TW201518421A - Optical filter, solid imaging apparatus, camera module and resin composition - Google Patents
Optical filter, solid imaging apparatus, camera module and resin composition Download PDFInfo
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- TW201518421A TW201518421A TW103128426A TW103128426A TW201518421A TW 201518421 A TW201518421 A TW 201518421A TW 103128426 A TW103128426 A TW 103128426A TW 103128426 A TW103128426 A TW 103128426A TW 201518421 A TW201518421 A TW 201518421A
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- 229910018179 Al—F Inorganic materials 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
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- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- CMJCEVKJYRZMIA-UHFFFAOYSA-M thallium(i) iodide Chemical compound [Tl]I CMJCEVKJYRZMIA-UHFFFAOYSA-M 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical class Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- 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
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明是有關於一種濾光器及使用濾光器的裝置。詳細而言是有關於一種包含特定的溶劑可溶型的色素化合物的濾光器,以及使用該濾光器的固體攝像裝置及照相機模組。 The present invention relates to a filter and a device using the same. More specifically, it relates to a filter including a specific solvent-soluble pigment compound, and a solid-state imaging device and a camera module using the same.
於攝影機(video camera)、數位靜態照相機(digital still camera)、帶有照相機功能的行動電話等固體攝像裝置中,使用作為彩色圖像的固體攝像元件的電荷耦合元件(Charge-Coupled Device,CCD)或互補式金屬氧化物半導體(Complementary Metal-Oxide-Semiconductor,CMOS)影像感測器,該些固體攝像元件於其受光部中使用對人眼所無法感知的近紅外線具有感度的矽光電二極體(silicon photodiode)。對於該些固體攝像元件而言,必須進行視感度修正以使人眼看起來色調自然,大多情況下使用選擇性地透射或截止特定的波長範圍的光線的濾光器(例如近紅外線截止濾波器)。 A charge-coupling device (CCD) that uses a solid-state imaging device as a color image in a solid-state imaging device such as a video camera, a digital still camera, or a camera-equipped mobile phone. Or a complementary metal-oxide-semiconductor (CMOS) image sensor, wherein the solid-state imaging device uses a germanium photodiode that is sensitive to near-infrared rays that are invisible to the human eye in the light receiving portion thereof. (silicon photodiode). For these solid-state imaging elements, it is necessary to perform visual sensitivity correction so that the human eye looks natural in color, and in many cases, a filter that selectively transmits or cuts light of a specific wavelength range (for example, a near-infrared cut filter) is used. .
作為此種近紅外線截止濾波器,一直以來使用藉由各種方法所製造者。例如已知有一種使用透明樹脂作為基材,且使透 明樹脂中含有近紅外線吸收色素的近紅外線截止濾波器(例如參照專利文獻1),特別是使用酞菁系化合物作為近紅外線吸收色素的近紅外線截止濾波器已廣為人知(例如參照專利文獻2)。 As such a near-infrared cut filter, those manufactured by various methods have been used. For example, it is known to use a transparent resin as a substrate and to make it transparent. A near-infrared cut filter including a near-infrared absorbing dye in a bright resin (see, for example, Patent Document 1), and a near-infrared cut filter using a phthalocyanine-based compound as a near-infrared absorbing dye is widely known (for example, see Patent Document 2).
然而,通常的酞菁系化合物的最大吸收波長多為650nm~小於700nm,若設為可對最大吸收波長進行長波長位移而將其移至特別適合用作固體攝像裝置用途的波長範圍(700nm~800nm)的結構,則存在430nm~460nm附近的短波長側可見透射率顯著降低的問題。 However, the maximum absorption wavelength of a typical phthalocyanine-based compound is usually 650 nm to less than 700 nm, and if it is set to a long wavelength shift of the maximum absorption wavelength, it is moved to a wavelength range particularly suitable for use as a solid-state imaging device (700 nm~ The structure of 800 nm) has a problem that the visible transmittance on the short-wavelength side near 430 nm to 460 nm is remarkably lowered.
作為使酞菁系化合物的最大吸收進行長波長位移的方法,通常已知:將烷氧基或經烷基取代的胺基、烷硫基等供電子性基導入至酞菁環(phthalocyanine ring)的方法(例如參照專利文獻3)。然而,若此種取代基鍵結於酞菁環,則會產生自取代基上的非共有電子對朝酞菁環的電荷轉移躍遷(charge transfer transition),於短波長側可見範圍產生由該躍遷引起的吸收,故430nm~460nm附近的透射率尤其降低。 As a method of shifting the maximum absorption of the phthalocyanine-based compound by a long wavelength, it is generally known to introduce an alkoxy group or an electron-donating group such as an alkyl-substituted amine group or an alkylthio group into a phthalocyanine ring. (for example, refer to Patent Document 3). However, if such a substituent is bonded to the phthalocyanine ring, a charge transfer transition from the non-consensus electron pair on the substituent to the phthalocyanine ring occurs, and the visible range on the short-wavelength side is generated by the transition. The absorption is caused, so the transmittance near 430 nm to 460 nm is particularly lowered.
而且,已知:通常的酞菁系化合物於樹脂中等容易成為環彼此堆積的H締合狀態。若酞菁系化合物產生H締合,則如例如日本專利特開2013-083915號公報(專利文獻4)的實施例1所記載的光譜般,成為最大吸收附近的吸收強度弱的寬波形,存在無法達成固體攝像元件用途所要求的光學特性的情形。 Further, it is known that a general phthalocyanine-based compound easily forms a H-associated state in which the rings are stacked on each other in a resin. When the phthalocyanine-based compound is H-associated, a wide waveform having a weak absorption intensity near the maximum absorption is present as in the spectrum described in Example 1 of JP-A-2013-083915 (Patent Document 4). The optical characteristics required for the use of the solid-state imaging device cannot be achieved.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開平6-200113號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-200113
[專利文獻2]日本專利特開2013-064975號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-064975
[專利文獻3]日本專利第4278923號公報 [Patent Document 3] Japanese Patent No. 4287923
[專利文獻4]日本專利特開2013-083915號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2013-083915
本發明的目的在於提供一種對現有的近紅外線截止濾波器等濾光器所具有的缺點加以改良,近紅外線吸收色素於700nm~750nm附近的波長範圍內具有充分的吸收強度,且於短波長側的可見波長範圍內透射率亦優異的濾光器及使用該濾光器的裝置。 An object of the present invention is to provide an improvement in the disadvantages of a filter such as a conventional near-infrared cut filter, which has sufficient absorption intensity in a wavelength range of around 700 nm to 750 nm and on a short wavelength side. A filter having excellent transmittance in the visible wavelength range and a device using the filter.
本發明者等人為了達成所述課題而進行了潛心研究,結果發現,藉由應用具有特定的結構的酞菁系化合物,可獲得達成目標最大吸收波長及樹脂中的吸收強度、且近紅外線吸收特性及可見透射率優異的濾光器,從而完成了本發明。以下示出本發明的態樣的例子。 The present inventors have conducted intensive studies to achieve the above-mentioned problems, and as a result, it has been found that by applying a phthalocyanine-based compound having a specific structure, it is possible to obtain a target maximum absorption wavelength and an absorption intensity in a resin, and to absorb near-infrared rays. The present invention is completed by a filter having excellent characteristics and visible transmittance. An example of the aspect of the invention is shown below.
[1]一種濾光器,其特徵在於具有:透明樹脂製基板,含有下述式(I)所表示的化合物(A);以及近紅外線反射膜,形成於所述基板的至少一個面上。 [1] A filter comprising: a transparent resin substrate comprising a compound (A) represented by the following formula (I); and a near-infrared reflective film formed on at least one surface of the substrate.
[化1]
式(I)中,M表示2個氫原子、2個一價的金屬原子、二價的金屬原子、或者包含三價或四價的金屬原子的經取代的金屬原子;多個Ra獨立地表示L1,多個Rb獨立地表示氫原子、鹵素原子、L1或-SO2-L2;L1表示下述La、Lb或Lc,L2表示下述La、Lb、Lc、Ld或Le;(La)碳數1~12的脂肪族烴基 In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R a independently It represents L 1, a plurality of R b independently represent a hydrogen atom, a halogen atom, L 1 or -SO 2 -L 2; L 1 represented by the following L a, L b or L c, L 2 represented by the following L a, L b , L c , L d or L e ; (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms
(Lb)碳數1~12的經鹵素取代的烷基 (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms
(Lc)碳數3~14的脂環式烴基 (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms
(Ld)碳數6~14的芳香族烴基 (L d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms
(Le)碳數3~14的雜環基 (L e ) a heterocyclic group having 3 to 14 carbon atoms
所述La~Le亦可更具有選自由碳數1~12的脂肪族烴基、碳數1~12的經鹵素取代的烷基、碳數3~14的脂環式烴基、碳數6~14的芳香族烴基、碳數3~14的雜環基、及碳數1~12的烷氧基所組成的組群中的至少一種取代基L。 The L a ~L e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
[2]如項[1]所記載的濾光器,其中所述式(I)中,M為屬於元素週期表第4族~第12族且第4週期~第5週期的二價 過渡金屬、三價或四價的金屬鹵化物或者四價的金屬氧化物;Ra獨立地為碳數1~10的烷基、碳數1~6的經氟取代的烷基、環戊基或環己基;Rb獨立地為氫原子、氟原子、碳數1~10的烷基、環戊基、環己基或-SO2-L2;L2為碳數1~6的烷基、碳數6~12的芳香族烴基或碳數3~6的雜環基。 [2] The optical filter according to [1], wherein, in the formula (I), M is a divalent transition metal belonging to Group 4 to Group 12 of the periodic table and the fourth to fifth periods a trivalent or tetravalent metal halide or a tetravalent metal oxide; R a is independently an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 6 carbon atoms, a cyclopentyl group or a ring. Hexyl; R b is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group or -SO 2 -L 2 ; and L 2 is an alkyl group having 1 to 6 carbon atoms; 6 to 12 aromatic hydrocarbon groups or 3 to 6 carbon heterocyclic groups.
[3]如項[1]或項[2]所記載的濾光器,其中構成所述透明樹脂製基板的透明樹脂為選自由環狀烯烴系樹脂、芳香族聚醚系樹脂、聚醯亞胺系樹脂、茀聚碳酸酯(fluorene polycarbonate)系樹脂、茀聚酯系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚芳酯系樹脂、聚碸(polysulfone)系樹脂、聚醚碸系樹脂、聚對苯(polyparaphenylene)系樹脂、聚醯胺醯亞胺系樹脂、聚萘二甲酸乙二酯系樹脂、氟化芳香族聚合物系樹脂、(改質)丙烯酸系樹脂、環氧系樹脂、烯丙酯系樹脂及倍半矽氧烷系樹脂所組成的組群中的至少一種樹脂。 [3] The optical filter according to the item [1], wherein the transparent resin constituting the transparent resin substrate is selected from the group consisting of a cyclic olefin resin, an aromatic polyether resin, and a polysiloxane. Amine resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polysulfone resin, polyether oxime Resin, polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy At least one of a group consisting of a resin, an allyl ester resin, and a sesquioxan resin.
[4]如項[1]至項[3]中任一項所記載的濾光器,其中所述近紅外線反射膜形成於所述基板的兩面上。 [4] The optical filter according to any one of [1], wherein the near-infrared reflective film is formed on both surfaces of the substrate.
[5]如項[1]至項[4]中任一項所記載的濾光器,其為固體攝像裝置用。 [5] The optical filter according to any one of [1] to [4], which is for a solid-state imaging device.
[6]一種固體攝像裝置,具備如項[1]至項[5]中任一項所記載的濾光器。 [6] A solid-state imaging device comprising the optical filter according to any one of [1] to [5].
[7]一種照相機模組,具備如項[1]至項[5]中任一項所記載的濾光器。 [7] A camera module comprising the optical filter according to any one of [1] to [5].
[8]一種樹脂組成物,含有下述式(I)所表示的化合物(A),及選自由環狀烯烴系樹脂、芳香族聚醚系樹脂、聚醯亞胺系樹脂、茀聚碳酸酯系樹脂、茀聚酯系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚芳酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚對苯系樹脂、聚醯胺醯亞胺系樹脂、聚萘二甲酸乙二酯系樹脂、氟化芳香族聚合物系樹脂、(改質)丙烯酸系樹脂、環氧系樹脂、烯丙酯系樹脂及倍半矽氧烷系樹脂所組成的組群中的至少一種樹脂。 [8] A resin composition comprising the compound (A) represented by the following formula (I), and a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, and a fluorene polycarbonate. Resin, bismuth polyester resin, polycarbonate resin, polyamido resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine Resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin and sesquiterpene oxide resin At least one resin in the group.
式(I)中,M表示2個氫原子、2個一價的金屬原子、二價的金屬原子、或者包含三價或四價的金屬原子的經取代的金屬原子;多個Ra獨立地表示L1,多個Rb獨立地表示氫原子、鹵素原子、L1或-SO2-L2;L1表示下述La、Lb或Lc,L2表示下述La、Lb、Lc、Ld或Le;(La)碳數1~12的脂肪族烴基 In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R a independently It represents L 1, a plurality of R b independently represent a hydrogen atom, a halogen atom, L 1 or -SO 2 -L 2; L 1 represented by the following L a, L b or L c, L 2 represented by the following L a, L b , L c , L d or L e ; (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms
(Lb)碳數1~12的經鹵素取代的烷基 (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms
(Lc)碳數3~14的脂環式烴基 (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms
(Ld)碳數6~14的芳香族烴基 (L d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms
(Le)碳數3~14的雜環基 (L e ) a heterocyclic group having 3 to 14 carbon atoms
所述La~Le亦可更具有選自由碳數1~12的脂肪族烴基、碳數1~12的經鹵素取代的烷基、碳數3~14的脂環式烴基、碳數6~14的芳香族烴基、碳數3~14的雜環基、及碳數1~12的烷氧基所組成的組群中的至少一種取代基L。 The L a ~L e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
根據本發明,可提供一種入射角依存性低、耐光性或700nm~750nm附近的近紅外線吸收特性及可見波長範圍下的透射率特性優異的濾光器。 According to the present invention, it is possible to provide a filter having low incident angle dependency, light resistance, near-infrared absorption characteristics in the vicinity of 700 nm to 750 nm, and excellent transmittance characteristics in the visible wavelength range.
1‧‧‧濾光器 1‧‧‧ Filter
2‧‧‧分光光度計 2‧‧‧Spectrophotometer
3‧‧‧光 3‧‧‧Light
圖1(a)為表示對自濾光器的垂直方向測定的情形的透射率進行測定的方法的概略圖。圖1(b)為表示對自相對於濾光器的垂直方向成30°的角度測定的情形的透射率進行測定的方法的概略圖。 Fig. 1(a) is a schematic view showing a method of measuring transmittance in a case where the filter is measured in the vertical direction. Fig. 1(b) is a schematic view showing a method of measuring the transmittance in the case of measuring at an angle of 30° with respect to the vertical direction of the filter.
以下,對本發明加以具體說明。 Hereinafter, the present invention will be specifically described.
本發明的濾光器具有:含有由特定的結構所表示的酞菁系化合物(化合物(A))的透明樹脂製基板、及形成於所述基板的至 少一個面上的近紅外線反射膜。 The optical filter of the present invention has a transparent resin substrate containing a phthalocyanine-based compound (compound (A)) represented by a specific structure, and a substrate formed on the substrate. A near-infrared reflective film on one side.
[透明樹脂製基板] [Transparent resin substrate]
構成本發明的濾光器的透明樹脂製基板(以下亦稱為「樹脂製基板」)可為單層亦可為多層(於多層的情形時,例如構成為於作為基底的樹脂基板上積層包含硬化樹脂的外塗層等),至少含有一種以上的化合物(A)作為近紅外線吸收色素,且最大吸收在波長700nm~800nm、更佳為705nm~750nm的範圍內,最大吸收波長的透射率較佳為10%以下,進而佳為8%以下。若基板的最大吸收波長或最大吸收波長的透射率在此種範圍內,則該基板可選擇性地效率良好地截止近紅外線,並且於在透明樹脂基板的面上將近紅外線反射膜成膜時,可降低可見波長~近紅外波長範圍附近的光學特性的入射角依存性。 The transparent resin substrate (hereinafter also referred to as "resin substrate") constituting the optical filter of the present invention may be a single layer or a plurality of layers (in the case of a plurality of layers, for example, it is configured to be laminated on a resin substrate as a base) The outer layer of the cured resin, etc.) contains at least one compound (A) as a near-infrared absorbing pigment, and the maximum absorption is in the range of 700 nm to 800 nm, more preferably 705 nm to 750 nm, and the transmittance at the maximum absorption wavelength is higher. Preferably, it is 10% or less, and further preferably 8% or less. When the transmittance of the maximum absorption wavelength or the maximum absorption wavelength of the substrate is within such a range, the substrate can selectively cut off near-infrared rays efficiently, and when a near-infrared reflective film is formed on the surface of the transparent resin substrate, It can reduce the incident angle dependence of the optical characteristics near the visible wavelength to the near-infrared wavelength range.
根據照相機模組等的用途,亦存在如下情形:要求於波長400nm~700nm的所謂可見光範圍內,將含有化合物(A)的樹脂製基板的厚度設為100μm時的該基板的平均透射率為50%以上、較佳為65%以上。 According to the use of the camera module or the like, there is a case where the average transmittance of the substrate when the thickness of the resin substrate containing the compound (A) is 100 μm in the so-called visible light range of 400 nm to 700 nm. More than %, preferably more than 65%.
樹脂製基板的厚度可根據所需的用途而適當選擇,並無特別限制,較佳為以該基板具有如上所述的入射角依存改良性的方式進行調整,更佳為30μm~250μm,進而佳為40μm~200μm,尤佳為50μm~150μm。 The thickness of the resin substrate can be appropriately selected depending on the intended use, and is not particularly limited. It is preferably adjusted such that the substrate has an improvement in incident angle as described above, and more preferably 30 μm to 250 μm. It is 40 μm to 200 μm, and particularly preferably 50 μm to 150 μm.
若樹脂製基板的厚度在所述範圍內,則可使利用該基板的濾光器小型化及輕量化,可較佳地用於固體攝像裝置等各種用 途。尤其於將所述樹脂性基板用於照相機模組等的透鏡單元(lens unit)的情形時,可實現透鏡單元的薄型化,故較佳。 When the thickness of the resin substrate is within the above range, the filter using the substrate can be reduced in size and weight, and can be preferably used for various applications such as a solid-state imaging device. way. In particular, when the resin substrate is used for a lens unit such as a camera module, it is preferable to reduce the thickness of the lens unit.
所述樹脂製基板除所述化合物(A)以外,可進而含有選自由方酸菁(squarylium)系化合物、化合物(A)以外的酞菁系化合物及花青(cyanine)系化合物所組成的組群中的至少一種近紅外線吸收色素(X)。藉由使用此種樹脂製基板,可進一步減小可見波長範圍~近紅外波長範圍下的入射角依存性,並且可使吸收帶的波形更窄,可獲得視角廣的濾光器。 In addition to the compound (A), the resin substrate may further contain a group selected from the group consisting of a squary sulphate-based compound and a phthalocyanine-based compound and a cyanine-based compound other than the compound (A). At least one near-infrared absorbing pigment (X) in the group. By using such a resin substrate, the incident angle dependency in the visible wavelength range to the near-infrared wavelength range can be further reduced, and the waveform of the absorption band can be made narrower, and a filter having a wide viewing angle can be obtained.
所述化合物(A)與所述近紅外線吸收色素(X)可含有於同一層中亦可含有於不同的層中。於含有於同一層中的情形時,例如可列舉使化合物(A)與近紅外線吸收色素(X)均含有於作為基底的樹脂基板中的形態;於含有於不同的層中的情形時,例如可列舉於含有化合物(A)的樹脂製基板上積層含有所述近紅外線吸收色素(X)的層的形態。 The compound (A) and the near-infrared absorbing pigment (X) may be contained in the same layer or may be contained in different layers. In the case of being contained in the same layer, for example, a form in which both the compound (A) and the near-infrared absorbing dye (X) are contained in a resin substrate as a base is included, and when it is contained in a different layer, for example, A form in which a layer containing the near-infrared absorbing dye (X) is laminated on a resin substrate containing the compound (A).
化合物(A)與近紅外線吸收色素(X)更佳為含有於同一層中,此種情形下,相較於含有於不同的層中的情形,變得更容易控制化合物(A)與近紅外線吸收色素(X)的含量比率。 The compound (A) and the near-infrared absorbing pigment (X) are preferably contained in the same layer, and in this case, it is easier to control the compound (A) and the near-infrared rays than in the case of being contained in a different layer. The content ratio of the absorbing pigment (X).
<化合物(A)> <compound (A)>
化合物(A)為下述式(I)所表示的酞菁系化合物。 The compound (A) is a phthalocyanine compound represented by the following formula (I).
[化3]
式(I)中,M表示2個氫原子、2個一價的金屬原子、二價的金屬原子、或者包含三價或四價的金屬原子的經取代的金屬原子;多個Ra獨立地表示L1,多個Rb獨立地表示氫原子、鹵素原子、L1或-SO2-L2;L1表示下述La、Lb或Lc,L2表示下述La、Lb、Lc、Ld或Le;(La)碳數1~12的脂肪族烴基 In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R a independently It represents L 1, a plurality of R b independently represent a hydrogen atom, a halogen atom, L 1 or -SO 2 -L 2; L 1 represented by the following L a, L b or L c, L 2 represented by the following L a, L b , L c , L d or L e ; (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms
(Lb)碳數1~12的經鹵素取代的烷基 (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms
(Lc)碳數3~14的脂環式烴基 (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms
(Ld)碳數6~14的芳香族烴基 (L d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms
(Le)碳數3~14的雜環基 (L e ) a heterocyclic group having 3 to 14 carbon atoms
所述La~Le亦可更具有選自由碳數1~12的脂肪族烴基、碳數1~12的經鹵素取代的烷基、碳數3~14的脂環式烴基、碳數6~14的芳香族烴基、碳數3~14的雜環基、及碳數1~12的烷氧基所組成的組群中的至少一種取代基L。 The L a ~L e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
關於所述La~Le,含有取代基的碳數的合計分別較佳為50以下,更佳為碳數40以下,尤佳為碳數30以下。若碳數多於 該範圍,則色素的合成有時變困難,並且有每單位重量的吸收強度變小的傾向。 With respect to the above-mentioned L a to L e , the total number of carbon atoms having a substituent is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the carbon number is more than the above range, the synthesis of the dye may become difficult, and the absorption strength per unit weight tends to be small.
作為所述La及L的碳數1~12的脂肪族烴基,例如可列舉:甲基(Me)、乙基(Et)、正丙基(n-Pr)、異丙基(i-Pr)、正丁基(n-Bu)、第二丁基(s-Bu)、第三丁基(t-Bu)、戊基、己基、辛基、壬基、癸基及十二烷基等烷基;乙烯基、1-丙烯基、2-丙烯基、丁烯基、1,3-丁二烯基、2-甲基-1-丙烯基、2-戊烯基、己烯基及辛烯基等烯基;以及乙炔基、丙炔基、丁炔基、2-甲基-1-丙炔基、己炔基及辛炔基等炔基。 Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms of L a and L include methyl (Me), ethyl (Et), n-propyl (n-Pr), and isopropyl (i-Pr). ), n-butyl (n-Bu), second butyl (s-Bu), tert-butyl (t-Bu), pentyl, hexyl, octyl, decyl, decyl and dodecyl Alkyl; vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl and octyl An alkenyl group such as an alkenyl group; and an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, a hexynyl group, and an octynyl group.
作為所述Lb及L的碳數1~12的經鹵素取代的烷基,例如可列舉:三氯甲基、三氟甲基、1,1-二氯乙基、五氯乙基、五氟乙基、七氯丙基及七氟丙基。 Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms of L b and L include trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl and five. Fluoroethyl, heptachloropropyl and heptafluoropropyl.
作為所述Lc及L的碳數3~14的脂環式烴基,例如可列舉:環丁基、環戊基、環己基、環庚基及環辛基等環烷基;降冰片烷基及金剛烷基等多環脂環式基。 Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms of L c and L include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and a norbornyl group; And polycyclic alicyclic groups such as adamantyl.
作為所述Ld及L的碳數6~14的芳香族烴基,例如可列舉:苯基、甲苯基、二甲苯基、均三甲苯基(mesityl)、枯烯基(cumenyl)、1-萘基、2-萘基、蒽基、菲基、苊基(acenaphthyl)、萉基(phenalenyl)、四氫萘基、二氫茚基及聯苯基。 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms of L d and L include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, and a 1-naphthalene group. Base, 2-naphthyl, anthracenyl, phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenyl.
作為所述Le及L的碳數3~14的雜環基,例如可列舉:包含呋喃、噻吩、吡咯、吡唑、咪唑、三唑、噁唑、噁二唑、噻唑、噻二唑、吲哚、吲哚啉、假吲哚(indolenine)、苯并呋喃、苯 并噻吩、咔唑、二苯并呋喃、二苯并噻吩、吡啶、嘧啶、吡嗪、噠嗪、喹啉、異喹啉、吖啶、嗎啉及啡嗪等雜環的基團。 Examples of the heterocyclic group having 3 to 14 carbon atoms of L e and L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, and thiadiazole. Anthraquinone, porphyrin, indolenine, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquine a heterocyclic group such as a porphyrin, an acridine, a morpholine or a morphazine.
作為所述La,較佳為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、4-苯基丁基、2-環己基乙基,更佳為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、己基。 As the L a , a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, a pentyl group, a hexyl group, an octyl group or a 4-phenyl group are preferable. Further, 2-cyclohexylethyl, more preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, hexyl.
作為所述Lb,較佳為三氯甲基、五氯乙基、三氟甲基、五氟乙基、5-環己基-2,2,3,3-四氟戊基,更佳為三氯甲基、五氯乙基、三氟甲基、五氟乙基。 As the L b , preferred is trichloromethyl, pentachloroethyl, trifluoromethyl, pentafluoroethyl, 5-cyclohexyl-2,2,3,3-tetrafluoropentyl, more preferably Trichloromethyl, pentachloroethyl, trifluoromethyl, pentafluoroethyl.
作為所述Lc,較佳為環丁基、環戊基、環己基、4-乙基環己基、環辛基、4-苯基環庚基,更佳為環戊基、環己基、4-乙基環己基。 The L c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group or a 4-phenylcycloheptyl group, more preferably a cyclopentyl group, a cyclohexyl group, or 4 - Ethylcyclohexyl.
作為所述Ld,較佳為苯基、1-萘基、2-萘基、甲苯基、二甲苯基、均三甲苯基、枯烯基、3,5-二-第三丁基苯基、4-環戊基苯基、2,3,6-三苯基苯基、2,3,4,5,6-五苯基苯基,更佳為苯基、甲苯基、二甲苯基、均三甲苯基、枯烯基、2,3,4,5,6-五苯基苯基。 As the L d , a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 3,5-di-tert-butylphenyl group are preferable. , 4-cyclopentylphenyl, 2,3,6-triphenylphenyl, 2,3,4,5,6-pentaphenylphenyl, more preferably phenyl, tolyl, xylyl, Mesitylene, cumenyl, 2,3,4,5,6-pentaphenylphenyl.
作為所述Le,較佳為包含呋喃、噻吩、吡咯、吲哚、吲哚啉、假吲哚、苯并呋喃、苯并噻吩、嗎啉的基團,更佳為包含呋喃、噻吩、吡咯、嗎啉的基團。 The L e is preferably a group containing furan, thiophene, pyrrole, anthracene, porphyrin, pyrene, benzofuran, benzothiophene, morpholine, more preferably furan, thiophene or pyrrole. a group of morpholine.
所述La~Le亦可更具有選自由鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基及胺基所組成的組群中的至少一種原子或基團。此種例可列舉:4-磺基丁基、4-氰基丁基、5-羧基戊基、 5-胺基戊基、3-羥基丙基、2-磷醯基乙基、6-胺基-2,2-二環己基、2-氯-4-羥基丁基、2-氰基環丁基、3-羥基環戊基、3-羧基環戊基、4-胺基環己基、4-羥基環己基、4-羥基苯基、2-羥基萘基、4-胺基苯基、2,3,4,5,6-五氟苯基、4-硝基苯基、包含3-甲基吡咯的基團、2-羥基乙氧基、3-氰基丙氧基、4-氟苯甲醯基、2-羥基乙氧基羰基、4-氰基丁氧基羰基。 The L a to L e may further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, and an amine group. Examples thereof include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphonylethyl group, and 6-amine. Base-2,2-dicyclohexyl, 2-chloro-4-hydroxybutyl, 2-cyanocyclobutyl, 3-hydroxycyclopentyl, 3-carboxycyclopentyl, 4-aminocyclohexyl, 4 -hydroxycyclohexyl, 4-hydroxyphenyl, 2-hydroxynaphthyl, 4-aminophenyl, 2,3,4,5,6-pentafluorophenyl, 4-nitrophenyl, 3-3-yl A group of a pyrrolidine, 2-hydroxyethoxy, 3-cyanopropoxy, 4-fluorobenzylidene, 2-hydroxyethoxycarbonyl, 4-cyanobutoxycarbonyl.
所述M中,作為一價的金屬原子,可列舉Li、Na、K、Rb、Cs等。 In the above, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.
所述M中,作為二價的金屬原子,可列舉Be、Mg、Ca、Ba、Ti、Cr、Mn、Fe、Ru、Co、Rh、Ni、Pd、Pt、Cu、Zn、Cd、Hg、Sn、Pb等。 In the above M, examples of the divalent metal atom include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, and Hg. Sn, Pb, etc.
所述M中,作為包含三價的金屬原子的經取代的金屬原子,可列舉Al-F、Al-Cl、Al-Br、Al-I、Ga-F、Ga-Cl、Ga-Br、Ga-I、In-F、In-Cl、In-Br、In-I、Tl-F、Tl-Cl、Tl-Br、Tl-I、Fe-Cl、Ru-Cl、Mn-OH等。 In the above M, as the substituted metal atom containing a trivalent metal atom, Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga may be mentioned. -I, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH, and the like.
所述M中,作為包含四價的金屬原子的經取代的金屬原子,可列舉TiF2、TiCl2、TiBr2、TiI2、ZrCl2、HfCl2、CrCl2、SiF2、SiCl2、SiBr2、SiI2、GeF2、GeCl2、GeBr2、GeI2、SnF2、SnCl2、SnBr2、SnI2、Zr(OH)2、Hf(OH)2、Mn(OH)2、Si(OH)2、Ge(OH)2、Sn(OH)2、TiR2、CrR2、SiR2、GeR2、SnR2、Ti(OR)2、Cr(OR)2、Si(OR)2、Ge(OR)2、Sn(OR)2(R表示脂肪族基或芳香族基)、TiO、VO、MnO等。 The M, as the metal atom comprises a substituted tetravalent metal atom include TiF 2, TiCl 2, TiBr 2 , TiI 2, ZrCl 2, HfCl 2, CrCl 2, SiF 2, SiCl 2, SiBr 2 , SiI 2, GeF 2, GeCl 2, GeBr 2, GeI 2, SnF 2, SnCl 2, SnBr 2, SnI 2, Zr (OH) 2, Hf (OH) 2, Mn (OH) 2, Si (OH) 2 , Ge(OH) 2 , Sn(OH) 2 , TiR 2 , CrR 2 , SiR 2 , GeR 2 , SnR 2 , Ti(OR) 2 , Cr(OR) 2 , Si(OR) 2 , Ge(OR 2 , Sn(OR) 2 (R represents an aliphatic group or an aromatic group), TiO, VO, MnO, or the like.
作為所述M,較佳為屬於元素週期表第4族~第12族且第4週期~第5週期的二價過渡金屬、三價或四價的金屬鹵化物或者四價的金屬氧化物,其中,尤其就可達成高的可見光透射率及色素穩定性的觀點而言,更佳為Cu、Ni、Co、Zn、TiO及VO,尤佳為Cu及VO。 As the M, a divalent transition metal, a trivalent or tetravalent metal halide or a tetravalent metal oxide belonging to Group 4 to Group 12 of the periodic table and the fourth to fifth cycles is preferable. Among them, Cu, Ni, Co, Zn, TiO, and VO are more preferable, and Cu and VO are particularly preferable from the viewpoint of achieving high visible light transmittance and pigment stability.
作為所述Ra,就合成的容易性或化合物(A)對有機溶劑的溶解性的觀點而言,較佳為獨立地為碳數1~10的烷基、碳數1~6的氟取代烷基、環戊基或環己基,更佳為碳數1~10的烷基,尤佳為碳數3~8的烷基。 The R a is preferably an alkyl group having 1 to 10 carbon atoms or a fluorine atom having 1 to 6 carbon atoms from the viewpoint of easiness of synthesis or solubility of the compound (A) in an organic solvent. The alkyl group, the cyclopentyl group or the cyclohexyl group is more preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 3 to 8 carbon atoms.
作為所述Rb,就合成的容易性或化合物(A)的穩定性的觀點而言,較佳為獨立地為氫原子、氟原子、碳數1~10的烷基、環戊基、環己基或-SO2-L2(L2較佳為碳數1~6的烷基、碳數6~12的芳香族烴基、碳數3~6的雜環基),更佳為氫原子或碳數1~6的烷基。 The R b is preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group or a ring, from the viewpoint of easiness of synthesis or stability of the compound (A). Hexyl or -SO 2 -L 2 (L 2 is preferably an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a heterocyclic group having 3 to 6 carbon atoms), more preferably a hydrogen atom or An alkyl group having 1 to 6 carbon atoms.
通常已知藉由下述式(II)所表示的鄰苯二甲腈(phthalonitrile)衍生物等的環化反應來合成所述化合物(A)的方法,所得的酞菁系化合物成為如下述式(II-1)~式(II-4)般的4種異構體的混合物。本發明中,只要事先無特別說明,則針對一種酞菁系化合物僅例示一種異構體,但其他三種異構體亦可同樣地使用。再者,該些異構體亦可視需要分開來使用,本發明中是總括使用異構體混合物。 A method of synthesizing the compound (A) by a cyclization reaction such as a phthalonitrile derivative represented by the following formula (II), and the obtained phthalocyanine-based compound is as follows. (II-1)~ a mixture of four isomers of the formula (II-4). In the present invention, only one isomer is exemplified for one phthalocyanine-based compound unless otherwise specified, but the other three isomers may be used in the same manner. Further, the isomers may also be used separately as needed, and in the present invention, a mixture of isomers is used in total.
[化4]
作為所述化合物(A)的具體例,只要滿足所述式(I)中記載的條件則並無特別限定,例如可列舉具有下述式(I-1)所表示的基本骨架的下述表1中記載的化合物(a-1)~化合物(a-35)等。 The specific example of the compound (A) is not particularly limited as long as it satisfies the conditions described in the above formula (I), and examples thereof include the following table having the basic skeleton represented by the following formula (I-1). The compound (a-1) to the compound (a-35) described in 1.
[化6]
[表1]表1
化合物(A)只要利用通常已知的方法來合成即可,例如可參 照日本專利第4081149號公報、「酞菁-化學與功能」(IPC、1997年)、日本專利特開平2-138382號公報等中記載的方法等來合成。 The compound (A) can be synthesized by a generally known method, for example, It is synthesized by the method described in Japanese Patent No. 4,081,149, "Phase-Chemistry and Function" (IPC, 1997), and Japanese Patent Laid-Open No. Hei 2-138382.
樹脂製基板中,相對於製造樹脂製基板時所用的透明樹脂100重量份,樹脂層中的化合物(A)的含量較佳為0.01重量份~5.0重量份,更佳為0.02重量份~3.5重量份,尤佳為0.03重量份~2.5重量份。若化合物(A)的含量在所述範圍內,則可兼具良好的近紅外線吸收特性與高的可見光透射率。 In the resin substrate, the content of the compound (A) in the resin layer is preferably from 0.01 part by weight to 5.0 parts by weight, more preferably from 0.02 part by weight to 3.5% by weight based on 100 parts by weight of the transparent resin used for producing the resin substrate. It is particularly preferably 0.03 parts by weight to 2.5 parts by weight. When the content of the compound (A) is within the above range, both good near-infrared absorption characteristics and high visible light transmittance can be obtained.
<近紅外線吸收色素(X)> <Near infrared absorbing pigment (X)>
所述近紅外線吸收色素(X)為選自由方酸菁系化合物、酞菁系化合物及花青系化合物所組成的組群中的至少一種,尤佳為含有方酸菁系化合物。近紅外線吸收色素(X)的最大吸收波長較佳為620nm以上,進而佳為650nm以上,尤佳為670nm以上,且較佳為小於800nm,進而佳為750nm以下,尤佳為730nm以下,並且,理想的是較所同時含有的化合物(A)的最大吸收波長於更短波長側具有最大吸收。若最大吸收波長在此種波長範圍內,則可使吸收帶的波形更窄,並且可充分擴展近紅外吸收色素的吸收帶,可達成更優異的入射角依存改良性能或重影(ghost)降低效果。 The near-infrared absorbing pigment (X) is at least one selected from the group consisting of a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound, and particularly preferably a squaraine-based compound. The maximum absorption wavelength of the near-infrared absorbing pigment (X) is preferably 620 nm or more, more preferably 650 nm or more, particularly preferably 670 nm or more, and preferably less than 800 nm, more preferably 750 nm or less, still more preferably 730 nm or less, and It is desirable that the maximum absorption wavelength of the compound (A) contained at the same time has a maximum absorption on the shorter wavelength side. If the maximum absorption wavelength is within such a wavelength range, the absorption band can be made narrower, and the absorption band of the near-infrared absorbing pigment can be sufficiently extended, thereby achieving better incident angle dependency improvement performance or ghost reduction. effect.
於樹脂製基板中,相對於製造樹脂製基板時所用的透明樹脂100重量份,樹脂層中的近紅外線吸收色素(X)的含量較佳為0.01重量份~5.0重量份,更佳為0.02重量份~3,5重量份,尤佳為0.03重量份~2.5重量份。若近紅外線吸收色素的含量在所述 範圍內,則可兼具良好的近紅外線吸收特性與高的可見光透射率。 In the resin substrate, the content of the near-infrared absorbing pigment (X) in the resin layer is preferably 0.01 parts by weight to 5.0 parts by weight, more preferably 0.02% by weight based on 100 parts by weight of the transparent resin used for producing the resin substrate. It is preferably from 3 to 5 parts by weight, particularly preferably from 0.03 parts by weight to 2.5 parts by weight. If the content of the near infrared absorbing pigment is in the Within the range, it has good near-infrared absorption characteristics and high visible light transmittance.
《方酸菁系化合物》 "Squaraine Cyanine Compound"
方酸菁系化合物較佳為含有選自由式(III-1)所表示的方酸菁系化合物及式(III-2)所表示的方酸菁系化合物所組成的組群中的至少一種。 The squarylium-based compound preferably contains at least one selected from the group consisting of a squaraine-based compound represented by the formula (III-1) and a squaraine-based compound represented by the formula (III-2).
式(III-1)中,Rm、Rn及Y滿足下述(i)或(ii)的條件。 In the formula (III-1), R m , R n and Y satisfy the conditions of the following (i) or (ii).
條件(i)Condition (i)
多個Rm分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-L1或-NReRf基。Re及Rf分別獨立地表示氫原子、-La、-Lb、-Lc、-Ld或-Le。 The plurality of R m each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L 1 or a -NR e R f group. R e and R f each independently represent a hydrogen atom, -L a , -L b , -L c , -L d or -L e .
多個Rn分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-L1或-NRgRh基。Rg及Rh分別獨立地表示氫原子、-La、-Lb、-Lc、-Ld、-Le或-C(O)Ri基(Ri表示-La、-Lb、-Lc、-Ld或-Le)。 The plurality of R n each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L 1 or a -NR g R h group. R g and R h each independently represent a hydrogen atom, -L a , -L b , -L c , -L d , -L e or -C(O)R i group (R i represents -L a , -L b , -L c , -L d or -L e ).
多個Y分別獨立地表示-NRjRk基。Rj及Rk分別獨立地 表示氫原子、-La、-Lb、-Lc、-Ld或-Le。 A plurality of Y independently represent the -NR j R k basis. R j and R k each independently represent a hydrogen atom, -L a , -L b , -L c , -L d or -L e .
所述L1、La、Lb、Lc、Ld、Le分別獨立地與所述式(I)中定義的L1、La、Lb、Lc、Ld、Le為相同涵義。 The L 1, L a, L b , L c, L d, L e are each independently defined as in the formula (I), L 1, L a, L b , L c, L d, L e is The same meaning.
條件(ii)Condition (ii)
一個苯環上的2個Rm中的至少一個與相同苯環上的Y相互鍵結,形成含有至少一個氮原子的構成原子數為5或6的雜環,所述雜環亦可具有取代基,Rn及未參與所述雜環的形成的Rm分別獨立地與所述(i)的Rn及Rm為相同涵義。 At least one of the two R m on one benzene ring is bonded to Y on the same benzene ring to form a hetero ring having at least one nitrogen atom and having a number of 5 or 6 atoms, and the hetero ring may have a substitution. The radicals, R n and R m not participating in the formation of the heterocyclic ring are each independently of the same meaning as R n and R m of the above (i).
式(III-2)中,X表示-O-、-S-、-Se-、-N(Rc)-或-C(RdRd)-;多個Rc分別獨立地表示氫原子、-La、-Lb、-Lc、-Ld或-Le;多個Rd分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-L1或-NReRf基,相鄰的Rd彼此亦可連結而形成可具有取代基的環;La~Le、L1與所述式(I)中定義的La~Le為相同涵義,Re及Rf與所述(i)的Re及Rf為相同涵義。 In the formula (III-2), X represents -O-, -S-, -Se-, -N(R c )- or -C(R d R d )-; and a plurality of R c each independently represent a hydrogen atom , -L a , -L b , -L c , -L d or -L e ; a plurality of R d independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group , -L 1 or -NR e R f group, adjacent R d may also be bonded to each other to form a ring which may have a substituent; L a ~L e , L 1 and L a as defined in the formula (I) ~ L e are the same meaning, R e, and R f of the (i) of R e and R f is the same meaning.
鍵結於所述方酸菁系化合物的中央的四員環上的左右的取代基可相同亦可不同,相同時於合成方面容易,故較佳。 The substituents on the four-membered ring bonded to the center of the squaraine-based compound may be the same or different, and are preferably synthesized in the same manner, which is preferable.
所述方酸菁系化合物只要利用通常已知的方法來合成即可,例如可參照日本專利特開平1-228960號公報、日本專利特開2001-40234號公報、日本專利第3196383號公報等中記載的方法等來合成。 The squarylium-based compound may be synthesized by a generally known method. For example, Japanese Patent Laid-Open No. Hei 1-228960, Japanese Patent Laid-Open No. 2001-40234, Japanese Patent No. 3196383, and the like can be used. The method described is synthesized.
《酞菁系化合物》 "Phthalocyanine Compounds"
酞菁系化合物可使用除化合物(A)以外的通常已知的任意結構的化合物,例如可利用日本專利第4081149號公報或「酞菁-化學與功能」(IPC、1997年)中記載的方法來合成。 As the phthalocyanine-based compound, a compound of any structure generally known other than the compound (A) can be used, and for example, the method described in Japanese Patent No. 4081149 or "Phthalocyanine-Chemistry and Function" (IPC, 1997) can be used. To synthesize.
《花青系化合物》 "Cyanine Compound"
花青系化合物可使用通常已知的任意結構的化合物,例如可利用日本專利特開2009-108267號公報中記載的方法來合成。 As the cyanine compound, a compound of any structure generally known can be used, and for example, it can be synthesized by the method described in JP-A-2009-108267.
<透明樹脂> <Transparent Resin>
樹脂製基板是含有透明樹脂及化合物(A)而成。 The resin substrate is composed of a transparent resin and a compound (A).
透明樹脂只要不損及本發明的效果,則並無特別限制,例如為了確保熱穩定性及成形為膜的成形性,且製成可藉由在100℃以上的蒸鍍溫度下進行的高溫蒸鍍來形成介電質多層膜的膜,可列舉玻璃轉移溫度(Tg)較佳為110℃~380℃、更佳為110℃~370℃、進而佳為120℃~360℃的樹脂。另外,若所述樹脂的玻璃轉移溫度為140℃以上,則可獲得可於更高的溫度下蒸鍍形成介電質多層膜的膜,故尤佳。 The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, in order to ensure thermal stability and formability of the film, it is possible to form a high-temperature steam which can be carried out at a vapor deposition temperature of 100 ° C or higher. The film which is plated to form the dielectric multilayer film may, for example, be a resin having a glass transition temperature (Tg) of preferably from 110 ° C to 380 ° C, more preferably from 110 ° C to 370 ° C, even more preferably from 120 ° C to 360 ° C. Further, when the glass transition temperature of the resin is 140 ° C or higher, a film which can be vapor-deposited at a higher temperature to form a dielectric multilayer film can be obtained, which is particularly preferable.
關於透明樹脂,於形成包含該樹脂的厚度0.1mm的樹脂板的情形時,可使用該樹脂板的總光線透射率(日本工業標準 (Japanese Industrial Standards,JIS)K7105)成為較佳為75%~95%、更佳為78%~95%、尤佳為80%~95%的樹脂。若使用總光線透射率成為此種範圍的樹脂,則所得的基板顯示出作為光學膜而良好的透明性。 Regarding the transparent resin, in the case of forming a resin sheet having a thickness of 0.1 mm of the resin, the total light transmittance of the resin sheet can be used (Japanese Industrial Standard) (Japanese Industrial Standards, JIS) K7105) is preferably a resin of 75% to 95%, more preferably 78% to 95%, and particularly preferably 80% to 95%. When a resin having a total light transmittance of such a range is used, the obtained substrate exhibits excellent transparency as an optical film.
透明樹脂的藉由凝膠滲透層析(Gel Permeation Chromatography,GPC)法所測定的聚苯乙烯換算的重量平均分子量(Mw)通常為15,000~350,000,較佳為30,000~250,000;數量平均分子量(Mn)通常為10,000~150,000,較佳為20,000~100,000。 The polystyrene-equivalent weight average molecular weight (Mw) of the transparent resin measured by Gel Permeation Chromatography (GPC) is usually 15,000 to 350,000, preferably 30,000 to 250,000; and the number average molecular weight (Mn) ) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
透明樹脂例如可列舉:環狀烯烴系樹脂、芳香族聚醚系樹脂、聚醯亞胺系樹脂、茀聚碳酸酯系樹脂、茀聚酯系樹脂、聚碳酸酯系樹脂、聚醯胺(芳族聚醯胺)系樹脂、聚芳酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚對苯系樹脂、聚醯胺醯亞胺系樹脂、聚萘二甲酸乙二酯(polyethylene naphthalate,PEN)系樹脂、氟化芳香族聚合物系樹脂、(改質)丙烯酸系樹脂、環氧系樹脂、烯丙酯系樹脂及倍半矽氧烷系樹脂。 Examples of the transparent resin include a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, and a polyamine. Polyamide resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate , PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene oxide resin.
《環狀烯烴系樹脂》 "Ring olefin resin"
環狀烯烴系樹脂較佳為由選自由下述式(X0)所表示的單體及下述式(Y0)所表示的單體所組成的組群中的至少一種單體所得的樹脂、及藉由將該樹脂氫化而所得的樹脂。 The cyclic olefin-based resin is preferably a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ). And a resin obtained by hydrogenating the resin.
[化9]
式(X0)中,Rx1~Rx4分別獨立地表示選自下述(i')~(ix')中的原子或基團,kx、mx及px分別獨立地表示0或正整數。 In the formula (X 0 ), R x1 to R x4 each independently represent an atom or a group selected from the following (i') to (ix'), and k x , m x and p x each independently represent 0 or A positive integer.
(i')氫原子 (i') hydrogen atom
(ii')鹵素原子 (ii') halogen atom
(iii')三烷基矽烷基 (iii') trialkyldecylalkyl
(iv')具有含有氧原子、硫原子、氮原子或矽原子的連結基的經取代或未經取代的碳數1~30的烴基 (iv') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom
(v')經取代或未經取代的碳數1~30的烴基 (v') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms
(vi')極性基(其中(iv')除外) (vi') polar group (except (iv'))
(vii')Rx1與Rx2或Rx3與Rx4相互鍵結而形成的亞烷基(其中,不參與所述鍵結的Rx1~Rx4分別獨立地表示選自所述(i')~(vi')中的原子或基團) (vii') an alkylene group formed by bonding R x1 and R x2 or R x3 and R x4 to each other (wherein R x1 to R x4 not participating in the bonding are independently represented from the above (i' ) an atom or group in ~(vi')
(viii')Rx1與Rx2或Rx3與Rx4相互鍵結而形成的單環或多環的烴環或雜環(其中,不參與所述鍵結的Rx1~Rx4分別獨立地表示選自所述(i')~(vi')中的原子或基團) (viii') a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding R x1 and R x2 or R x3 and R x4 to each other (wherein R x1 to R x4 not participating in the bonding are independently Representing an atom or group selected from the group (i') to (vi')
(ix')Rx2與Rx3相互鍵結而形成的單環的烴環或雜環(其中,不參與所述鍵結的Rx1與Rx4分別獨立地表示選自所述(i')~(vi') 中的原子或基團) (ix') a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R x2 and R x3 to each other (wherein R x1 and R x4 which do not participate in the bonding are independently represented from the above (i') An atom or group in ~(vi')
式(Y0)中,Ry1及Ry2分別獨立地表示選自所述(i')~(vi')中的原子或基團,或者表示Ry1與Ry2相互鍵結而形成的單環或多環的脂環式烴、芳香族烴或雜環,ky及py分別獨立地表示0或正整數。 In the formula (Y 0 ), R y1 and R y2 each independently represent an atom or a group selected from the above (i') to (vi'), or a single bond formed by bonding R y1 and R y2 to each other. A cyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring, k y and p y each independently represent 0 or a positive integer.
《芳香族聚醚系樹脂》 "Aromatic Polyether Resin"
芳香族聚醚系樹脂較佳為含有選自由下述式(1)所表示的結構單元及下述式(2)所表示的結構單元所組成的組群中的至少一種結構單元。 The aromatic polyether-based resin preferably contains at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
式(1)中,R1~R4分別獨立地表示碳數1~12的一價有機基,a~d分別獨立地表示0~4的整數。 In the formula (1), R 1 to R 4 each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4.
式(2)中,R1~R4及a~d分別獨立地與所述式(1)中的R1~R4及a~d為相同涵義,Y表示單鍵、-SO2-或>C=O,R7及R8分別獨立地表示鹵素原子、碳數1~12的一價有機基或硝基,g及h分別獨立地表示0~4的整數,m表示0或1。其中,於m為0時,R7並非氰基。 In the formula (2), R 1 to R 4 and a to d are each independently the same meaning as R 1 to R 4 and a to d in the formula (1), and Y represents a single bond, -SO 2 - or >C=O, R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent an integer of 0 to 4, and m represents 0 or 1. Wherein, when m is 0, R 7 is not a cyano group.
另外,所述芳香族聚醚系樹脂較佳為更含有選自由下述式(3)所表示的結構單元及下述式(4)所表示的結構單元所組成的組群中的至少一種結構單元。 In addition, the aromatic polyether-based resin preferably further contains at least one structure selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). unit.
式(3)中,R5及R6分別獨立地表示碳數1~12的一價有機基,Z表示單鍵、-O-、-S-、-SO2-、>C=O、-CONH-、-COO-或碳數1~12的二價有機基,e及f分別獨立地表示0~4的整數,n表示0或1。 In the formula (3), R 5 and R 6 each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, -O-, -S-, -SO 2 -, >C=O, - CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, and e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.
式(4)中,R7、R8、Y、m、g及h分別獨立地與所述式(2)中的R7、R8、Y、m、g及h為相同涵義,R5、R6、Z、n、e及f分別獨立地與所述式(3)中的R5、R6、Z、n、e及f為相同涵義。 In the formula (4), R 7 , R 8 , Y, m, g and h are each independently the same meaning as R 7 , R 8 , Y, m, g and h in the formula (2), R 5 R 6 , Z, n, e and f are each independently the same meaning as R 5 , R 6 , Z, n, e and f in the formula (3).
《聚醯亞胺系樹脂》 Polyimide Resin
聚醯亞胺系樹脂並無特別限制,只要為重複單元中含有醯亞胺鍵的高分子化合物即可,例如可利用日本專利特開2006-199945號公報或日本專利特開2008-163107號公報中記載的方法來合成。 The polyimine-based resin is not particularly limited as long as it is a polymer compound containing a quinone bond in the repeating unit. For example, JP-A-2006-199945 or JP-A-2008-163107 can be used. The method described in the synthesis.
《茀聚碳酸酯系樹脂》 "茀 polycarbonate resin"
茀聚碳酸酯系樹脂並無特別限制,只要為含有茀部位的聚碳酸酯樹脂即可,例如可利用日本專利特開2008-163194號公報中記載的方法來合成。 The fluorene-based polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.
《茀聚酯系樹脂》 "茀 polyester resin"
茀聚酯系樹脂並無特別限制,只要為含有茀部位的聚酯樹脂即可,例如可利用日本專利特開2010-285505號公報或日本專利特開2011-197450號公報中記載的方法來合成。 The oxime-based polyester resin is not particularly limited as long as it is a polyester resin containing a ruthenium moiety, and can be synthesized, for example, by the method described in JP-A-2010-285505 or JP-A-2011-197450. .
《氟化芳香族聚合物系樹脂》 Fluorinated Aromatic Polymer Resins
氟化芳香族聚合物系樹脂並無特別限制,只要為含有具有至少一個氟的芳香族環、與具有選自由醚鍵、酮鍵、碸鍵、醯胺鍵、醯亞胺鍵及酯鍵所組成的組群中的至少一個鍵的重複單元的聚合物即可,例如可利用日本專利特開2008-181121號公報中記載的方法來合成。 The fluorinated aromatic polymer-based resin is not particularly limited as long as it contains an aromatic ring having at least one fluorine and has an ether bond, a ketone bond, a hydrazone bond, a guanamine bond, a quinone bond, and an ester bond. The polymer of the repeating unit of at least one of the bonds in the group may be synthesized, for example, by the method described in JP-A-2008-181121.
《市售品》 "commercial goods"
透明樹脂的市售品可列舉以下的市售品等。環狀烯烴系樹脂的市售品可列舉:日本合成橡膠(JSR)股份有限公司製造的亞頓(Arton)、日本瑞翁(Zeon Japan)股份有限公司製造的瑞諾(Zeonor)、三井化學股份有限公司製造的奧佩爾(APEL)、寶理塑膠(Polyplastics)股份有限公司製造的托帕斯(TOPAS)等。聚醚碸系樹脂的市售品可列舉住友化學股份有限公司製造的蘇米卡艾克賽爾(Sumika Excel)PES等。聚醯亞胺系樹脂的市售品可列舉三菱瓦斯化學股份有限公司製造的尼奧普利(Neoprim)L等。聚碳酸酯系樹脂的市售品可列舉帝人股份有限公司製造的比艾斯(Pureace)等。茀聚碳酸酯系樹脂的市售品可列舉三菱瓦斯化學股份有限公司製造的優比澤塔(Iupizeta)EP-5000等。茀聚酯系樹脂的市售品可列舉大阪瓦斯化學股份有限公司製造的OKP4HT 等。丙烯酸系樹脂的市售品可列舉日本觸媒股份有限公司製造的亞克力瓦(Acryviewa)等。倍半矽氧烷系樹脂的市售品可列舉新日鐵化學股份有限公司製造的西普拉斯(Silplus)等。 Commercially available products of the transparent resin include the following commercial products. Commercial products of the cyclic olefin resin include Arton manufactured by Japan Synthetic Rubber (JSR) Co., Ltd., Zeonor manufactured by Japan Zeon Japan Co., Ltd., and Mitsui Chemicals Co., Ltd. APEL, TOPAS manufactured by Polyplastics Co., Ltd., etc. A commercially available product of a polyether oxime resin is Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd., and the like. Commercially available products of the polyimine-based resin include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. A commercially available product of a polycarbonate resin is, for example, Pureace manufactured by Teijin Co., Ltd. Commercial products of the fluorene-based polycarbonate resin include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Commercially available products of 茀 polyester resin include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Wait. Commercially available products of the acrylic resin include Acryviewa manufactured by Nippon Shokubai Co., Ltd., and the like. A commercially available product of a sesquioxane-based resin is, for example, Silplus manufactured by Nippon Steel Chemical Co., Ltd.
<其他成分> <Other ingredients>
所述樹脂製基板亦可於不損及本發明的效果的範圍內,更含有抗氧化劑、近紫外線吸收劑、化合物(A)及近紅外線吸收色素(X)以外的吸收近紅外線的色素(以下稱為「其他近紅外線吸收色素」)、螢光消光劑及金屬錯合物系化合物等添加劑。另外,於藉由後述的澆鑄成形來製造樹脂製基板的情形時,藉由添加調平劑或消泡劑,可使樹脂製基板的製造變容易。該些其他成分可單獨使用一種,亦可併用兩種以上。 The resin substrate may further contain a near-infrared absorbing dye other than the antioxidant, the near ultraviolet ray absorbing agent, the compound (A), and the near infrared absorbing dye (X), within a range that does not impair the effects of the present invention (hereinafter, It is called "other near infrared absorbing pigment"), an additive such as a fluorescent matting agent and a metal complex compound. In the case where a resin substrate is produced by casting molding described later, the addition of a leveling agent or an antifoaming agent can facilitate the production of a resin substrate. These other components may be used alone or in combination of two or more.
所述抗氧化劑例如可列舉:2,6-二-第三丁基-4-甲基苯酚、2,2'-二氧基-3,3'-二-第三丁基-5,5'-二甲基二苯基甲烷、及四[亞甲基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]甲烷等。 The antioxidant may, for example, be 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.
所述近紫外線吸收劑例如可列舉:偶氮亞甲基系化合物、吲哚系化合物、苯并三唑系化合物、三嗪系化合物等。 Examples of the near-ultraviolet absorber include an azomethylene-based compound, an anthraquinone-based compound, a benzotriazole-based compound, and a triazine-based compound.
所述其他近紅外線吸收色素例如可列舉:二硫醇系色素、二亞銨(diimonium)系色素、卟啉系色素、克酮酸(croconium)系色素等。該些色素的結構並無特別限定,只要不損及本發明的效果,則可使用通常已知者。 Examples of the other near-infrared absorbing dye include a dithiol-based dye, a diimonium-based dye, a porphyrin-based dye, and a croconium-based dye. The structure of these dyes is not particularly limited, and those generally known can be used as long as the effects of the present invention are not impaired.
再者,該些添加劑可於製造樹脂製基板時與樹脂等一起混合,亦可於製造樹脂時添加。另外,添加量是根據所需的特性 而適當選擇,相對於樹脂100重量份,通常為0.01重量份~5.0重量份,較佳為0.05重量份~2.0重量份。 Further, these additives may be mixed with a resin or the like in the production of a resin substrate, or may be added at the time of resin production. In addition, the amount added is based on the desired characteristics. Suitably, it is usually 0.01 parts by weight to 5.0 parts by weight, preferably 0.05 parts by weight to 2.0 parts by weight, per 100 parts by weight of the resin.
<樹脂製基板的製造方法> <Method for Producing Resin Substrate>
所述樹脂製基板例如可藉由熔融成形或澆鑄成形來形成,視需要可藉由在成形後塗佈抗反射劑、硬塗劑及/或抗靜電劑等塗佈劑的方法來製造。 The resin substrate can be formed, for example, by melt molding or cast molding, and can be produced by a method of applying a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent after molding, if necessary.
《熔融成形》 Melt Forming
所述樹脂製基板可藉由以下方法來製造:對將樹脂與近紅外線吸收色素進行熔融混練所得的顆粒進行熔融成形的方法;對含有樹脂與近紅外線吸收色素的樹脂組成物進行熔融成形的方法;或對自含有近紅外線吸收色素、樹脂及溶劑的樹脂組成物中去除溶劑所得的顆粒進行熔融成形的方法等。熔融成形方法例如可列舉射出成形、熔融擠出成形或吹塑成形等。 The resin substrate can be produced by a method of melt-molding particles obtained by melt-kneading a resin and a near-infrared absorbing dye, and a method of melt-molding a resin composition containing a resin and a near-infrared absorbing dye. Or a method of melt-molding particles obtained by removing a solvent from a resin composition containing a near-infrared absorbing dye, a resin, and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.
《澆鑄成形》 Casting
所述樹脂製基板亦可藉由以下方法來製造:將含有近紅外線吸收色素、樹脂及溶劑的樹脂組成物澆鑄於適當的基材上並將溶劑去除的方法;將含有近紅外線吸收色素及樹脂的硬化性樹脂組成物塗佈於適當的基材上並加以乾燥及使之硬化的方法等。 The resin substrate can also be produced by casting a resin composition containing a near-infrared absorbing dye, a resin, and a solvent onto a suitable substrate and removing the solvent; and containing the near-infrared absorbing pigment and resin. A method in which a curable resin composition is applied onto a suitable substrate, dried, and hardened.
所述基材例如可列舉:玻璃板、鋼帶(steel band)、鋼桶(steel drum)及透明樹脂(例如聚酯膜、環狀烯烴系樹脂膜)。 Examples of the substrate include a glass plate, a steel band, a steel drum, and a transparent resin (for example, a polyester film or a cyclic olefin resin film).
所述樹脂製基板可藉由自基材上剝離而獲得,另外,只要不損及本發明的效果,則亦可不自基材上剝離而將基材與塗膜的積 層體作為所述樹脂製基板。 The resin substrate can be obtained by peeling off from the substrate, and the product of the substrate and the coating film can be removed without peeling off from the substrate as long as the effect of the present invention is not impaired. The layer body is used as the resin substrate.
進而,亦可藉由以下方法而於光學零件上直接形成樹脂製基板:於玻璃板、石英製或透明塑膠製等的光學零件上塗佈所述樹脂組成物並使溶劑乾燥的方法;或塗佈所述硬化性樹脂組成物並加以硬化及使之乾燥的方法等。 Further, a resin substrate may be directly formed on the optical component by a method of applying the resin composition to an optical component such as a glass plate, a quartz or a transparent plastic, and drying the solvent; or coating A method of hardening and drying the curable resin composition, and the like.
利用所述方法所得的樹脂製基板中的殘留溶劑量較佳為儘可能少。具體而言,相對於樹脂基板的重量,所述殘留溶劑量較佳為3重量%以下,更佳為1重量%以下,進而佳為0.5重量%以下。若殘留溶劑量在所述範圍內,則不易變形或特性不易變化,可獲得可容易地發揮所需功能的樹脂製基板。 The amount of residual solvent in the resin substrate obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the weight of the resin substrate. When the amount of the residual solvent is within the above range, deformation or deformation is not easily changed, and a resin substrate which can easily exhibit a desired function can be obtained.
[近紅外線反射膜] [Near Infrared Reflective Film]
構成本發明的濾光器的近紅外線反射膜為具有反射近紅外線的能力的膜。本發明中,近紅外線反射膜可設置於樹脂製基板的單面上,亦可設置於兩面上。於設置於單面上的情形時,製造成本或製造容易性優異,於設置於兩面上的情形時,可獲得具有高的強度、不易產生翹曲(warp)的濾光器。於將濾光器應用於固體攝像元件用途的情形時,較佳的是濾光器的翹曲小,因此較佳為將近紅外線反射膜設置於樹脂製基板的兩面上。 The near-infrared reflecting film constituting the optical filter of the present invention is a film having the ability to reflect near-infrared rays. In the present invention, the near-infrared reflective film may be provided on one surface of the resin substrate or on both surfaces. When it is provided on one surface, it is excellent in manufacturing cost or ease of manufacture, and when it is provided on both surfaces, a filter having high strength and warp is unlikely to be obtained. When the filter is applied to the use of a solid-state imaging device, it is preferable that the warpage of the filter is small. Therefore, it is preferable to provide the near-infrared reflective film on both surfaces of the resin substrate.
近紅外線反射膜例如可列舉:鋁蒸鍍膜、貴金屬薄膜、分散有以氧化銦作為主成分且少量含有氧化錫的金屬氧化物微粒子的樹脂膜、將高折射率材料層與低折射率材料層交替積層而成的介電質多層膜。近紅外線反射膜中,更佳為將高折射率材料層 與低折射率材料層交替積層而成的介電質多層膜。 Examples of the near-infrared reflective film include an aluminum deposited film, a noble metal thin film, and a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, and a high refractive index material layer and a low refractive index material layer are alternated. A dielectric multilayer film laminated. In the near-infrared reflective film, it is more preferable to have a high refractive index material layer A dielectric multilayer film in which a layer of a low refractive index material is alternately laminated.
構成高折射率材料層的材料可使用折射率為1.7以上的材料,選擇折射率通常為1.7~2.5的材料。此種材料例如可列舉:氧化鈦、氧化鋯、五氧化鉭、五氧化鈮、氧化鑭、氧化釔、氧化鋅、硫化鋅,或以氧化銦等作為主成分且少量(例如相對於主成分而為0重量%~10重量%)含有氧化鈦、氧化錫及/或氧化鈰等者。 As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such a material include titanium oxide, zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide, or indium oxide or the like as a main component and a small amount (for example, relative to the main component). From 0% by weight to 10% by weight, titanium oxide, tin oxide, and/or cerium oxide are contained.
構成低折射率材料層的材料可使用折射率為1.6以下的材料,選擇折射率通常為1.2~1.6的材料。此種材料例如可列舉:二氧化矽、氧化鋁、氟化鑭、氟化鎂及六氟化鋁鈉。 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 usually 1.2 to 1.6 is selected. Examples of such a material include cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride.
關於將高折射率材料層與低折射率材料層積層的方法,只要形成將該些材料層積層而成的介電質多層膜,則並無特別限制。例如可於樹脂製基板上直接藉由化學氣相沈積(Chemical Vapor Deposition,CVD)法、濺鍍法、真空蒸鍍法、離子輔助蒸鍍法或離子鍍敷法等,形成將高折射率材料層與低折射率材料層交替積層而成的介電質多層膜。 The method of laminating the high refractive index material layer and the low refractive index material is not particularly limited as long as the dielectric multilayer film in which the materials are laminated is formed. For example, a high refractive index material can be formed directly on a resin substrate by a chemical vapor deposition (CVD) method, a sputtering method, a vacuum deposition method, an ion assist evaporation method, or an ion plating method. A dielectric multilayer film in which a layer and a low refractive index material layer are alternately laminated.
通常若將欲阻斷的近紅外線波長設定為λ(nm),則高折射率材料層及低折射率材料層各層的厚度較佳為0.1λ~0.5λ的厚度。λ(nm)的值例如為700nm~1400nm,較佳為750nm~1300nm。若厚度為該範圍,則由λ/4對折射率(n)與膜厚(d)之積(n×d)進行計算所得的光學膜厚與高折射率材料層及低折射率材料層的各層的厚度成為大致相同的值,根據反射、折射的光學特 性的關係,有可容易地控制特定波長的阻斷、透射的傾向。 Generally, when the near-infrared wavelength to be blocked is set to λ (nm), the thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0.1 λ to 0.5 λ. The value of λ (nm) is, for example, 700 nm to 1400 nm, preferably 750 nm to 1300 nm. When the thickness is in this range, the optical film thickness calculated from the product of λ/4 versus the refractive index (n) and the film thickness (d) (n×d) and the high refractive index material layer and the low refractive index material layer are The thickness of each layer becomes approximately the same value, depending on the optical properties of reflection and refraction Sexual relationships have a tendency to easily control the blocking and transmission of specific wavelengths.
介電質多層膜的高折射率材料層與低折射率材料層的合計積層數於濾光器總體中較佳為5層~60層,更佳為10層~50層。 The total number of layers of the high refractive index material layer and the low refractive index material layer of the dielectric multilayer film is preferably 5 to 60 layers, more preferably 10 to 50 layers, in the entire filter.
[其他功能膜] [Other functional films]
本發明的濾光器中,可於不損及本發明的效果的範圍內,於樹脂製基板與介電質多層膜等近紅外線反射膜之間等適當設置抗反射膜、硬塗膜及抗靜電膜等功能膜,以提高樹脂製基板或近紅外線反射膜的表面硬度,提高耐化學品性,抗靜電及消除損傷等。 In the optical filter of the present invention, an antireflection film, a hard coat film, and an anti-reflection film are appropriately provided between a resin substrate and a near-infrared reflective film such as a dielectric multilayer film, etc., within a range that does not impair the effects of the present invention. A functional film such as an electrostatic film improves the surface hardness of a resin substrate or a near-infrared reflective film, improves chemical resistance, and is resistant to static electricity and damage.
為了提高樹脂製基板與功能膜及/或近紅外線反射膜的密接性、或功能膜與近紅外線反射膜的密接性,亦可對樹脂製基板或功能膜的表面實施電暈處理或電漿處理等表面處理。 In order to improve the adhesion between the resin substrate and the functional film and/or the near-infrared reflective film, or the adhesion between the functional film and the near-infrared reflective film, the surface of the resin substrate or the functional film may be subjected to corona treatment or plasma treatment. Wait for surface treatment.
[濾光器的特性等] [The characteristics of the filter, etc.]
本發明的濾光器具有所述樹脂製基板。因此,本發明的濾光器的透射率特性優異,於使用時不會受到制約。而且,樹脂製基板所含的化合物(A)於波長700nm~800nm內具有最大吸收,故可高效地吸收近紅外光,藉由與所述近紅外線反射膜組合,可獲得入射角依存性低的濾光器。 The optical filter of the present invention has the resin substrate. Therefore, the optical filter of the present invention is excellent in transmittance characteristics and is not restricted in use. Further, since the compound (A) contained in the resin substrate has maximum absorption at a wavelength of from 700 nm to 800 nm, it is possible to efficiently absorb near-infrared light, and by combining with the near-infrared reflecting film, low incident angle dependency can be obtained. Filter.
藉由將所述樹脂製基板用於近紅外線截止濾波器等濾光器,可獲得:在波長560nm~800nm的範圍內自光學膜的垂直方向測定時的透射率成為50%的波長的值(Xa)、與自相對於光學膜的垂直方向成30°的角度測定時的透射率成為50%的波長的值 (Xb)的差的絕對值變小,以及在波長560nm~800nm的區域內自光學膜的垂直方向測定時的透射率成為10%的波長的值(Za)、與自相對於光學膜的垂直方向成30°的角度測定時的透射率成為10%的波長的值(Zb)的差的絕對值變小,吸收波長的入射角依存性變小,即使在透射波長範圍的邊緣附近視角亦廣的濾光器。本發明的濾光器中,(Xa)與(Xb)的差的絕對值較佳為小於20nm,更佳為小於15nm,尤佳為小於10nm,且(Za)與(Zb)的差的絕對值較佳為18nm以下,尤佳為15nm以下。 By using the resin substrate as a filter such as a near-infrared cut filter, it is possible to obtain a value of a wavelength at which the transmittance is 50% when measured in the vertical direction of the optical film in the range of 560 nm to 800 nm. Xa), a value of a wavelength at which the transmittance is 50% when measured at an angle of 30° with respect to the vertical direction of the optical film The absolute value of the difference of (Xb) is small, and the value (Za) of the wavelength at which the transmittance is 10% from the vertical direction of the optical film in the region of the wavelength of 560 nm to 800 nm, and the vertical from the optical film. When the angle is 30°, the absolute value of the difference (Zb) of the wavelength at which the transmittance is 10% becomes small, and the incident angle dependence of the absorption wavelength becomes small, and the viewing angle is wide even near the edge of the transmission wavelength range. Filter. In the optical filter of the present invention, the absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, still more preferably less than 10 nm, and the absolute difference between (Za) and (Zb) The value is preferably 18 nm or less, and particularly preferably 15 nm or less.
於將所述濾光器用於固體攝像元件用的情形時,較佳的是可見光透射率高。尤其近年來,於照相機模組中亦強烈要求高畫質化,為了提高攝像感度或色彩再現性,而需提高波長430nm~460nm的短波長側的透射率。具體而言,波長430nm~460nm的平均透射率較佳為81%以上,更佳為83%以上,尤佳為85%以上。而且,較佳的是波長461nm~580nm的平均透射率亦同樣地高,較佳為85%以上,更佳為88%以上,尤佳為90%以上。若各個波長範圍內平均透射率在該範圍內,則於用作固體攝像元件用途時,可達成優異的攝像感度與色彩再現性。 When the filter is used for a solid-state image sensor, it is preferred that the visible light transmittance is high. In particular, in recent years, high image quality has been strongly demanded in camera modules, and in order to improve image sensitivity or color reproducibility, it is necessary to increase the transmittance on the short-wavelength side of wavelengths of 430 nm to 460 nm. Specifically, the average transmittance of the wavelength of 430 nm to 460 nm is preferably 81% or more, more preferably 83% or more, and particularly preferably 85% or more. Further, it is preferable that the average transmittance of the wavelength of 461 nm to 580 nm is also high, preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. When the average transmittance in each wavelength range is within this range, excellent imaging sensitivity and color reproducibility can be achieved when used as a solid-state imaging device.
於將所述濾光器用於固體攝像元件用的情形時,較佳的是近紅外波長範圍的透射率低。尤其,已知波長800nm~1000nm的區域中固體攝像元件的受光感度較高,藉由降低該波長範圍的透射率,可有效地進行照相機圖像與人眼的視感度修正,可達成優異的色彩再現性。波長800nm~1000nm的平均透射率較佳為 15%以下,進而佳為10%以下,尤佳為5%以下。若波長800nm~1000nm的平均透射率在該範圍內,則可充分截止近紅外線,可達成優異的色彩再現性,故較佳。 In the case where the filter is used for a solid-state image sensor, it is preferable that the transmittance in the near-infrared wavelength range is low. In particular, it is known that the solid-state imaging device has a high light-receiving sensitivity in a region having a wavelength of 800 nm to 1000 nm, and by reducing the transmittance in the wavelength range, the camera image and the human eye can be effectively corrected in visibility, and excellent color can be achieved. Reproducibility. The average transmittance of the wavelength of 800 nm to 1000 nm is preferably 15% or less, and further preferably 10% or less, and particularly preferably 5% or less. When the average transmittance of the wavelength of 800 nm to 1000 nm is within this range, the near-infrared rays can be sufficiently cut off, and excellent color reproducibility can be achieved, which is preferable.
[濾光器的用途] [Use of filter]
本發明的濾光器的視角廣,具有優異的近紅外線截止功能等。因此,有效用作照相機模組的CCD或CMOS影像感測器等固體攝像元件的視感度修正用。尤其有效用於數位靜態照相機、行動電話用照相機、數位攝影機、個人電腦用照相機、監視照相機、汽車用照相機、電視、汽車導航系統用車載裝置、行動資訊終端機、視訊遊戲機、可攜式遊戲機、指紋認證系統用裝置、數位音樂播放器等中。進而,亦有效用作安裝於汽車或建築物等的玻璃板等上的熱線截止濾波器等。 The filter of the present invention has a wide viewing angle and an excellent near-infrared cut-off function. Therefore, it is effectively used as a photographic sensitivity correction for a solid-state imaging device such as a CCD or a CMOS image sensor of a camera module. It is especially effective for digital still cameras, mobile phone cameras, digital cameras, personal computer cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, mobile information terminals, video game consoles, and portable games. Machine, fingerprint authentication system device, digital music player, etc. Further, it is also effective as a hot wire cut filter or the like attached to a glass plate or the like of an automobile or a building.
[固體攝像裝置] [Solid camera]
本發明的固體攝像裝置具備本發明的濾光器。此處,所謂固體攝像裝置,是指具備CCD或CMOS影像感測器等固體攝像元件的影像感測器,具體而言為數位靜態照相機、行動電話用照相機、數位攝影機等。例如,本發明的照相機模組具備本發明的濾光器。 The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device refers to an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor, and is specifically a digital still camera, a mobile phone camera, a digital camera, or the like. For example, the camera module of the present invention is provided with the filter of the present invention.
[實施例] [Examples]
以下,基於實施例對本發明加以更具體說明,但本發明不受該些實施例的任何限定。再者,「份」只要無特別說明,則是指「重量份」。另外,各物性值的測定方法及物性的評價方法如下。 Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples. In addition, "parts" means "parts by weight" unless otherwise specified. Moreover, the measuring method of each physical property value and the evaluation method of physical property are as follows.
<分子量> <molecular weight>
樹脂的分子量是考慮各樹脂於溶劑中的溶解性等,利用下述(a)或(b)的方法進行測定。 The molecular weight of the resin is measured by the method of the following (a) or (b) in consideration of the solubility of each resin in a solvent.
(a)使用沃特世(WATERS)公司製造的凝膠滲透層析(GPC)裝置(150C型,管柱:東曹公司製造的H型管柱,展開溶劑:鄰二氯苯),測定標準聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)。 (a) Using a gel permeation chromatography (GPC) apparatus manufactured by WATERS (150C type, column: H-type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), measurement standard The polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn).
(b)使用東曹公司製造的GPC裝置(HLC-8220型,管柱:TSKgelα-M,展開溶劑:四氫呋喃(tetrahydrofuran,THF)),測定標準聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)。 (b) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: tetrahydrofuran (THF)), measuring the weight average molecular weight (Mw) and quantity in terms of standard polystyrene Average molecular weight (Mn).
再者,關於後述樹脂合成例3中合成的樹脂,不進行利用上述方法的分子量的測定,而進行利用下述方法(c)的對數黏度的測定。 In the resin synthesized in the resin synthesis example 3 to be described later, the measurement of the molecular weight by the above method was not carried out, and the measurement of the logarithmic viscosity by the following method (c) was carried out.
(c)將聚醯亞胺樹脂溶液的一部分投入至無水甲醇中而使聚醯亞胺樹脂析出,進行過濾而自未反應單體中分離。將於80°℃下進行12小時真空乾燥所得的聚醯亞胺0.1g溶解於N-甲基-2-吡咯啶酮20mL中,使用堪農-芬斯基式(Cannon-Fenske)黏度計,藉由下述式來求出30℃的對數黏度(μ)。 (c) A part of the polyimine resin solution is poured into anhydrous methanol to precipitate a polyimine resin, which is filtered and separated from the unreacted monomer. 0.1 g of polyimine obtained by vacuum drying at 80 ° C for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone using a Cannon-Fenske viscometer. The logarithmic viscosity (μ) at 30 ° C was obtained by the following formula.
μ={ln(ts/t0)}/C μ={ln(t s /t 0 )}/C
t0:溶劑的流下時間 t 0 : the flow time of the solvent
ts:稀薄高分子溶液的流下時間 t s : the flow time of the thin polymer solution
C:0.5g/dL C: 0.5g/dL
<玻璃轉移溫度(Tg)> <glass transition temperature (Tg)>
使用SII奈米科技(SII-Nanotechnologies)股份有限公司製造的示差掃描熱量計(DSC6200),於升溫速度為每分鐘20℃的條件下於氮氣流下測定。 Using a differential scanning calorimeter (DSC6200) manufactured by SII-Nanotechnologies Co., Ltd., the temperature was measured at a rate of 20 ° C per minute under a nitrogen stream.
<分光透射率> <Spectral transmittance>
樹脂製基板的最大吸收波長及最大吸收波長的透射率、濾光器的各波長範圍的透射率、(Xa)、(Xb)、(Za)及(Zb)是使用日立高新技術(Hitachi High-technologies)股份有限公司製造的分光光度計(U-4100)來測定。 The maximum absorption wavelength and the transmittance of the maximum absorption wavelength of the resin substrate, the transmittance of each wavelength range of the filter, and (Xa), (Xb), (Za), and (Zb) are Hitachi High-Tech (Hitachi High- Spectrophotometer (U-4100) manufactured by the company).
此處,關於自濾光器的垂直方向測定的情形的透射率,對如圖1(a)般相對於濾波器垂直地透射的光進行測定。另外,關於自相對於濾光器的垂直方向成30°的角度測定的情形的反射率,對如圖1(b)般以相對於濾波器的垂直方向成30°的角度透射的光進行測定。 Here, the transmittance of the case where the measurement was performed from the vertical direction of the optical filter was measured for light that was transmitted perpendicularly to the filter as shown in FIG. 1(a). Further, the reflectance in the case of measuring at an angle of 30° with respect to the vertical direction of the filter is measured for light transmitted at an angle of 30° with respect to the vertical direction of the filter as shown in Fig. 1(b). .
再者,除測定(Xb)或(Zb)的情形外,該透射率是於光相對於基板及濾波器垂直地入射的條件下使用該分光光度計進行測定而得。於測定(Xb)或(Zb)的情形時,該透射率是於光相對於濾波器的垂直方向成30°的角度入射的條件下使用該分光光度計進行測定而得。 Further, in addition to the measurement (Xb) or (Zb), the transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the substrate and the filter. In the case of measuring (Xb) or (Zb), the transmittance is measured using the spectrophotometer under the condition that light is incident at an angle of 30° with respect to the vertical direction of the filter.
<近紅外吸收色素的耐光性評價> <Evaluation of light resistance of near-infrared absorbing pigments>
使樹脂製基板於室內螢光燈(照度為1000勒克斯(lux))下暴露500小時,對樹脂中所含的近紅外線吸收色素的耐光性(環境光耐性)進行評價。根據樹脂製基板的吸收強度最高的波長(以下稱為「λa」;於樹脂製基板具有多個最大吸收時,λa為該些中吸收強度最高的波長)的螢光燈暴露前後的吸光度變化,算出色素殘存率(%)來評價耐光性。於螢光燈下暴露500小時後的色素殘存率較佳為85%以上,進而佳為90%以上,尤佳為95%以上。 The resin substrate was exposed to an indoor fluorescent lamp (illuminance of 1000 lux) for 500 hours, and the light resistance (ambient light resistance) of the near-infrared absorbing pigment contained in the resin was evaluated. The absorbance change before and after exposure of the fluorescent lamp according to the wavelength at which the absorption strength of the resin substrate is the highest (hereinafter referred to as "λa"; when the resin substrate has a plurality of maximum absorption, λa is the wavelength at which the absorption intensity is the highest). The color residual ratio (%) was calculated to evaluate the light resistance. The residual ratio of the pigment after exposure to the fluorescent lamp for 500 hours is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
[合成例] [Synthesis example]
關於下述實施例中所用的化合物(A)、方酸菁系化合物、酞菁系化合物及花青系化合物,利用通常已知的方法來合成。通常的合成方法例如可列舉:日本專利第3366697號公報、日本專利第2846091號公報、日本專利第2864475號公報、日本專利第3703869號公報、日本專利特開昭60-228448號公報、日本專利特開平1-146846號公報、日本專利特開平1-228960號公報、日本專利第4081149號公報、日本專利特開昭63-124054號公報、「酞菁-化學與功能」(IPC、1997年)、日本專利特開2007-169315號公報、日本專利特開2009-108267號公報、日本專利特開2010-241873號公報、日本專利第3699464號公報、日本專利第4740631號公報等中記載的方法。 The compound (A), the squaraine-based compound, the phthalocyanine-based compound, and the cyanine compound used in the following examples were synthesized by a generally known method. For example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. Hei 60-228448, and Japanese Patent No. Japanese Patent Laid-Open No. Hei 1-128960, Japanese Patent Laid-Open No. Hei No. 1-228960, Japanese Patent No. 4,081,149, Japanese Patent Laid-Open No. SHO-63-124054, "Phthadium-Chemistry and Function" (IPC, 1997), The method described in JP-A-2007-169315, JP-A-2009-108267, JP-A-2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4,746,631.
<樹脂合成例1> <Resin Synthesis Example 1>
將下述式(a)所表示的8-甲基-8-甲氧基羰基四環[4.4.0.12,5.17,10]十二-3-烯(以下亦稱為「DNM」)100份、1-己烯 (分子量調節劑)18份及甲苯(開環聚合反應用溶劑)300份添加至經氮氣置換的反應容器中,將該溶液加熱至80℃。繼而,於反應容器內的溶液中添加作為聚合觸媒的三乙基鋁的甲苯溶液(0.6mol/L)0.2份、甲醇改質的六氯化鎢的甲苯溶液(濃度為0.025mol/L)0.9份,將該溶液於80℃下加熱攪拌3小時,藉此進行開環聚合反應而獲得開環聚合物溶液。該聚合反應的聚合轉化率為97%。 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 .1 7,10 ]dodecene represented by the following formula (a) (hereinafter also referred to as "DNM") 100 parts, 18 parts of 1-hexene (molecular weight modifier), and 300 parts of toluene (solvent for ring-opening polymerization reaction) were added to a reaction vessel substituted with nitrogen, and the solution was heated to 80 °C. Then, 0.2 parts of a toluene solution (0.6 mol/L) of triethylaluminum as a polymerization catalyst, and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/L) were added to the solution in the reaction vessel. 0.9 parts, the solution was heated and stirred at 80 ° C for 3 hours, thereby performing ring-opening polymerization to obtain a ring-opening polymer solution. The polymerization conversion ratio of this polymerization reaction was 97%.
將如此所得的開環聚合物溶液1,000份放入至高壓釜中,於該開環聚合物溶液中添加0.12份的RuHCl(CO)[P(C6H5)3]3,於氫氣壓為100kg/cm2、反應溫度為165℃的條件下加熱攪拌3小時而進行氫化反應。將所得的反應溶液(氫化聚合物溶液)冷卻後,釋放氫氣壓。將該反應溶液注入至大量的甲醇中並將凝固物分離回收,將其乾燥而獲得氫化聚合物(以下亦稱為「樹脂A」)。所得的樹脂A的數量平均分子量(Mn)為32,000,重量平均分子量(Mw)為137,000,玻璃轉移溫度(Tg)為165℃。 1,000 parts of the thus obtained ring-opening polymer solution was placed in an autoclave, and 0.12 part of RuHCl(CO)[P(C 6 H 5 ) 3 ] 3 was added to the ring-opening polymer solution at a hydrogen pressure of The hydrogenation reaction was carried out by heating and stirring for 3 hours at 100 kg/cm 2 and a reaction temperature of 165 °C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen pressure was released. This reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 °C.
<樹脂合成例2> <Resin Synthesis Example 2>
於3L的四口燒瓶中添加2,6-二氟苄腈35.12g(0.253mol)、9,9-雙(4-羥基苯基)茀87.60g(0.250mol)、碳酸鉀41.46g(0.300mol)、N,N-二甲基乙醯胺(以下亦稱為「DMAc」)443g及甲苯111g。繼而,於四口燒瓶上安裝溫度計、攪拌機、帶有氮氣導入管的三通旋塞(three-way cock)、迪恩-斯達克(Dean-stark)管及冷凝管。繼而,對燒瓶內進行氮氣置換後,使所得的溶液於140℃下反應3小時,將所生成的水自迪恩-斯達克(Dean-stark)管中隨時去除。於確認不到水的生成時,使溫度緩緩上升至160℃為止,保持該溫度而進行6小時反應。冷卻至室溫(25℃)為止後,利用濾紙將所生成的鹽去除,將濾液投入至甲醇中進行再沈澱,藉由過濾分離來離析出過濾物(殘渣)。將所得的過濾物於60℃下真空乾燥一夜,獲得白色粉末(以下亦稱為「樹脂B」)(產率為95%)。所得的樹脂B的數量平均分子量(Mn)為75,000,重量平均分子量(Mw)為188,000,玻璃轉移溫度(Tg)為285℃。 2,6-difluorobenzonitrile 35.12 g (0.253 mol), 9,9-bis(4-hydroxyphenyl)phosphonium 87.60 g (0.250 mol), potassium carbonate 41.46 g (0.300 mol) were added to a 3 L four-necked flask. ), N,N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene 111 g. Then, a four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-stark tube, and a condenser. Then, after the inside of the flask was purged with nitrogen, the resulting solution was reacted at 140 ° C for 3 hours, and the generated water was removed from the Dean-stark tube at any time. When the formation of water was not confirmed, the temperature was gradually raised to 160 ° C, and the temperature was maintained to carry out a reaction for 6 hours. After cooling to room temperature (25 ° C), the formed salt was removed by a filter paper, and the filtrate was poured into methanol to be reprecipitated, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60 ° C overnight to obtain a white powder (hereinafter also referred to as "resin B") (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 °C.
<樹脂合成例3> <Resin Synthesis Example 3>
於具備溫度計、攪拌器、氮氣導入管、帶有側管的滴液漏斗、迪恩-斯達克管及冷凝管的500mL的五口燒瓶中,於氮氣流下加入1,4-雙(4-胺基-α,α-二甲基苄基)苯27.66g(0.08莫耳)及4,4'-雙(4-胺基苯氧基)聯苯7.38g(0.02莫耳),使其溶解於γ-丁內酯68.65g及N,N-二甲基乙醯胺17.16g中。使用冰水浴將所得的溶液冷卻至5℃,一面保持於該溫度,一面一次性添加1,2,4,5-環己烷四羧酸二酐22.62g(0.1莫耳)及作為醯亞胺化觸媒的三乙胺 0.50g(0.005莫耳)。添加結束後,升溫至180℃,一面隨時將餾出液蒸餾去除,一面回流6小時。反應結束後,氣冷至內溫成為100℃為止後,添加N,N-二甲基乙醯胺143.6g進行稀釋,一面攪拌一面冷卻,獲得固體成分濃度為20重量%的聚醯亞胺樹脂溶液264.16g。將該聚醯亞胺樹脂溶液的一部分注入至1L的甲醇中而使聚醯亞胺沈澱。以甲醇將過濾分離的聚醯亞胺清洗後,於100℃的真空乾燥機中乾燥24小時而獲得白色粉末(以下亦稱為「樹脂C」)。對所得的樹脂C的紅外(Infrared,IR)光譜進行測定,結果可見醯亞胺基所特有的1704cm-1、1770cm-1的吸收。樹脂C的玻璃轉移溫度(Tg)為310℃,對對數黏度進行測定,結果為0.87。 In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, a Dean-Stark tube, and a condenser tube, 1,4-double (4-) was added under a nitrogen stream. 27.66 g (0.08 mol) of amino-α,α-dimethylbenzyl)benzene and 7.38 g (0.02 mol) of 4,4′-bis(4-aminophenoxy)biphenyl to dissolve In γ-butyrolactone 68.65 g and N,N-dimethylacetamide 17.16 g. The resulting solution was cooled to 5 ° C using an ice water bath, and while maintaining the temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in one portion and as a quinone imine. Catalyst triethylamine 0.50 g (0.005 mol). After the completion of the addition, the temperature was raised to 180 ° C, and the distillate was distilled off at any time, and refluxed for 6 hours. After completion of the reaction, the mixture was air-cooled to an internal temperature of 100 ° C, and then diluted with 143.6 g of N,N-dimethylacetamide, and cooled while stirring to obtain a polyimide resin having a solid concentration of 20% by weight. The solution was 264.16 g. A part of the polyimine resin solution was poured into 1 L of methanol to precipitate a polyimine. After the filter-separated polyimine was washed with methanol, it was dried in a vacuum dryer at 100 ° C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (Infrared, IR) spectrum of the obtained resin C was measured, and as a result, absorption of 1704 cm -1 and 1770 cm -1 peculiar to the quinone imine group was observed. The glass transition temperature (Tg) of the resin C was 310 ° C, and the logarithmic viscosity was measured and found to be 0.87.
<樹脂合成例4> <Resin Synthesis Example 4>
將9,9-雙(4-(2-羥基乙氧基)苯基)茀9.167kg(20.90莫耳)、雙酚A 4.585kg(20.084莫耳)、碳酸二苯酯9.000kg(42.01莫耳)及碳酸氫鈉0.02066kg(2.459×10-4莫耳)放入至具備攪拌機及餾出裝置的50L反應器中,於氮氣環境下於760托(Torr)下用1小時加熱至215℃並進行攪拌。其後,用15分鐘將減壓度調整為150Torr,於215℃、150Torr的條件下保持20分鐘,進行酯交換反應。進而,以37.5℃/Hr的速度升溫至240℃為止,於240℃、150Torr下保持10分鐘後,用10分鐘調整至120Torr,於240℃、120Torr下保持70分鐘後,進而用10分鐘調整至100Torr,於240℃、100Torr下保持10分鐘。其後,用40分鐘調整為1Torr以下,於240℃、1Torr以下的條件下攪拌10分鐘來進行聚合反 應。反應結束後,於反應器內導入氮氣而成為加壓狀態,將所生成的聚碳酸酯樹脂(以下亦稱為「樹脂D」)一面顆粒化一面抽出。所得的樹脂D的重量平均分子量為41,000,玻璃轉移溫度(Tg)為152℃。 9,9-bis(4-(2-hydroxyethoxy)phenyl)phosphonium 9.167 kg (20.90 mol), bisphenol A 4.585 kg (20.084 mol), diphenyl carbonate 9.000 kg (42.01 mol) And 0.02066 kg (2.459 × 10 -4 mol) of sodium hydrogencarbonate were placed in a 50 L reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C for 1 hour under a nitrogen atmosphere at 760 Torr. Stir. Thereafter, the degree of pressure reduction was adjusted to 150 Torr over 15 minutes, and the mixture was kept at 215 ° C and 150 Torr for 20 minutes to carry out a transesterification reaction. Further, the temperature was raised to 240 ° C at a rate of 37.5 ° C / Hr, and the temperature was maintained at 240 ° C and 150 Torr for 10 minutes, adjusted to 120 Torr for 10 minutes, and maintained at 240 ° C and 120 Torr for 70 minutes, and further adjusted to 10 minutes. 100 Torr, kept at 240 ° C, 100 Torr for 10 minutes. Thereafter, the mixture was adjusted to 1 Torr or less in 40 minutes, and stirred at 240 ° C for 1 minute or less to carry out a polymerization reaction. After the completion of the reaction, nitrogen gas was introduced into the reactor to be pressurized, and the produced polycarbonate resin (hereinafter also referred to as "resin D") was taken out while being pelletized. The obtained resin D had a weight average molecular weight of 41,000 and a glass transition temperature (Tg) of 152 °C.
<樹脂合成例5> <Resin Synthesis Example 5>
於反應器中添加9,9-雙{4-(2-羥基乙氧基)-3,5-二甲基苯基}茀0.8莫耳、乙二醇2.2莫耳及間苯二甲酸二甲酯1.0莫耳,一面攪拌一面緩緩加熱熔融而進行酯交換反應。繼而,添加氧化鍺20×10-4莫耳,一面緩緩進行升溫及減壓直至達到290℃、1Torr以下為止一面去除乙二醇。其後,將內容物自反應器中取出,獲得聚酯樹脂(以下亦稱為「樹脂E」)的顆粒。所得的樹脂E的數量平均分子量為40,000,玻璃轉移溫度為145℃。 9,9-bis{4-(2-hydroxyethoxy)-3,5-dimethylphenyl}fluorene 0.8 mol, ethylene glycol 2.2 mol and isophthalic acid were added to the reactor. The ester was 1.0 mol, and was slowly heated and melted while stirring to carry out a transesterification reaction. Then, while adding cerium oxide 20 × 10 -4 mol, the ethylene glycol was removed while gradually raising the temperature and reducing the pressure until it reached 290 ° C and 1 Torr or less. Thereafter, the contents were taken out from the reactor to obtain pellets of a polyester resin (hereinafter also referred to as "resin E"). The obtained resin E had a number average molecular weight of 40,000 and a glass transition temperature of 145 °C.
<樹脂合成例6> <Resin Synthesis Example 6>
於具備溫度計、冷凝管、氣體導入管及攪拌機的反應器中,添加4,4'-雙(2,3,4,5,6-五氟苯甲醯基)二苯基醚(BPDE)16.74份、9,9-雙(4-羥基苯基)茀(HF)10.5份、碳酸鉀4.34份及DMAc 90份。將該混合物加溫至80℃,反應8小時。反應結束後,一面利用摻合機(blender)劇烈攪拌反應溶液,一面添加至1%乙酸水溶液中。將析出的反應物過濾分離,以蒸餾水及甲醇進行清洗後,進行減壓乾燥,獲得氟化聚醚酮(以下亦稱為「樹脂F」)。所得的樹脂F的數量平均分子量為71000,玻璃轉移溫度(Tg)為242℃。 Add 4,4'-bis(2,3,4,5,6-pentafluorobenzylidene) diphenyl ether (BPDE) 16.74 to a reactor equipped with a thermometer, a condenser, a gas introduction tube and a stirrer. Parts: 9,0.5 parts of 9,9-bis(4-hydroxyphenyl)fluorene (HF), 4.34 parts of potassium carbonate, and 90 parts of DMAc. The mixture was warmed to 80 ° C and allowed to react for 8 hours. After completion of the reaction, the reaction solution was vigorously stirred by a blender, and added to a 1% aqueous acetic acid solution. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as "resin F"). The obtained resin F had a number average molecular weight of 71,000 and a glass transition temperature (Tg) of 242 °C.
[實施例1] [Example 1]
於容器中添加樹脂合成例1中所得的樹脂A 100重量份、作為化合物(A)的上述表1中記載的化合物(a-12)(二氯甲烷(dichloromethane)中的最大吸收波長為736nm)0.06重量份、及二氯甲烷(methylene chloride)而獲得樹脂濃度為20重量%的溶液。繼而,將所得的溶液澆鑄至平滑的玻璃板上,於20℃下乾燥8小時後,自玻璃板上剝離。將所剝離的塗膜進一步於減壓下、於100℃下乾燥8小時,獲得厚度為0.1mm、縱長為60mm、橫長為60mm的基板。 100 parts by weight of the resin A obtained in the resin synthesis example 1 and the compound (a-12) described in the above Table 1 as the compound (A) (the maximum absorption wavelength in dichloromethane was 736 nm) was added to the container. 0.06 parts by weight and methylene chloride were used to obtain a solution having a resin concentration of 20% by weight. Then, the obtained solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a longitudinal length of 60 mm, and a lateral length of 60 mm.
對該基板的分光透射率進行測定,求出樹脂製基板的最大吸收波長、最大吸收波長下的透射率及耐光性試驗後的色素殘存率,結果分別為736nm、2%及100%。將結果示於表2中。 The spectral transmittance of the substrate was measured, and the maximum absorption wavelength of the resin substrate, the transmittance at the maximum absorption wavelength, and the residual ratio of the dye after the light resistance test were determined and found to be 736 nm, 2%, and 100%, respectively. The results are shown in Table 2.
繼而,於所得的基板的單面上於蒸鍍溫度100℃下形成反射近紅外線的多層蒸鍍膜[二氧化矽(SiO2;膜厚83nm~199nm)層與氧化鈦(TiO2;膜厚101nm~125nm)層交替積層而成,積層數為20],進而於基板的另一面上於蒸鍍溫度100℃下形成反射近紅外線的多層蒸鍍膜[二氧化矽(SiO2;膜厚77nm~189nm)層與氧化鈦(TiO2;膜厚84nm~118nm)層交替積層而成,積層數為26],獲得厚度為0.105mm的濾光器。對該濾光器的分光透射率進行測定,評價各波長範圍的光學特性。 Then, a multilayer vapor-deposited film of near-infrared rays was formed on one surface of the obtained substrate at a vapor deposition temperature of 100 ° C [cerium oxide (SiO 2 ; film thickness: 83 nm to 199 nm) layer and titanium oxide (TiO 2 ; film thickness: 101 nm). ~125nm) layer is alternately laminated, the number of layers is 20], and a multilayer vapor-deposited film reflecting near-infrared rays is formed on the other surface of the substrate at a vapor deposition temperature of 100 ° C [SiO 2 (film thickness 77 nm to 189 nm) The layer was formed by alternately laminating layers of titanium oxide (TiO 2 ; film thickness: 84 nm to 118 nm), and the number of layers was 26], and a filter having a thickness of 0.105 mm was obtained. The spectral transmittance of the filter was measured, and the optical characteristics in each wavelength range were evaluated.
波長430nm~460nm的透射率的平均值為87%,波長461nm~580nm的透射率的平均值為91%,波長800nm~1000nm的透射率的平均值為1%以下,絕對值|Xa-Xb|為5nm、|Za-Zb |為12nm。將結果示於表2中。 The average value of the transmittance at a wavelength of 430 nm to 460 nm is 87%, the average value of the transmittance at a wavelength of 461 nm to 580 nm is 91%, and the average value of the transmittance at a wavelength of 800 nm to 1000 nm is 1% or less, and the absolute value |Xa-Xb| 5nm, |Za-Zb | is 12nm. The results are shown in Table 2.
[實施例2]~[實施例17]及[比較例1]~[比較例5] [Example 2] to [Example 17] and [Comparative Example 1] to [Comparative Example 5]
於實施例1中,採用表2所示的透明樹脂、近紅外線吸收色素、溶劑、及膜乾燥條件,除此以外,與實施例1同樣地製造厚度為0.105mm的濾光器。將評價結果示於表2中。再者,於表2中,樹脂的添加份數均為100重量份,且樹脂溶液的濃度均為20重量%。而且,實施例及比較例中使用的各種化合物如下。 In the same manner as in Example 1, except that the transparent resin, the near-infrared absorbing dye, the solvent, and the film drying conditions shown in Table 2 were used, a filter having a thickness of 0.105 mm was produced. The evaluation results are shown in Table 2. Further, in Table 2, the number of parts of the resin added was 100 parts by weight, and the concentration of the resin solution was 20% by weight. Further, the various compounds used in the examples and comparative examples are as follows.
<透明樹脂> <Transparent Resin>
樹脂A:環狀烯烴系樹脂(樹脂合成例1) Resin A: cyclic olefin resin (resin synthesis example 1)
樹脂B:芳香族聚醚系樹脂(樹脂合成例2) Resin B: Aromatic polyether resin (Resin Synthesis Example 2)
樹脂C:聚醯亞胺系樹脂(樹脂合成例3) Resin C: Polyimine resin (Resin Synthesis Example 3)
樹脂D:茀聚碳酸酯系樹脂(樹脂合成例4) Resin D: 茀 polycarbonate resin (Resin Synthesis Example 4)
樹脂E:茀聚酯系樹脂(樹脂合成例5) Resin E: 茀 polyester resin (Resin Synthesis Example 5)
樹脂F:氟化聚醚酮(樹脂合成例6) Resin F: fluorinated polyether ketone (Resin Synthesis Example 6)
樹脂G:環狀烯烴系樹脂「瑞諾(Zeonor)1420R」(日本瑞翁(Zeon Japan)(股)製造) Resin G: a cyclic olefin resin "Zeonor 1420R" (manufactured by Zeon Japan Co., Ltd.)
樹脂H:環狀烯烴系樹脂「奧佩爾(APEL)# 6015」(三井化學(股)製造) Resin H: Cyclic olefin resin "APEL #6015" (manufactured by Mitsui Chemicals Co., Ltd.)
樹脂I:聚碳酸酯系樹脂「比艾斯(Pureace)」(帝人(股)製造) Resin I: polycarbonate resin "Pureace" (manufactured by Teijin Co., Ltd.)
樹脂J:聚醚碸系樹脂「斯密萊特(Sumilite)FS-1300」 (住友貝克萊特(Sumitomo Bakelite)(股)製造) Resin J: Polyether oxime resin "Sumilite FS-1300" (made by Sumitomo Bakelite (share))
樹脂K:耐熱丙烯酸系樹脂「亞克力瓦(Acryviewa)」(日本觸媒(股)製造) Resin K: Heat-resistant acrylic resin "Acryviewa" (manufactured by Nippon Shokubai Co., Ltd.)
<近紅外線吸收色素> <Near infrared absorbing pigment>
《化合物(A)》 Compound (A)
化合物(a-8):上述表1中記載的化合物(a-8)(二氯甲烷中的最大吸收波長為735nm) Compound (a-8): Compound (a-8) described in Table 1 above (maximum absorption wavelength in dichloromethane is 735 nm)
化合物(a-11):上述表1中記載的化合物(a-11)(二氯甲烷中的最大吸收波長為707nm) Compound (a-11): Compound (a-11) described in Table 1 above (maximum absorption wavelength in dichloromethane is 707 nm)
化合物(a-12):上述表1中記載的化合物(a-12)(二氯甲烷中的最大吸收波長為736nm) Compound (a-12): Compound (a-12) described in Table 1 above (maximum absorption wavelength in dichloromethane is 736 nm)
《近紅外線吸收色素(X)》 "Near infrared absorption pigment (X)"
化合物(X-1):下述式(X-1)所表示的方酸菁系化合物(二氯甲烷中的最大吸收波長為670nm) Compound (X-1): a squaraine-based compound represented by the following formula (X-1) (maximum absorption wavelength in dichloromethane is 670 nm)
化合物(X-2):下述式(X-2)所表示的方酸菁系化合物(二氯甲烷中的最大吸收波長為698nm) Compound (X-2): a squaraine-based compound represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane is 698 nm)
[化17]
化合物(X-3):下述式(X-3)所表示的花青系化合物(二氯甲烷中的最大吸收波長為681nm) Compound (X-3): a cyanine compound represented by the following formula (X-3) (maximum absorption wavelength in dichloromethane is 681 nm)
化合物(X-4):下述式(X-4)所表示的酞菁系化合物(二氯甲烷中的最大吸收波長為698nm) Compound (X-4): a phthalocyanine-based compound represented by the following formula (X-4) (maximum absorption wavelength in dichloromethane is 698 nm)
化合物(X-5):下述式(X-5)所表示的酞菁系化合物(二氯甲烷中的最大吸收波長為733nm) Compound (X-5): a phthalocyanine compound represented by the following formula (X-5) (maximum absorption wavelength in dichloromethane is 733 nm)
化合物(X-6):下述式(X-6)所表示的花青系化合物(二氯甲烷中的最大吸收波長為760nm) Compound (X-6): a cyanine compound represented by the following formula (X-6) (maximum absorption wavelength in dichloromethane is 760 nm)
化合物(X-7):下述式(X-7)所表示的酞菁系化合物(二氯甲烷中的最大吸收波長為681nm) Compound (X-7): a phthalocyanine compound represented by the following formula (X-7) (maximum absorption wavelength in dichloromethane is 681 nm)
[化22]
<溶劑> <solvent>
溶劑(1):二氯甲烷 Solvent (1): dichloromethane
溶劑(2):N,N-二甲基乙醯胺 Solvent (2): N,N-dimethylacetamide
溶劑(3):乙酸乙酯/甲苯(重量比:5/5) Solvent (3): ethyl acetate / toluene (weight ratio: 5/5)
溶劑(4):環己烷/二甲苯(重量比:7/3) Solvent (4): cyclohexane / xylene (weight ratio: 7/3)
溶劑(5):環己烷/二氯甲烷(重量比:99/1) Solvent (5): cyclohexane / dichloromethane (weight ratio: 99/1)
溶劑(6):N-甲基-2-吡咯啶酮 Solvent (6): N-methyl-2-pyrrolidone
表2中實施例及比較例的膜乾燥條件如下。再者,於減壓乾燥前將塗膜自玻璃板上剝離。 The film drying conditions of the examples and comparative examples in Table 2 are as follows. Further, the coating film was peeled off from the glass plate before drying under reduced pressure.
<膜乾燥條件> <film drying conditions>
條件(1):20℃/8hr→減壓下、100℃/8hr Condition (1): 20 ° C / 8 hr → reduced pressure, 100 ° C / 8 hr
條件(2):60℃/8hr→80℃/8hr→減壓下、140℃/8hr Condition (2): 60 ° C / 8 hr → 80 ° C / 8 hr → reduced pressure, 140 ° C / 8 hr
條件(3):60℃/8hr→80℃/8hr→減壓下、100℃/24hr Condition (3): 60 ° C / 8 hr → 80 ° C / 8 hr → reduced pressure, 100 ° C / 24 hr
條件(4):40℃/4hr→60℃/4hr→減壓下、100℃/8hr Condition (4): 40 ° C / 4 hr → 60 ° C / 4 hr → reduced pressure, 100 ° C / 8 hr
[產業上之可利用性] [Industrial availability]
本發明的濾光器可較佳地用於數位靜態照相機、行動電話用照相機、數位攝影機、個人電腦用照相機、監視照相機、汽車用照相機、電視、汽車導航系統用車載裝置、行動資訊終端機、視訊遊戲機、可攜式遊戲機、指紋認證系統用裝置、數位音樂播放器等中。進而,亦可較佳地用作安裝於汽車或建築物等的玻璃等上的熱線截止濾波器等。 The optical filter of the present invention can be preferably used for a digital still camera, a mobile phone camera, a digital camera, a personal computer camera, a surveillance camera, a car camera, a television, an in-vehicle device for a car navigation system, a mobile information terminal, Video game consoles, portable game consoles, devices for fingerprint authentication systems, digital music players, and the like. Further, it can be preferably used as a hot wire cut filter or the like attached to glass or the like of an automobile or a building.
1‧‧‧濾光器 1‧‧‧ Filter
2‧‧‧分光光度計 2‧‧‧Spectrophotometer
3‧‧‧光 3‧‧‧Light
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JP (1) | JP6398980B2 (en) |
KR (1) | KR102205190B1 (en) |
CN (2) | CN105531608B (en) |
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WO (1) | WO2015025779A1 (en) |
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KR20210055808A (en) * | 2016-03-22 | 2021-05-17 | 제이에스알 가부시끼가이샤 | Optical filter and apparatus using optical filter |
CN112596141B (en) * | 2016-06-08 | 2022-11-15 | Jsr株式会社 | Optical filter and optical sensor |
JP6870005B2 (en) * | 2017-02-01 | 2021-05-12 | 富士フイルム株式会社 | Curable composition, film, optical filter, solid-state image sensor, image display device and infrared sensor |
CN110741049A (en) * | 2017-06-08 | 2020-01-31 | 富士胶片株式会社 | Resin composition, resin molded article, and method for producing resin molded article |
WO2019151348A1 (en) | 2018-02-05 | 2019-08-08 | Agc株式会社 | Optical filter and imaging device |
KR20200128009A (en) | 2018-03-02 | 2020-11-11 | 제이에스알 가부시끼가이샤 | Optical filters, camera modules and electronic devices |
CN112639584A (en) * | 2018-09-05 | 2021-04-09 | 富士胶片株式会社 | Lens for spectacles and spectacles |
WO2021085372A1 (en) * | 2019-11-01 | 2021-05-06 | Jsr株式会社 | Resin composition, compound (z), optical filter, and use thereof |
JP7441686B2 (en) * | 2020-03-10 | 2024-03-01 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
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JPH0730300B2 (en) * | 1988-04-01 | 1995-04-05 | 三井東圧化学株式会社 | Alkyl phthalocyanine near infrared absorber and display / recording material using the same |
JP3163813B2 (en) | 1992-12-28 | 2001-05-08 | 日本ゼオン株式会社 | Near-infrared absorbing resin composition and molded article |
EP1247655B1 (en) * | 1999-12-28 | 2006-05-31 | Mitsui Chemicals, Inc. | Optical recording medium and novel azaporphyrin compounds |
JP4278923B2 (en) | 2002-06-12 | 2009-06-17 | 株式会社日本触媒 | Phthalocyanine compound and production method and use thereof |
JP4513420B2 (en) * | 2004-05-26 | 2010-07-28 | Jsr株式会社 | Near-infrared cut filter and manufacturing method thereof |
JP4926074B2 (en) * | 2005-05-10 | 2012-05-09 | 株式会社日本触媒 | Adhesive composition containing near infrared absorber |
JP5449659B2 (en) * | 2007-09-04 | 2014-03-19 | 株式会社ブリヂストン | Near-infrared shield, laminate using the same, optical filter for display, and display |
JP5823119B2 (en) * | 2010-12-27 | 2015-11-25 | キヤノン電子株式会社 | Optical filter for UV-IR cut |
JP5996901B2 (en) | 2011-09-02 | 2016-09-21 | 株式会社日本触媒 | Light selective transmission filter, resin sheet, and solid-state image sensor |
JP5741347B2 (en) * | 2011-09-21 | 2015-07-01 | 旭硝子株式会社 | Optical filter and imaging apparatus using the same |
JP5848654B2 (en) | 2011-09-28 | 2016-01-27 | 株式会社日本触媒 | Light selective transmission filter, resin sheet, and solid-state image sensor |
KR101969612B1 (en) * | 2011-10-14 | 2019-04-16 | 제이에스알 가부시끼가이샤 | Optical filter, solid state image-capturing device using same, and camera module using same |
JP7030300B2 (en) * | 2016-09-30 | 2022-03-07 | 国立研究開発法人産業技術総合研究所 | Activated sludge containing 1,4-dioxane-degrading bacteria, wastewater treatment method using it, and method for identifying 1,4-dioxane-degrading bacteria. |
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KR20160045690A (en) | 2016-04-27 |
KR102205190B1 (en) | 2021-01-20 |
TWI582173B (en) | 2017-05-11 |
CN110669318A (en) | 2020-01-10 |
JPWO2015025779A1 (en) | 2017-03-02 |
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