat ray cut filter or the like attached to a glass plate or the like of an automobile or a building.
[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、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 image sensor]
The solid-state image sensor of the present invention includes the optical filter of the present invention. Here, the solid-state image sensor is an image sensor provided with a solid-state image sensor such as a CCD or CMOS image sensor, and specifically, a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, or a digital camera. It can be used for applications such as video cameras. For example, the camera module of the present invention comprises 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「質量部」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。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, "part" means "mass part" unless otherwise specified. The method for measuring each physical property value and the method for evaluating 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。
(a)ウォターズ(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:東ソー社製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質量平均分子量(Mw)および数平均分子量(Mn)を測定した。
(b)東ソー社製GPC装置(HLC−8220型、カラム:TSKgelα‐M、展開溶剤:THF)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。<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 and the like.
(A) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, mass average molecular weight in terms of standard polystyrene. (Mw) and number average molecular weight (Mn) were measured.
(B) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured.
<ガラス転移温度(Tg)>
エスアイアイ・ナノテクノロジーズ株式会社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 Co., Ltd., the temperature was measured at a heating rate of 20 ° C. per minute under a nitrogen stream.
<平均粒子径>
有機顔料の平均粒子径は以下の方法で測定した。調製した有機顔料の分散液を分散媒と同一組成の溶剤で顔料濃度が0.5質量%となるまで希釈し、これをガラス板に滴下して乾燥した後、走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製「S4800」)にて観察を行った。複数の視野でSEM画像を撮り、任意で選択した100個の粒子について粒子径をスケールで測定して倍率換算し、平均粒子径を算出した。なお、極端に大きい又は小さい粒子は除外し、粒子形状が球状では無い場合には観察される最も長い径(長径)を粒子径とした。<Average particle size>
The average particle size of the organic pigment was measured by the following method. The prepared dispersion of organic pigment is diluted with a solvent having the same composition as the dispersion medium until the pigment concentration becomes 0.5% by mass, and this is dropped onto a glass plate to dry, and then a scanning electron microscope (SEM) (SEM) ( Observation was performed at "S4800" manufactured by Hitachi High-Technologies Corporation. SEM images were taken from a plurality of fields of view, and the particle size of 100 arbitrarily selected particles was measured on a scale and converted into magnifications to calculate the average particle size. In addition, extremely large or small particles were excluded, and when the particle shape was not spherical, the longest diameter (major diameter) observed was defined as the particle diameter.
<分光透過率>
基材および光学フィルターの各波長域における透過率は、株式会社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。なお、この透過率は、光が基材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。<Spectroscopic transmittance>
The transmittance of the base material and the optical filter in each wavelength range was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation. This transmittance was measured using the spectrophotometer under the condition that the light is vertically incident on the base material and the filter.
<ヘイズ>
基材および光学フィルターのヘイズは、株式会社東洋精機製作所製ヘイズメーター(ヘイズガードII)を用いて測定した。異なる3か所について測定を行い、その平均値を用いた。<Haze>
The haze of the base material and the optical filter was measured using a haze meter (Haze Guard II) manufactured by Toyo Seiki Seisakusho Co., Ltd. Measurements were made at three different locations, and the average value was used.
<耐熱性>
光学フィルターを85℃×1000hrの条件で処理し、該処理前後の波長430〜580nmにおける平均透過率を測定した。次式により算出される透過率の維持率を耐熱性の指標とした。維持率の数値が高い程、耐熱性が良好である。
透過率の維持率(%)=(処理後の430〜580nm平均透過率)/(処理前の430〜580nm平均透過率)×100<Heat resistance>
The optical filter was treated under the condition of 85 ° C. × 1000 hr, and the average transmittance at a wavelength of 430 to 580 nm before and after the treatment was measured. The maintenance rate of transmittance calculated by the following formula was used as an index of heat resistance. The higher the maintenance rate value, the better the heat resistance.
Maintainability of transmittance (%) = (average transmittance of 430 to 580 nm after treatment) / (average transmittance of 430 to 580 nm before treatment) × 100
<カメラ画像の色シェーディング評価>
光学フィルターをカメラモジュールに組み込んだ際の色シェーディング評価は下記の方法で行った。特開2016−110067号公報と同様の方法でカメラモジュールを作成し、作成したカメラモジュールを用いて300mm×400mmサイズの白色板をD65光源(X−Rite社製標準光源装置「マクベスジャッジII」)下で撮影し、カメラ画像における白色板の中央部と端部における色目の違いを以下の基準で評価した。<Color shading evaluation of camera image>
The color shading evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and a white plate having a size of 300 mm × 400 mm is used as a D65 light source (standard light source device “Macbeth Judge II” manufactured by X-Rite). The image was taken below, and the difference in color between the center and the edge of the white plate in the camera image was evaluated according to the following criteria.
全く問題がなく許容可能なレベルをA、若干色目の違いは認められるが高画質カメラモジュールとして実用上問題がなく許容可能なレベルをB、色目の違いが有り高画質カメラモジュール用途としては許容不可能なレベルをC、明らかな色目の違いが有り一般的なカメラモジュール用途としても許容不可能なレベルをDと判定した。 There is no problem at all and the acceptable level is A, there is a slight difference in color, but there is no practical problem as a high-quality camera module, and the acceptable level is B. There is a difference in color and it is not acceptable for high-quality camera module applications. The possible level was determined to be C, and the level that was unacceptable for general camera module applications due to a clear difference in color was determined to be D.
なお、図3に示すように、撮影を行う際はカメラ画像111の中で白色板112が面積の90%以上を占めるように白色板112とカメラモジュールの位置関係を調節した。
As shown in FIG. 3, when shooting, the positional relationship between the
<カメラ画像のゴースト評価>
光学フィルターをカメラモジュールに組み込んだ際のゴースト評価は下記の方法で行った。特開2016−110067号公報と同様の方法でカメラモジュールを作成し、作成したカメラモジュールを用いて暗室中ハロゲンランプ光源(林時計工業社製「ルミナーエースLA−150TX」)下で撮影し、カメラ画像における光源周辺のゴースト発生具合を以下の基準で評価した。<Ghost evaluation of camera image>
The ghost evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and the camera module is used to take a picture under a halogen lamp light source in a dark room (“Luminer Ace LA-150TX” manufactured by Hayashi Clock Industry Co., Ltd.). The degree of ghost generation around the light source in the image was evaluated according to the following criteria.
全く問題がなく許容可能なレベルをA、若干のゴーストは認められるが高画質カメラモジュールとして実用上問題がなく許容可能なレベルをB、ゴーストが発生しており高画質カメラモジュール用途としては許容不可能なレベルをC、ゴーストの度合いがひどく一般的なカメラモジュール用途としても許容不可能なレベルをDと判定した。 There is no problem at all and the acceptable level is A, some ghosts are recognized, but there is no practical problem as a high-quality camera module and the acceptable level is B, ghosts are generated and it is unacceptable for high-quality camera module applications. The possible level was determined to be C, and the level that was unacceptable for general camera module applications with a severe degree of ghost was determined to be D.
なお、図4に示すように、撮影を行う際は、光源122がカメラ画像121の右上端部となるように調節した。
As shown in FIG. 4, the
[合成例]
下記実施例で用いた化合物(A)および化合物(S)は、一般的に知られている方法で合成した。前記方法としては、例えば、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、「フタロシアニン −化学と機能―」(アイピーシー、1997年)、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挙げることができる。[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. Examples of the method include JP-A-60-228448, JP-A-1-146846, JP-A-1-228960, Patent No. 4081149, "Parthalocyanine-Chemistry and Function-" (IPC, 1997), Japanese Patent Application Laid-Open No. 2009-108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like can be mentioned.
<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(以下「DNM」ともいう。)100g、1−ヘキセン(分子量調節剤)18gおよびトルエン(開環重合反応用溶媒)300g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(0.6mol/リットル)0.2g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)0.9g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。<Synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 2,5 . 1 7,10 ] 100 g of dodeca-3-ene (hereinafter also referred to as “DNM”), 18 g of 1-hexene (molecular weight modifier) and 300 g of toluene (solvent for ring-opening polymerization reaction) are charged in a nitrogen-substituted reaction vessel. , This solution was heated to 80 ° C. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / liter) and 0.9 g of a methanol-modified tungsten hexachloride toluene solution (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. 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%.
<合成例2>
攪拌装置、温度計およびコンデンサーを備えた反応容器に、室温にて2,6−ジ−t−ブチル−4−クレゾール0.0194g、3−ヒドロキシ−1−アダマンチルアクリレート(三菱ガス化学(株)製、分子量:222)27.047g、および、イソホロンジイソシアネート(エボニック社製、分子量:222)26.481gをメチルエチルケトン(MEK)19gに溶解させ、ジオクチルスズジラウレート0.405gを加えた後、撹拌しながら70℃に昇温した。3−ヒドロキシ−1−アダマンチルアクリレートが溶解し、溶液が透明化したことを確認した後、3−ヒドロキシ−1−アダマンチルアクリレート27.047gを追加投入し、70℃にて反応を継続した。赤外吸収スペクトルでイソシアネート基の吸収スペクトル(2280cm-1)がほぼ消失したことを確認して反応を終了した。溶出液として酢酸エチル/ヘキサンを用いたシリカゲルカラムクロマトグラフィーにて反応混合物を精製した後、イソプロピルアルコールで希釈することで、ウレタンアクリレート化合物(I)(50質量%溶液)を得た。<Synthesis example 2>
In a reaction vessel equipped with a stirrer, thermometer and condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol at room temperature, 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.) , Molecular weight: 222) 27.047 g, and Isophorone diisocyanate (manufactured by Ebonic, molecular weight: 222) 26.481 g are dissolved in 19 g of methyl ethyl ketone (MEK), 0.405 g of dioctyltin dilaurate is added, and then 70 with stirring. The temperature was raised to ° C. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was additionally added, and the reaction was continued at 70 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm -1) had almost disappeared from the infrared absorption spectrum. The reaction mixture was purified by silica gel column chromatography using ethyl acetate / hexane as an eluent, and then diluted with isopropyl alcohol to obtain urethane acrylate compound (I) (50% by mass solution).
[有機顔料の調製例]
<調製例1>
0.25Lのプラスチック容器に、上記表2−4に記載の化合物(s−15)(ジクロロメタン中での吸収極大波長1083nm)5g、酸性官能基を有する分散剤(日油株式会社製「マリアリムSC−0505K」)5g、分散媒としてイソプロピルアルコール(IPA)95g、直径0.05mmのジルコニアビーズ(ニッカトー社製「YTZ−0.05」)175gを投入し、ペイントシェーカー(株式会社東洋精機製作所製)にて1hr分散処理を行った。その後、室温まで冷却し、金属メッシュでジルコニアビーズをろ別することで有機顔料分散液(S−1)を得た。[Example of preparation of organic pigment]
<Preparation Example 1>
Dispersant having 5 g of the compound (s-15) (absorption maximum wavelength 1083 nm in dichloromethane) and an acidic functional group shown in Table 2-4 above in a 0.25 L plastic container (Nikki Co., Ltd. "Marialim SC" -0505K ”), 95 g of isopropyl alcohol (IPA) as a dispersion medium, and 175 g of zirconia beads (“YTZ-0.05” manufactured by Nikkato Corporation) with a diameter of 0.05 mm were added to the paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) 1 hr dispersion processing was performed in. Then, the mixture was cooled to room temperature, and the zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-1).
<調製例2>
0.25Lのプラスチック容器に上記表2−4に記載の化合物(s−15)5g、分散媒としてメチルイソブチルケトン(MIBK)95g、直径0.05mmのジルコニアビーズ(ニッカトー社製「YTZ−0.05」)175gを投入し、ペイントシェーカーにて1hr分散処理を行った。その後、室温まで冷却し、金属メッシュでジルコニアビーズをろ別することで有機顔料分散液(S−2)を得た。<Preparation Example 2>
In a 0.25 L plastic container, 5 g of the compound (s-15) shown in Table 2-4 above, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, and zirconia beads having a diameter of 0.05 mm (Nikkato Corporation "YTZ-0. 05 ") 175 g was added, and 1 hr dispersion treatment was performed with a paint shaker. Then, the mixture was cooled to room temperature, and the zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-2).
<調製例3>
0.25Lのプラスチック容器に上記表2−4に記載の化合物(s−4)(ジクロロメタン中での吸収極大波長1100nm)5g、分散媒としてメチルイソブチルケトン(MIBK)95g、直径0.05mmのジルコニアビーズ(ニッカトー社製「YTZ−0.05」)175gを投入し、ペイントシェーカーにて1hr分散処理を行った。その後、室温まで冷却し、金属メッシュでジルコニアビーズをろ別することで有機顔料分散液(S−3)を得た。<Preparation Example 3>
5 g of the compound (s-4) (absorption maximum wavelength in dichloromethane, 1100 nm) shown in Table 2-4 above, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, and zirconia having a diameter of 0.05 mm in a 0.25 L plastic container. 175 g of beads (“YTZ-0.05” manufactured by Nikkato Corporation) were added and subjected to 1 hr dispersion treatment with a paint shaker. Then, the mixture was cooled to room temperature, and the zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-3).
<調製例4>
0.25Lのプラスチック容器に上記表2−4に記載の化合物(s−6)(ジクロロメタン中での吸収極大波長1093nm)5g、分散媒としてメチルイソブチルケトン(MIBK)95g、直径0.05mmのジルコニアビーズ(ニッカトー社製「YTZ−0.05」)175gを投入し、ペイントシェーカーにて1hr分散処理を行った。その後、室温まで冷却し、金属メッシュでジルコニアビーズをろ別することで有機顔料分散液(S−4)を得た。<Preparation Example 4>
5 g of the compound (s-6) (absorption maximum wavelength in dichloromethane, 1093 nm) shown in Table 2-4 above, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, and zirconia having a diameter of 0.05 mm in a 0.25 L plastic container. 175 g of beads (“YTZ-0.05” manufactured by Nikkato Corporation) were added and subjected to 1 hr dispersion treatment with a paint shaker. Then, the mixture was cooled to room temperature, and the zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-4).
<調製例5>
調製例1で得た有機顔料分散液(S−1)を遠心分離装置(himac製「冷却遠心機 CR−22N」)にて36000Gの遠心加速度で10分間、遠心分離処理し、処理後の分散液をポリプロピレン製フィルター(孔径3μm)にて濾過することで、有機顔料分散液(S−5)を得た。<Preparation Example 5>
The organic pigment dispersion (S-1) obtained in Preparation Example 1 was centrifuged in a centrifuge (“Cool Centrifuge CR-22N” manufactured by himac) at a centrifugal acceleration of 36000 G for 10 minutes, and dispersed after the treatment. The liquid was filtered through a polypropylene filter (pore diameter 3 μm) to obtain an organic pigment dispersion liquid (S-5).
[実施例1]
実施例1では、化合物(A)を含む透明樹脂製基板の両面に有機顔料(S)を含む透明樹脂層を形成して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 substrate having a transparent resin layer containing an organic pigment (S) formed on both sides of a transparent resin substrate containing the compound (A) was prepared by the following procedure and conditions.
容器に、合成例1で得られた樹脂A 100g、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713nm)0.07g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736nm)0.06gおよび塩化メチレンを加えて樹脂濃度が20質量%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の透明樹脂製基板を得た。 In a container, 100 g of the resin A obtained in Synthesis Example 1, 0.07 g of the compound (a-1) represented by the following formula (a-1) as the compound (A) (absorption maximum wavelength in dichloromethane, 713 nm) and the following A solution having a resin concentration of 20% by mass was prepared by adding 0.06 g of the compound (a-2) represented by the formula (a-2) (absorption maximum wavelength in dichloromethane, 736 nm) and methylene chloride. 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 under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
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3分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが3μm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透明樹脂層を形成した。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)からなる透明樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に有機顔料(S)を含む透明樹脂層を有する基材を得た。
The 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 3 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 3 μm. Next, using a conveyer-type exposure apparatus performs exposure (
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100g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例1で得られた顔料分散液(S−1)50g(有機顔料(S)換算で2.5g)、イソプロピルアルコール117g。 Resin composition (1): 100 g of tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of the pigment dispersion (S-1) obtained in Preparation Example 1 (2.5 g in terms of organic pigment (S)). ), 117 g of isopropyl alcohol.
続いて、得られた基材の片面に第一光学層として誘電体多層膜(I)を形成し、さらに基材のもう一方の面に第二光学層として誘電体多層膜(II)を形成し、厚さ約0.105mmの光学フィルターを得た。 Subsequently, a dielectric multilayer film (I) is formed as a first optical layer on one surface of the obtained substrate, and a dielectric multilayer film (II) is formed as a second optical layer on the other surface of the substrate. An optical filter having a thickness of about 0.105 mm was obtained.
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26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20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。 The dielectric multilayer film (I) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a vapor deposition temperature of 100 ° C. (26 layers in total). The dielectric multilayer film (II) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a vapor deposition temperature of 100 ° C. (20 layers in total). In both the dielectric multilayer films (I) and (II), the silica layer and the titania layer are formed in the 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 layers were alternately laminated, and 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、可視光領域の反射防止効果と近赤外線領域の選択的な透過・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、適用した有機顔料(S)および化合物(A)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3の通りとした。The design of the dielectric multilayer films (I) and (II) was performed as follows.
Regarding the thickness and number of layers of each layer, the wavelength-dependent characteristics of the refractive index of the base material and the applied organic pigment (S) and the organic pigment (S) so as to achieve the antireflection effect in the visible light region and the selective transmission / reflection performance in the near infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the absorption characteristics of the compound (A). When optimizing, the input parameters (Target values) to the software in this example are as shown in Table 3 below.
また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を表5に示す。得られたカメラ画像はシェーディングおよびゴーストにおいて良好な結果であった。 In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5. The camera images obtained gave good results in shading and ghosting.
[実施例2]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(2)を用いたこと以外は実施例1と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 2]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (2) shown below was used instead of the resin composition (1). The results are shown in Table 5.
樹脂組成物(2):合成例2で得られたウレタンアクリレート化合物(1)50g(固形分換算)、トリシクロデカンジメタノールアクリレート50g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例1で得られた顔料分散液(S−1)50g(有機顔料(S)換算で2.5g)、イソプロピルアルコール117g。 Resin composition (2): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), tricyclodecanedimethanol acrylate 50 g, 1-hydroxycyclohexylphenyl ketone 3 g, obtained in Preparation Example 1. Pigment dispersion (S-1) 50 g (2.5 g in terms of organic pigment (S)), isopropyl alcohol 117 g.
[実施例3]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(3)を用いたこと以外は実施例1と同様にして光学フィルターを得て、同様の評価を行った。結果を表5に示す。[Example 3]
An optical filter was obtained in the same manner as in Example 1 except that the resin composition (3) shown below was used instead of the resin composition (1), and the same evaluation was performed. The results are shown in Table 5.
樹脂組成物(3):合成例2で得られたウレタンアクリレート化合物(1)50g(固形分換算)、3−ヒドロキシ−1−アダマンチルアクリレート30g、トリシクロデカンジメタノールアクリレート20g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例1で得られた顔料分散液(S−1)50g(有機顔料(S)換算で2.5g)、イソプロピルアルコール117g。 Resin composition (3): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 50 g of the pigment dispersion (S-1) obtained in Preparation Example 1 (2.5 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.
[実施例4]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(4)を用いたこと以外は実施例1と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 4]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (4) shown below was used instead of the resin composition (1). The results are shown in Table 5.
樹脂組成物(4):トリシクロデカンジメタノールアクリレート100g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例2で得られた顔料分散液(S−2)50g(有機顔料(S)換算で2.5g)、メチルイソブチルケトン117g。 Resin composition (4): 100 g of tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of the pigment dispersion (S-2) obtained in Preparation Example 2 (2.5 g in terms of organic pigment (S)). ), Methyl isobutyl ketone 117 g.
[実施例5]
透明樹脂基板の代わりにガラス基板(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150μm)」(日本電気硝子(株)製)を用い、樹脂組成物(1)の代わりに下記に示す樹脂組成物(5)を用いたこと以外は実施例1と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 5]
Instead of the transparent resin substrate, a glass substrate (transparent glass substrate "OA-10G (thickness 150 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width is used, and the resin composition (1) An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (5) shown below was used instead of the above. The results are shown in Table 5.
樹脂組成物(5):トリシクロデカンジメタノールアクリレート100g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例2で得られた顔料分散液(S−2)50g(有機顔料(S)換算で2.5g)、化合物(a−1)0.5g、化合物(a−2)0.4g、メチルイソブチルケトン112g。 Resin composition (5): 100 g of tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of the pigment dispersion (S-2) obtained in Preparation Example 2 (2.5 g in terms of organic pigment (S)). ), Compound (a-1) 0.5 g, compound (a-2) 0.4 g, methyl isobutyl ketone 112 g.
[実施例6]
ガラス基板の代わりに縦60mm、横60mmの大きさにカットした透明樹脂フィルム(ゼオノアフィルムZF16(厚み100μm)」(日本ゼオン(株)製)を用いたこと以外は実施例5と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 6]
Optical in the same manner as in Example 5 except that a transparent resin film (Zeonoa film ZF16 (
[実施例7]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(6)を用いたこと以外は実施例3と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 7]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (6) shown below was used instead of the resin composition (1). The results are shown in Table 5.
樹脂組成物(6):合成例2で得られたウレタンアクリレート化合物(1)50g(固形分換算)、3−ヒドロキシ−1−アダマンチルアクリレート30g、トリシクロデカンジメタノールアクリレート20g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例3で得られた顔料分散液(S−3)56g(有機顔料(S)換算で2.8g)、イソプロピルアルコール117g。 Resin composition (6): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 56 g of the pigment dispersion (S-3) obtained in Preparation Example 3 (2.8 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.
[実施例8]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(7)を用いたこと以外は実施例3と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 8]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (7) shown below was used instead of the resin composition (1). The results are shown in Table 5.
樹脂組成物(7):合成例2で得られたウレタンアクリレート化合物(1)50g(固形分換算)、3−ヒドロキシ−1−アダマンチルアクリレート30g、トリシクロデカンジメタノールアクリレート20g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例4で得られた顔料分散液(S−4)52g(有機顔料(S)換算で2.6g)、イソプロピルアルコール117g。 Resin composition (7): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 52 g of the pigment dispersion (S-4) obtained in Preparation Example 4 (2.6 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.
[実施例9]
樹脂組成物(1)の代わりに下記に示す樹脂組成物(8)を用いたこと以外は実施例3と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Example 9]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (8) shown below was used instead of the resin composition (1). The results are shown in Table 5.
樹脂組成物(8):合成例2で得られたウレタンアクリレート化合物(1)50g(固形分換算)、3−ヒドロキシ−1−アダマンチルアクリレート30g、トリシクロデカンジメタノールアクリレート20g、1−ヒドロキシシクロヘキシルフェニルケトン3g、調製例5で得られた顔料分散液(S−5)50g(有機顔料(S)換算で2.5g)、イソプロピルアルコール117g。 Resin composition (8): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 50 g of the pigment dispersion (S-5) obtained in Preparation Example 5 (2.5 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.
[比較例1]
容器に、合成例1で得られた樹脂A 100部、化合物(A)として上記化合物(a−1)(ジクロロメタン中での吸収極大波長713nm)0.07gおよび上記化合物(a−2)(ジクロロメタン中での吸収極大波長736nm)0.06g、および上記表2−2に記載の化合物(s−6)(ジクロロメタン中での吸収極大波長1093nm)0.2gおよび塩化メチレンを加えて樹脂濃度が20質量%の溶液を調製した。なお、化合物(s−6)は塩化メチレンに溶解して染料化していた。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の透明樹脂製基板を得た。[Comparative Example 1]
In a container, 100 parts of the resin A obtained in Synthesis Example 1, 0.07 g of the above compound (a-1) (absorption maximum wavelength 713 nm in dichloromethane) and the above compound (a-2) (dichloromethane) as the compound (A). 0.06 g of absorption maximum wavelength 736 nm, 0.2 g of the compound (s-6) (absorption maximum wavelength 1093 nm in dichloromethane) and methylene chloride shown in Table 2-2 above were added to bring the resin concentration to 20. A mass% solution was prepared. The compound (s-6) was dissolved in methylene chloride and dyed. 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 under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
得られた透明樹脂製基板を用い、かつ、樹脂組成物(1)の代わりに下記に示す樹脂組成物(6)を用いたこと以外は実施例1と同様にして光学フィルターを得て評価を行った。結果を表5に示す。 An optical filter was obtained and evaluated in the same manner as in Example 1 except that the obtained transparent resin substrate was used and the resin composition (6) shown below was used instead of the resin composition (1). went. The results are shown in Table 5.
樹脂組成物(6):トリシクロデカンジメタノールアクリレート100g、1−ヒドロキシシクロヘキシルフェニルケトン3g、メチルエチルケトン154.5g。 Resin composition (6): Tricyclodecanedimethanol acrylate 100 g, 1-hydroxycyclohexylphenyl ketone 3 g, methyl ethyl ketone 154.5 g.
[比較例2]
樹脂組成物(5)の代わりに下記に示す樹脂組成物(7)を用いたこと以外は実施例5と同様にして光学フィルターを得て評価を行った。なお、化合物(s−15)は塩化メチレンに溶解して染料化していた。結果を表5に示す。[Comparative Example 2]
An optical filter was obtained and evaluated in the same manner as in Example 5 except that the resin composition (7) shown below was used instead of the resin composition (5). The compound (s-15) was dissolved in methylene chloride and dyed. The results are shown in Table 5.
樹脂組成物(7):トリシクロデカンジメタノールアクリレート100g、1−ヒドロキシシクロヘキシルフェニルケトン3g、化合物(s−15)2.5g、化合物(a−1)0.5g、化合物(a−2)0.4g、塩化メチレン155g。 Resin composition (7): tricyclodecanedimethanol acrylate 100 g, 1-hydroxycyclohexylphenyl ketone 3 g, compound (s-15) 2.5 g, compound (a-1) 0.5 g, compound (a-2) 0 .4 g, methylene chloride 155 g.
[比較例3〜4]
表5に示す構成としたこと以外は、実施例1と同様にして光学フィルターを得て評価を行った。結果を表5に示す。[Comparative Examples 3 to 4]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the configurations shown in Table 5 were adopted. The results are shown in Table 5.
<基材の形態>
形態(1):化合物(A)を含む透明樹脂製基板の両面に有機顔料(S)を含む透明樹脂層を有する
形態(2):透明ガラス基板(日本電気硝子(株)製「OA−10G(厚み150μm)」)の両面に有機顔料(S)を含む透明樹脂層を有する
形態(3):樹脂製支持体(日本ゼオン(株)製「ゼオノアフィルムZF16」)の両面に化合物(A)および有機顔料(S)を含む透明樹脂層を有する
形態(4):樹脂製支持体の両面に有機顔料(S)を含む透明樹脂層を有する
形態(5):化合物(A)および化合物(S)を含む透明樹脂製基板の両面に樹脂層を有する
形態(6):透明ガラス基板の両面に化合物(S)を含む透明樹脂層を有する
形態(7):化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する<Form of base material>
Form (1): A transparent resin substrate containing the compound (A) has a transparent resin layer containing an organic pigment (S) on both sides. Form (2): A transparent glass substrate ("OA-10G" manufactured by Nippon Electric Glass Co., Ltd.) (Thickness 150 μm) ”) with a transparent resin layer containing an organic pigment (S) on both sides Form (3): Compound (A) on both sides of a resin support (“Zeonoa Film ZF16” manufactured by Nippon Zeon Co., Ltd.) And having a transparent resin layer containing the organic pigment (S) (4): Having a transparent resin layer containing the organic pigment (S) on both sides of the resin support (5): Compound (A) and compound (S) ) Is provided on both sides of the transparent resin substrate (6): The transparent glass substrate is provided with the transparent resin layer containing the compound (S) on both sides (7): Made of transparent resin containing the compound (A) Has resin layers on both sides of the substrate
<透明樹脂>
樹脂A:環状ポリオレフィン系樹脂(樹脂合成例1)
モノマーA:トリシクロデカンジメタノールアクリレート
モノマーB:合成例2で得られたウレタンアクリレート化合物(1)
モノマーC:3−ヒドロキシ−1−アダマンチルアクリレート<Transparent resin>
Resin A: Cyclic polyolefin resin (resin synthesis example 1)
Monomer A: Tricyclodecanedimethanol acrylate Monomer B: Urethane acrylate compound obtained in Synthesis Example 2 (1)
Monomer C: 3-Hydroxy-1-adamantyl acrylate
<希釈溶媒>
希釈溶媒(1):イソプロピルアルコール
希釈溶媒(2):メチルイソブチルケトン
希釈溶媒(3):メチルエチルケトン
希釈溶媒(4):塩化メチレン<Diluting solvent>
Diluting solvent (1): Isopropyl alcohol Diluting solvent (2): Methyl isobutyl ketone Diluting solvent (3): Methyl ethyl ketone Diluting solvent (4): Methylene chloride
10:基材
11:第一光学層
12:第二光学層
13:第三光学層
14:第四光学層
111:カメラ画像
112:白色板
113:白色板の中央部の例
114:白色板の端部の例
121:カメラ画像
122:光源
123:光源周辺のゴーストの例10: Base material 11: First optical layer 12: Second optical layer 13: Third optical layer 14: Fourth optical layer 111: Camera image 112: White plate 113: Example of central portion of white plate 114: White plate Example of edge 121: Camera image 122: Light source 123: Example of ghost around the light source
Claims (11)
(a)波長900nm以上1200nm以下の領域に吸収極大を有する有機顔料(S)を含む層を有する。An optical filter having a base material satisfying the following requirement (a) and having a dielectric multilayer film formed on at least one surface of the base material:
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a region having a wavelength of 900 nm or more and 1200 nm or less.
(b)波長650nm以上760nm以下の領域に吸収極大を有する化合物(A)を含む層を有する。The optical filter according to claim 1, wherein the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength of 650 nm or more and 760 nm or less.
R1は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、−SRi基、−SO2Ri基、−OSO2Ri基または下記La〜Lhのいずれかを表し、R2は、独立にハロゲン原子、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、−SRi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2〜14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種であり、
nは0〜4の整数を表し、
Xは電荷を中和させるのに必要なアニオンを表す。)The optical filter according to any one of claims 1 to 3, wherein the organic pigment (S) contains a diimonium-based compound represented by the following formula (I).
R 1 is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphoric acid group, -SR i group, -SO 2 R i groups, -OSO 2 R i group or a group represented by L a ~ Represents any of L h , R 2 is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR g R h group, -SR i group, -SO 2 It represents any of R i group, -OSO 2 R i group or L a to L h below, and R g and R h are independently hydrogen atom, -C (O) R i group or L a to L below, respectively. represents either e, R i represents any of the following L a ~L e,
(L a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L d) carbon Aromatic hydrocarbon group of number 6 to 14 (L e ) Heterocyclic group having 2 to 14 carbon atoms (L f ) An alkoxy group having 1 to 12 carbon atoms (L g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, 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. Yes,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge. )
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018032979 | 2018-02-27 | ||
JP2018032979 | 2018-02-27 | ||
PCT/JP2019/007035 WO2019167876A1 (en) | 2018-02-27 | 2019-02-25 | Optical filter and device using optical filter |
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- 2019-02-25 JP JP2020503489A patent/JP7207395B2/en active Active
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JP7207395B2 (en) | 2023-01-18 |
TW201945179A (en) | 2019-12-01 |
WO2019167876A1 (en) | 2019-09-06 |
KR20200125604A (en) | 2020-11-04 |
CN111684320B (en) | 2023-03-31 |
CN111684320A (en) | 2020-09-18 |
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