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KR-20260067141-A - Near-infrared absorption materials and near-infrared blocking filter including the same

KR20260067141AKR 20260067141 AKR20260067141 AKR 20260067141AKR-20260067141-A

Abstract

The present invention relates to a near-infrared absorber capable of simultaneously achieving excellent near-infrared blocking performance and thermal stability, and a near-infrared blocking filter containing the same.

Inventors

  • 박영일
  • 정효철
  • 김진철
  • 정지은
  • 진영재
  • 신다영
  • 이나은

Assignees

  • 한국화학연구원

Dates

Publication Date
20260512
Application Date
20241105

Claims (19)

  1. A near-infrared absorber comprising: a cationic dye represented by the following chemical formula 1; and a borate anion represented by the following chemical formula 2, chemical formula 3, or chemical formula 4. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 1 to 4, R1 and R2 are each independently a C1-C30 alkyl, a C3-C10 cycloalkyl, a C6-C20 aryl C1-C30 alkyl, or a halo C1-C30 alkyl; R3 and R4 are each independently hydrogen, C1-C7 alkyl, C3-C12 cycloalkyl, or C6-C12 aryl; R5 and R6 are each independently C1-C7 alkyl, or R5 and R6 can be connected to each other to form a ring; X1 and X2 are each independently halogens; L1 and L2 are each independently , or And; D1 and D2 are each independently -C(=O)- or -CR a R b -; a is 0 or 1 and; R a and R b are each independently hydrogen, C1-C7 alkyl, C6-C12 aryl, C1-C7 alkoxycarbonyl, carboxyl C1-C7 alkyl, or -C(=O)NHR c ; R c is hydrogen, C1-C7 alkyl, C6-C12 aryl or -L a -C(=O)R d and; L a is a C1-C7 alkylene or a C6-C12 arylene; R d is a C1-C7 alkyl or C1-C7 alkoxy; Ar is a C6-C30 arylene, and the arylene of Ar can be further substituted with a halogen; D3 is a single bond or -C(=O)- and; Ar 1 to Ar 4 are each independently C6-C30 arylenes, and the arylenes of Ar 1 to Ar 4 may be further substituted with one or more selected from halogens and halo-C1-C7 alkyls.
  2. In Article 1, A near-infrared absorber, wherein the cationic dye represented by the above chemical formula 1 is represented by the following chemical formula 5. [Chemical Formula 5] In the above chemical formula 5, R1 and R2 are C7-C20 alkyl, C3-C8 cycloalkyl, C6-C20 aryl C1-C20 alkyl, or halo C7-C20 alkyl.
  3. In Paragraph 2, The above R1 and R2 are identical to each other and are straight-chain C7-C20 alkyls, a near-infrared absorber.
  4. In Paragraph 2, The above cationic dye is a near-infrared absorber having the following structure.
  5. In Article 1, A near-infrared absorber in which the borate anion represented by the above chemical formula 2 is represented by the following chemical formula 6 or chemical formula 7. [Chemical Formula 6] [Chemical Formula 7] In the above chemical formulas 6 and 7, R7 and R8 are each independently C1-C7 alkyl; n is 0 or 1.
  6. In Article 1, Near-infrared absorbers, wherein L1 and L2 are each independently selected from the following structures. In the above structure, a is 0 or 1 and; D 11 is -C(=O)- or -CR a R b - and; R a and R b are each independently hydrogen, C1-C7 alkyl, C6-C12 aryl, C1-C7 alkoxycarbonyl, carboxyl C1-C7 alkyl or -C(=O)NH-L a -C(=O)R d ; L a is a C1-C7 alkylene; R d is a C1-C7 alkoxy; Ar is a C6-C30 arylene, and the arylene of Ar can be further substituted with a halogen; D3 is a single bond or -C(=O)-.
  7. In Paragraph 6, Near-infrared absorbers, wherein L1 and L2 are each independently selected from the following structures. In the above structure, a is 0 or 1 and; R 11 to R 13 are each independently a C6-C12 aryl, C1-C7 alkoxycarbonyl, carboxyl C1-C7 alkyl, or -C(=O)NH-L a -C(=O)OCH 3 ; L a is a C1-C7 alkylene; The A1 ring and the A2 ring are each independently C6-C30 arylenes; X 11 is a halogen and n is an integer from 0 to 4.
  8. In Article 1, A near-infrared absorber in which the borate anion represented by the above chemical formula 4 is represented by the following chemical formula 8. [Chemical Formula 8] In the above chemical formula 8, R 31 to R 34 are each independently a halogen or a halo-C1-C7 alkyl; w, x, y, and z are each independently integers from 1 to 5.
  9. In Article 1, The above borate anion is a near-infrared absorber selected from the following structure. In the above structure, R 21 to R 28 are each independently a C6-C12 aryl, C1-C7 alkoxycarbonyl, carboxyl C1-C7 alkyl, or -C(=O)NH-L a -C(=O)OCH 3 ; L a is a C1-C7 alkylene; A3 to A8 rings are each independently C6-C20 arylenes; p and q are each independently integers from 0 to 4; w, x, y, and z are each independently integers from 1 to 5.
  10. In Article 9, The above borate anion is a near-infrared absorber selected from the following structure.
  11. In Article 1, A near-infrared absorber having a maximum absorption wavelength (λ max ) located between 740 nm and 840 nm.
  12. A near-infrared blocking composition comprising a near-infrared absorber and a resin selected from any one of claims 1 to 11.
  13. In Paragraph 12, A near-infrared blocking composition in which the above near-infrared absorber is included in an amount of 0.01 to 10 weight% based on the total weight of the composition.
  14. In Paragraph 13, A near-infrared blocking composition comprising 1 to 20 parts by weight of a near-infrared absorber per 100 parts by weight of the resin.
  15. A near-infrared blocking filter obtained by curing the near-infrared blocking composition of claim 12.
  16. In Paragraph 15, The above near-infrared blocking filter is a near-infrared blocking filter having a light transmittance of 99% or more for a visible light wavelength (430 to 560 nm).
  17. In Paragraph 16, The above near-infrared blocking filter is a near-infrared blocking filter having a change rate of light transmittance (△T%) according to the following Equation 1 of 10 or less. [Equation 1] △T% = (T 0 -T B /T 0 ) In the above Equation 1, T0 is the light transmittance of the visible light wavelength measured before baking; T B is the transmittance of the visible wavelength measured after baking at 135°C for 2 hours.
  18. A solid-state imaging device comprising the near-infrared blocking filter of claim 15.
  19. A camera module comprising the near-infrared blocking filter of claim 15.

Description

Near-infrared absorption materials and near-infrared blocking filter including the same The present invention relates to a near-infrared absorber with excellent thermal stability and a near-infrared blocking filter using the same. Near-infrared dyes are materials that absorb wavelengths in the near-infrared region (650 to 1700 nm) and are used in various industrial fields, such as optical filters, optical lenses, and semiconductor photosensitive materials. In particular, the need for high-performance infrared blocking filters has increased recently due to the advancement of digital imaging devices, including smartphones equipped with high-resolution cameras. This is because ultraviolet and infrared rays, which fall outside the visible light spectrum, cause optical distortion when they reach camera sensors, negatively affecting image quality. Therefore, filters that absorb only ultraviolet and infrared rays to the maximum extent are essential for realizing high-quality, clear images. However, conventional near-infrared blocking filters have the problem that their near-infrared blocking effect is insufficient, or that attempting to improve the blocking effect also leads to a decrease in light transmittance in the visible light range. In addition, cyanine-based compounds, which are representative materials with high near-infrared absorption selectivity, have low stability against heat and light, so there is a limitation in that visible light transmittance decreases due to external stimuli such as heat. This causes difficulties in maintaining image quality in digital imaging devices. Therefore, there is a continuous demand for the development of near-infrared absorbing materials with high selectivity and reliability. These materials play a crucial role in realizing sharp images in digital cameras and sensors by being applied to infrared cut-off filters to effectively block near-infrared radiation. In particular, for high-performance optical devices such as high-resolution cameras, it is essential for these materials to maintain visible light transmittance while minimizing the influence of external environments (e.g., heat, light). Unless otherwise defined in this specification, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention. The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context. Additionally, numerical ranges used herein include lower and upper limits and all values within the range, increments logically derived from the form and width of the defined range, all of which are limited values, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise specifically defined in this specification, values outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range. The term "comprising" in this specification is an open description having an equivalent meaning to expressions such as "comprising," "containing," "having," or "characterizing," and does not exclude elements, materials, or processes not additionally listed. The term "CA-CB" in this specification means "having a carbon number of A or more and B or less." The term "alkyl" in this specification means a monovalent straight-chain or branched saturated hydrocarbon group composed only of carbon and hydrogen atoms. Specifically, it may be a straight-chain saturated hydrocarbon group. Examples of such alkyls include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, heptadecyl, octadecyl, nonadecyl, etc. The term "alkylene" in this specification refers to a divalent organic radical derived from an aliphatic hydrocarbon by the removal of two hydrogens, and may include both straight-chain and pulverized forms. Examples include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, hexylene, octylene, nonylene, etc. The term "aryl" in this specification refers to a functional group derived from an aromatic hydrocarbon by the removal of one hydrogen, comprising a single or fused ring system having, suitably, 4 to 9, preferably 5 or 6 ring atoms in each ring, and including forms in which multiple aryls are connected by single bonds. In this case, the terms "fusion" and "condensation" as described in this invention may be interpreted identically. Examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. The term "arylene" in this specif