JPS62181381A - Near infrared ray absorbing composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a specific compound having the maximum absorption wavelength at a specific wavelength or above and useful as a near infrared rays absorbing material for safe light filters used in infrared- sensitive photosensitive materials, control of plant growth and shielding of heat rays, etc. CONSTITUTION:A composition containing at least one kind of compound expressed by formula I [R<1> is (substituted) alkyl, (substituted) aryl or (substituted) heterocyclic ring; R<2> and R<5> are H or substitutive group; R<3> and R<4> are H, halogen, (substituted) alkoxy or (substituted) alkyl; R<6> and R<7> are (substituted) alkyl, (substituted) aryl, acry, sulfonyl or nonmetallic atomic group required for forming 5--6-membered ring by mutually linking R<6> and R<7>, provided that R<3> and R<4> are not H at the same time] and having the maximum absorption wavelength at >=720nm, e.g. a compound expressed by formula II, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a near-infrared absorbing composition that absorbs near-infrared rays. More specifically, the present invention relates to a near-infrared absorbing composition useful for optical filters that absorb near-infrared light having a wavelength of 720 nm or more or recording layers using near-infrared light as a light source.

``Prior Art'' Compositions that selectively absorb far-red light or near-infrared light with a wavelength of 720 nm have been considered for various uses and have been strongly desired, but until now there has been no suitable material. I couldn't get it. Examples of uses of conventional infrared absorbing compositions will be explained below.

■ Safelight filter for infrared-sensitive photosensitive materials In recent years, many silver halide photosensitive materials (hereinafter referred to as "sensitized materials") that are sensitive to far-red or near-infrared light with a wavelength of 200 nm or more have been developed. It's coming. This K is a silver halide photosensitive material that has infrared sensitivity, regardless of whether it is black and white or color, as well as ordinary type, instant type or heat developable type, and can be used to create pseudo-color photographs for use in resource surveys, etc. Alternatively, there are devices that can be exposed using semiconductor lasers or diodes that emit light in the infrared region.

Until now, safelight filters suitable for these sensitive materials had not been developed. As a safelight filter, it is desired to develop a filter that absorbs near-infrared light and substantially transmits visible light.

■ Control of plant growth It has been known for a long time that light affects the so-called morphogenesis related to plant growth and differentiation, such as seed germination, stem elongation, leaf expansion, and flower bud and tuber formation. It is being studied as a photomorphogenetic effect.

If a plastic film that selectively absorbs light with a wavelength of 700 nm or more could be obtained, for example, crops could be coated with a near-infrared absorbing film at a specific time to block light with a wavelength of 70θ nm or more, thereby delaying the time of heading. Or,
It is expected to have the effect of controlling growth (see Katsumi Inada, "Chemical Regulation of Plants", Vol. 6, No. 1 (2017)).

■ Blocking of heat rays Of the solar radiant energy, light in the near-infrared and infrared regions with a wavelength of 0 nm or more is absorbed by objects and converted into thermal energy. Moreover, most of the energy distribution is concentrated in the near-infrared region with a wavelength of 100-2θθonm. Therefore, a film that selectively absorbs near-infrared rays is extremely effective in blocking solar heat, and can suppress the rise in indoor temperature while allowing in sufficient visible light. This can be applied not only to horticultural greenhouses but also to windows of houses, offices, stores, automobiles, airplanes, etc. In these cases, visible light transmission is of great importance.

Conventionally, to block heat rays, a plastic film with a very thin metal layer deposited on the surface, or a glass with an inorganic compound such as FeO dispersed therein have been used.

■ Infrared rays that are harmful to human eye tissue Infrared rays contained in sunlight and infrared rays emitted during welding have a harmful effect on human eye tissue. . One of the main uses of infrared cut filters is as eyeglasses that protect human eyes from such harmful infrared rays.

For example, sunglasses, safety glasses for welders, etc.

In this case as well, substantial transparency of visible light is very important.

(2) Infrared cut filter for semiconductor photodetector Currently, silicon photodiodes (hereinafter referred to as SPDs) are mainly used as photodetectors for photodetectors used in automatic exposure meters such as cameras.

In order to use an SPD as a light meter, it is necessary to cut out infrared light that is invisible to Iruma's eyes, and to make the spectral sensitivity curve of the SPD similar to the specific luminous efficiency curve.

Especially for light with a wavelength of 700~//θ0nm, SPD
The output of this area is large, and the light in this area is not perceptible to the human eye, which can cause the exposure meter to malfunction. For this reason, if it is possible to use an infrared absorbing plastic film that has low absorption in the visible region and absorbs the entire infrared region of 7θθ ~ / / 00 nnl, the light transmittance in the visible region will be large, and the output of the SPD will be large. It is clear that the performance of light meters can be significantly improved.

Conventionally, this type of photodetection device has been put into practical use by attaching a glass infrared cut filter using an inorganic infrared absorbing agent to the front of the SPD.

(2) Laser recording layer A recording layer that uses laser light to record by absorbing infrared rays and converting it into heat, such as the recording layer of an optical disk or a thermosensitive color recording material using a laser.

For example, JP-A Sho JF-J/4/, No. 4, JP-A Sho J/-2
/ No. 7397, Tokukai Sho! ? -/2!2< et al. Each of the publications discloses a recording layer containing a bicarbonate dye.

■ Ink for inkjet printers Ink for inkjet printers uses a solvent such as ethyl cellosolve and a dye that dissolves in this organic solvent as an infrared absorber.
It is used in a method of reading with an optical reader using an infrared light source of 4t0 to 900 nm. Conventional infrared absorbers for inkjet printers include nigrosine, chromium complex salts, etc. ≦−73j! Otsu? The compounds disclosed in No.

Further applications include: (1) ink for bar codes, (2) antihalation agent for photosensitive materials, and (F) infrared couplers forming infrared absorbing dyes for soundtracks.

[Problems to be solved by the invention] However, the absorption characteristics of conventional general organic dye-based infrared absorbers become unstable as the wavelength range increases, and their light emitting properties and heat resistance are low, making them practically unsatisfactory. Ta.

In addition, when using the complex as an infrared absorber, light resistance,
Although it has good heat resistance, it lacks solubility in organic solvents, which is a major drawback when creating thin plastic films.

That is, for the above-mentioned applications, such as SPD filters, an extremely thin film with high infrared absorption efficiency is desired, but for this purpose, a large amount of infrared mRF! is required in the resin. Infrared absorbers with low solubility in organic solvents have not been able to satisfy this purpose.

Therefore, the first object of the present invention is to provide a near-infrared absorbing composition that has high solubility in organic solvents.

The second object is to provide a near-infrared absorbing composition that has high solubility in organic solvents and good compatibility with plastic films. Third, it is an object of the present invention to provide a near-infrared absorbing composition that has high solubility in organic solvents and good compatibility with film-forming binders.

The present inventors have completed the present invention as a result of various studies to achieve the above object.

"Means for Solving Problems J" The above-mentioned near-infrared absorbing material is characterized by containing at least one compound represented by the following general formula (I) and having a maximum absorption wave at 7201 m or more. solved by the composition.

General formula N) In the formula, R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group (e.g., phenyl group, naphthyl group, etc.), a substituted or unsubstituted heterocyclic group, and R
2 and R5 may be the same or different and represent a hydrogen atom or a group capable of substituting it; R3 and R
4 may be the same or different from each other, and hydrogen atoms,
・Represents a substituted or unsubstituted alkoxy group (such as a methoxy group, ethoxy group, octoxy group, etc.) having 7 to 1' carbon atoms, or a substituted or unsubstituted alkyl group , preferably R
3 and R4 are carbon numbers/~! represents an alkyl group (methyl group, ethyl group, etc.). However, R3 and R4 are never hydrogen atoms at the same time. R6 and R may be the same or different from each other, and are substituted or unsubstituted alkyl groups,
Substituted or unsubstituted aryl groups (e.g. phenyl group,
naphthyl group), acyl,! (for example, acetyl group, propionyl group, etc.), sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), or R6 and R7 are connected! Or it represents a nonmetallic atomic group necessary to form a member term (for example, a pyrrolidine ring, a lysine ring, a morpholine ring, etc.).

The compound represented by general formula (I) is R1゜R2, R3
, R4, R5, R6 or R7 may form a 211: body.

The alkyl groups represented by R1, R6 or R7 may be the same or different, and have a carbon number of /~/? Alkyl groups (e.g. methyl group, ethyl group, propyl L i-butyl group, n-octyl L n-dodecyl group, n-octadecyl group, etc.) are preferable, and substituents (e.g. cyan group, hydroxyl group, methoxy group, etoyasi group) are preferable. , an aryloxy group such as a phenoxy group, an amide group such as an acetamide group or a methanesulfonamide group, or a halogen atom such as a chlorine atom or a fluorine atom).

The aryl groups represented by R1, R6, or R7 may be the same or different, and may include a substituted or unsubstituted phenyl group (substituents include, for example, a hydroxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a fluorine atom, etc.), a carbon Number 2
~/l acyl group (e.g. acetyl group, propionyl group, stearoyl group, etc.), carbon number /~// sulfonyl group (e.g. Lij' mep sulfonyl group, ethanesulfonyl group, octanesulfonyl group, etc.), carbon number /~/l carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, octylcarbamoyl group, etc.), carbon number /~// sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, butyl sulfamoyl group) Famoyl group, etc.), carbon! ! l~/r alkoxycarbonyl group (e.g. methoxycarbonyl group, trichloroethoxycarbonyl group, tethyloxycarbonyl group),
Alkoxy groups (e.g. methoxy group, butoxy group, pentadecyloxy group, etc.) having 7 to ♂ carbon atoms, amino groups (e.g. dimethylamino group, diethylamino group, diethylamino group, etc.) or substituted or unsubstituted naphthyl groups ( The same substituents as those for the phenyl group are preferred).

The substituted or unsubstituted heterocycle represented by R1 represents a single heterocycle or a fused heterocycle, such as /, 3 hethiazole ring, /, 3. II-) Riazole ring, benzothiazole ring, benzimidazole ring, benzoxazole ring, /, 3. Preferred examples include a y-thiadiazole ring (substituents include alkyl groups such as methyl, ethyl, and octyl, alkoxy groups such as methoxy, ethoxy, and decyloxy, and hydroxyl).

The groups capable of substituting hydrogen atoms represented by R2 and R5 are:
Number of substituted or unsubstituted carbon atoms bonded directly or via a halogen atom (e.g. fluorine atom, chlorine, atom, bromine atom, etc.), hydroxyl group, cyanide group, or a divalent linking group/~
// represents an alkyl group (for example, methyl group, ethyl group, butyl group, =-ethylhexyl group, stearyl group, etc.), and the divalent linking group is, for example, -〇-1-N)ICO-1-
NH8O2-1'-NHCOO-1-NHCONH-1
-COO-1-CO-1-SO2-1-NR- (R represents a hydrogen atom or a substituted or unsubstituted alkyl group having a carbon number of /~/♂).

More preferably, R1 represents a heterocyclic group or a phenyl group substituted with a monovalent group having a value of Hammett's substituent constant δ or δ greater than 0.23. Hammett's substituent constant δ. Or monovalent groups with a value of δ greater than 0.23 include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), cyan groups, formyl groups, carboxy groups, carbamoyl groups (unsubstituted carbamoyl groups,
methylcarbamoyl group, etc.), alkoxylponyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.)
, an acyl group (acetyl group, benzoyl group), a nitro group, a sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group), and a sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.). Said...Met's δ or δ, the value is ``
It is described in "Structure-Activity Relationship of Drugs" (Nankodo), page 96 (/979), and substituents can be selected based on this table.

Specific examples of the compound represented by the general formula (I) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

(+-/) Ha H5C2C2H5 (I--?) (I-6) ・N /\.

I (5C2C2H5 (I-, f') (I-/I H5C7\.2H5 (+-//) α (I-/riα Heha H5C2C2H5 (I-/-?) (l-/da) I-I5C2 ”CH2゜H2O), (I-/Otsu) H5C2'\C2H3 (I-/, r) H5C';\.2H5 (I-koθ) CH3CH3 (I-22>H5C2'\.2H5 (I-, 2-?) (■-Cog) 115C2C2■(5 (I-2ri(I-,27) (I-2?) (I-,29) (I-31 (I-,?/) (l- 32) H5C/″″c2H5 (I-3J) (I~3g) (I-36> The compound represented by the general formula (I) is produced by condensation of dialkylanilines and mononitrosonaphthols in concentrated sulfuric acid. Method, method of condensing α-naphthols and p-phenylenediamines in the presence of a base and oxidizing agent, oxidative condensation of q-amino-/-naphthols and dialkylanilines with a sodium hypochlorite solution It can be synthesized by the condensation method of p-nitrone dialkylanilines and α-naphthols, for example, by the method disclosed in JP-A-Sho!
θ-10θ// issue and JP-A-Sho tO-32F! No. 7 and Journal of Organic Chemistry (S, Fu
“Journal of Organic” written by jita
ChemistryJ, <it, i77~/r3
(/9.1rJ)).

Synthesis Example/(Synthesis of Exemplified Compound 1-7) 9.2 g of s-(g-7 cetyl phenylcarpamoyl)-7-nafdo/l, 7 nml and ethyl acetate/! Add 9 g of an aqueous solution of 2/g of sodium carbonate to 2 θ ml of an aqueous solution of 2/g of sodium carbonate and dimethylaniline, and add 20 ml of an aqueous solution of qg to ammonium persulfate for 3Q minutes while stirring. It dripped. After stirring for several hours after dropping, the reaction solution was allowed to stand still.
The ethyl acetate phase was taken out, washed with water, and then concentrated. The concentrated residue was recrystallized from chloroform to give greenish-blue crystals of the exemplified compound.

/gel#l. Melting point 2/9~2200C1λCHCe3
aX = 2g! nm (ε=7.23×10 4 )Synthesis Example λ The exemplified compounds were obtained in the same manner as in Synthesis, except that α-naphthols and p-phenylenediamines were used in the combinations shown in Table 1 below. The results are also shown in Table 1.

When the near-infrared absorbing composition of the present invention is used as an optical filter, the compound represented by the general formula (I) can be appropriately incorporated into a binder. Any binder, organic or inorganic, can be used as long as it exhibits near-infrared absorbing properties; for example, in the case of optical filters, polymeric materials such as plastics, inorganic materials such as glass, etc. can be used. Can be mentioned.

Preferably, a binder having excellent transparency and mechanical properties is used as the binder. Examples of such binders include polyesters represented by polyethylene terephthalate, cellulose esters such as cellulose diacetate, cellulose IJ acetate, and cellulose acetate butyrate;
-i Polyolefins such as Robylene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl compounds such as polystyrene, acrylic addition polymers such as polymethyl methacrylate, polycarbonates consisting of polycarbonate esters, urethanes Examples thereof include known film-forming binders such as resins and hydrophilic binders such as gelatin.

More preferably, cellulose esters such as cellulose IJ acetate are preferred because of their excellent transparency and mechanical properties.

As a method for forming a film by adding and retaining the compound of general formula (I) to the above-mentioned plastic material, there is first a method of blending it into the plastic at the time of film production. That is, the compound of formula (I) is mixed with various additives into polymer powder or pellets, and then melted to form T.
A film in which the above compound is uniformly dispersed can be obtained by extruding by a die method or an inflation method, or by forming a film by a calendar method. In addition, when producing a film from a polymer solution by a casting method, the general formula (
The compound I) may be included.

Second, a near-infrared absorbing layer is formed by applying a polymer solution or dispersion containing the compound of general formula (I) to the surface of various plastic films or glass plates manufactured by an appropriate method. There is a way to do it. As the binder used in the coating solution, one is selected that dissolves the compound of general formula (I) as well as possible and has excellent adhesiveness to the plastic film or glass plate serving as the support. Polymethyl methacrylate, cellulose acetate butyrate, polycarbonate, etc. are suitable for this purpose. The support film may be previously coated with a suitable primer to improve adhesion.

The third method is to mix the compound of general formula (+) and the main synthetic monomer in the light incident window frame of the element that is to be blocked from infrared rays, add an appropriate polymerization initiator, and apply heat or light. There is a method of polymerizing and forming a filter on the window frame using the resulting polymer. In this method, the entire device can also be embedded in plastics made from ethylenically unsaturated polymerizable monomers or polyaddition compositions such as epoxy resins.

The fourth method is a method in which the compound (I) according to the present invention is vapor-deposited on a suitable support. In this process, a suitable film-forming binder layer may also be provided as a protective layer at a position remote from the support.

The optical filter obtained from the near-infrared absorbing composition of the present invention is disclosed in JP-A-Shoj? -2ff/θ7, same! Tar 93/7
No. and same! It can also be used in combination with a color separation filter such as that described in No. 9-30!09.

When the near-infrared absorbing composition of the present invention is used as an optical filter, two or more compounds represented by the general formula (I) may be used in combination.

In particular, in order to improve the expansion of the absorption wavelength range, it is preferable to add a compound represented by the following general formula (It).

General formula (n) In the formula, R8, R9, RIO, RN, R12, R13゜RI4 and R15 are hydrogen atoms, halogen atoms (e.g. chlorine, bromine, etc.) or direct or divalent linking groups (e.g. -〇-, - NHCO-, -CO-.

-COO-, -8O2-, -NHCOO-, -NHCO
NH-.

-NH8O2-, etc.), L< represents an unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, n-octyl group, etc.),
M represents nickel, cobalt, copper, palladium or platinum, preferably L< represents nickel.

cat Iri cation (for example, sodium, potassium, ammonium, 9th ammonium, &th grade phosphonium, etc.), preferably I ram, more preferably 9th phosphonium.

L 1 , L 2 , L 3 and L4 have carbon numbers/~
20 substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, n-butyl group, n-dodecyl group, n-octadecyl group, etc.) or substituted or unsubstituted aryl groups having 2 to 4t carbon atoms (e.g. phenyl group, tolyl group,
α-naphthyl group, etc.).

Preferred examples of the compounds represented by the general formula ([1)] are as follows, but it goes without saying that the present invention is not limited to these exemplified compounds.

(II-/) (■-acknowledgement) (n,?) (II-1 (n-1) (■-ni) (n-7) (■-♂) (n-9) B-10) (II -//) (n -/'ko) (II-/3) (I-/j) (II-#) (n-/7) (II-//) (■-/ri) (■-ko θ) (II-,2/) (If-2-2) F-111-C When the near-infrared absorbing composition of the present invention is used as an optical filter,! It is preferable that light having a wavelength of 00 to ≦o nm is substantially transmitted. Furthermore, ultraviolet absorbers may be used in combination, such as substituted or unsubstituted benzoic acid esters such as resolcif monobenzoate and methyl salicylate;
Cinnamate esters such as butyl co-oxy-3-methoxycinnamate &-2. &-benzophenones such as dioxybenzophenone, α, β- such as dibenzalacetone, etc.
Unsaturated ketones! , coumarins such as 7-cyoxycoumarin, carbostyrils such as 4t-dimethyl-7-oxycarbostyryl, azoles such as cophenylpenzimidazole, X-(,Z-hydroquinphenyl)benzotriazole etc. are used. Furthermore, in the near-infrared absorbing composition of the present invention, a yellow dye and a cyan dye can be used in combination.

In the case of a film made by a coating method using the near-infrared absorbing composition of the present invention, a thin plastic film may be attached to the surface of the coating layer for the purpose of protecting the coating layer, imparting droplet properties, etc. It can be painted.

For example 0. A laminated film is obtained by stacking polyvinyl chloride films with a thickness of θtmm and heat-pressing them at /20 to /(70°C).

When the near-infrared absorbing composition of the present invention is used as an optical filter, the compound represented by the general formula (I) is added in a range of 0.7 to 700 parts by weight per 700 parts of the binder. θ part, preferably 0
．． Contain 1 to 10 parts.

The optical filter obtained from the near-infrared absorbing composition of the present invention only needs to have a transmittance in the wavelength range that should be blocked functionally as low as to achieve the intended purpose. At wavelengths of 72θnm and above, the transmittance is /θ
preferably 2.0% or less, particularly preferably 0.7%
It is important to adjust the amount added per binder and the thickness of the filter so that the transmittance is less than or equal to %. Even more! The transmittance is at least 00 to oonm! It is preferable to have at least 70%, preferably at least 70%, particularly preferably at least 100%. The practical thickness is 0.002 mm to θ, tmm, but it is possible to design a filter with a thickness outside this range depending on the application.

Next, an embodiment in which the near-infrared absorbing composition of the present invention is used in a laser-based optical recording medium will be described.

An optical recording medium basically consists of a substrate and a recording layer, but depending on the purpose, an undercoat layer can be provided on the substrate and a protective layer can be provided on the recording layer.

Any known substrate can be used as long as it is transparent to the laser used. Typical examples include glass or plastic, and examples of the plastic include acrylic, polycarbonate, polysulfone, polyimide, and polyester. Its shape can be various, such as a disk, card, sheet, or roll film.

A guide groove may be formed on the glass or plastic substrate to facilitate tracking during recording. Further, a subbing layer of a plastic binder, an inorganic oxide, an inorganic sulfide, or the like may be provided on the glass or plastic substrate. An undercoat layer having a lower thermal conductivity than the substrate is preferred.

The recording layer is divided into one consisting of a near-infrared absorber alone or a combination thereof with other materials, and one consisting of a reflective layer and a light-absorbing layer containing the near-infrared absorber.

The recording layer composed of this near-infrared absorber alone or in combination with other materials can be prepared by dissolving the nuclear near-infrared absorber in a solvent and applying it, by vapor depositing it on a substrate, or by mixing it with a resin solution and applying it. It is formed by a method of coating a mixed solution with other pigments, a method of dissolving it together with other pigments in a resin solution, and applying it.

Known resins such as PVAX PVP, polyvinyl butyral, polycarbonate, nitrocellulose, polyvinyl formal, methyl vinyl ether, maleic anhydride copolymer, and styrene-butadiene copolymer are used as the resin, and in the near-infrared absorbing composition. It is desirable that the weight ratio of the near-infrared absorbent represented by the general formula (I) to the resin is 0.07 or more. When using other dyes, such as triarylmethane dyes, merocyanine dyes, cyanine dyes, azo dyes, and anthraquinone dyes, which have absorption outside the wavelength range of the semiconductor laser, it is possible to However, it is suitable because it can be recorded.

Seven or more recording layers are provided.

The thickness of the recording layer is usually 0.07 μm to 7 μm, preferably θ, O♂ to 0. It is in the range of tμm.

In the case of reflective readout, it is particularly preferably an odd multiple of //<t of the laser wavelength used for readout.

When providing a reflective layer for a semiconductor laser or a He-Ne laser, the reflective layer can be provided on the substrate by providing a recording layer on the next two reflective layers using the method described above, or by forming a recording layer on the substrate. One of the methods is to provide a layer and then provide a reflective layer thereon.

The reflective layer can also be formed by other methods such as vapor deposition, sputtering, and ion blating.

For example, a metal salt or a metal complex salt is dissolved in a water bath resin (PVP, PVA, etc.), and a reducing agent is added to the solution, and the solution is applied to the substrate! 08C~/! 00C preferably ≦0
It is formed by heating and drying at 0C to 7008C.

The purity of metal salt or metal complex salt to resin is M amount ratio θ2
/~10 preferably 0. j~7.5. In this case, the appropriate thickness of the recording layer is 0.0/-0.1 .mu.m for the metal particle reflective layer and 0.07-7 .mu.m for the light absorption layer.

As the metal salt or metal complex salt, silver nitrate, potassium silver cyanide, potassium gold cyanide, silver ammine complex, silver cyanide complex, gold salt, or gold cyanide complex can be used. As a reducing agent, formalin, tartaric acid, tartrate, reducing agent,
Hypophosphite, sodium borohydride, dimethylamine borane, etc. can be used. The reducing agent can be used in an amount of θ, i to 70 mol, preferably 0.5 to 1 mol, per mol of the metal salt or metal complex salt.

In optical recording media, information is recorded by irradiating the recording layer with a spot-shaped high-energy beam such as a laser through the substrate or from the opposite side of the substrate, and the light absorbed by the recording layer is converted into heat. and pits (holes) are formed in the recording layer.

Further, information is read by irradiating a laser beam with a low output power below a recording threshold energy, and detecting a change in the amount of reflected light from a pit portion and a portion where no pits are formed.

Next, embodiments in which the infrared absorbing composition of the present invention is used in inkjet inks will be described.

Inkjet printer inks that use organic solvents as solvents are mainly used in electrostatic acceleration type and electrostatic air flow type, both of which apply high-pressure pulses to the ink to enable ink flow or ink droplet formation. Must be. This is a problem not only with the electrical properties of the ink but also with physical properties related to fluidity such as surface tension and viscosity. -6
It can be carried out according to the method described in No. 093, f and Japanese Patent Application Laid-open No. Sho rt-i3stter.

The ink for inkjet printers uses a near-infrared absorber, and the solvents include ethylcelonorb, toluene, ethanol, n-butanol, ethyl methyl ketone,
Organic solvents such as methyl isobutyl ketone, dichloromethane, triethanolamine, dimethylformamide, and isoamyl acetate are used, and glycerin, metallic soap, etc. are added to adjust the viscosity.

The content is viscosity at room temperature /θCp, below, specific resistance is /×7
The composition ratio of the organic solvent and the viscosity modifier is selected so that it becomes 04~/X/011Ω·Cm.

The content ratio of the near-infrared absorber to the solvent is 0.07 to 0.2 part of the near-infrared absorber to solvent/part by weight, and preferably dissolves or at least has an average particle diameter of θ,! It must be finely dispersed to micrometers or less. In some cases, a dye that absorbs visible light may also be added to the ink.

The near-infrared absorbing composition of the present invention can also be used in combination with known organic or metal complex based near-infrared absorbers. In particular, when used in combination with absorbers having different absorption maximums, the absorption wavelength range can be expanded.

Although the compound of the present invention has sufficiently high light resistance even when used alone,
In order to further increase light resistance, use Tokkai Sho! Tokukai Akira gets 0- and 2! Goo 6.2♂2 Otsu, Tokukai Akira! Gootsuko 9/7, Tokukai Akira! Goo 3j/♂, Tokukai Akira! Goo 9yo♂θ, Tokukai Akira! 4'-72770, Tokukai Sho! Goo r223'lX Tokukaisho! q-! Ko3♂y1 Tokukai Akira! Goo? 23rj, Tokukai Sho! Goo ♂23/, US-<t2, θ! , US-
e, 3 Otsu 330, Tokukai Sho! ! -/ko/29, Tokukai Shoj≦
-/7/3♂ and July 2q, 1939 by the present applicant
It can also be used in combination with a metal complex described in the specification of ``Method for stabilizing an organic substrate substance against light'' filed in Japan (A).

"Effects of the Invention" According to the present invention, light can be substantially transmitted and
Since the above near-infrared absorbing composition can be obtained, an optical filter with excellent fastness to light and heat can be obtained, and a low-cost optical filter can be obtained.

Furthermore, in the near-infrared absorbing composition of the present invention, the solubility in solvents can be adjusted by appropriately selecting and combining the substituents in the compound represented by the general formula (I), so that a wide variety of binders can be used. It has the advantage of being able to

The optical filter obtained from the near-infrared absorbing composition of the present invention can be used as a near-infrared absorbing material, as a safelight filter for infrared-sensitive materials, for controlling plant growth, for blocking heat rays,
Infrared cut filters that are harmful to human eye tissues, infrared cut filters for semiconductor photodetectors and color solid-state image sensors, optoelectronic integrated devices that incorporate electrical and optical functions on the same substrate. In addition to being used as an infrared light cut filter in circuits, it can be used for a variety of other purposes.

Furthermore, the composition according to the present invention can be used in laser recording media and inks for inkjet printers.

Furthermore, the composition of the present invention has the property of converting absorbed near-infrared light into heat, and can also be used as an infrared/heat exchange agent. A typical example is /) JP-A-57-/gθ9! It can be added to a laser heat-sensitive recording medium as described in the Orr/Gu OQT issue to enhance the mixed color reaction caused by the heat generated by irradiation with an infrared laser.

e) For example, JP-A Showo, whose solubility changes due to the action of heat based on laser light? -4t02jrg No. 3) JP-A-Sho! The reaction can be accelerated by incorporating the compound of the present invention into a heat-drying or thermosetting composition as described in No. 1/4t324t.

The compounds according to the present invention are also disclosed in JP-A-Sho! ! -2/'l
As described in No. 62, it can also be used as an electrophotographic photosensitive film for an electrophotographic printer using a semiconductor laser as a light source. It can also be incorporated into toner compositions for electrophotography to improve heat fixability.

Of course, the above description does not limit the uses of the compounds according to the present invention.

"Examples" Next, the present invention will be described in more detail based on Examples. Note that "parts" indicating weight indicate "parts by weight."

Example/ An optical filter was prepared by preparing the following near-infrared absorbing composition using Exemplified Compound 1-t. That is, each component is mixed with the composition shown below in parts by weight, stirred thoroughly, filtered, and coated on a metal support by a casting method. After film formation, the desired optical filter is peeled off. I got it. The dry film thickness is θ,
Several optical filters were obtained, varying in diameter from 0° to 0°3 mm. The optical density of the optical filter thus obtained (thickness: 2! microns) is shown in FIG.

〔Composition〕

Cellulose triacetate 720 parts triphenylphosphatide) 10 parts methylene chloride ♂00 parts methanol
/ to θ part Exemplary compound (I-5)
As can be seen from Figure 7 of Part 2, an optical filter with high transmittance in the visible light range and low transmittance in near-infrared light was obtained.

Example 2 An optical filter with a thickness of 0.16 mm containing a compound represented by general formula (II) in addition to the compound represented by general formula (I) was prepared in the same manner as in Example. The composition of the casting composition is shown below.

The optical density of the optical filter thus obtained is shown in FIG.

〔Composition〕

Cellulose triacetate 770 parts Triphenyl phosphate 70 parts Methylene chloride ? 0θ part methanol
/ to θ part Exemplary compound (l-o)
Part 2 Exemplary Compound (U-3)
As can be seen from Fig. 2, an optical filter with low near-infrared transmittance was obtained similarly to Example.

Example 3 Exemplified Compound (I-t)o, 2 parts Oil-soluble blue dye 0.7 parts Ethyl cellosolve! Part/2-Pentinthiazolone (antifungal agent) 0.007 parts Glycerin 3 parts The above components were mixed homogeneously, and the resulting composition had a specific resistance of 103 Ω·cm and a viscosity of tcp.
, is. This ink composition was applied to an inkjet recording device, and a good image was obtained, which was obtained using a semiconductor laser (7
It was possible to read it with a reading device using a light source of ♂0 nm).

Example Guisoamyl acetate 7 parts Illustrative compound (I-t) 7 parts Oil-soluble dye (Oil Black HBB) 0.0 parts Metal soap 0.0 μ part Ink composition obtained by homogeneously mixing the above components is specific resistance/θ7Ω・am
A good image was obtained by applying it to an inkjet recording device with a viscosity of 4 tcp, which could be read by a reading device using a semiconductor laser (2♂θnm) as a light source.

Example: Illustrated Compound (■-32) o, qg Nitrocellulose Oo, g Dichloromethane 7 ml A solution of the above composition was spin-coated on a glass plate, dried at 00C, and the thickness was 0. <1
A recording layer of 0 μm was obtained.

The reflectance and absorption at a wavelength of 7♂onm were 72% and 3θ chi, respectively.

The thus obtained recording medium was heated with a semiconductor laser having a wavelength of 7♂onm, amW on the irradiation surface, and a beam diameter of 75zμm/MHz.
When I recorded the signal, it was 0. qμ seconds of irradiation (/,
A pit with a diameter of /, /μm was formed with J/pit).

This recording medium was stored for 77 months at a temperature of 0° C. in room light and a humidity of 90° C., but there was no change in the recording and reading characteristics.

Example B Illustrated compound (I-/) 0.7g polycarbonate resin /, θgC, 1, acid blue ♂3 (C, 1, 3θ in Guco) i, 2g 7.2
-Dichloroethane/2 ml A solution having the above composition was spin-coated onto a surface-hardened acrylic plate and dried at 00C to obtain a recording layer with a thickness of 0.9 μm. wavelength? θθnm
The reflectance and absorption at are 72 and 2, respectively.
It was 2%.

In addition, the reflectance and absorption rate at the wavelength O3θnm are 77% and ! It was a male. This recording medium has a wavelength of gmW on the irradiation surface and a beam diameter of 7.6 μm! When a signal was recorded at 0.41 MHz with a semiconductor laser beam of θ0 nm, a diameter of 7
．． A bit of 0 μm was formed. Also, this recording medium
An e-N e laser was used to record a MHz signal with a beam diameter of 3 gμm and an energy of smW on the recording surface [~0. With qμ seconds of irradiation (/, t nJ/pit)/
.

A focus of 0 μm was formed.

Example! A storage test was conducted in the same manner as above, but there were no changes in characteristics.

Example 2 Exemplified Compound (I-j) 0.9 g Nitrocellulose 0.7 g Dichloromethane = θml A coating solution with the above composition was spin coated on a glass plate, dried at θ0C, and the thickness was θ, 4
A recording layer of tQ μm was obtained. The reflectance and absorption at a wavelength of 7 J' Onm were 0% and 0%, respectively.

The recording medium thus obtained had a wavelength of 7♂o nm.

When a signal was recorded on the irradiation surface with a semiconductor laser of ymW and a beam diameter of /, μm at /MH2, it was found that the irradiation time of θ, 3 μs (
/, nJ/pit), a pit with a diameter of 7.0 μm was formed. This recording medium was stored at a temperature of θQC1 in room light and humidity of 90% for several months, but there was no change in the recording and reading characteristics.

Example! Exemplary compound 1-s 0.9g Polycarbonate resin θ, 7gC, 1, acid pull = ♂3 (C, 1,4t, ! to 3θ) /・-2g/
Codichloroethane/comml A solution of the above composition was spin-coated on a surface-hardened acrylic plate, and
After drying at C., a recording layer having a thickness of o and 4t .mu.m was obtained. wavelength 7
The reflectance and absorption at f Onm are respectively
and 59%.

In addition, the absorption rate at wavelength ≦ 30 nm is 73%.
and 60%. +mW on the irradiated surface of this recording medium
, When a signal was recorded at O, gMHz using a semiconductor laser beam with a beam diameter of 6 μm and a wavelength of 71 θ nm, θ,
Diameter /, 0 μm with 3 μs irradiation (/, rnJ/pit)
A pit was formed.

In addition, using a He-Ne laser for this recording medium, the beam diameter /, μm and the energy rmW on the recording surface are 4tMHz.
When the signal of 0.4tμsec was recorded (/, ≦n
J/pit), a pit of 0 μm was formed.

A storage test was conducted in the same manner as in Example 2, but there was no change in characteristics.

Example 9 A solution with the following composition was spin coated on a polycarbonate disk,
A subbing layer with a dry film thickness of 0.72 m was obtained.

Cellulose acetate butyrate 0. ♂g Acetone 32ml A liquid having the following composition containing Exemplified Compound (I-j) was spin-coated with Exemplified Compound (I-,,t) 0.9g polyvinyl formal 0.7g dichloromethane 70g to a thickness of 0. A recording layer with a dry film thickness of qμ was obtained. Furthermore, silver was vacuum-deposited to a thickness of 0.7 μm on top of this to create a recording medium, and the silver layers were placed facing each other, and spacers were placed in the center and around the disks to form two disk-shaped recording media. A recording medium was obtained by sandwiching and bonding the two.

On this, a semiconductor laser beam with a wavelength of 2rθnm and a beam diameter of 1 μm is applied to the irradiation surface from the polycarbonate plate side.
Irradiated with W for 0.7 μs (4t.

, tnJ/aec), a pit with a diameter of 0.9 μm was formed.

This recording medium was stored for one month under indoor light at ♂θ0C19θ, but there was almost no deterioration in the recording and reading characteristics.

Example 10 Exemplary compound (I-,?) 0.9g polyvinyl formal 0.7g dichloromethane/2ml A solution of the above composition was mixed with aluminum at θ, θ! A polycarbonate resin plate deposited to a thickness of .mu.m was spin coated to obtain a light absorption layer having a thickness of .theta. and .mu.m. The reflectance and absorption at wavelength 7 f Onm are /! Chi and Otsu! He was in charge. A semiconductor laser with a wavelength of 710 nm is used for this recording medium, and the irradiation surface energy is 6 m.
When a 2MH2 signal was recorded from the substrate side with W and beam diameter/μm, it was 0. ! With an irradiation time of μsec (3
,0 nJ/pit), a pit with a diameter of o and qpm was formed. Even after this recording medium was stored at gθQC1 humidity of 90% for several months, the recording characteristics and the reproduction characteristics of the recorded pits did not deteriorate.

Example // Nitrocellulose 0.41 g dichloromethane / θml A liquid with the above composition was spin-coated on an acrylic plate to form an undercoat layer, and exemplified compound (I-j) was vacuum-deposited on this to form a 0.2 μm thick layer. Got layers. A solution prepared by dissolving gelatin θ,jg in 10ml of water was applied to this by spinning to a thickness of θ,! A protective layer of μm was applied. 7 from the board side? A laser beam with a wavelength of θnm was irradiated in the same manner as in Example 2, and the irradiation time was 0952 seconds (ko, θnJ/p
It), a pit with a diameter of 0.9 μm was formed. This recording material was stored in room light at a temperature of 600 C and a humidity of 90 m for 7 evenings, but there was no change in its characteristics.

Example/2 Noanilino-3-methyl-t-N-cyclohexyl-
N-Methylaminofluorane
．． Three parts of the solution was dissolved in two parts of diimpropylnaphthalene to prepare a solution serving as a core material.

In addition, 72 parts of xylylene/diincyanate trimethylolpropane (J:/) adduct and 7 parts of methylene chloride
7 parts were added and dissolved.

Add this coloring agent solution to 3° polyvinyl alcohol! Department,
7.7 parts of gelatin and/or Q-di(hydroxyethoxy)benzene, 4 parts of water! It was added to an aqueous solution dissolved in 1 part male and emulsified and dispersed at a temperature of 1000 to obtain an emulsion with an average particle size of 3 μm.

700 parts of water was added to the emulsion, and the mixture was heated to 0°C while stirring, and after a period of time, a microcapsule liquid containing a color former, a color inhibitor, and an ultraviolet absorber in the core substance was obtained.

Separately, bisphenol A-! Part 0!
The mixture was added to 100 parts of an aqueous polyvinyl alcohol solution and dispersed in a sand mill for about 29 hours to obtain a bisphenol A dispersion having an average diameter of 3 μm.

One part of the obtained microcapsule liquid and three parts of the bisphenol A dispersion were mixed to prepare a coating liquid.

This coating solution was applied to the surface of smooth high-quality paper (50 g/m2) and dried for 30 minutes at a temperature of <10°C to provide a heat-sensitive recording layer with a dry weight of 7 g/m2.

In this way, thermosensitive recording sheet A containing microcapsules was produced.

Separately, a heat-sensitive recording sheet B to which the exemplified compound (I-//) was not added was prepared.

Next, thermal recording was performed using each of the obtained thermal recording sheets.

When the thermal recording sheet was loaded into a G mode thermal printer (Panafax 7.200, manufactured by Hitachi, Ltd.) and the thermal head was activated to record heat on the recording sheet, the following results were obtained on each thermal recording sheet. A clear black image was obtained.

Thermal recording sheet A Thermal recording sheet B (with exemplified compound) (Exemplary compound location) Color density /,, 23
/, θ9 Example/3 70 g of hexahydrophthalic acid, tetraglycidyl isocyanurate og, CX-22/ (manufactured by Chisso ■,
Product name) 30g1 imidazole θ.

l! Illustrated compound (I-j
A silicon diode for a photodetector of a camera was molded using the resin composition (A) obtained by dissolving the near-infrared absorbers θ, jg.

Set the silicon diode in the mold heated to about /-tO0C, and pour the resin composition (A) to a thickness of about 2 mm on the surface of the diode! After curing for minutes, the silicon diode molded with resin composition (A) is removed from the mold. It was further cured at 0°C for about 2 hours.

Example 4 was deposited on a transparent glass substrate with a thickness of θ, rmm, and the exemplified compound (I-
1) A composition liquid containing a thermosetting acrylic resin and dimethylformamide in a ratio of /, g:r:i (weight ratio: 81) is applied to form a near-infrared absorbing resin film with a thickness of 3 μm,
/! The infrared ray blocking layer was formed by heating and curing at θ0C for 20 minutes.

A 9 chromium nitride layer is formed on this infrared blocking layer by sputtering! 90 to a thickness, and then a chrome layer on top of it! It was deposited to a thickness of θOA. Next, AZ-itx! is applied on this chromium layer. After applying a θ resist (manufactured by Silapray, USA), it was exposed to light using a prescribed photomask, developed, and dried, and then the exposed chromium layer and chromium nitride layer were removed by etching with a cerium ammonium nitrate-based etching solution. . Thereafter, the resist layer is peeled off to form a photoshield layer having a predetermined pattern on the infrared blocking layer. This photo shield layer has a reflectance of 7 from the glass surface! The problem of flare disappears because it is less than

Next, a water-soluble photosensitive solution consisting of casein-ammonium dichromate is applied to a thickness of 0.2 μm on the infrared shielding layer with a photoshield layer, and after drying, a prescribed photomask is precisely aligned and adhered. The layer is exposed to light and developed with warm water to form a dyed layer having a predetermined pattern, and this dyed layer is dyed in a red dyeing bath to form an R colored layer. Next, after carrying out a predetermined resist dyeing treatment, a water-soluble photosensitive solution is applied to a film thickness of 0.2 μm using the same method as above, dried, exposed, developed, and then dyed with a green dyeing bath to form a predetermined pattern. A colored layer of G was formed, and a colored layer of C was formed. Furthermore, by the same method as the method for forming the second colored layer, three layers with a predetermined pattern were formed using a blue dyeing bath.
A colored layer of color B was formed. In this way, a color separation filter layer consisting of R, G, and H colored layers having a predetermined pattern is obtained. Thereafter, an acrylic resin was applied to a thickness of 7 μm on one layer of this color separation filter to form a security film. The chip size of the color separation filter was set to be the size of the photosensitive area of the solid-state image sensor.

This color separation filter had an excellent ability to block long wavelength light of 700 nm or more.

The compositions of the R, G, and H dye baths used above are as follows.

Red dyeing bath Kayanol Milling Red R8 (manufactured by Nippon Kapaku Co., Ltd.) 7 parts acetic acid
6 parts water
100 parts green dye bath Brilliant India Blue (manufactured by Hoechst) 7 parts Suminol Yellow MR (manufactured by Sumitomo Chemical) 7 parts acetic acid
3 parts water
/θO part Blue dyeing bath Kayanol cyanine 6B (manufactured by Nippon Kapaku Co., Ltd.) 7 parts acetic acid
3 parts water
/θO section

[Brief explanation of drawings]

FIG. 1 shows the optical filter obtained in Example/
Further, FIG. 2 shows the relationship between wavelength and transmittance of the optical filter obtained in Example 2. Patent applicant: Fuji Photo Film Co., Ltd. Figure 1 Wavelength (nm) Figure 2 Large mourning (nm) Procedural amendment February 1988 Per Nisshin

Claims (1)

[Claims] A compound represented by the following general formula (I) and having a maximum absorption wavelength of 72
A near-infrared absorbing composition comprising at least one compound having a wavelength of 0 nm or more. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ^2 and R^5 may be the same or different from each other and represent a hydrogen atom or a group capable of substituting it; R^3 and R^4 may be the same or different from each other and represent a hydrogen atom, Represents a halogen atom, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkyl group, R^6 and R^7 may be the same or different from each other, and represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, An unsubstituted aryl group, acyl group, sulfonyl group, or R^6 and R^7 connected to each other to form a 5- or 6-membered
Represents a group of nonmetallic atoms necessary to form a membered ring. However, R^3 and R^4 are never hydrogen atoms at the same time.