WO2022049862A1 - 色素組成物、インクジェット記録方法、画像記録物、及び色素化合物 - Google Patents
色素組成物、インクジェット記録方法、画像記録物、及び色素化合物 Download PDFInfo
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- WO2022049862A1 WO2022049862A1 PCT/JP2021/022899 JP2021022899W WO2022049862A1 WO 2022049862 A1 WO2022049862 A1 WO 2022049862A1 JP 2021022899 W JP2021022899 W JP 2021022899W WO 2022049862 A1 WO2022049862 A1 WO 2022049862A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
Definitions
- the present disclosure relates to dye compositions, inkjet recording methods, image recordings, and dye compounds.
- the near-infrared absorbing dye is used for optical films such as infrared cut films and heat ray shielding films for plasma display panels or CCDs (imaging elements); applications for photothermal conversion materials for write-once optical disks or flash melt fixing materials; security inks, It is used in a wide variety of applications such as information display materials such as invisible barcode inks; medical materials such as diagnostic markers and photodynamic therapy agents.
- this near-infrared absorbing dye it is required to have strong absorption in the infrared or infrared region and to have as little absorption in the visible light region as possible (invisibility). It is also required that the infrared absorbing ability is maintained for a long time.
- Japanese Patent Application Laid-Open No. 2000-292758 describes a compound composed of a cyanine dye moiety having a sulfo group and bipyridine.
- Japanese Unexamined Patent Publication No. 2002-90521 describes a cyanine dye in which a cyanine dye moiety having a sulfo group and a potassium cation form an intramolecular salt.
- Japanese Unexamined Patent Publication No. 2000-141898 describes a compound composed of a cyanine cation and an anion.
- the near-infrared absorbing dye has excellent invisibility and the infrared absorbing ability is maintained longer than before.
- the present disclosure has been made in view of such circumstances, and according to one embodiment of the present invention, it is possible to obtain an image recording material having excellent invisibility and maintaining infrared absorption ability longer than before.
- a dye composition capable of the above, and an inkjet recording method are provided.
- a novel dye compound capable of obtaining an image recording material having excellent invisibility and maintaining infrared absorption ability longer than before is provided.
- a dye composition comprising a dye compound represented by the following formula 1 and a medium.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
- Cy represents an anion portion
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4. .. n is non-zero and represents the number required to neutralize the charge.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 11 independently represents a divalent linking group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- R 1a , R 1b , R 1c , and R 1d may be coupled to each other to form a ring.
- m1 is an integer of 1 or more.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 21 and B 22 each independently represent a divalent linking group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 31 represents a divalent linking group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- B 41 independently represents a single bond or a divalent linking group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- One of R 4a , R 4b and R 4c may be combined with E 41 or E 42 to form a ring.
- m4 is an integer of 2 or more.
- B 11 , B 21 , B 22 and B 31 are independently divalent linking groups having 2 to 8 carbon atoms. , ⁇ 1>.
- X 1 represents an organic cation represented by the formula 2-1 or an organic cation having a structure represented by the formula 2-4, whichever is ⁇ 1> to ⁇ 3>.
- the dye composition according to one.
- ⁇ 5> The dye composition according to any one of ⁇ 1> to ⁇ 4>, wherein Cy is represented by the following formula 4 in the formula 1.
- Y 1 and Y 2 independently represent CR 3 R 4- , -O-, -S-, -Se-, or -NR 5- .
- R 3 , R 4 , and R 5 each independently represent a hydrogen atom, an aliphatic group, or an aromatic ring group.
- R 3 and R 4 may be combined with each other to form a ring.
- a 1 and A 2 each independently represent a group of non-metal atoms forming an aromatic ring or an aromatic heterocycle.
- L 2 independently represents a methine chain consisting of one, two, or three methine groups, and L 2 has no substituent.
- R 6 and R 7 each independently represent a hydrogen atom or an aliphatic group. R 6 and R 7 may be connected to each other to form a ring.
- R 8 is represented by the following formula A.
- RL2 represents an alkylene group, an arylene group, or a divalent heterocyclic group
- TA represents a hydrogen atom, a halogen atom, or an alkyl group.
- ⁇ 6> The dye composition according to ⁇ 5>, wherein A 1 and A 2 independently represent a group of non-metal atoms forming a benzene ring or a naphthalene ring, respectively.
- a 1 and A 2 independently represent a group of non-metal atoms forming a benzene ring or a naphthalene ring, respectively.
- the medium is a liquid.
- ⁇ 8> The dye composition according to any one of ⁇ 1> to ⁇ 7>, wherein the medium is a liquid containing water.
- ⁇ 9> The dye composition according to any one of ⁇ 1> to ⁇ 8>, wherein the medium contains water and an organic solvent having a boiling point of 100 ° C. or higher.
- ⁇ 10> The dye composition according to any one of ⁇ 1> to ⁇ 9>, which is an ink.
- ⁇ 11> The dye composition according to ⁇ 10>, which is used for inkjet recording.
- An inkjet recording method comprising a step of applying the dye composition according to ⁇ 11> onto a substrate.
- An image recording material comprising a base material and an infrared absorption image which is a solidified product of the dye composition according to ⁇ 10> or ⁇ 11>, which is arranged on the base material.
- the infrared absorption image includes a substrate and an infrared absorption image arranged on the substrate, and the infrared absorption image contains a dye compound represented by the following formula 1, and the maximum absorption wavelength of the infrared absorption image is 700 nm to 1 , Image recordings in the range of 300 nm.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
- Cy represents an anion portion
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4. .. n is non-zero and represents the number required to neutralize the charge.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 11 independently represents a divalent linking group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- R 1a , R 1b , R 1c , and R 1d may be coupled to each other to form a ring.
- m1 is an integer of 1 or more.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 21 and B 22 each independently represent a divalent linking group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 31 represents a divalent linking group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- B 41 independently represents a single bond or a divalent linking group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- One of R 4a , R 4b and R 4c may be combined with E 41 or E 42 to form a ring.
- m4 is an integer of 2 or more.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
- Cy represents an anion portion
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4. .. n is non-zero and represents the number required to neutralize the charge.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 11 independently represents a divalent linking group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- R 1a , R 1b , R 1c , and R 1d may be coupled to each other to form a ring.
- m1 is an integer of 1 or more.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 21 and B 22 each independently represent a divalent linking group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 31 represents a divalent linking group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- B 41 independently represents a single bond or a divalent linking group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- One of R 4a , R 4b and R 4c may be combined with E 41 or E 42 to form a ring.
- m4 is an integer of 2 or more.
- Equations 2-1 and 2-2, Equations 2-3, and Equations 2-4, A11, A12, A21 , A22 , A23 , A31 , A32 , and A41 are , The dye compound according to ⁇ 15> or ⁇ 16>, which is a nitrogen atom.
- X 1 is any one of ⁇ 15> to ⁇ 17> representing an organic cation represented by the formula 2-1 or an organic cation having a structure represented by the formula 2-4.
- Cy is the dye compound according to any one of ⁇ 15> to ⁇ 18> represented by the following formula 4.
- Y 1 and Y 2 independently represent CR 3 R 4- , -O-, -S-, -Se-, or -NR 5- .
- R 3 , R 4 , and R 5 each independently represent a hydrogen atom, an aliphatic group, or an aromatic ring group.
- R 3 and R 4 may be combined with each other to form a ring.
- a 1 and A 2 each independently represent a group of non-metal atoms forming an aromatic ring or an aromatic heterocycle.
- L 2 independently represents a methine chain consisting of one, two, or three methine groups, and L 2 has no substituent.
- R 6 and R 7 each independently represent a hydrogen atom or an aliphatic group.
- R 6 and R 7 may be connected to each other to form a ring.
- R 8 is represented by the following formula A.
- RL2 represents an alkylene group, an arylene group, or a divalent heterocyclic group
- TA represents a hydrogen atom, a halogen atom, or an alkyl group.
- a 1 and A 2 independently represent a group of non-metal atoms forming a benzene ring or a naphthalene ring, respectively.
- a dye composition and an inkjet recording method capable of obtaining an image recording material having excellent invisibility and maintaining infrared absorption ability longer than before. Further, according to the present disclosure, there is provided an image recording material which is excellent in invisibility and whose infrared absorption ability is maintained longer than before. Further, according to the present disclosure, there is provided a novel dye compound capable of obtaining an image recording material having excellent invisibility and maintaining infrared absorption ability longer than before.
- the numerical range indicated by using "-" in the present specification means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description.
- the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
- the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means. In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.
- (meth) acrylate is a concept that includes both acrylates and methacrylates.
- (meth) acrylic is a concept that includes both acrylic and methacrylic.
- a monovalent heterocyclic group means a group obtained by removing one hydrogen atom from a heterocyclic compound
- a divalent heterocyclic group means a group obtained by removing two hydrogen atoms from a heterocyclic compound. Refers to the base.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
- Cy represents an anion portion
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4. .. n is non-zero and represents the number required to neutralize the charge.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 11 independently represents a divalent linking group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- R 1a , R 1b , R 1c , and R 1d may be coupled to each other to form a ring.
- m1 is an integer of 1 or more.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 21 and B 22 each independently represent a divalent linking group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- m2 is an integer of 0 or more.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 31 represents a divalent linking group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- B 41 independently represents a single bond or a divalent linking group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- One of R 4a , R 4b and R 4c may be combined with E 41 or E 42 to form a ring.
- m4 is an integer of 2 or more.
- the dye compound represented by the formula 1 is excellent in infrared absorption ability and is excellent in invisibility because it absorbs little in the visible region. Further, the dye compound represented by the formula 1 can maintain the infrared absorption ability longer than before.
- Cyanine pigments tend to form aggregates.
- the cyanine dye When the cyanine dye forms an aggregate, it absorbs light of a long wavelength, so that it is excellent in invisibility and also excellent in durability such as light resistance and moisture heat resistance.
- the dye compound represented by the formula 1 has a cyanine dye structure and an organic cation represented by the formula 2-1 or the formula 2-2 or the formula 2-3, or a structure represented by the formula 2-4. It has an organic cation. Since these organic cations have a flexible molecular structure, it is presumed that they are highly effective in binding cyanine dyes to each other at positions where aggregates can be appropriately formed. As a result, it is considered that the cyanine dye using the organic cation of the present application has an improved association forming ability in the dye composition and can maintain the infrared absorption ability longer than before.
- Japanese Patent Application Laid-Open No. 2000-292758 describes a dye compound in which a cyanine dye structure as an anion portion and an organic cation having a bipyridine skeleton form a salt.
- the bipyridine skeleton has a rigid molecular structure, it is presumed that the effect of binding the cyanine dyes to each other at a position where an aggregate can be appropriately formed is low.
- the cyanine dye using an organic cation having a bipyridine skeleton is difficult to form an aggregate in the dye composition, and maintenance of infrared absorption ability cannot be expected.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
- Cy represents an anion portion
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4. .. n is non-zero and represents the number required to neutralize the charge.
- L 1 represents a methine chain consisting of an odd number of methine groups.
- L 1 preferably represents a methine chain consisting of 5, 7, or 9 methine groups, and more preferably represents a methine chain consisting of 5 or 7 methine groups.
- the methine group in the center of the methine chain preferably has a substituent represented by the formula A.
- SA and TA in the formula A will be described later. * -S A -TA type A
- the methine group other than the methine group in the center of the methine chain may have a substituent, but it is preferable that the methine group does not have a substituent.
- the methine chain may have a crosslinked structure at any position.
- the methine chain may form a ring structure by bonding carbon atoms constituting the methine chain to each other.
- the ring structure is not particularly limited, but an aliphatic ring is preferable, and a 5-membered aliphatic ring or a 6-membered aliphatic ring is more preferable.
- L 1 is preferably a group represented by the following formula L1-1, L1-2, L2-1 or L2-2, and is represented by the following formula L1-2 or formula L2-2. It is more preferable to be a group.
- A represents a substituent represented by the above formula A, and the wavy line portion independently represents the substituent in the formula 1.
- Y L represents a group of non-metal atoms forming an aliphatic ring or a heterocycle, and preferably represents a group of non-metal atoms forming an aliphatic ring.
- Y L is preferably an alkylene group, and examples of the alkylene group include -CH 2 CH 2- and -CH 2 C (Z) 2 -CH 2- .
- the aliphatic ring is preferably a 5-membered aliphatic ring or a 6-membered aliphatic ring.
- Z independently represents a hydrogen atom or an alkyl group.
- Z is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group. The two Zs may be combined to form a ring structure.
- the group represented by the above formula L2-1 or L2-2 is preferably a group represented by the following formulas L3-1 to L3-4.
- Z independently represents a hydrogen atom or an alkyl group.
- Z is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group. The two Zs may be combined to form a ring structure.
- A represents a substituent represented by the above formula A, and the wavy line portion independently represents a bonding position with a structure other than L1 in formula 1 .
- SA is preferably a single bond, an alkylene group, an alkenylene group or an alkynylene group, and more preferably a single bond.
- the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and further preferably a methylene group or an ethylene group.
- the alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and further preferably an alkenylene group having 2 or 3 carbon atoms.
- the alkynylene group is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 4 carbon atoms, and even more preferably an alkynylene group having 2 or 3 carbon atoms.
- the alkylene group, the alkenylene group, and the alkynylene group may be linear or branched, and even if a part or all of the carbon atoms contained in each group form a cyclic structure. good.
- the carbon atom may be bonded to L 1 and the oxygen atom may be bonded to TA , the oxygen atom may be bonded to L 1 , and the carbon atom may be bonded to TA . May be.
- the carbon atom may be bonded to L 1 and the nitrogen atom may be bonded to TA , the nitrogen atom may be bonded to L 1 , and the carbon atom may be bonded to TA . May be.
- RL1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.
- a hydrogen atom, an alkyl group or an aryl group is preferable, and a hydrogen atom is more preferable.
- halogen atom examples include a fluorine atom (F atom), a chlorine atom (Cl atom), a bromine atom (Br atom) and an iodine atom (I atom).
- the halogen atom is preferably a Cl atom or a Br atom, and more preferably a Cl atom.
- the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group or a naphthyl group.
- the heterocycle in the monovalent heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the heterocycle may form a fused ring with an aliphatic ring, an aromatic ring or another heterocycle. Examples of the hetero atom in the hetero ring include N atom, O atom, and S atom, and N atom is preferable.
- the heterocycle includes a pyridine ring, a piperidine ring, a furan ring, a flufuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, and an indole ring.
- Pyrolidone ring, thiazole ring, pyrazine ring, thiadiazine ring benzoquinoline ring and thiazylazole ring.
- RL2 represents an alkylene group, an arylene group or a divalent heterocyclic group, and is preferably an alkylene group.
- the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.
- the arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably a phenylene group or a naphthylene group, and even more preferably a phenylene group.
- the divalent heterocyclic group preferably has a structure in which one hydrogen is further removed from the monovalent heterocyclic group in RL1 .
- TA is a halogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a cyano group, a hydroxy group, a formyl group, a carboxy group, an amino group, a thiol group, a sulfo group, a phosphoryl group and a boryl group.
- TA is preferably an aryl group, a monovalent heterocyclic group or a trialkylsilyl group.
- halogen atom examples include a fluorine atom (F atom), a chlorine atom (Cl atom), a bromine atom (Br atom) and an iodine atom (I atom).
- the halogen atom is preferably a Cl atom or a Br atom, and more preferably a Cl atom.
- the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
- TA when TA represents an alkyl group, TA may form a ring structure with other carbon atoms in the methine chain.
- a ring structure As the ring structure, a 5-membered ring or a 6-membered ring is preferable.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
- the heterocycle in the monovalent heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the heterocycle may form a fused ring with an aliphatic ring, an aromatic ring or another heterocycle.
- hetero atom in the hetero ring examples include N atom, O atom, and S atom, and N atom is preferable.
- the heterocycle includes a pyridine ring, a triazine ring, a piperidine ring, a furan ring, a flufuran ring, a merdrum acid ring, a carbazole acid ring, a succinimide ring, a thiophene ring, a pyrrol ring, a quinoline ring, a morpholine ring, a thiomorpholin ring, and an indole ring.
- Imidazole ring Imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring, indolin ring, pyrrolidone ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiathiazole ring.
- the heterocycle may form a salt structure.
- the pyridine ring may form a pyridinium salt or may exist as a pyridinium ion.
- the aryl group and the monovalent heterocyclic group may have a substituent.
- Each of RT independently represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, and a hydrogen atom, an alkyl group or an aryl group is preferable.
- the alkyl group in RT is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group or an ethyl group.
- the aryl group in RT is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
- the heterocycle in the monovalent heterocyclic group in RT is preferably a 5-membered ring or a 6-membered ring. Further, the heterocycle may form a fused ring with an aliphatic ring, an aromatic ring, or another heterocycle.
- hetero atom in the hetero ring examples include N atom, O atom, and S atom, and N atom is preferable.
- the heterocycle includes a pyridine ring, a piperazine ring, a piperazine ring, a pyrrolidine ring, a furan ring, a tetrahydrofuran ring, a tetrahydropyran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, and a carbazole ring.
- Phenothiazine ring Phenothiazine ring, phenoxazine ring, indolin ring, pyrrolidine ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring, and thiathiazole ring.
- the monovalent heterocyclic group in RT may further have a substituent.
- substituents include a group represented by RT , and the same applies to preferred embodiments.
- amino group examples include an unsubstituted amino group and a substituted amino group, and a diarylamino group or a diheteroarylamino group is preferable.
- substituent in the substituted amino group examples include an alkyl group, an aryl group or a monovalent heterocyclic group.
- the alkyl group, aryl group or monovalent heterocyclic group in the substituted amino group is synonymous with the alkyl group, aryl group or monovalent heterocyclic group in TA , and the preferred embodiment is also the same.
- trialkylsilyl group a trialkylsilyl group having 1 to 10 carbon atoms of the alkyl group is preferable, and a trialkylsilyl group having 1 to 4 carbon atoms of the alkyl group is more preferable.
- examples of the trialkylsilyl group include a trimethylsilyl group, a dimethylbutylsilyl group, a triethylsilyl group, and a triisopropylsilyl group.
- the trialkoxysilyl group is preferably a trialkoxysilyl group having 1 to 10 carbon atoms, and more preferably a trialkoxysilyl group having 1 to 4 carbon atoms.
- Examples of the trialkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.
- the total number of carbon atoms contained in SA and TA is preferably 3 or more from the viewpoint of invisibility. It is preferably 4 or more, and more preferably 5 or more.
- the total number of carbon atoms is preferably 20 or less, more preferably 10 or less, from the viewpoint of dispersibility.
- TA is preferably a heterocyclic group containing a nitrogen atom, an aryl group, or a halogen atom.
- substituent A represented by the formula A
- substituents A-1 to A-55 include the following substituents A-1 to A-55.
- substituent A in the present disclosure is not limited to this.
- substituents A-1 to A-55 i-C 10 represents an isodecyl group
- i-C 8 represents an isooctyl group
- * indicates a binding site with L 1 in the formula 1.
- substituents A-1 to A-55 from the viewpoint that the cyanine dye is more likely to form an aggregate, the substituents A-1, A-4, A-5, A-8, A-10, A- 24, A-34, A-39, A-41 to 43, A-48, or A49 to A55 are preferable.
- the methine chain represented by L 1 is not limited to the following specific examples.
- the wavy line portions independently represent the coupling positions with the structures other than L1 in the equation 1 .
- Me represents a methyl group
- Et represents an ethyl group
- Ph represents a phenyl group.
- the methine chain represented by L1 is preferably LA1 to LA8, LA11 to 19, LA21 to 24, or LA27 to 30 from the viewpoint that the cyanine dye is more likely to form an aggregate.
- R 1 and R 2 independently represent an aliphatic group or an aromatic group, respectively.
- the aliphatic group and the aromatic group may have a substituent.
- Substituents include halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, and iodine atom), cyano group, nitro group, aliphatic group, aromatic group, heterocyclic group, -OR 10 , -COR 11 , -COOR 12 , -OCOR 13 , -NR 14 R 15 , -NHCOR 16 , -CONR 17 R 18 , -NHCONR 19 R 20 , -NHCOOR 21 , -SR 22 , -SO 2 R 23 , -SO 2 OR 24 , -NHSO 2 R 25 and SO 2 NR 26 R 27 .
- halogen atoms eg, fluorine atom, chlorine atom, bromine atom, and iodine atom
- R 10 to R 27 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Examples thereof include a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group. Among them, the substituent is preferably an aliphatic group, an aromatic group, —OR 10 , —COOR 12 or —SO 2 OR 24 , and more preferably an aromatic group, —SO 2 OR 24 .
- R 12 of ⁇ COOR 12 is a hydrogen atom (that is, a carboxy group)
- the hydrogen atom may be dissociated (that is, a carboxylate group) or may be in a salt state.
- R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
- the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.
- Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group.
- Examples of the aromatic group include an aryl group.
- the alkyl group represented by each of R 1 and R 2 may be cyclic or chain-like.
- the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.
- the number of carbon atoms of the alkyl group (in the case of having a substituent, the number of carbon atoms of the portion excluding the substituent) is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8.
- alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a t-butyl group, a cyclopropyl group, a cyclohexyl group and a 2-ethylhexyl group.
- alkyl group having a substituent examples include 2-hydroxyethyl group, 2-carboxyethyl group, 2-methoxyethyl group, 2-phenoxyethyl group, 2- (1-naphthoxy) ethyl group, 2-diethylaminoethyl group, and 2 -Sulfoethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-sulfopropyl group, 3-sulfobutyl group, and 4-sulfobutyl group can be mentioned.
- the alkenyl group represented by each of R 1 and R 2 may be cyclic or chain-shaped.
- the chain alkenyl group may be a linear alkenyl group or a branched chain alkenyl group.
- the carbon number of the alkenyl group (in the case of having a substituent, the carbon number of the portion excluding the substituent) is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8.
- Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 2-pentenyl group and a 2-hexenyl group.
- the alkynyl group represented by each of R 1 and R 2 may be cyclic or chain-like.
- the chain alkynyl group may be a linear alkynyl group or a branched chain alkenyl group.
- the number of carbon atoms of the alkynyl group (in the case of having a substituent, the number of carbon atoms of the portion excluding the substituent) is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8.
- Examples of the alkynyl group include an ethynyl group and a 2-propynyl group.
- the alkyl moiety of the aralkyl group represented by each of R 1 and R 2 is the same as the above-mentioned alkyl group.
- the aryl moiety of the aralkyl group which may have a substituent is the same as the aryl group described later. Examples of the aralkyl group include a benzyl group and a phenethyl group.
- the number of carbon atoms of the aryl group represented by each of R 1 and R 2 is preferably 6 to 25, more preferably 6 to 15. 6 to 10 are more preferable.
- Examples of the aryl group include a phenyl group and a naphthyl group.
- Examples of the aryl group having a substituent include a 4-carboxyphenyl group, a 4-acetamidophenyl group, a 3-methanesulfonamidephenyl group, a 4-methoxyphenyl group, a 3-carboxyphenyl group, and a 3,5-dicarboxyphenyl group. Examples thereof include 4-methanesulfonamidephenyl group and 4-butanesulfonamidephenyl group.
- T 1 and T 2 each independently represent a group of non-metal atoms forming a nitrogen-containing heterocycle which is a 5-membered ring or a 6-membered ring which may be fused.
- the nitrogen-containing heterocycle may be condensed with another heterocycle, an aromatic ring or an aliphatic ring.
- the nitrogen-containing heterocycle is preferably a 5-membered ring. It is more preferable that a benzene ring or a naphthalene ring is condensed with a 5-membered nitrogen-containing heterocycle.
- nitrogen-containing heterocycle examples include an oxazole ring, an isooxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazologibenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthoazole ring, an indolenin ring, and a benzo.
- Examples thereof include an indorenine ring, an imidazole ring, a benzoimidazole ring, a naphthoimidazole ring, a quinoline ring, a pyridine ring, a pyrolopyridine ring, a flopyrol ring, an indridin ring, an imidazoline quinoxaline ring, and a quinoxalin ring.
- the nitrogen-containing heterocycle is preferably a quinoline ring, an indorenine ring, a benzowearnin ring, a benzoxazole ring, a benzothiazole ring, or a benzimidazole ring, and an indorenine ring, a benzowearnine ring, a benzothiazole ring, or a benzo. It is more preferably an imidazole ring.
- the nitrogen-containing heterocycle and the ring condensed with it may have a substituent.
- Substituents include halogen atom, cyano group, nitro group, aliphatic group, aromatic group, heterocyclic group, -OR 10 , -COR 11 , -COOR 12 , -OCOR 13 , -NR 14 R 15 , -NHCOR. 16 , -CONR 17 R 18 , -NHCONR 19 R 20 , -NHCOOR 21 , -SR 22 , -SO 2 R 23 , -SO 2 OR 24 , -NHSO 2 R 25 , and SO 2 NR 26 R 27 . .. R 10 to R 27 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
- R 12 of ⁇ COOR 12 is a hydrogen atom (that is, a carboxy group)
- the hydrogen atom may be dissociated (that is, a carboxylate group) or may be in a salt state.
- R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
- the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.
- the substituent is preferably -COOR 12 or -SO 2 OR 24 , and more preferably -SO 2 OR 24 .
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the aliphatic group and aromatic group represented by each of R 10 to R 27 include the same as the aliphatic group and aromatic group represented by R 1 and R 2 , respectively.
- the heterocyclic group may have a substituent.
- substituents include the substituents that the above-mentioned aliphatic group may have, and the preferred range is also the same.
- the heterocycle of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
- the heterocycle may be a monocyclic ring or a fused ring.
- the heterocycle includes a pyridine ring, a piperidine ring, a furan ring group, a flufuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, and an indolin. Examples thereof include a ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiazylazole ring.
- the substituent is preferably -COOR 12 or -SO 2 OR 24 , and more preferably -SO 2 OR 24 .
- Cy is an anion moiety. Cy has one or more anionic groups so that the entire anion portion has a negative charge. When the anionic group is a monovalent anionic group, Cy has two or more anionic groups. The position of the anionic group is not particularly limited. The anionic group may be contained in L 1 , R 1 , and R 2 , or may be contained in the substituents of T 1 and T 2 . The anionic group is preferably a sulfo group or a carboxy group, more preferably a sulfo group.
- Cy is preferably an anion portion represented by the following formula 3.
- Y 1 and Y 2 independently represent CR 3 R 4- , -O-, -S-, -Se-, or -NR 5- .
- R 3 , R 4 , and R 5 each independently represent a hydrogen atom, an aliphatic group, or an aromatic ring group. R 3 and R 4 may be combined with each other to form a ring.
- a 1 and A 2 each independently represent a group of non-metal atoms forming an aromatic ring or an aromatic heterocycle.
- L 1 , R 1 , and R 2 are synonymous with L 1 , R 1 , and R 2 in Equation 1.
- Y 1 and Y 2 independently represent CR 3 R 4- , -O-, -S-, -Se-, or -NR 5- .
- Y 1 and Y 2 are preferably CR 3 R 4- , -O-, and -S-, respectively, and more preferably CR 3 R 4- .
- Examples of the aliphatic group and aromatic group represented by each of R 3 , R 4 , and R 5 include the same as the aliphatic group and aromatic group represented by R 1 and R 2 , respectively. ..
- R 3 , R 4 and R 5 are independently alkyl groups.
- the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
- the alkyl group may be any of a linear alkyl group, a branched chain alkyl group, and a cyclic alkyl group.
- R 3 , R 4 and R 5 are each independently preferably a linear alkyl group or a branched chain alkyl group, more preferably a linear alkyl group, and a methyl group or ethyl. It is more preferably a group, and particularly preferably a methyl group.
- a 1 and A 2 each independently represent a group of non-metal atoms forming an aromatic ring or an aromatic heterocycle.
- the aromatic ring and the aromatic heterocycle may have a substituent.
- the substituents that the aromatic ring and the aromatic heterocycle formed by each of A 1 and A 2 may have are the nitrogen-containing heterocycle formed by T 1 and T 2 in the formula 1 and the nitrogen-containing heterocycle thereof. Examples include the same substituents that the fused ring may have.
- the substituent is preferably -COOR 12 or -SO 2 OR 24 , and more preferably -SO 2 OR 24 .
- Examples of the aromatic ring formed by each of A 1 and A 2 include a benzene ring and a naphthalene ring.
- the aromatic heterocycle formed by each of A 1 and A 2 is preferably an aromatic heterocycle in which at least one of the atoms forming the ring is a nitrogen atom, an oxygen atom or a sulfur atom.
- the aromatic heterocycle formed by each of A 1 and A 2 may be fused with another ring (aliphatic ring, aromatic ring, or heterocycle).
- the aromatic heterocycle formed by each of A 1 and A 2 is preferably a 5-membered ring to a 10-membered ring.
- Examples of the aromatic heterocycle formed by each of A 1 and A 2 include a pyridine ring, a dibenzofuran ring, and a carbazole ring.
- a 1 and A 2 are preferably non-metal atom groups that independently form an aromatic ring, and are non-metals that form a benzene ring or a naphthalene ring. It is more preferably a group of atoms.
- the anion portion represented by the formula 3 is preferably an anion portion represented by the following formula 3A or formula 3B.
- R 1 , R 2 , Y 1 , and Y 2 are synonymous with R 1 , R 2 , Y 1 , and Y 2 in formula 3.
- V 1A and V 2A each independently represent a hydrogen atom or a substituent.
- the substituents represented by each of V 1A and V 2A include a halogen atom, a cyano group, a nitro group, an aliphatic group, an aromatic group, a heterocyclic group, -OR 10 , -COR 11 , -COOR 12 , and-.
- R 10 to R 27 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
- R 12 of ⁇ COOR 12 is a hydrogen atom (that is, a carboxy group)
- the hydrogen atom may be dissociated (that is, a carboxylate group) or may be in a salt state.
- R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
- the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.
- the substituent represented by each of V 1A and V 2A is preferably -COOR 12 or -SO 2 OR 24 , and more preferably -SO 2 OR 24 .
- V 1A and V 2A may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- the bond position of V 1A to the benzene ring is not particularly limited, but the position farthest from the nitrogen atom that binds to R 1 from the viewpoint that the cyanine dye is more likely to form an aggregate. Is preferable.
- the bond position of V 2A to the benzene ring is not particularly limited, but from the viewpoint that the cyanine dye is more likely to form an aggregate, the nitrogen atom that binds to R 2 is the most suitable. It is preferably in a distant position.
- R 1 , R 2 , Y 1 , and Y 2 are synonymous with R 1 , R 2 , Y 1 , and Y 2 in Equation 3.
- V 1B and V 2B each independently represent a hydrogen atom or a substituent.
- Examples of the substituent represented by each of V 1B and V 2B include the same substituents represented by each of V 1A and V 2A .
- the substituent represented by each of V 1B and V 2B is preferably -COOR 12 or -SO 2 OR 24 , and more preferably -SO 2 OR 24 .
- V 1B and V 2B may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- the binding position of V 1B to the naphthalene ring is not particularly limited, but the position farthest from the nitrogen atom that binds to R 1 from the viewpoint that the cyanine dye is more likely to form an aggregate. Is preferable.
- the bond position of V 2B to the naphthalene ring is not particularly limited, but from the viewpoint that the cyanine dye is more likely to form an aggregate, the nitrogen atom that binds to R 2 is the most important. It is preferably in a distant position.
- Cy is more preferably an anion moiety represented by the following formula 4.
- Y 1 and Y 2 independently represent CR 3 R 4- , -O-, -S-, -Se-, or -NR 5- .
- R 3 , R 4 , and R 5 each independently represent a hydrogen atom, an aliphatic group, or an aromatic ring group.
- R 3 and R 4 may be combined with each other to form a ring.
- a 1 and A 2 each independently represent a group of non-metal atoms forming an aromatic ring or an aromatic heterocycle.
- L 2 independently represents a methine chain consisting of one, two, or three methine groups, and L 2 has no substituent.
- R 6 and R 7 each independently represent a hydrogen atom or an aliphatic group.
- R 6 and R 7 may be connected to each other to form a ring.
- R 8 is represented by the following formula A.
- RL2 represents an alkylene group, an arylene group, or a divalent heterocyclic group
- TA represents a hydrogen atom, a halogen atom, or an alkyl group.
- R 1 , R 2 , R 3 , R 4 , R 5 , Y 1 , and Y 2 are R 1 , R 2 , R 3 , R 4 , R 5 , Y 1 , and Y in Equation 3. It is synonymous with 2 .
- L 2 independently represents a methine chain consisting of one, two, or three methine groups. It is preferable that L 2 is a methine chain consisting of one or two methine groups independently.
- the two L 2s may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- R 6 and R 7 each independently represent a hydrogen atom or an aliphatic group. It is preferable that R 6 and R 7 are hydrogen atoms or aliphatic groups and are linked to each other to form a ring.
- the ring formed by connecting R 6 and R 7 to each other is preferably a 5-membered aliphatic ring or a 6-membered aliphatic ring.
- examples of -R 6 R 7- in which R 6 and R 7 are connected to each other include -CH 2 CH 2- and -CH 2 C (Z) 2 -CH 2- .
- Z is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group. The two Zs may be combined to form a ring structure.
- R 8 represents a substituent represented by the formula A.
- the preferred embodiment of the substituent represented by the formula A is as described above.
- the basic nucleus 1 and the basic nucleus 2 that bind to the methine chain represented by L1 in the formula 1 are shown.
- the basic nucleus 1 is described as a cationic structure in which the nitrogen atom is cationic
- the basic nucleus 2 is described as a neutral structure in which the nitrogen atom is not charged. Since the nitrogen atom contained in the basic nucleus 1 and the nitrogen atom contained in the basic nucleus 2 are conjugated carbon chains, it is considered that the electrons are actually delocalized. Therefore, in the formula 1, it is also possible to describe the basic nucleus 1 as a neutral structure and the basic nucleus 2 as a cationic structure.
- the basic nucleus 1 and the basic nucleus 2 have the same structure from the viewpoint of ease of manufacture.
- the fact that the basic nucleus 1 and the basic nucleus 2 have the same structure means that the constituent atoms are the same and the skeleton is the same.
- the basic nucleus 1 and the basic nucleus 2 have the same structure, one is described as a cationic structure and the other is described as a neutral structure in the structural formula.
- the basic nuclei 1 and the basic nuclei 2 are preferably TA1 to TA13, TA16, TA28, TA29, or TA31 to TA36 from the viewpoint that the cyanine dye is more likely to form an aggregate.
- X 1 represents an organic cation represented by the following formula 2-1 or formula 2-2 or formula 2-3, or an organic cation having a structure represented by formula 2-4.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 11 independently represents a divalent linking group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- R 1a , R 1b , R 1c , and R 1d may be coupled to each other to form a ring.
- m1 is an integer of 1 or more.
- a 11 and A 12 independently represent a nitrogen atom or a phosphorus atom. It is preferable that A 11 and A 12 are nitrogen atoms.
- a 11 and A 12 may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- B 11 independently represents a divalent linking group.
- the divalent linking group represented by B 11 is preferably a group having 2 or more carbon atoms, and more preferably a group having 2 to 8 carbon atoms.
- the number of carbon atoms is 2 or more, the molecular structure becomes more flexible, and it is presumed that the effect of binding the cyanine dyes to each other at a position where an aggregate can be appropriately formed is high. As a result, aggregates are easily formed between the cyanine pigments, and the infrared absorption ability tends to be maintained for a long period of time.
- a linking group can be mentioned.
- R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the divalent linking group represented by B 11 is preferably an alkylene group.
- the alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms.
- the alkylene group is preferably a linear alkylene group.
- R 1a , R 1b , R 1c , R 1d , E 11 and E 12 each independently represent an aliphatic or aromatic group.
- Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group and an aralkyl group.
- Examples of the aromatic group include an aryl group.
- R 1a , R 1b , R 1c , and R 1d are preferably alkyl groups.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- E 11 and E 12 are independently alkyl groups or aryl groups, respectively.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- the aryl group is preferably a phenyl group.
- M1 is an integer of 1 or more. m1 is preferably 1 to 3, preferably 1 or 2.
- a 11 and A 12 are nitrogen atoms
- B 11 is an alkylene group
- R 1a , R 1b , R 1c and R 1d are alkyl groups.
- Organic cations in which E 11 and E 12 are alkyl groups are more preferred.
- organic cation represented by the formula 2-1 is not limited to the following specific examples.
- Me represents a methyl group
- Et represents an ethyl group
- Ph represents a phenyl group.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 21 and B 22 each independently represent a divalent linking group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- m2 is an integer of 0 or more.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- a 21 , A 22 and A 23 independently represent a nitrogen atom or a phosphorus atom. It is preferable that A 21 , A 22 and A 23 are nitrogen atoms.
- a 21 , A 22 and A 23 may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- B 21 and B 22 each independently represent a divalent linking group.
- the divalent linking group represented by B 21 and B 22 is preferably a group having 2 or more carbon atoms, and more preferably a group having 2 to 8 carbon atoms.
- the number of carbon atoms is 2 or more, the molecular structure becomes more flexible, and it is presumed that the effect of binding the cyanine dyes to each other at a position where an aggregate can be appropriately formed is high. As a result, aggregates are easily formed between the cyanine pigments, and the infrared absorption ability tends to be maintained for a long period of time.
- R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the divalent linking groups represented by B 21 and B 22 are independently alkylene groups.
- the alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms.
- the alkylene group is preferably a linear alkylene group.
- R 2a and R 2b independently represent an aliphatic group or an aromatic group, respectively.
- Examples of the aliphatic group represented by R 2a and R 2b include an alkyl group, an alkenyl group, an alkynyl group and an aralkyl group.
- Examples of the aromatic group include an aryl group.
- R 2a and R 2b are independently alkyl groups.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- M2 is an integer of 0 or more. It is preferable that m2 is an integer of 0 to 2.
- G 21 represents a group of non-metal atoms forming an aromatic ring containing A 21 in the ring.
- G 22 represents a group of non-metal atoms forming an aromatic ring containing A 23 in the ring.
- the aromatic ring containing A 21 in the ring is preferably a pyridine ring, an imidazole ring, an oxazole ring, or a thiazole ring. Further, the aromatic ring containing A 21 in the ring may be condensed with another ring (aliphatic ring, aromatic ring, or heterocycle).
- the aromatic ring containing A23 in the ring is preferably a pyridine ring, an imidazole ring, an oxazole ring, or a thiazole ring. Further, the aromatic ring containing A 23 in the ring may be condensed with another ring (aliphatic ring, aromatic ring, or heterocycle).
- a 21 , A 22 and A 23 are nitrogen atoms
- B 21 and B 22 are independently alkylene groups
- m2 is 0 or 1.
- G 21 and G 22 are more preferably pyridine rings, imidazole rings, oxazole rings, or thiazole rings.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom, respectively.
- B 31 represents a divalent linking group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- a 31 and A 32 independently represent a nitrogen atom or a phosphorus atom. It is preferable that A 31 and A 32 are nitrogen atoms.
- a 31 and A 32 may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture.
- B 31 represents a divalent linking group.
- the divalent linking group represented by B 31 preferably has 2 or more carbon atoms, and more preferably 2 to 8 carbon atoms. When the number of carbon atoms is 2 or more, the aggregate formed by the cyanine dyes is held at an appropriate position, and the infrared absorption ability tends to be maintained for a long period of time.
- a linking group can be mentioned.
- R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the divalent linking group represented by B 31 is preferably an alkylene group.
- the alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms.
- the alkylene group is preferably a linear alkylene group.
- R 3a and R 3b independently represent an aliphatic group or an aromatic group, respectively.
- Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group and an aralkyl group.
- Examples of the aromatic group include an aryl group.
- R 3a and R 3b are independently alkyl groups.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- G 31 represents a group of non-metal atoms forming an aromatic ring containing A 31 in the ring.
- G 32 represents a group of non-metal atoms forming an aromatic ring containing A 32 in the ring.
- the aromatic ring containing A 31 in the ring is preferably a pyridine ring. Further, the aromatic ring containing A 31 in the ring may be condensed with another ring (aliphatic ring, aromatic ring, or heterocycle). Similarly, the aromatic ring containing A 32 in the ring is preferably a pyridine ring. Further, the aromatic ring containing A 32 in the ring may be condensed with another ring (aliphatic ring, aromatic ring, or heterocycle).
- a 31 and A 32 are nitrogen atoms
- B 31 is an alkylene group
- R 3a and R 3b are independently alkyl groups
- G 31 and G are independently alkyl groups
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- B 41 independently represents a single bond or a divalent linking group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- One of R 4a , R 4b and R 4c may be combined with E 41 or E 42 to form a ring.
- m4 is an integer of 2 or more.
- the organic cation having the structure represented by the formula 2-4 has a flexible molecular structure and the cation sites are regularly arranged, the cyanine dyes are regularly arranged at appropriate positions and aggregated. Is thought to form. As a result, the infrared absorption capacity tends to be maintained for a long period of time.
- a 41 independently represents a nitrogen atom or a phosphorus atom.
- a 41 is preferably a nitrogen atom.
- B 41 independently represents a single bond or a divalent linking group.
- a linking group can be mentioned.
- R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the divalent linking group represented by B 41 is preferably an alkylene group.
- the alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the alkylene group is preferably a linear alkylene group.
- R 4a , R 4b and R 4c each independently represent an aliphatic group or an aromatic group.
- Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group and an aralkyl group.
- Examples of the aromatic group include an aryl group.
- R 4a , R 4b and R 4c are independently alkyl groups.
- the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- E 41 and E 42 each independently represent a single bond or an aliphatic group.
- E 11 and E 12 are independently single-bonded or alkyl groups, respectively.
- the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the aryl group is preferably a phenyl group.
- M4 is an integer of 2 or more. m4 is preferably 50 to 3000, more preferably 100 to 2000.
- a 41 is a nitrogen atom, and one of R 4a , R 4b and R 4c is bonded to E 41 or E 42 to form a ring.
- Organic cations are more preferred.
- X 1 is preferably an organic cation represented by the formula 2-1 or an organic cation having a structure represented by the formula 2-4. It is considered that the aggregate formed by the cyanine dye is held at an appropriate position for a long period of time by the organic cation represented by the formula 2-1 or the organic cation having the structure represented by the formula 2-4. Be done.
- X 1 is an organic cation represented by the formula 2-1 or an organic cation having a structure represented by the formula 2-4, the invisibility is excellent and the infrared absorbing ability is maintained for a longer period of time. .. [N] n is non-zero and represents the number required to neutralize the charge. For example, when the anion portion is a monovalent anion and the organic cation is a divalent cation, n is 0.5.
- the dye compound of the present disclosure has excellent invisibility and the infrared absorption capacity is maintained longer than before, so that it is expected to be applied to various uses.
- the dye compound of the present disclosure can be made into a dye composition by mixing with other components.
- compound 41, compound 42, and 2-propanol are mixed, and then acetic anhydride and triethylamine are added. Further, an aqueous solution of potassium acetate and methanol are added to obtain compound 43.
- Compound 43 is a potassium salt.
- the compound 44, which is the target compound is obtained by performing a cation exchange in which X 1 which is a counter cation of the target dye compound and a potassium cation are exchanged.
- the dye composition of the present disclosure includes a dye compound represented by the above formula 1 and a medium.
- the medium is not particularly limited as long as it can disperse the dye compound represented by the formula 1, and examples thereof include water, an organic solvent, a resin, and a mixture of two or more thereof.
- the medium is preferably a liquid, more preferably a liquid containing water.
- the dye composition of the present disclosure can be used as an ink.
- the dye composition of the present disclosure can be used as a water-based ink, preferably a water-based ink for inkjet recording.
- the dye composition of the present disclosure can be a resin composition containing a dye compound and a resin.
- the resin composition can be processed into a resin film or a resin molded product.
- the type of resin is not particularly limited, but a thermoplastic resin is preferable from the viewpoint of ease of molding.
- the thermoplastic resin include polyester, polystyrene, polyamide, polyurethane, polycarbonate, cellulose acetate, polyacrylic, polyacetal, polypropylene, polyvinyl, polysulfone, polyimide, and polyolefin.
- the resin is preferably at least one resin selected from the group consisting of polyester, polyamide, and polyurethane.
- the resin contains a polymer and an oligomer, and can be appropriately selected from compounds having a weight average molecular weight of 5,000 to 1,000,000.
- the resin composition may contain only one type of resin, or may contain two or more types of resin.
- resins having a similar glass transition temperature or SP value (solubility parameter) it is preferable to use resins having a similar glass transition temperature or SP value (solubility parameter) in combination from the viewpoint of compatibility and moldability.
- the resin composition may contain various additives in addition to the dye compound and the resin represented by the formula 1 as long as the effects of the present disclosure are not impaired.
- the dye composition according to the present disclosure may contain at least one colorant.
- a desired color can be imparted to the resin composition and the resin molded product produced from the resin composition.
- the colorant may be either a dye or a pigment.
- the dyes and pigments conventionally known dyes and pigments can be used.
- the content of the colorant is preferably 0.0001% by mass to 20% by mass, more preferably 0.001% by mass to 10% by mass, based on the total amount of the resin composition.
- the resin composition may contain impact resistance, antibacterial property, gas barrier property, conductivity, magnetism, piezoelectricity, vibration damping property, sound insulation property, slidability, electromagnetic wave absorption, flame retardancy, dehydration property, if necessary.
- An inorganic filler may be further contained for the purpose of improving physical properties such as deodorizing property, anti-blocking property, oil absorption property, water absorption property and moldability.
- the inorganic filler examples include carbon fiber, glass fiber, glass flake, zeolite, mica, graphite, metal powder, ferrite, alumina, barium titanate, potassium titanate, barium sulfate, Teflon (registered trademark) powder, talc, and the like.
- examples thereof include charcoal powder, carbon nanotubes (CNT), carbon microcoils (CMC), antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, calcium oxide, silica, and calcium carbonate.
- the inorganic filler is preferably contained in a content that does not reduce the transparency of the resin molded product described later.
- the resin composition may include, for example, a leveling agent, a pigment dispersant, an ultraviolet absorber, an antioxidant, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, a metal deactivator, a peroxide decomposition agent, and processing.
- a leveling agent e.g., a leveling agent, a pigment dispersant, an ultraviolet absorber, an antioxidant, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, a metal deactivator, a peroxide decomposition agent, and processing.
- Stabilizers, nucleating agents, crystallization accelerators, crystallization retarders, antigelling agents, fillers, reinforcing agents, plasticizers, lubricants, flame retardants, rust inhibitors, fluorescent whitening agents, fluidity modifiers e.g., a known additive such as an antistatic agent may be contained.
- the method for preparing the resin composition is not particularly limited.
- the dye compound represented by the formula 1 in order to contain the dye compound represented by the formula 1, the dye compound represented by the formula 1 is directly kneaded with the masterbatch and the resin pellet as the resin raw material. It may be mixed, kneaded and melt-molded. Further, the dye compound represented by the formula 1 may be attached to the resin by a method such as coating or dipping.
- the dye compound represented by the formula 1 when directly kneaded into the resin, kneaded and melt-molded, the dye compound represented by the formula 1 is hard to be separated from the resin surface, and the infrared absorption capacity is maintained for a longer time.
- the dye compound represented by the formula 1 and the resin when producing a resin molded product, it is preferable to mix the dye compound represented by the formula 1 and the resin and uniformly disperse them before forming the molded product.
- a method of mixing the dye compound represented by the formula 1 and the resin a method of heating and kneading the resin and the dye compound represented by the formula 1 and a method of heating and kneading the resin and the dye compound represented by the formula 1 Examples thereof include a method of stirring and mixing with a solvent.
- the shape and use of the resin molded product are not particularly limited.
- the resin molded body include resin films; synthetic fibers; bottles, cosmetic containers, resin containers such as food containers; resin plates; lenses; toners; various home appliances such as general decorative items, and electronic devices.
- Exterior parts such as; interior materials, housing building material parts such as exterior materials; and interior / exterior parts such as aircraft and vehicles.
- the method for producing the resin molded product is not particularly limited, and a known resin molding method can be appropriately applied.
- the dye composition of the present disclosure preferably contains a liquid as a medium.
- the liquid as a medium is referred to as a liquid medium.
- the type of the liquid medium is not particularly limited and can be appropriately selected according to the purpose of use of the dye composition.
- the dye composition of the present disclosure when applied to an ink (for example, an ink for inkjet recording), the liquid medium preferably contains water, and more preferably contains water and an organic solvent.
- the liquid medium preferably contains water and an organic solvent having a boiling point of 100 ° C. or higher from the viewpoint of ejection stability.
- the boiling point means the boiling point under 1 atm (101325 Pa).
- the boiling point is measured by a boiling point meter, for example, using a boiling point measuring device (product name "DosaTherm300") manufactured by Titan Technologies.
- the water is preferably distilled water, ion-exchanged water, ion-exchanged distilled water or pure water from the viewpoint of having few impurities.
- Examples of the organic solvent having a boiling point of 100 ° C. or higher include, for example. Ethylene glycol (boiling point: 198 ° C), propylene glycol (boiling point: 188 ° C), 1,2-butanediol (boiling point: 194 ° C), 2,3-butanediol (boiling point: 183 ° C), 2-methyl-1, 3-Propylene diol (boiling point: 124 ° C), 2-methyl-2,4-pentanediol (boiling point: 198 ° C), 1,2,6-hexanetriol (boiling point: 178 ° C), 1,2,3-butane Triol (boiling point: 175 ° C.), 1,2,4-butanetriol (boiling point: 170 ° C.), diethylene glycol (boiling point: 244 ° C.), dipropylene glycol (boiling point
- Polyhydric alcohol alkyl ethers such as (° C), 3-methoxybutanol (boiling point: 161 ° C); Polyhydric alcohol aryl ethers such as ethylene glycol phenyl ether (boiling point: 237 ° C), propylene glycol phenyl ether (boiling point: 243 ° C), ethylene glycol monobenzyl ether (boiling point: 256 ° C); ⁇ -caprolactum (boiling point: 137 ° C), N-methylformamide (boiling point: 199 ° C), N, N-dimethylformamide (boiling point: 153 ° C), N-methyl-2-pyrrolidone (boiling point: 204 ° C), 2- Nitrogen-containing compounds such as pyrrolidone (boiling point: 245 ° C.), 1,3-dimethylimidazolidinone (boiling point: 220 ° C
- the content of water in the dye composition is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass, based on the total mass of the dye composition. % Or more.
- the content of the organic solvent having a boiling point of 100 ° C. or higher in the dye composition is preferably 1% by mass to 50% by mass, preferably 2% by mass or more, based on the total mass of the dye composition. It is more preferably 40% by mass.
- the dye composition of the present disclosure may contain a surfactant.
- the surfactant may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a betaine-based surfactant.
- the nonionic surfactant is preferable, and the acetylene glycol-based surfactant is more preferable, from the viewpoint of suppressing the droplet interference of the ink.
- acetylene glycol-based surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and 2,4,7,9-tetramethyl-5-decyne-4, Included are alkylene oxide adducts of 7-diol.
- acetylene glycol-based surfactants examples include the Surfinol series such as Surfinol 104PG manufactured by Nisshin Chemical Industry Co., Ltd. and the E series such as Orfin E1010 manufactured by Nissin Chemical Industry Co., Ltd.
- a fluorine-based surfactant is preferable.
- the fluorine-based surfactant include Capstone (registered trademark) FS-63, Capstone FS-61 (manufactured by DuPont), Futagent (registered trademark, the same applies hereinafter) 100, Futergent 110, and Futergent 150 (Neos). ), And CHEMGUARD® (registered trademark) S-760P (manufactured by Chemguard Inc.).
- the content of the surfactant is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, and further preferably 0.2% by mass to 3% by mass with respect to the total mass of the dye composition. preferable.
- the dye composition of the present disclosure may contain a polymerizable compound as a liquid medium.
- the dye composition may contain a polymerizable compound, the dye composition can be cured by irradiating it with active energy rays.
- the dye composition of the present disclosure may further contain a known additive used in the ink.
- Additives include, for example, surfactants, resins, anti-drying agents (in other words, wetting agents), anti-fading agents, emulsion stabilizers, penetration promoters, preservatives, fungicides, pH regulators, surface tension regulators.
- surfactants for example, surfactants, resins, anti-drying agents (in other words, wetting agents), anti-fading agents, emulsion stabilizers, penetration promoters, preservatives, fungicides, pH regulators, surface tension regulators.
- examples include agents, defoaming agents, viscosity regulators, dispersants, rust preventives, and chelating agents.
- the dye composition When the dye composition is applied to an ink, it may contain a dye other than the dye compound represented by the formula 1.
- the other dyes are not particularly limited, and dyes known in the field of ink can be used.
- the content of other dyes is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total mass of the ink.
- the dye composition of the present disclosure may be a dye composition containing a dye having absorption in the visible light region and capable of forming a visible image having absorption in the near infrared region, depending on the purpose.
- the dye composition of the present disclosure can be applied to ink.
- the ink is preferably for inkjet recording.
- the pH of the ink is preferably 7 to 10 and more preferably 7.5 to 9.5 from the viewpoint of ejection stability.
- the pH of the ink is measured at 25 ° C. using a pH meter, and is measured, for example, using a pH meter (model number "HM-31") manufactured by Toa DKK Corporation.
- the viscosity of the ink is preferably 0.5 mPa ⁇ s to 30 mPa ⁇ s, more preferably 2 mPa ⁇ s to 20 mPa ⁇ s, preferably 2 mPa ⁇ s to 15 mPa ⁇ s, and 3 mPa ⁇ s. It is more preferably about 10 mPa ⁇ s.
- the viscosity of the ink is measured at 25 ° C. using a viscometer, and is measured, for example, using a TV-22 type viscometer manufactured by Toki Sangyo Co., Ltd.
- the surface tension of the ink is preferably 60 mN / m or less, more preferably 20 mN / m to 50 mN / m, and even more preferably 25 mN / m to 45 mN / m.
- the surface tension of the ink is measured at 25 ° C. using a surface tensiometer, and is measured by a plate method using, for example, an automatic surface tension meter (product name "CBVP-Z”) manufactured by Kyowa Surface Science Co., Ltd.
- examples of the use of the dye composition of the present disclosure include an image recording material for recording an image, particularly an invisible image.
- the image recording material include an inkjet recording material, a heat-sensitive recording material, a pressure-sensitive recording material, a recording material using an electrophotographic method, a transfer-type silver halide photosensitive material, a printing ink, and a recording pen.
- the dye composition of the present disclosure is preferably used as an inkjet recording material, a heat-sensitive recording material, or a recording material using an electrophotographic method.
- the dye composition of the present disclosure includes a solid-state image pickup device such as a charge-coupled device (CCD) and a complementary metal oxide semiconductor (CMOS); an infrared sensor; various devices such as an image display device; a plasma display panel (PDP) and the like. It can also be applied to an infrared cut filter used in the display of the above, or a dyeing solution for dyeing various fibers. Further, the dye composition of the present disclosure can also be applied to a photothermal conversion material such as a write-once optical disc or a flash melt fixing material. Further, since the dye composition of the present disclosure has absorption in the near infrared region excellent in human body permeability, it can be applied to a diagnostic marker and a photodynamic therapy drug in addition to the above-mentioned uses.
- the dye composition of the present disclosure can be applied to fibers (heat retention and heat storage); camouflage against reconnaissance by infrared rays (camouflage performance); prevention of eye strain; or marking agents for positioning such as photographs and films. Further, by using the dye composition of the present invention as a cured film, the application can be expanded.
- the dye composition of the present disclosure is a lens having a function of absorbing or cutting near infrared rays (for example, a lens for a camera such as a digital camera, a mobile phone, an in-vehicle camera; an optical lens such as an f- ⁇ lens or a pickup lens).
- Optical filters for semiconductor light-receiving elements for example, a lens for a camera such as a digital camera, a mobile phone, an in-vehicle camera; an optical lens such as an f- ⁇ lens or a pickup lens.
- Optical filters for semiconductor light-receiving elements for the selective use of sunlight; Recording media that utilize the heat absorbed by near-infrared rays; Near-infrared filters for electronic devices or photographs; Protective glasses; Sunglasses It can be applied to a heat ray blocking filter; optical character reading and recording; an application for preventing copying of confidential documents; an electrophotographic photosensitive member; or laser welding.
- the dye composition of the present disclosure
- the inkjet recording method of the present disclosure includes a step of applying the above ink onto a substrate.
- the base material is not particularly limited as long as it can form an image, and examples thereof include paper, cloth, wood, metal plates, and resin films.
- the base material may be surface-treated in advance.
- Examples of paper include pure white roll paper, kraft paper, paperboard, high-quality paper, OCR paper, art paper, coated paper, mirror coated paper, condenser paper, and paraffin paper.
- polyester film polypropylene (PP) film, cellophane, acetate film, polycarbonate (PC) film, acrylic resin film, polyethylene terephthalate (PET) film, biaxially stretched polystyrene (OPS) film, biaxially stretched polypropylene ( Examples include OPP) film, biaxially stretched nylon (ONy) film, polyvinyl chloride (PVC) film, polyethylene (PE) film, and triacetate (TAC) film.
- the inkjet recording method is not particularly limited as long as it can record an image, and is a known method, for example, a charge control method for ejecting ink by using electrostatic attraction, and a drop using the vibration pressure of a piezo element.
- the on-demand method pressure pulse method
- the acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink to eject the ink using the radiation pressure
- the acoustic inkjet method that heats the ink to form bubbles and applies the generated pressure. It may be any of the thermal inkjet (bubble jet (registered trademark)) methods to be used.
- the ink subjected to the action of heat energy causes a rapid volume change, and the ink is ejected from the nozzle by the acting force due to this state change.
- the inkjet recording method for ejecting can be effectively used.
- the inkjet head used in the inkjet recording method a short serial head is used, and a shuttle method in which recording is performed while scanning the head in the width direction of the base material and a recording element are arranged corresponding to the entire area of one side of the base material.
- a line method using a line head that has been used can be mentioned.
- a pattern can be formed on the entire surface of the base material by scanning the base material in a direction intersecting the arrangement direction of the recording elements, and a transport system such as a carriage that scans a short head becomes unnecessary.
- the movement of the carriage and the complicated scanning control with the base material are not required, and only the base material moves, so that the recording speed can be increased compared to the shuttle method.
- the amount of ink ejected from the inkjet head is preferably 1 pL (picolitre) to 20 pL, and more preferably 1.5 pL to 10 pL from the viewpoint of obtaining a high-definition image.
- the inkjet recording method of the present disclosure may include a step other than the step of recording an image on a substrate by an inkjet recording method. Other steps include, for example, a step of recording an image and then drying the image. Further, the image recording method of the present disclosure may include a step of irradiating an active energy ray when the ink contains a polymerizable compound.
- the image recording material of the present disclosure includes a base material and an infrared absorption image which is a solidified product of the ink arranged on the base material.
- the solidified product contains a dried product of the ink and a cured product obtained by polymerizing the polymerizable compound in the ink.
- the image recording material of the present disclosure includes a base material and an infrared absorption image arranged on the base material, and the infrared absorption image contains a dye compound represented by the above formula 1 and is an infrared absorption image.
- the maximum absorption wavelength is in the range of 700 nm to 1,300 nm.
- the base material is as described above, and the description is omitted.
- the pattern of the infrared absorption image arranged on the substrate is not particularly limited, and is appropriately selected depending on the intended use.
- the maximum absorption wavelength of the infrared absorption image is determined by measuring the optical density (OD) of the infrared absorption image using a spectroscopic clock UV-3100PC equipped with a 150 mm large-sized spheroidal attachment device LISR-3100 manufactured by Shimadzu Corporation. You can check.
- the maximum absorption wavelength of the infrared absorption image is preferably in the range of 700 nm to 1,300 nm from the viewpoint of invisibility and readability of the infrared absorption image.
- the image record of this disclosure can be applied to a security system for the purpose of preventing forgery. Since the image recording material of the present disclosure is excellent in invisibility and the infrared absorption ability is maintained longer than before, the security property can be maintained for a long time.
- Compounds 1 to 60 are all dye compounds represented by the formula 1, and the basic nuclei 1 and the basic nuclei 2 have the same structure.
- Tables 1 to 3 show L 1 , basic nuclei 1 and basic nuclei 2 (referred to as "two basic nuclei in Cy" in the table), and X 1 .
- Comparative Compound 1 Comparative Compound 1 ... Compound No. 1 described in JP-A-2017-226820. 2 Comparative compound 2 ... The compound (I-13) described in JP-A-2002-90521. Comparative Compound 3: A combination of Compound A-1 and Compound B-19 described in JP-A-2000-292758.
- Comparative Compound 1 The structures of Comparative Compound 1 to Comparative Compound 3 are as follows.
- an ink was prepared using a dye compound (any of Compound 1 to Compound 60 and Comparative Compound 1 to Comparative Compound 3). Each component was mixed so as to have the following composition. Further, 100 parts by mass of zirconia beads having a diameter of 0.1 mm were added and subjected to a dispersion treatment at 400 rpm (rotation / min) for 5 hours using a planetary ball mill to obtain ink.
- Dye compound 0.5 parts by mass Ultrapure water (specific resistance value: 18 M ⁇ ⁇ cm or more): 78.8 parts by mass
- Organic solvent Propylene glycol: 19.7 parts by mass
- Acetylene glycol-based surfactant Orphine E1010 (Nissin Kagaku) (Manufactured by the company) ... 1 part by mass
- Dye residual rate (%) (OD after light irradiation) ⁇ (OD before light irradiation) ⁇ 100 All optical densities were measured using a spectroscopic clock UV-3100PC equipped with a 150 mm large-sized spheroidal attachment device LISR-3100 manufactured by Shimadzu Corporation.
- the evaluation criteria are as follows. A, B and C are practically acceptable levels.
- C The dye residual rate is less than 75% in at least one of the three types of image recordings, and the dye residual rate is 60% or more in all three types of image recordings.
- E The dye residual rate is less than 60% in all three types of image recordings.
- Dye residual rate (%) (OD after storage) ⁇ (OD before storage) x 100 All optical densities were measured using a spectroscopic clock UV-3100PC equipped with a 150 mm large-sized spheroidal attachment device LISR-3100 manufactured by Shimadzu Corporation.
- the evaluation criteria are as follows. A, B and C are practically acceptable levels.
- C The dye residual rate is less than 75% in at least one of the three types of image recordings, and the dye residual rate is 60% or more in all three types of image recordings.
- D The dye residual rate is less than 60% in one or two of the three types of image recordings.
- E The dye residual rate is less than 60% in all three types of image recordings.
- Example 100 0.02 g of compound 9 and 10 g of polyethylene terephthalate resin (Tg: 60 ° C.) were put into the hopper of the twin-screw kneader, and kneaded for 5 minutes under the conditions of a temperature of 120 ° C. and a screw rotation speed of 200 rpm (revolutions per minute). Was carried out to prepare a resin kneaded product.
- Tg polyethylene terephthalate resin
- the absorption spectrum of the obtained resin kneaded product was excellent in invisibility because the maximum absorption wavelength was 900 nm or more and the absorbance at 450 nm / the absorbance at the maximum absorption wavelength was 1/10 or less. Further, when the above-mentioned light resistance of the obtained resin kneaded product was evaluated, it was found that the dye residual ratio was 90% or more in all three types of image recordings, and the light resistance was excellent.
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Abstract
Description
また、本発明の他の実施形態によれば、不可視性に優れ、かつ、赤外線吸収能が従来よりも長く維持される画像記録物が提供される。
また、本発明の他の実施形態によれば、不可視性に優れ、かつ、赤外線吸収能が従来よりも長く維持される画像記録物を得ることが可能な新規な色素化合物が提供される。
<1>下記式1で表される色素化合物と、媒体と、を含む色素組成物。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。
式4中、Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。R3、R4、及びR5は、それぞれ独立に、水素原子、脂肪族基、又は芳香環基を表す。R3及びR4は、互いに結合して環を形成してもよい。A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。また、L2はそれぞれ独立に、1個、2個、又は3個のメチン基からなるメチン鎖を表し、L2は置換基を有さない。R6及びR7はそれぞれ独立に、水素原子又は脂肪族基を表す。R6及びR7は、互いに連結して環を形成してもよい。R8は下記式Aで表される。
-SA-TA 式A
式A中、SAは、単結合、アルキレン基、アルケニレン基、アルキニレン基、-O-、-S-、-NRL1-、-C(=O)-、-C(=O)O-、-C(=O)NRL1-、-S(=O)2-、-ORL2-、又は、これらの少なくとも2つを組み合わせてなる基を表し、RL1はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、又は一価のヘテロ環基を表し、RL2は、アルキレン基、アリーレン基、又は二価のヘテロ環基を表し、TAは、水素原子、ハロゲン原子、アルキル基、アリール基、一価のヘテロ環基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、トリアルキルシリル基、又はトリアルコキシシリル基を表す。
<6>式4中、A1及びA2はそれぞれ独立に、ベンゼン環又はナフタレン環を形成する非金属原子群を表す、<5>に記載の色素組成物。
<7>媒体は、液体である、<1>~<6>のいずれか1つに記載の色素組成物。
<8>媒体は、水を含む液体である、<1>~<7>のいずれか1つに記載の色素組成物。
<9>媒体は、水と、沸点が100℃以上の有機溶剤とを含む、<1>~<8>のいずれか1つに記載の色素組成物。
<10>インクである、<1>~<9>のいずれか1つに記載の色素組成物。
<11>インクジェット記録用である、<10>に記載の色素組成物。
<12>基材上に、<11>に記載の色素組成物を付与する工程を含むインクジェット記録方法。
<13>基材と、基材上に配置された、<10>又は<11>に記載の色素組成物の固化物である赤外線吸収画像と、を含む画像記録物。
<14>基材と、基材上に配置された赤外線吸収画像と、を含み、赤外線吸収画像は、下記式1で表される色素化合物を含み、赤外線吸収画像の極大吸収波長が700nm~1,300nmの範囲にある、画像記録物。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-1中、A11及びA12はそれぞれ独立に、窒素原子又はリン原子を表す。B11はそれぞれ独立に、2価の連結基を表す。R1a、R1b、R1c、R1d、E11、及びE12はそれぞれ独立に、脂肪族基又は芳香族基を表す。R1a、R1b、R1c、及びR1dは、互いに結合して環を形成してもよい。m1は1以上の整数である。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-1中、A11及びA12はそれぞれ独立に、窒素原子又はリン原子を表す。B11はそれぞれ独立に、2価の連結基を表す。R1a、R1b、R1c、R1d、E11、及びE12はそれぞれ独立に、脂肪族基又は芳香族基を表す。R1a、R1b、R1c、及びR1dは、互いに結合して環を形成してもよい。m1は1以上の整数である。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。
<16>式2-1、式2-2、及び式2-3中、B11、B21、B22、及びB31はそれぞれ独立に、炭素数2~8の2価の連結基である、<15>に記載の色素化合物。
<17>式2-1、式2-2、式2-3、及び式2-4中、A11、A12、A21、A22、A23、A31、A32、及びA41は、窒素原子である、<15>又は<16>に記載の色素化合物。
<18>式1中、X1は、式2-1で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す、<15>~<17>のいずれか1つに記載の色素化合物。
<19>式1中、Cyは下記式4で表される<15>~<18>のいずれか1つに記載の色素化合物。
式4中、Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。R3、R4、及びR5は、それぞれ独立に、水素原子、脂肪族基、又は芳香環基を表す。R3及びR4は、互いに結合して環を形成してもよい。A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。また、L2はそれぞれ独立に、1個、2個、又は3個のメチン基からなるメチン鎖を表し、L2は置換基を有さない。R6及びR7はそれぞれ独立に、水素原子又は脂肪族基を表す。R6及びR7は、互いに連結して環を形成してもよい。R8は下記式Aで表される。
-SA-TA 式A
式A中、SAは、単結合、アルキレン基、アルケニレン基、アルキニレン基、-O-、-S-、-NRL1-、-C(=O)-、-C(=O)O-、-C(=O)NRL1-、-S(=O)2-、-ORL2-、又は、これらの少なくとも2つを組み合わせてなる基を表し、RL1はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、又は一価のヘテロ環基を表し、RL2は、アルキレン基、アリーレン基、又は二価のヘテロ環基を表し、TAは、水素原子、ハロゲン原子、アルキル基、アリール基、一価のヘテロ環基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、トリアルキルシリル基、又はトリアルコキシシリル基を表す。
<20>式4中、A1及びA2はそれぞれ独立に、ベンゼン環又はナフタレン環を形成する非金属原子群を表す、<19>に記載の色素化合物。
また、本開示によれば、不可視性に優れ、かつ、赤外線吸収能が従来よりも長く維持される画像記録物が提供される。
また、本開示によれば、不可視性に優れ、かつ、赤外線吸収能が従来よりも長く維持される画像記録物を得ることが可能な新規な色素化合物が提供される。
本明細書に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
本明細書において、「工程」という語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば、本用語に含まれる。
本明細書において、一価のヘテロ環基とは、ヘテロ環式化合物から1つの水素原子を除いた基をいい、二価のヘテロ環基とは、ヘテロ環式化合物から2つの水素原子を除いた基をいう。
本開示の色素化合物は、下記式1で表される。
式(1)中、L1は奇数個のメチン基からなるメチン鎖を表す。L1は5個、7個、又は9個のメチン基からなるメチン鎖を表すことが好ましく、5個又は7個のメチン基からなるメチン鎖を表すことがより好ましい。
*-SA-TA 式A
アルキル基は、炭素数1~10のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましく、炭素数1又は2のアルキル基がさらに好ましい。
R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。脂肪族基及び芳香族基は、置換基を有していてもよい。置換基としては、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子、及びヨウ素原子)、シアノ基、ニトロ基、脂肪族基、芳香族基、ヘテロ環基、-OR10、-COR11、-COOR12、-OCOR13、-NR14R15、-NHCOR16、-CONR17R18、-NHCONR19R20、-NHCOOR21、-SR22、-SO2R23、-SO2OR24、-NHSO2R25、及びSO2NR26R27が挙げられる。R10~R27はそれぞれ独立に、水素原子、脂肪族基、芳香族基、又はヘテロ環基を表す。ヒドロキシ基、カルボキシ基、スルホ基、アルコキシ基、及びアミノ基が挙げられる。中でも、置換基は、脂肪族基、芳香族基、-OR10、-COOR12又は-SO2OR24であることが好ましく、芳香族基、-SO2OR24であることがより好ましい。なお、-COOR12のR12が水素原子の場合(すなわち、カルボキシ基)は、水素原子が解離してもよく(すなわち、カルボキシレート基)、塩の状態であってもよい。また、-SO2OR24のR24が水素原子の場合(すなわち、スルホ基)は、水素原子が解離してもよく(すなわち、スルホネート基)、塩の状態であってもよい。
T1及びT2はそれぞれ独立に、縮環していてもよい5員環又は6員環である含窒素複素環を形成する非金属原子群を表す。
Cyはアニオン部である。Cyはアニオン部全体として電荷が負になるように、アニオン性基を1つ以上有する。アニオン性基が1価のアニオン性基である場合には、Cyはアニオン性基を2つ以上有する。アニオン性基の位置は特に限定されない。アニオン性基は、L1、R1、及びR2に含まれていてもよく、T1及びT2の置換基に含まれていてもよい。アニオン性基は、スルホ基又はカルボキシ基であることが好ましく、スルホ基であることがより好ましい。
Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-であることが好ましく、CR3R4-であることがさらに好ましい。
A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。芳香族環及び芳香族複素環は、置換基を有してもよい。
式4中、Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。R3、R4、及びR5は、それぞれ独立に、水素原子、脂肪族基、又は芳香環基を表す。R3及びR4は、互いに結合して環を形成してもよい。A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。また、L2はそれぞれ独立に、1個、2個、又は3個のメチン基からなるメチン鎖を表し、L2は置換基を有さない。R6及びR7はそれぞれ独立に、水素原子又は脂肪族基を表す。R6及びR7は、互いに連結して環を形成してもよい。R8は下記式Aで表される。
-SA-TA 式A
式A中、SAは、単結合、アルキレン基、アルケニレン基、アルキニレン基、-O-、-S-、-NRL1-、-C(=O)-、-C(=O)O-、-C(=O)NRL1-、-S(=O)2-、-ORL2-、又は、これらの少なくとも2つを組み合わせてなる基を表し、RL1はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、又は一価のヘテロ環基を表し、RL2は、アルキレン基、アリーレン基、又は二価のヘテロ環基を表し、TAは、水素原子、ハロゲン原子、アルキル基、アリール基、一価のヘテロ環基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、トリアルキルシリル基、又はトリアルコキシシリル基を表す。
X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。
[n]
nは0ではない、電荷を中和するために必要な数を表す。例えば、アニオン部が1価のアニオンであり、有機カチオンが2価のカチオンである場合、nは0.5である。
本開示の色素組成物は、上記式1で表される色素化合物と、媒体と、を含む。
媒体として樹脂を用いた場合には、本開示の色素組成物を、色素化合物と樹脂とを含む樹脂組成物とすることができる。樹脂組成物は、樹脂フィルム、又は樹脂成形体へ加工することができる。
樹脂の種類は特に限定されないが、成形容易性の観点から、熱可塑性樹脂が好ましい。熱可塑性樹脂としては、ポリエステル、ポリスチレン、ポリアミド、ポリウレタン、ポリカーボネート、酢酸セルロース、ポリアクリル、ポリアセタール、ポリプロピレン、ポリビニル、ポリスルホン、ポリイミド、及びポリオレフィンが挙げられる。中でも、樹脂は、ポリエステル、ポリアミド、及びポリウレタンからなる群から選択される少なくとも1種の樹脂であることが好ましい。
本開示の色素組成物は、媒体として液体を含むことが好ましい。以下、媒体としての液体を液状媒体という。
エチレングリコール(沸点:198℃)、プロピレングリコール(沸点:188℃)、1,2-ブタンジオール(沸点:194℃)、2,3-ブタンジオール(沸点:183℃)、2-メチル-1,3-プロパンジオール(沸点:124℃)、2-メチル-2,4-ペンタンジオール(沸点:198℃)、1,2,6-ヘキサントリオール(沸点:178℃)、1,2,3-ブタントリオール(沸点:175℃)、1,2,4-ブタントリオール(沸点:170℃)、ジエチレングリコール(沸点:244℃)、ジプロピレングリコール(沸点:231℃)、1,3-プロパンジオール(沸点:214℃)、1,3-ブタンジオール(沸点:208℃)、1,4-ブタンジオール(沸点:230℃)、1,2-ペンタンジオール(沸点:206℃)、2,4-ペンタンジオール(沸点:201℃)、2-メチル-1,3-ブタンジオール(沸点:203℃)、3-メチル-1,3-ブタンジオール(沸点:203℃)、1,5-ペンタンジオール(沸点:242℃)、2,2-ジメチル-1,3-プロパンジオール(沸点:208℃)、1,2-ヘキサンジオール(沸点:223℃)、1,6-ヘキサンジオール(沸点:250℃)、2,5-ヘキサンジオール(沸点:217℃)、2-エチル-1,3-ヘキサンジオール(沸点:243℃)、トリエチレングリコール(沸点:287℃)、トリプロピレングリコール(沸点:273℃)、グリセリン(沸点:290℃)等の多価アルコール;
エチレングリコールモノメチルエーテル(沸点:124℃)、エチレングリコールモノエチルエーテル(沸点:135℃)、エチレングリコール-n-プロピルエーテル(沸点:150℃)、エチレングリコールモノブチルエーテル(沸点:171℃)、プロピレングリコールモノメチルエーテル(沸点:120℃)、プロピレングリコールモノエチルエーテル(沸点:133℃)、プロピレングリコール-n-ブチルエーテル(沸点:171℃)、プロピレングリコール-t-ブチルエーテル(沸点:153℃)、テトラエチレングリコールモノメチルエーテル(沸点:159℃)、ジエチレングリコールメチルエーテル(沸点:194℃)、ジエチレングリコールジエチルエーテル(沸点:162℃)、ジエチレングリコール-n-ブチルエーテル(沸点:230℃)、ジプロピレングリコールモノメチルエーテル(沸点:188℃)、ジエチレングリコールモノエチルエーテル(沸点:202℃)、ジエチレングリコールモノブチルエーテル(沸点:230℃)、トリエチレングリコールメチルエーテル(沸点:249℃)、ジプロピレングリコール-n-プロピルエーテル(沸点:213℃)、トリプロピレングリコールメチルエーテル(沸点:243℃)、トリエチレングリコールエチルエーテル(沸点:256℃)、ジエチレングリコール-n-ヘキシルエーテル(沸点:259℃)、トリプロピレングリコール-n-プロピルエーテル(沸点:261℃)、3-メトキシブタノール(沸点:161℃)等の多価アルコールアルキルエーテル;
エチレングリコールフェニルエーテル(沸点:237℃)、プロピレングリコールフェニルエーテル(沸点:243℃)、エチレングリコールモノベンジルエーテル(沸点:256℃)等の多価アルコールアリールエーテル;
ε-カプロラクタム(沸点:137℃)、N-メチルホルムアミド(沸点:199℃)、N,N-ジメチルホルムアミド(沸点:153℃)、N-メチル-2-ピロリドン(沸点:204℃)、2-ピロリドン(沸点:245℃)、1,3-ジメチルイミダゾリジノン(沸点:220℃)、N-メチルピロリジノン(沸点:202℃)等の含窒素化合物;
プロピレングリコールモノメチルエーテルアセテート(沸点:146℃)、酢酸3-メトキシブチル(沸点:172℃)等のエステル化合物;
ダイアセトンアルコール(沸点:169℃)、γ-ブチロラクトン(沸点:204℃)等のケトン化合物が挙げられる。
本開示のインクジェット記録方法は、基材上に上記インクを付与する工程を含む。
本開示の画像記録物は、基材と、基材上に配置された上記インクの固化物である赤外線吸収画像と、を含む。
・比較化合物1…特開2017-226820号公報に記載の化合物No.2
・比較化合物2…特開2002-90521号公報に記載の化合物(I-13)
・比較化合物3…特開2000-292758号公報に記載の化合物A-1と化合物B-19との組み合わせ
色素化合物…0.5質量部
超純水(比抵抗値18MΩ・cm以上)…78.8質量部
有機溶剤:プロピレングリコール…19.7質量部
アセチレングリコール系界面活性剤:オルフィンE1010(日信化学社製)…1質量部
調製したインクを、インクジェット記録装置(製品名「DMP-2831」、FUJIFILM DIMATIX社製)のインクタンクに装填した。基材として、OKトップコート紙(王子製紙社製)を準備した。基材上にインクを吐出した後、100℃の温風で1分間乾燥し、ベタ画像を記録した。
450nmにおける光学濃度(OD)、及び、極大吸収波長における光学濃度(OD)を、150mmφ大形積分球付属装置LISR-3100(島津製作所製)を備えた分光光度計UV-3100PC(島津製作所製)を用いて測定した。極大吸収波長におけるODに対する450nmにおけるODの比率P(450nmのOD/極大吸収波長のOD)に基づいて、不可視性を評価した。評価基準は以下のとおりである。比率Pが小さいほど不可視性に優れるといえる。評価基準は以下のとおりである。A、B及びCは実用上問題ないレベルである。
A:比率Pが1/10以下である。
B:比率Pが1/10超1/7以下である。
C:比率Pが1/7超1/5以下である。
D:比率Pが1/5超である。
調製したインクを用いて、極大吸収波長における光学濃度(OD)が0.5、1.0、及び1.5である3種の画像記録物を作製した。ODは、インクの吐出量を調整することによって、調整した。
作製した各画像記録物に対して、キセノンウェザーメーター(アトラスC.I65)を用いて、照度85,000ルクスのキセノン光を1日間照射した。光照射後の画像記録物について、極大吸収波長における光学濃度(OD)を測定した。下記式に基づいて色素残存率を算出した。色素残存率が高いほど、耐光性に優れるといえる。
色素残存率(%)=(光照射後のOD)÷(光照射前のOD)×100
全ての光学濃度は、島津製作所社製150mm大型析分球付属装置LISR-3100を備えた分光時計UV-3100PCを用いて測定した。
評価基準は以下のとおりである。A、B及びCは実用上問題ないレベルである。
A:3種の画像記録物全てにおいて、色素残存率が90%以上である。
B:3種の画像記録物全てにおいて、色素残存率が75%以上90%未満である。
C:3種の画像記録物のうち少なくとも1つにおいて、色素残存率が75%未満であり、3種の画像記録物全てにおいて、色素残存率が60%以上である。
D:3種の画像記録物のうち1つ又は2つにおいて、色素残存率が60%未満である。
E:3種の画像記録物全てにおいて、色素残存率が60%未満である。
調製したインクを用いて、極大吸収波長における光学濃度(OD)が0.5、1.0、及び1.5である3種の画像記録物を作製した。ODは、インクの吐出量を調整することによって、調整した。
作製した各画像記録物を、温度45℃、湿度85%に設定されたボックス内に7日間保管した。保管後の画像記録物について、極大吸収波長における光学濃度(OD)を測定した。下記式に基づいて色素残存率を算出した。色素残存率が高いほど、耐光性に優れるといえる。
色素残存率(%)=(保管後のOD)÷(保管前のOD)×100
全ての光学濃度は、島津製作所社製150mm大型析分球付属装置LISR-3100を備えた分光時計UV-3100PCを用いて測定した。
評価基準は以下のとおりである。A、B及びCは実用上問題ないレベルである。
A:3種の画像記録物全てにおいて、色素残存率が90%以上である。
B:3種の画像記録物全てにおいて、色素残存率が75%以上90%未満である。
C:3種の画像記録物のうち少なくとも1つにおいて、色素残存率が75%未満であり、3種の画像記録物全てにおいて、色素残存率が60%以上である。
D:3種の画像記録物のうち1つ又は2つにおいて、色素残存率が60%未満である。
E:3種の画像記録物全てにおいて、色素残存率が60%未満である。
一方、比較例1では、色素化合物がフタロシアニン色素であるため、不可視性に劣ることが分かった。
比較例2では、色素化合物が有機カチオンを有していないため、耐光性及び耐湿熱性に劣ることが分かった。
比較例3では、色素化合物が、ビピリジン骨格を有する有機カチオンを有しているため、耐光性及び耐湿熱性に劣ることが分かった。
化合物9を0.02g、及びポリエチレンテレフタラート樹脂(Tg:60℃)10gを二軸混練機のホッパーに投入し、温度120℃、スクリュ回転数200rpm(revolutions per minute)の条件で5分間混練操作を行い、樹脂混練物を作製した。
Claims (20)
- 下記式1で表される色素化合物と、媒体と、を含む色素組成物。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-1中、A11及びA12はそれぞれ独立に、窒素原子又はリン原子を表す。B11はそれぞれ独立に、2価の連結基を表す。R1a、R1b、R1c、R1d、E11、及びE12はそれぞれ独立に、脂肪族基又は芳香族基を表す。R1a、R1b、R1c、及びR1dは、互いに結合して環を形成してもよい。m1は1以上の整数である。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。 - 前記式2-1、式2-2、及び式2-3中、B11、B21、B22、及びB31はそれぞれ独立に、炭素数2~8の2価の連結基である、請求項1に記載の色素組成物。
- 前記式2-1、式2-2、式2-3、及び式2-4中、A11、A12、A21、A22、A23、A31、A32、及びA41は、窒素原子である、請求項1又は請求項2に記載の色素組成物。
- 前記式1中、X1は、前記式2-1で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す、請求項1~請求項3のいずれか1項に記載の色素組成物。
- 前記式1中、Cyは下記式4で表される、請求項1~請求項4のいずれか1項に記載の色素組成物。
式4中、Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。R3、R4、及びR5は、それぞれ独立に、水素原子、脂肪族基、又は芳香環基を表す。R3及びR4は、互いに結合して環を形成してもよい。A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。また、L2はそれぞれ独立に1個、2個、又は3個のメチン基からなるメチン鎖を表し、L2は置換基を有さない。R6及びR7はそれぞれ独立に、水素原子又は脂肪族基を表す。R6及びR7は、互いに連結して環を形成してもよい。R8は下記式Aで表される。
-SA-TA 式A
式A中、SAは、単結合、アルキレン基、アルケニレン基、アルキニレン基、-O-、-S-、-NRL1-、-C(=O)-、-C(=O)O-、-C(=O)NRL1-、-S(=O)2-、-ORL2-、又は、これらの少なくとも2つを組み合わせてなる基を表し、RL1はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、又は一価のヘテロ環基を表し、RL2は、アルキレン基、アリーレン基、又は二価のヘテロ環基を表し、TAは、水素原子、ハロゲン原子、アルキル基、アリール基、一価のヘテロ環基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、トリアルキルシリル基、又はトリアルコキシシリル基を表す。 - 前記式4中、A1及びA2はそれぞれ独立に、ベンゼン環又はナフタレン環を形成する非金属原子群を表す、請求項5に記載の色素組成物。
- 前記媒体は、液体である、請求項1~請求項6のいずれか1項に記載の色素組成物。
- 前記媒体は、水を含む液体である、請求項1~請求項7のいずれか1項に記載の色素組成物。
- 前記媒体は、水と、沸点が100℃以上の有機溶剤とを含む、請求項1~請求項8のいずれか1項に記載の色素組成物。
- インクである、請求項1~請求項9のいずれか1項に記載の色素組成物。
- インクジェット記録用である、請求項10に記載の色素組成物。
- 基材上に、請求項11に記載の色素組成物を付与する工程を含むインクジェット記録方法。
- 基材と、
前記基材上に配置された、請求項10又は請求項11に記載の色素組成物の固化物である赤外線吸収画像と、を含む画像記録物。 - 基材と、
前記基材上に配置された赤外線吸収画像と、を含み、
前記赤外線吸収画像は、下記式1で表される色素化合物を含み、前記赤外線吸収画像の極大吸収波長が700nm~1,300nmの範囲にある、画像記録物。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-1中、A11及びA12はそれぞれ独立に、窒素原子又はリン原子を表す。B11はそれぞれ独立に、2価の連結基を表す。R1a、R1b、R1c、R1d、E11、及びE12はそれぞれ独立に、脂肪族基又は芳香族基を表す。R1a、R1b、R1c、及びR1dは、互いに結合して環を形成してもよい。m1は1以上の整数である。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。 - 下記式1で表される色素化合物。
式1中、L1は奇数個のメチン基からなるメチン鎖を表す。R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表す。T1及びT2はそれぞれ独立に、縮環していてもよい5員又は6員の含窒素複素環を形成する非金属原子群を表す。Cyはアニオン部であり、X1は下記式2-1、式2-2、若しくは式2-3で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す。nは0ではない、電荷を中和するために必要な数を表す。
式2-1中、A11及びA12はそれぞれ独立に、窒素原子又はリン原子を表す。B11はそれぞれ独立に、2価の連結基を表す。R1a、R1b、R1c、R1d、E11、及びE12はそれぞれ独立に、脂肪族基又は芳香族基を表す。R1a、R1b、R1c、及びR1dは、互いに結合して環を形成してもよい。m1は1以上の整数である。
式2-2中、A21、A22、及びA23はそれぞれ独立に、窒素原子又はリン原子を表す。B21及びB22はそれぞれ独立に、2価の連結基を表す。R2a及びR2bはそれぞれ独立に、脂肪族基又は芳香族基を表す。m2は0以上の整数である。G21は、A21を環中に含む芳香族環を形成する非金属原子群を表す。G22は、A23を環中に含む芳香族環を形成する非金属原子群を表す。
式2-3中、A31及びA32はそれぞれ独立に、窒素原子又はリン原子を表す。B31は、2価の連結基を表す。R3a及びR3bはそれぞれ独立に、脂肪族基又は芳香族基を表す。G31は、A31を環中に含む芳香族環を形成する非金属原子群を表す。G32は、A32を環中に含む芳香族環を形成する非金属原子群を表す。
式2-4中、A41はそれぞれ独立に、窒素原子又はリン原子を表す。B41はそれぞれ独立に、単結合又は2価の連結基を表す。R4a、R4b及びR4cはそれぞれ独立に、脂肪族基又は芳香族基を表す。E41及びE42はそれぞれ独立に、単結合又は脂肪族基を表す。R4a、R4b及びR4cのうち1つはE41又はE42と結合して環を形成してもよい。m4は2以上の整数である。 - 前記式2-1、式2-2、及び式2-3中、B11、B21、B22、及びB31はそれぞれ独立に、炭素数2~8の2価の連結基である、請求項15に記載の色素化合物。
- 前記式2-1、式2-2、式2-3、及び式2-4中、A11、A12、A21、A22、A23、A31、A32、及びA41は、窒素原子である、請求項15又は請求項16に記載の色素化合物。
- 前記式1中、X1は、前記式2-1で表される有機カチオン、又は、式2-4で表される構造を有する有機カチオンを表す、請求項15~請求項17のいずれか1項に記載の色素化合物。
- 前記式1中、Cyは下記式4で表される、請求項15~請求項18のいずれか1項に記載の色素化合物。
式4中、Y1及びY2は、それぞれ独立に、CR3R4-、-O-、-S-、-Se-、又は-NR5-を表す。R3、R4、及びR5は、それぞれ独立に、水素原子、脂肪族基、又は芳香環基を表す。R3及びR4は、互いに結合して環を形成してもよい。A1及びA2はそれぞれ独立に、芳香族環又は芳香族複素環を形成する非金属原子群を表す。また、L2はそれぞれ独立に1個、2個、又は3個のメチン基からなるメチン鎖を表し、L2は置換基を有さない。R6及びR7はそれぞれ独立に、水素原子又は脂肪族基を表す。R6及びR7は、互いに連結して環を形成してもよい。R8は下記式Aで表される。
-SA-TA 式A
式A中、SAは、単結合、アルキレン基、アルケニレン基、アルキニレン基、-O-、-S-、-NRL1-、-C(=O)-、-C(=O)O-、-C(=O)NRL1-、-S(=O)2-、-ORL2-、又は、これらの少なくとも2つを組み合わせてなる基を表し、RL1はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、又は一価のヘテロ環基を表し、RL2は、アルキレン基、アリーレン基、又は二価のヘテロ環基を表し、TAは、水素原子、ハロゲン原子、アルキル基、アリール基、一価のヘテロ環基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、トリアルキルシリル基、又はトリアルコキシシリル基を表す。 - 前記式4中、A1及びA2はそれぞれ独立に、ベンゼン環又はナフタレン環を形成する非金属原子群を表す、請求項19に記載の色素化合物。
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