TW202346373A - Near-infrared absorbing composition, near-infrared absorbing cured film and optical member wherein the near-infrared absorbing composition includes a dispersion medium containing a solvent whose polar item of the Hansen solubility parameter is in the range of 3 to 6, and whose hydrogen bonding item is in the range of 3 to 6 - Google Patents
Near-infrared absorbing composition, near-infrared absorbing cured film and optical member wherein the near-infrared absorbing composition includes a dispersion medium containing a solvent whose polar item of the Hansen solubility parameter is in the range of 3 to 6, and whose hydrogen bonding item is in the range of 3 to 6 Download PDFInfo
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- TW202346373A TW202346373A TW112100865A TW112100865A TW202346373A TW 202346373 A TW202346373 A TW 202346373A TW 112100865 A TW112100865 A TW 112100865A TW 112100865 A TW112100865 A TW 112100865A TW 202346373 A TW202346373 A TW 202346373A
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- Prior art keywords
- infrared absorbing
- range
- general formula
- compound
- absorbing composition
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical compound CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- KBNZVKRXIOSIEG-UHFFFAOYSA-L copper ethyl acetate diacetate Chemical compound C(C)(=O)[O-].[Cu+2].C(C)(=O)OCC.C(C)(=O)[O-] KBNZVKRXIOSIEG-UHFFFAOYSA-L 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 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
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- OGDSVONAYZTTDA-UHFFFAOYSA-N tert-butylphosphonic acid Chemical compound CC(C)(C)P(O)(O)=O OGDSVONAYZTTDA-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000005106 triarylsilyl group Chemical group 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000008096 xylene Substances 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
Images
Landscapes
- Optical Filters (AREA)
- Solid State Image Pick-Up Elements (AREA)
Abstract
Description
本發明關於近紅外線吸收性組成物、近紅外線吸收性硬化膜及光學構件。更詳細而言，關於分散安定性及樹脂相溶性優異，且能減低環境負荷之近紅外線吸收性組成物、近紅外線吸收性硬化膜及光學構件。The present invention relates to a near-infrared absorbing composition, a near-infrared absorbing cured film, and an optical member. More specifically, it relates to near-infrared absorbing compositions, near-infrared absorbing cured films and optical components that are excellent in dispersion stability and resin compatibility and can reduce environmental load.
近年來，於攝影機、數位靜態相機、附相機功能之行動電話等中使用彩色圖像之固體攝像元件的CCD(Charge Coupled Device)或CMOS(Complementary Metal Oxide Semiconductor)影像感測器，但該等固體攝像元件由在其受光部中使用對近紅外線波長區域的光具有感度之矽光電二極體，故必須進行視感度修正，大多使用近紅外線截止濾光片作為光學濾光片。In recent years, CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) image sensors with color image solid-state imaging elements have been used in cameras, digital still cameras, mobile phones with camera functions, etc., but these solid-state imaging sensors The imaging element uses a silicon photodiode that is sensitive to light in the near-infrared wavelength range in its light-receiving part. Therefore, visual sensitivity correction is required. In most cases, a near-infrared cutoff filter is used as an optical filter.
於這樣的近紅外線截止濾光片中，大致區分為吸收型與反射型，以往使用反射型，為了遮蔽紅外線或紫外線，利用介電體多層膜所致的光反射。 然而，適用於反射型的反射層由於具有容易依賴入射角度的特性，故最近主要檢討全吸收型，近年來，使用含有光吸收劑的膜之光學濾光片受到注目。 如上述，使用含有光吸收劑的膜之光學濾光片係在攝像裝置的小型化及薄型化之點上亦有利，於光入射時，該光學濾光片的穿透率特性由於不易受到入射角之影響，故即使光斜地入射時，在攝影時亦可得到色調變化少的良好圖像。 Such near-infrared cut filters are roughly divided into absorptive and reflective types. The reflective type has been used in the past. In order to block infrared or ultraviolet rays, light reflection by a dielectric multilayer film is utilized. However, since the reflective layer suitable for the reflective type has characteristics that easily depend on the incident angle, the total absorption type has been mainly examined recently. In recent years, optical filters using films containing light absorbers have attracted attention. As mentioned above, using an optical filter using a film containing a light absorber is also advantageous in terms of miniaturization and thinning of an imaging device. When light is incident, the transmittance characteristics of the optical filter are less likely to be affected by the incident light. Because of the influence of the angle, even when light is incident obliquely, a good image with little color change can be obtained during photography.
例如專利文獻1中揭示一種含有膦酸化合物及銅離子的近紅外線吸收劑分散液之製造方法及近紅外線吸收劑分散液。
然而，作為上述分散液之調製中使用的有機溶劑，僅記載近紅外線吸收劑的反應溶劑，使用甲苯作為該反應溶劑。
但是，苯、甲苯、二甲苯等之揮發性芳香族烴由於是PRTR制度的對象物質，故有造成環境負荷之問題。
For example,
專利文獻2中揭示一種具備透明介電體基板與光吸收層之光學濾光片及用於形成該光吸收層之光吸收性組成物，該光吸收層含有藉由具有苯基或鹵化苯基的膦酸與銅離子所形成的光吸收劑。
此處，上述光吸收劑由於具有在醇等之具有比較高極性的有機溶劑中凝聚或沉降之可能性，故該光吸收劑的極性被認為低到對甲苯等低極性的有機溶劑顯示親和性的程度，為了使該光吸收劑良好地分散，被認為需要那樣的低極性有機溶劑，但使用甲苯等者係有與上述同樣的造成環境負荷之問題，另外亦有與含有甲苯的分散液相容性差的樹脂，從而存在光吸收性組成物所含有的樹脂之選擇範圍受限之問題。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2016-94512號公報 [專利文獻2]日本發明專利6339755號公報 [Patent Document 1] Japanese Patent Application Publication No. 2016-94512 [Patent Document 2] Japanese Invention Patent No. 6339755
[發明所欲解決的課題][Problem to be solved by the invention]
本發明係鑒於上述問題、狀況而完成者，其解決課題係提供分散安定性及樹脂相溶性優異，且能減低環境負荷之近紅外線吸收性組成物、近紅外線吸收性硬化膜及光學構件。 [解決課題的手段] The present invention was completed in view of the above-mentioned problems and situations, and its problem to be solved is to provide a near-infrared-absorbing composition, a near-infrared-absorbing cured film, and an optical member that are excellent in dispersion stability and resin compatibility and can reduce environmental load. [Means to solve the problem]
本發明者為了解決上述問題，對於上述問題之原因等進行檢討，結果發現：藉由近紅外線吸收性組成物所含有的分散介質含有溶劑，該溶劑之漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內，而可解決上述課題，達成本發明。 亦即，本發明之上述課題係可藉由以下手段而解決。 In order to solve the above problems, the present inventors examined the causes of the above problems and found that the dispersion medium contained in the near-infrared absorbing composition contains a solvent, and the value of the polar term δ P of the Hansen solubility parameter of the solvent is is in the range of 3 to 6, and the value of the hydrogen bond term δ H is in the range of 3 to 6, the above problems can be solved and the present invention can be achieved. That is, the above-mentioned problems of the present invention can be solved by the following means.
1.一種近紅外線吸收性組成物，其係含有近紅外線吸收劑及分散介質之近紅外線吸收性組成物，其特徵為：前述分散介質含有漢森(Hansen)溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 1. A near-infrared absorbing composition, which is a near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium, characterized in that the aforementioned dispersion medium contains the value of the polar term δ P of the Hansen solubility parameter is a solvent in the range of 3 to 6, and the value of the hydrogen bond term δ H is in the range of 3 to 6.
2.如第1項記載之近紅外線吸收性組成物，其中前述近紅外線吸收劑至少含有下述(A)成分或下述(B)成分。2. The near-infrared absorbing composition according to
＜成分＞： (A)成分：由具有下述通式(I)所示的結構之化合物、具有下述通式(II)所示的結構之化合物及銅離子所成之成分。 (B)成分：由具有下述通式(I)所示的結構之化合物配位的銅錯合物及具有下述通式(II)所示的結構之化合物配位的銅錯合物所成之成分。 ＜Ingredients＞: (A) Component: A component composed of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions. (B) Component: a copper complex coordinated by a compound having a structure represented by the following general formula (I) and a copper complex coordinated by a compound having a structure represented by the following general formula (II) ingredients.
[上述通式(I)中，R 1表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基]。 [In the above general formula (I), R 1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent].
[上述通式(II)中，R 2表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基；R 21~R 24各自獨立地表示氫原子或碳數為1~4的烷基；m表示R 21~R 24全部為氫原子的部分結構單元之平均加成數，且為0~19之範圍內；n表示R 21~R 24之至少1個是碳數為1~4的烷基的部分結構單元之平均加成數，且為0~19之範圍內；m+n為m及n之總數，且為1~20之範圍內；Z表示由下述通式(Z-1)~(Z-3)所選出的結構單元]。 [In the above general formula (II), R 2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent; R 21 to R 24 each independently represents a hydrogen atom or Alkyl group with 1 to 4 carbon atoms; m represents the average addition number of partial structural units in which all R 21 to R 24 are hydrogen atoms, and is in the range of 0 to 19; n represents at least one of R 21 to R 24 is the average addition number of some structural units of alkyl groups with 1 to 4 carbon atoms, and is in the range of 0 to 19; m+n is the total number of m and n, and is in the range of 1 to 20; Z represents Structural units selected from the following general formulas (Z-1)~(Z-3)].
3.如第1項或第2項記載之近紅外線吸收性組成物，其中前述分散介質含有至少一種以上的前述漢森溶解度參數的分散項δ
D之值為16~22之範圍內的溶劑。
3. The near-infrared absorbing composition according to
4.如第1項至第3項中任一項記載之近紅外線吸收性組成物，其中前述分散介質含有至少一種以上的前述漢森溶解度參數的極性項δ
P之值為3~5之範圍內，且氫鍵項δ
H之值為3~5之範圍內的溶劑。
4. The near-infrared absorbing composition as described in any one of
5.如第1項至第4項中任一項記載之近紅外線吸收性組成物，其中前述分散介質含有沸點為80~150℃之範圍內的溶劑。5. The near-infrared absorbing composition according to any one of
6.如第1項至第5項中任一項記載之近紅外線吸收性組成物，其中前述分散介質含有至少具有環烷基或環醚基的醚。6. The near-infrared absorbing composition according to any one of
7.如第6項記載之近紅外線吸收性組成物，其中前述環烷基為環戊基或環己基。7. The near-infrared absorbing composition according to
8.如第6項記載之近紅外線吸收性組成物，其中前述環醚基為四氫呋喃基或四吡喃基。8. The near-infrared absorbing composition according to
9.如第1項至第8項中任一項記載之近紅外線吸收性組成物，其中前述分散介質至少含有環戊基甲基醚或4-甲基四氫吡喃。9. The near-infrared absorbing composition according to any one of
10.如第1項至第9項中任一項記載之近紅外線吸收性組成物，其中前述分散介質係相對於近紅外線吸收性組成物全量，以20~95質量%之範圍內含有漢森溶解度參數的極性項δ
P之值為3~6之範圍內，且氫鍵項δ
H之值為3~6之範圍內的溶劑。
10. The near-infrared absorbing composition according to any one of
11.如第1項至第10項中任一項記載之近紅外線吸收性組成物，其中前述通式(II)中的m為1~19之範圍內，且n為1~19之範圍內。11. The near-infrared absorbing composition as described in any one of
12.如第1項至第11項中任一項記載之近紅外線吸收性組成物，其中將具有前述通式(I)所示的結構之化合物的莫耳含量設為C
A，將具有前述通式(II)所示的結構之化合物的莫耳含量設為C
E時，莫耳比C
A/C
E之值為3.8~10之範圍內，且將銅離子的莫耳含量設為C
C，將具有前述通式(I)所示的結構之化合物及具有前述通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量設為C
H時，莫耳比C
H/C
C之值為1.5~2.5之範圍內。
12. The near-infrared absorbing composition according to any one of
13.一種近紅外線吸收性硬化膜，其特徵為含有如第1項至第12項中任一項記載之近紅外線吸收性組成物的硬化物。13. A near-infrared ray-absorbing cured film, characterized by being a cured product containing the near-infrared ray-absorbing composition according to any one of
14.一種光學構件，其特徵為含有如第1項至第12項中任一項記載之近紅外線吸收性組成物的硬化物。
[發明的效果]
14. An optical member characterized by a cured product containing the near-infrared absorbing composition according to any one of
藉由本發明之上述手段，可提供分散安定性及樹脂相溶性優異，且能減低環境負荷之近紅外線吸收性組成物、近紅外線吸收性硬化膜及光學構件。 關於本發明的效果之展現機構或作用機構尚不明確，但推測如以下。 By the above means of the present invention, it is possible to provide a near-infrared absorbing composition, a near-infrared absorbing cured film and an optical member that are excellent in dispersion stability and resin compatibility and can reduce environmental load. The mechanism by which the effects of the present invention are exhibited or acted upon is not yet clear, but it is estimated as follows.
本發明之近紅外線吸收性組成物係含有近紅外線吸收劑及分散介質之近紅外線吸收性組成物，其特徵為：前述分散介質含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium, and is characterized in that the dispersion medium contains the polar term δ P of the Hansen solubility parameter with a value of 3 to 6. Within the range, and the value of the hydrogen bond term δ H is within the range of 3 to 6.
如前述，以往之光學濾光片所用的膜中含有的光吸收劑係極性低，藉由與同樣極性低的甲苯等有機溶劑同時使用，可防止該光吸收劑之凝聚或沉降，但甲苯等由於是PRTR制度的對象物質，故有造成環境負荷之問題。 本發明中，即使不使用甲苯等極性低的有機溶劑，也可藉由將漢森溶解度參數之值控制在一定之範圍內，而防止光吸收劑之凝聚或沉降，推測藉此可提高分散安定性及樹脂相溶性，且減低環境負荷。 As mentioned above, the light absorbing agent contained in the film used for conventional optical filters has low polarity. By using it together with an organic solvent of similarly low polarity such as toluene, the aggregation or sedimentation of the light absorbing agent can be prevented. However, toluene, etc. Since it is a target substance of the PRTR system, there is a problem of environmental load. In the present invention, even if a low-polarity organic solvent such as toluene is not used, the value of the Hansen solubility parameter can be controlled within a certain range to prevent the aggregation or sedimentation of the light absorber. It is speculated that this can improve the dispersion stability. properties and resin compatibility, and reduce environmental load.
[實施發明的形態][Form of carrying out the invention]
本發明之近紅外線吸收性組成物係含有近紅外線吸收劑及分散介質之近紅外線吸收性組成物，其特徵為：前述分散介質含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 該特徵係共通或對應於下述各實施形態(態樣)之技術特徵。 The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium, and is characterized in that the dispersion medium contains the polar term δ P of the Hansen solubility parameter with a value of 3 to 6. Within the range, and the value of the hydrogen bond term δ H is within the range of 3 to 6. This feature is a technical feature common to or corresponding to each of the following embodiments (aspects).
作為本發明之實施態樣，前述近紅外線吸收劑至少含有前述(A)成分或前述(B)成分者，從分散安定性及樹脂相溶性之觀點來看較佳。As an embodiment of the present invention, the near-infrared absorber preferably contains at least the component (A) or the component (B) from the viewpoint of dispersion stability and resin compatibility.
前述分散介質含有至少一種以上的前述漢森溶解度參數的分散項δ D之值為16~22之範圍內的溶劑者，從分散安定性之觀點來看較佳。 From the viewpoint of dispersion stability, it is preferable that the dispersion medium contains at least one solvent in which the dispersion term δ D of the Hansen solubility parameter has a value in the range of 16 to 22.
前述分散介質含有至少一種以上的前述漢森溶解度參數的極性項δ P之值為3~5之範圍內，且氫鍵項δ H之值為3~5之範圍內的溶劑者，從分散安定性之觀點來看較佳。 If the aforementioned dispersion medium contains at least one solvent in which the polar term δ P of the Hansen solubility parameter has a value in the range of 3 to 5, and the hydrogen bond term δ H has a value in the range of 3 to 5, the dispersion is stable. It's better from a sexual point of view.
前述分散介質含有沸點為80~150℃之範圍內的溶劑者，從防止製膜時的龜裂之觀點來看較佳。The dispersion medium preferably contains a solvent with a boiling point in the range of 80 to 150° C. from the viewpoint of preventing cracks during film formation.
前述分散介質含有至少具有環烷基或環醚基的醚者，從分散性之觀點來看較佳。The dispersion medium preferably contains an ether having at least a cycloalkyl group or a cyclic ether group from the viewpoint of dispersibility.
前述環烷基為環戊基或環己基，從分散性之觀點來看更佳。The cycloalkyl group is a cyclopentyl group or a cyclohexyl group, which is more preferred from the viewpoint of dispersibility.
前述環醚基為四氫呋喃基或四吡喃基者，從分散性之觀點來看更佳。The cyclic ether group is preferably a tetrahydrofuryl group or a tetrapyranyl group from the viewpoint of dispersibility.
前述分散介質至少含有環戊基甲基醚或4-甲基四氫吡喃者，從分散性之觀點來看更佳。The dispersion medium containing at least cyclopentyl methyl ether or 4-methyltetrahydropyran is more preferred from the viewpoint of dispersibility.
前述分散介質係相對於近紅外線吸收性組成物全量，以20~95質量%之範圍內含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑者，從分散安定性之觀點來看更佳。 The aforementioned dispersion medium contains the polar term δ P of the Hansen solubility parameter in the range of 20 to 95 mass % relative to the total amount of the near-infrared absorbing composition, and the hydrogen bond term δ H is in the range of 3 to 6. A solvent with a value in the range of 3 to 6 is better from the viewpoint of dispersion stability.
前述通式(II)中的m為1~19之範圍內，且n為1~19之範圍內者，從分散性及分散安定性之觀點來看較佳。It is preferable from the viewpoint of dispersibility and dispersion stability that m in the general formula (II) is in the range of 1 to 19 and n is in the range of 1 to 19.
將具有前述通式(I)所示的結構之化合物的莫耳含量設為C A，將具有前述通式(II)所示的結構之化合物的莫耳含量設為C E時，莫耳比C A/C E之值為3.8~10之範圍內，且將銅離子的莫耳含量設為C C，將具有前述通式(I)所示的結構之化合物及具有前述通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量設為C H時，莫耳比C H/C C之值為1.5~2.5之範圍內者，從使近紅外線吸收性、濕熱耐性及錯合物微粒子的分散性成為良好，且視感度修正優異之觀點來看較佳。 When the molar content of the compound having the structure represented by the general formula (I) is C A and the molar content of the compound having the structure represented by the general formula (II) is C E , the molar ratio The value of C A /C E is in the range of 3.8 to 10, and assuming that the molar content of copper ions is C C , the compound having the structure represented by the aforementioned general formula (I) and the compound having the aforementioned general formula (II) When the molar content of the reactive hydroxyl group in the compound of the structure shown is set to C H , the molar ratio C H /C C is in the range of 1.5 to 2.5, thereby improving the near-infrared ray absorptivity and moisture-heat resistance. It is preferable from the viewpoint of good dispersibility of complex fine particles and excellent visual sensitivity correction.
本發明之近紅外線吸收性硬化膜之特徵為含有近紅外線吸收性組成物的硬化物。 藉此，可展現本發明的效果，解決課題。 The near-infrared absorbing cured film of the present invention is characterized by a cured product containing a near-infrared absorbing composition. Thereby, the effect of the present invention can be demonstrated and the problem can be solved.
本發明之光學構件之特徵為含有近紅外線吸收性組成物的硬化物。 藉此，可展現本發明的效果，解決課題。 The optical member of the present invention is characterized by a cured product containing a near-infrared absorbing composition. Thereby, the effect of the present invention can be demonstrated and the problem can be solved.
以下，對於本發明及其構成要素及用於實施本發明之形態、態樣，詳細說明。又，本申請案中，「~」係以包含將其前後記載之數值作為下限值及上限值之意義使用。Hereinafter, the present invention, its constituent elements, and forms and aspects for implementing the present invention will be described in detail. In addition, in this application, "~" is used in the sense that the numerical values described before and after it are used as the lower limit value and the upper limit value.
1.近紅外線吸收性組成物之概要 本發明之近紅外線吸收性組成物係含有近紅外線吸收劑及分散介質之近紅外線吸收性組成物，其特徵為：前述分散介質含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 又，本發明之近紅外線吸收性組成物亦可含有其他添加劑，例如含有有機色素者，從能調整吸收波長之觀點來看較佳。 另外，進一步含有紫外線吸收劑者，從分光特性及耐光性之觀點來看較佳。 1. Overview of the near-infrared absorbing composition. The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium. The characteristic is that the dispersion medium contains the polarity of the Hansen solubility parameter. The value of the term δ P is in the range of 3 to 6, and the value of the hydrogen bond term δ H is in the range of 3 to 6. In addition, the near-infrared absorbing composition of the present invention may also contain other additives, such as organic pigments, which are preferable from the viewpoint of being able to adjust the absorption wavelength. In addition, it is preferable from the viewpoint of spectral characteristics and light resistance to further contain an ultraviolet absorber.
(1.1)分散介質 本發明之分散介質含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 (1.1) Dispersion medium The dispersion medium of the present invention contains a solvent whose polar term δ P of the Hansen solubility parameter is in the range of 3 to 6, and the hydrogen bond term δ H is in the range of 3 to 6.
(1.1.1)漢森溶解度參數 漢森的溶解度參數(Hansen solubility parameter，以下亦稱為HSP值)係成為表示某物質多少溶解於其他物質的溶解性之指標的值，將藉由希爾德布蘭特(Hildebrand)導入的溶解度參數分割成分散項δ D、極性項δ P、氫鍵項δ H的3成分，在三次元空間中表示者。 (1.1.1) Hansen solubility parameter Hansen solubility parameter (hereinafter also referred to as HSP value) is a value that becomes an indicator of the solubility of a substance in other substances. It will be determined by Hildebub. The solubility parameter introduced by Hildebrand is divided into three components: the dispersion term δ D , the polarity term δ P , and the hydrogen bond term δ H , and is expressed in a three-dimensional space.
分散項δ D表示分散力所致的效果，極性項δ P表示偶極間力所致的效果，氫鍵項δ H表示氫鍵力所致的效果，記載為 δ D：來自分子間的分散力之能量 δ P：來自分子間的極性力之能量 δ H：來自分子間的氫鍵力之能量 (其中，各值δ D、δ P及δ H各自的單位為MPa 1/2)。 The dispersion term δ D represents the effect caused by the dispersion force, the polar term δ P represents the effect caused by the inter-dipole force, and the hydrogen bond term δ H represents the effect caused by the hydrogen bond force, which is recorded as δ D : from intermolecular dispersion Energy of force δ P : Energy derived from polar force between molecules δ H : Energy derived from hydrogen bonding force between molecules (wherein, the unit of each value δ D , δ P and δ H is MPa 1/2 ).
HSP值之定義與計算方法係記載於「Charles M. Hansen著，Hansen Solubility Parameters: A Users Handbook(CRC出版社，2007年)」。The definition and calculation method of HSP value are recorded in "Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)".
分散項δ D反映凡得瓦力，極性項δ P反映偶極矩，氫鍵項δ H反映水、醇等之作用。 而且，HSP值的向量相似者之彼此可以判斷為溶解性高，向量的類似度可以漢森溶解度參數之距離(HSP距離)來判斷。 又，漢森的溶解度參數係不僅可作為判斷溶解性的指標，還可作為某物質存在於其他物質中的難易程度，即分散性好壞程度的判斷指標。 The dispersion term δ D reflects the van der Waals force, the polar term δ P reflects the dipole moment, and the hydrogen bond term δ H reflects the effects of water, alcohol, etc. Furthermore, vectors with similar HSP values can be judged to have high solubility, and vector similarity can be judged by the Hansen solubility parameter distance (HSP distance). In addition, Hansen's solubility parameter system can be used not only as an index to judge solubility, but also as an index to judge the ease with which a substance exists in other substances, that is, the degree of dispersibility.
尚且，作為本發明所用的各種溶劑之HSP值記載之值，為以市售的電腦軟體Hansen Solubility Parameters in Practice (HSPiP)求出之值。In addition, the values described as HSP values of various solvents used in the present invention are values calculated using the commercially available computer software Hansen Solubility Parameters in Practice (HSPiP).
本發明之前述分散介質含有至少一種以上的前述漢森溶解度參數的分散項δ D之值為16~22之範圍內的溶劑者，從分散安定性之觀點來看較佳。 In the present invention, the dispersion medium containing at least one solvent in which the dispersion term δ D of the Hansen solubility parameter has a value in the range of 16 to 22 is preferred from the viewpoint of dispersion stability.
本發明之前述分散介質含有至少一種以上的前述漢森溶解度參數的極性項δ P之值為3~5之範圍內，且氫鍵項δ H之值為3~5之範圍內的溶劑者，從分散安定性之觀點來看較佳。 In the present invention, the aforementioned dispersion medium contains at least one solvent in which the value of the polar term δ P of the aforementioned Hansen solubility parameter is in the range of 3 to 5, and the value of the hydrogen bond term δ H is in the range of 3 to 5, It is better from the viewpoint of dispersion stability.
本發明之前述分散介質係相對於近紅外線吸收性組成物全量，以20~95質量%之範圍內含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑者，從分散安定性之觀點來看更佳。 The aforementioned dispersion medium of the present invention contains the polar term δ P of the Hansen solubility parameter in the range of 20 to 95 mass % relative to the total amount of the near-infrared absorbing composition. The value of the polar term δ P of the Hansen solubility parameter is in the range of 3 to 6, and the hydrogen bond term Solvents with a δ H value in the range of 3 to 6 are more preferable from the viewpoint of dispersion stability.
(1.1.2)溶劑 本發明之分散介質需要含有漢森溶解度參數的極性項δ P之值為3~6之範圍內，且氫鍵項δ H之值為3~6之範圍內的溶劑。 作為本發明可用的溶劑，只要滿足上述漢森溶解度參數之要件，就沒有特別的限定，但例如可舉出烴系溶劑，於該烴系溶劑之中，較佳可舉出脂肪族烴系溶劑、醚系溶劑等。 再者，只要不妨礙本發明的效果，則可使用具有他種化學結構的溶劑。 (1.1.2) Solvent The dispersion medium of the present invention needs to contain a solvent whose polar term δ P of the Hansen solubility parameter is in the range of 3 to 6, and whose hydrogen bond term δ H is in the range of 3 to 6. The solvent that can be used in the present invention is not particularly limited as long as it satisfies the requirements of the Hansen solubility parameter mentioned above. Examples thereof include hydrocarbon-based solvents. Among the hydrocarbon-based solvents, aliphatic hydrocarbon-based solvents are preferred. , ether solvents, etc. Furthermore, solvents with other chemical structures may be used as long as the effects of the present invention are not hindered.
作為脂肪族烴系溶劑，例如可舉出環己烷等之環狀脂肪族烴系溶劑、二乙基醚、二異丙基醚、四氫呋喃、1,4-二㗁烷、乙二醇單甲基醚等之醚系溶劑等。 特別地，前述分散介質含有至少具有環烷基或環醚基的醚作為溶劑者，從分散性之觀點來看較佳。 再者，前述環烷基為環戊基或環己基，且前述環醚基為四氫呋喃基或四吡喃基者，從分散性之觀點來看更佳。 Examples of aliphatic hydrocarbon solvents include cyclic aliphatic hydrocarbon solvents such as cyclohexane, diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol monomethyl. Ether-based solvents such as base ethers, etc. In particular, the dispersion medium preferably contains an ether having at least a cycloalkyl group or a cyclic ether group as a solvent from the viewpoint of dispersibility. Furthermore, it is more preferable from the viewpoint of dispersibility that the aforementioned cycloalkyl group is a cyclopentyl group or a cyclohexyl group, and the aforementioned cyclic ether group is a tetrahydrofuryl group or a tetrapyranyl group.
尚且，本發明中所謂「分散性」，就是指使作為構成近紅外線吸收性組成物的成分所含有之銅離子、銅錯合物、具有通式(I)或(II)所示的結構之化合物等，以適當的狀態分散於該近紅外線吸收性組成物中的分散介質之性能或功能。 又，所謂「分散安定性」，就是指構成近紅外線吸收性組成物的各種成分之分散狀態，隨著時間經過、環境條件變化等而變化者係無或少，被維持在適當的狀態之性能或功能。 In addition, "dispersibility" in the present invention refers to the copper ions, copper complexes, and compounds having the structure represented by the general formula (I) or (II) contained as components constituting the near-infrared absorbing composition. etc., the performance or function of the dispersion medium dispersed in the near-infrared absorbing composition in an appropriate state. In addition, "dispersion stability" refers to the performance of maintaining the dispersed state of various components constituting the near-infrared absorbing composition in an appropriate state with little or no change due to the passage of time, changes in environmental conditions, etc. or function.
例如，前述分散介質至少含有環戊基甲基醚或4-甲基四氫吡喃及具有源自該等化合物的結構之衍生物或具有類似的結構之化合物者，從分散性之觀點來看更佳。 特別地，若前述分散介質含有環戊基甲基醚作為溶劑，則分散性更提升。 For example, if the aforementioned dispersion medium contains at least cyclopentyl methyl ether or 4-methyltetrahydropyran and derivatives having a structure derived from these compounds or compounds having a similar structure, from the viewpoint of dispersibility Better. In particular, if the aforementioned dispersion medium contains cyclopentyl methyl ether as a solvent, the dispersibility is further improved.
作為環戊基甲基醚或4-甲基四氫吡喃及具有源自此等或類似的結構之化合物，例如可舉出具有以下結構的化合物。 Examples of compounds having structures derived from cyclopentyl methyl ether, 4-methyltetrahydropyran and these or similar structures include compounds having the following structures.
(沸點) 本發明之前述分散介質含有沸點為80~150℃之範圍內的溶劑者，從防止製膜時的龜裂之觀點來看較佳。 (boiling point) In the present invention, it is preferable from the viewpoint of preventing cracks during film formation that the dispersion medium contains a solvent with a boiling point in the range of 80 to 150°C.
(溶劑以外的成分) 後述固體成分(溶劑以外的成分)相對於近紅外線吸收性組成物(分散液)全體之比率為5~30質量%之範圍內者，於固體物(例如銅錯合物微粒子)之濃度為恰當，抑制保存期間中的粒子凝聚性，且能得到更優異的隨著時間經過安定性(銅錯合物微粒子的分散安定性與近紅外線吸收性)之點上較佳，更佳為10~20質量%之範圍內。 (Ingredients other than solvents) The concentration of the solid matter (for example, copper complex fine particles) is appropriate when the ratio of the solid content (components other than the solvent) mentioned below to the entire near-infrared absorbing composition (dispersion) is in the range of 5 to 30 mass %. , which is preferable in terms of suppressing particle aggregation during storage and obtaining better stability over time (dispersion stability and near-infrared absorption of copper complex fine particles), more preferably 10 to 20 Within the range of mass %.
(1.2)近紅外線吸收劑 本發明之前述近紅外線吸收劑至少含有下述(A)成分或下述(B)成分者，從分散安定性及樹脂相溶性之觀點來看較佳。 (1.2) Near infrared absorber The near-infrared absorber of the present invention preferably contains at least the following component (A) or the following component (B) from the viewpoint of dispersion stability and resin compatibility.
＜成分＞： (A)成分：由具有下述通式(I)所示的結構之化合物、具有下述通式(II)所示的結構之化合物及銅離子所成之成分。 (B)成分：由具有下述通式(I)所示的結構之化合物配位的銅錯合物及具有下述通式(II)所示的結構之化合物配位的銅錯合物所成之成分。 ＜Ingredients＞: (A) Component: A component composed of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions. (B) Component: a copper complex coordinated by a compound having a structure represented by the following general formula (I) and a copper complex coordinated by a compound having a structure represented by the following general formula (II) ingredients.
(1.2.1)具有通式(I)所示的結構之化合物 具有下述通式(I)所示的結構之化合物為膦酸化合物，藉由形成後述膦酸銅錯合物，可吸收近紅外線。 (1.2.1) Compounds having the structure represented by general formula (I) The compound having the structure represented by the following general formula (I) is a phosphonic acid compound and can absorb near-infrared rays by forming a copper phosphonate complex described below.
[上述通式(I)中，R 1表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基]。 [In the above general formula (I), R 1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent].
作為R 1可具有之取代基，例如可舉出烷基(例如甲基、乙基、三氟甲基、異丙基等)、烷氧基(例如甲氧基、乙氧基等)、鹵素原子(例如氟原子等)、氰基、硝基、二烷基胺基(例如二甲基胺基等)、三烷基矽烷基(例如三甲基矽烷基等)、三芳基矽烷基(例如三苯基矽烷基等)、三雜芳基矽烷基(例如三吡啶基矽烷基等)、苄基、雜芳基(例如吡啶基、咔唑基等)，作為縮合環，可舉出9,9′-二甲基茀、咔唑、二苯并呋喃等。 Examples of substituents that R 1 may have include alkyl groups (such as methyl, ethyl, trifluoromethyl, isopropyl, etc.), alkoxy groups (such as methoxy groups, ethoxy groups, etc.), and halogens. Atoms (such as fluorine atoms, etc.), cyano groups, nitro groups, dialkylamino groups (such as dimethylamino groups, etc.), trialkylsilyl groups (such as trimethylsilyl groups, etc.), triarylsilyl groups (such as Triphenylsilyl group, etc.), triheteroarylsilyl group (such as tripyridylsilyl group, etc.), benzyl group, heteroaryl group (such as pyridyl group, carbazolyl group, etc.), as condensed rings, 9, 9′-Dimethylfluoride, carbazole, dibenzofuran, etc.
於上述通式(I)所示的結構中，R 1為碳數1~20的烷基者，在濕熱耐性與近紅外線吸收性良好之點上較佳。 又，R 1為碳數1~4的烷基者，在能兼顧近紅外線吸收性與可見透光性之點上更佳。 In the structure represented by the above-mentioned general formula (I), R 1 is preferably an alkyl group having 1 to 20 carbon atoms, which is preferable in terms of good moisture-heat resistance and near-infrared ray absorption. In addition, those in which R 1 is an alkyl group having 1 to 4 carbon atoms are more preferable in that they can achieve both near-infrared ray absorption and visible light transmittance.
(化合物例) 於具有通式(I)所示的結構之化合物(膦酸化合物)之中，作為R 1為碳數1~20的烷基者，例如可舉出甲基膦酸、乙基膦酸、丙基膦酸、丁基膦酸、戊基膦酸、己基膦酸、庚基膦酸、辛基膦酸、壬基膦酸、癸基膦酸等。 又，作為R 1為碳數6~20的芳基者，例如可舉出苯基膦酸、4-甲氧基苯基膦酸、(4-胺基苯基)膦酸、(4-溴苯基)膦酸、3-膦醯基苯甲酸、4-膦醯基苯甲酸及(4-羥基苯基)膦酸等。 (Compound examples) Among the compounds (phosphonic acid compounds) having the structure represented by the general formula (I), examples of R 1 being an alkyl group having 1 to 20 carbon atoms include methylphosphonic acid, ethyl Phosphonic acid, propylphosphonic acid, butylphosphonic acid, amylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, etc. In addition, examples of R 1 being an aryl group having 6 to 20 carbon atoms include phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl)phosphonic acid, and (4-bromo Phenyl) phosphonic acid, 3-phosphonyl benzoic acid, 4-phosphonyl benzoic acid and (4-hydroxyphenyl) phosphonic acid, etc.
所添加的具有通式(I)所示的結構之化合物(膦酸化合物)係可使用市售品。 將具有通式(I)所示的結構之化合物(膦酸化合物)之例作為下述化合物(H-1)~(H-8)表示。 As the compound (phosphonic acid compound) having a structure represented by general formula (I) to be added, a commercially available product can be used. Examples of compounds (phosphonic acid compounds) having a structure represented by general formula (I) are shown as the following compounds (H-1) to (H-8).
本發明中，具有通式(I)所示的結構之化合物(膦酸化合物)較佳為選自下述膦酸化合物群之至少一種烷基膦酸。In the present invention, the compound (phosphonic acid compound) having a structure represented by general formula (I) is preferably at least one alkylphosphonic acid selected from the group of phosphonic acid compounds described below.
1：甲基膦酸 2：乙基膦酸 3：丙基膦酸 4：丁基膦酸 5：戊基膦酸 6：己基膦酸 7：辛基膦酸 8：2-乙基己基膦酸 9：2-氯乙基膦酸 10：3-溴丙基膦酸 11：3-甲氧基丁基膦酸 12：1,1-二甲基丙基膦酸 13：1,1-二甲基乙基膦酸 14：1-甲基丙基膦酸 1: Methylphosphonic acid 2: Ethylphosphonic acid 3: Propylphosphonic acid 4: Butylphosphonic acid 5: Pentylphosphonic acid 6: Hexylphosphonic acid 7: Octylphosphonic acid 8: 2-Ethylhexylphosphonic acid 9: 2-Chloroethylphosphonic acid 10: 3-bromopropylphosphonic acid 11: 3-Methoxybutylphosphonic acid 12: 1,1-dimethylpropylphosphonic acid 13: 1,1-dimethylethylphosphonic acid 14: 1-Methylpropylphosphonic acid
(1.2.2)具有通式(II)所示的結構之化合物 具有下述通式(II)所示的結構之化合物為磷酸酯化合物或硫酸酯化合物，有助於使上述膦酸銅錯合物分散，抑制膦酸銅錯合物所形成之粒子的粒徑變大。 (1.2.2) Compounds having the structure represented by general formula (II) The compound having the structure represented by the following general formula (II) is a phosphate compound or a sulfate compound, which helps to disperse the copper phosphonate complex and suppress the particle size of the particles formed by the copper phosphonate complex. get bigger.
[上述通式(II)中，R 2表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基；R 21~R 24各自獨立地表示氫原子或碳數為1~4的烷基；m表示R 21~R 24全部為氫原子的部分結構單元之平均加成數，且為0~19之範圍內；n表示R 21~R 24之至少1個是碳數為1~4的烷基的部分結構單元之平均加成數，且為0~19之範圍內；m+n為m及n之總數，且為1~20之範圍內；Z表示由下述通式(Z-1)~(Z-3)所選出的結構單元]。 [In the above general formula (II), R 2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent; R 21 to R 24 each independently represents a hydrogen atom or Alkyl group with 1 to 4 carbon atoms; m represents the average addition number of partial structural units in which all R 21 to R 24 are hydrogen atoms, and is in the range of 0 to 19; n represents at least one of R 21 to R 24 is the average addition number of some structural units of alkyl groups with 1 to 4 carbon atoms, and is in the range of 0 to 19; m+n is the total number of m and n, and is in the range of 1 to 20; Z represents Structural units selected from the following general formulas (Z-1)~(Z-3)].
(環氧乙烷結構及經烷基取代的環氧乙烷結構) 於本申請案中，將下述通式(II)所示的結構中的R 21~R 24全部為氫原時之式中括弧內的部分結構稱為「環氧乙烷結構」，式中m為該環氧乙烷結構單元之平均加成數。 又，將下述通式(II)所示的結構中的R 21~R 24之至少1個為碳數1~4的烷基，且其他為氫原子之式中括弧內的部分結構亦稱為「經烷基取的環氧乙烷結構」，式中n為該經烷基取代的環氧乙烷結構單元之平均加成數。 (Ethylene oxide structure and alkyl-substituted ethylene oxide structure) In this application, in the structure represented by the following general formula (II), R 21 to R 24 are all hydrogen atoms. The partial structure in square brackets is called "ethylene oxide structure", where m is the average addition number of ethylene oxide structural units. In addition, in the structure represented by the following general formula (II), at least one of R 21 to R 24 is an alkyl group having 1 to 4 carbon atoms, and the other is a hydrogen atom. The partial structure in brackets in the formula is also called It is "ethylene oxide structure obtained by alkyl group", where n is the average addition number of ethylene oxide structural units substituted by alkyl group.
本發明之具有通式(II)所示的結構之化合物為磷酸及硫酸結構，其特徵為環氧乙烷結構的平均加成數m及經烷基取代的環氧乙烷結構之平均加成數n皆為1以上，其係與銅的錯合物形成能力高，有助於提高作為分散劑的效果。The compound having the structure represented by the general formula (II) of the present invention is a phosphoric acid and a sulfuric acid structure, and is characterized by the average addition number m of the ethylene oxide structure and the average addition number n of the alkyl-substituted ethylene oxide structure. If all are 1 or more, they have a high complex-forming ability with copper and contribute to improving the effect as a dispersant.
前述通式(II)中的m為1~19之範圍內，且n為1~19之範圍內者，從分散性及分散安定性之觀點來看較佳。It is preferable from the viewpoint of dispersibility and dispersion stability that m in the general formula (II) is in the range of 1 to 19 and n is in the range of 1 to 19.
通式(II)中，藉由組合環氧乙烷結構及經烷基取代的環氧乙烷結構而異構物之種類變多，因此熵增加而有助於提高作為分散劑的效果。 又，可抑制取代基(R 21~R 24)的立體障礙之影響，銅錯合物形成微細的分散狀態，平衡良好地發揮環氧乙烷結構與經烷基取代的環氧乙烷結構各自之效果，推測可確保分散性及分散安定性。 In the general formula (II), by combining an ethylene oxide structure and an alkyl-substituted ethylene oxide structure, the types of isomers increase, so the entropy increases, which contributes to improving the effect as a dispersant. In addition, the influence of steric hindrance of the substituents (R 21 ~ R 24 ) can be suppressed, the copper complex forms a finely dispersed state, and the ethylene oxide structure and the alkyl-substituted ethylene oxide structure are well balanced. The effect is presumed to ensure dispersion and dispersion stability.
於通式(II)所示的結構中，碳數為6~16的烷基者，從銅錯合物的分散性與濕熱耐性之觀點來看較佳。Among the structures represented by the general formula (II), an alkyl group having a carbon number of 6 to 16 is preferred from the viewpoint of dispersibility and moisture-heat resistance of the copper complex.
(結構單元Z：通式(Z-1)~(Z-3)) 通式(II)中，Z表示由下述通式(Z-1)~(Z-3)所選出的結構單元。 (Structural unit Z: general formula (Z-1)~(Z-3)) In the general formula (II), Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).
具有通式(II)所示的結構之化合物係在Z為(Z-1)時變成二酯，在Z為(Z-2)或(Z-3)時變成單酯。The compound having the structure represented by general formula (II) becomes a diester when Z is (Z-1), and becomes a monoester when Z is (Z-2) or (Z-3).
二酯與單酯之混合比，較佳相對於二酯與單酯之合計量，單酯之莫耳比率為20~95%之範圍內。The mixing ratio of the diester and the monoester is preferably in the range of 20 to 95% relative to the total amount of the diester and the monoester.
(化合物例) 下述表I~V中顯示具有通式(II)所示的結構之化合物(磷酸酯化合物或硫酸酯化合物)化合物之具體例，但本發明之具有通式(II)所示的結構之化合物不限定於該等化合物。 (Examples of compounds) Specific examples of compounds (phosphate ester compounds or sulfate ester compounds) having a structure represented by general formula (II) are shown in the following Tables I to V. However, the compound having a structure represented by general formula (II) of the present invention It is not limited to these compounds.
表I~V中，「環氧乙烷結構」係如前述，指前述通式(II)所示的結構中的R 21~R 24全部為氫原子時的之式中括弧內的部分結構，式中m為該環氧乙烷結構單元之平均加成數。 又，「經烷基取代的環氧乙烷結構」係前述通式(II)所示的結構中的R 21~R 24之至少1個為碳數1~4的烷基，其他為氫原子之式中括弧內的部分結構，式中n為該經烷基取代的環氧乙烷結構單元之平均加成數。 In Tables I to V, "ethylene oxide structure" refers to the partial structure in brackets in the formula (II) when all R 21 to R 24 in the structure represented by the general formula (II) are hydrogen atoms. In the formula, m is the average addition number of the ethylene oxide structural unit. Moreover, the "alkyl-substituted ethylene oxide structure" is a structure represented by the aforementioned general formula (II) in which at least one of R 21 to R 24 is an alkyl group having 1 to 4 carbon atoms, and the others are hydrogen atoms. The partial structure in the brackets in the formula, where n is the average addition number of the alkyl-substituted ethylene oxide structural unit.
表I~V中，「Z：結構」之列表示式中之Z為通式(Z-1)、通式(Z-2)、通式(Z-3)之任一者，記載通式(Z-1)及通式(Z-2)兩者之例示化合物係Z為(Z-1)的化合物及Z為(Z-2)的化合物之混合物。 又，表I~V中，「Z：單酯的莫耳比率[%]」之列表示單酯的莫耳比率[%]。 In Tables I to V, the column "Z: Structure" indicates that Z in the formula is any one of general formula (Z-1), general formula (Z-2), and general formula (Z-3), and the general formula is recorded Exemplary compounds of both (Z-1) and general formula (Z-2) are mixtures of compounds in which Z is (Z-1) and Z is (Z-2). In addition, in Tables I to V, the column "Z: molar ratio of monoester [%]" indicates the molar ratio of monoester [%].
以下，具體說明表I~V中記載的例示化合物中之幾個。Hereinafter, some of the exemplary compounds described in Tables I to V will be specifically described.
[例示化合物1]
例示化合物1係Z為通式(Z-1)的化合物(二酯)及Z為通式(Z-2)的化合物(單酯)之混合物。
Z為通式(Z-2)的化合物(單酯)例如係以下述例示化合物1-1之結構表示，Z為通式(Z-1)的化合物(二酯)例如係以下述例示化合物1-2之結構表示。
[Exemplary compound 1]
例示化合物1之情況，Z為通式(Z-2)的化合物(單酯)之莫耳比率為50%，上述例示化合物1-1及上述例示化合物1-2係以相同莫耳量被含有。In the case of
m及n為平均加成數，因此即使m為5、n為5之例示化合物1，也不限於1個分子中的環氧乙烷結構之數為5個，經烷基取代的環氧乙烷結構之數為5個。m and n are average addition numbers. Therefore, even if exemplified
[例示化合物6]
例示化合物6係Z為通式(Z-3)的化合物，例如以下述例示化合物6-1表示。
[Exemplary compound 6]
m及n為平均加成數，因此即使m為10、n為5之例示化合物6，也不限於1個分子中的環氧乙烷結構之數為10個、經烷基取代的環氧乙烷結構之數為5個。m and n are average addition numbers. Therefore, even if exemplified
本發明中，環氧乙烷結構與經烷基取代的環氧乙烷結構之順序係沒有特別的限制，各自的結構無規排列之化合物亦被包含於本發明所規定之化合物中。
環氧乙烷結構與經烷基取代的環氧乙烷構造之順序係可藉由合成方法而任意變更。
例如下述例示化合物6-2亦被包含於例示化合物6中。
In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the respective structures are randomly arranged are also included in the compounds specified in the present invention.
The order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure can be arbitrarily changed by synthetic methods.
For example, the following Exemplary Compound 6-2 is also included in
(1.2.3)具有通式(II)所示的結構之化合物之合成方法 本發明之具有通式(II)所示的結構之化合物，例如可參考日本特開2005-255608號公報、日本特開2015-000396號公報、日本特開2015-000970號公報、日本特開2015-178072號公報、日本特開2015-178073號公報、日本發明專利第4422866號公報等中記載之眾所周知的方法來合成。 (1.2.3) Synthesis method of compounds having the structure represented by general formula (II) For the compound having the structure represented by the general formula (II) of the present invention, for example, refer to Japanese Patent Application Laid-Open No. 2005-255608, Japanese Patent Application Laid-Open No. 2015-000396, Japanese Patent Application Laid-Open No. 2015-000970, and Japanese Patent Application Laid-Open No. 2015 -178072, Japanese Patent Application Laid-Open No. 2015-178073, Japanese Invention Patent No. 4422866, etc. It is synthesized by a well-known method.
以下，具體說明表I~V中記載的一些例示化合物之合成方法。 尚且，本發明之具有通式(II)所示的結構之化合物之合成方法係不限定於下述之合成方法。 Hereinafter, the synthesis methods of some exemplary compounds described in Tables I to V will be described in detail. In addition, the synthesis method of the compound having the structure represented by the general formula (II) of the present invention is not limited to the following synthesis method.
(例示化合物53之合成方法) 將正辛醇130g(1.0莫耳)加入高壓釜中，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷116g(2.0莫耳)後，加成環氧乙烷88g(2.0莫耳)。 (Synthesis method of exemplified compound 53) Add 130g (1.0 mole) of n-octanol into the autoclave, use potassium hydroxide as a catalyst, and add 116g (2.0 mole) of propylene oxide under the conditions of pressure 147kPa and temperature 130°C. Oxyethane 88g (2.0 mol).
其次，確認正辛醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到下述所示之例示化合物53。Next, after confirming that n-octanol does not remain, put the above-mentioned adduct into a reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and evaporate under reduced pressure. By removing the solvent, the exemplary compound 53 shown below can be obtained.
(例示化合物54之合成方法) 將正辛醇130g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷116g(2.0莫耳)後，加成環氧乙烷44g(1.0莫耳)。 (Synthesis method of exemplified compound 54) Add 130g (1.0 mole) of n-octanol into the autoclave, use potassium hydroxide as the catalyst, and add 116g (2.0 mole) of propylene oxide under the conditions of pressure 147kPa and temperature 130°C, and then add cyclo Oxyethane 44g (1.0 mol).
其次，確認正辛醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到下述所示之例示化合物54。Next, after confirming that n-octanol does not remain, put the above-mentioned adduct into a reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and evaporate under reduced pressure. By removing the solvent, the exemplary compound 54 shown below can be obtained.
(例示化合物60之合成方法) 將2-乙基己醇130g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷145g(2.5莫耳)後，加成環氧乙烷110g(2.5莫耳)。 (Exemplary synthesis method of compound 60) Add 130g (1.0 mol) of 2-ethylhexanol into the autoclave, use potassium hydroxide as a catalyst, and add 145g (2.5 mol) of propylene oxide under the conditions of pressure 147kPa and temperature 130°C. Add 110g (2.5 mol) of ethylene oxide.
其次，確認2-乙基己醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到下述所示之例示化合物60。Next, after confirming that there is no residual 2-ethylhexanol, put the above adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, and then wash it with distilled water. The solvent was distilled off under reduced pressure to obtain exemplary compound 60 shown below.
(例示化合物61之合成方法) 將2-乙基己醇130g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷87g(1.5莫耳)後，加成環氧乙烷66g(1.5莫耳)。 (Synthetic method of exemplary compound 61) Add 130g (1.0 mole) of 2-ethylhexanol into the autoclave, use potassium hydroxide as the catalyst, and add 87g (1.5 mole) of propylene oxide under the conditions of pressure 147kPa and temperature 130°C. Add 66g (1.5 mol) of ethylene oxide.
其次，確認2-乙基己醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到下述所示之例示化合物61。Next, after confirming that there is no residual 2-ethylhexanol, put the above adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, and then wash it with distilled water. The solvent was distilled off under reduced pressure to obtain exemplary compound 61 shown below.
(1.2.4)銅成分 本發明之(A)成分為由具有前述通式(I)所示的結構之化合物、具有前述通式(II)所示的結構之化合物及銅離子所成之成分，因此含有銅離子。 另一方面，本發明之(B)成分為由具有前述通式(I)所示的結構之化合物配位的銅錯合物及具有前述通式(II)所示的結構之化合物配位的銅錯合物所成之成分，因此含有銅錯合物。 以下說明銅離子與銅錯合物。 (1.2.4) Copper composition The component (A) of the present invention is a component composed of a compound having a structure represented by the aforementioned general formula (I), a compound having a structure represented by the aforementioned general formula (II), and copper ions, and therefore contains copper ions. On the other hand, component (B) of the present invention is a copper complex coordinated by a compound having a structure represented by the aforementioned general formula (I) and a compound having a structure represented by the aforementioned general formula (II). It is composed of copper complexes and therefore contains copper complexes. The following describes copper ions and copper complexes.
(銅離子及成為銅離子源的化合物) 本發明之近紅外線吸收劑所含有的銅離子為二價銅離子，亦可進行溶劑和(solvation)。 作為成為銅離子源的化合物，使用能供給二價銅離子的銅鹽，例如可使用有機酸的銅鹽或無機酸的銅鹽。 具體而言，可舉出無水乙酸銅、無水甲酸銅、無水硬脂酸銅、無水苯甲酸銅、無水乙醯乙酸銅、無水乙基乙醯乙酸銅、無水甲基丙烯酸銅、無水焦磷酸銅、無水環烷酸銅、無水檸檬酸銅等之有機酸的銅鹽、此等之有機酸的銅鹽之水合物或水化物；酸化銅、鹽化銅、硫酸銅、硝酸銅、磷酸銅、鹼性硫酸銅、鹼性碳酸銅等之無機酸的銅鹽、此等之無機酸的銅鹽之水合物或水化物；氫氧化銅等。 (Copper ions and compounds that serve as copper ion sources) The copper ions contained in the near-infrared absorber of the present invention are divalent copper ions and can also be solvated. As a compound serving as a copper ion source, a copper salt capable of supplying divalent copper ions is used. For example, a copper salt of an organic acid or a copper salt of an inorganic acid can be used. Specific examples include anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper acetyl acetate, anhydrous copper ethyl acetate acetate, anhydrous copper methacrylate, and anhydrous copper pyrophosphate. , copper salts of organic acids such as anhydrous copper naphthenate, anhydrous copper citrate, hydrates or hydrates of copper salts of these organic acids; acidified copper, salted copper, copper sulfate, copper nitrate, copper phosphate, Copper salts of inorganic acids such as alkaline copper sulfate and alkaline copper carbonate, hydrates or hydrates of copper salts of these inorganic acids; copper hydroxide, etc.
(銅錯合物) 前述(B)成分係具有通式(I)所示的結構之化合物配位的銅錯合物及具有通式(II)所示的結構之化合物配位的銅錯合物。 尚且，本發明之近紅外線吸收劑亦可具有其他化合物配位的銅錯合物(例如乙酸銅等)。 (copper complex) The component (B) is a copper complex in which a compound having a structure represented by the general formula (I) is coordinated, and a copper complex in which a compound having a structure represented by the general formula (II) is coordinated. Moreover, the near-infrared absorber of the present invention may also have a copper complex coordinated by other compounds (such as copper acetate, etc.).
本發明之磷酸酯銅錯合物或硫酸酯銅錯合物係藉由併用膦酸化合物，而在可得到更優異的隨著時間經過安定性(銅錯合物粒子的分散安定性與近紅外線截止安定性)之近紅外線吸收性組成物之點上較佳。The copper phosphate complex or copper sulfate complex of the present invention can obtain more excellent stability over time (dispersion stability of copper complex particles and near-infrared rays) by using a phosphonic acid compound in combination. The near-infrared absorbing composition is better in terms of cut-off stability.
又，於磷酸酯銅錯合物與硫酸酯銅錯合物中，磷酸酯銅錯合物係在具有更優異的分散性與近紅外線截止安定性之點上較佳。Moreover, among the phosphate copper complex and the sulfate copper complex, the phosphate copper complex is preferable in that it has more excellent dispersibility and near-infrared cutoff stability.
＜具有通式(I)所示的結構之化合物配位的銅錯合物＞ 具有下述通式(I)所示的結構之化合物配位的銅錯合物(膦酸銅錯合物)，只要具有下述通式(I)所示的結構之化合物至少1個配位即可，也可包含其他化合物一起配位者。 <Copper complex coordinated by a compound having a structure represented by general formula (I)> A copper complex (copper phosphonate complex) coordinated by a compound having the structure represented by the following general formula (I), as long as at least one compound having the structure represented by the following general formula (I) is coordinated That is, it may also include those coordinated with other compounds.
[上述通式(I)中，R 1表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基]。 [In the above general formula (I), R 1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent].
上述具有通式(I)所示的結構之化合物配位的銅錯合物(膦酸銅錯合物)之結構，例如可以下述通式(IC)表示。The structure of the copper complex (copper phosphonate complex) coordinated by the compound having the structure represented by the general formula (I) can be represented by the following general formula (IC), for example.
[上述通式(IC)中，R 1表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基]。 [In the above general formula (IC), R 1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent].
於本發明之近紅外線吸收性組成物中，具有前述通式(I)所示的結構之化合物配位的銅錯合物(膦酸銅錯合物)主要為微粒子之狀態。In the near-infrared absorbing composition of the present invention, the copper complex (copper phosphonate complex) coordinated with the compound having the structure represented by the general formula (I) is mainly in the state of fine particles.
本申請案中，於具有前述通式(I)所示的結構之化合物所具有的羥基之中，將與磷原子直接鍵結之羥基亦稱為「反應性羥基」。In this application, among the hydroxyl groups of the compound having the structure represented by the aforementioned general formula (I), the hydroxyl group directly bonded to the phosphorus atom is also called a "reactive hydroxyl group".
尚且，具有上述通式(IC)所示的結構之銅錯合物，係具有前述通式(I)所示的結構之化合物所具有的2個反應性羥基係2個都與同一銅離子反應而形成，但本發明之具有前述通式(I)所示的結構之化合物配位的銅錯合物之形態係不限於該形態。Furthermore, the copper complex having the structure represented by the above-mentioned general formula (IC) has two reactive hydroxyl groups of the compound having the structure represented by the above-mentioned general formula (I), both of which react with the same copper ion. However, the form of the copper complex of the present invention coordinated with the compound having the structure represented by the general formula (I) is not limited to this form.
＜具有通式(II)所示的結構之化合物配位的銅錯合物＞ 所謂具有下述通式(II)所示的結構之化合物配位的銅錯合物(磷酸酯銅錯合物或硫酸酯銅錯合物)，只要具有下述通式(II)所示的結構之化合物至少1個配位即可，也可包含其他化合物一起配位者。 <Copper complex in which a compound having a structure represented by the general formula (II) is coordinated> A copper complex in which a compound having a structure represented by the following general formula (II) is coordinated (phosphate copper complex or copper sulfate complex), as long as at least one compound having the structure represented by the following general formula (II) is coordinated, and other compounds may be coordinated together.
[上述通式(II)中，R 2表示碳數為1~20的烷基或碳數為6~20的芳基，可進一步具有取代基；R 21~R 24各自獨立地表示氫原子或碳數為1~4的烷基；m表示R 21~R 24全部為氫原子的部分結構單元之平均加成數，且為0~19之範圍內；n表示R 21~R 24之至少1個是碳數為1~4的烷基的部分結構單元之平均加成數，且為0~19之範圍內；m+n為m及n之總數，且為1~20之範圍內；Z表示由下述通式(Z-1)~(Z-3)所選出的結構單元]。 [In the above general formula (II), R 2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent; R 21 to R 24 each independently represents a hydrogen atom or Alkyl group with 1 to 4 carbon atoms; m represents the average addition number of partial structural units in which all R 21 to R 24 are hydrogen atoms, and is in the range of 0 to 19; n represents at least one of R 21 to R 24 is the average addition number of some structural units of alkyl groups with 1 to 4 carbon atoms, and is in the range of 0 to 19; m+n is the total number of m and n, and is in the range of 1 to 20; Z represents Structural units selected from the following general formulas (Z-1)~(Z-3)].
。 .
於本發明之近紅外線吸收性組成物中，具有通式(II)所示的結構之化合物配位的銅錯合物(磷酸酯銅錯合物或硫酸酯銅錯合物)主要為微粒子或溶解狀態。In the near-infrared absorbing composition of the present invention, the copper complex (phosphate copper complex or sulfate copper complex) coordinated with the compound having the structure represented by the general formula (II) is mainly fine particles or dissolved state.
本申請案中，於具有通式(II)所示的結構之化合物所具有的羥基之中，將與磷原子或硫原子直接鍵結之羥基亦稱為「反應性羥基」。In this application, among the hydroxyl groups of the compound having the structure represented by the general formula (II), the hydroxyl group directly bonded to a phosphorus atom or a sulfur atom is also called a "reactive hydroxyl group".
尚且，本發明之具有通式(II)所示的結構之化合物配位的銅錯合物之形態，不限於具有通式(II)所示的結構之化合物所具有的2個反應性羥基係2個都與同一銅離子反應而形成之形態。Furthermore, the form of the copper complex coordinated by the compound having the structure represented by the general formula (II) of the present invention is not limited to the two reactive hydroxyl groups possessed by the compound having the structure represented by the general formula (II). Both react with the same copper ion to form a form.
(銅錯合物微粒子之平均粒徑) 於本發明之近紅外線吸收性組成物中，從分光特性之觀點來看，銅錯合物微粒子較佳為在形成後述近紅外線吸收性硬化膜時均勻地分散，因此，近紅外線吸收性分散液中的銅錯合物微粒子之粒徑小者為佳。 (Average particle size of copper complex fine particles) In the near-infrared ray-absorbing composition of the present invention, from the viewpoint of spectral characteristics, it is preferable that the copper complex fine particles are uniformly dispersed when forming the near-infrared ray-absorbing cured film described below. Therefore, the near-infrared ray-absorbing dispersion liquid The smaller the particle size of the copper complex particles is, the better.
近紅外線吸收性分散液中的銅錯合物微粒子之平均粒徑較佳為200nm以下，更佳為100nm以下，尤佳為80nm以下。The average particle diameter of the copper complex fine particles in the near-infrared absorbing dispersion is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less.
近紅外線吸收性分散液中的銅錯合物微粒子之平均粒徑，可藉由使用大塚電子股份有限公司製的界達(zeta)電位・粒徑測定系統ELSZ-1000ZS的動態光散射法進行測定。The average particle size of the copper complex fine particles in the near-infrared absorbing dispersion can be measured by the dynamic light scattering method using the zeta potential and particle size measuring system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd. .
(1.2.5)莫耳比C A/C E及莫耳比C H/C C之值 將具有前述通式(I)所示的結構之化合物的莫耳含量設為C A，將具有前述通式(II)所示的結構之化合物的莫耳含量設為C E時，莫耳比C A/C E之值為3.8~10之範圍內，且將銅離子的莫耳含量設為C C，將具有前述通式(I)所示的結構之化合物及具有前述通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量設為C H時，莫耳比C H/C C之值為1.5~2.5之範圍內者，從使近紅外線吸收性、濕熱耐性及錯合物微粒子之分散性成為良好，視感度修正優異之觀點來看較佳。 (1.2.5) Values of the molar ratio C A /C E and the molar ratio C H /C C Let the molar content of the compound having the structure represented by the aforementioned general formula (I) be C A , and let the molar content of the compound having the aforementioned structure represented by the general formula (I) be C A When the molar content of the compound represented by the general formula (II) is C E , the molar ratio C A /C E is in the range of 3.8 to 10, and the molar content of copper ions is C C , when the molar content of the reactive hydroxyl group of the compound having the structure represented by the aforementioned general formula (I) and the compound having the aforementioned general formula (II) is set to C H , the molar ratio C The value of H /C C is preferably in the range of 1.5 to 2.5 from the viewpoint of improving near-infrared ray absorption, moisture-heat resistance, dispersibility of complex fine particles, and excellent visual sensitivity correction.
具有前述通式(I)所示的結構之化合物為膦酸化合物，具有前述通式(II)所示的結構之化合物為磷酸酯或硫酸酯化合物。The compound having the structure represented by the aforementioned general formula (I) is a phosphonic acid compound, and the compound having the structure represented by the aforementioned general formula (II) is a phosphate ester or sulfate ester compound.
具有前述通式(I)所示的結構之化合物的莫耳含量與具有前述通式(II)所示的結構之化合物的莫耳含量之比，亦即莫耳比C A/C E為3.8以上時，藉由有效於近紅外線的吸收之膦酸銅錯合物的比例大，而近紅外線吸收性變良好。 又，由於高溫高濕環境下成為白濁之原因的酯化合物之比例小，濕熱耐性亦變良好。 The ratio of the molar content of the compound having the structure represented by the aforementioned general formula (I) to the molar content of the compound having the structure represented by the aforementioned general formula (II), that is, the molar ratio C A /C E is 3.8 In the above case, since the proportion of the copper phosphonate complex effective in absorbing near infrared rays is large, the near infrared ray absorbance becomes good. In addition, since the proportion of ester compounds that cause cloudiness in high-temperature and high-humidity environments is small, the moisture-heat resistance also becomes good.
磷酸酯化合物或硫酸酯化合物係為了保持銅錯合物微粒子的分散性，而需要一定量。 因此，莫耳比C A/C E較佳為10以下。 A certain amount of the phosphate compound or sulfate compound is required to maintain the dispersibility of the copper complex fine particles. Therefore, the molar ratio C A /C E is preferably 10 or less.
若上述莫耳比C H/C C在該範圍內，則可見光的400~700nm之波長範圍區域的光之穿透率升高，沒有近紅外線區域的1100nm附近之穿透光的洩漏，可高效率地維持吸收性能。 又，可實現在可見光的長波長之端部的700nm亦具有某程度的吸收特性之分光透過特性，適用於視感度修正。 If the above molar ratio C H /C C is within this range, the light transmittance in the wavelength range of 400 to 700 nm of visible light increases, and there is no leakage of transmitted light near 1100 nm in the near infrared region, which can be high Efficiently maintain absorbent properties. In addition, it is possible to realize spectral transmission characteristics that also have a certain degree of absorption characteristics at 700 nm, the long wavelength end of visible light, and is suitable for visual sensitivity correction.
所謂「具有通式(I)所示的結構之化合物」，不限於原料所用之具有通式(I)所示的結構之化合物本身，亦包含與其他成分反應者。 例如具有通式(I)所示的結構之化合物與銅離子反應而形成銅錯合物時，該銅錯合物中的「通式(I)所示的結構之部分」亦視為C A之規定中的「具有通式(I)所示的結構之化合物」。 亦即，具有複數的「通式(I)所示的結構之部分」之銅錯合物時，C A之規定中的「具有通式(I)所示的結構之化合物」不是以化合物單位，而是以該銅錯合物中的「通式(I)所示的結構之部分」單位來計數。 例如具有2個「通式(I)所示的結構之部分」之銅錯合物時，C A之規定中的「具有通式(I)所示的結構之化合物」係計數為2個。 The so-called "compound having a structure represented by general formula (I)" is not limited to the compound having a structure represented by general formula (I) used as a raw material itself, but also includes those that react with other components. For example, when a compound having a structure represented by general formula (I) reacts with copper ions to form a copper complex, the "part of the structure represented by general formula (I)" in the copper complex is also regarded as C A "Compounds having a structure represented by general formula (I)" are included in the regulations. In other words, when there are plural copper complexes having "parts of the structure represented by the general formula (I)", the "compounds having the structure represented by the general formula (I)" in the provisions of C A are not in compound units. , but is counted in units of "the part of the structure represented by the general formula (I)" in the copper complex. For example, in the case of a copper complex having two "compounds having a structure represented by general formula (I)", the number of "compounds having a structure represented by general formula (I)" in the provisions of C A is two.
C E之規定中「具有通式(II)所示的結構之化合物」係不限於原料所用之具有通式(II)所示的結構之化合物本身，亦包含與其他成分反應者。 例如具有通式(II)所示的結構之化合物與銅離子反應而形成銅錯合物時，該銅錯合物中的「通式(II)所示的結構之部分」亦視為C E之規定中的「具有通式(II)所示的結構之化合物」。 亦即，具有複數的「通式(II)所示的結構之部分」之銅錯合物時，C E之規定中的「具有通式(II)所示的結構之化合物」不是以化合物單位，而是以該銅錯合物中的「通式(II)所示的結構之部分」單位來計數。 例如具有2個「通式(II)所示的結構之部分」之銅錯合物時，C E之規定中的「具有通式(II)所示的結構之化合物」係計數為2個。 The "compounds having the structure represented by the general formula (II)" in the provisions of C E are not limited to the compounds having the structure represented by the general formula (II) used as raw materials themselves, but also include those that react with other components. For example, when a compound having a structure represented by general formula (II) reacts with copper ions to form a copper complex, the "part of the structure represented by general formula (II)" in the copper complex is also regarded as C E "Compounds having a structure represented by general formula (II)" are included in the regulations. That is, in the case of copper complexes having a plurality of "parts of a structure represented by general formula (II)", the "compounds having a structure represented by general formula (II)" in the provisions of C E are not in compound units , but is counted as the unit of "the part of the structure represented by the general formula (II)" in the copper complex. For example, in the case of a copper complex having two "compounds having a structure represented by general formula (II)", the number of "compounds having a structure represented by general formula (II)" in the provisions of CE is two.
前述銅離子的莫耳含量C C之規定中的「銅離子或構成銅化合物的銅」係指銅離子或構成銅化合物的原子單位之銅。 The "copper ions or copper constituting the copper compound" in the aforementioned provisions on the molar content C of copper ions refers to copper ions or the atomic units of copper constituting the copper compound.
具有前述通式(I)所示的結構之化合物及具有前述通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量C H之規定中的「具有通式(I)所示的結構之化合物及具有通式(II)所示的結構之化合物所具有之反應性羥基」，係指於具有通式(I)所示的結構之化合物及具有通式(II)所示的結構之化合物所具有的羥基之中，直接鍵結於磷原子或硫原子之羥基，再者，亦包含該羥基與其他成分反應者，例如氫游離而氧配位於銅離子者。 又，於不損害本發明目的效果之範圍內，亦可採用其他添加劑。 In the regulations on the molar content CH of the reactive hydroxyl group of the compound having the structure represented by the aforementioned general formula (I) and the compound having the aforementioned general formula (II), “having the general formula (I)” "The reactive hydroxyl group possessed by the compound having the structure shown and the compound having the structure represented by the general formula (II)" refers to the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II). Among the hydroxyl groups of the compound having the structure shown, the hydroxyl group is directly bonded to the phosphorus atom or the sulfur atom. Furthermore, it also includes those in which the hydroxyl group reacts with other components, such as those in which hydrogen is free and oxygen is coordinated with copper ions. In addition, other additives may also be used within the scope that does not impair the intended effect of the present invention.
2.近紅外線吸收性硬化膜 本發明之近紅外線吸收性硬化膜之特徵為含有近紅外線吸收性組成物的硬化物。 2. Near infrared absorbing hardened film The near-infrared absorbing cured film of the present invention is characterized by a cured product containing a near-infrared absorbing composition.
本發明之近紅外線吸收性硬化膜(與硬化性樹脂一起硬化之膜的狀態之近紅外線吸收性組成物)，例如適合構成CCD用、CMOS用或其他受光元件用之視感度修正構件、測光用構件、熱線吸收用構件、複合光學濾光片、透鏡構件(眼鏡、太陽眼鏡、護目鏡、光學系、光波導系)、光纖構件(光纖)、降噪用構件、電漿顯示器前面板等之顯示器或顯示器濾光片、投影器前面板、光源熱線截止構件、色調校正構件、照明亮度調節構件、光學元件(光放大元件、波長轉換元件等)、法拉第元件、隔離器等之光通信功能裝置、光碟用元件等。The near-infrared-absorbing cured film of the present invention (a near-infrared-absorbing composition in a film state cured together with a curable resin) is suitable for constituting, for example, a sensitivity correction member for a CCD, a CMOS, or other light-receiving elements, or a photometry member. Components, heat ray absorption components, composite optical filters, lens components (glasses, sunglasses, goggles, optical systems, optical waveguide systems), optical fiber components (optical fibers), noise reduction components, plasma display front panels, etc. Optical communication functional devices such as displays or display filters, projector front panels, light source hotline cutoff components, hue correction components, lighting brightness adjustment components, optical components (light amplification components, wavelength conversion components, etc.), Faraday components, isolators, etc. , optical disc components, etc.
前述近紅外線吸收性硬化膜，係可藉由在含有前述近紅外線吸收性組成物與分散介質之本發明之近紅外線吸收性組成物(分散液)中，溶解硬化性樹脂而調製近紅外線吸收性硬化膜形成用塗佈液，藉由旋塗或分配器的濕式塗佈方式將該塗佈液塗佈於基板上，進行特定的加熱處理，使塗膜硬化之步驟來製造。The near-infrared absorbing cured film can be prepared by dissolving a curable resin in the near-infrared absorbing composition (dispersion) of the present invention containing the near-infrared absorbing composition and a dispersion medium. The coating liquid for forming a cured film is produced by applying the coating liquid on a substrate by spin coating or wet coating with a dispenser, and subjecting it to a specific heat treatment to harden the coating film.
本發明之近紅外線吸收性硬化膜之膜厚較佳為10~500μm之範圍內，更佳為10~300μm之範圍內。The film thickness of the near-infrared absorbing cured film of the present invention is preferably in the range of 10 to 500 μm, more preferably in the range of 10 to 300 μm.
本發明之近紅外線吸收性硬化膜之膜厚，例如可使用下述組合的膜厚計進行測定。 端子：DIGIMICRO MH-15M(NIKON公司製) 架台：DIGIMICRO STAND MS-5C(NIKON公司製) 讀取機：DIGITAL READ OUT TC-101A(NIKON公司製) The film thickness of the near-infrared absorbing cured film of the present invention can be measured using, for example, the following combination of film thickness meters. Terminal: DIGIMICRO MH-15M (manufactured by NIKON Corporation) Stand: DIGIMICRO STAND MS-5C (manufactured by NIKON Corporation) Reader: DIGITAL READ OUT TC-101A (manufactured by NIKON Corporation)
(2.1)硬化性樹脂 近紅外線吸收性硬化膜之形成所用的基質樹脂(亦稱為黏結劑樹脂)為硬化性樹脂，較佳為對可見光線及近紅外線具有透光性，且可分散近紅外線吸收性組成物的微粒子。 本發明之具有通式(I)所示的結構之化合物配位的銅錯合物(膦酸銅錯合物)為極性比較低的物質，可良好地分散於疏水性材料中。 因此，作為近紅外線吸收性膜形成用的基質樹脂，較佳使用具有聚矽氧烷結構的樹脂(聚矽氧)或具有丙烯酸基、環氧基或苯基的樹脂。 (2.1) Hardening resin The matrix resin (also called binder resin) used to form the near-infrared-absorbing cured film is a curable resin, preferably a microparticle that is translucent to visible rays and near-infrared rays and can disperse the near-infrared-absorbing composition. . The copper complex (copper phosphonate complex) coordinated by the compound having the structure represented by the general formula (I) of the present invention is a substance with relatively low polarity and can be well dispersed in hydrophobic materials. Therefore, as the matrix resin for forming the near-infrared absorbing film, it is preferable to use a resin having a polysiloxane structure (polysiloxane) or a resin having an acrylic group, an epoxy group, or a phenyl group.
其中，具有聚矽氧烷結構的樹脂由於不易熱分解、對可見光線及近紅外線具有高的透光性，耐熱性亦高，因此特佳。Among them, resins with a polysiloxane structure are particularly preferred because they are not easily decomposed by heat, have high transmittance to visible rays and near-infrared rays, and have high heat resistance.
作為具有聚矽氧烷結構的樹脂之具體例，例如可舉出信越化學工業公司製的KR-255、KR-300、KR-2621-1、KR-211、KR-311、KR-216、KR-212、KR-251或SANYU REC公司製之SS-6203、SS-6309、VS-9301、VS-9506等。Specific examples of the resin having a polysiloxane structure include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, and KR manufactured by Shin-Etsu Chemical Industry Co., Ltd. -212, KR-251 or SS-6203, SS-6309, VS-9301, VS-9506, etc. made by SANYU REC.
從低的氣體穿透性、耐濕性之觀點來看，使用具有環氧基的基質樹脂亦為較佳態樣。From the viewpoint of low gas permeability and moisture resistance, it is also better to use a matrix resin with an epoxy group.
作為具有環氧基的樹脂之具體例，可使用KJC-X5(信越化學工業公司製)、NLD-L-672(SANYU REC公司製)、LE-1421(SANYU REC公司製)、EpiFine系列(KISCO公司製)等。As specific examples of the resin having an epoxy group, KJC-X5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), NLD-L-672 (manufactured by SANYU REC Co., Ltd.), LE-1421 (manufactured by SANYU REC Co., Ltd.), EpiFine series (KISCO company system), etc.
又，作為前述基質樹脂，亦較佳為使用具有上述列舉的聚矽氧烷結構與環氧基兩者的樹脂，該樹脂由於發揮高的耐熱性、耐濕性，因此具有適用作為固體攝像元件用影像感測器之材料的特性。In addition, as the matrix resin, it is also preferable to use a resin having both the polysiloxane structure and the epoxy group listed above. Since this resin exhibits high heat resistance and moisture resistance, it is suitable for use as a solid-state imaging element. Characteristics of materials used in image sensors.
作為具有聚矽氧烷結構與環氧基兩者的樹脂之具體例，例如可使用EpiFine系列(KISCO公司製)、ILLUMIKA系列(KANEKA公司製)。As specific examples of the resin having both a polysiloxane structure and an epoxy group, EpiFine series (manufactured by KISCO Corporation) and ILLUMIKA series (manufactured by KANEKA Corporation) can be used.
(溶劑以外的成分) 尚且，相對於近紅外線吸收性組成物(分散液)全體，固體成分(溶劑以外的成分)之比率為5~30質量%之範圍內者，係在固體物(例如銅錯合物微粒子)之濃度為恰當，抑制保存期間中的粒子凝聚性，可得到更優異的隨著時間經過安定性(銅錯合物微粒子的分散安定性與近紅外線吸收性)之點上較佳，更佳為10~20質量%之範圍內。 (Ingredients other than solvents) Furthermore, when the ratio of solid content (components other than solvent) to the entire near-infrared absorbing composition (dispersion) is in the range of 5 to 30 mass %, it is the proportion of solid matter (for example, copper complex fine particles) An appropriate concentration is preferred in that it suppresses particle aggregation during storage and obtains better stability over time (dispersion stability and near-infrared absorbability of copper complex fine particles), and is more preferably 10 Within the range of ~20 mass%.
(2.2)其他添加劑 於近紅外線吸收性硬化膜形成用塗佈液中，在不損害本發明目的效果之範圍內，可採用其他添加劑，例如可舉出增感劑、交聯劑、硬化促進劑、填料、熱硬化促進劑、熱聚合抑制劑、可塑劑等，再者亦可併用對基材表面之密著促進劑及其他助劑類(例如導電性粒子、填充劑、消泡劑、難燃劑、調平劑、剝離促進劑、抗氧化劑、香料、表面張力調節劑、鏈轉移劑、表面處理劑等)等之成分。藉由適宜含有該等成分，可調整目的之近紅外線吸收性膜之安定性、膜物性等之性質。 (2.2)Other additives In the coating liquid for forming a near-infrared absorbing cured film, other additives may be used within the scope that does not impair the intended effect of the present invention. Examples include sensitizers, cross-linking agents, hardening accelerators, fillers, and thermosetting agents. Accelerators, thermal polymerization inhibitors, plasticizers, etc. Furthermore, adhesion accelerators to the substrate surface and other additives (such as conductive particles, fillers, defoaming agents, flame retardants, leveling agents, etc.) can also be used in combination. agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, surface treatment agents, etc.). By appropriately containing these components, properties such as stability and film physical properties of the intended near-infrared absorbing film can be adjusted.
上述成分例如可參考日本特開2012-003225號公報之段落編號0183~0260、日本特開2008-250074號公報之段落編號0101~0102、日本特開2008-250074號公報之段落編號0103~0104、日本特開2008-250074號公報之段落編號0107~0109等中記載的內容。For the above-mentioned components, for example, refer to paragraph numbers 0183 to 0260 of Japanese Patent Application Publication No. 2012-003225, paragraph numbers 0101 to 0102 of Japanese Patent Application Publication No. 2008-250074, and paragraph numbers 0103 to 0104 of Japanese Patent Application Publication No. 2008-250074. The contents described in Japanese Patent Application Publication No. 2008-250074, paragraph numbers 0107 to 0109, etc.
3.近紅外線吸收性組成物及近紅外線吸收性硬化膜之分光特性 (3.1)近紅外線吸收性組成物(分散液)之分光特性 (分光穿透率) 本發明之近紅外線吸收性組成物係於近紅外線吸收性分散液之狀態下，以在波長850~1000nm的最大分光穿透率成為10%之方式用溶劑稀釋而進行測定時，在波長450~600nm的波長區域之平均分光穿透率為70%以上者，在可見光穿透率之點上較佳，更佳為80%以上，尤佳為90%以上。 3. Spectral characteristics of near-infrared absorbing composition and near-infrared absorbing cured film (3.1) Spectral characteristics of near-infrared absorbing composition (dispersion) (spectral transmittance) When the near-infrared-absorbing composition of the present invention is diluted with a solvent in the state of a near-infrared-absorbing dispersion so that the maximum spectral transmittance at a wavelength of 850 to 1000 nm becomes 10%, the result is measured at a wavelength of 450 to 1000 nm. Those with an average spectral transmittance of 70% or more in the wavelength region of 600 nm are better in terms of visible light transmittance, more preferably 80% or more, and even more preferably 90% or more.
分光穿透率之測定裝置例如可使用日本分光公司製的分光光度計V-570。As a measuring device for the spectral transmittance, a spectrophotometer V-570 manufactured by JASCO Corporation can be used, for example.
(3.2)近紅外線吸收性硬化膜之分光特性 (平均分光穿透率) 本發明之近紅外線吸收性組成物係在近紅外線吸收性硬化膜之狀態下，平均分光穿透率在波長450~600nm之範圍內為80%以上者，在可見光穿透率之點上較佳。 (3.2) Spectral characteristics of near-infrared absorbing cured film (average spectral transmittance) The near-infrared absorbing composition of the present invention, in the state of the near-infrared absorbing cured film, has an average spectral transmittance of more than 80% in the wavelength range of 450 to 600 nm, preferably in terms of visible light transmittance. .
又，在波長850~1000nm之範圍內為10%以下者，在近紅外線吸收性之點上較佳。In addition, those with a wavelength of 10% or less in the range of 850 to 1000 nm are preferable in terms of near-infrared ray absorptivity.
另外，在波長850~1080nm之範圍內為1%以下者，在近紅外線吸收性之點上更佳。In addition, those with a wavelength of less than 1% in the range of 850 to 1080nm are better in terms of near-infrared absorption.
(截止波長) 本發明之近紅外線吸收性組成物係於近紅外線吸收性硬化膜之狀態下，分光穿透率在波長600~700nm之範圍內隨著波長增加而減少，將在波長600~800nm之範圍內分光穿透率成為50%之波長當作截止波長時，對於相對於表面以0°的入射角入射的光之截止波長為600~750nm的範圍內者，在近紅外線吸收性之點上較佳。 (cutoff wavelength) The near-infrared absorbing composition of the present invention is in the state of a near-infrared absorbing cured film. The spectral transmittance decreases as the wavelength increases in the range of 600 to 700 nm, and will split light in the range of 600 to 800 nm. When the wavelength at which the transmittance becomes 50% is used as the cut-off wavelength, the cut-off wavelength of light incident at an incident angle of 0° with respect to the surface is in the range of 600 to 750 nm, which is better in terms of near-infrared absorption.
近紅外線吸收性膜之狀態下的分光穿透率亦可使用日本分光公司製的分光光度計V-570進行測定。The spectral transmittance in the state of the near-infrared absorbing film can also be measured using a spectrophotometer V-570 manufactured by JASCO Corporation.
4.光學構件 本發明之光學構件之特徵為含有近紅外線吸收性組成物的硬化物。 本發明之近紅外線吸收性硬化膜可使用作為各種的光學構件或零件。 例如適合構成CCD用、CMOS用或其他受光元件用之視感度修正構件、測光用構件、熱線吸收用構件、光學濾光片、光纖構件(光纖)、降噪用構件、電漿顯示器前面板等之顯示器或顯示器濾光片、投影器前面板、光源熱線截止構件、色調校正構件、照明亮度調節構件、光學元件(光放大元件、波長轉換元件等)、法拉第元件、隔離器等之光通信功能裝置、光碟用元件等。 以下，說明將近紅外線吸收性組成物或近紅外線吸收性硬化膜應用作為光學構件或零件之例。 4. Optical components The optical member of the present invention is characterized by a cured product containing a near-infrared absorbing composition. The near-infrared absorbing cured film of the present invention can be used as various optical members or parts. For example, it is suitable for constituting visual sensitivity correction members for CCD, CMOS or other light-receiving elements, photometry members, heat ray absorption members, optical filters, fiber optic members (optical fibers), noise reduction members, plasma display front panels, etc. Optical communication functions of displays or display filters, projector front panels, light source hotline cutoff components, hue correction components, lighting brightness adjustment components, optical components (light amplification components, wavelength conversion components, etc.), Faraday components, isolators, etc. Devices, optical disc components, etc. Hereinafter, examples in which the near-infrared-absorbing composition or the near-infrared-absorbing cured film are used as optical members or parts will be described.
(4.1)近紅外線截止濾光片 本發明之近紅外線截止濾光片為在透明介電體基板之至少一面上具備近紅外線吸收層之近紅外線截止濾光片，其特徵為：前述近紅外線吸收層含有本發明之近紅外線吸收性組成物或近紅外線吸收性硬化膜。 (4.1) Near infrared cut filter The near infrared cut filter of the present invention is a near infrared cut filter provided with a near infrared absorbing layer on at least one side of a transparent dielectric substrate, and is characterized in that the near infrared absorbing layer contains the near infrared absorbing property of the present invention. Composition or near-infrared absorbing hardened film.
又，在前述透明介電體基板之至少一面上進一步具備介電體多層膜者，在能更自由地調整近紅外線截止濾光片的分光特性之點上較佳。Furthermore, it is preferable to further provide a dielectric multilayer film on at least one side of the transparent dielectric substrate in that the spectral characteristics of the near-infrared cut filter can be more freely adjusted.
近紅外線吸收層及介電體多層膜可相接於透明介電體基板而具備，也可隔著其他中間層而具備The near-infrared absorbing layer and the dielectric multilayer film may be provided in contact with the transparent dielectric substrate, or may be provided through other intermediate layers.
圖1係顯示本發明之近紅外線截止濾光片的構成例之概略剖面圖。FIG. 1 is a schematic cross-sectional view showing a structural example of the near-infrared cut filter of the present invention.
圖1所示之近紅外線截止濾光片9係在透明介電體基板21之一面上具備近紅外線吸收層22，更在另一面上具備介電體多層膜23。The near-
透明介電體基板，只要可達到本發明之目的，則材質沒有特別的限制。例如可為玻璃製，另外也可為聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、環烯烴聚合物(COP)、聚矽氧等之光學樹脂製。The material of the transparent dielectric substrate is not particularly limited as long as the object of the present invention can be achieved. For example, it may be made of glass, or it may be made of optical resin such as polycarbonate (PC), polymethylmethacrylate (PMMA), cycloolefin polymer (COP), or polysiloxane.
透明介電體基板之厚度較佳為0.01~1mm。The thickness of the transparent dielectric substrate is preferably 0.01~1mm.
透明介電體基板由於必須使可見光穿透，故在波長450~600nm範圍內的平均分光穿透率較佳為80%以上。Since the transparent dielectric substrate must transmit visible light, the average spectral transmittance in the wavelength range of 450 to 600 nm is preferably more than 80%.
近紅外線吸收層可應用本發明之近紅外線吸收性膜。 如前述，於透明介電體基板上，直接形成近紅外線吸收性膜作為近紅外線吸收層，可製造近紅外線截止濾光片。 The near-infrared absorbing film of the present invention can be applied to the near-infrared absorbing layer. As mentioned above, a near-infrared ray-absorbing film can be directly formed on a transparent dielectric substrate as a near-infrared ray-absorbing layer to produce a near-infrared ray cutoff filter.
介電體多層膜係積層複數層由折射率不同之材料所成的層而形成之膜，用於控制光之各波長的穿透率。 藉由一併具備近紅外線吸收層，可更自由地調整近紅外線截止濾光片的分光特性。 A dielectric multilayer film is a film formed by laminating multiple layers of materials with different refractive indexes, and is used to control the transmittance of each wavelength of light. By also having a near-infrared absorbing layer, the spectral characteristics of the near-infrared cut filter can be adjusted more freely.
介電體多層膜之分光特性可根據各層厚度及材料種類而調整。 於各層之材料中，例如可使用氧化鈦、氧化矽、氧化鋁、氧化鋯、五氧化鉭、五氧化二鈮、氧化鑭、氧化銥、氧化鋅、硫化鋅、氧化銦、二氧化矽、氧化鋁、氟化鑭、氟化鎂、六氟化鋁鈉等之介電體。 The spectroscopic characteristics of dielectric multilayer films can be adjusted according to the thickness of each layer and the type of material. Among the materials of each layer, for example, titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, iridium oxide, zinc oxide, zinc sulfide, indium oxide, silicon dioxide, oxide Dielectrics such as aluminum, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, etc.
具備介電體多層膜之近紅外線截止濾光片，可藉由於透明介電體基板上，以真空蒸鍍法、化學氣相蒸鍍(CVD：chemical vapor deposition)法、濺鍍法等之方法積層各介電體層而製造。 又，亦可以接著劑將另外製作之介電體多層膜貼合於透明介電體基板而製造。 A near-infrared cut filter with a dielectric multilayer film can be formed on a transparent dielectric substrate by vacuum evaporation, chemical vapor deposition (CVD: chemical vapor deposition), sputtering, etc. Each dielectric layer is laminated and manufactured. Alternatively, a separately prepared dielectric multilayer film may be bonded to a transparent dielectric substrate using an adhesive.
(4.2)固體攝像元件用影像感測器 本發明之固體攝像元件用影像感測器之特徵為具備本發明之近紅外線截止濾光片。 (4.2) Image sensors for solid-state imaging devices The image sensor for a solid-state imaging element of the present invention is characterized by having the near-infrared cut filter of the present invention.
所謂固體攝像元件用影像感測器，就是指以具備受光元件的固體攝像元件基板為主之構件。The so-called image sensor for solid-state imaging devices refers to a component mainly composed of a solid-state imaging device substrate equipped with a light-receiving element.
本發明之固體攝像元件用影像感測器只要具備本發明之近紅外線截止濾光片，則其他構件等係沒有特別的限定。 例如，可具備平坦化層或玻璃基板等。 As long as the image sensor for a solid-state imaging device of the present invention is equipped with the near-infrared cut filter of the present invention, other components are not particularly limited. For example, a planarization layer, a glass substrate, etc. may be provided.
圖2係顯示本發明之固體攝像元件用影像感測器的構成例之概略剖面圖。FIG. 2 is a schematic cross-sectional view showing a structural example of an image sensor for a solid-state imaging element of the present invention.
圖2所示之固體攝像元件用影像感測器14係由下述構件所構成：固體攝像元件基板10，其係在矽基板之受光側的面上具備受光元件者；平坦化層8，其係設於固體攝像元件基板10上者；近紅外線截止濾光片9，其係設於平坦化層8上者；玻璃基板3(透光性基板)，其係配置於近紅外線截止濾光片9之上方者。各構件係藉由接著劑2接著。The
(4.3)相機模組 本發明之相機模組之特徵為具備本發明之固體攝像元件用影像感測器。 (4.3)Camera module The camera module of the present invention is characterized by including the image sensor for the solid-state imaging element of the present invention.
本發明之相機模組只要具備本發明之固體攝像元件用影像感測器，則其他構件等係沒有特別的限定。例如可由攝像透鏡、透鏡支架、遮光兼電磁屏蔽等構成。As long as the camera module of the present invention includes the image sensor for the solid-state imaging device of the present invention, other components are not particularly limited. For example, it can be composed of an imaging lens, a lens holder, a light shielding and electromagnetic shielding, and the like.
圖3係顯示本發明之相機模組的構成例之概略剖面圖。FIG. 3 is a schematic cross-sectional view showing a structural example of the camera module of the present invention.
圖3所示之相機模組1係具備如下而構成：固體攝像元件用影像感測器(固體攝像元件基板10、平坦化層8、近紅外線截止濾光片9、玻璃基板3)；配置於固體攝像元件用影像感測器之上方並於內部空間具有攝像透鏡4之透鏡支架5；以包圍固體攝像元件用影像感測器周圍之方式配置之遮光兼電磁屏蔽6。各構件係藉由接著劑7接著。The
再者，相機模組1係經由連接構件的焊球11(連接材料)連接於安裝基板的電路基板12。Furthermore, the
於相機模組1中，將來自外部之入射光L依序穿透過攝像透鏡4、玻璃基板3、近紅外線截止濾光片9、平坦化層8後，到達固體攝像元件基板10之受光元件。
[實施例]
In the
以下，舉出實施例來具體說明本發明，但本發明不限定於該等。再者，實施例中使用「份」或「%」之表示，只要沒有特別預先指明，則表示「質量份」或「質量%」。Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. Furthermore, the expression "part" or "%" is used in the examples. Unless otherwise specified in advance, it means "part by mass" or "% by mass".
A.近紅外線吸收劑 於實施例或比較例中，使用下述的膦酸化合物與磷酸酯或硫酸酯組合之近紅外線吸收材料。 A. Near infrared absorber In the examples or comparative examples, a near-infrared absorbing material in which the following phosphonic acid compound is combined with a phosphate ester or a sulfate ester is used.
(具有通式(I)所示的結構之化合物：膦酸化合物) ・苯基膦酸｢Phenylphosphonic Acid｣(東京化成工業股份有限公司製) ・乙基膦酸｢Ethylphosphonic Acid｣(東京化成工業股份有限公司製) ・丙基膦酸｢Propylphosphonic Acid｣(東京化成工業股份有限公司製) ・丁基膦酸｢Butylphosphonic Acid｣(東京化成工業股份有限公司製) ・4-溴苯基膦酸｢(4-Bromophenyl)phosphonic Acid｣(東京化成工業股份有限公司製) (Compound having a structure represented by general formula (I): phosphonic acid compound) ・Phenylphosphonic Acid｢(Manufactured by Tokyo Chemical Industry Co., Ltd.) ・Ethylphosphonic Acid｢(Manufactured by Tokyo Chemical Industry Co., Ltd.) ・Propylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ・Butylphosphonic Acid｢Butylphosphonic Acid｣(Manufactured by Tokyo Chemical Industry Co., Ltd.) ・4-Bromophenylphosphonic acid｢(4-Bromophenyl)phosphonic Acid｣(Manufactured by Tokyo Chemical Industry Co., Ltd.)
(具有通式(II)所示的結構之化合物：磷酸酯或硫酸酯) ・例示化合物68 ・例示化合物70 ・例示化合物76 ・例示化合物92 ・例示化合物99 ・例示化合物100 (Compounds having a structure represented by general formula (II): phosphate or sulfate) ・Exemplary compound 68 ・Exemplary compound 70 ・Exemplary compound 76 ・Exemplary compound 92 ・Exemplary compound 99 ・Exemplary compound 100
關於上述例示化合物68、70、76、92及100，使用以下之合成方法所合成者。The above-mentioned exemplary compounds 68, 70, 76, 92 and 100 were synthesized using the following synthesis method.
(例示化合物68之合成方法) 將正癸醇158g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丁烷108g(1.5莫耳)後，加成環氧乙烷66g(1.5莫耳)。 (Synthetic method of exemplified compound 68) Add 158g of n-decanol (1.0 mole) into the autoclave, use potassium hydroxide as the catalyst, and add 108g (1.5 mole) of butylene oxide under the conditions of pressure 147kPa and temperature 130°C. Ethylene oxide 66g (1.5 mol).
其次，確認正癸醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得前述之表IV中所示之例示化合物68。Next, after confirming that n-decanol does not remain, put the above adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and distill under reduced pressure. The solvent was removed to obtain the exemplary compound 68 shown in the aforementioned Table IV.
(例示化合物70之合成方法) 將正癸醇158g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷87g(1.5莫耳)後，加成環氧乙烷66g(1.5莫耳)。 (Synthetic method of exemplary compound 70) Add 158g of n-decanol (1.0 mole) into the autoclave, use potassium hydroxide as a catalyst, and add 87g of propylene oxide (1.5 mole) under the conditions of pressure 147kPa and temperature 130°C. Oxyethane 66g (1.5 mol).
其次，確認正癸醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到前述表IV中所示之例示化合物70。Next, after confirming that n-decanol does not remain, put the above adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and distill under reduced pressure. The solvent was removed to obtain the exemplary compound 70 shown in the aforementioned Table IV.
(例示化合物76之合成方法) 將正十二醇186g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷116g(2.0莫耳)後，加成環氧乙烷88g(2.0莫耳)。 (Exemplary synthesis method of compound 76) Add 186g of n-dodecyl alcohol (1.0 mole) into the autoclave, use potassium hydroxide as the catalyst, and add 116g of propylene oxide (2.0 mole) under the conditions of pressure 147kPa and temperature 130°C. Ethylene oxide 88g (2.0 mol).
其次，確認正十二醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到前述表IV中所示之例示化合物76。Next, after confirming that n-dodecanol does not remain, put the above-mentioned adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and reduce the pressure. The solvent was distilled off to obtain the exemplary compound 76 shown in the aforementioned Table IV.
(例示化合物92之合成方法) 將正硬脂醇270g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件下，加成環氧丙烷174g(3.0莫耳)後，加成環氧乙烷132g(3.0莫耳)。 (Synthesis method of exemplary compound 92) Add 270g (1.0 mole) of n-stearyl alcohol into the autoclave, use potassium hydroxide as a catalyst, and add 174g (3.0 mole) of propylene oxide under the conditions of pressure 147kPa and temperature 130°C. Ethylene oxide 132g (3.0 mol).
其次，確認正硬脂醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到前述表IV中所示之例示化合物70。Next, after confirming that n-stearyl alcohol does not remain, put the above-mentioned adduct into a reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, wash with distilled water, and reduce the pressure. The solvent was distilled off to obtain the exemplary compound 70 shown in the aforementioned Table IV.
(例示化合物99) 例示化合物99並非合成者，而是使用既有製品的Plysurf A208F(磷酸酯型陰離子界面活性劑，第一工業製藥公司製)(詳細係參照前述表V)。 例示化合物99係通式(II)中R 2為碳數8的烷基，環氧乙烷結構的平均加成數n為3，且經烷基取代的環氧乙烷結構之平均加成數m為0之磷酸酯化合物。 (Illustrated Compound 99) Illustrated Compound 99 was not synthesized but used existing product Plysurf A208F (phosphate ester type anionic surfactant, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) (see Table V above for details). Exemplary compound 99 is a compound of general formula (II) in which R 2 is an alkyl group with 8 carbon atoms, the average addition number n of the ethylene oxide structure is 3, and the average addition number m of the ethylene oxide structure substituted by an alkyl group is 0 phosphate compound.
(例示化合物100之合成方法) 將正十二醇186g(1.0莫耳)加入高壓釜內，以氫氧化鉀作為觸媒，在壓力147kPa、溫度130℃之條件，加成環氧丙烷174g(3.0莫耳)。 (Synthesis method of exemplified compound 100) Add 186 g (1.0 mol) of n-dodecanol into the autoclave, use potassium hydroxide as a catalyst, and add 174 g (3.0 mol) of propylene oxide under the conditions of pressure 147 kPa and temperature 130°C.
其次，確認正十二醇沒有殘留後，將上述加成物放入反應器中，於甲苯溶液中使磷酸酐47g(0.33莫耳)在80℃反應5小時後，以蒸餾水洗淨，減壓餾去溶劑，藉此可得到前述表V中所示之例示化合物100。Next, after confirming that n-dodecanol does not remain, put the above adduct into the reactor, react 47g (0.33 mol) of phosphoric anhydride in a toluene solution at 80°C for 5 hours, then wash with distilled water and reduce the pressure. The solvent was distilled off to obtain the exemplary compound 100 shown in the aforementioned Table V.
B.分散介質所含有的溶劑 分散介質所含有的溶劑選自下述之表VI來使用。 尚且，表VI中，雖然在實施例及比較例中未使用，但亦登載可作為本發明之實施例及比較例使用的參考用之候補。 分散介質所含有的溶劑之名稱、結構式、HSP值及其沸點係如表VI。 又，在下述顯示表VI中的各結構式No.(1)~(20)之具體結構。 B. Solvent contained in the dispersion medium The solvent contained in the dispersion medium is selected from Table VI below. Table VI also lists candidates for reference that can be used in the Examples and Comparative Examples of the present invention, although they are not used in the Examples and Comparative Examples. The names, structural formulas, HSP values and boiling points of the solvents contained in the dispersion medium are as shown in Table VI. In addition, the specific structures of each structural formula No. (1) to (20) in Table VI are shown below.
尚且，HSP值之定義與計算方法係如前述，記載於「Charles M. Hansen著，Hansen Solubility Parameters: A Users Handbook(CRC出版社，2007年)」，關於此次表VI中記載者，使用各溶劑中以HSPiP算出的值。In addition, the definition and calculation method of HSP value are as mentioned above and are recorded in "Hansen Solubility Parameters: A Users Handbook by Charles M. Hansen (CRC Press, 2007)". For those recorded in Table VI this time, use each Value calculated with HSPiP in solvent.
C.近紅外線吸收性組成物(分散液)之調製 (C.1)近紅外線吸收性組成物(分散液)No.1之調製 (C.1.1)乙酸銅溶液之調製 將下述成為銅離子源的化合物及溶劑以下述分量混合，攪拌3小時，過濾該液而去除不溶物，調製乙酸銅溶液[1]。 C. Preparation of near-infrared absorbing composition (dispersion) (C.1) Preparation of near-infrared absorbing composition (dispersion) No. 1 (C.1.1) Preparation of copper acetate solution The following compound to be a copper ion source and a solvent were mixed in the following amounts and stirred for 3 hours. The solution was filtered to remove insoluble matter and a copper acetate solution [1] was prepared.
(成為銅離子源的化合物及溶劑) 乙酸銅(II)一水合物(關東化學公司製) 1.82g (莫耳含量C C=10mmol) THF(四氫呋喃) 82g 尚且，上述乙酸銅(II)一水合物係在以下亦僅稱「乙酸銅」。 (Compounds and solvents that serve as copper ion sources) Copper (II) acetate monohydrate (manufactured by Kanto Chemical Co., Ltd.) 1.82g (Molar content C C =10mmol) THF (tetrahydrofuran) 82g In addition, the above copper (II) acetate monohydrate The material is also referred to as "copper acetate" below.
(C.1.2)溶液[1]之調製 使下述具有通式(II)所示的結構之化合物(磷酸酯)以下述分量溶解於下述溶劑中而調製溶液，於其中添加乙酸銅溶液[1]，在室溫下攪拌30分鐘而調製溶液[1]。 尚且，下述具有通式(II)所示的結構之化合物係使用以前述方法所合成者。 (C.1.2) Preparation of solution [1] A solution was prepared by dissolving the following compound (phosphate ester) having the structure represented by the general formula (II) in the following amount in the following solvent, adding copper acetate solution [1] thereto, and stirring at room temperature for 30 minutes. Prepare the solution [1]. In addition, the following compound having the structure represented by general formula (II) was synthesized using the above-mentioned method.
(具有通式(II)所示的結構之化合物(磷酸酯)及溶劑) 例示化合物76(磷酸酯) 0.99g (莫耳含量C E=1.6mmol) THF 7g (Compound (phosphate ester) having a structure represented by general formula (II) and solvent) Exemplary compound 76 (phosphate ester) 0.99g (Molar content C E =1.6mmol) THF 7g
(C.1.3)溶液[2]之調製 使下述具有通式(I)所示的結構之化合物(膦酸)以下述分量溶解於下述溶劑中，而調製溶液[2]。 (C.1.3) Preparation of solution [2] The following compound (phosphonic acid) having the structure represented by the general formula (I) is dissolved in the following solvent in the following amount to prepare a solution [2].
(具有通式(I)所示的結構之化合物(膦酸)及溶劑) 丙基膦酸(東京化成工業股份有限公司製) 1.09g (莫耳含量C A=8.8mmol) THF 7g (Compound (phosphonic acid) having a structure represented by general formula (I) and solvent) Propylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.09g (Molar content C A =8.8mmol) THF 7g
(C.1.4)近紅外線吸收性組成物(分散液)之最終調製 邊攪拌溶液[1]邊將溶液[2]添加於溶液[1]後，在室溫下攪拌16小時，而調製溶液[1]與溶液[2]之混合液(莫耳含量C H=20.2mmol)，將該混合液與THF30g置入燒瓶內，一邊以油浴(東京理化器械公司製，型式：OSB-2100)在50~ 100℃下加溫，一邊藉由旋轉蒸發器(東京理化器械公司製，型式：N-1000)進行30分鐘的脫溶劑及脫乙酸處理。 (C.1.4) Final preparation of the near-infrared absorbing composition (dispersion). Add the solution [2] to the solution [1] while stirring the solution [1], and stir at room temperature for 16 hours to prepare the solution [ 1] and a mixture of solution [2] (molar content C H =20.2mmol), put the mixture and 30g of THF into a flask, while using an oil bath (manufactured by Tokyo Rika Instruments Co., Ltd., type: OSB-2100) in a flask. While heating at 50 to 100°C, desolvation and acetic acid removal were performed for 30 minutes using a rotary evaporator (manufactured by Tokyo Rika Instruments Co., Ltd., model: N-1000).
然後，於燒瓶中調整溶劑量而使得固體成分濃度(溶劑以外的成分)成為10質量%，將其當作近紅外線吸收性組成物(分散液)No.1。 尚且，此處所言的「固體成分濃度(溶劑以外的成分)」，就是指乙酸銅溶液之調製中使用的乙酸銅、溶液[1]之調製中使用的具有通式(II)所示的結構之化合物(磷酸酯)及溶液[2]之調製中使用的具有通式(I)所示的結構之化合物(膦酸)，且表VII及表VIII中之「溶劑以外的成分」指的就是此等。 Then, the amount of the solvent in the flask was adjusted so that the solid content concentration (components other than the solvent) became 10% by mass, and this was regarded as near-infrared absorbing composition (dispersion) No. 1. In addition, the "solid content concentration (components other than solvent)" mentioned here refers to the copper acetate used in the preparation of the copper acetate solution and the structure represented by the general formula (II) used in the preparation of the solution [1]. The compound (phosphate ester) and the compound (phosphonic acid) having the structure represented by the general formula (I) used in the preparation of the solution [2], and the "components other than solvents" in Table VII and Table VIII refer to And so on.
(莫耳含量C H之算出方法) 尚且，具有通式(I)所示的結構之化合物及具有通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量C H係如下述般求出。 (Method for calculating molar content C H ) Furthermore, the molar content CH of the reactive hydroxyl group possessed by the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is Find it as follows.
具有通式(I)所示的結構之化合物所具有之反應性羥基的莫耳含量係(a)8.8mmol×2而為17.6mmol。 具有通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量係(b)(1.6mmol×60%×2)+(1.6mmol×40%×1)而為2.56mmol。 因此，具有通式(I)所示的結構之化合物及具有通式(II)所示的結構之化合物所具有之反應性羥基的莫耳含量之總量C H係(a)mmol+(b)mmol而為1.16mmol≒20.2mmol。 The molar content of the reactive hydroxyl group of the compound having the structure represented by the general formula (I) is (a) 8.8 mmol×2 and is 17.6 mmol. The molar content of the reactive hydroxyl group of the compound having the structure represented by the general formula (II) is (b) (1.6 mmol × 60% × 2) + (1.6 mmol × 40% × 1), which is 2.56 mmol. Therefore, the total molar content CH of the reactive hydroxyl groups of the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is (a) mmol + (b) mmol and 1.16mmol≒20.2mmol.
(C.2)近紅外線吸收性組成物(分散液)No.2~6及11~35之調製 除了將溶液[1]之調製中的具有通式(II)所示的結構之化合物(磷酸酯)及溶劑、溶液[2]之調製中的具有通式(I)所示的結構之化合物(膦酸)及溶劑變更為如表VII及表VIII以外，與上述近紅外線吸收性組成物(分散液)No.1之調製同樣地，調製近紅外線吸收性組成物(分散液)No.2~6及11~35。 (C.2) Preparation of near-infrared absorbing compositions (dispersions) Nos. 2 to 6 and 11 to 35 In addition to the compound having the structure represented by the general formula (II) (phosphate ester) and the solvent in the preparation of the solution [1], the compound having the structure represented by the general formula (I) in the preparation of the solution [2] ( Phosphonic acid) and the solvent were changed to Table VII and Table VIII, and the near-infrared absorbing composition (dispersion) No. 2~ was prepared in the same manner as the preparation of the near-infrared absorbing composition (dispersion) No. 1. 6 and 11~35.
尚且，例如於近紅外線吸收性組成物(分散液)No.1之調製中，在溶液[1]與溶液[2]所用的溶劑為THF，溶液[1]與溶液[2]係以同種的溶劑來調製，但表VII及表VIII中的溶劑之含量為在脫溶劑及脫乙酸處理後分散液中含有的溶劑之合計量。Furthermore, for example, in the preparation of the near-infrared absorbing composition (dispersion) No. 1, the solvent used in the solution [1] and the solution [2] is THF, and the solution [1] and the solution [2] are made of the same kind. The solvents are used to prepare the dispersion, but the solvent content in Table VII and Table VIII is the total amount of solvents contained in the dispersion after desolvation and deacetic acid treatment.
又，表VII及表VIII中之溶劑以外的成分係相對於近紅外線吸收性組成物(分散液)全體而言的固體成分(溶劑以外的成分)。In addition, the components other than the solvent in Table VII and Table VIII refer to the solid content (components other than the solvent) with respect to the entire near-infrared absorbing composition (dispersion).
(C.3)近紅外線吸收性組成物(分散液)No.7之調製 近紅外線吸收性組成物(分散液)之最終調製以外係以與近紅外線吸收性組成物(分散液)No.1同樣之方法調製。 在下述顯示上述最終調製方法。 (C.3) Preparation of near-infrared absorbing composition (dispersion) No. 7 The near-infrared absorbing composition (dispersion) was prepared in the same manner as the near-infrared absorbing composition (dispersion) No. 1 except for the final preparation. The final modulation method described above is shown below.
邊攪拌溶液[1]邊將溶液[2]添加於溶液[1]後，在室溫下攪拌16小時，而調製溶液[1]與溶液[2]之混合液(莫耳含量C H=20.2mmol)，將該混合液與甲基環己烷(溶劑1)30g置入燒瓶內，一邊以油浴(東京理化器械公司製，型式：OSB-2100)在50~100℃下加溫，一邊藉由旋轉蒸發器(東京理化器械公司製，型式：N-1000)進行40分鐘的脫溶劑及脫乙酸處理，以固體成分濃度(溶劑以外的成分)成為20質量%之方式調製。 然後添加環戊基甲基醚(溶劑2)，於燒瓶中以固體成分濃度(溶劑以外的成分)成為10質量%之方式調製。 Add solution [2] to solution [1] while stirring solution [1], and stir at room temperature for 16 hours to prepare a mixture of solution [1] and solution [2] (molar content C H =20.2 mmol), put this mixture and 30 g of methylcyclohexane (solvent 1) into a flask, and heat it at 50 to 100°C with an oil bath (manufactured by Tokyo Rika Instruments Co., Ltd., type: OSB-2100). Desolvation and deacetic acid treatment were performed for 40 minutes with a rotary evaporator (manufactured by Tokyo Rika Instruments Co., Ltd., model: N-1000), and the solid content concentration (components other than the solvent) was prepared so that it became 20 mass %. Then, cyclopentyl methyl ether (solvent 2) was added, and the solid content concentration (components other than the solvent) in the flask was prepared so that it became 10 mass %.
(C.4)近紅外線吸收性組成物(分散液)No.8~10之調製 除了於近紅外線吸收性組成物(分散液)之最終調製中，將溶劑1與溶劑2變更為如表VII以外，以與近紅外線吸收性組成物(分散液)No.7同樣之方法調製。 (C.4) Preparation of near-infrared absorbing composition (dispersion) No. 8~10 The near-infrared absorbing composition (dispersion) was prepared in the same manner as the near-infrared absorbing composition (dispersion) No. 7, except that solvent 1 and solvent 2 were changed as shown in Table VII.
D.評價 (D.1)分散性：分散液中的微粒子之平均粒徑 (評價方法) 將近紅外線吸收性組成物(分散液)No.1~35分別以甲苯稀釋而使得固體成分濃度成為0.5質量%。 使用大塚電子股份有限公司製的界達電位・粒徑測定系統ELSZ-1000ZS，藉由動態光散射法測定經稀釋之分散液中的微粒子之平均粒徑。依照下述基準進行評價。評價結果係記載於表IX及表X中。 D.evaluation (D.1) Dispersibility: average particle size of microparticles in dispersion liquid (evaluation method) Near-infrared absorbing composition (dispersion) No. 1 to 35 were each diluted with toluene so that the solid content concentration became 0.5 mass %. The average particle size of the microparticles in the diluted dispersion was measured by the dynamic light scattering method using a boundary potential and particle size measuring system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd. Evaluation was performed based on the following criteria. The evaluation results are recorded in Table IX and Table X.
(評價基準) ◎：平均粒徑為100nm以下。 ○：平均粒徑大於100nm且150nm以下。 △：平均粒徑大於150nm且200nm以下。 ×：平均粒徑大於200nm。 (evaluation criteria) ◎: The average particle diameter is 100 nm or less. ○: The average particle diameter is greater than 100 nm and less than 150 nm. △: The average particle size is greater than 150 nm and less than 200 nm. ×: The average particle diameter is greater than 200 nm.
(D.2)分散(保存)安定性 (評價方法) 將近紅外線吸收性組成物(分散液)No.1~35在室溫下放置1星期後，分別以甲苯稀釋而使得固體成分濃度成為0.5質量%。 使用大塚電子股份有限公司製的界達電位・粒徑測定系統ELSZ-1000ZS，藉由動態光散射法測定經稀釋之各分散液中的微粒子之平均粒徑。依照下述基準進行評價。評價結果係記載於表X及表XI中。 (D.2) Dispersion (preservation) stability (evaluation method) After the near-infrared absorbing compositions (dispersions) No. 1 to 35 were left at room temperature for one week, they were diluted with toluene so that the solid content concentration became 0.5 mass %. The average particle size of the microparticles in each diluted dispersion liquid was measured by the dynamic light scattering method using a boundary potential and particle size measuring system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd. Evaluation was performed based on the following criteria. The evaluation results are recorded in Table X and Table XI.
(評價基準) ◎：平均粒徑為100nm以下。 ○：平均粒徑大於100nm且150nm以下。 △：平均粒徑大於150nm且200nm以下。 ×：平均粒徑大於200nm。 (evaluation criteria) ◎: The average particle diameter is 100 nm or less. ○: The average particle diameter is greater than 100 nm and less than 150 nm. △: The average particle size is greater than 150 nm and less than 200 nm. ×: The average particle diameter is greater than 200 nm.
(D.3)樹脂相溶性 (評價方法) 混合上述調製的近紅外線吸收性組成物(分散液)No.1~35各自與樹脂(1)~(4)，使得各自樹脂的固體成分比率成為70質量%，而調製各近紅外線吸收性硬化膜形成用塗佈液。 尚且，表X及表XI中記載的樹脂之詳細係如以下。 (D.3) Resin compatibility (evaluation method) The near-infrared absorbing compositions (dispersions) No. 1 to 35 prepared above were mixed with the resins (1) to (4) so that the solid content ratio of the respective resins became 70 mass %, and each near-infrared absorbing hardened composition was prepared. Coating liquid for film formation. In addition, the details of the resins described in Table X and Table XI are as follows.
・樹脂1：胺基甲酸酯丙烯酸酯「CN975N」(Satomer公司製) ・樹脂2：胺基甲酸酯丙烯酸酯「R1403M」(第一工業製藥股份有限公司製) ・樹脂3：超分支聚酯「CN2304」(Satomer公司製) ・樹脂4：聚矽氧樹脂「KR311」(信越化學工業股份有限公司製) ・Resin 1: Urethane acrylate "CN975N" (manufactured by Satomer Corporation) ・Resin 2: Urethane acrylate "R1403M" (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.) ・Resin 3: Hyperbranched polyester "CN2304" (manufactured by Satomer Corporation) ・Resin 4: Silicone resin "KR311" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
其次，將各近紅外線吸收性硬化膜形成用塗佈液澆鑄於玻璃基板上，形成硬化後在波長850~1000nm之範圍內之最大分光穿透率成為10%之膜厚，在加熱板上，進行在50℃的60分鐘之烘烤處理。 接著，在加熱板上，藉由在150℃2小時的加溫處理而使其硬化，藉由近紅外線吸收性組成物No.1~35各自與樹脂(1)~(4)而形成各近紅外線吸收性硬化膜，使用日本分光公司製的分光光度計V-570，測定該近紅外線吸收性硬化膜No.1~35在波長450~600nm之範圍內的分光穿透率，算出該範圍的平均分光穿透率。 此時，界面反射之影響係以玻璃基板作為基底(base)而去除。 依照下述基準，評價所算出的波長450~600nm之範圍內的平均分光穿透率。評價結果係記載於表IX及表X中。 Next, each near-infrared absorbing cured film-forming coating liquid is cast on the glass substrate to form a film thickness with a maximum spectral transmittance of 10% in the wavelength range of 850 to 1000 nm after curing. On the heating plate, Bake at 50°C for 60 minutes. Next, it is cured by heat treatment at 150° C. for 2 hours on a hot plate, and each near-infrared absorbing composition No. 1 to 35 and the resins (1) to (4) are formed. For the infrared absorbing cured film, a spectrophotometer V-570 manufactured by JASCO Corporation was used to measure the spectral transmittance of the near infrared absorbing cured film No. 1 to 35 in the wavelength range of 450 to 600 nm, and calculate the Average spectral transmittance. At this time, the influence of interface reflection is removed using the glass substrate as the base. The calculated average spectral transmittance in the wavelength range of 450 to 600 nm is evaluated based on the following standards. The evaluation results are recorded in Table IX and Table X.
(評價基準) ◎：該範圍的平均分光穿透率為90%以上。 ○：該範圍的平均分光穿透率為80%以上且未達90%。 △：該範圍的平均分光穿透率為70%以上且未達80%。 ×：該範圍的平均分光穿透率未達70%。 (evaluation criteria) ◎: The average spectral transmittance in this range is over 90%. ○: The average spectral transmittance in this range is more than 80% and less than 90%. △: The average spectral transmittance in this range is more than 70% and less than 80%. ×: The average spectral transmittance in this range does not reach 70%.
E.彙總 由表IX及表X可知，實施例係對於全部的評價項目均無「×」之評價，關於比較例，由於有至少1個以上的「×」之評價，故實施例為實用上無問題，綜合性優異。 又，實施例中由於不使用甲苯等之PRTR制度的對象物質，故可知能減低環境負荷。 [產業上的利用可能性] E. Summary As can be seen from Table IX and Table Excellent comprehensiveness. In addition, since the substances subject to the PRTR system such as toluene are not used in the examples, it can be seen that the environmental load can be reduced. [Industrial utilization possibility]
可提供一種分散安定性及樹脂相溶性優異，且能減低環境負荷之近紅外線吸收性組成物、近紅外線吸收性硬化膜及光學構件。It can provide a near-infrared ray-absorbing composition, a near-infrared ray-absorbing cured film and an optical component that are excellent in dispersion stability and resin compatibility and can reduce environmental load.
1:相機模組
2,7:接著劑
3:玻璃基板
4:攝像透鏡
5:透鏡支架
6:遮光兼電磁屏蔽
8:平坦化層
9:近紅外線截止濾光片
10:固體攝像元件基板
11:焊球
12:電路基板
14:固體攝像元件用影像感測器
21:透明介電體基板
22:近紅外線吸收層
23:介電體多層膜
1:
[圖1]係顯示近紅外線截止濾光片之構成的一例之概略剖面圖。 [圖2]係顯示固體攝像元件用影像感測器之構成的一例之概略剖面圖。 [圖3]係顯示相機模組之構成的一例之概略剖面圖。 [Fig. 1] is a schematic cross-sectional view showing an example of the structure of a near-infrared cut filter. [Fig. 2] is a schematic cross-sectional view showing an example of the structure of an image sensor for a solid-state imaging device. [Fig. 3] is a schematic cross-sectional view showing an example of the structure of a camera module.
1:相機模組 1:Camera module
2,7:接著劑 2,7: Adhesive
3:玻璃基板 3:Glass substrate
4:攝像透鏡 4:Camera lens
5:透鏡支架 5: Lens holder
6:遮光兼電磁屏蔽 6: Light shielding and electromagnetic shielding
8:平坦化層 8: Planarization layer
9:近紅外線截止濾光片 9: Near infrared cut filter
10:固體攝像元件基板 10:Solid imaging element substrate
11:焊球 11: Solder ball
12:電路基板 12:Circuit substrate
L:入射光 L: incident light
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| JP2023132403A (en) | 2023-09-22 |
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