WO2008026786A1 - Salt for near infrared ray absorbing composition and near infrared ray absorbing pressure sensitive adhesive composition - Google Patents

Salt for near infrared ray absorbing composition and near infrared ray absorbing pressure sensitive adhesive composition Download PDF

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Publication number
WO2008026786A1
WO2008026786A1 PCT/JP2007/067544 JP2007067544W WO2008026786A1 WO 2008026786 A1 WO2008026786 A1 WO 2008026786A1 JP 2007067544 W JP2007067544 W JP 2007067544W WO 2008026786 A1 WO2008026786 A1 WO 2008026786A1
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Prior art keywords
group
near infrared
infrared ray
ray absorbing
sensitive adhesive
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PCT/JP2007/067544
Other languages
French (fr)
Inventor
Nobuhiro Kobayashi
Takako Harigae
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Nippon Shokubai Co., Ltd.
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Priority to JP2009506854A priority Critical patent/JP2010502563A/en
Publication of WO2008026786A1 publication Critical patent/WO2008026786A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • C09B53/00—Quinone imides
    • C09B53/02—Indamines; Indophenols
    • 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
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the present invention concerning a salt relates to a salt for a near infrared ray absorbing composition, a near infrared ray absorbing composition including the salt, a near infrared ray absorbent material including the near infrared ray absorbing composition, an optical filter for thin displays in which the near infrared ray absorbing composition and a near infrared ray absorbent material are used.
  • the present invention concerning a salt relates to a salt capable of improving durability of a near infrared ray absorbing dye, a near infrared ray absorbing composition including the salt and being excellent in transparency in the visible region and durability, an near infrared ray absorbent material comprising the near infrared ray absorbing composition , an optical filter for optical semiconductor elements in which the near infrared ray absorbing composition or the near infrared ray absorbent material is used, an optical filter for thin displays in which the near infrared ray absorbing composition or the near infrared ray absorbent material is used, and the like.
  • the present invention concerning a pressure sensitive adhesive composition relates to a near infrared ray absorbing pressure sensitive adhesive composition, a near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition, an optical filter for thin displays in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used.
  • the present invention concerning a pressure sensitive adhesive composition relates to a near infrared ray absorbing pressure sensitive adhesive composition that is excellent in transparency in the visible region and persistence of the infrared ray absorptivity, a near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition, an optical filter for optical semiconductor elements in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used, an optical filter for thin displays in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used, and the like.
  • a near infrared ray absorbing pressure sensitive adhesive composition that is excellent in transparency in the visible region and persistence of the infrared ray absorptivity
  • a near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition
  • an optical filter for optical semiconductor elements in which the near infrared ray
  • Thin displays generate a near infrared ray at a wavelength of 800 nm to 1100 nm.
  • This near infrared ray causes problems of production of improper operating signals on remote-control devices for home electric appliances.
  • optical semiconductor elements used in CCD cameras and the like are also highly sensitive to the near infrared ray region, the near infrared ray must be eliminated.
  • near infrared ray absorbing materials having high absorptivity of the near infrared ray, and having high transparency in the visible region have been demanded.
  • the near infrared ray absorbing dye that absorbs the near infrared ray cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles have been conventionally used.
  • diimonium dyes have been in heavy usage because of high absorptivity of the near infrared ray, and high transparency in the visible light region (for example, see Japanese Unexamined Patent Application Publication No. 2003-96040 and Japanese Unexamined Patent Application Publication No. 2000-80071) .
  • an optical filter for plasma displays is generally produced by laminating a near infrared ray absorbing film, an electromagnetic wave shielding film and an antireflection film on a glass or a shock absorber that serves as a supporting substrate.
  • Such optical filter for plasma displays is mounted on the front face side of the PDP. In some cases, this optical filter for plasma displays is directly bonded on the glass or the shock absorber as a supporting substrate using an adhesive or a pressure sensitive adhesive.
  • near infrared ray absorbing dyes such as diimonium dyes
  • diimonium dyes may be inferior in durability, whereby deterioration of near infrared ray absorption ability and coloring may cause a significant problem when it is used in applications such as displays and optical semiconductor elements.
  • Such deterioration is believed to be caused by alteration of the dye by a variety of factor s such as heat, moisture, light and the like. Accordingly, improvement of durability of near infrared ray absorbing dyes have been conventionally attempted, however, satisfactory effect has not been achieved yet .
  • an object of the present invention concerning a salt is to provide a salt which can be suitably used in a near infrared ray absorbing composition that permits improvement of durability of near infrared ray absorbing dyes, particularly improvement of heat resistance and resistance to moist heat.
  • Other object of the present invention concerning a salt is to provide a near infrared ray absorbing composition that is excellent in transparency in the visible region and durability.
  • An object of the present invention concerning a salt is to provide a near infrared ray absorbing composition that has high transparency in the visible region and long persistence of the near infrared ray absorptivity, and is excellent in durability irrespective of the resin shape.
  • an object of the present invention concerning a salt is to provide a near infrared ray absorbent material, an optical filter for optical semiconductor elements, an optical filter for thin displays, and thin displays in which the composition is used.
  • some diimonium dyes may be inferior in durability, and lowering of absorptivity of the near infrared ray and coloring may cause a significant problem when it is used in applications such as optical semiconductor elements and displays.
  • the dyes are seriously deteriorated in a resin having a low glass transition point (Tg) such as a pressure sensitive adhesive resin. Therefore, a pressure sensitive adhesive containing a diimonium dye that can be satisfactorily subjected to practical applications has not been obtained yet .
  • Tg glass transition point
  • Japanese Unexamined Patent Application Publication No. 2005-325292 discloses a diimonium dye having improved durability by introducing a halogen atom to an alkyl group of a diimonium cation. Improvement of durability is surely found according to the near infrared ray shielding filter in which this diimonium dye and a binder resin having high Tg are used, as compared with the case of conventional diimonium dyes. However, combination with the pressure sensitive adhesive resin having low Tg that exhibits serious deterioration achieves insufficient durability.
  • an object of the present invention concerning a pressure sensitive adhesive composition is to provide a near infrared ray absorbing pressure sensitive adhesive composition that is useful in production of a near infrared ray absorbent material having high transparency in the visible region and long persistence of the near infrared ray absorptivity.
  • an object of the present invention concerning a pressure sensitive adhesive composition is to provide a near infrared ray absorbent material, an optical filter for optical semiconductor elements, an optical filter for thin displays, and a thin display in which the composition is used.
  • the inventors of the present invention concerning a salt elaborately investigated improvement of durability of a near infrared ray absorbing dye, particularly a near infrared ray absorbing composition for use in optical filters, and consequently found that a salt having a certain structure improves durability, particularly heat resistance and resistance to moist heat, of a near infrared ray absorbing dye, and that a near infrared ray absorbing composition including such a salt is excellent in transparency in the visible region and durability
  • the present invention concerning a salt was accomplished. [0017] Accordingly, the aforementioned object is achieved by adding a salt for a near infrared ray absorbing composition having an anion represented by the following formula (1) , formula (2) , formula (3) or formula (4) but not substantially having near infrared ray absorptivity per se.
  • R a , R b and R g each represent a fluoroalkyl group which may be the same or different; in the formula (2) , R c represents a fluoroalkylene group; and in the formula (4), m represents an integer of from 1 to 6.
  • the aforementioned other object is achieved by a near infrared ray absorbing composition including the salt of the present invention and a near infrared ray absorbing dye.
  • the aforementioned further object is achieved by an optical filter for thin displays and a filter for optical semiconductor elements in which the near infrared ray absorbent material of the present invention is used, and by a thin display and an optical semiconductor element in which any of these filters is used.
  • the inventors of the present invention concerning a pressure sensitive adhesive composition elaborately investigated combinations of a diimonium dye and a resin. Consequently, it was found that when a diimonium dye having a specific maximum absorption wavelength is combined with a res ' in having a specific calculated glass transition temperature, a near infrared ray absorbing pressure sensitive adhesive composition that is excellent in durability of the dye can be obtained. Additionally, particular definition of the acid value of the resin can still further improve the durability of the dye.
  • the aforementioned object is achieved by a near infrared ray absorbing pressure sensitive adhesive composition containing a diimonium dye having a maximum absorption wavelength in the acetone solution of 1000 to 1060 ran, and a resin having a calculated glass transition temperature of -20 °C or lower.
  • a near infrared ray absorbing pressure sensitive adhesive composition containing a diimonium dye having a maximum absorption wavelength in the acetone solution of 1000 to 1060 ran, and a resin having a calculated glass transition temperature of -20 °C or lower.
  • the salt of the present invention improves durability, particularly heat resistance and resistance to moist heat, of near infrared ray absorbing dyes. Additionally, the salt of the present invention does not deteriorate the transparency in the visible region, it can be suitably used in near infrared ray absorbing materials including a variety of dyes such as diimonium dyes, typically, which have conventionally raised problems. [0028]
  • the optical filter in which the near infrared ray absorbing composition containing the salt of the present invention is applied to thin displays and optical semiconductor elements, appearance of displays and optical semiconductor elements can be improved because absorptivity of the near infrared ray and transparency in the visible light region are maintained for a long period of time.
  • the near infrared ray absorbing material in which the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is used results in maintenance of near infrared ray absorptivity of the dye for a long period of time.
  • this near infrared ray absorbing pressure sensitive adhesive composition in production of an optical filter for optical semiconductor elements and thin displays enables thinning of the optical filter, and simplification of production step of the optical filter.
  • Fig. 1 shows a visible-near infrared ray absorption spectrum of a test sample according to Example 2 before and after a heat resistance test.
  • Fig. 2 shows a visible-near infrared ray absorption spectrum of a test sample according to Example 2 before and after a heat resistance test.
  • Fig. 2 shows a visible-near infrared ray absorption spectrum of a test sample according to Example 6 before and after a heat resistance test.
  • Fig. 3 shows a visible-near infrared ray absorption spectrum of a test sample according to Comparative Example 3 before and after a heat resistance test.
  • Fig. 4 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 9.
  • Fig. 5 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 25.
  • FIG. 6 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Comparative Example 4.
  • FIG. 7 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Comparative Example 4.
  • Fig. 7 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 27. [Best Mode for Carrying Out the Invention] [0031]
  • the present invention concerning a salt will be explained in the following item numbers of from 1-1 to 1-8.
  • the present invention concerning a pressure sensitive adhesive composition will be explained in the following item numbers of from 2-1 to 2-6.
  • An aspect of the present invention concerning a salt for a near infrared ray absorbing composition is directed to a salt for a near infrared ray absorbing composition having an anion represented by the following formula (1), formula (2), formula (3) or formula (4) but not substantially having near infrared ray absorptivity per se.
  • R a , R b and R 9 each represent a fluoroalkyl group which may be the same or different; in the formula (2) , R c represents a fluoroalkylene group; and in the formula (4) ; and m represents an integer of from 1 to 6.
  • R 1 is not limited. R 1 may be any atom or any atomic group. Addition of this salt can improve durability of near infrared ray absorbing dyes.
  • the phrase "not substantially having near infrared ray absorptivity" means that transmittance determined by the following determination method (A) is equal to or greater than 80% in any wavelength of from 800 nm to 1100 ran.
  • the determination method (A) is as in the followings.
  • Determination method (A) The salt or ion to be subjected to the determination is dissolved in methyl ethyl ketone such that the solid content of the salt becomes 0.1% by weight, and absorbance of this solution is measured.
  • UV-3600 Shiadzu Corporation
  • a quartz measurement cell having an optical path length of 10 mm is used.
  • R a and R b each represent a fluoroalkyl group which may be the same or different.
  • R 9 represents a fluoroalkyl group.
  • R a , R b and R g the number of fluorine atoms and the number of carbon atoms are not particularly limited.
  • examples of preferable R a and R b include perfluoroalkyl groups having 1 to 10 carbon atoms.
  • the anion represented by the formula (1) includes the anion in which R a and R b are the same, and the anion in which R a and R b are different.
  • R a and R b are the same include bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (heptafluoropropylsulfonyl) imide and bis (nonafluorobutanesulfonyl) imide.
  • R a and R b are different include pentafluoroethanesulfonyltrifluoromethanesulfonyl imide, trifluoromethanesulfonylheptafluoropropanesulfonyl imide, nonafluorobutanesulfonyltrifluoromethanesulfonyl imide, and the like.
  • R g S ⁇ 3 ⁇ represented by the formula (3) include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropylsulfonic acid, nonafluorobutanesulfonic acid, and the like.
  • bis (trifluoromethanesulfonyl) imide in which R a and R b are the same is preferred in the formula (1)
  • trifluoromethanesulfonic acid is preferred in the formula (3) .
  • R c in the formula (2) is a fluoroalkylene group.
  • R c includes a perfluoroalkylene group having 2 to 10 carbon atoms.
  • R c is more preferably a perfluoroalkylene group having 2 to 8 carbon atoms, and more preferably a perfluoroalkylene group having 3 carbon atoms.
  • As the perfluoroalkylene group having 3 carbon atoms 1, 3-disulfonylhexafluoropropylene imide is exemplified. [0043]
  • R 1 is preferably selected from the group consisting of phosphorus, antimony, arsenic, boron and tin.
  • R 1 F m includes one, or two or more anions selected from the group consisting of hexafluoroantimonate anion, hexafluorophosphate anion, hexafluorostannate anion, tetrafluoroborate anion and hexafluoroarsenate anion.
  • the salt including the anion represented by the formulae (1) to (4) is a salt comprising the anion represented by the above formulae (1) to (4), and a cation not substantially having near infrared ray absorptivity.
  • Examples of the salt including the anion represented by the above formulae (1) to (4) which can be used according to the present invention include alkali metal salts, alkaline earth metal salts, transition metal salts, ammonium salts, pyridinium salts, imidazolium salts, pyrrolidinium salts, quinolinium salts, carbenium salts, phosphonium salts, iodonium salts and the like of the anion described above.
  • Exemplary alkali metal salts include salts of lithium, sodium, potassium, rubidium, cesium or the like.
  • Exemplary alkaline earth metal salts include salts of beryllium, magnesium, calcium, strontium, barium or the like.
  • Exemplary transition metal salts include salts of silver, copper or the like.
  • Exemplary ammonium salts include salts of ammonium, n-butylammonium, dimethylammonium, trimethylammonium, triethylammonium, triisopropylammonium, tri-n-butylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, N,N-dimethylcyclohexylammonium or the like.
  • Exemplary anilinium salts include salts of N-methylanilinium, N, N-dimethylanilinium,
  • pyridinium salts include salts of pyridinium, N-methylpyridinium, N-butylpyridinium,
  • Exemplary imidazolium salts include salts of imidazolium, 1-methyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, l-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, l-methyl-3-octylimidazolium, 1-methyl-N-benzylimidazolium, l-methyl-3- (3-phenylpropyl) imidazolium, l-butyl-2, 3-dimethylimidazolium, l-ethyl-2, 3-dimethylimidazolium or the like.
  • Exemplary pyrrolidinium salts include salts of 1-ethyl-l-methyl-pyrrolidinium,
  • Exemplary quinolinium salts include salts of quinolinium, isoquinolinium or the like.
  • Exemplary carbenium salts include salts of triphenylcarbenium, tri-4-methoxyphenyl carbenium or the like.
  • Exemplary phosphonium salts include salts of dimethylphenylphosphonium, triphenylphosphonium, tetraethylphosphonium, tetraphenylphosphonium or the like.
  • Exemplary sulfonium salts include salts of trimethylsulfonium, triphenylsulfonium or the like.
  • Exemplary iodonium salts include salts of diphenyliodonium, di-4-methoxyphenyliodonium or the like.
  • alkali metal salts particularly preferred salts are alkali metal salts.
  • Particularly preferred cations are alkali metal cations .
  • Preferable alkali metals as the cation include lithium, sodium, potassium, rubidium, cesium and the like.
  • the salt of the present invention can improve durability, particularly heat resistance and resistance to moist heat of the near infrared ray absorbing composition including the near infrared ray absorbing dye. Therefore, another aspect of the present invention relates to a near infrared ray absorbing composition including the salt of the present invention and a near infrared ray absorbing dye. Since the salt of the present invention can improve durability, particularly heat resistance and resistance to moist heat of the near infrared ray absorbing dye or the near infrared ray absorbing composition as described above, the near infrared ray absorbing composition of the present invention can exhibit excellent durability, particularly heat resistance and resistance to moist heat.
  • the near infrared ray absorbing composition of the present invention is also excellent in transparency in the visible region.
  • the near infrared ray absorbing dye which can be used in the near infrared ray absorbing composition is not particularly limited, and for example, cyanine, polymethine, squarylium, porphyrin, dithiol metal complexes, phthalocyanine, diimonium near infrared ray absorbing dyes and the like may be exemplified.
  • the aforementioned diimonium dye preferred in the present invention is a salt of a cation represented by the following formula (5) , and a counter anion.
  • R 1 to R 8 each independently represent, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms and having a substituent.
  • halogen atom constituting R 1 to R 8 examples include e.g., a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the alkyl group having 1 to 10 carbon atoms constituting R 1 to R 8 include linear, branched or alicyclic alkyl groups, and the like. Specific examples include e.g., a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a 1, 1-dimethylpropyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, and the like.
  • examples of the substituent which can bind to the alkyl group having 1 to 10 carbon atoms which may have a substituent include a cyano group; a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a n-propoxy group and a n-butoxy group; alkoxyalkoxy groups having 2 to 8 carbon atoms such a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group, a methoxybutoxy group and an ethoxybutoxy group; alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group
  • R 1 to R 8 include a trifluoromethyl group, a 2, 2, 2-trifluoroethyl group, a 3, 3, 3, -trifluoropropyl group, a 4, 4, 4-trifluorobutyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and the like.
  • R 1 to R 8 may be the same or different, but preferably all of them are the same.
  • the counter anion of the diimonium dye is not particularly limited, and a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a nitrate ion, a benzenesulfonate ion, a P-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, a propylsulfate ion, a tetrafluoroborate ion, a tetraphenylborate ion, a tetrakis (pentafluorophenyl) borate ion, a bis (trifluoromethanesulfonyl) imide ion, a bis (pentafluoroethanesulfonyl) imide ion, a pentafluoroethanesulfon
  • the diimonium cation is a bivalent cation as represented by the above formula (5). Therefore, for example, when a monovalent anion such as a chloride ion is used, in the diimonium dye according to the present invention, two anions are bound to one diimonium cation.
  • the counter anion of the diimonium dye is preferably an anion represented by the following formulae (6) to (9).
  • R d and R e in the above formula (6) the number of fluorine atoms and the number of carbon atoms are not particularly limited. Examples of preferable R d and R e include perfluoroalkyl groups having 1 to 10 carbon atoms .
  • the anion represented by the formula (6) includes the anion in which R d and R e are the same, and the anion in which R d and R e are different.
  • R d and R e are the same include bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (heptafluoropropylsulfonyl) imide and bis (nonafluorobutanesulfonyl) imide.
  • R d and R e are different include pentafluoroethanesulfonyltrifluoromethanesulfonyl imide, trifluoromethanesulfonylheptafluoropropanesulfonyl imide, nonafluorobutanesulfonyltrifluoromethanesulfonyl imide, and the like.
  • R f in the above formula (7) is a fluoroalkylene group.
  • R f examples include perfluoroalkylene groups having 2 to 10 carbon atoms.
  • R f is more preferably a perfluoroalkylene group having 2 to 8 carbon atoms, and more preferably a perfluoroalkylene group having 3 carbon atoms.
  • As the perfluoroalkylene group having 3 carbon atoms 1, 3-disulfonylhexafluoropropyleneimide is exemplified. [0063]
  • R ⁇ SO 3 ⁇ represented by the above formula (8) include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropylsulfonic acid, nonafluorobutanesulfonic acid and the like.
  • R k in R k F n ⁇ represented by the above formula (9) is selected from the group consisting of phosphorus, antimony, arsenic, boron and tin.
  • more preferred R k F n ⁇ is one, or two or more anions selected from the group consisting of a hexafluoroantimonate anion, a hexafluorophosphate anion, a hexafluorostannate anion, a tetrafluoroborate anion and a hexafluoroarsenate anion.
  • preferred anions are a hexafluoroantimonate ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a bis (trifluoromethanesulfonyl) imide ion, a tetrakis (pentafluorophenyl) borate ion, and a 1, 3-disulfonylhexafluoropropyleneimide ion.
  • the diimonium dye particularly preferably used in the present invention concerning a salt is a diimonium dye having a maximum absorption wavelength ⁇ in the acetone solution of 1000 nm or greater and 1060 nm or less. More preferably, this maximum absorption wavelength ⁇ is 1010 nm or greater and 1055 nm or less, and more preferably 1020 nm or greater and 1050 nm or less. Such a diimonium dye is excellent in transparency in the visible region and persistence of the near infrared ray absorptivity. [0067]
  • Illustrative examples of the compound of the diimonium dye include bishexafluoroantimonate-N,N,N' ,N' -tetrakis ⁇ p-di (4,4, 4-triflu orobutyl) aminophenyl ⁇ -p-phenylenediimonium (1048 nm) , bishexafluoroantimonate-N, N, N' , N' -tetrakis ⁇ p-di (2,2, 2-trifIu oroethyl) aminophenyl ⁇ -p-phenylenediimonium (1020 nm) , bishexafluoroantimonate-N, N, N' , N' -tetrakis ⁇ p-di (perfluorobut yl) aminophenyl ⁇ -p-phenylenedii
  • CIR-1085F As a specific manufactured article of the diimonium dye, CIR-1085F (manufactured by Japan Carlit Co., Ltd.) is exemplified. This CIR-1085F has a maximum absorption wavelength in the acetone solution of 1049 nm.
  • the maximum absorption wavelength in the acetone solution is determined as follows.
  • the diimonium dye to be determined is dissolved in a certain volume of acetone, and after verifying the absence of undissolved matter, the absorbance is measured.
  • UV-1600 Shiadzu Corporation
  • a quartz measurement cell having an optical path length of 10 mm is used.
  • the dye other than the diimonium dye examples include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particle and the like.
  • the near infrared ray absorbing composition of present invention concerning a salt is used as an optical filter for thin displays
  • a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm, a cyanine dye having a maximum absorption wavelength of 800 to 950 nm, or a dithiol metal complex dye having a maximum absorption wavelength of 800 to 950 nm be used in combination with the diimonium dye described above.
  • This use in combination enables effective absorption of a near infrared ray of 800 to 1100 ran.
  • use of a phthalocyanine dye in combination is particularly preferred.
  • the phthalocyanine-based compound which can be used in the present invention concerning a salt is preferably excellent in near infrared ray absorptivity, and known phthalocyanine-based compound can be used.
  • Exemplary preferable phthalocyanine-based compound includes the compounds represented by the following formula (X) , or the compounds represented by the following formula (Y) .
  • a 1 to A 16 represent a functional group.
  • a 1 to A 16 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, an alkylthio group having 1 to 20 carbon atoms which may be substituted, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 1 to 20 carbon atoms which may be substituted,
  • the functional groups A 1 to A 16 may be of the same type or the different type, and may be the same or different in the case of the same type.
  • the functional groups may be linked via a linking group.
  • M 1 represents two hydrogen atoms, a bivalent metal atom, a trivalent substituted metal atom, a quadrivalent substituted metal atom, or an oxy metal.
  • acyl group is similarly defined to the definition described in Dictionary of Scientific and Technical Terms, 3rd Edition, Published by THE NIKKAN KOGYO SHIMBUN, LTD., p. 17.
  • the "acyl group” is a group derived from an organic acid by deleting a hydroxyl group, and is a group represented by the formula: RCO- (wherein R is an aliphatic group, an alicyclic group or aromatic group) .
  • examples of the halogen atom in the functional groups A 1 to A 16 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n-heptyl group, a n-octyl group, a 2-ethylhexyl group and the like, but not limited thereto.
  • alkoxy group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkoxy groups such as a methoxy group, an ethoxy group, a n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, and the like, but not limited thereto.
  • Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group, a naphthyl group, and the like, but not limited thereto.
  • Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted include a phenoxy group, a naphthoxy group, and the like, but not limited thereto.
  • Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group, a diphenylmethyl group, and the like, but not limited thereto.
  • aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group, and the like, but not limited thereto.
  • alkylthio group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylthio groups such as a methylthio group, an ethylthio group, a n-propylthio group, an iso-propylthio group, a n-butylthio group, an iso-butylthio group, a sec-butylthio group, a t-butylthio group, a n-pentylthio group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a n-octylthio group, a 2-ethylhexylthio group, and the like, but not limited thereto.
  • Examples of the arylthio group having 6 to 20 carbon atoms which may be substituted include a phenylthio group, a naphthylthio group, and the like, but not limited thereto.
  • Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but not limited thereto.
  • alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an iso-propylsulfonyl group, a n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a t-butylsulfonyl group, a n-pentylsulfonyl group, a n-hexylsulfonyl group, a cyclohexylsulfonyl group, a n-heptylsulfonyl group, a n-octylsulfonyl group, a methyl
  • Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group, a naphthylsulfonyl group, and the like, but not limited thereto.
  • Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but not limited thereto.
  • acyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylcarbonyl groups such as a methylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a n-octylcarbonyl group and a 2-ethylhexylcarbonyl group, arylcarbonyl groups such as a benzylcarbonyl group and a phenylcarbonyl group, aral alky
  • alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propyloxy carbonyl group, an iso-propyloxy carbonyl group, a n-butyloxy carbonyl group, an iso-butyloxy carbonyl group, a sec-butyloxy carbonyl group, a t-butyloxy carbonyl group, a n-pentyloxy carbonyl group, a n-hexyloxy carbonyl group, a cyclohexyloxy carbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, a 2-ethylhexyloxy carbonyl group, and the like, but not limited thereto.
  • Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include a phenoxy carbonyl, a naphthylcarbonyl group, and the like, but not limited thereto.
  • Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, a diphenylmethyloxycarbonyl group, and the like, but not limited thereto.
  • alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted include an acetyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, a n-butylcarbonyloxy group, an iso-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a t-butylcarbonyloxy group, a n-pentylcarbonyloxy group, a n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, a n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, a n-octylcarbonyloxy group, and the like, but not limited thereto.
  • Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include a benzoyloxy group, and the like, but not limited thereto.
  • Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include a benzylcarbonyloxy group, and the like, but not limited thereto.
  • Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted include a pyrrole group, an imidazole group, a piperidine group, a morpholine group, and the like, but not limited thereto.
  • substituents may be present in a plural number. When there are a plural number of the substituents, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group.
  • examples of the candidate substituent in the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted of the functional groups A 1 to A 16 include a hydrogen atom; linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a sec-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group and a cyclohexyl group; aryl groups such as a phenyl group and a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; linear, branched or cyclic alkylcarbonyl groups such
  • substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2. When there are two substituents, each may be of the same type or the different type, and may be the same or different in the case of the same type. Also, when there are two substituents, the substituents may be linked via a linking group. [0079]
  • Examples of the substituent which may be further present in the alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl group, or aralkylcarbonyl group that is the candidate substituent of the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted include e.g.
  • a halogen atom an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, a cyano group, and a heterocyclic group, but not limited thereto.
  • substituents may be present in a plural number. When there are a plural number of the substituent, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group. [ 0080 ]
  • examples of the bivalent metal as the metal M 1 include Cu(II), Co(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Ti(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Pb(II), Sn(II), and the like, but not limited thereto.
  • Examples of the trivalent substituted metal atom include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5 , Al-C 6 H 4 (CH 3 ), In-C 6 H 5 , In-C 6 H 4 (CH 3 ), In-C 6 H 5 , Mn(OH), Mn(OC 6 H 5 ), Mn [OSi (CH 3 ) 3 ] , Ru-Cl, and the like, but not limited thereto.
  • Examples of the quadrivalent substituted metal atom include CrCl 2 , SiF 2 , SiCl 2 , SiBr 2 , SiI 2 , ZrCl 2 , GeF 2 , GeCl 2 , GeBr 2 , GeI 2 , SnF 2 , SnCl 2 , SnBr 2 , TiF 2 , TiCl 2 , TiBr 2 , Ge(OH) 2 , Mn(OH) 2 , Si(OH) 2 , Sn(OH) 2 , Zr(OH) 2 , Cr(R 1 ),, Ge(R 1 J 2 , Si(R 1 J 2 , Sn(R 1 J 2 , Ti(Ri) 2 (R 1 represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof ⁇ , Cr(OR 2 J 2 , Ge (OR 2 ) 2 , Si(OR 2 J 2 , Sn(OR 2 J 2 , Ti(OR 2 J
  • B 1 to B 24 represent a functional group.
  • B 1 to B 24 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, an alkylthio group having 1 to 20 carbon atoms which may be substituted, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms having 7 to 20 carbon
  • the functional groups B 1 to B 24 may be of the same type or the different type, and may be the same or different in the case of the same type.
  • the functional groups may be linked via a linking group.
  • M 2 represents two hydrogen atoms, a bivalent metal atom, a trivalent substituted metal atom, a quadrivalent substituted metal atom or an oxy metal.
  • examples of the halogen atom in the functional groups B 1 to B 24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n-heptyl group, a n-octyl group, a 2-ethylhexyl group and the like, but not limited thereto.
  • alkoxy group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkoxy groups such as a methoxy group, an ethoxy group, a n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, and the like, but not limited thereto.
  • Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group, a naphthyl group, and the like, but not limited thereto.
  • Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted include a phenoxy group, a naphthoxy group, and the like, but not limited thereto.
  • Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group, a diphenylmethyl group, and the like, but not limited thereto.
  • aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group, and the like, but not limited thereto.
  • alkylthio group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylthio groups such as a methylthio group, an ethylthio group, a n-propylthio group, an iso-propylthio group, a n-butylthio group, an iso-butylthio group, a sec-butylthio group, a t-butylthio group, a n-pentylthio group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a n-octylthio group, a 2-ethylhexylthio group, and the like, but not limited thereto.
  • Examples of the arylthio group having 6 to 20 carbon atoms which may be substituted include a phenylthio group, a naphthylthio group, and the like, but not limited thereto.
  • Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but not limited thereto.
  • alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an iso-propylsulfonyl group, a n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a t-butylsulfonyl group, a n-pentylsulfonyl group, a n-hexylsulfonyl group, a cyclohexylsulfonyl group, a n-heptylsulfonyl group, a n-octylsulfonyl group, a methyl
  • Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group, a naphthylsulfonyl group, and the like, but not limited thereto.
  • Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but not limited thereto.
  • acyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylcarbonyl groups such as a methylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a n-octylcarbonyl group and a 2-ethylhexylcarbonyl group, arylcarbonyl groups such as a benzylcarbonyl group and a phenylcarbonyl group, aral alky
  • alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propyloxy carbonyl group, an iso-propyloxy carbonyl group, a n-butyloxy carbonyl group, an iso-butyloxy carbonyl group, a sec-butyloxy carbonyl group, a t-butyloxy carbonyl group, a n-pentyloxy carbonyl group, a n-hexyloxy carbonyl group, a cyclohexyloxy carbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, a 2-ethylhexyloxy carbonyl group, and the like, but not limited thereto.
  • Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include a phenoxy carbonyl, a naphthylcarbonyl group, and the like, but not limited thereto.
  • Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, a diphenylmethyloxycarbonyl group, and the like, but not limited thereto.
  • alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted include an acetyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, a n-butylcarbonyloxy group, an iso-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a t-butylcarbonyloxy group, a n-pentylcarbonyloxy group, a n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, a n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, a n-octylcarbonyloxy group, and the like, but not limited thereto.
  • Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include a benzoyloxy group, and the like, but not limited thereto.
  • Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include a benzylcarbonyloxy group, and the like, but not limited thereto.
  • Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted include a pyrrole group, an imidazole group, a piperidine group, a morpholine group, and the like, but not limited thereto.
  • substituents may be present in a plural number. When there are a plural number of the substituents, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group.
  • examples of the candidate substituent in the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted of the functional groups B 1 to B 24 include a hydrogen atom; linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a sec-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group and a cyclohexyl group; aryl groups such as a phenyl group and a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; linear, branched or cyclic alkylcarbonyl groups such as an acetyl group, an ethylcarbonyl
  • substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2. When there are two substituents, each may be of the same type or the different type, and may be the same or different in the case of the same type. Also, when there are two substituents, the substituents may be linked via a linking group. [0086]
  • Examples of the substituent which may be further present in the alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl group, or aralkylcarbonyl group that is the candidate substituent of the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted include e.g., a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group
  • substituents may be present in a plural number. When there are a plural number of the substituent, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group. [0087]
  • examples of the bivalent metal as the metal M 2 include Cu(II), Co(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Ti(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Pb(II), Sn(II), and the like, but not limited thereto.
  • Examples of the trivalent substituted metal atom include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5 , Al-C 6 H 4 (CH 3 ), In-C 6 H 5 , In-C 6 H 4 (CH 3 ), In-C 6 H 5 , Mn(OH), Mn(OC 6 H 5 ), Mn [OSi (CH 3 ) 3 ] , Ru-Cl, and the like, but not limited thereto.
  • Examples of the quadrivalent substituted metal atom include CrCl 2 , SiF 2 , SiCl 2 , SiBr 2 , SiI 2 , ZrCl 2 , GeF 2 , GeCl 2 , GeBr 2 , GeI 2 , SnF 2 , SnCl 2 , SnBr 2 , TiF 2 , TiCl 2 , TiBr 2 , Ge(OH) 2 , Mn(OH) 2 , Si(OH) 2 , Sn(OH) 2 , Zr(OH) 2 , Cr(Ri) 2 , Ge(R 1 J 2 , Si(Ri) 2 , Sn(Ri) 2 , Ti(Ri) 2 ⁇ Ri represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof ⁇ , Cr (OR 2 ) 2 , Ge (OR 2 ) 2 , Si (OR 2 ) 2 , Sn (OR 2 ) 2 ,
  • a cyanine dye may be used as the near infrared ray absorbing dye in the near infrared ray absorbing composition of the present invention.
  • the cyanine dye is not particularly limited as long as it is excellent in the near infrared ray absorptivity, and a salt including an indolium cation or a benzothiazolium cation, and a counter anion can be preferably used.
  • a cation represented by the following formulae (a) to (i) can preferably used, but not limited thereto.
  • the counter anion of the indolium cation or the benzothiazolium cation is not particularly limited, and a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a nitrate ion, a benzenesulfonate ion, a P-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, a propylsulfate ion, a tetrafluoroborate ion, a tetraphenylborate ion, a hexafluorophosphate ion, a benzenesulfinate ion, an acetate ion, a trifluoroacetate ion, a propionate ion, a benzoate ion, an oxalate ion
  • commercially available products include: as the cyanine dye including a cation represented by the above general formula (a) , ADS812MI (counter anion being an iodide ion) manufactured by American Dye Source, Inc.; as the cyanine dye including a cation represented by the above general formula (b) , S0712 manufactured by FEW Chemicals GmbH (counter anion being a hexafluorophosphate ion) ; as the cyanine dye including a cation represented by the above general formula (c) , S0726 manufactured by FEW Chemicals GmbH (counter anion being a chloride ion) ; as the cyanine dye including a cation represented by the above general formula (d) , ADS780MT manufactured by American Dye Source, Inc.
  • the near infrared ray absorbing composition of the present invention may further include a resin.
  • the resin which may be used in the present invention is not particularly limited as long as it is one which can be generally used in optical materials, but its transparency is preferably as high as possible. More specifically, examples of preferable resin include polyolefin-based resins such as polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin and cycloolefin polymers, vinyl-based polymers such as polystyrene, acrylate ester-based polymers, methacrylate ester-based polymers, vinyl acetate-based polymers, halogenated vinyl-based polymers and polyvinyl alcohol, polyamide such as nylon, polyesters such as polyurethane and PET, polyvinylacetal-based resins such as polycarbonate, epoxy resins and butyral resins, and the like.
  • Particularly preferable resin is a polymer produced by polymerizing a (meth) acrylate ester, and this (meth) acrylate ester has a linear, branched, alicyclic, or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms.
  • Specific examples include polymers constituted with methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate or the like.
  • the monomer one type may be used alone, or multiple types may be used to subject to copolymerization.
  • the using amount of each monomer is not particularly limited.
  • resins which can be molten or dissolved are preferably used.
  • the near infrared ray absorbing composition which can be employed in molding fabrication is obtained.
  • a resin which can be molten and has Tg of 80°C or higher can be formed into a molding material by kneading with the near infrared ray absorbing dye.
  • Suitable examples of such a resin include methacrylic polymers such as methyl polymethacrylate, and ⁇ -hydroxymethyl acrylate ester copolymers, polycarbonate, butyral resins, cyclopolyolefin polymers, ARTON (manufactured by Japan Synthetic Rubber Co., Ltd.), ZEONOR (manufactured by Zeon Corporation) , O-PET (manufactured by Kanebo, Ltd.), SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), Optoplex (manufactured by Hitachi Chemical Co., Ltd.) and the like.
  • the resin which can be dissolved enables dissolution of the near infrared ray absorbing composition.
  • the near infrared ray absorbing composition can serve as a coating agent.
  • preferable resin include methacrylate ester-based polymers, ARTON (manufactured by Japan Synthetic Rubber Co.,
  • Examples of particularly preferable polymer is a polymer produced by polymerizing a methacrylate ester having a linear, branched, alicyclic or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms.
  • Examples of this methacrylate ester include methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and the like.
  • This polymer may be either a polymer constituting with one type of a methacrylate ester monomer, or a copolymer constituting with multiple methacrylate ester monomers.
  • a polymer produced by copolymerizing a monomer other than the aforementioned methacrylate ester with the aforementioned methacrylate ester is also acceptable.
  • the other monomer include aromatic monomers such as styrene and methylstyrene; maleimide-based monomers such as phenylmaleimide and cyclohexyl maleimide; monomers having a carboxyl group such as methacrylic acid and acrylic acid; acrylate esters having an alkyl group having 1 to 15 carbon atoms; monomers having a hydroxy group such as hydroxyethyl methacrylate and hydroxyethyl acrylate, and the like.
  • the using amount of the monomer other than the aforementioned methacrylate ester is preferably less than 50% by weight, more preferably less than 30% by weight, and still more preferably less than 10% by weight.
  • Specific examples include SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), Optoplex (manufactured by Hitachi Chemical Co. , Ltd. ) , HALSHYBRID IR (manufactured by Nippon Shokubai Co. , Ltd. ) , and the like.
  • a resin having a glass transition temperature (Tg) higher than 85 0 C can effectively suppress deterioration of the dye due to heat and moisture.
  • the weight average molecular weight indicated on the basis of polystyrene is equal to or greater than 50,000, and more preferably equal to or greater than 100,000.
  • the near infrared ray absorbing composition of the present invention exhibits favorable durability even though Tg is not higher than 85 0 C.
  • the type of the resin is not particularly limited, and acrylic resin, polyester resin and the like can be used.
  • Tg of the resin is 65 to 85 "C, and preferably 70 to 80 0 C.
  • polymeric structure of the resin is more preferably branched than linear.
  • the branched structure results in low viscosity of the resin even when the molecular weight is increased, thereby leading to easy handling.
  • a macromonomer In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, or a polyfunctional chain transfer agent can be used.
  • a macromonomer AA- ⁇ , AA-2, AS-6, AB- ⁇ , AK-5 (all manufactured by Toagosei Chemical Industry Co., Ltd.) and the like can be used.
  • the polyfunctional monomer include LIGHT-ESTER EG, LIGHT-ESTER 1 • 4BG, LIGHT-ESTER NP, LIGHT-ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • polyfunctional initiator examples include PERTETRA A, BTTB-50 (both manufactured by NOF Corporation) , Trigonox 17-40MB, Percadox 12-XL25 (both manufactured by Kayaku Akzo Co.Ltd.), and the like.
  • polyfunctional chain transfer agent examples include pentaerythritoltetrakis (3-mercaptopropionate) , trimethylolpropanetris (3-mercaptopropionate) , pentaerythritoltetrakis (thioglycolate) , and the like.
  • this resin may be either a pressure sensitive adhesive or an adhesive, or may be a mixture of a pressure sensitive adhesive and an adhesive.
  • the resin that is a pressure sensitive adhesive is also referred to as a pressure sensitive adhesive resin below.
  • the near infrared ray absorbing composition of the present invention in which the pressure sensitive adhesive or the adhesive is used as the resin can be bonded on other functional film, whereby optical filters can be conveniently and economically produced.
  • the resin suited as a pressure sensitive adhesive include acrylic, silicon-based, SBR-based resins, and the like.
  • Particularly preferable resins are polymers produced by polymerization of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate or the like as a principal component.
  • the resin has Tg of preferably not higher than -20°C, and more preferably not higher than -30° C.
  • the used monomer is not particularly limited as long as the glass transition temperature calculated using the formula of Fox represented by the following formula (calculated glass transition temperature) Tg falls within a certain value range:
  • Tgi ( 0 C) glass transition temperature of homopolymer of each monomer component .
  • the glass transition temperature Tg of this resin when the resin includes one type of the monomer, shall be an actual value.
  • the glass transition temperature Tg of this resin can be the calculated glass transition temperature which is calculated by the above formula of Fox.
  • the solubility parameter is preferably equal to or less than 9.80.
  • the calculated solubility parameter is a value determined by the method described in "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2), pp. 147 to 154. The method will be briefly explained below.
  • ⁇ vi molar volume of atom or atomic group of i component.
  • the solubility parameter of the copolymer is determined by: determining the summation ( ⁇ ei) of products derived by multiplying the evaporation energy of each component monomer constituting the copolymer by the molar fraction; determining the summation ( ⁇ vi) of the product derived by multiplying the molar volume of each component monomer by the molar fraction; dividing the summation ( ⁇ ei) by the summation ( ⁇ vi) ; and determining one half power of thus derived quotient.
  • (meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group in an amount of preferably 0.05 to 40% by weight, more preferably 0.5 to 40% by weight, and particularly preferably 5 to 40% by weight are preferred because favorable durability of the diimonium dye is achieved.
  • heat resistance and resistance to moist heat are improved by a stacking structure provided by the diimonium dye and the alkyl moiety of the alicyclic, polycyclic alicyclic, aromatic, polycyclic aromatic group.
  • Preferable pressure sensitive adhesive resin is obtained by copolymerization of a
  • (meth) acrylate ester having an aromatic alkyl group with other monomer is particularly preferred.
  • a pressure sensitive adhesive resin produced by copolymerization of the (meth) acrylate ester and other monomer.
  • this (meth) acrylate ester has an alkyl group having an aromatic ring, satisfactory balance of the durability and the pressure sensitive adhesive property of the diimonium dye is achieved.
  • More preferable pressure sensitive adhesive resin may be a resin produced by copolymerization of the following (ml) and (m2) , or copolymerization of the following (ml) to (m3) .
  • (m2) a (meth) acrylate ester having an alkyl group, wherein the alkyl group may be either linear or branched, and the alkyl group has 1 to 10 carbon atoms;
  • the copolymer resin preferable proportion of the monomers may be: the (meth) acrylate ester of (ml) of 5 to 40% by weight; the (meth) acrylate ester of (m2) of 60 to 95% by weight; and the other monomer of (m3) of 0 to 30% by weight. [0116]
  • the monomer (ml) examples include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxy propyl (meth) acrylate, and the like.
  • the monomer (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, and the like.
  • the monomer (m3) include (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; styrene-based monomers typified by ⁇ -methylstyrene, vinyltoluene, styrene and the like; vinyl ether-based monomers typified by methylvinyl ether, ethylvinyl ether, isobutyl vinyl ether and the like; fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid; maleic acid; monoalkyl esters of maleic acid; dialkyl esters of maleic acid; itaconic acid; monoalkyl esters of itaconic acid; dialkyl
  • a monomer having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group or a fluoroalkyl group may be also subjected to copolymerization in the range not to impair the object of the present invention.
  • the initiator which can be used in the polymerization is any commercially available article such as a peroxide-based, azo-based initiator and the like .
  • peroxide-based initiator examples include peroxy ester-based ones such as PERBUTYL 0 and PERHEXYL O (both manufactured by NOF Corporation) ; peroxydicarbonate-based ones such as PEROYL L and PEROYL 0 (both manufactured by NOF Corporation) ; diacylperoxide-based ones such as NYPER BW and NYPER BMT (both manufactured by NOF Corporation) ; peroxyketal-based ones such as PERHEXA 3M and PERHEXA MC (both manufactured by NOF Corporation) ; dialkylperoxide-based ones such as PERBUTYL P and PERCUMYL D (both manufactured by NOF Corporation) ; hydroperoxide-based ones such as PERCUMYL P and PERMENTA H (both manufactured by NOF Corporation) , and the like.
  • the azo-based initiator examples include ABN-E, ABN-R, ABN-V (all manufactured by JAPAN HYDRAZINE COMPANY,
  • a chain transfer agent may be used as needed.
  • the chain transfer agent is not particularly limited as long as it can adjust to give a predetermined molecular weight, and a thiol compound such as n-dodecyl mercaptan, dithioglycol, octyl thioglycolate or mercaptoethanol can be used.
  • polymerization of the resin may be carried out in a solvent free system, or may be carried out in an organic solvent.
  • an aromatic solvent such as toluene or xylene
  • an ester-based solvent such as ethyl acetate or butyl acetate
  • a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone; or other known organic solvent can be used.
  • Type of the used organic solvent may be determined taking consideration of polymerization temperature and solubility of the resulting resin, and in light of likelihood of yielding less residual solvent following drying, an organic solvent having a boiling point of not higher than 120°C such as toluene, ethyl acetate or methyl ethyl ketone is preferred.
  • the resin may be constituted with single component, or may be a polymer alloy or a polymer blend in which different components are complexed.
  • the near infrared ray absorbing composition of the present invention contains a cation and an anion derived from a salt not substantially having near infrared ray absorptivity.
  • the near infrared ray absorbing composition of the present invention contains a cation and an anion derived from a near infrared ray absorbing dye.
  • the near infrared ray absorbing composition of the present invention has an anion represented by the above formula (1) , the above formula (2), the above formula (3) or the above formula (4) .
  • the near infrared ray absorbing composition of the present invention has a cation as a counter cation of the anion represented by the above formulae (1) to (4) .
  • This cation is preferably an alkali metal cation.
  • the near infrared ray absorbing composition of the present invention contains the near infrared ray absorbing dye described above .
  • the near infrared ray absorbing composition of the present invention contains a diimonium cation represented by the above formula (5) .
  • the near infrared ray absorbing composition of the present invention contains an anion represented by the above formulae (6) to (9) .
  • the near infrared ray absorbing composition of the present invention may include a near infrared ray absorbing dye.
  • the amount of the blended near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications. For example, when the diimonium dye is used, the amount of the blended diimonium dye, or total amount of the blended diimonium dye and other near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications.
  • the amount of the blended near infrared ray absorbing dye is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin.
  • the amount is less than 0.01% by weight, it is likely to fail to attain sufficient near infrared ray absorptivity.
  • the amount is beyond 10% by weight, the effect to meet the addition is not achieved thereby leading to diseconomy, and it is likely to rather deteriorate the transparency in the visible region.
  • the near infrared ray absorbing composition of the present invention is characterized by transparency in the visible region, persistence of the near infrared ray absorptivity, and satisfactory processibility.
  • To the near infrared ray absorbing composition of the present invention may be added a dye that absorbs a visible light as needed.
  • dye that absorbs a visible light conventionally known dye can be extensively used such as a cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metaldithiol complex, sguarylium, azulenium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo, azometal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indigo, azomethine, xanthene, oxanol, indoaniline, quinoline, diketopyrrolopyrrole dye, and the like.
  • a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm is preferably used in combination for permitting absorption of unwanted neon emission.
  • Type of the dye for absorbing the neon emission is not particularly limited, and for example, a cyanine dye or a tetraazaporphyrin dye can be used.
  • ADEKA ARKLS TY-102 manufactured by Asahi Denka Kogyo K. K.
  • ADEKA ARKLS TY-14 manufactured by Asahi Denka Kogyo K.K.
  • ADEKA ARKLS TY-15 manufactured by Asahi Denka Kogyo K.K.
  • TAP-2 manufactured by Yamada Chemical Co. , Ltd.
  • TAP-18 manufactured by Yamada Chemical Co., Ltd.
  • TAP-45 manufactured by Yamada Chemical Co. , Ltd.
  • NK-5451 manufactured by Hayashibara Biochamical Labs., Inc.
  • NK-5532 manufactured by Hayashibara Biochamical Labs., Inc.
  • NK-5450 manufactured by Hayashibara Biochamical Labs., Inc.
  • Adding amount of the dye for permitting absorption of the neon emission may vary depending on the type of the dye, it is preferred to add such that transmittance at the maximum absorption wavelength becomes approximately 20 to 80%.
  • a visible light absorbing dye for color toning may be added.
  • Type of the dye for color-toning is not particularly limited, and 1:2 chromium complex, 1:2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole and the like can be used.
  • Orazol Blue GN (manufactured by Ciba Specialty Chemicals)
  • Orazol Blue BL (manufactured by Ciba Specialty Chemicals)
  • Orazol Red 2B (manufactured by Ciba Specialty Chemicals)
  • Orazol Red G (manufactured by Ciba Specialty Chemicals)
  • Orazol Black CN (manufactured by Ciba Specialty Chemicals)
  • Orazol Yellow 2GLN (manufactured by Ciba Specialty Chemicals)
  • Orazol Yellow 2RLN (manufactured by Ciba Specialty Chemicals)
  • Microris DPP Red B-K (manufactured by Ciba Specialty Chemicals), and the like.
  • the near infrared ray absorbing composition of the present invention may include one, or two or more kinds of a solvent or an additive, as well as a curing agent in .the range not to deteriorate the performance as needed.
  • the near infrared ray absorbing composition of the present invention may be prepared by mixing the near infrared ray absorbing dye in the form of a solid (for example, powder) in the resin.
  • the near infrared ray absorbing composition can be utilized as a coating agent .
  • the near infrared ray absorbing dye is preferably in the form of a solution, a dispersion or a suspension in a solvent.
  • solvents examples include e.g., aliphatic solvents such as cyclohexane and methylcyclohexane; aromatic solvents such as toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and acetate; nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and dibutyl ether; glycol ethers such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate; amides such as formamide and N,N-dimethyl formamide; halogen-based solvents such as methylene chloride and chloroform, and
  • solvents may be used alone, or multiple solvents may be used as mixture.
  • a solvent having a boiling point of not higher than 100° C such as methyl ethyl ketone or ethyl acetate is suitable.
  • a solvent having a boiling point of 100 to 150 °C such as toluene, methyl isobutyl ketone or butyl acetate is suitable.
  • a solvent having a boiling point of 150 to 200 "C such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether or propylene glycol monomethyl ether acetate is suitable.
  • the viscosity of the coating agent is selected ad libitum depending on the type of the coater, in general, the viscosity is 1 to 1000 mPa-s when the coating is carried out according to Gravure kiss-reverse of minor diameter such as one with a microgravure coater and the like, while the viscosity is 100 to 10000 mPa-s when the coating is carried out according to a extrusion format such as one with a die coater and the like.
  • the solid content of the coating agent may be adjusted to meet the viscosity of the coating material.
  • any conventionally known additives which have been used in the resin composition for forming films, coating films and the like can be used, and examples include dispersants, levelling agents, defoaming agents, viscosity adjusting agents, matting agents, tackifiers, antistatic agent, antioxidant, ultraviolet ray absorbents, light stabilizers, quenching agents, curing agents, antiblocking agents, and the like.
  • an isocyanate compound, a thiol compound, an epoxy compound, an amine-based compound, an imine-based compound, an oxazoline compound, a silane coupling agent, an UV curing agent, and the like can be used.
  • the near infrared ray absorbing composition of the present invention can be used in: a near infrared ray absorbing material for optical applications, agricultural applications, architectural applications or for vehicles; image recording media such as photosensitive paper; information recording media such as ones for optical disc; solar batteries such as dye sensitizing solar batteries; photosensitive materials for which a semiconductor laser beam and the like is employed as a light source; or materials for preventing eye fatigue.
  • the near infrared ray absorbing composition of the present invention is preferably used in the shape of a film or a sheet.
  • the present invention concerning a near infrared ray absorbent material is directed to a near infrared ray absorbent material including the near infrared ray absorbing composition of the present invention.
  • the near infrared ray absorbent material of the present invention may be produced by molding the aforementioned near infrared ray absorbing composition into a film, or may be produced by laminating a coated film including the aforementioned near infrared ray absorbing material on a transparent substrate.
  • the transparent substrate is not particularly limited as long as it can be generally used for optical materials, and is substantially transparent.
  • Specific examples of the transparent substrate include glass; olefin-based polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl-based polymers such as vinyl acetate and halogenated vinyl; polyesters such as PET; polyvinylacetals such as polycarbonate and butyral resins; polyaryl ether-based resins, and the like.
  • the transparent substrate may be subjected to a surface treatment according to conventionally known process such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or may be subjected to coating with an anchor coating agent, a primer and the like.
  • the transparent substrate can be blended a known additive, a heat resistant anti-aging agent, a lubricant, an antistatic agent, and the like.
  • the transparent substrate is molded into a film or sheet using a known process such as injection molding, T die molding, calendar molding or compression molding, or a process of casting after allowing it to melt in an organic solvent.
  • the substrate constructing such a transparent substrate may be either unstretched or stretched, and may be laminated with other substrate.
  • Preferable transparent substrate in the case in which the near infrared ray absorbing film is obtained by a coating process is a PET film, and a PET film subjected to a readily adhesive treatment is particularly suitable.
  • a PET film is particularly suitable.
  • Specific examples include COSMOSHINE A4300 (manufactured by Toyobo Co., Ltd.), Lumirror U34 (manufactured by Toray Industries, Inc.), Melinex 705 (manufactured by Teijin DuPont Limited), and the like.
  • a functional film such as a TAC (triacetyl cellulose) film, an antireflection film, an antiglare film, a shock absorbing film, an electromagnetic wave shielding film or an ultraviolet ray absorbing film can be also used as a transparent substrate. Accordingly, optical filters for thin displays and optical semiconductor elements can be easily produced. It is preferred that the transparent substrate be a film. [0139]
  • glass a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film and an electromagnetic wave shielding film is preferably used as the transparent substrate.
  • an inorganic substrate such as glass is used as the transparent substrate, one including a lower amount of an alkaline component is preferred in light of durability of the near infrared ray absorbing dye.
  • the near infrared ray absorbent material of the present invention has a thickness of approximately from 0.1 ⁇ m to 10 mm, in general, it may be determined ad libitum in accordance with the intended use.
  • the content of the near infrared ray absorbing dye included in the near infrared ray absorbent material may be determined ad libitum in accordance with the intended use.
  • the method of the production (I) in general, a method in which the near infrared ray absorbing composition of the present invention is added to a resin powder or pellet, and after heating the mixture to 150 to 350 1 C to permit dissolution, it is either molded to produce a resin plate, or subjected to film formation (resin plate formation) by an extruder, and the like may be exemplified although the conditions and the like such as fabrication temperature, film formation (resin plate formation) may vary to some extent depending on the used resin.
  • the method of the production (II) a method of molding in which the near infrared ray absorbing material of the present invention and a monomer or an oligomer are subjected to cast polymerization in the presence of a polymerization catalyst, and the mixture is injected into a mold, and allowed to react for curing, or the mixture is casted into a mold and allowed to be harden until a hard product is obtained in the mold may be exemplified. Many resins can be molded by the step as listed above.
  • Such a resin examples include acrylic resins, diethylene glycolbis (allyl carbonate) resins, epoxy resin, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like.
  • a casting method of block polymerization of methyl methacrylate is preferred. According to this casting method, an acryl sheet that is excellent in hardness, heat resistance and chemical resistance is obtained.
  • a known radical thermal polymerization initiator can be utilized, and examples thereof include e.g., peroxide such as benzoylperoxide, p-chlorobenzoylperoxide, and diisopropylperoxycarbonate, and azo compounds such as azobisisobutyronitrile.
  • the using amount may be generally 0.01 to 5% by weight based on the total amount of the mixture.
  • the heating temperature in the thermal polymerization is generally 40 to 200 °C, and the polymerize period is generally approximately 30 min to 8 hrs.
  • any method to permit photopolymerization through adding a photopolymerization initiator or a sensitizer can be also utilized.
  • a method of coating the near infrared absorbing composition of the present invention on a transparent substrate a method in which the near infrared ray absorbing composition of the present invention is fixed on fine particles, and a coating material including the fine particles dispersed therein is coated on a transparent substrate, and the like may be exemplified.
  • any known coater can be used.
  • knife coaters such as comma coaters, fountain coaters such as slot die coaters, and lip coaters
  • kiss coaters such as microgravure coaters
  • roll coaters such as gravure coaters and reverse roll coaters
  • flow coaters spray coaters
  • bar coaters bar coaters
  • a surface treatment of the substrate may be carried out by any known method such as a corona discharge treatment, a plasma treatment and the like.
  • a known method can be used such as hot air, far infrared radiation, UV curing and the like. Following the drying and curing, the product may be rolled up together with a known protective film.
  • the drying method of the coated film is not particularly- limited, but hot-air drying or far-infrared drying can be employed.
  • the drying temperature may be determined taking into consideration of the dried line length, line speed, application quantity, amount of residual solvent, type of the substrate and the like.
  • the substrate is a PET film
  • generally employed drying temperature is 50 to 150 "C.
  • respective dryers may be preset to yield different temperatures and wind velocities.
  • the near infrared ray absorbing composition of the present invention can be a component material of an excellent optical filter having high transparency in the visible region and absorptivity of near infrared ray.
  • the near infrared ray absorbing composition of the present invention has enhanced durability, particularly heat resistance and resistance to moist heat as compared with conventional near infrared ray absorbing materials, therefore, the appearance and the near infrared ray absorptivity can be maintained even though it is stored or used for a long period of time.
  • the near infrared ray absorbing composition of the present invention can be readily formed to have a sheet or film shape, it is efficacious for use in thin displays, and in optical semiconductor elements.
  • the near infrared ray absorbing composition of the present invention can be also used in filters and films that necessitate cutting of infrared rays, for example, films for agricultural use, thermal insulating films, sunglasses, optical recording materials, and the like.
  • the near infrared ray absorbing material of the present invention is suited for optical filters.
  • the present invention concerning an optical filter is directed to an optical filter for optical semiconductor elements or for thin displays in which the near infrared ray absorbent material of the present invention is used.
  • the transmittance of entire rays of light in the visible region is preferably equal to or greater than 40%, more preferably equal to or greater than 50%, and still more preferably equal to or greater than 60%.
  • the transmittance of the near infrared ray having a wavelength of 800 to 1100 nm is preferably equal to or less than 30%, more preferably equal to or less than 15%, and still more preferably equal to or less than 5%.
  • the optical filter of the present invention may be provided with, in addition to a near infrared ray absorbing layer composed of the aforementioned near infrared ray absorbing material, an electromagnetic wave shielding layer, an antireflection layer, a glare preventive (antiglare) layer, a sticking preventive layer, a color adjusting layer, a support such as glass and the like.
  • each layer of the optical filter may be arbitrarily selected, and an optical filter in which at least two layers are provided in combination of either one layer of the antireflection layer and the antiglare layer, and the near infrared ray absorbing layer is preferred. Further, an optical filter having at least three layers in combination, i.e., the aforementioned at least two layers, and further the electromagnetic wave shielding layer is more preferred. [0152]
  • the antireflection layer, or the antiglare layer be provided as the front most layer positioned on the closest side to human.
  • the order of lamination of the near infrared ray absorbing layer and the electromagnetic wave shielding layer with respect to each other may be arbitrarily determined.
  • other layer such as a sticking preventive layer, a color adjusting layer, a shock absorbing layer, a support or a transparent substrate may be also inserted.
  • each layer Upon lamination of each layer, it may be subjected to a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent.
  • a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent.
  • the antireflection layer or antiglare layer be provided as the front most layer positioned on the closest side to human for accelerating visibility of the screen.
  • the antireflection layer is provided for suppressing reflection on the surface, and for preventing unwanted image visualization on the surface due to the external light such as a light from the fluorescent lamp.
  • the antireflection layer There are two types of the antireflection layer, i.e., those composed of a thin film of an inorganic substance such as metal oxide, fluoride, suicide, boride, carbide, nitride, sulfide and the like, and those obtained by lamination of resins having different refractive indices such as an acrylic resin and a fluorocarbon resin into monolayer or multiple layers.
  • the manufacture method may include forming the antireflection coating on a transparent substrate with a vacuum evaporation or sputtering process to give monolayer or multilayer.
  • the antiglare layer is formed by making an ink from fine powder of silica, a melamine resin, an acrylic resin or the like, and coating on any one of the layers of the filter of the present invention by a conventionally known coating method, followed by allowing for heat-curing or photo-curing. Also, a film which had been subjected to an antiglare treatment may be pasted on the filter.
  • the sticking preventive layer is formed by dissolving or dispersing an acrylate such as urethaneacrylate, epoxyacrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent to prepare a coating liquid, applying this coating liquid on any of the layers of the filter of the present invention by a conventionally known method of application followed by drying and allowing for photo-curing .
  • the optical filter having the antireflection layer or the antiglare layer and the near infrared ray absorbing layer is obtained by laminating a layer composed of the near infrared ray absorbing composition of the present invention on the back face of the antireflection film or the antiglare film.
  • the near infrared ray absorbing composition of the present invention formed into a film may be pasted with the antireflection film or the antiglare film by a pressure sensitive adhesive, or dissolved near infrared ray absorbing material of the present invention may be directly applied on the back face of the antireflection film or the antiglare film.
  • the near infrared ray absorbing layer and the other layer may be directly pasted by way of this adhesiveness.
  • the ultraviolet ray absorbing film is preferably used as a transparent substrate for suppressing the deterioration of the dye resulting from the ultraviolet ray.
  • the electromagnetic wave shielding layer for removing the electromagnetic wave generated from the panel.
  • the electromagnetic wave shielding layer a film produced by patterning a metal mesh on a film by a process such as etching or printing, followed by leveling, or a film produced by embedding a metal vacuum evaporated on a fiber mesh into a resin may be used.
  • the optical filter having two layers of the near infrared ray absorbing layer and the electromagnetic wave shielding layer is obtained by combination of an electromagnetic wave preventive material and a near infrared ray absorbing composition.
  • the electromagnetic wave shielding film may be pasted with the near infrared ray absorbing composition of the present invention formed to have a film shape using the pressure sensitive adhesive, the dissolved near infrared ray absorbing material of the present invention may be directly applied on the electromagnetic wave shielding film.
  • the near infrared ray absorbing composition is adhesive
  • the near infrared ray absorbing composition of the present invention formed to have a film shape may be directly pasted with the electromagnetic wave shielding film.
  • the near infrared ray absorbing composition of the present invention can be used. Further, when the fiber to which a metal is vacuum evaporated is embedded, the near infrared ray absorbing composition of the present invention can be also used.
  • the optical filter having three layers i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film by a pressure sensitive adhesive.
  • a support such as glass, or a functional film such as a color adjusting film may be also pasted as needed.
  • the near infrared ray absorbing composition has adhesiveness
  • the near infrared ray absorbing film may be laminated such that it is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film. In this case, use of the pressure sensitive adhesive can be unnecessary because the three films are bonded utilizing the adhesive force of the near infrared ray absorbing film.
  • a combination film providing multiple functions may be used.
  • the optical filter obtained by pasting a combination film including the near infrared ray absorbing layer and the reflection or antiglare layer with the electromagnetic wave shielding film by a pressure sensitive adhesive the optical filter obtained by pasting a combination film including the near infrared ray absorbing layer and the electromagnetic wave shielding layer is pasted with the reflection or antiglare film by a pressure sensitive adhesive
  • the optical filter obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer with the near infrared ray absorbing film by a pressure sensitive adhesive may be exemplified.
  • the optical filter having three layers i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film.
  • the near infrared ray absorbing composition has adhesiveness
  • an optical filter having a structure in which the near infrared ray absorbing film is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film is preferred.
  • the adhesive layer conventionally provided only for the purpose of pasting of the film can be omitted.
  • a support such as glass, or a functional film such as a color adjusting film may be also pasted as needed.
  • a combination film providing multiple functions may be used.
  • Preferable optical filter may be obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer in one film with the near infrared ray absorbing adhesive layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
  • the optical filter of the present invention for thin display may be either provided away from the display unit, or directly pasted to the display unit.
  • glass is preferably used as the support.
  • the optical filter without use of the glass is preferred.
  • the present invention concerning a thin display is directed to a thin display in which the near infrared ray absorbing material of the present invention, the near infrared ray absorbent material of the present invention, or the optical filter of the present invention is used.
  • the thin display in which the optical filter is directly pasted to the display body can produce more clear image quality.
  • Examples of the pressure sensitive adhesive used in pasting the optical filter of the present invention to the display unit include rubbers such as styrene butadiene rubbers, polyisoprene rubbers, polyisobutylene rubbers, natural rubbers, neoprene rubbers, chloroprene rubbers and butyl rubbers, alkyl esters of polyacrylic acid such as methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate and the like, which may be used alone, or as a mixture prepared by further adding Piccolite, Polyvel, a rhodine ester or the like as a tackifiers.
  • a pressure sensitive adhesive having shock absorptivity as disclosed in Japanese Unexamined Patent Application Publication No. 2004-263084 can be used as the pressure sensitive adhesive, but not limited thereto.
  • This pressure sensitive adhesive layer has a thickness of generally 5 to 2000 ⁇ m, and preferably 10 to 1000 ⁇ m.
  • a releasable film may be provided on the surface of the pressure sensitive adhesive layer, and thus the pressure sensitive adhesive layer may be protected by this releasable film so as to avoid attachment of dirts and the like to the pressure sensitive adhesive layer during the time period until the optical filter is pasted to the surface of the thin display.
  • a nonadhesive part may be formed between the releasable film and the pressure sensitive adhesive layer of the filter at the surrounding edge by providing a part not having the pressure sensitive adhesive layer, or by interposing a nonadhesive film. This nonadhesive part may be used as a release initiation site. In such a case, operation in release will be easily conducted.
  • the shock absorbing layer is provided for the purpose of protecting the display unit from external shock. It is preferred that the shock absorbing layer be used for the optical filter without having the support.
  • Example of the shock absorber which can be used include ethylene-vinyl acetate copolymers, acrylic polymers, polyvinyl chloride, urethane-based, silicon-based resins and the like as disclosed in Japanese Unexamined Patent Application Publication No. 2004-246365 or No. 2004-264416, but not limited thereto.
  • the diimonium dye used in the present invention has a maximum absorption wavelength in the acetone solution of 1000 or greater and 1060 nm or less.
  • the diimonium dye has a maximum absorption wavelength in the acetone solution of
  • Such a diimonium dye is excellent in persistence of the near infrared ray absorptivity and the transparency in the visible region.
  • diimonium dyes including a diimonium cation represented by the following formula (10), and an anion represented by the following formula (11) or (12) may be illustrated.
  • R 9 to R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent.
  • R L and R M each represent a fluoroalkyl group which may be the same or different.
  • R N represents a fluoroalkylene group.
  • alkyl group having 1 to 10 carbon atoms constituting R 9 to R 16 a linear, branched or alicyclic alkyl group, or the like may be exemplified.
  • alkyl group include e.g., a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a 1, 1-dimethylpropyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, and the like.
  • examples of the substituent which can bind to the alkyl group in R 9 to R 16 include a cyano group; a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a n-propoxy group and n-butoxy group; alkoxyalkoxy groups having 2 to 8 carbon atoms such as a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group, a methoxybutoxy group and an ethoxybutoxy group; alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group and
  • Type of the anion in the diimonium dye is not particularly limited.
  • Preferable anion is an imide anion. More preferable anion is an anion represented by the above formula (11) or the formula (12) . [0181]
  • the fluoroalkyl group represented by R L or R M may be a perfluoroalkyl group such as CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , and the like.
  • R L and R M may be the same or different.
  • the fluoroalkylene group represented by R N may be (CF 2 ) n (wherein, n is an integer of from 2 to 12) , and the like.
  • Examples of preferable imide anion include bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion,
  • Exemplary compound names of the diimonium dye include bishexafluoroantimonate-N,N,N' ,N' -tetrakis- ⁇ p-di (4, 4, 4-trifl uorobutyl) aminophenyl ⁇ -p-phenylenediimonium (1048 nm) , bishexafluoroantimonate-N,N, N' , N' -tetrakis- ⁇ p-di (2, 2, 2-trif1 uoroethyl) aminophenyl ⁇ -p-phenylenediimonium (1020 nm) , bishexafluoroantimonate-N,N,N' , N' -tetrakis- ⁇ p-di (perfluorobu tyl) aminophenyl ⁇
  • Specific manufactured article which can be referred to as the diimonium dye according to the present invention may be CIR-1085F (manufactured by Japan Carlit Co., Ltd.). This CIR-1085F has a maximum absorption wavelength in the acetone solution being 1049 nm. [0186]
  • the resin according to the present invention is not particularly limited as long as it has a calculated glass transition temperature of equal to or lower than -20 "C.
  • the resin according to the present invention has adhesiveness. This adhesiveness enables the near infrared ray absorbing pressure sensitive adhesive composition to directly bond to the adherend.
  • the near infrared ray absorbing pressure sensitive adhesive composition can be bonded to the adherend without the adhesive interposed therebetween.
  • this resin may be also referred to as pressure sensitive adhesive resin.
  • the pressure sensitive adhesive resin has a calculated glass transition temperature of equal to or lower than -20 °C, and more preferably equal to or lower than -30°C. When it is higher than -20 'C, the adhesiveness may be insufficient.
  • the calculated glass transition temperature Tg may be determined according to the Fox formula described above.
  • the monomer used in polymerization of the resin is not particularly limited as long as the glass transition temperature (calculated glass transition temperature) Tg calculated using the aforementioned Fox formula falls within a specified value range. [0189] 2-2-2. Acid Value
  • the pressure sensitive adhesive resin is generally copolymerized with a carboxyl group-containing monomer such as acrylic acid.
  • the functional group such as a carboxyl group may deteriorate the diimonium dye
  • the pressure sensitive adhesive has an acid value of preferably equal to or less than 25, more preferably 0 or greater and 20 or less, still more preferably 0 or greater and 10 or less, and most preferably 0.
  • the "acid value” refers to the amount represented by mg of potassium hydroxide required for neutralization of 1 g of the pressure sensitive adhesive resin.
  • the solubility parameter is preferably equal to or less than 9.80. Details of the calculated solubility parameter, and the calculation method are as described above. The method of determining the solubility parameter of the copolymer is as described above.
  • the pressure sensitive adhesive resin may be a copolymer.
  • the pressure sensitive adhesive resin according to present invention those obtained by copolymerization with a
  • (meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group in an amount of preferably 0.05 to 40% by weight, more preferably 0.5 to 40% by weight, and particularly preferably 5 to 40% by weight are preferred because favorable durability of the diimonium dye is achieved.
  • heat resistance and resistance to moist heat are improved by a stacking structure provided by the diimonium dye and the alkyl moiety of the alicyclic, polycyclic alicyclic, aromatic, polycyclic aromatic group.
  • Preferable pressure sensitive adhesive resin is obtained by copolymerization of a
  • (meth) acrylate ester having an aromatic alkyl group with other monomer Particularly preferred is a pressure sensitive adhesive resin produced by copolymerization of the (meth) aerylate ester and other monomer.
  • this (meth) acrylate ester has an alkyl group having an aromatic ring, satisfactory balance of the durability and the pressure sensitive adhesive property of the diimonium dye is achieved.
  • More preferable pressure sensitive adhesive resin may be a resin produced by copolymerization of the following (m4) and (m5) , or copolymerization of the following (m4) to (m ⁇ ) .
  • (m5) a (meth) acrylate ester having an alkyl group, wherein the alkyl group may be either linear or branched, and the alkyl group has 1 to 10 carbon atoms; (m ⁇ ) other copolymerizable monomer.
  • preferable proportion of the monomers may be: the (meth) acrylate ester of (m4) of 5 to 40% by weight; the (meth) acrylate ester of (m5) of 60 to 95% by weight; and the other monomer of (m ⁇ ) of 0 to 30% by weight.
  • Examples of the (meth) acrylate ester of (m4) are the same as those of (ml) described above.
  • Examples of the (meth) acrylate ester of (m5) are the same as those of (m2) described above.
  • Examples of the monomer of (m ⁇ ) are the same as those of (m3) described above.
  • the initiator which can be used in the polymerization of the pressure sensitive adhesive resin is any commercially available article such as a peroxide-based, azo-based initiator and the like.
  • the peroxide-based initiator include peroxy ester-based ones such as PERBUTYL 0 and PERHEXYL 0 (both manufactured by NOF Corporation) ; peroxydicarbonate-based ones such as PEROYL L and PEROYL 0 (both manufactured by NOF Corporation) ; diacylperoxide-based ones such as NYPER BW and NYPER BMT (both manufactured by NOF Corporation) ; peroxyketal-based ones such as PERHEXA 3M and PERHEXA MC (both manufactured by NOF Corporation) ; dialkylperoxide-based ones such as PERBUTYL P and PERCUMYL D (both manufactured by NOF Corporation) ; hydroperoxide-based ones such as PERCUMYL P and PERMENTA H (both manufactured by NOF Corporation)
  • a chain transfer agent may be used as needed.
  • the chain transfer agent is not particularly limited, and a thiol compound such as n-dodecyl mercaptan, dithioglycol, octyl thioglycolate or mercaptoethanol can be used.
  • polymerization of the pressure sensitive adhesive resin may be carried out in a solvent free system, or may be carried out in an organic solvent .
  • an aromatic solvent such as toluene or xylene
  • an ester-based solvent such as ethyl acetate or butyl acetate
  • a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone; or other known organic solvent
  • Type of the used organic solvent may be determined taking consideration of polymerization temperature and solubility of the resulting resin, and in light of likelihood of yielding less residual solvent following drying, an organic solvent having a boiling point of not higher than 120° C such as toluene, ethyl acetate or methyl ethyl ketone is preferred.
  • the resin may be constituted with single component, or may be a polymer alloy or a polymer blend in which different components are complexed.
  • a macromonomer a polyfunctional monomer, a polyfunctional initiator, or a polyfunctional chain transfer agent can be used.
  • the macromonomer AA- ⁇ , AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Chemical Industry Co., Ltd.) and the like can be used.
  • Examples of the polyfunctional monomer include LIGHT-ESTER EG, LIGHT-ESTER 1 • 4BG, LIGHT-ESTER NP, LIGHT-ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • Examples of the polyfunctional initiator include PERTETRA A, BTTB-50 (both manufactured by NOF Corporation) , Trigonox 17-40MB, Percadox 12-XL25 (both manufactured by Kayaku Akzo Co.Ltd.), and the like.
  • polyfunctional chain transfer agent examples include pentaerythritoltetrakis (3-mercaptopropionate) , trimethylolpropanetris (3-mercaptopropionate) , pentaerythritoltetrakis (thioglycolate) , and the like.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention contains a diimonium dye having a maximum absorption wavelength in the acetone solution of 1000 nm or greater and 1060 nm or less, it is excellent in the transparency in the visible region and the near infrared ray absorptivity. Since the near infrared ray absorbing pressure sensitive adhesive composition of the present invention contains the resin having adhesiveness, it can be readily bonded to the adherend. [0201] To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be also added other near infrared ray absorbing dye.
  • Examples of the other near infrared ray absorbing dye which can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like.
  • the near infrared ray absorbing pressure sensitive adhesive composition of present invention is used as an optical filter for thin displays, it is preferred that a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm, a cyanine dye having a maximum absorption wavelength of 800 to 950 nm, or a dithiol metal complex dye having a maximum absorption wavelength of 800 to 950 nm be used in combination with the diimonium dye described above.
  • This use in combination enables effective absorption of a near infrared ray of 800 to 1100 nm.
  • use of a phthalocyanine dye in combination is particularly preferred.
  • the phthalocyanine-based compound which can be used in the present invention is not particularly limited as long as it is excellent in near infrared ray absorptivity, and known phthalocyanine-based compound can be used.
  • Exemplary preferable phthalocyanine-based compound includes the compounds represented by the formula (X) , or the compounds represented by the formula (Y) as described above. All details in regard to these formula (X) and formula (Y) are as set forth in connection with the present invention concerning a salt.
  • a cyanine dye may be used in combination with the near infrared ray absorbing dye.
  • the cyanine dye is not particularly limited as long as it is excellent in the near infrared ray absorptivity, a salt composed of an indolium cation or a benzothiazolium cation, and a counter anion can be preferably used.
  • the cations represented by the formula (a) , the formula (b) , the formula (c) , the formula (d) , the formula (e) , the formula (f) , the formula (g) , the formula (h) and the formula (i) described above can be preferably used, but not limited thereto. All details described above in connection with the formula (a) , the formula (b) , the formula (c) , the formula (d) , the formula (e) , the formula (f) , the formula (g) , the formula (h) and the formula (i) can be applied also to the present invention concerning a pressure sensitive adhesive composition.
  • the cyanine dye the near infrared ray absorbing pressure sensitive adhesive composition having high transparency in the visible region can be obtained.
  • the amount of the blended diimonium dye of the present invention, or total amount of the blended diimonium dye of the present invention and other near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications.
  • the blended amount is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin.
  • total amount of these dyes is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin.
  • the amount is less than 0.01% by weight, it is likely to fail to attain sufficient near infrared ray absorptivity.
  • the amount is beyond 10% by weight, the effect to meet the addition is not achieved thereby leading to diseconomy, and it is likely to rather deteriorate the transparency in the visible region.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is characterized by transparency in the visible region, persistence of the near infrared ray absorptivity, and satisfactory adhesiveness.
  • To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be added a dye that absorbs a visible light as needed. Examples of the dye that absorbs the visible light include those described above in connection with the present invention concerning a salt.
  • a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm is preferably used in combination for permitting absorption of unwanted neon emission.
  • Type of the dye for absorbing the neon emission is not particularly limited, and for example, the dyes described above in connection with the present invention concerning a salt may be exemplified. Adding amount of the dye for permitting absorption of the neon emission may vary depending on the type of the dye, it is preferred to add such that transmittance at the maximum absorption wavelength becomes approximately 20 to 80%.
  • a visible light absorbing dye for color toning may be added.
  • Type of the dye for color-toning is not particularly limited, and for example, the dyes described above in connection with the present invention concerning a salt may be exemplified.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may include one, or two or more kinds of a solvent or an additive, as well as a curing agent in the range not to deteriorate the performance as needed.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be prepared by mixing the near infrared ray absorbing dye in the form of a solid (for example, powder) in the resin.
  • the near infrared ray pressure sensitive adhesive absorbing composition is coated on the film, the near infrared ray absorbing dye is preferably in the form of a solution, a dispersion or a suspension in a solvent.
  • the solvents described above in connection with the present invention concerning a salt may be exemplified. These may be used alone, or as a mixture.
  • a solvent having a boiling point of not higher than 100 0 C such as methyl ethyl ketone or ethyl acetate is suitable.
  • a solvent having a boiling point of 100 to 15O 0 C such as toluene, methyl isobutyl ketone or butyl acetate is suitable.
  • a solvent having a boiling point of 150 to 200 "C such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether or propylene glycol monomethyl ether acetate is suitable.
  • the viscosity of the coating agent is selected ad libitum depending on the type of the coater, and is similar to that described above in connection with the present invention concerning a salt.
  • the solid content of the coating agent may be adjusted to meet the viscosity of the coating material.
  • any conventionally known additives which have been used in the resin composition for forming films, coating films and the like can be used.
  • the additive include dispersants, levelling agents, defoaming agents, viscosity adjusting agents, matting agents, tackifiers, antistatic agent, antioxidant, ultraviolet ray absorbents, light stabilizers, quenching agents, curing agents, antiblocking agents, and the like.
  • an isocyanate compound, a thiol compound, an epoxy compound, an amine-based compound, an imine-based compound, an oxazoline compound, a silane coupling agent, an UV curing agent, and the like can be used.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be used in: a near infrared ray absorbing material for optical applications, agricultural applications, architectural applications or for vehicles; image recording media such as photosensitive paper; information recording media such as ones for optical disc; solar batteries such as dye sensitizing solar batteries; photosensitive materials for which a semiconductor laser beam or the like is employed as a light source; or materials for preventing eye fatigue.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is preferably used in the shape of a film or a sheet.
  • To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be added the salt described above in connection with the present invention concerning a salt. Addition of this salt makes the balance of the pressure sensitive adhesive property and the durability more favorable . [0217]
  • the near infrared ray absorbent material according to the present invention includes the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
  • the near infrared ray absorbent material of the present invention may be produced by molding the aforementioned near infrared ray absorbing pressure sensitive adhesive composition into a film, or may be produced by laminating a coated film including the aforementioned near infrared ray absorbing pressure sensitive adhesive composition on a transparent substrate .
  • the transparent substrate is not particularly limited as long as it can be generally used for optical materials, and is substantially transparent.
  • Specific examples of the transparent substrate include glass; olefin-based polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl-based polymers such as vinyl acetate and halogenated vinyl; polyesters such as PET; polyvinylacetals such as polycarbonate and butyral resins; polyaryl ether-based resins, and the like.
  • the transparent substrate may be subjected to a surface treatment according to conventionally known process such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or may be subjected to coating with an anchor coating agent, a primer and the like.
  • a surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or may be subjected to coating with an anchor coating agent, a primer and the like.
  • a known additive e.g., a heat resistant anti-aging agent, a lubricant, an antistatic agent, and the like.
  • the transparent substrate is molded into a film or sheet using a known process such as injection molding, T die molding, calendar molding or compression molding, or a process of casting after allowing it to melt in an organic solvent.
  • the substrate constructing such a transparent substrate may be either unstretched or stretched, and may
  • Preferable transparent substrate in the case in which the near infrared ray absorbing film is obtained by a coating process is a PET film, and a PET film subjected to a readily adhesive treatment is particularly suitable.
  • Specific examples include
  • COSMOSHINE A4300 manufactured by Toyobo Co., Ltd.
  • a functional film such as a TAC (triacetyl cellulose) film, an antireflection film, an antiglare film, a shock absorbing film, an electromagnetic wave shielding film or an ultraviolet ray absorbing film can be also used as a transparent substrate. Accordingly, optical filters for thin displays and optical semiconductor elements can be easily produced. It is preferred that the transparent substrate be a film.
  • glass a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film and an electromagnetic wave shielding film is preferably used as the transparent substrate.
  • an inorganic substrate such as glass is used as the transparent substrate, one including a lower amount of an alkaline component is preferred in light of durability of the near infrared ray absorbing dye.
  • the thickness of the near infrared ray absorbent material of the present invention may be approximately from 0.1 ⁇ m to 10 mm, in general, it may be determined ad libitum in accordance with the intended use.
  • the content of the near infrared ray absorbing dye included in the near infrared ray absorbent material may be determined ad libitum in accordance with the intended use.
  • the method of the production (I) in general, a method in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention is added to a resin powder or pellet, and after heating the mixture to 150 to 350 ° C to permit dissolution, it is either molded to produce a resin plate, or subjected to film formation (resin plate formation) by an extruder, and the like may be exemplified although the conditions and the like such as fabrication temperature, film formation (resin plate formation) may vary to some extent depending on the used resin. [0224]
  • a method of molding in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention and a monomer or an oligomer are subjected to cast polymerization in the presence of a polymerization catalyst, and the mixture is injected into a mold, and allowed to react for curing, or casted into a mold and allowed to be harden until a hard product is obtained in the mold may be exemplified.
  • Many resins can be molded by the step as listed above. Specific examples of such a resin include acrylic resins, diethylene glycolbis (allyl carbonate) resins, epoxy resin, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, a casting method of block polymerization of methyl methacrylate is preferred, which can produce an acryl sheet that is excellent in hardness, heat resistance and chemical resistance. [0225]
  • a known radical thermal polymerization initiator can be utilized, and examples thereof include e.g., peroxide such as benzoylperoxide, p-chlorobenzoylperoxide, and diisopropylperoxycarbonate, and azo compounds such as azobisisobutyronitrile.
  • the using amount may be generally 0.01 to 5% by weight based on the total amount of the mixture.
  • the heating temperature in the thermal polymerization is generally 40 to 200 0 C, and the polymerize period is generally approximately 30 min to 8 hrs .
  • any method to permit photopolymerization through adding a photopolymerization initiator or a sensitizer can be also utilized.
  • any known coater can be used.
  • the coater for example, the coaters described above in connection with the present invention concerning a salt may be exemplified.
  • a surface treatment of the substrate may be carried out by any known method such as a corona discharge treatment, a plasma treatment and the like.
  • a drying and curing method a known method can be used such as hot air, far infrared radiation, UV curing and the like.
  • the product may be rolled up together with a known protective film.
  • the drying method of the coated film is not particularly limited, but hot-air drying or far-infrared drying can be employed.
  • the drying temperature may be determined taking into consideration of the dried line length, line speed, application quantity, amount of residual solvent, type of the substrate and the like.
  • the substrate is a PET film
  • generally employed drying temperature is 50 to 150° C.
  • respective dryers may be preset to yield different temperatures and wind velocities. In order to obtain a coated film having satisfactory coating appearance, it is preferred to employ a milder drying condition on the inlet side.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be a component material of an excellent optical filter having high transparency in the visible region and absorptivity of near infrared ray.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention has enhanced durability, particularly heat resistance and resistance to moist heat as compared with conventional near infrared ray absorbing materials, therefore, the appearance and the near infrared ray absorptivity can be maintained even though it is stored or used for a long period of time.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be readily formed to have a sheet or film shape, it is efficacious for use in thin displays, and in optical semiconductor elements.
  • the near infrared ray absorbing composition of the present invention can be also used in filters and films that necessitate cutting of infrared rays, for example, films for agricultural use, thermal insulating films, sunglasses, optical recording materials, and the like. [0230] 2-5. (Optical Filter)
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is suited for optical filters .
  • this optical filter the aforementioned near infrared ray absorbent material is used.
  • This optical filter is suitable as an optical filter for optical semiconductor elements or an optical filter for thin displays.
  • the transmittance of entire rays of light in the visible region is equal to or greater than 40%, preferably equal to or greater than 50%, and still more preferably equal to or greater than 60%.
  • the transmittance of the near infrared ray having a wavelength of 800 to 1100 nm is preferably equal to or less than 30%, more preferably equal to or less than 15%, and still more preferably equal to or less than 5%.
  • the optical filter of the present invention may be provided with, in addition to a near infrared ray absorbing layer composed of the aforementioned near infrared ray absorbing pressure sensitive adhesive composition, an electromagnetic wave shielding layer, an antireflection layer, a glare preventive (antiglare) layer, a sticking preventive layer, a color adjusting layer, a support such as glass and the like.
  • Constitution of each layer of the optical filter may be arbitrarily selected.
  • an optical filter in which at least two layers are provided in combination of either one layer of the antireflection layer and the antiglare layer, and the near infrared ray absorbing layer is suitable.
  • an optical filter having at least three layers in combination, i.e. , the aforementioned at least two layers, and further the electromagnetic wave shielding layer is more preferred.
  • the antireflection layer, or the antiglare layer be provided as the front most layer positioned on the closest side to human.
  • the order of lamination of the near infrared ray absorbing layer and the electromagnetic wave shielding layer with respect to each other may be arbitrarily determined.
  • other layer such as a sticking preventive layer, a color adjusting layer, a shock absorbing layer, a support or a transparent substrate may be also inserted.
  • each layer Upon lamination of each layer, it may be subjected to a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent.
  • a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent.
  • the antireflection layer or antiglare layer be provided as the front most layer positioned on the closest side to human for accelerating visibility of the screen.
  • the antireflection layer is provided for suppressing reflection on the surface, and for preventing unwanted image visualization on the surface due to the external light such as a light from the fluorescent lamp.
  • the antireflection layer There are two types of the antireflection layer, i.e., those composed of a thin film of an inorganic substance such as metal oxide, fluoride, suicide, boride, carbide, nitride, sulfide and the like, and those obtained by lamination of resins having different refractive indices such as an acrylic resin and a fluorocarbon resin into monolayer or multiple layers.
  • the manufacture method may include forming the antireflection coating on a transparent substrate with a vacuum evaporation or sputtering process to give monolayer or multilayer.
  • a manufacture method in which an antireflection coating is applied on the surface of the transparent substrate, on a transparent film, using a knife coater such as a comma coater, a fountain coater such as a slot coater or a lip coater, a gravure coater, a flow coater, a spray coater or a bar coater may be exemplified.
  • the antiglare layer is formed by making an ink from fine powder of silica, a melamine resin, an acrylic resin or the like, and coating on any one of the layers of the filter of the present invention by a conventionally known coating method, followed by allowing for heat-curing or photo-curing. Also, a film which had been subjected to an antiglare treatment may be pasted on the filter.
  • the sticking preventive layer is formed by applying a coating liquid, which was prepared by dissolving or dispersing an acrylate such as urethaneacrylate, epoxyacrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent, on any of the layers of the filter of the present invention by a conventionally known method of application followed by drying and allowing for photo-curing.
  • a coating liquid which was prepared by dissolving or dispersing an acrylate such as urethaneacrylate, epoxyacrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent, on any of the layers of the filter of the present invention by a conventionally known method of application followed by drying and allowing for photo-curing.
  • the optical filter having the antireflection layer or the antiglare layer and the near infrared ray absorbing layer is obtained by laminating a layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention or the near infrared ray absorbent material on
  • the near infrared ray absorbing layer according to the present invention formed into a film may be directly pasted with the antireflection film or the antiglare film, or dissolved near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be directly applied on the back face of the antireflection film or the antiglare film.
  • the ultraviolet ray absorbing film is preferably used as a transparent substrate for suppressing the deterioration of the dye resulting from the ultraviolet ray.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention has adhesiveness.
  • the near infrared ray absorbing layer is a layer that includes the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
  • the electromagnetic wave shielding layer for removing the electromagnetic wave generated from the panel.
  • the electromagnetic wave shielding layer a film produced by patterning a metal mesh on a film by a process such as etching or printing, followed by leveling, or a film produced by embedding a metal vacuum evaporated on a fiber mesh into a resin may be used.
  • the optical filter having two layers of the near infrared ray absorbing pressure sensitive adhesive layer and the electromagnetic wave shielding layer is obtained by combination of an electromagnetic wave preventive material and a near infrared ray absorbing composition.
  • the electromagnetic wave shielding film may be pasted with the near infrared ray absorbing pressure sensitive adhesive composition of the present invention formed to have a film shape using the pressure sensitive adhesive, the dissolved near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be directly applied on the electromagnetic wave shielding film.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be used.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be also used.
  • the optical filter having three layers, i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film.
  • An optical filter having a structure in which the near infrared ray absorbing film composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film is preferred. Since the optical filter is laminated utilizing the adhesiveness of the near infrared ray absorbing film, it can be produced without need of the adhesive layer conventionally provided only for the purpose of pasting of the film. A support such as glass, or a functional film such as a color adjusting film may be also pasted as needed. [0244] In order to further simplify the steps of manufacturing the optical filter and construction of the film, a combination film providing multiple functions may be used.
  • Preferable optical filter may be obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer in one film with the near infrared ray absorbing adhesive layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
  • the optical filter of the present invention for thin display may be either provided away from the display unit, or directly pasted to the display unit.
  • glass is preferably used as the support.
  • the optical filter without use of the glass is preferred.
  • the present invention concerning a thin display is directed to a thin display in which the near infrared ray absorbing pressure sensitive adhesive composition of the present invention, the near infrared ray. absorbent material of the present invention, or the optical filter of the present invention is used.
  • the thin display in which the optical filter is directly pasted to the display body can produce more clear image quality.
  • Examples of the pressure sensitive adhesive tackifier used in pasting the optical filter of the present invention to the display unit include the aforementioned substances described above in connection with the present invention concerning a salt.
  • the optical filter of the present invention may be pasted to the display unit without using the pressure sensitive adhesive, by way of adhesiveness of the near infrared ray.
  • This adhesive layer has a thickness of generally 5 to 2000 ⁇ m, and preferably 10 to 1000 ⁇ m.
  • a releasable film may be provided on the surface of the pressure sensitive adhesive layer, and thus the pressure sensitive adhesive layer may be protected by this releasable film so as to avoid attachment of dirts and the like to the pressure sensitive adhesive layer during the time period until the optical filter is pasted to the surface of the thin display.
  • a nonadhesive part may be formed between the releasable film and the pressure sensitive adhesive layer of the filter at the surrounding edge by providing a part not having the pressure sensitive adhesive layer, or by interposing a nonadhesive film.
  • this nonadhesive part is employed as a release initiation site, operation in release will be easily conducted.
  • the shock absorbing layer is provided for the purpose of protecting the display unit from external shock. It is preferred that the shock absorbing layer be used for the optical filter without having the support.
  • Example of the shock absorber which can be used include ethylene-vinyl acetate copolymers, acrylic polymers, polyvinyl chloride, urethane-based, silicon-based resins and the like as disclosed in Japanese Unexamined Patent Application Publication No. 2004-246365 and No. 2004-264416, but not limited thereto.
  • the present invention concerning a salt may be combined with the present invention concerning a pressure sensitive adhesive composition.
  • the present invention concerning a pressure sensitive adhesive composition may include the present invention concerning a salt.
  • the present invention concerning a salt may include the present invention concerning a pressure sensitive adhesive composition. Any detailed description of the present invention concerning a salt can be combined with any detailed description of the present invention concerning a pressure sensitive adhesive composition. (EXAMPLES)
  • Examples 1 to 8 , and Comparative Examples 1 to 3 relate to the present invention concerning a salt. Meanwhile, Production
  • Examples 1 to 16, Examples 9 to 26, and Comparative Examples 4 and 5 relate to the present invention concerning a pressure sensitive adhesive composition.
  • Table 1 shows the effect of the present invention concerning a salt.
  • Synthesis Example 1 Synthesis Example 2, Examples 1 to 8, and Comparative Examples 1 to 3 were evaluated in accordance with (Evaluation 1) to (Evaluation 3) described later.
  • the test sample was stood still in a 8O 0 C, 95% RH incubator with constant temperature and humidity for 120 hrs, and the transmission spectrum of 350 to 1250 nm before and after the test was determined.
  • UV-3700 manufactured by Shimadzu Corporation
  • alteration of the transmittance according as the test of resistance to moist heat was determined. Values derived by subtracting the transmittance (%) before the test of resistance to moist heat from the transmittance (%) after the test are shown in the column of " ⁇ T2" in the following Table 1.
  • the alteration ⁇ T2 of the transmittance at a wavelength of 850 nm and a wavelength of 1000 nm is shown in the following Table 1.
  • a monomer As a monomer, 371.5 g of methyl methacrylate, 59 g of n-butyl methacrylate and 69.5 g of butyl acrylate were mixed to obtain a polymerizable monomer mixture (1).
  • Percadox 12XL25 (manufactured by Kayaku Akzo Co. Ltd.) in an amount of 6 g and 100 g of toluene were mixed to obtain an initiator solution 1.
  • Into a flask were charged 350 g of the polymerizable monomer mixture (1) , and 225 g of toluene. This flask was equipped with a thermometer, an agitator, a nitrogen gas inlet tube, a reflux condenser and a dropping funnel.
  • the polymerizable monomer mixture (1) in an amount of 150 g was mixed with 31.8 g of the initiator solution 1, and the mixture was placed in the dropping funnel. While allowing a nitrogen gas to be circulated at 20 ml/min, The flask was heat to give the internal temperature of 100 0 C. To the flask was added 74.2 g of the initiator solution
  • the internal temperature of the flask was elevated to 95° C while allowing a nitrogen gas to be circulated at 20 ml/min.
  • NYPER BMT-K40 (0.15 g) that is a polymerization initiator was charged to the flask, whereby the polymerization reaction was initiated. Thirty minutes after charging the polymerization initiator, the dropwise addition of the mixture for dropwise addition (2) was started from the dropping funnel. The mixture for dropwise addition (2) was uniformly added dropwise over 90 min. After completing the dropwise addition of the mixture for dropwise addition (2), aging was carried out for 6 hrs while diluting the mixture with ethyl acetate ad libitum to meet elevation of the viscosity, and while maintaining the reflux temperature. [0261]
  • Bis (trifluoromethanesulfonyl) imide sodium was dissolved in a methyl ethyl ketone solution to give an additive solution 2 having a solid content of 5%.
  • the resin (Ia), the diimonium dye solution I 1 the phthalocyanine dye solution 1 and the additive solution 2 were mixed such that the weight ratio on the solid content basis became 100/2.8/2.5/0.63 to prepare a near infrared ray absorbing composition A2.
  • This weight ratio is represented in the order of: [resin (Ia) /diimonium dye solution 1/phthalocyanine dye solution 1/additive solution 2] .
  • a near infrared ray absorbent material A2 was obtained in a similar manner to Example 1 except that the near infrared ray absorbing composition A2 was used in place of the near infrared ray absorbing composition Al. This near infrared ray absorbent material A2 was employed as a test sample. The visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 1. Further, the results of evaluation on the test sample according to Example 2 are shown in the following Table 1. In Table 1, bis (trifluoromethanesulfonyl) imide sodium is represented by denotation of "TFSINa".
  • CIR-1085F (manufactured by Japan Carlit Co., Ltd.) having a bis (trifluoromethanesulfonyl) imide anion, and having a maximum absorption wavelength in an acetone solution of 1049 nm was used as a diimonium dye.
  • This "CIR-1085F” was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 2 having a solid content of 5%.
  • the resin (2a) obtained in Synthesis Example 2 the diimonium dye solution 2 and the additive solution 2 were mixed such that the weight ratio on the solid content basis became 100/1.88/2.0 to give a near infrared ray absorbing pressure sensitive adhesive composition A3. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/additive solution 2] . [0266]
  • the near infrared ray absorbing pressure sensitive adhesive composition A3 was applied on an easy-adhesion treated PET film (manufactured by Toyobo Co., Ltd., COSMOSHINE A4300) with an applicator such that the pressure sensitive adhesive layer after drying had a thickness of 25 ⁇ m, and dried in a 100 ° C hot-air circulating oven for 2 min. After pasting a releasable film (PET film subjected to a silicon treatment) thereon, it was left to stand at 23° C for one day to obtain a near infrared ray absorbent material A3.
  • PET film easy-adhesion treated PET film
  • COSMOSHINE A4300 COSMOSHINE A4300
  • this near infrared ray absorbent material A3 was pasted on a glass plate to give a test sample. Evaluation of the near infrared ray transmittance, heat resistance and the resistance to moist heat was made on this test sample. The results of evaluation are shown in the following Table 1.
  • Example 4 hexafluorophosphate lithium (PF 6 Li) was dissolved in methyl ethyl ketone to prepare an additive solution 3 having a solid content of 5%.
  • the resin (2a) , the diimonium dye solution 2 and the additive solution 3 were mixed such that the weight ratio on the solid content basis became 100/1.88/0.33 to give a near infrared ray absorbing pressure sensitive adhesive composition A4.
  • This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/additive solution 3] .
  • a near infrared ray absorbent material A4 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A4 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results are shown in the following Table 1. [0268] (Example 5) Lithium trifluoromethanesulfonate was dissolved in methyl ethyl ketone to prepare an additive solution 4 having a solid content of 5%.
  • CoronateL-55E (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.) that is a crosslinking agent was dissolved in methyl ketone solution to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • Di-n-butyltin dilaurylate crosslinking accelerator was dissolved in the methyl ketone solution to prepare a crosslinking accelerator solution 1 having a solid content of 1%.
  • the resin (2a), the diimonium dye solution 2, the phthalocyanine dye solution 1, the additive solution 4, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became 100/1.88/1.1/0.34/0.25/0.05 to give a near infrared ray absorbing pressure sensitive adhesive composition A5.
  • This weight ratio is represented in the order of: [resin
  • a near infrared ray absorbent material A5 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A5 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results are shown in the following Table 1. In Table 1, lithium trifluoromethanesulfonate is represented by denotation of "TFSLi”. [0270] (Example 6)
  • the resin (2a) , the diimonium dye solution 2, the phthalocyanine dye 1, the additive solution 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became
  • a near infrared ray absorbent material A ⁇ and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A6 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample.
  • the visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 2.
  • the results of evaluation on the test sample are shown in the following Table 1.
  • a near infrared ray absorbent material A7 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A7 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results on this test sample are shown in the following Table 1. [0274]
  • the resin (Ia) , the diimonium dye solution 1, and the phthalocyanine dye solution 1 were mixed such that the weight ratio on the solid content basis became 100/2.8/2.5 to give a near infrared ray absorbing composition Bl.
  • This weight ratio is represented in the order of: [resin (Ia) /diimonium dye solution 1/phthalocyanine dye solution 1] .
  • a near infrared ray absorbent material Bl was obtained in a similar manner to Example 1 except that the near infrared ray absorbing composition Bl was used in place of the near infrared ray absorbing composition Al. This near infrared ray absorbent material Bl was employed as a test sample. Similar evaluation to Example 1 was made on this test sample. The evaluation results are shown in the following Table 1. [0276] (Comparative Example 2)
  • the resin (2a) and the diimonium dye solution 2 were mixed such that the weight ratio on the solid content basis became 100/1.88 to obtain a near infrared ray absorbing composition B2.
  • This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2].
  • a near infrared ray absorbent material B2 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing composition B2 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was made on this test sample. The evaluation results are shown in the following Table 1.
  • the resin (2a) , the diimonium dye solution 2, the phthalocyanine dye 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became
  • a near infrared ray absorbent material B3 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition B3 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 3. Further, the evaluation results are shown in the following Table 1.
  • thermometer To a 300-ml four-necked flask equipped with an agitator, a thermometer and a condenser tube were placed 144.5 parts of tetramethoxysilane, 23.6 parts of ⁇ -methacryloxypropyltrimethoxysilane, 19.0 parts of water, 30.0 parts of methanol and 5.0 parts of Amberlist 15 (trade name : cation exchange resin manufactured by ORGANO CORPORATION) , which are agitated at 65 °C for 2 hrs to allow them to react. After cooling the reaction mixture to room temperature, a distillation column, and a condenser tube and an outlet which were connected to this distillation column were attached in place of the condenser tube.
  • Amberlist 15 trade name : cation exchange resin manufactured by ORGANO CORPORATION
  • the stock solution A is a mixture of 10 parts of the organic polymer (P-I) solution in n-butyl acetate, 30 parts of tetramethoxysilane and 5 parts of n-butyl acetate.
  • the stock solution B is a mixture of 5 parts of 25% aqueous ammonia, 10 parts of deionized water, and 15 parts of methanol.
  • the proportion (inorganic fine particle/organic polymer) of the inorganic fine particles to the organic polymer in the organic polymer-complexed inorganic fine particle was 70/30. This proportion is a ratio on the weight basis.
  • organic polymer-complexed inorganic fine particles had a mean particle size of 23.9 nm.
  • the proportion of the organic polymer to the inorganic fine particles in the organic polymer-complexed inorganic fine particle was determined by performing an elemental analysis of the dispersion of the organic polymer-complexed fine particles under a pressure of 1.33 x 10 kPa at 130 0 C for 24 hrs, and calculating the ash content in terms of the content of the organic polymer-complexed inorganic fine particle.
  • a solution prepared by diluting 1 part of the dispersion of the organic polymer-complexed inorganic fine particles (S-I) in 99 parts of n-butyl acetate was used to take a transmission electron micrograph of the particles. The diameter of arbitrary 100 particles was measured, and the average of the diameters was defined as the mean particle size.
  • the solution F2 is a solution including 0.5 parts of a photopolymerization initiator (IRGACURE907, manufactured by Ciba Specialty Chemicals Co. in 2 parts of methyl ethyl ketone .
  • the hard coat layer coating liquid Hl was applied on a polyethylene terephthalate film having a thickness of 188 ⁇ m (COSMOSHINE A4300, manufactured by Toyobo Co., Ltd.,) using a bar coater to obtain a coated layer h. After drying the layer h at 100° C for 15 min, an ultraviolet ray of 200 mJ/cm 2 was irradiated with a high-pressure mercury arc lamp to allow the layer h to be cured. Following this curing, a hard coat layer having a film thickness of 5 ⁇ m was formed. On this hard coat layer was applied a low-refractive index coating liquid Tl using a bar coater. This application yielded an antireflection film
  • Rl having an antireflection film provided on the polyethylene terephthalate film.
  • This antireflection film is constructed with the coated layer h, and a low-refractive index layer formed adjacent to this coated layer h.
  • This low-refractive index layer is formed by curing a low-refractive index coating liquid Tl.
  • the surface of the film Rl opposite to the antireflection film was roughened with steel wool, and to this roughened face was applied a black ink.
  • a specular reflection spectrum of the face on the antireflection film side was measured at an incidence angle of 5° using an ultraviolet visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) . From this measurement, a wavelength at which a minimum reflectance was attained, and the reflectance at the wavelength were determined. The wavelength at which a minimum reflectance was attained was 550 nm, and the reflectance at this wavelength was 0.45%.
  • the near infrared ray absorbing composition A6 obtained in Example 6 was applied on the back face side of the antireflection film Rl and dried, in a similar manner to Example 6 to obtain an optical filter 1.
  • the optical filter 1 exhibited favorable near infrared ray transmittance, transmittance of entire rays of light, heat resistance, crack resistance, and solvent resistance.
  • the evaluation method of the near infrared ray absorptivity, the heat resistance, the resistance to moist heat and the acid value are as in the following.
  • 0.5 g of the pressure sensitive adhesive resin solution was precisely weighed to which 50 g of toluene was added, and the resin was uniformly dissolved. Thereto was added two to three drops of a phenolphthalein/alcohol solution as an indicator, titration with a 0.1 N potassium hydroxide/alcohol solution was carried out. The endpoint was specified when the reddish color of the liquid disappeared in about 30 sec.
  • the acid value was determined from the titer and the solid content of the resin. The acid value is represented by mg of potassium hydroxide required for neutralization of 1 g of the resin solid content.
  • the internal temperature of the flask was elevated to 90° C while allowing a nitrogen gas to be circulated at 20 ml/min.
  • NYPER BMT-K40 (0.13 g) that is a polymerization initiator was charged to the flask, whereby the polymerization reaction was initiated.
  • the dropwise addition of the polymerizable monomer mixture for dropwise addition charged in the dropping funnel was started.
  • the polymerizable monomer mixture for dropwise addition was uniformly added dropwise over 90 min.
  • aging was carried out for 6 hrs while diluting the mixture with ethyl acetate ad libitum to meet elevation of the viscosity, and while maintaining the reflux temperature.
  • Production Examples 2 to 16 were similar to Production Example 1 except that the employed composition of the polymerizable monomer mixture was as shown in Table 2. According to these Production Examples 2 to 16, the pressure sensitive adhesive resins (2) to (16) were obtained. The calculated Tg, the calculated solubility parameter, Mw and the acid value of thus resulting pressure sensitive adhesive resins are shown in the following Table 2. [0301]
  • composition represents % by weight of each monomer based on total weight of the monomer mixture.
  • 2EHA represents 2-ethylhexyl acrylate (Tg: -70 'C); BA represents n-butyl acrylate (Tg: -55°C); EA represents ethyl acrylate (Tg: -22°C); MA represents methyl acrylate (Tg: -9°C); MMA represents methyl methacrylate (Tg: 105 'C) ; CHMA represents cyclohexyl methacrylate (Tg: 83°C); CHA represents cyclohexyl acrylate (Tg: 19°C); BzA represents benzyl acrylate (Tg: ⁇ °C); IBA represents isobornyl acrylate (Tg: 94 'C); HEA represents hydroxyethyl acrylate (Tg: -15 0 C) ; and AA represents acrylic acid (Tg
  • Example 9 “CIR-1085F” (manufactured by Japan Carlit Co., Ltd.) having a bis (trifluoromethanesulfonyl) imide anion and having a maximum absorption wavelength in the acetone solution of 1049 ran, as the diimonium dye, was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 5%.
  • CoronateL-55E manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.
  • di-n-butyltin dilaurate as a crosslinking accelerator
  • a crosslinking agent solution Ia having a solid content of 1% and a crosslinking accelerator solution Ia having a solid content of 1%.
  • the pressure sensitive adhesive resin (1) , the diimonium solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia obtained in Production Example 1 were mixed such that the weight ratio on the solid content basis became 100/1.88/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition Cl.
  • This weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (1) /diimonium solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] .
  • the near infrared ray absorbing pressure sensitive adhesive composition Cl was applied on an easy-adhesion treated PET film (manufactured by Toyobo Co., Ltd., COSMOSHINE A4300) with an applicator.
  • the coating thickness was defined such that the thickness after drying became 25 ⁇ m.
  • the film was dried in a 100 "C hot-air circulating oven for 2 min.
  • a releasable film PET film subjected to a silicon treatment
  • this near infrared ray absorbent material Cl was pasted on a glass plate to give a test sample according to Example 9. Evaluation of the near infrared ray transmittance, heat resistance and the resistance to moist heat was made on this test sample.
  • the visible-near infrared absorption spectrum of this test sample is shown in Fig. 4, and the evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat on the test sample are shown in Table 3.
  • the near infrared ray absorbing pressure sensitive adhesive compositions C2 to C16, the near infrared ray absorbent materials C2 to Cl ⁇ , and the test samples according to Examples 10 to 24 were obtained in a similar manner to Example 9 except that the pressure sensitive adhesive resin (1) was changed to the pressure sensitive adhesive resins (2) to (16). Similar evaluation to Example 9 was made on these test samples. Specifications and the evaluation results of Examples 10 to 24 are shown in the following Table 3.
  • EXCOLOR IR-IOA manufactured by Nippon Shokubai Co., Ltd. ) that is a phthalocyanine dye was dissolved in methyl ethyl ketone to prepare a phthalocyanine solution 1 having a solid content of 5%.
  • the pressure sensitive adhesive resin (11) obtained in Production Example 11 the diimonium solution 1, the phthalocyanine solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.88/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition C17.
  • the weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (11) /diimonium solution 1/phthalocyanine solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] .
  • the test sample according to Example 25 was obtained in a similar manner to Example 9 except that the near infrared ray absorbing pressure sensitive adhesive composition C17 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition Cl. Similar evaluation to Example 9 was made on this test sample.
  • the visible-near infrared absorption spectrum of the test sample according to Example 25 is shown in the following Fig. 5.
  • the evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample according to Example 25 are shown in the following Table 3.
  • CIR-1085 (manufactured by Japan Carlit Co. , Ltd. ) having a bis (trifluoromethanesulfonyl) imide anion and having a maximum absorption wavelength in the acetone solution of 1073 ran, as the diimonium dye, was used.
  • This "CIR-1085” was dissolved in methyl ethyl ketone to prepare a diimonium solution 2 having a solid content of 5%.
  • the pressure sensitive adhesive resin (8) obtained in Production Example 8 the diimonium solution 2, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition Dl.
  • the weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (8) /diimonium solution 2/ crosslinking agent solution la/crosslinking accelerator solution Ia] .
  • the test samples according to the near infrared ray absorbent material Dl and the Comparative Example 4 were obtained in a similar manner to Example 9 except that this near infrared ray absorbing pressure sensitive adhesive composition Dl was used in place of the near infrared ray absorbing pressure sensitive adhesive composition Cl. Similar evaluation to Example 9 was made on the test sample.
  • the visible-near infrared absorption spectrum of the test sample according to Comparative Example 4 is shown in Fig. 6.
  • the evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample according to Comparative Example 4 are shown in the following Table 3.
  • Comparative Example 5 The pressure sensitive adhesive resin (8) obtained in Production Example 8, the diimonium solution 2, the phthalocyanine solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.1/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition D2.
  • the weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (8) /diimonium solution 2/phthalocyanine solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] .
  • the near infrared ray absorbent material D2 and the test samples according to the Comparative Example 5 were obtained in a similar manner to Example 9 except that the near infrared ray absorbing pressure sensitive adhesive composition D2 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition D2. Similar evaluation to Example 9 was made on this test sample .
  • the evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample are shown in the following Table 3.
  • EA Ethyl Acrylate (Tg -22 # C)
  • IBA Isobornyl Acrylate (Tg 94 ° C)
  • MMA Methyl Methacrylate (Tg 105 * C)
  • AA Acrylic Acid (Tg 106 ° C)
  • CHMA Cyclohexyl Methacrylate (Tg 83 ° C)
  • the near infrared ray absorbent materials of the present invention Cl to C17 according to Examples 9 to 25 are excellent in durability since they exhibited less alteration of the transmittance at 1000 nm and b* in the heat resistance test and the test of resistance to moist heat.
  • the near infrared ray absorbent materials Dl and D2 of Comparative Examples 4 and 5 in which a dye having, a maximum absorption wavelength in the acetone solution exceeding 1060 nm was used as the diimonium dye are inferior in durability, exhibiting alterations of the transmittance at 1000 nm and b* in the heat resistance test and the test of resistance to moist heat .
  • the near infrared ray absorbing pressure sensitive adhesive composition Cl obtained in Example 9 was applied on the back face side of the antireflection film Rl obtained in Example 8, and dried, in a similar manner to Example 9 to obtain an optical filter 2.
  • the optical filter 2 exhibited favorable near infrared ray transmittance, transmittance of entire rays of light, heat resistance, crack resistance, and solvent resistance.
  • Example 27 To the pressure sensitive adhesive resin (14) obtained in the above Production Example 14 of the present invention concerning a pressure sensitive adhesive composition were mixed the diimonium dye solution 2 obtained in Example 3 of the present invention concerning a salt, the phthalocyanine dye solution 1 obtained in Example 1, the additive solution 1 obtained in Example 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 obtained in Example 5 such that the weight ratio on the solid content basis became 100/1.88/0.7/0.3/0.27/0.14 to prepare a near infrared ray absorbing pressure sensitive adhesive composition El.
  • This weight ratio is represented in the order of: [pressure sensitive adhesive resin (14) /diimonium dye solution 2/phthalocyanine dye solution 1/additive solution 1/crosslinking agent solution 1/crosslinking accelerator solution 1] .
  • pressure sensitive adhesive resin (14) /diimonium dye solution 2/phthalocyanine dye solution 1/additive solution 1/crosslinking agent solution 1/crosslinking accelerator solution 1] .
  • the near infrared ray absorbent material according to Example 27 and the test sample were obtained in a similar manner to Example 9. Similar evaluation to Example 9 was made on this test sample.
  • the visible-near infrared absorption spectrum of the test sample according to Example 27 before and after the heat resistance test is shown in the following Fig. 7.
  • the evaluation results of the heat resistance and the resistance to moist heat of this test sample are shown in the following Table 4.
  • the near infrared ray absorbing composition of the present invention is useful as an optical filter for thin displays since it has high near infrared ray absorptivity and transparency in the visible region, and is excellent in the heat resistance and the resistance to moist heat. Further, it can be also used as an optical recording material.
  • the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is useful as an optical filter for thin displays since it has high near infrared ray absorptivity and transparency in the visible region, and is excellent in the heat resistance and the resistance to moist heat. Further, it can be also used as an optical recording material.

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Abstract

The present invention concerning a salt is a salt for a near infrared ray absorbing composition having an anion represented by a specified formula, but not substantially having near infrared ray absorptivity per se. The counter cation of the salt having the anion is preferably an alkali metal cation. The present invention concerning a pressure sensitive adhesive composition includes a diimonium dye (A) having a maximum absorption wavelength in the acetone solution of 1000 to 1060 nm, and a resin (B) having a calculated glass transition temperature of equal to or lower than -20°C. Preferably, the diimonium dye includes a certain diimonium cation, and a certain imide anion. Preferably, the resin (B) has an acid value of equal to or less than 25. Preferably, the resin (B) has a calculated solubility parameter of equal to or less than 9.80. The present invention can be suitably utilized in optical filters for thin displays, optical filters for optical semiconductor elements, thin displays, and the like.

Description

DESCRIPTION
SALT FOR NEAR INFRARED RAY ABSORBING COMPOSITION AND NEAR INFRARED RAY ABSORBING PRESSURE SENSITIVE ADHESIVE COMPOSITION
[Technical Field] [0001]
The present invention concerning a salt relates to a salt for a near infrared ray absorbing composition, a near infrared ray absorbing composition including the salt, a near infrared ray absorbent material including the near infrared ray absorbing composition, an optical filter for thin displays in which the near infrared ray absorbing composition and a near infrared ray absorbent material are used. More specifically, the present invention concerning a salt relates to a salt capable of improving durability of a near infrared ray absorbing dye, a near infrared ray absorbing composition including the salt and being excellent in transparency in the visible region and durability, an near infrared ray absorbent material comprising the near infrared ray absorbing composition , an optical filter for optical semiconductor elements in which the near infrared ray absorbing composition or the near infrared ray absorbent material is used, an optical filter for thin displays in which the near infrared ray absorbing composition or the near infrared ray absorbent material is used, and the like. [0002]
The present invention concerning a pressure sensitive adhesive composition relates to a near infrared ray absorbing pressure sensitive adhesive composition, a near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition, an optical filter for thin displays in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used. More specifically, the present invention concerning a pressure sensitive adhesive composition relates to a near infrared ray absorbing pressure sensitive adhesive composition that is excellent in transparency in the visible region and persistence of the infrared ray absorptivity, a near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition, an optical filter for optical semiconductor elements in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used, an optical filter for thin displays in which the near infrared ray absorbing pressure sensitive adhesive composition or the near infrared ray absorbent material is used, and the like. [Background Art] [0003]
In recent years, thin displays such as liquid crystal displays, PDPs (Plasma Display Panels) and the like which are applicable to large screens being of thin type have been attracting attention. Thin displays generate a near infrared ray at a wavelength of 800 nm to 1100 nm. This near infrared ray causes problems of production of improper operating signals on remote-control devices for home electric appliances. In addition, optical semiconductor elements used in CCD cameras and the like are also highly sensitive to the near infrared ray region, the near infrared ray must be eliminated. Hence, near infrared ray absorbing materials having high absorptivity of the near infrared ray, and having high transparency in the visible region have been demanded. [ 0004 ]
As the near infrared ray absorbing dye that absorbs the near infrared ray, cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles have been conventionally used. Among them, diimonium dyes have been in heavy usage because of high absorptivity of the near infrared ray, and high transparency in the visible light region (for example, see Japanese Unexamined Patent Application Publication No. 2003-96040 and Japanese Unexamined Patent Application Publication No. 2000-80071) . [0005]
Additionally, in PDP, discharge is caused in a rare gas, particularly a gas predominantly including neon, which is encapsulated in the panel, and the vacuum ultraviolet ray generated upon the discharge allows the phosphors of R, G and B provided in the cell inside the panel to emit light. Thus, in this light emission step, an electromagnetic wave that is unnecessary for operation of PDP is also emitted. It is also necessary to shield this electromagnetic wave. In addition, for suppressing the reflected light, an antireflection film, and an antiglare film are also required. To this end, an optical filter for plasma displays is generally produced by laminating a near infrared ray absorbing film, an electromagnetic wave shielding film and an antireflection film on a glass or a shock absorber that serves as a supporting substrate. Such optical filter for plasma displays is mounted on the front face side of the PDP. In some cases, this optical filter for plasma displays is directly bonded on the glass or the shock absorber as a supporting substrate using an adhesive or a pressure sensitive adhesive. [ 0006 ]
Recently, for the purpose of thinning of the optical filter, and simplification of the production step of the optical filter, attempts to integrate the near infrared ray absorbing film and a pressure sensitive adhesive layer have been made by including a near infrared ray absorbing dye in a pressure sensitive adhesive (See Japanese Patent No. 3621322) . [Patent Citation 1]
Japanese Unexamined Patent Application Publication No. 2003-96040
[Patent Citation 2]
Japanese Unexamined Patent Application Publication No. 2000-80071 [Patent Citation 3] Japanese Patent No. 3621322 [Disclosure of Invention] [Technical Problem] [0007]
However, near infrared ray absorbing dyes such as diimonium dyes, representatively, may be inferior in durability, whereby deterioration of near infrared ray absorption ability and coloring may cause a significant problem when it is used in applications such as displays and optical semiconductor elements. Such deterioration is believed to be caused by alteration of the dye by a variety of factor s such as heat, moisture, light and the like. Accordingly, improvement of durability of near infrared ray absorbing dyes have been conventionally attempted, however, satisfactory effect has not been achieved yet . In addition, since it is difficult to increase the content of copper phosphate based compounds in near infrared ray absorbing compositions, to obtain a material for thin films that is excellent in near infrared ray absorptivity is difficult. [0008]
Accordingly, an object of the present invention concerning a salt is to provide a salt which can be suitably used in a near infrared ray absorbing composition that permits improvement of durability of near infrared ray absorbing dyes, particularly improvement of heat resistance and resistance to moist heat.
[0009] Other object of the present invention concerning a salt is to provide a near infrared ray absorbing composition that is excellent in transparency in the visible region and durability. [0010]
Moreover, recently, for the purpose of thinning of the optical filter, and simplification of the production step of the optical filter, attempts to integrate the near infrared ray absorbing film and a pressure sensitive adhesive layer have been made through including a near infrared ray absorbing dye in a pressure sensitive adhesive. However, the dyes are more seriously deteriorated in a resin having a low Tg such as a pressure sensitive adhesive. Therefore, under such circumstances, a pressure sensitive adhesive containing a diimonium dye that can be satisfactorily subjected to practical applications has not been obtained yet. [0011]
An object of the present invention concerning a salt is to provide a near infrared ray absorbing composition that has high transparency in the visible region and long persistence of the near infrared ray absorptivity, and is excellent in durability irrespective of the resin shape. [ 0012 ]
Furthermore, an object of the present invention concerning a salt is to provide a near infrared ray absorbent material, an optical filter for optical semiconductor elements, an optical filter for thin displays, and thin displays in which the composition is used. [0013]
As described above, some diimonium dyes may be inferior in durability, and lowering of absorptivity of the near infrared ray and coloring may cause a significant problem when it is used in applications such as optical semiconductor elements and displays. In particular, the dyes are seriously deteriorated in a resin having a low glass transition point (Tg) such as a pressure sensitive adhesive resin. Therefore, a pressure sensitive adhesive containing a diimonium dye that can be satisfactorily subjected to practical applications has not been obtained yet .
[0014]
Japanese Unexamined Patent Application Publication No. 2005-325292 discloses a diimonium dye having improved durability by introducing a halogen atom to an alkyl group of a diimonium cation. Improvement of durability is surely found according to the near infrared ray shielding filter in which this diimonium dye and a binder resin having high Tg are used, as compared with the case of conventional diimonium dyes. However, combination with the pressure sensitive adhesive resin having low Tg that exhibits serious deterioration achieves insufficient durability.
[0015] Hence, an object of the present invention concerning a pressure sensitive adhesive composition is to provide a near infrared ray absorbing pressure sensitive adhesive composition that is useful in production of a near infrared ray absorbent material having high transparency in the visible region and long persistence of the near infrared ray absorptivity. Moreover, an object of the present invention concerning a pressure sensitive adhesive composition is to provide a near infrared ray absorbent material, an optical filter for optical semiconductor elements, an optical filter for thin displays, and a thin display in which the composition is used. [Technical Solution] [0016]
The inventors of the present invention concerning a salt elaborately investigated improvement of durability of a near infrared ray absorbing dye, particularly a near infrared ray absorbing composition for use in optical filters, and consequently found that a salt having a certain structure improves durability, particularly heat resistance and resistance to moist heat, of a near infrared ray absorbing dye, and that a near infrared ray absorbing composition including such a salt is excellent in transparency in the visible region and durability
(in particular, heat resistance and resistance to moist heat) .
Additionally, it was found that an optical filter for thin displays and an optical filter for optical semiconductor elements that are excellent in durability and is excellent in transparency in the visible region can be obtained by using this near infrared ray absorbing composition. On the basis of the foregoing findings, the present invention concerning a salt was accomplished. [0017] Accordingly, the aforementioned object is achieved by adding a salt for a near infrared ray absorbing composition having an anion represented by the following formula (1) , formula (2) , formula (3) or formula (4) but not substantially having near infrared ray absorptivity per se.
[0018] [Chem. 1]
Ra-SO2 N" (D
Rb-SOo
[0019] [Chem. 2]
Figure imgf000009_0001
[0020] [Chem. 3]
RgS03 " O)
[0021] [Chem. 4]
Figure imgf000010_0001
[0022]
In the formula (1) and the formula (3), Ra, Rb and Rg each represent a fluoroalkyl group which may be the same or different; in the formula (2) , Rc represents a fluoroalkylene group; and in the formula (4), m represents an integer of from 1 to 6. [0023]
Moreover, according to the present invention concerning a salt, the aforementioned other object is achieved by a near infrared ray absorbing composition including the salt of the present invention and a near infrared ray absorbing dye. [0024]
According to the present invention concerning a salt, the aforementioned further object is achieved by an optical filter for thin displays and a filter for optical semiconductor elements in which the near infrared ray absorbent material of the present invention is used, and by a thin display and an optical semiconductor element in which any of these filters is used.
[0025] The inventors of the present invention concerning a pressure sensitive adhesive composition elaborately investigated combinations of a diimonium dye and a resin. Consequently, it was found that when a diimonium dye having a specific maximum absorption wavelength is combined with a res'in having a specific calculated glass transition temperature, a near infrared ray absorbing pressure sensitive adhesive composition that is excellent in durability of the dye can be obtained. Additionally, particular definition of the acid value of the resin can still further improve the durability of the dye.
[0026] More specifically, according to the present invention concerning a pressure sensitive adhesive composition, the aforementioned object is achieved by a near infrared ray absorbing pressure sensitive adhesive composition containing a diimonium dye having a maximum absorption wavelength in the acetone solution of 1000 to 1060 ran, and a resin having a calculated glass transition temperature of -20 °C or lower. [Advantageous Effect] [0027]
The salt of the present invention improves durability, particularly heat resistance and resistance to moist heat, of near infrared ray absorbing dyes. Additionally, the salt of the present invention does not deteriorate the transparency in the visible region, it can be suitably used in near infrared ray absorbing materials including a variety of dyes such as diimonium dyes, typically, which have conventionally raised problems. [0028]
Further, when the optical filter in which the near infrared ray absorbing composition containing the salt of the present invention is applied to thin displays and optical semiconductor elements, appearance of displays and optical semiconductor elements can be improved because absorptivity of the near infrared ray and transparency in the visible light region are maintained for a long period of time.
[0029] The near infrared ray absorbing material in which the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is used results in maintenance of near infrared ray absorptivity of the dye for a long period of time.
Therefore, use of this near infrared ray absorbing pressure sensitive adhesive composition in production of an optical filter for optical semiconductor elements and thin displays enables thinning of the optical filter, and simplification of production step of the optical filter.
[Brief Description of Drawings] [0030]
[Fig. 1] Fig. 1 shows a visible-near infrared ray absorption spectrum of a test sample according to Example 2 before and after a heat resistance test. [Fig. 2]
Fig. 2 shows a visible-near infrared ray absorption spectrum of a test sample according to Example 6 before and after a heat resistance test.
[Fig. 3] Fig. 3 shows a visible-near infrared ray absorption spectrum of a test sample according to Comparative Example 3 before and after a heat resistance test.
[Fig. 4]
Fig. 4 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 9.
[Fig. 5] Fig. 5 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 25.
[Fig. 6] Fig. 6 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Comparative Example 4. [Fig. 7]
Fig. 7 shows a graph illustrating a visible-near infrared absorption spectrum of a test sample obtained in Example 27. [Best Mode for Carrying Out the Invention] [0031]
Hereinafter, the present invention will be explained in detail. First, the present invention concerning a salt will be explained, and subsequently, the present invention concerning a pressure sensitive adhesive composition will be explained. The present invention concerning a salt will be explained in the following item numbers of from 1-1 to 1-8. The present invention concerning a pressure sensitive adhesive composition will be explained in the following item numbers of from 2-1 to 2-6.
[0032] 1-1. (Anion of the Formulae (1) to (4))
An aspect of the present invention concerning a salt for a near infrared ray absorbing composition is directed to a salt for a near infrared ray absorbing composition having an anion represented by the following formula (1), formula (2), formula (3) or formula (4) but not substantially having near infrared ray absorptivity per se.
[0033] [Chem. 5]
Figure imgf000013_0001
[0034] [Chem. 6]
Figure imgf000014_0001
[0035] [Chem. 7]
RgSO (3)
[0036] [Chem. 8]
R1 F (4) [ 0037 ]
In the formula (1) and the formula (3), Ra, Rb and R9 each represent a fluoroalkyl group which may be the same or different; in the formula (2) , Rc represents a fluoroalkylene group; and in the formula (4) ; and m represents an integer of from 1 to 6. In the formula (4) , R1 is not limited. R1 may be any atom or any atomic group. Addition of this salt can improve durability of near infrared ray absorbing dyes. [0038] The phrase "not substantially having near infrared ray absorptivity" means that transmittance determined by the following determination method (A) is equal to or greater than 80% in any wavelength of from 800 nm to 1100 ran. The determination method (A) is as in the followings. Determination method (A) : The salt or ion to be subjected to the determination is dissolved in methyl ethyl ketone such that the solid content of the salt becomes 0.1% by weight, and absorbance of this solution is measured. For determination of the spectrum, UV-3600 (Shimadzu Corporation) is used. In the measurement, a quartz measurement cell having an optical path length of 10 mm is used. [0039]
In the above formula (1), Ra and Rb each represent a fluoroalkyl group which may be the same or different. In the above formula (3), R9 represents a fluoroalkyl group. [0040]
In Ra, Rb and Rg, the number of fluorine atoms and the number of carbon atoms are not particularly limited. Examples of preferable Ra and Rb include perfluoroalkyl groups having 1 to 10 carbon atoms. The anion represented by the formula (1) includes the anion in which Ra and Rb are the same, and the anion in which Ra and Rb are different. Specific preferred examples in which Ra and Rb are the same include bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (heptafluoropropylsulfonyl) imide and bis (nonafluorobutanesulfonyl) imide. Specific preferred examples in which Ra and Rb are different include pentafluoroethanesulfonyltrifluoromethanesulfonyl imide, trifluoromethanesulfonylheptafluoropropanesulfonyl imide, nonafluorobutanesulfonyltrifluoromethanesulfonyl imide, and the like.
[0041]
Specific examples of RgSθ3 ~ represented by the formula (3) include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropylsulfonic acid, nonafluorobutanesulfonic acid, and the like. In light of the effect to improve durability, bis (trifluoromethanesulfonyl) imide in which Ra and Rb are the same is preferred in the formula (1) , while trifluoromethanesulfonic acid is preferred in the formula (3) .
[0042]
Additionally, Rc in the formula (2) is a fluoroalkylene group. Preferable Rc includes a perfluoroalkylene group having 2 to 10 carbon atoms. Rc is more preferably a perfluoroalkylene group having 2 to 8 carbon atoms, and more preferably a perfluoroalkylene group having 3 carbon atoms. As the perfluoroalkylene group having 3 carbon atoms, 1, 3-disulfonylhexafluoropropylene imide is exemplified. [0043]
In R1F1n " represented by the formula (4), R1 is preferably selected from the group consisting of phosphorus, antimony, arsenic, boron and tin. In light of the effect to improve durability, more preferred R1Fm " includes one, or two or more anions selected from the group consisting of hexafluoroantimonate anion, hexafluorophosphate anion, hexafluorostannate anion, tetrafluoroborate anion and hexafluoroarsenate anion.
[0044] 1-2. (Salt Including Anion of the formulae (1) to (4)) The salt including the anion represented by the formulae (1) to (4) is a salt comprising the anion represented by the above formulae (1) to (4), and a cation not substantially having near infrared ray absorptivity. [0045]
Examples of the salt including the anion represented by the above formulae (1) to (4) which can be used according to the present invention include alkali metal salts, alkaline earth metal salts, transition metal salts, ammonium salts, pyridinium salts, imidazolium salts, pyrrolidinium salts, quinolinium salts, carbenium salts, phosphonium salts, iodonium salts and the like of the anion described above. Exemplary alkali metal salts include salts of lithium, sodium, potassium, rubidium, cesium or the like. Exemplary alkaline earth metal salts include salts of beryllium, magnesium, calcium, strontium, barium or the like. Exemplary transition metal salts include salts of silver, copper or the like. Exemplary ammonium salts include salts of ammonium, n-butylammonium, dimethylammonium, trimethylammonium, triethylammonium, triisopropylammonium, tri-n-butylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, N,N-dimethylcyclohexylammonium or the like. Exemplary anilinium salts include salts of N-methylanilinium, N, N-dimethylanilinium,
N, N-dimethyl-4-methylanilinium, N, N-diethylanilinium, N, N-diphenylanilinium, N,N,N-trimethylanilinium or the like. Exemplary pyridinium salts include salts of pyridinium, N-methylpyridinium, N-butylpyridinium,
N-methyl-4-methyl-pyridinium, N-benzylpyridinium,
3-methyl-N-butylpyridinium, 2-methylpyridinium, 3-methylpyridinium, 4-methylpyridinium, 2 , 3-dimethylpyridinium, 2 , 4-dimethylpyridinium,
2, β-dimethylpyridinium, 3, 4-dimethylpyridinium,
3, 5-dimethylpyridinium, 2,4, 6-trimethylpyridinium,
2-fluoropyridinium, 3-fluoropyridinium, 4-fluoropyridinium, 2, 6-difluoropyridinium, 2, 3, 4, 5, 6-pentafluoropyridinium, 2-chloropyridinium, 3-chloropyridinium, 4-chloropyridinium, 2, 3-dichloropyridinium, 2, 5-dichloropyridinium,
2, 6-dichloropyridinium, 3, 5-dichloropyridinium,
3, 5-dichloro-2, 4 , 6-trifluoropyridinium, 2-bromopyridinium, 3-bromopyridinium, 4-bromopyridinium, 2, 5-dibromopyridinium, 2, 6-dibromopyridinium, 3, 5-dibromopyridinium,
2-cyanopyridinium, 3-cyanopyridinium, 4-cyanopyridinium, 2-hydroxypyridinium, 3-hydroxypyridinium,
4-hydroxypyridinium, 2 , 3-dihydroxypyridinium, 2, 4-dihydroxypyridinium, 2-methyl-5-ethylpyridinium, 2-ch'loro-3-cyanopyridinium, 4-carboxamidepyridinium, 4-carboxyaldehydepyridinium, 2-phenylpyridinium,
3-phenylpyridinium, 4-phenylpyridinium,
2, 6-diphenylpyridinium, 4-nitropyridinium, 4-methoxypyridinium, 4-vinylpyridinium, 4-mercaptopyridinium, 4-t-butylpyridinium, 2, β-di-t-butylpyridinium,
2-benzylpyridinium, 3-acetyl pyridinium, 4-ethylpyridinium, 2-carboxylate pyridinium, 4-carboxylate pyridinium, 2-benzoylpyridinium or the like. Exemplary imidazolium salts include salts of imidazolium, 1-methyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, l-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, l-methyl-3-octylimidazolium, 1-methyl-N-benzylimidazolium, l-methyl-3- (3-phenylpropyl) imidazolium, l-butyl-2, 3-dimethylimidazolium, l-ethyl-2, 3-dimethylimidazolium or the like. Exemplary pyrrolidinium salts include salts of 1-ethyl-l-methyl-pyrrolidinium,
1-butyl-l-methyl-pyrrolidinium or the like. Exemplary quinolinium salts include salts of quinolinium, isoquinolinium or the like. Exemplary carbenium salts include salts of triphenylcarbenium, tri-4-methoxyphenyl carbenium or the like. Exemplary phosphonium salts include salts of dimethylphenylphosphonium, triphenylphosphonium, tetraethylphosphonium, tetraphenylphosphonium or the like. Exemplary sulfonium salts include salts of trimethylsulfonium, triphenylsulfonium or the like. Exemplary iodonium salts include salts of diphenyliodonium, di-4-methoxyphenyliodonium or the like. [0046]
Among the salts presented above, particularly preferred salts are alkali metal salts. Particularly preferred cations are alkali metal cations . Preferable alkali metals as the cation include lithium, sodium, potassium, rubidium, cesium and the like.
[0047] 1-3. (Near Infrared Ray Absorbing Dye)
The salt of the present invention can improve durability, particularly heat resistance and resistance to moist heat of the near infrared ray absorbing composition including the near infrared ray absorbing dye. Therefore, another aspect of the present invention relates to a near infrared ray absorbing composition including the salt of the present invention and a near infrared ray absorbing dye. Since the salt of the present invention can improve durability, particularly heat resistance and resistance to moist heat of the near infrared ray absorbing dye or the near infrared ray absorbing composition as described above, the near infrared ray absorbing composition of the present invention can exhibit excellent durability, particularly heat resistance and resistance to moist heat. Additionally, the near infrared ray absorbing composition of the present invention is also excellent in transparency in the visible region. [0048] Herein, the near infrared ray absorbing dye which can be used in the near infrared ray absorbing composition is not particularly limited, and for example, cyanine, polymethine, squarylium, porphyrin, dithiol metal complexes, phthalocyanine, diimonium near infrared ray absorbing dyes and the like may be exemplified. Among these, preferred are the cyanine and diimonium near infrared ray absorbing dyes due to excellent transparency in the visible region, and the phthalocyanine near infrared ray absorbing dyes due to excellent durability. [0049] The aforementioned diimonium dye preferred in the present invention is a salt of a cation represented by the following formula (5) , and a counter anion. In the formula (5) , R1 to R8 each independently represent, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms and having a substituent. [0050] [Chem. 9]
Figure imgf000021_0001
[0051]
Examples of the halogen atom constituting R1 to R8 include e.g., a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0052]
Examples of the alkyl group having 1 to 10 carbon atoms constituting R1 to R8 include linear, branched or alicyclic alkyl groups, and the like. Specific examples include e.g., a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a 1, 1-dimethylpropyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, and the like.
[0053] Moreover, examples of the substituent which can bind to the alkyl group having 1 to 10 carbon atoms which may have a substituent include a cyano group; a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a n-propoxy group and a n-butoxy group; alkoxyalkoxy groups having 2 to 8 carbon atoms such a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group, a methoxybutoxy group and an ethoxybutoxy group; alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group and an ethoxyethoxyethoxy group; an allyloxy group; aryloxy groups having 6 to 12 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group and a naphthyloxy group; alkoxycarbonyl groups having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group and a n-butoxycarbonyl group; alkylcarbonyloxy groups having 2 to 7 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group and a n-butylcarbonyloxy group; alkoxycarbonyloxy groups having 2 to 7 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group and a n-butoxycarbonyloxy group, and the like. Specific examples of R1 to R8 include a trifluoromethyl group, a 2, 2, 2-trifluoroethyl group, a 3, 3, 3, -trifluoropropyl group, a 4, 4, 4-trifluorobutyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and the like. [0054] In the present invention, R1 to R8 may be the same or different, but preferably all of them are the same. [0055]
The counter anion of the diimonium dye is not particularly limited, and a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a nitrate ion, a benzenesulfonate ion, a P-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, a propylsulfate ion, a tetrafluoroborate ion, a tetraphenylborate ion, a tetrakis (pentafluorophenyl) borate ion, a bis (trifluoromethanesulfonyl) imide ion, a bis (pentafluoroethanesulfonyl) imide ion, a pentafluoroethanesulfonyltrifluoromethanesulfonyl imide ion, a trifluoromethanesulfonylheptafluoropropanesulfonylimide ion, a nonafluorobutanesulfonyltrifluoromethanesulfonyl imide ion, a 1, 3-disulfonylhexafluoropropyleneimide ion, a hexafluorophosphate ion, a benzenesulfinate ion, an acetate ion, a trifluoroacetate ion, a propionacetate ion, a benzoate ion, an oxalate ion, a succinate ion, a malonate ion, an oleate ion, a stearate ion, a citrate ion, a monohydrogen a diphosphate ion, a dihydrogen monophosphate ion, a pentachlorostannate ion, a chlorosulfonate ion, a fluorosulfonate ion, a trifluoromethanesulfonate ion, a hexafluoroarsenate ion, a hexafluoroantimonate ion, a molybdate ion, a tungstate ion, a titanate ion, a zirconate ion, a sulfate ion, a vanadate ion, a borate ion and the like can be used. The diimonium cation is a bivalent cation as represented by the above formula (5). Therefore, for example, when a monovalent anion such as a chloride ion is used, in the diimonium dye according to the present invention, two anions are bound to one diimonium cation. [0056] The counter anion of the diimonium dye is preferably an anion represented by the following formulae (6) to (9).
[0057] [Chem. 10]
Figure imgf000024_0001
[0058] [Chem. 11]
Figure imgf000024_0002
[0059] [Chem. 12]
RjS03 " (8)
[0060] [Chem. 13]
RkTn " O) [ 0061 ]
In Rd and Re in the above formula (6) , the number of fluorine atoms and the number of carbon atoms are not particularly limited. Examples of preferable Rd and Re include perfluoroalkyl groups having 1 to 10 carbon atoms . The anion represented by the formula (6) includes the anion in which Rd and Re are the same, and the anion in which Rd and Re are different. Specific preferred examples in which Rd and Re are the same include bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (heptafluoropropylsulfonyl) imide and bis (nonafluorobutanesulfonyl) imide. Specific preferred examples in which Rd and Re are different include pentafluoroethanesulfonyltrifluoromethanesulfonyl imide, trifluoromethanesulfonylheptafluoropropanesulfonyl imide, nonafluorobutanesulfonyltrifluoromethanesulfonyl imide, and the like.
[0062]
Further, Rf in the above formula (7) is a fluoroalkylene group. Examples of preferable Rf include perfluoroalkylene groups having 2 to 10 carbon atoms. Rf is more preferably a perfluoroalkylene group having 2 to 8 carbon atoms, and more preferably a perfluoroalkylene group having 3 carbon atoms. As the perfluoroalkylene group having 3 carbon atoms, 1, 3-disulfonylhexafluoropropyleneimide is exemplified. [0063]
Specific examples of R^SO3 ~ represented by the above formula (8) include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropylsulfonic acid, nonafluorobutanesulfonic acid and the like. [ 0064 ]
Rk in RkFn ~ represented by the above formula (9) is selected from the group consisting of phosphorus, antimony, arsenic, boron and tin. In light of enhancement of the effect to improve the durability, more preferred RkFn ~ is one, or two or more anions selected from the group consisting of a hexafluoroantimonate anion, a hexafluorophosphate anion, a hexafluorostannate anion, a tetrafluoroborate anion and a hexafluoroarsenate anion.
[0065] Among the aforementioned ones, preferred anions are a hexafluoroantimonate ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a bis (trifluoromethanesulfonyl) imide ion, a tetrakis (pentafluorophenyl) borate ion, and a 1, 3-disulfonylhexafluoropropyleneimide ion. [0066]
The diimonium dye particularly preferably used in the present invention concerning a salt is a diimonium dye having a maximum absorption wavelength λ in the acetone solution of 1000 nm or greater and 1060 nm or less. More preferably, this maximum absorption wavelength λ is 1010 nm or greater and 1055 nm or less, and more preferably 1020 nm or greater and 1050 nm or less. Such a diimonium dye is excellent in transparency in the visible region and persistence of the near infrared ray absorptivity. [0067]
Examples of specific structure of the diimonium dye are shown in Japanese Unexamined Patent Application Publication No. 2005-325292. [0068] Illustrative examples of the compound of the diimonium dye include bishexafluoroantimonate-N,N,N' ,N' -tetrakis {p-di (4,4, 4-triflu orobutyl) aminophenyl} -p-phenylenediimonium (1048 nm) , bishexafluoroantimonate-N, N, N' , N' -tetrakis {p-di (2,2, 2-trifIu oroethyl) aminophenyl} -p-phenylenediimonium (1020 nm) , bishexafluoroantimonate-N, N, N' , N' -tetrakis {p-di (perfluorobut yl) aminophenyl} -p-phenylenediimonium (1032 nm) , bishexafluoroantimonate-N, N, N' , N' -tetrakis {p-di (4,4, 4-trichl orobutyl) aminophenyl} -p-phenylenediimonium (1049 nm) , bis{bis (trifluoromethanesulfonyl) imide} -N, N, N' ,N' -tetrakis{p -di (4,4, 4-trifluorobutyl) aminophenyl} -p-phenylenediimonium (1048 nm) , bis {bis (trifluoromethanesulfonyl) imide} -N, N, N' , N' -tetrakis {p -di (2, 2, 2-trifluoroethyl) aminophenyl} -p-phenylenediimonium (1020 nm) , bis {bis (trifluoromethanesulfonyl) imide} -N, N, N' , N' -tetrakis {p -di (perfluorobutyl) aminophenyl} -p-phenylenediimonium (1032 nm) , bis{bis (trifluoromethanesulfonyl) imide} -N, N, N' ,N' -tetrakis{p -di (4,4, 4-trichlorobutyl) aminophenyl} -p-phenylenediimonium
(1049 nm) , bis (1, 3-disulfonylhexafluoropropyleneimide) -N,N, N' , N' -tetrak is{p-di (4,4, 4-trifluorobutyl) aminophenyl }-p-phenylenediimoni urn (1048 nm) , bis (1, 3-disulfonylhexafluoropropyleneimide) -N,N, N' ,N' -tetrak is {p-di (2,2, 2-trifluoroethyl) aminophenyl }-p-phenylenediimoni urn (1020 nm) , bis (1, 3-disulfonylhexafluoropropyleneimide) -N, N, N' ,N' -tetrak is {p-di (perfluorobutyl) aminophenyl} -p-phenylenediimonium (1032 nm) , bis (1, 3-disulfonylhexafluoropropyleneimide) -N, N, N' ,N' -tetrak is{p-di (4,4, 4-trichlorobutyl) aminophenyl}-p-phenylenediimoni urn (1049 nm) . The value in parenthesis indicates the maximum absorption wavelength in the acetone solution. [0069]
As a specific manufactured article of the diimonium dye, CIR-1085F (manufactured by Japan Carlit Co., Ltd.) is exemplified. This CIR-1085F has a maximum absorption wavelength in the acetone solution of 1049 nm. [0070]
The maximum absorption wavelength in the acetone solution is determined as follows. The diimonium dye to be determined is dissolved in a certain volume of acetone, and after verifying the absence of undissolved matter, the absorbance is measured. For determination of the spectrum, UV-1600 (Shimadzu Corporation) is used. In the measurement, a quartz measurement cell having an optical path length of 10 mm is used. [0071]
Examples of the dye other than the diimonium dye include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particle and the like. [0072]
When the near infrared ray absorbing composition of present invention concerning a salt is used as an optical filter for thin displays, it is preferred that a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm, a cyanine dye having a maximum absorption wavelength of 800 to 950 nm, or a dithiol metal complex dye having a maximum absorption wavelength of 800 to 950 nm be used in combination with the diimonium dye described above. This use in combination enables effective absorption of a near infrared ray of 800 to 1100 ran. In light of acquisition of the near infrared ray absorbing composition having favorable durability, use of a phthalocyanine dye in combination is particularly preferred. [0073]
The phthalocyanine-based compound which can be used in the present invention concerning a salt is preferably excellent in near infrared ray absorptivity, and known phthalocyanine-based compound can be used. Exemplary preferable phthalocyanine-based compound includes the compounds represented by the following formula (X) , or the compounds represented by the following formula (Y) .
[0074] (Phthalocyanine-based Compound Represented by the Formula
(X)) [Chem. 14]
Figure imgf000030_0001
[0075]
In the above formula (X) , A1 to A16 represent a functional group. In the above formula (X), A1 to A16 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, an alkylthio group having 1 to 20 carbon atoms which may be substituted, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms which may be substituted, an alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted, an arylsulfonyl group having 6 to 20 carbon atoms which may be substituted, an aralkylsulfonyl group having 7 to 20 carbon atoms which may be substituted, an acyl group having
1 to 20 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an aryloxycarbonyl group having 6 to 20 carbon atoms which may be substituted, an aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having
2 to 20 carbon atoms which may be substituted, an arylcarbonyloxy group having β to 20 carbon atoms which may be substituted, an aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, an amino group which may be substituted, an aminosulfonyl group which may be substituted, or an aminocarbonyl group which may be substituted. The functional groups A1 to A16 may be of the same type or the different type, and may be the same or different in the case of the same type. The functional groups may be linked via a linking group. M1 represents two hydrogen atoms, a bivalent metal atom, a trivalent substituted metal atom, a quadrivalent substituted metal atom, or an oxy metal. Herein, the term "acyl group" is similarly defined to the definition described in Dictionary of Scientific and Technical Terms, 3rd Edition, Published by THE NIKKAN KOGYO SHIMBUN, LTD., p. 17. Specifically, the "acyl group" is a group derived from an organic acid by deleting a hydroxyl group, and is a group represented by the formula: RCO- (wherein R is an aliphatic group, an alicyclic group or aromatic group) . [0076]
(Case of Functional Group Having the End other than Amino Group) In the above formula (X) , examples of the halogen atom in the functional groups A1 to A16 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n-heptyl group, a n-octyl group, a 2-ethylhexyl group and the like, but not limited thereto. Examples of the alkoxy group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkoxy groups such as a methoxy group, an ethoxy group, a n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, and the like, but not limited thereto. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group, a naphthyl group, and the like, but not limited thereto. Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted include a phenoxy group, a naphthoxy group, and the like, but not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group, a diphenylmethyl group, and the like, but not limited thereto. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group, and the like, but not limited thereto. Examples of the alkylthio group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylthio groups such as a methylthio group, an ethylthio group, a n-propylthio group, an iso-propylthio group, a n-butylthio group, an iso-butylthio group, a sec-butylthio group, a t-butylthio group, a n-pentylthio group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a n-octylthio group, a 2-ethylhexylthio group, and the like, but not limited thereto. Examples of the arylthio group having 6 to 20 carbon atoms which may be substituted include a phenylthio group, a naphthylthio group, and the like, but not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but not limited thereto. Examples of the alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an iso-propylsulfonyl group, a n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a t-butylsulfonyl group, a n-pentylsulfonyl group, a n-hexylsulfonyl group, a cyclohexylsulfonyl group, a n-heptylsulfonyl group, a n-octylsulfonyl group, a 2-ethylhexylsulfonyl group, and the like, but not limited thereto. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group, a naphthylsulfonyl group, and the like, but not limited thereto. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but not limited thereto. Examples of the acyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylcarbonyl groups such as a methylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a n-octylcarbonyl group and a 2-ethylhexylcarbonyl group, arylcarbonyl groups such as a benzylcarbonyl group and a phenylcarbonyl group, aralkylcarbonyl groups such as a benzoyl group, and the like, but not limited thereto. Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propyloxy carbonyl group, an iso-propyloxy carbonyl group, a n-butyloxy carbonyl group, an iso-butyloxy carbonyl group, a sec-butyloxy carbonyl group, a t-butyloxy carbonyl group, a n-pentyloxy carbonyl group, a n-hexyloxy carbonyl group, a cyclohexyloxy carbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, a 2-ethylhexyloxy carbonyl group, and the like, but not limited thereto. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include a phenoxy carbonyl, a naphthylcarbonyl group, and the like, but not limited thereto. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, a diphenylmethyloxycarbonyl group, and the like, but not limited thereto. Examples of the alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted include an acetyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, a n-butylcarbonyloxy group, an iso-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a t-butylcarbonyloxy group, a n-pentylcarbonyloxy group, a n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, a n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, a n-octylcarbonyloxy group, and the like, but not limited thereto. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include a benzoyloxy group, and the like, but not limited thereto. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include a benzylcarbonyloxy group, and the like, but not limited thereto. Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted include a pyrrole group, an imidazole group, a piperidine group, a morpholine group, and the like, but not limited thereto. [0077] Further, in the above formula (X) , when the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, arylsulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group in the functional groups A1 to A16 is substituted, examples of the substituent present in these functional groups A1 to A16 include e.g., a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, a cyano group, a heterocyclic group, and the like, but not limited thereto. These substituents may be present in a plural number. When there are a plural number of the substituents, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group.
[0078]
(Case of Functional Group Having the End being Amino Group) In the above formula (X) , examples of the candidate substituent in the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted of the functional groups A1 to A16 include a hydrogen atom; linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a sec-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group and a cyclohexyl group; aryl groups such as a phenyl group and a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; linear, branched or cyclic alkylcarbonyl groups such as an acetyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a 3-heptylcarbonyl group and a n-octylcarbonyl group; arylcarbonyl groups such as a benzoyl group and a naphthylcarbonyl group; aralkylcarbonyl groups such as a benzylcarbonyl group, and the like, but not limited thereto. These substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2. When there are two substituents, each may be of the same type or the different type, and may be the same or different in the case of the same type. Also, when there are two substituents, the substituents may be linked via a linking group. [0079]
Examples of the substituent which may be further present in the alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl group, or aralkylcarbonyl group that is the candidate substituent of the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted include e.g. , a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, a cyano group, and a heterocyclic group, but not limited thereto. These substituents may be present in a plural number. When there are a plural number of the substituent, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group. [ 0080 ]
In addition, examples of the bivalent metal as the metal M1 include Cu(II), Co(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Ti(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Pb(II), Sn(II), and the like, but not limited thereto. Examples of the trivalent substituted metal atom include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C6H5, Al-C6H4(CH3), In-C6H5, In-C6H4(CH3), In-C6H5, Mn(OH), Mn(OC6H5), Mn [OSi (CH3) 3] , Ru-Cl, and the like, but not limited thereto. Examples of the quadrivalent substituted metal atom include CrCl2, SiF2, SiCl2, SiBr2, SiI2, ZrCl2, GeF2, GeCl2, GeBr2, GeI2, SnF2, SnCl2, SnBr2, TiF2, TiCl2, TiBr2, Ge(OH)2, Mn(OH)2, Si(OH)2, Sn(OH)2, Zr(OH)2, Cr(R1),, Ge(R1J2, Si(R1J2, Sn(R1J2, Ti(Ri)2 (R1 represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof}, Cr(OR2J2, Ge (OR2) 2, Si(OR2J2, Sn(OR2J2, Ti(OR2J2, {R2 represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, dialkylalkoxysilyl group or a derivative thereof}, Sn(SR3J2, Ge(SR3J2 (R3 represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof}, and the like, but not limited thereto. Examples of the oxy metal include VO, MnO, TiO, and the like, but not limited thereto .
[0081] (Phthalocyanine-based Compound Represented by the Formula
(Y)) [Chem. 15]
Figure imgf000039_0001
[ 0082 ]
In the above formula (Y) , B1 to B24 represent a functional group. B1 to B24 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, an alkylthio group having 1 to 20 carbon atoms which may be substituted, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms which may be substituted, an alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted, an arylsulfonyl group having 6 to 20 carbon atoms which may be substituted, an aralkylsulfonyl group having 7 to 20 carbon atoms which may be substituted, an acyl group having 1 to 20 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an aryloxycarbonyl group having 6 to 20 carbon atoms which may be substituted, an aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted, an arylcarbonyloxy group having 6 to 20 carbon atoms which may be substituted, aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, an amino group which may be substituted, an aminosulfonyl group which may be substituted, or an aminocarbonyl group which may be substituted. The functional groups B1 to B24 may be of the same type or the different type, and may be the same or different in the case of the same type. The functional groups may be linked via a linking group. M2 represents two hydrogen atoms, a bivalent metal atom, a trivalent substituted metal atom, a quadrivalent substituted metal atom or an oxy metal. [0083]
(Case of Functional Group Having the End other than Amino Group)
In the above formula (Y) , examples of the halogen atom in the functional groups B1 to B24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n-heptyl group, a n-octyl group, a 2-ethylhexyl group and the like, but not limited thereto. Examples of the alkoxy group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkoxy groups such as a methoxy group, an ethoxy group, a n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, and the like, but not limited thereto. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group, a naphthyl group, and the like, but not limited thereto. Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted include a phenoxy group, a naphthoxy group, and the like, but not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group, a diphenylmethyl group, and the like, but not limited thereto.
Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group, and the like, but not limited thereto. Examples of the alkylthio group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylthio groups such as a methylthio group, an ethylthio group, a n-propylthio group, an iso-propylthio group, a n-butylthio group, an iso-butylthio group, a sec-butylthio group, a t-butylthio group, a n-pentylthio group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a n-octylthio group, a 2-ethylhexylthio group, and the like, but not limited thereto. Examples of the arylthio group having 6 to 20 carbon atoms which may be substituted include a phenylthio group, a naphthylthio group, and the like, but not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but not limited thereto. Examples of the alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an iso-propylsulfonyl group, a n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a t-butylsulfonyl group, a n-pentylsulfonyl group, a n-hexylsulfonyl group, a cyclohexylsulfonyl group, a n-heptylsulfonyl group, a n-octylsulfonyl group, a 2-ethylhexylsulfonyl group, and the like, but not limited thereto. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group, a naphthylsulfonyl group, and the like, but not limited thereto. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but not limited thereto. Examples of the acyl group having 1 to 20 carbon atoms which may be substituted include linear, branched or cyclic alkylcarbonyl groups such as a methylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a n-octylcarbonyl group and a 2-ethylhexylcarbonyl group, arylcarbonyl groups such as a benzylcarbonyl group and a phenylcarbonyl group, aralkylcarbonyl groups such as a benzoyl group, and the like, but not limited thereto. Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propyloxy carbonyl group, an iso-propyloxy carbonyl group, a n-butyloxy carbonyl group, an iso-butyloxy carbonyl group, a sec-butyloxy carbonyl group, a t-butyloxy carbonyl group, a n-pentyloxy carbonyl group, a n-hexyloxy carbonyl group, a cyclohexyloxy carbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, a 2-ethylhexyloxy carbonyl group, and the like, but not limited thereto. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include a phenoxy carbonyl, a naphthylcarbonyl group, and the like, but not limited thereto. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, a diphenylmethyloxycarbonyl group, and the like, but not limited thereto. Examples of the alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted include an acetyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, a n-butylcarbonyloxy group, an iso-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a t-butylcarbonyloxy group, a n-pentylcarbonyloxy group, a n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, a n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, a n-octylcarbonyloxy group, and the like, but not limited thereto. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include a benzoyloxy group, and the like, but not limited thereto. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include a benzylcarbonyloxy group, and the like, but not limited thereto. Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted include a pyrrole group, an imidazole group, a piperidine group, a morpholine group, and the like, but not limited thereto. [0084] In the above formula (Y) , when the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, arylsulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group in the functional groups B1 to B24 is substituted, examples of the substituent present in these functional groups B1 to B24 include e.g., a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, a cyano group, a heterocyclic group, and the like, but not limited thereto. These substituents may be present in a plural number. When there are a plural number of the substituents, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group.
[0085]
(Case of Functional Group Having the End being Amino Group)
In the above formula (Y) , examples of the candidate substituent in the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted of the functional groups B1 to B24 include a hydrogen atom; linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a sec-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group and a cyclohexyl group; aryl groups such as a phenyl group and a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; linear, branched or cyclic alkylcarbonyl groups such as an acetyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an iso-propylcarbonyl group, a n-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonyl group, a t-butylcarbonyl group, a n-pentylcarbonyl group, a n-hexylcarbonyl group, a cyclohexylcarbonyl group, a n-heptylcarbonyl group, a 3-heptylcarbonyl group and a n-octylcarbonyl group; arylcarbonyl groups such as a benzoyl group and a naphthylcarbonyl group; aralkylcarbonyl groups such as a benzylcarbonyl group, and the like, but not limited thereto. These substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2. When there are two substituents, each may be of the same type or the different type, and may be the same or different in the case of the same type. Also, when there are two substituents, the substituents may be linked via a linking group. [0086]
Examples of the substituent which may be further present in the alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl group, or aralkylcarbonyl group that is the candidate substituent of the amino group which may be substituted, the aminosulfonyl group which may be substituted or the aminocarbonyl group which may be substituted include e.g., a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, a cyano group, and a heterocyclic group, but not limited thereto. These substituents may be present in a plural number. When there are a plural number of the substituent, they may be of the same type or the different type, and may be the same or different in the case of the same type. Also, the substituents may be linked via a linking group. [0087]
In addition, examples of the bivalent metal as the metal M2 include Cu(II), Co(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Ti(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Pb(II), Sn(II), and the like, but not limited thereto. Examples of the trivalent substituted metal atom include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C6H5, Al-C6H4(CH3), In-C6H5, In-C6H4(CH3), In-C6H5, Mn(OH), Mn(OC6H5), Mn [OSi (CH3) 3] , Ru-Cl, and the like, but not limited thereto. Examples of the quadrivalent substituted metal atom include CrCl2, SiF2, SiCl2, SiBr2, SiI2, ZrCl2, GeF2, GeCl2, GeBr2, GeI2, SnF2, SnCl2, SnBr2, TiF2, TiCl2, TiBr2, Ge(OH)2, Mn(OH)2, Si(OH)2, Sn(OH)2, Zr(OH)2, Cr(Ri)2, Ge(R1J2, Si(Ri)2, Sn(Ri)2, Ti(Ri)2 {Ri represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof}, Cr (OR2) 2, Ge (OR2) 2, Si (OR2) 2, Sn (OR2) 2, Ti (OR2) 2, (R2 represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, dialkylalkoxysilyl group or a derivative thereof}, Sn (SR3) 2, Ge (SR3) 2 {R3 represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof}, and the like, but not limited thereto. Examples of the oxy metal include VO, MnO, TiO, and the like, but not limited thereto.
[0088]
Specifically, trade name EXCOLOR IR-IOA, EXCOLOR IR-12, EXCOLOR IR-14 as well as TX-EX-906B, TX-EX-910B, TX-EX-902K (all manufactured by Nippon Shokubai Co., Ltd.) may be exemplified. [0089]
Further, a cyanine dye may be used as the near infrared ray absorbing dye in the near infrared ray absorbing composition of the present invention. The cyanine dye is not particularly limited as long as it is excellent in the near infrared ray absorptivity, and a salt including an indolium cation or a benzothiazolium cation, and a counter anion can be preferably used. As the indolium cation and the benzothiazolium cation, a cation represented by the following formulae (a) to (i) can preferably used, but not limited thereto.
[0090] [Chem. 16]
Figure imgf000048_0001
[0091] [Chem. 17]
Figure imgf000048_0002
[0092] [Chem. 18]
Figure imgf000049_0001
[0093] [Chem. 19]
Figure imgf000049_0002
[0094] [Chem. 20]
Figure imgf000049_0003
[0095: [Chem. 21]
Figure imgf000050_0001
[0096] [Chem. 22]
Figure imgf000050_0002
[0097] [Chem. 23]
Figure imgf000050_0003
[0098] [Chem. 24]
Figure imgf000051_0001
[0099]
The counter anion of the indolium cation or the benzothiazolium cation is not particularly limited, and a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a nitrate ion, a benzenesulfonate ion, a P-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, a propylsulfate ion, a tetrafluoroborate ion, a tetraphenylborate ion, a hexafluorophosphate ion, a benzenesulfinate ion, an acetate ion, a trifluoroacetate ion, a propionate ion, a benzoate ion, an oxalate ion, a succinate ion, a malonate ion, an oleate ion, a stearate ion, a citrate ion, a monohydrogen a diphosphate ion, a dihydrogen monophosphate ion, a pentachlorostannate ion, a chlorosulfonate ion, a fluorosulfonate ion, a trifluoromethanesulfonate ion, a hexafluoroarsenate ion, a hexafluoroantimonate ion, a molybdate ion, a tungstate ion, a titanate ion, a zirconate ion, a sulfate ion, a vanadate ion, a borate ion, a bis (trifluoromethanesulfonyl) imide ion, a tetrakis (pentafluorophenyl) borate ion and the like can be used. The counter anion of the indolium cation or the benzothiazolium cation may be any of the anions represented by the above formulae (1) to (4), similarly to the salt of the present invention as described above. [ 0100 ]
More specifically, commercially available products can be used include: as the cyanine dye including a cation represented by the above general formula (a) , ADS812MI (counter anion being an iodide ion) manufactured by American Dye Source, Inc.; as the cyanine dye including a cation represented by the above general formula (b) , S0712 manufactured by FEW Chemicals GmbH (counter anion being a hexafluorophosphate ion) ; as the cyanine dye including a cation represented by the above general formula (c) , S0726 manufactured by FEW Chemicals GmbH (counter anion being a chloride ion) ; as the cyanine dye including a cation represented by the above general formula (d) , ADS780MT manufactured by American Dye Source, Inc. (counter anion being a p-toluenesulfonate ion) ; as the cyanine dye including a cation represented by the above general formula (e) , S0006 manufactured by FEW Chemicals GmbH (counter anion being a perchlorate ion) ; as the cyanine dye including a cation represented by the above general formula (f), S0081 manufactured by FEW Chemicals GmbH
(counter anion being a perchlorate ion) ; as the cyanine dye including a cation represented by the above general formula (g) , S0773 manufactured by FEW Chemicals GmbH (counter anion being a tetrafluoroborate ion) ; as the cyanine dye including a cation represented by the above general formula (h) , trade name S0772 manufactured by FEW Chemicals GmbH (counter anion being a tetrafluoroborate ion) ; as the cyanine dye including a cation represented by the above general formula (i) , trade name S0734 manufactured by FEW Chemicals GmbH (counter anion being a tetrafluoroborate ion), and the like. A near infrared ray absorbing composition having high transparency in the visible region can be obtained by the use of the cyanine dye. [ 0101] 1-4 . (Resin)
The near infrared ray absorbing composition of the present invention may further include a resin. The resin which may be used in the present invention is not particularly limited as long as it is one which can be generally used in optical materials, but its transparency is preferably as high as possible. More specifically, examples of preferable resin include polyolefin-based resins such as polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin and cycloolefin polymers, vinyl-based polymers such as polystyrene, acrylate ester-based polymers, methacrylate ester-based polymers, vinyl acetate-based polymers, halogenated vinyl-based polymers and polyvinyl alcohol, polyamide such as nylon, polyesters such as polyurethane and PET, polyvinylacetal-based resins such as polycarbonate, epoxy resins and butyral resins, and the like. [0102]
Particularly preferable resin is a polymer produced by polymerizing a (meth) acrylate ester, and this (meth) acrylate ester has a linear, branched, alicyclic, or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms. Specific examples include polymers constituted with methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate or the like. As the monomer, one type may be used alone, or multiple types may be used to subject to copolymerization.
The using amount of each monomer is not particularly limited.
[0103] Among these, resins which can be molten or dissolved are preferably used. In this stage, when a resin having high Tg which can be molten is used, the near infrared ray absorbing composition which can be employed in molding fabrication is obtained. For example, a resin which can be molten and has Tg of 80°C or higher can be formed into a molding material by kneading with the near infrared ray absorbing dye. Suitable examples of such a resin include methacrylic polymers such as methyl polymethacrylate, and α-hydroxymethyl acrylate ester copolymers, polycarbonate, butyral resins, cyclopolyolefin polymers, ARTON (manufactured by Japan Synthetic Rubber Co., Ltd.), ZEONOR (manufactured by Zeon Corporation) , O-PET (manufactured by Kanebo, Ltd.), SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), Optoplex (manufactured by Hitachi Chemical Co., Ltd.) and the like. [0104] In addition, use of the resin which can be dissolved enables dissolution of the near infrared ray absorbing composition. According as such dissolution, the near infrared ray absorbing composition can serve as a coating agent. In this respect, examples of preferable resin include methacrylate ester-based polymers, ARTON (manufactured by Japan Synthetic Rubber Co.,
Ltd.), ZEONOR (manufactured by Zeon Corporation), and O-PET
(manufactured by Kanebo, Ltd. ) . Examples of particularly preferable polymer is a polymer produced by polymerizing a methacrylate ester having a linear, branched, alicyclic or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms. Examples of this methacrylate ester include methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and the like. This polymer may be either a polymer constituting with one type of a methacrylate ester monomer, or a copolymer constituting with multiple methacrylate ester monomers. In addition, a polymer produced by copolymerizing a monomer other than the aforementioned methacrylate ester with the aforementioned methacrylate ester is also acceptable. Examples of the other monomer include aromatic monomers such as styrene and methylstyrene; maleimide-based monomers such as phenylmaleimide and cyclohexyl maleimide; monomers having a carboxyl group such as methacrylic acid and acrylic acid; acrylate esters having an alkyl group having 1 to 15 carbon atoms; monomers having a hydroxy group such as hydroxyethyl methacrylate and hydroxyethyl acrylate, and the like. The using amount of the monomer other than the aforementioned methacrylate ester is preferably less than 50% by weight, more preferably less than 30% by weight, and still more preferably less than 10% by weight. Specific examples include SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), Optoplex (manufactured by Hitachi Chemical Co. , Ltd. ) , HALSHYBRID IR (manufactured by Nippon Shokubai Co. , Ltd. ) , and the like. Moreover, a resin having a glass transition temperature (Tg) higher than 850C can effectively suppress deterioration of the dye due to heat and moisture. [0105]
Although the resin having a high Tg has extremely favorable durability, it is accompanied by a drawback of fragility in the case of use in applications of films. For suppressing fracture of the resin, the weight average molecular weight indicated on the basis of polystyrene is equal to or greater than 50,000, and more preferably equal to or greater than 100,000. [0106]
The near infrared ray absorbing composition of the present invention exhibits favorable durability even though Tg is not higher than 850C. The type of the resin is not particularly limited, and acrylic resin, polyester resin and the like can be used. For accomplishing both fracture toughness and high durability, Tg of the resin is 65 to 85 "C, and preferably 70 to 800C. [0107]
In order to impart the fracture toughness, polymeric structure of the resin is more preferably branched than linear. The branched structure results in low viscosity of the resin even when the molecular weight is increased, thereby leading to easy handling.
[0108]
In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, or a polyfunctional chain transfer agent can be used. As the macromonomer, AA-β, AA-2, AS-6, AB-β, AK-5 (all manufactured by Toagosei Chemical Industry Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT-ESTER EG, LIGHT-ESTER 1 • 4BG, LIGHT-ESTER NP, LIGHT-ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include PERTETRA A, BTTB-50 (both manufactured by NOF Corporation) , Trigonox 17-40MB, Percadox 12-XL25 (both manufactured by Kayaku Akzo Co.Ltd.), and the like. Examples of the polyfunctional chain transfer agent which can be used include pentaerythritoltetrakis (3-mercaptopropionate) , trimethylolpropanetris (3-mercaptopropionate) , pentaerythritoltetrakis (thioglycolate) , and the like. [0109] Meanwhile, this resin may be either a pressure sensitive adhesive or an adhesive, or may be a mixture of a pressure sensitive adhesive and an adhesive. The resin that is a pressure sensitive adhesive is also referred to as a pressure sensitive adhesive resin below. The near infrared ray absorbing composition of the present invention in which the pressure sensitive adhesive or the adhesive is used as the resin can be bonded on other functional film, whereby optical filters can be conveniently and economically produced. Examples of the resin suited as a pressure sensitive adhesive include acrylic, silicon-based, SBR-based resins, and the like. Particularly preferable resins are polymers produced by polymerization of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate or the like as a principal component. In light of imparting the adhesiveness to the adherend, the resin has Tg of preferably not higher than -20°C, and more preferably not higher than -30° C. The used monomer is not particularly limited as long as the glass transition temperature calculated using the formula of Fox represented by the following formula (calculated glass transition temperature) Tg falls within a certain value range:
1/ (Tg + 273) = Σ[Wi/ (Tgi + 273)]: Fox formula Tg ("C): glass transition temperature (calculated glass transition temperature)
Wi : weight fraction of each monomer
Tgi (0C): glass transition temperature of homopolymer of each monomer component . [0110]
In the present invention, when the resin includes one type of the monomer, the glass transition temperature Tg of this resin shall be an actual value. When the resin is a copolymer, the glass transition temperature Tg of this resin can be the calculated glass transition temperature which is calculated by the above formula of Fox. [0111]
When the calculated solubility parameter of the pressure sensitive adhesive resin is too high, durability of the diimonium dye may be deteriorated. Therefore, the solubility parameter is preferably equal to or less than 9.80. The calculated solubility parameter is a value determined by the method described in "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2), pp. 147 to 154. The method will be briefly explained below.
[0112]
The solubility parameter (δ) of the homopolymer is determined by the calculation process according to the following formula on the basis of molar volume (Δvi) and evaporation energy (Δei) of the constitutional unit forming the polymer: δ= (ΣΔei/ ΣΔvi)1/2
Δei: evaporation energy of atom or atomic group of i component
Δvi: molar volume of atom or atomic group of i component. [0113]
The solubility parameter of the copolymer is determined by: determining the summation (ΣΔei) of products derived by multiplying the evaporation energy of each component monomer constituting the copolymer by the molar fraction; determining the summation (ΣΔvi) of the product derived by multiplying the molar volume of each component monomer by the molar fraction; dividing the summation (ΣΔei) by the summation (ΣΔvi) ; and determining one half power of thus derived quotient.
[0114] As the pressure sensitive adhesive resin according to present invention, those obtained by copolymerization with a
(meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group in an amount of preferably 0.05 to 40% by weight, more preferably 0.5 to 40% by weight, and particularly preferably 5 to 40% by weight are preferred because favorable durability of the diimonium dye is achieved. Although the grounds are uncertain, it is speculated that heat resistance and resistance to moist heat are improved by a stacking structure provided by the diimonium dye and the alkyl moiety of the alicyclic, polycyclic alicyclic, aromatic, polycyclic aromatic group. Preferable pressure sensitive adhesive resin is obtained by copolymerization of a
(meth) acrylate ester having an aromatic alkyl group with other monomer. Particularly preferred is a pressure sensitive adhesive resin produced by copolymerization of the (meth) acrylate ester and other monomer. When this (meth) acrylate ester has an alkyl group having an aromatic ring, satisfactory balance of the durability and the pressure sensitive adhesive property of the diimonium dye is achieved. More preferable pressure sensitive adhesive resin may be a resin produced by copolymerization of the following (ml) and (m2) , or copolymerization of the following (ml) to (m3) .
(ml) a (meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group;
(m2) a (meth) acrylate ester having an alkyl group, wherein the alkyl group may be either linear or branched, and the alkyl group has 1 to 10 carbon atoms;
(m3) other copolymerizable monomer. [0115] In the copolymer resin, preferable proportion of the monomers may be: the (meth) acrylate ester of (ml) of 5 to 40% by weight; the (meth) acrylate ester of (m2) of 60 to 95% by weight; and the other monomer of (m3) of 0 to 30% by weight. [0116]
Specific examples of the monomer (ml) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxy propyl (meth) acrylate, and the like. [0117] Specific examples of the monomer (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, and the like. [0118]
Specific examples of the monomer (m3) include (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; styrene-based monomers typified by α-methylstyrene, vinyltoluene, styrene and the like; vinyl ether-based monomers typified by methylvinyl ether, ethylvinyl ether, isobutyl vinyl ether and the like; fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid; maleic acid; monoalkyl esters of maleic acid; dialkyl esters of maleic acid; itaconic acid; monoalkyl esters of itaconic acid; dialkyl esters of itaconic acid; (meth) acrylonitrile; vinyl chloride; vinylidene chloride ; vinyl acetate; vinyl ketone; vinylpyridine; vinylcarbazole, and the like. Additionally, a monomer having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group or a fluoroalkyl group may be also subjected to copolymerization in the range not to impair the object of the present invention. [0119] The initiator which can be used in the polymerization is any commercially available article such as a peroxide-based, azo-based initiator and the like . Examples of the peroxide-based initiator include peroxy ester-based ones such as PERBUTYL 0 and PERHEXYL O (both manufactured by NOF Corporation) ; peroxydicarbonate-based ones such as PEROYL L and PEROYL 0 (both manufactured by NOF Corporation) ; diacylperoxide-based ones such as NYPER BW and NYPER BMT (both manufactured by NOF Corporation) ; peroxyketal-based ones such as PERHEXA 3M and PERHEXA MC (both manufactured by NOF Corporation) ; dialkylperoxide-based ones such as PERBUTYL P and PERCUMYL D (both manufactured by NOF Corporation) ; hydroperoxide-based ones such as PERCUMYL P and PERMENTA H (both manufactured by NOF Corporation) , and the like. Examples of the azo-based initiator include ABN-E, ABN-R, ABN-V (all manufactured by JAPAN HYDRAZINE COMPANY, INC.), and the like.
[0120]
Upon polymerization of the resin, a chain transfer agent may be used as needed. The chain transfer agent is not particularly limited as long as it can adjust to give a predetermined molecular weight, and a thiol compound such as n-dodecyl mercaptan, dithioglycol, octyl thioglycolate or mercaptoethanol can be used. [0121]
Moreover, polymerization of the resin may be carried out in a solvent free system, or may be carried out in an organic solvent. When the polymerization is carried out in an organic solvent, an aromatic solvent such as toluene or xylene; an ester-based solvent such as ethyl acetate or butyl acetate; a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone; or other known organic solvent can be used. Type of the used organic solvent may be determined taking consideration of polymerization temperature and solubility of the resulting resin, and in light of likelihood of yielding less residual solvent following drying, an organic solvent having a boiling point of not higher than 120°C such as toluene, ethyl acetate or methyl ethyl ketone is preferred.
[0122]
Additionally, the resin may be constituted with single component, or may be a polymer alloy or a polymer blend in which different components are complexed.
1-5. (Near Infrared Ray Absorbing Composition) [0123]
The near infrared ray absorbing composition of the present invention contains a cation and an anion derived from a salt not substantially having near infrared ray absorptivity. Preferably, the near infrared ray absorbing composition of the present invention contains a cation and an anion derived from a near infrared ray absorbing dye.
[0124] The near infrared ray absorbing composition of the present invention has an anion represented by the above formula (1) , the above formula (2), the above formula (3) or the above formula (4) . The near infrared ray absorbing composition of the present invention has a cation as a counter cation of the anion represented by the above formulae (1) to (4) . This cation is preferably an alkali metal cation. Preferably, the near infrared ray absorbing composition of the present invention contains the near infrared ray absorbing dye described above . Preferably, the near infrared ray absorbing composition of the present invention contains a diimonium cation represented by the above formula (5) . Preferably, the near infrared ray absorbing composition of the present invention contains an anion represented by the above formulae (6) to (9) . [0125] As described above, the near infrared ray absorbing composition of the present invention may include a near infrared ray absorbing dye. The amount of the blended near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications. For example, when the diimonium dye is used, the amount of the blended diimonium dye, or total amount of the blended diimonium dye and other near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications. When the near infrared ray absorbing composition of the present invention is used as a thin film having a thickness of approximately 10 μm, the amount of the blended near infrared ray absorbing dye is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin. When the amount is less than 0.01% by weight, it is likely to fail to attain sufficient near infrared ray absorptivity. To the contrary, when the amount is beyond 10% by weight, the effect to meet the addition is not achieved thereby leading to diseconomy, and it is likely to rather deteriorate the transparency in the visible region.
[0126] The near infrared ray absorbing composition of the present invention is characterized by transparency in the visible region, persistence of the near infrared ray absorptivity, and satisfactory processibility. To the near infrared ray absorbing composition of the present invention may be added a dye that absorbs a visible light as needed. As the dye that absorbs a visible light, conventionally known dye can be extensively used such as a cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metaldithiol complex, sguarylium, azulenium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo, azometal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indigo, azomethine, xanthene, oxanol, indoaniline, quinoline, diketopyrrolopyrrole dye, and the like. [0127] When the near infrared ray absorbing composition of the present invention is used as an optical filter for PDP, a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm is preferably used in combination for permitting absorption of unwanted neon emission. Type of the dye for absorbing the neon emission is not particularly limited, and for example, a cyanine dye or a tetraazaporphyrin dye can be used. Specifically, ADEKA ARKLS TY-102 (manufactured by Asahi Denka Kogyo K. K. ) , ADEKA ARKLS TY-14 (manufactured by Asahi Denka Kogyo K.K.), ADEKA ARKLS TY-15 (manufactured by Asahi Denka Kogyo K.K.), TAP-2 (manufactured by Yamada Chemical Co. , Ltd.), TAP-18 (manufactured by Yamada Chemical Co., Ltd.)/ TAP-45 (manufactured by Yamada Chemical Co. , Ltd. ) , trade name NK-5451 (manufactured by Hayashibara Biochamical Labs., Inc.), NK-5532 (manufactured by Hayashibara Biochamical Labs., Inc.), NK-5450 (manufactured by Hayashibara Biochamical Labs., Inc.) and the like may be exemplified. Adding amount of the dye for permitting absorption of the neon emission may vary depending on the type of the dye, it is preferred to add such that transmittance at the maximum absorption wavelength becomes approximately 20 to 80%.
[0128]
Furthermore, for adjusting the color tone of the thin film including the near infrared ray absorbing composition, a visible light absorbing dye for color toning may be added. Type of the dye for color-toning is not particularly limited, and 1:2 chromium complex, 1:2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole and the like can be used. Specific examples include Orazol Blue GN (manufactured by Ciba Specialty Chemicals) , Orazol Blue BL (manufactured by Ciba Specialty Chemicals), Orazol Red 2B (manufactured by Ciba Specialty Chemicals) , Orazol Red G (manufactured by Ciba Specialty Chemicals) , Orazol Black CN (manufactured by Ciba Specialty Chemicals) , Orazol Yellow 2GLN (manufactured by Ciba Specialty Chemicals) , Orazol Yellow 2RLN (manufactured by Ciba Specialty Chemicals) , Microris DPP Red B-K (manufactured by Ciba Specialty Chemicals), and the like. [0129]
Moreover, the near infrared ray absorbing composition of the present invention may include one, or two or more kinds of a solvent or an additive, as well as a curing agent in .the range not to deteriorate the performance as needed. [0130]
The near infrared ray absorbing composition of the present invention may be prepared by mixing the near infrared ray absorbing dye in the form of a solid (for example, powder) in the resin. The near infrared ray absorbing composition can be utilized as a coating agent . When the near infrared ray absorbing composition is coated on the film, the near infrared ray absorbing dye is preferably in the form of a solution, a dispersion or a suspension in a solvent. [0131]
Examples of the solvent which can be used in such a case include e.g., aliphatic solvents such as cyclohexane and methylcyclohexane; aromatic solvents such as toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and acetate; nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and dibutyl ether; glycol ethers such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate; amides such as formamide and N,N-dimethyl formamide; halogen-based solvents such as methylene chloride and chloroform, and the like. These solvents may be used alone, or multiple solvents may be used as mixture. In order to improve durability of the dye, a solvent having a boiling point of not higher than 100° C such as methyl ethyl ketone or ethyl acetate is suitable. Furthermore, for improving the appearance of the coated film upon coating, a solvent having a boiling point of 100 to 150 °C such as toluene, methyl isobutyl ketone or butyl acetate is suitable. In order to improve the crack resistance of the coated film, a solvent having a boiling point of 150 to 200 "C such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether or propylene glycol monomethyl ether acetate is suitable. [0132]
Although the viscosity of the coating agent is selected ad libitum depending on the type of the coater, in general, the viscosity is 1 to 1000 mPa-s when the coating is carried out according to Gravure kiss-reverse of minor diameter such as one with a microgravure coater and the like, while the viscosity is 100 to 10000 mPa-s when the coating is carried out according to a extrusion format such as one with a die coater and the like. The solid content of the coating agent may be adjusted to meet the viscosity of the coating material. [0133]
Moreover, as the additive, any conventionally known additives which have been used in the resin composition for forming films, coating films and the like can be used, and examples include dispersants, levelling agents, defoaming agents, viscosity adjusting agents, matting agents, tackifiers, antistatic agent, antioxidant, ultraviolet ray absorbents, light stabilizers, quenching agents, curing agents, antiblocking agents, and the like. As the curing agent, an isocyanate compound, a thiol compound, an epoxy compound, an amine-based compound, an imine-based compound, an oxazoline compound, a silane coupling agent, an UV curing agent, and the like can be used.
[0134]
The near infrared ray absorbing composition of the present invention can be used in: a near infrared ray absorbing material for optical applications, agricultural applications, architectural applications or for vehicles; image recording media such as photosensitive paper; information recording media such as ones for optical disc; solar batteries such as dye sensitizing solar batteries; photosensitive materials for which a semiconductor laser beam and the like is employed as a light source; or materials for preventing eye fatigue. The near infrared ray absorbing composition of the present invention is preferably used in the shape of a film or a sheet. [0135]
1-6. (Near Infrared Ray Absorbent Material)
The present invention concerning a near infrared ray absorbent material is directed to a near infrared ray absorbent material including the near infrared ray absorbing composition of the present invention. The near infrared ray absorbent material of the present invention may be produced by molding the aforementioned near infrared ray absorbing composition into a film, or may be produced by laminating a coated film including the aforementioned near infrared ray absorbing material on a transparent substrate. [0136]
The transparent substrate is not particularly limited as long as it can be generally used for optical materials, and is substantially transparent. Specific examples of the transparent substrate include glass; olefin-based polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl-based polymers such as vinyl acetate and halogenated vinyl; polyesters such as PET; polyvinylacetals such as polycarbonate and butyral resins; polyaryl ether-based resins, and the like. Additionally, the transparent substrate may be subjected to a surface treatment according to conventionally known process such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or may be subjected to coating with an anchor coating agent, a primer and the like. [0137]
Furthermore, into the substrate resin constituting the transparent substrate can be blended a known additive, a heat resistant anti-aging agent, a lubricant, an antistatic agent, and the like. The transparent substrate is molded into a film or sheet using a known process such as injection molding, T die molding, calendar molding or compression molding, or a process of casting after allowing it to melt in an organic solvent. The substrate constructing such a transparent substrate may be either unstretched or stretched, and may be laminated with other substrate.
[0138]
Preferable transparent substrate in the case in which the near infrared ray absorbing film is obtained by a coating process is a PET film, and a PET film subjected to a readily adhesive treatment is particularly suitable. Specific examples include COSMOSHINE A4300 (manufactured by Toyobo Co., Ltd.), Lumirror U34 (manufactured by Toray Industries, Inc.), Melinex 705 (manufactured by Teijin DuPont Limited), and the like. Furthermore, a functional film such as a TAC (triacetyl cellulose) film, an antireflection film, an antiglare film, a shock absorbing film, an electromagnetic wave shielding film or an ultraviolet ray absorbing film can be also used as a transparent substrate. Accordingly, optical filters for thin displays and optical semiconductor elements can be easily produced. It is preferred that the transparent substrate be a film. [0139]
Among these, glass, a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film and an electromagnetic wave shielding film is preferably used as the transparent substrate. When an inorganic substrate such as glass is used as the transparent substrate, one including a lower amount of an alkaline component is preferred in light of durability of the near infrared ray absorbing dye. [0140]
Although the near infrared ray absorbent material of the present invention has a thickness of approximately from 0.1 μm to 10 mm, in general, it may be determined ad libitum in accordance with the intended use. The content of the near infrared ray absorbing dye included in the near infrared ray absorbent material may be determined ad libitum in accordance with the intended use. [0141] Although the method of producing the near infrared ray absorbent material of the present invention is not particularly limited, for example, any of the following methods can be employed. For example, (I) a method in which the near infrared ray absorbing composition of the present invention is kneaded in a resin, and the mixture is subjected to heat molding to produce a resin plate or film; (II) a method in which the near infrared ray absorbing composition of the present invention and a monomer or an oligomer are subjected to cast molding in the presence of a polymerization catalyst to produce a resin plate or film; (III) a method in which the near infrared ray absorbing composition of the present invention is coated on the aforementioned transparent substrate, and the like may be exemplified. [0142]
As the method of the production (I) , in general, a method in which the near infrared ray absorbing composition of the present invention is added to a resin powder or pellet, and after heating the mixture to 150 to 3501C to permit dissolution, it is either molded to produce a resin plate, or subjected to film formation (resin plate formation) by an extruder, and the like may be exemplified although the conditions and the like such as fabrication temperature, film formation (resin plate formation) may vary to some extent depending on the used resin. [0143] As the method of the production (II) , a method of molding in which the near infrared ray absorbing material of the present invention and a monomer or an oligomer are subjected to cast polymerization in the presence of a polymerization catalyst, and the mixture is injected into a mold, and allowed to react for curing, or the mixture is casted into a mold and allowed to be harden until a hard product is obtained in the mold may be exemplified. Many resins can be molded by the step as listed above. Specific examples of such a resin include acrylic resins, diethylene glycolbis (allyl carbonate) resins, epoxy resin, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, a casting method of block polymerization of methyl methacrylate is preferred. According to this casting method, an acryl sheet that is excellent in hardness, heat resistance and chemical resistance is obtained.
[0144] As the polymerization catalyst, a known radical thermal polymerization initiator can be utilized, and examples thereof include e.g., peroxide such as benzoylperoxide, p-chlorobenzoylperoxide, and diisopropylperoxycarbonate, and azo compounds such as azobisisobutyronitrile. The using amount may be generally 0.01 to 5% by weight based on the total amount of the mixture. The heating temperature in the thermal polymerization is generally 40 to 200 °C, and the polymerize period is generally approximately 30 min to 8 hrs. Furthermore, in addition to the thermal polymerization, any method to permit photopolymerization through adding a photopolymerization initiator or a sensitizer can be also utilized. [0145]
As the method of the production (III) , a method of coating the near infrared absorbing composition of the present invention on a transparent substrate, a method in which the near infrared ray absorbing composition of the present invention is fixed on fine particles, and a coating material including the fine particles dispersed therein is coated on a transparent substrate, and the like may be exemplified. [0146]
When the near infrared ray absorbing composition is applied on a substrate, any known coater can be used. For example, knife coaters such as comma coaters, fountain coaters such as slot die coaters, and lip coaters, kiss coaters such as microgravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters, bar coaters may be exemplified. Before the application, a surface treatment of the substrate may be carried out by any known method such as a corona discharge treatment, a plasma treatment and the like. As a drying and curing method after the application, a known method can be used such as hot air, far infrared radiation, UV curing and the like. Following the drying and curing, the product may be rolled up together with a known protective film.
[0147] The drying method of the coated film is not particularly- limited, but hot-air drying or far-infrared drying can be employed. The drying temperature may be determined taking into consideration of the dried line length, line speed, application quantity, amount of residual solvent, type of the substrate and the like. When the substrate is a PET film, generally employed drying temperature is 50 to 150 "C. When multiple dryers are provided on one line, respective dryers may be preset to yield different temperatures and wind velocities. In order to obtain a coated film having satisfactory coating appearance, it is preferred to employ a milder drying condition on the inlet side. [0148]
The near infrared ray absorbing composition of the present invention can be a component material of an excellent optical filter having high transparency in the visible region and absorptivity of near infrared ray. The near infrared ray absorbing composition of the present invention has enhanced durability, particularly heat resistance and resistance to moist heat as compared with conventional near infrared ray absorbing materials, therefore, the appearance and the near infrared ray absorptivity can be maintained even though it is stored or used for a long period of time. In addition, the near infrared ray absorbing composition of the present invention can be readily formed to have a sheet or film shape, it is efficacious for use in thin displays, and in optical semiconductor elements. Additionally, the near infrared ray absorbing composition of the present invention can be also used in filters and films that necessitate cutting of infrared rays, for example, films for agricultural use, thermal insulating films, sunglasses, optical recording materials, and the like. [0149]
1-7. (Optical Filter)
The near infrared ray absorbing material of the present invention is suited for optical filters. The present invention concerning an optical filter is directed to an optical filter for optical semiconductor elements or for thin displays in which the near infrared ray absorbent material of the present invention is used. In this optical filter, the transmittance of entire rays of light in the visible region is preferably equal to or greater than 40%, more preferably equal to or greater than 50%, and still more preferably equal to or greater than 60%. In this optical filter, the transmittance of the near infrared ray having a wavelength of 800 to 1100 nm is preferably equal to or less than 30%, more preferably equal to or less than 15%, and still more preferably equal to or less than 5%. [0150]
The optical filter of the present invention may be provided with, in addition to a near infrared ray absorbing layer composed of the aforementioned near infrared ray absorbing material, an electromagnetic wave shielding layer, an antireflection layer, a glare preventive (antiglare) layer, a sticking preventive layer, a color adjusting layer, a support such as glass and the like.
[0151]
Constitution of each layer of the optical filter may be arbitrarily selected, and an optical filter in which at least two layers are provided in combination of either one layer of the antireflection layer and the antiglare layer, and the near infrared ray absorbing layer is preferred. Further, an optical filter having at least three layers in combination, i.e., the aforementioned at least two layers, and further the electromagnetic wave shielding layer is more preferred. [0152]
It is preferred that the antireflection layer, or the antiglare layer be provided as the front most layer positioned on the closest side to human. The order of lamination of the near infrared ray absorbing layer and the electromagnetic wave shielding layer with respect to each other may be arbitrarily determined. Moreover, in between the three layers, other layer such as a sticking preventive layer, a color adjusting layer, a shock absorbing layer, a support or a transparent substrate may be also inserted.
[0153]
Upon lamination of each layer, it may be subjected to a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent. [0154]
In the optical filter for thin display, it is preferred that the antireflection layer or antiglare layer be provided as the front most layer positioned on the closest side to human for accelerating visibility of the screen. [0155]
The antireflection layer is provided for suppressing reflection on the surface, and for preventing unwanted image visualization on the surface due to the external light such as a light from the fluorescent lamp. There are two types of the antireflection layer, i.e., those composed of a thin film of an inorganic substance such as metal oxide, fluoride, suicide, boride, carbide, nitride, sulfide and the like, and those obtained by lamination of resins having different refractive indices such as an acrylic resin and a fluorocarbon resin into monolayer or multiple layers. In the former case, the manufacture method may include forming the antireflection coating on a transparent substrate with a vacuum evaporation or sputtering process to give monolayer or multilayer. In the latter case, a manufacture method in which an antireflection coating is applied on the surface of the transparent substrate, on a transparent film, using a knife coater such as a comma coater, a fountain coater such as a slot coater or a lip coater, a gravure coater, a flow coater, a spray coater or a bar coater may be exemplified. [0156] The antiglare layer is formed by making an ink from fine powder of silica, a melamine resin, an acrylic resin or the like, and coating on any one of the layers of the filter of the present invention by a conventionally known coating method, followed by allowing for heat-curing or photo-curing. Also, a film which had been subjected to an antiglare treatment may be pasted on the filter. [0157]
Moreover, the sticking preventive layer is formed by dissolving or dispersing an acrylate such as urethaneacrylate, epoxyacrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent to prepare a coating liquid, applying this coating liquid on any of the layers of the filter of the present invention by a conventionally known method of application followed by drying and allowing for photo-curing . [0158]
The optical filter having the antireflection layer or the antiglare layer and the near infrared ray absorbing layer is obtained by laminating a layer composed of the near infrared ray absorbing composition of the present invention on the back face of the antireflection film or the antiglare film. In the method of lamination, the near infrared ray absorbing composition of the present invention formed into a film may be pasted with the antireflection film or the antiglare film by a pressure sensitive adhesive, or dissolved near infrared ray absorbing material of the present invention may be directly applied on the back face of the antireflection film or the antiglare film. Additionally, when an adhesive near infrared ray absorbing composition is used, the near infrared ray absorbing layer and the other layer may be directly pasted by way of this adhesiveness. When the near infrared ray absorbing layer is provided on the back face of the antireflection film or the antiglare film, the ultraviolet ray absorbing film is preferably used as a transparent substrate for suppressing the deterioration of the dye resulting from the ultraviolet ray. [0159]
In the optical filter for plasma displays, it is preferred to provide the electromagnetic wave shielding layer for removing the electromagnetic wave generated from the panel. [0160] As the electromagnetic wave shielding layer, a film produced by patterning a metal mesh on a film by a process such as etching or printing, followed by leveling, or a film produced by embedding a metal vacuum evaporated on a fiber mesh into a resin may be used. [0161]
The optical filter having two layers of the near infrared ray absorbing layer and the electromagnetic wave shielding layer is obtained by combination of an electromagnetic wave preventive material and a near infrared ray absorbing composition. In the method of combination, the electromagnetic wave shielding film may be pasted with the near infrared ray absorbing composition of the present invention formed to have a film shape using the pressure sensitive adhesive, the dissolved near infrared ray absorbing material of the present invention may be directly applied on the electromagnetic wave shielding film. Furthermore, when the near infrared ray absorbing composition is adhesive, the near infrared ray absorbing composition of the present invention formed to have a film shape may be directly pasted with the electromagnetic wave shielding film. Also, when the metal on the film is subjected to levelling, the near infrared ray absorbing composition of the present invention can be used. Further, when the fiber to which a metal is vacuum evaporated is embedded, the near infrared ray absorbing composition of the present invention can be also used. [0162]
The optical filter having three layers, i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film by a pressure sensitive adhesive. A support such as glass, or a functional film such as a color adjusting film may be also pasted as needed. When the near infrared ray absorbing composition has adhesiveness, the near infrared ray absorbing film may be laminated such that it is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film. In this case, use of the pressure sensitive adhesive can be unnecessary because the three films are bonded utilizing the adhesive force of the near infrared ray absorbing film. [0163]
In order to simplify the steps of manufacturing the optical filter and construction of the film, a combination film providing multiple functions may be used. For example, the optical filter obtained by pasting a combination film including the near infrared ray absorbing layer and the reflection or antiglare layer with the electromagnetic wave shielding film by a pressure sensitive adhesive; the optical filter obtained by pasting a combination film including the near infrared ray absorbing layer and the electromagnetic wave shielding layer is pasted with the reflection or antiglare film by a pressure sensitive adhesive; the optical filter obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer with the near infrared ray absorbing film by a pressure sensitive adhesive may be exemplified. [0164] The optical filter having three layers, i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film. When the near infrared ray absorbing composition has adhesiveness, an optical filter having a structure in which the near infrared ray absorbing film is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film is preferred. Since the film having these three layers are laminated utilizing the adhesiveness of the near infrared ray absorbing film, the adhesive layer conventionally provided only for the purpose of pasting of the film can be omitted. A support such as glass, or a functional film such as a color adjusting film may be also pasted as needed. [0165]
In order to further simplify the steps of manufacturing the optical filter and construction of the film, a combination film providing multiple functions may be used. Preferable optical filter may be obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer in one film with the near infrared ray absorbing adhesive layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
[0166]
The optical filter of the present invention for thin display may be either provided away from the display unit, or directly pasted to the display unit. When it is provided away from the display unit, glass is preferably used as the support. When it is directly pasted to the display unit, the optical filter without use of the glass is preferred.
[0167]
1-8. (Thin Display) When the optical filter including the near infrared ray absorbing composition of the present invention laminated therein is built in a thin display, a satisfactory image quality is maintained for a long period of time. The present invention concerning a thin display is directed to a thin display in which the near infrared ray absorbing material of the present invention, the near infrared ray absorbent material of the present invention, or the optical filter of the present invention is used. The thin display in which the optical filter is directly pasted to the display body can produce more clear image quality. When the optical filter is directly pasted, it is preferred to either use tempered glass as the glass for the display body, or use the optical filter provided with a shock absorbing layer.
[0168]
Examples of the pressure sensitive adhesive used in pasting the optical filter of the present invention to the display unit include rubbers such as styrene butadiene rubbers, polyisoprene rubbers, polyisobutylene rubbers, natural rubbers, neoprene rubbers, chloroprene rubbers and butyl rubbers, alkyl esters of polyacrylic acid such as methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate and the like, which may be used alone, or as a mixture prepared by further adding Piccolite, Polyvel, a rhodine ester or the like as a tackifiers. Also, a pressure sensitive adhesive having shock absorptivity as disclosed in Japanese Unexamined Patent Application Publication No. 2004-263084 can be used as the pressure sensitive adhesive, but not limited thereto. [0169]
This pressure sensitive adhesive layer has a thickness of generally 5 to 2000 μm, and preferably 10 to 1000 μm. A releasable film may be provided on the surface of the pressure sensitive adhesive layer, and thus the pressure sensitive adhesive layer may be protected by this releasable film so as to avoid attachment of dirts and the like to the pressure sensitive adhesive layer during the time period until the optical filter is pasted to the surface of the thin display. In this case, a nonadhesive part may be formed between the releasable film and the pressure sensitive adhesive layer of the filter at the surrounding edge by providing a part not having the pressure sensitive adhesive layer, or by interposing a nonadhesive film. This nonadhesive part may be used as a release initiation site. In such a case, operation in release will be easily conducted.
[0170]
The shock absorbing layer is provided for the purpose of protecting the display unit from external shock. It is preferred that the shock absorbing layer be used for the optical filter without having the support. Example of the shock absorber which can be used include ethylene-vinyl acetate copolymers, acrylic polymers, polyvinyl chloride, urethane-based, silicon-based resins and the like as disclosed in Japanese Unexamined Patent Application Publication No. 2004-246365 or No. 2004-264416, but not limited thereto.
[0171]
In the foregoing item numbers from 1-1 to 1-8, the present invention concerning a salt is explained. Next, the present invention concerning a pressure sensitive adhesive composition will be explained in the following item numbers 2-1 to 2-6.
[0172] 2-1. (Diimonium Dye)
The diimonium dye used in the present invention has a maximum absorption wavelength in the acetone solution of 1000 or greater and 1060 nm or less. Preferably, the diimonium dye has a maximum absorption wavelength in the acetone solution of
1010 or greater and 1055 nm or less, and more preferably 1020 nm or greater and 1050 nm or less. Such a diimonium dye is excellent in persistence of the near infrared ray absorptivity and the transparency in the visible region.
[0173]
With respect to the specific structure of the diimonium dye, diimonium dyes including a diimonium cation represented by the following formula (10), and an anion represented by the following formula (11) or (12) may be illustrated.
[0174] [Chem. 25]
Figure imgf000084_0001
[0175] [Chem. 26]
RL-S^
N" (11)
RH-SO2
[0176] [Chem. 27]
Figure imgf000084_0002
[0177; In the formula (10) , R9 to R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent. In the formula (11), RL and RM each represent a fluoroalkyl group which may be the same or different. Further, in the formula (12) , RN represents a fluoroalkylene group. [0178]
As the alkyl group having 1 to 10 carbon atoms constituting R9 to R16, a linear, branched or alicyclic alkyl group, or the like may be exemplified. Examples of such an alkyl group include e.g., a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a 1, 1-dimethylpropyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, and the like. [0179]
Moreover, examples of the substituent which can bind to the alkyl group in R9 to R16 include a cyano group; a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a n-propoxy group and n-butoxy group; alkoxyalkoxy groups having 2 to 8 carbon atoms such as a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group, a methoxybutoxy group and an ethoxybutoxy group; alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group and an ethoxyethoxyethoxy group; an allyloxy group; an aryloxy groups having 6 to 12 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group and a naphthyloxy group; alkoxycarbonyl groups having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxy carbonyl group, an isopropoxy carbonyl group and a n-butoxycarbonyl group; alkylcarbonyloxy groups having 2 to 7 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group and a n-butylcarbonyloxy group; alkoxycarbonyloxy groups having 2 to 7 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, and the like. [0180]
Type of the anion in the diimonium dye is not particularly limited. Preferable anion is an imide anion. More preferable anion is an anion represented by the above formula (11) or the formula (12) . [0181]
In connection with the above formula (11) , the fluoroalkyl group represented by RL or RM may be a perfluoroalkyl group such as CF3, C2F5, C3F7, C4F9, and the like. RL and RM may be the same or different. In connection with the above formula (12), the fluoroalkylene group represented by RN may be (CF2) n (wherein, n is an integer of from 2 to 12) , and the like. [0182] Examples of preferable imide anion include bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion,
1, 3-disulfonylhexafluoropropyleneimide, pentafluoroethanesulfonyltrifluoromethanesulfonyl imide ion, nonafluorobutanesulfonyltrifluoromethanesulfonyl imide ion, and the like. Furthermore, as the anion of the diimonium dye, one, or two or more anions selected from the group consisting of hexafluoroantimonate anion, hexafluorophosphate anion, tetrafluoroborate anion and perchlorate anion can be also used. [0183]
With respect to the specific structure of the diimonium dye, those disclosed in Japanese Unexamined Patent Application Publication No. 2005-325292 may be exemplified. [0184] Exemplary compound names of the diimonium dye include bishexafluoroantimonate-N,N,N' ,N' -tetrakis-{p-di (4, 4, 4-trifl uorobutyl) aminophenyl}-p-phenylenediimonium (1048 nm) , bishexafluoroantimonate-N,N, N' , N' -tetrakis-{p-di (2, 2, 2-trif1 uoroethyl) aminophenyl}-p-phenylenediimonium (1020 nm) , bishexafluoroantimonate-N,N,N' , N' -tetrakis-{p-di (perfluorobu tyl) aminophenyl } -p-phenylenediimonium (1032 nm) , bishexafluoroantimonate-N,N,N' ,N' -tetrakis-{p-di (4,4, 4-trich lorobutyl) aminophenyl} -p-phenylenediimonium (1049 nm) , bis{bis (trifluoromethanesulfonyl) imidic acid}-N,N,N' ,N' -tetrakis-{p-di (4,4, 4-trifluorobutyl) aminophe nyl} -p-phenylenediimonium (1048 nm) , bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N' , N' -tetrakis- {p-di (2,2, 2-trifluoroethyl) aminophe nyl} -p-phenylenediimonium (1020 nm) , bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N' ,N' -tetrakis-{p-di (perfluorobutyl) aminophenyl }-p -phenylenediimonium (1032 nm) , bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N' ,N' -tetrakis-{p-di (4,4, 4-trichlorobutyl) aminophe nyl} -p-phenylenediimonium (1049 nm) , bis (1, 3-disulfonylhexafluoropropylene) imidic acid}-N,N,N' ,N' -tetrakis-{p-di (4,4, 4-trifluorobutyl) aminophe nyl}-p-phenylenediimonium (1048 nm), bis (1, 3-disulfonylhexafluoropropylene) imidic acid} -N, N, N' ,N' -tetrakis-{p-di (2, 2, 2-trifluoroethyl) aminophe nyl}-p-phenylenediimonium (1020 nm) , bis (1, 3-disulfonylhexafluoropropylene) imidic acid} -N, N, N' , N' -tetrakis- {p-di (perfluorobutyl) aminophenyl } -p -phenylenediimonium (1032 nm) , and bis (1, 3-disulfonylhexafluoropropylene) imidic acid}-N,N,N' ,N' -tetrakis-{p-di (4,4, 4-trichlorobutyl) aminophe nyl}-p-phenylenediimonium (1049 nm) . The values in the foregoing parentheses represent the maximum absorption wavelength in the acetone solution. [0185]
Specific manufactured article which can be referred to as the diimonium dye according to the present invention may be CIR-1085F (manufactured by Japan Carlit Co., Ltd.). This CIR-1085F has a maximum absorption wavelength in the acetone solution being 1049 nm. [0186]
The determination method of the maximum absorption wavelength in the acetone solution is as described above. [0187] 2-2. (Resin) the resin according to the present invention is not particularly limited as long as it has a calculated glass transition temperature of equal to or lower than -20 "C. The resin according to the present invention has adhesiveness. This adhesiveness enables the near infrared ray absorbing pressure sensitive adhesive composition to directly bond to the adherend. The near infrared ray absorbing pressure sensitive adhesive composition can be bonded to the adherend without the adhesive interposed therebetween. Hereinafter, this resin may be also referred to as pressure sensitive adhesive resin.
[0188] 2-2-1. Calculated Glass Transition Temperature
In light of the adhesiveness to be imparted to the adherend, the pressure sensitive adhesive resin has a calculated glass transition temperature of equal to or lower than -20 °C, and more preferably equal to or lower than -30°C. When it is higher than -20 'C, the adhesiveness may be insufficient. The calculated glass transition temperature Tg may be determined according to the Fox formula described above. The monomer used in polymerization of the resin is not particularly limited as long as the glass transition temperature (calculated glass transition temperature) Tg calculated using the aforementioned Fox formula falls within a specified value range. [0189] 2-2-2. Acid Value
For the purpose of improving coherent adhesiveness with the adherend, and enhancing the adhesive force, the pressure sensitive adhesive resin is generally copolymerized with a carboxyl group-containing monomer such as acrylic acid. However, since the functional group such as a carboxyl group may deteriorate the diimonium dye, the pressure sensitive adhesive has an acid value of preferably equal to or less than 25, more preferably 0 or greater and 20 or less, still more preferably 0 or greater and 10 or less, and most preferably 0. The "acid value" refers to the amount represented by mg of potassium hydroxide required for neutralization of 1 g of the pressure sensitive adhesive resin.
[0190]
2-2-3. Calculated Solubility Parameter When the calculated solubility parameter of the pressure sensitive adhesive resin is too high, the diimonium dye may be inferior in durability. Therefore, the solubility parameter is preferably equal to or less than 9.80. Details of the calculated solubility parameter, and the calculation method are as described above. The method of determining the solubility parameter of the copolymer is as described above.
[0191] 2-2-4. Copolymer Composition
The pressure sensitive adhesive resin may be a copolymer. As the pressure sensitive adhesive resin according to present invention, those obtained by copolymerization with a
(meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group in an amount of preferably 0.05 to 40% by weight, more preferably 0.5 to 40% by weight, and particularly preferably 5 to 40% by weight are preferred because favorable durability of the diimonium dye is achieved. Although the grounds are uncertain, it is speculated that heat resistance and resistance to moist heat are improved by a stacking structure provided by the diimonium dye and the alkyl moiety of the alicyclic, polycyclic alicyclic, aromatic, polycyclic aromatic group. Preferable pressure sensitive adhesive resin is obtained by copolymerization of a
(meth) acrylate ester having an aromatic alkyl group with other monomer. Particularly preferred is a pressure sensitive adhesive resin produced by copolymerization of the (meth) aerylate ester and other monomer. When this (meth) acrylate ester has an alkyl group having an aromatic ring, satisfactory balance of the durability and the pressure sensitive adhesive property of the diimonium dye is achieved. [0192]
More preferable pressure sensitive adhesive resin may be a resin produced by copolymerization of the following (m4) and (m5) , or copolymerization of the following (m4) to (mβ) .
(m4) a (meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group;
(m5) a (meth) acrylate ester having an alkyl group, wherein the alkyl group may be either linear or branched, and the alkyl group has 1 to 10 carbon atoms; (mβ) other copolymerizable monomer. [0193]
In the copolymer resin, preferable proportion of the monomers may be: the (meth) acrylate ester of (m4) of 5 to 40% by weight; the (meth) acrylate ester of (m5) of 60 to 95% by weight; and the other monomer of (mβ) of 0 to 30% by weight. [0194]
Examples of the (meth) acrylate ester of (m4) are the same as those of (ml) described above. Examples of the (meth) acrylate ester of (m5) are the same as those of (m2) described above. Examples of the monomer of (mβ) are the same as those of (m3) described above. [0195]
The initiator which can be used in the polymerization of the pressure sensitive adhesive resin is any commercially available article such as a peroxide-based, azo-based initiator and the like. Examples of the peroxide-based initiator include peroxy ester-based ones such as PERBUTYL 0 and PERHEXYL 0 (both manufactured by NOF Corporation) ; peroxydicarbonate-based ones such as PEROYL L and PEROYL 0 (both manufactured by NOF Corporation) ; diacylperoxide-based ones such as NYPER BW and NYPER BMT (both manufactured by NOF Corporation) ; peroxyketal-based ones such as PERHEXA 3M and PERHEXA MC (both manufactured by NOF Corporation) ; dialkylperoxide-based ones such as PERBUTYL P and PERCUMYL D (both manufactured by NOF Corporation) ; hydroperoxide-based ones such as PERCUMYL P and PERMENTA H (both manufactured by NOF Corporation) , and the like. Examples of the azo-based initiator include ABN-E, ABN-R, ABN-V (all manufactured by JAPAN HYDRAZINE COMPANY, INC.), and the like. [0196]
Upon polymerization of the pressure sensitive adhesive resin, a chain transfer agent may be used as needed. The chain transfer agent is not particularly limited, and a thiol compound such as n-dodecyl mercaptan, dithioglycol, octyl thioglycolate or mercaptoethanol can be used. [0197]
Moreover, polymerization of the pressure sensitive adhesive resin may be carried out in a solvent free system, or may be carried out in an organic solvent . When the polymerization is carried out in an organic solvent, an aromatic solvent such as toluene or xylene; an ester-based solvent such as ethyl acetate or butyl acetate; a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone; or other known organic solvent can be used. Type of the used organic solvent may be determined taking consideration of polymerization temperature and solubility of the resulting resin, and in light of likelihood of yielding less residual solvent following drying, an organic solvent having a boiling point of not higher than 120° C such as toluene, ethyl acetate or methyl ethyl ketone is preferred. [0198]
Additionally, the resin may be constituted with single component, or may be a polymer alloy or a polymer blend in which different components are complexed. [0199] In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, or a polyfunctional chain transfer agent can be used. As the macromonomer, AA-β, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Chemical Industry Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT-ESTER EG, LIGHT-ESTER 1 • 4BG, LIGHT-ESTER NP, LIGHT-ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include PERTETRA A, BTTB-50 (both manufactured by NOF Corporation) , Trigonox 17-40MB, Percadox 12-XL25 (both manufactured by Kayaku Akzo Co.Ltd.), and the like. Examples of the polyfunctional chain transfer agent which can be used include pentaerythritoltetrakis (3-mercaptopropionate) , trimethylolpropanetris (3-mercaptopropionate) , pentaerythritoltetrakis (thioglycolate) , and the like.
[0200]
2-3. (near infrared ray absorbing pressure sensitive adhesive composition)
Since the near infrared ray absorbing pressure sensitive adhesive composition of the present invention contains a diimonium dye having a maximum absorption wavelength in the acetone solution of 1000 nm or greater and 1060 nm or less, it is excellent in the transparency in the visible region and the near infrared ray absorptivity. Since the near infrared ray absorbing pressure sensitive adhesive composition of the present invention contains the resin having adhesiveness, it can be readily bonded to the adherend. [0201] To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be also added other near infrared ray absorbing dye. Examples of the other near infrared ray absorbing dye which can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, dithiol metal complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like. [0202]
When the near infrared ray absorbing pressure sensitive adhesive composition of present invention is used as an optical filter for thin displays, it is preferred that a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm, a cyanine dye having a maximum absorption wavelength of 800 to 950 nm, or a dithiol metal complex dye having a maximum absorption wavelength of 800 to 950 nm be used in combination with the diimonium dye described above. This use in combination enables effective absorption of a near infrared ray of 800 to 1100 nm. In light of acquisition of the near infrared ray absorbing pressure sensitive adhesive composition having favorable durability, use of a phthalocyanine dye in combination is particularly preferred. [0203] The phthalocyanine-based compound which can be used in the present invention is not particularly limited as long as it is excellent in near infrared ray absorptivity, and known phthalocyanine-based compound can be used. Exemplary preferable phthalocyanine-based compound includes the compounds represented by the formula (X) , or the compounds represented by the formula (Y) as described above. All details in regard to these formula (X) and formula (Y) are as set forth in connection with the present invention concerning a salt. [0204]
Specific examples of the phthalocyanine-based compound which can be used in the present invention concerning a pressure sensitive adhesive composition include trade names EXCOLOR IR-IOA, EXCOLOR IR-12, EXCOLOR IR-14, and TX-EX-906B, TX-EX-910B and TX-EX-902K (all manufactured by Nippon Shokubai Co., Ltd.) . [0205]
Additionally, in the near infrared ray absorbing pressure sensitive adhesive composition of the present invention, a cyanine dye may be used in combination with the near infrared ray absorbing dye. Although the cyanine dye is not particularly limited as long as it is excellent in the near infrared ray absorptivity, a salt composed of an indolium cation or a benzothiazolium cation, and a counter anion can be preferably used. As the indolium cation or benzothiazolium cation, the cations represented by the formula (a) , the formula (b) , the formula (c) , the formula (d) , the formula (e) , the formula (f) , the formula (g) , the formula (h) and the formula (i) described above can be preferably used, but not limited thereto. All details described above in connection with the formula (a) , the formula (b) , the formula (c) , the formula (d) , the formula (e) , the formula (f) , the formula (g) , the formula (h) and the formula (i) can be applied also to the present invention concerning a pressure sensitive adhesive composition. By using the cyanine dye, the near infrared ray absorbing pressure sensitive adhesive composition having high transparency in the visible region can be obtained. [0206]
The amount of the blended diimonium dye of the present invention, or total amount of the blended diimonium dye of the present invention and other near infrared ray absorbing dye can be selected ad libitum depending on the type of the dye and the applications. When the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is used as a thin film having a thickness of 10 to 30 μm, the blended amount is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin. For example, when the diimonium dye and the phthalocyanine dye are used in combination, total amount of these dyes is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight based on the solid content of the resin. When the amount is less than 0.01% by weight, it is likely to fail to attain sufficient near infrared ray absorptivity. To the contrary, when the amount is beyond 10% by weight, the effect to meet the addition is not achieved thereby leading to diseconomy, and it is likely to rather deteriorate the transparency in the visible region. [0207]
The near infrared ray absorbing pressure sensitive adhesive composition of the present invention is characterized by transparency in the visible region, persistence of the near infrared ray absorptivity, and satisfactory adhesiveness. To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be added a dye that absorbs a visible light as needed. Examples of the dye that absorbs the visible light include those described above in connection with the present invention concerning a salt. [0208]
When the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is used as an optical filter for PDP, a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm is preferably used in combination for permitting absorption of unwanted neon emission. Type of the dye for absorbing the neon emission is not particularly limited, and for example, the dyes described above in connection with the present invention concerning a salt may be exemplified. Adding amount of the dye for permitting absorption of the neon emission may vary depending on the type of the dye, it is preferred to add such that transmittance at the maximum absorption wavelength becomes approximately 20 to 80%. [0209] Furthermore, for adjusting the color tone of the thin film including the near infrared ray absorbing pressure sensitive adhesive composition, a visible light absorbing dye for color toning may be added. Type of the dye for color-toning is not particularly limited, and for example, the dyes described above in connection with the present invention concerning a salt may be exemplified. [0210]
Moreover, the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may include one, or two or more kinds of a solvent or an additive, as well as a curing agent in the range not to deteriorate the performance as needed. [0211]
The near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be prepared by mixing the near infrared ray absorbing dye in the form of a solid (for example, powder) in the resin. When the near infrared ray pressure sensitive adhesive absorbing composition is coated on the film, the near infrared ray absorbing dye is preferably in the form of a solution, a dispersion or a suspension in a solvent.
[0212]
As the solvent which can be used in coating, the solvents described above in connection with the present invention concerning a salt may be exemplified. These may be used alone, or as a mixture. In order to improve durability of the dye, a solvent having a boiling point of not higher than 1000C such as methyl ethyl ketone or ethyl acetate is suitable. Furthermore, for improving the appearance of the coated film upon coating, a solvent having a boiling point of 100 to 15O0C such as toluene, methyl isobutyl ketone or butyl acetate is suitable. In order to improve the crack resistance of the coated film, a solvent having a boiling point of 150 to 200 "C such as butylcellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether or propylene glycol monomethyl ether acetate is suitable.
[0213]
The viscosity of the coating agent is selected ad libitum depending on the type of the coater, and is similar to that described above in connection with the present invention concerning a salt. The solid content of the coating agent may be adjusted to meet the viscosity of the coating material. [0214]
Moreover, as the additive, any conventionally known additives which have been used in the resin composition for forming films, coating films and the like can be used. Examples of the additive include dispersants, levelling agents, defoaming agents, viscosity adjusting agents, matting agents, tackifiers, antistatic agent, antioxidant, ultraviolet ray absorbents, light stabilizers, quenching agents, curing agents, antiblocking agents, and the like. As the curing agent, an isocyanate compound, a thiol compound, an epoxy compound, an amine-based compound, an imine-based compound, an oxazoline compound, a silane coupling agent, an UV curing agent, and the like can be used. [0215]
The near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be used in: a near infrared ray absorbing material for optical applications, agricultural applications, architectural applications or for vehicles; image recording media such as photosensitive paper; information recording media such as ones for optical disc; solar batteries such as dye sensitizing solar batteries; photosensitive materials for which a semiconductor laser beam or the like is employed as a light source; or materials for preventing eye fatigue. The near infrared ray absorbing pressure sensitive adhesive composition of the present invention is preferably used in the shape of a film or a sheet. [0216] To the near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be added the salt described above in connection with the present invention concerning a salt. Addition of this salt makes the balance of the pressure sensitive adhesive property and the durability more favorable . [0217]
2-4. (Near Infrared Ray Absorbent Material)
The near infrared ray absorbent material according to the present invention includes the near infrared ray absorbing pressure sensitive adhesive composition of the present invention. The near infrared ray absorbent material of the present invention may be produced by molding the aforementioned near infrared ray absorbing pressure sensitive adhesive composition into a film, or may be produced by laminating a coated film including the aforementioned near infrared ray absorbing pressure sensitive adhesive composition on a transparent substrate .
[0218]
The transparent substrate is not particularly limited as long as it can be generally used for optical materials, and is substantially transparent. Specific examples of the transparent substrate include glass; olefin-based polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl-based polymers such as vinyl acetate and halogenated vinyl; polyesters such as PET; polyvinylacetals such as polycarbonate and butyral resins; polyaryl ether-based resins, and the like. Additionally, the transparent substrate may be subjected to a surface treatment according to conventionally known process such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or may be subjected to coating with an anchor coating agent, a primer and the like. Furthermore, into the substrate resin constituting the transparent substrate can be blended a known additive, a heat resistant anti-aging agent, a lubricant, an antistatic agent, and the like. The transparent substrate is molded into a film or sheet using a known process such as injection molding, T die molding, calendar molding or compression molding, or a process of casting after allowing it to melt in an organic solvent. The substrate constructing such a transparent substrate may be either unstretched or stretched, and may be laminated with other substrate. [0219]
Preferable transparent substrate in the case in which the near infrared ray absorbing film is obtained by a coating process is a PET film, and a PET film subjected to a readily adhesive treatment is particularly suitable. Specific examples include
COSMOSHINE A4300 (manufactured by Toyobo Co., Ltd.), Lumirror
034 (manufactured by Toray Industries, Inc.), Melinex 705
(manufactured by Teijin DuPont Limited), and the like. Furthermore, a functional film such as a TAC (triacetyl cellulose) film, an antireflection film, an antiglare film, a shock absorbing film, an electromagnetic wave shielding film or an ultraviolet ray absorbing film can be also used as a transparent substrate. Accordingly, optical filters for thin displays and optical semiconductor elements can be easily produced. It is preferred that the transparent substrate be a film. [0220]
Among these, glass, a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film and an electromagnetic wave shielding film is preferably used as the transparent substrate. When an inorganic substrate such as glass is used as the transparent substrate, one including a lower amount of an alkaline component is preferred in light of durability of the near infrared ray absorbing dye. [0221]
Although the thickness of the near infrared ray absorbent material of the present invention may be approximately from 0.1 μm to 10 mm, in general, it may be determined ad libitum in accordance with the intended use. The content of the near infrared ray absorbing dye included in the near infrared ray absorbent material may be determined ad libitum in accordance with the intended use. [0222] Although the method of producing the near infrared ray absorbent material of the present invention is not particularly limited, for example, any of the following methods can be employed. For example, (I) a method in which a resin and the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention are kneaded, and the mixture is subjected to heat molding to produce a resin plate or film; (II) a method in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention and a monomer or an oligomer are subjected to cast molding in the presence of a polymerization catalyst to produce a resin plate or film; (III) a method in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention is coated on the aforementioned transparent substrate, and the like may be exemplified. [0223] As the method of the production (I), in general, a method in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention is added to a resin powder or pellet, and after heating the mixture to 150 to 350 ° C to permit dissolution, it is either molded to produce a resin plate, or subjected to film formation (resin plate formation) by an extruder, and the like may be exemplified although the conditions and the like such as fabrication temperature, film formation (resin plate formation) may vary to some extent depending on the used resin. [0224]
As the method of the production (II) , a method of molding in which the near infrared ray absorbing pressure sensitive adhesive composition according to the present invention and a monomer or an oligomer are subjected to cast polymerization in the presence of a polymerization catalyst, and the mixture is injected into a mold, and allowed to react for curing, or casted into a mold and allowed to be harden until a hard product is obtained in the mold may be exemplified. Many resins can be molded by the step as listed above. Specific examples of such a resin include acrylic resins, diethylene glycolbis (allyl carbonate) resins, epoxy resin, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, a casting method of block polymerization of methyl methacrylate is preferred, which can produce an acryl sheet that is excellent in hardness, heat resistance and chemical resistance. [0225]
As the polymerization catalyst, a known radical thermal polymerization initiator can be utilized, and examples thereof include e.g., peroxide such as benzoylperoxide, p-chlorobenzoylperoxide, and diisopropylperoxycarbonate, and azo compounds such as azobisisobutyronitrile. The using amount may be generally 0.01 to 5% by weight based on the total amount of the mixture. The heating temperature in the thermal polymerization is generally 40 to 2000C, and the polymerize period is generally approximately 30 min to 8 hrs . Furthermore, in addition to the thermal polymerization, any method to permit photopolymerization through adding a photopolymerization initiator or a sensitizer can be also utilized. [0226] As the method of the production (III) , a method of coating the near infrared absorbing material of the present invention on a transparent substrate, a method in which the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is fixed on fine particles, and a coating material including the fine particles dispersed therein is coated on a transparent substrate, and the like may be exemplified. [0227]
When the near infrared ray absorbing pressure sensitive adhesive composition is applied on a substrate, any known coater can be used. As the coater, for example, the coaters described above in connection with the present invention concerning a salt may be exemplified. Before the application, a surface treatment of the substrate may be carried out by any known method such as a corona discharge treatment, a plasma treatment and the like. As a drying and curing method, a known method can be used such as hot air, far infrared radiation, UV curing and the like. Following the drying and curing, the product may be rolled up together with a known protective film. [0228] The drying method of the coated film is not particularly limited, but hot-air drying or far-infrared drying can be employed. The drying temperature may be determined taking into consideration of the dried line length, line speed, application quantity, amount of residual solvent, type of the substrate and the like. When the substrate is a PET film, generally employed drying temperature is 50 to 150° C. When multiple dryers are provided on one line, respective dryers may be preset to yield different temperatures and wind velocities. In order to obtain a coated film having satisfactory coating appearance, it is preferred to employ a milder drying condition on the inlet side. [0229]
The near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be a component material of an excellent optical filter having high transparency in the visible region and absorptivity of near infrared ray. The near infrared ray absorbing pressure sensitive adhesive composition of the present invention has enhanced durability, particularly heat resistance and resistance to moist heat as compared with conventional near infrared ray absorbing materials, therefore, the appearance and the near infrared ray absorptivity can be maintained even though it is stored or used for a long period of time. In addition, the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be readily formed to have a sheet or film shape, it is efficacious for use in thin displays, and in optical semiconductor elements. Additionally, the near infrared ray absorbing composition of the present invention can be also used in filters and films that necessitate cutting of infrared rays, for example, films for agricultural use, thermal insulating films, sunglasses, optical recording materials, and the like. [0230] 2-5. (Optical Filter)
The near infrared ray absorbing pressure sensitive adhesive composition of the present invention is suited for optical filters . In this optical filter, the aforementioned near infrared ray absorbent material is used. This optical filter is suitable as an optical filter for optical semiconductor elements or an optical filter for thin displays. In such an optical filter, the transmittance of entire rays of light in the visible region is equal to or greater than 40%, preferably equal to or greater than 50%, and still more preferably equal to or greater than 60%. The transmittance of the near infrared ray having a wavelength of 800 to 1100 nm is preferably equal to or less than 30%, more preferably equal to or less than 15%, and still more preferably equal to or less than 5%. [0231]
The optical filter of the present invention may be provided with, in addition to a near infrared ray absorbing layer composed of the aforementioned near infrared ray absorbing pressure sensitive adhesive composition, an electromagnetic wave shielding layer, an antireflection layer, a glare preventive (antiglare) layer, a sticking preventive layer, a color adjusting layer, a support such as glass and the like. [0232] Constitution of each layer of the optical filter may be arbitrarily selected. For example, an optical filter in which at least two layers are provided in combination of either one layer of the antireflection layer and the antiglare layer, and the near infrared ray absorbing layer is suitable. Further, an optical filter having at least three layers in combination, i.e. , the aforementioned at least two layers, and further the electromagnetic wave shielding layer is more preferred. [0233]
It is preferred that the antireflection layer, or the antiglare layer be provided as the front most layer positioned on the closest side to human. The order of lamination of the near infrared ray absorbing layer and the electromagnetic wave shielding layer with respect to each other may be arbitrarily determined. Moreover, in between the three layers, other layer such as a sticking preventive layer, a color adjusting layer, a shock absorbing layer, a support or a transparent substrate may be also inserted.
[0234]
Upon lamination of each layer, it may be subjected to a physical treatment such as a corona treatment or a plasma treatment, or a known highly polar polymer such as polyethyleneimine, an oxazoline-based polymer, a polyester or cellulose may be used as an anchor coating agent.
[0235] In the optical filter for thin display, it is preferred that the antireflection layer or antiglare layer be provided as the front most layer positioned on the closest side to human for accelerating visibility of the screen.
[0236] The antireflection layer is provided for suppressing reflection on the surface, and for preventing unwanted image visualization on the surface due to the external light such as a light from the fluorescent lamp. There are two types of the antireflection layer, i.e., those composed of a thin film of an inorganic substance such as metal oxide, fluoride, suicide, boride, carbide, nitride, sulfide and the like, and those obtained by lamination of resins having different refractive indices such as an acrylic resin and a fluorocarbon resin into monolayer or multiple layers. In the former case, the manufacture method may include forming the antireflection coating on a transparent substrate with a vacuum evaporation or sputtering process to give monolayer or multilayer. In the latter case, a manufacture method in which an antireflection coating is applied on the surface of the transparent substrate, on a transparent film, using a knife coater such as a comma coater, a fountain coater such as a slot coater or a lip coater, a gravure coater, a flow coater, a spray coater or a bar coater may be exemplified. [0237] The antiglare layer is formed by making an ink from fine powder of silica, a melamine resin, an acrylic resin or the like, and coating on any one of the layers of the filter of the present invention by a conventionally known coating method, followed by allowing for heat-curing or photo-curing. Also, a film which had been subjected to an antiglare treatment may be pasted on the filter. [0238]
Moreover, the sticking preventive layer is formed by applying a coating liquid, which was prepared by dissolving or dispersing an acrylate such as urethaneacrylate, epoxyacrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent, on any of the layers of the filter of the present invention by a conventionally known method of application followed by drying and allowing for photo-curing. [0239] The optical filter having the antireflection layer or the antiglare layer and the near infrared ray absorbing layer is obtained by laminating a layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention or the near infrared ray absorbent material on the back face of the antireflection film or the antiglare film. In the method of lamination, the near infrared ray absorbing layer according to the present invention formed into a film may be directly pasted with the antireflection film or the antiglare film, or dissolved near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be directly applied on the back face of the antireflection film or the antiglare film. When the near infrared ray absorbing layer is provided on the back face of the antireflection film or the antiglare film, the ultraviolet ray absorbing film is preferably used as a transparent substrate for suppressing the deterioration of the dye resulting from the ultraviolet ray. The near infrared ray absorbing pressure sensitive adhesive composition of the present invention has adhesiveness. Therefore when the near infrared ray absorbing layer is bonded to the other layer, use of the pressure sensitive adhesive or adhesive can be unnecessary. The near infrared ray absorbing layer is a layer that includes the near infrared ray absorbing pressure sensitive adhesive composition of the present invention. [0240]
In the optical filter for plasma displays, it is preferred to provide the electromagnetic wave shielding layer for removing the electromagnetic wave generated from the panel. [0241] As the electromagnetic wave shielding layer, a film produced by patterning a metal mesh on a film by a process such as etching or printing, followed by leveling, or a film produced by embedding a metal vacuum evaporated on a fiber mesh into a resin may be used. [0242]
The optical filter having two layers of the near infrared ray absorbing pressure sensitive adhesive layer and the electromagnetic wave shielding layer is obtained by combination of an electromagnetic wave preventive material and a near infrared ray absorbing composition. In the method of combination, the electromagnetic wave shielding film may be pasted with the near infrared ray absorbing pressure sensitive adhesive composition of the present invention formed to have a film shape using the pressure sensitive adhesive, the dissolved near infrared ray absorbing pressure sensitive adhesive composition of the present invention may be directly applied on the electromagnetic wave shielding film. Also, when the metal on the film is subjected to levelling, the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be used. Further, when the fiber to which a metal is vacuum evaporated is embedded, the near infrared ray absorbing pressure sensitive adhesive composition of the present invention can be also used. [0243] The optical filter having three layers, i.e., the near infrared ray absorbing layer, the reflection or antiglare layer and the electromagnetic wave shielding layer, which can be used may be provided by pasting three layers of: the near infrared ray absorbing film consisting of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention; the reflection or antiglare film and the electromagnetic wave shielding film. An optical filter having a structure in which the near infrared ray absorbing film composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is sandwiched between the reflection or antiglare film and the electromagnetic wave shielding film is preferred. Since the optical filter is laminated utilizing the adhesiveness of the near infrared ray absorbing film, it can be produced without need of the adhesive layer conventionally provided only for the purpose of pasting of the film. A support such as glass, or a functional film such as a color adjusting film may be also pasted as needed. [0244] In order to further simplify the steps of manufacturing the optical filter and construction of the film, a combination film providing multiple functions may be used. Preferable optical filter may be obtained by pasting a combination film including the electromagnetic wave shielding layer and the reflection or antiglare layer in one film with the near infrared ray absorbing adhesive layer composed of the near infrared ray absorbing pressure sensitive adhesive composition of the present invention.
[0245] the optical filter of the present invention for thin display may be either provided away from the display unit, or directly pasted to the display unit. When it is provided away from the display unit, glass is preferably used as the support. When it is directly pasted to the display unit, the optical filter without use of the glass is preferred. [0246] 2-6. (Thin Display)
When the optical filter including the near infrared ray absorbing pressure sensitive adhesive composition of the present invention laminated therein is built in a thin display, a satisfactory image quality is maintained for a long period of time. The present invention concerning a thin display is directed to a thin display in which the near infrared ray absorbing pressure sensitive adhesive composition of the present invention, the near infrared ray. absorbent material of the present invention, or the optical filter of the present invention is used. The thin display in which the optical filter is directly pasted to the display body can produce more clear image quality. When the optical filter is directly pasted, it is preferred to use tempered glass as the glass for the display body, or use the optical filter provided with a shock absorbing layer. [0247]
Examples of the pressure sensitive adhesive tackifier used in pasting the optical filter of the present invention to the display unit include the aforementioned substances described above in connection with the present invention concerning a salt. The optical filter of the present invention may be pasted to the display unit without using the pressure sensitive adhesive, by way of adhesiveness of the near infrared ray. [0248] This adhesive layer has a thickness of generally 5 to 2000 μm, and preferably 10 to 1000 μm. A releasable film may be provided on the surface of the pressure sensitive adhesive layer, and thus the pressure sensitive adhesive layer may be protected by this releasable film so as to avoid attachment of dirts and the like to the pressure sensitive adhesive layer during the time period until the optical filter is pasted to the surface of the thin display. In this case, a nonadhesive part may be formed between the releasable film and the pressure sensitive adhesive layer of the filter at the surrounding edge by providing a part not having the pressure sensitive adhesive layer, or by interposing a nonadhesive film. When this nonadhesive part is employed as a release initiation site, operation in release will be easily conducted. [0249] The shock absorbing layer is provided for the purpose of protecting the display unit from external shock. It is preferred that the shock absorbing layer be used for the optical filter without having the support. Example of the shock absorber which can be used include ethylene-vinyl acetate copolymers, acrylic polymers, polyvinyl chloride, urethane-based, silicon-based resins and the like as disclosed in Japanese Unexamined Patent Application Publication No. 2004-246365 and No. 2004-264416, but not limited thereto. [0250] Hereinabove, the present invention concerning a salt, and the present invention concerning a pressure sensitive adhesive composition are explained. The present invention concerning a salt may be combined with the present invention concerning a pressure sensitive adhesive composition. The present invention concerning a pressure sensitive adhesive composition may include the present invention concerning a salt. To the contrary, the present invention concerning a salt may include the present invention concerning a pressure sensitive adhesive composition. Any detailed description of the present invention concerning a salt can be combined with any detailed description of the present invention concerning a pressure sensitive adhesive composition. (EXAMPLES)
[0251]
The effect of the present invention will be clarified below by way of Examples, but the present invention should not be construed as being limited on the basis of the Examples. With respect to the following component proportion, "part" means part by weight, and >Λ%" means % by weight, unless otherwise stated specifically. [0252]
Hereinbelow, Synthesis Example 1, Synthesis Example 2,
Examples 1 to 8 , and Comparative Examples 1 to 3 relate to the present invention concerning a salt. Meanwhile, Production
Examples 1 to 16, Examples 9 to 26, and Comparative Examples 4 and 5 relate to the present invention concerning a pressure sensitive adhesive composition. Table 1 below shows the effect of the present invention concerning a salt. Table 2 and Table
3 below show the effect of the present invention concerning a pressure sensitive adhesive composition. [0253]
Synthesis Example 1, Synthesis Example 2, Examples 1 to 8, and Comparative Examples 1 to 3 were evaluated in accordance with (Evaluation 1) to (Evaluation 3) described later.
[0254] (Evaluation 1) Evaluation of Near Infrared Ray Absorptivity (Near Infrared Ray Transmittance)
Using UV-3700 (manufactured by Shimadzu Corporation) , a transmission spectrum at 350 to 1250 nm was determined. The near infrared ray absorptivity was evaluated based on the transmittance at a wavelength of 850 nm and a wavelength of 1000 nm. In the following Table 1, the transmittance (%) determined before performing the heat resistance test or the test of resistance to moist heat is shown in the column of ""initial transmittance (%)". [0255]
(Evaluation 2) Evaluation of Heat Resistance The test sample was stood still in a 100° C incubator with constant temperature and humidity for 120 hrs, and the transmission spectrum of 350 to 1250 nm before and after the test was determined. Upon determination of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used. Based on this transmission spectrum, alteration of the transmittance according as the heat resistance test was determined. Values (%) derived by subtracting the transmittance (%) before the heat resistance test from the transmittance (%) after the test are shown in the column of "ΔTl" in the following Table 1. The alteration ΔT1 of the transmittance at a wavelength of 850 nm and a wavelength of 1000 nm is shown in the following Table 1. [0256]
(Evaluation 3) Evaluation of Resistance to Moist Heat
The test sample was stood still in a 8O0C, 95% RH incubator with constant temperature and humidity for 120 hrs, and the transmission spectrum of 350 to 1250 nm before and after the test was determined. Upon determination of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used. Based on this transmission spectrum, alteration of the transmittance according as the test of resistance to moist heat was determined. Values derived by subtracting the transmittance (%) before the test of resistance to moist heat from the transmittance (%) after the test are shown in the column of "ΔT2" in the following Table 1. The alteration ΔT2 of the transmittance at a wavelength of 850 nm and a wavelength of 1000 nm is shown in the following Table 1. [0257]
(Synthesis Example 1)
As a monomer, 371.5 g of methyl methacrylate, 59 g of n-butyl methacrylate and 69.5 g of butyl acrylate were mixed to obtain a polymerizable monomer mixture (1). Percadox 12XL25 (manufactured by Kayaku Akzo Co. Ltd.) in an amount of 6 g and 100 g of toluene were mixed to obtain an initiator solution 1. Into a flask were charged 350 g of the polymerizable monomer mixture (1) , and 225 g of toluene. This flask was equipped with a thermometer, an agitator, a nitrogen gas inlet tube, a reflux condenser and a dropping funnel. The polymerizable monomer mixture (1) in an amount of 150 g was mixed with 31.8 g of the initiator solution 1, and the mixture was placed in the dropping funnel. While allowing a nitrogen gas to be circulated at 20 ml/min, The flask was heat to give the internal temperature of 1000C. To the flask was added 74.2 g of the initiator solution
1, whereby the polymerization reaction was initiated. Ten minutes after charging this initiator solution 1, the mixture
(mixture of the polymerizable monomer mixture (1) and the initiator solution 1) in the dropping funnel was added in the flask over 60 min. After adding the entire mixture in the dropping funnel, the dropping funnel was washed with 75 g of toluene, and the wash liquid was added into the flask. Thereafter, aging was allowed for 60 min, and 150 g of toluene was added into the flask as the diluent solvent. Aging was allowed for additional 60 min, and 150 g of toluene was added into the flask as the diluent solvent . Further, aging was allowed for additional 60 min, and 150 g of toluene was added into the flask as the diluent solvent, followed by additional aging for 60 min. Thereafter, the temperature was elevated to 108 °C, and aged for 300 min. Moreover, the 185.7 g of the diluent solvent was added, and thereafter, the mixture was cooled to room temperature to give a solution of resin (Ia) . This solution had a solid content of 32.4%. The resin (Ia) had Tg of 750C, and a weight average molecular weight converted based on polystyrene of the resin (Ia) was 220,000.
[0258] (Synthesis Example 2)
2-Ethylhexyl acrylate (264.6 g) , butyl acrylate (150 g) , cyclohexyl methacrylate (180 g) and hydroxyethyl acrylate (5.4 g) were weighed as the monomer, and sufficiently mixed to obtain a polymerizable monomer mixture (2) . [0259]
To a flask eguipped with a thermometer, an agitator, an inert gas inlet tube, a reflux condenser and a dropping funnel were charged 160 g of ethyl acetate and 300 g of the polymerizable monomer mixture (2) . Additionally, to the dropping funnel were placed, 300 g of the polymerizable monomer mixture (2), 16 g of ethyl acetate, and 0.15 g of NYPER BMT-K40 (polymerization initiator, manufactured by NOF Corporation) , which were mixed well to give a mixture for dropwise addition (2) . [0260]
The internal temperature of the flask was elevated to 95° C while allowing a nitrogen gas to be circulated at 20 ml/min.
NYPER BMT-K40 (0.15 g) that is a polymerization initiator was charged to the flask, whereby the polymerization reaction was initiated. Thirty minutes after charging the polymerization initiator, the dropwise addition of the mixture for dropwise addition (2) was started from the dropping funnel. The mixture for dropwise addition (2) was uniformly added dropwise over 90 min. After completing the dropwise addition of the mixture for dropwise addition (2), aging was carried out for 6 hrs while diluting the mixture with ethyl acetate ad libitum to meet elevation of the viscosity, and while maintaining the reflux temperature. [0261]
After completing the reaction, the reaction mixture was diluted with ethyl acetate such that the non-volatile matter accounted for about 40% to give a resin (2a) having a calculated glass transition temperature (Tg) of -350C, and a calculated solubility parameter of 9.57. This resin (2a) was a pressure sensitive adhesive resin. The weight average molecular weight (Mw) and the acid value of the resin (2a) were 440,000 and 0, respectively. [0262] (Example 1)
"CIR-1085" (manufactured by Japan Carlit Co. , Ltd. ) having a bis (trifluoromethanesulfonyl) imide anion, as the diimonium dye, was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 5%. Next, "EXCOLOR IR-IOA" (manufactured by Nippon Shokubai Co., Ltd.) that is a phthalocyanine dye was dissolved in methyl ethyl ketone to prepare a phthalocyanine dye solution 1 having a solid content of 5%. Subsequently, bis (trifluoromethanesulfonyl) imide lithium was dissolved in methyl ethyl ketone to prepare an additive solution 1 having a solid content of 5%. The resin (Ia) o
obtained in Synthesis Example 1, the diimonium dye solution 1, the phthalocyanine dye solution 1 and the additive solution 1 were mixed such that the weight ratio on the solid content basis became 100/2.8/2.5/0.63 to prepare a near infrared ray absorbing composition Al. This weight ratio is represented in the order of: [resin (Ia) /diimonium dye solution 1/phthalocyanine dye solution 1/additive solution 1] . [0263] The near infrared ray absorbing composition Al was applied on an easy-adhesion treated PET film (manufactured by Toyobo Co. , Ltd., COSMOSHINE A4300) with a bar coater, and dried in a 1200C hot-air drier for 3 min to obtain a near infrared ray absorbent material Al. This near infrared ray absorbent material Al was employed as a test sample. Evaluation of the near infrared ray transmittance, heat resistance and the resistance to moist heat was made on this test sample. The results of evaluation on the test sample according to Example 1 are shown in the following Table 1. In Table 1, bis (trifluoromethanesulfonyl) imide lithium is represented by denotation of "TFSILi". [0264] (Example 2)
Bis (trifluoromethanesulfonyl) imide sodium was dissolved in a methyl ethyl ketone solution to give an additive solution 2 having a solid content of 5%. The resin (Ia), the diimonium dye solution I1 the phthalocyanine dye solution 1 and the additive solution 2 were mixed such that the weight ratio on the solid content basis became 100/2.8/2.5/0.63 to prepare a near infrared ray absorbing composition A2. This weight ratio is represented in the order of: [resin (Ia) /diimonium dye solution 1/phthalocyanine dye solution 1/additive solution 2] . A near infrared ray absorbent material A2 was obtained in a similar manner to Example 1 except that the near infrared ray absorbing composition A2 was used in place of the near infrared ray absorbing composition Al. This near infrared ray absorbent material A2 was employed as a test sample. The visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 1. Further, the results of evaluation on the test sample according to Example 2 are shown in the following Table 1. In Table 1, bis (trifluoromethanesulfonyl) imide sodium is represented by denotation of "TFSINa".
[0265] (Example 3)
"CIR-1085F" (manufactured by Japan Carlit Co., Ltd.) having a bis (trifluoromethanesulfonyl) imide anion, and having a maximum absorption wavelength in an acetone solution of 1049 nm was used as a diimonium dye. This "CIR-1085F" was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 2 having a solid content of 5%. The resin (2a) obtained in Synthesis Example 2, the diimonium dye solution 2 and the additive solution 2 were mixed such that the weight ratio on the solid content basis became 100/1.88/2.0 to give a near infrared ray absorbing pressure sensitive adhesive composition A3. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/additive solution 2] . [0266]
The near infrared ray absorbing pressure sensitive adhesive composition A3 was applied on an easy-adhesion treated PET film (manufactured by Toyobo Co., Ltd., COSMOSHINE A4300) with an applicator such that the pressure sensitive adhesive layer after drying had a thickness of 25 μm, and dried in a 100 °C hot-air circulating oven for 2 min. After pasting a releasable film (PET film subjected to a silicon treatment) thereon, it was left to stand at 23° C for one day to obtain a near infrared ray absorbent material A3. After peeling the releasable film from the near infrared ray absorbent material A3, this near infrared ray absorbent material A3 was pasted on a glass plate to give a test sample. Evaluation of the near infrared ray transmittance, heat resistance and the resistance to moist heat was made on this test sample. The results of evaluation are shown in the following Table 1.
[0267] (Example 4) hexafluorophosphate lithium (PF6Li) was dissolved in methyl ethyl ketone to prepare an additive solution 3 having a solid content of 5%. The resin (2a) , the diimonium dye solution 2 and the additive solution 3 were mixed such that the weight ratio on the solid content basis became 100/1.88/0.33 to give a near infrared ray absorbing pressure sensitive adhesive composition A4. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/additive solution 3] . A near infrared ray absorbent material A4 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A4 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results are shown in the following Table 1. [0268] (Example 5) Lithium trifluoromethanesulfonate was dissolved in methyl ethyl ketone to prepare an additive solution 4 having a solid content of 5%. CoronateL-55E (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.) that is a crosslinking agent was dissolved in methyl ketone solution to prepare a crosslinking agent solution 1 having a solid content of 2.75%. Di-n-butyltin dilaurylate crosslinking accelerator was dissolved in the methyl ketone solution to prepare a crosslinking accelerator solution 1 having a solid content of 1%. The resin (2a), the diimonium dye solution 2, the phthalocyanine dye solution 1, the additive solution 4, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became 100/1.88/1.1/0.34/0.25/0.05 to give a near infrared ray absorbing pressure sensitive adhesive composition A5. This weight ratio is represented in the order of: [resin
(2a) /diimonium dye solution 2/phthalocyanine dye solution
1/additive solution 4/crosslinking agent solution
1/crosslinking accelerator solution 1] . [0269]
A near infrared ray absorbent material A5 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A5 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results are shown in the following Table 1. In Table 1, lithium trifluoromethanesulfonate is represented by denotation of "TFSLi". [0270] (Example 6)
The resin (2a) , the diimonium dye solution 2, the phthalocyanine dye 1, the additive solution 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became
100/1.88/1.1/0.63/0.25/0.05 to give a near infrared ray absorbing pressure sensitive adhesive composition A6. This weight ratio is represented in the order of: [resin
(2a) /diimonium dye solution 2/phthalocyanine dye 1/additive solution 1/crosslinking agent solution 1/crosslinking accelerator solution 1] . [0271]
A near infrared ray absorbent material Aβ and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A6 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 2. The results of evaluation on the test sample are shown in the following Table 1.
[0272] (Example 7) Hexafluoroantimonate sodium (SbFgNa) was dissolved in methyl ethyl ketone to prepare an additive solution 5 having a solid content of 5%. The resin (2a) , the diimonium dye solution 2, the phthalocyanine dye I1. the additive solution 5, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became 100/1.88/1.1/0.56/0.25/0.05 to give a near infrared ray absorbing pressure sensitive adhesive composition A7. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/phthalocyanine dye 1/additive solution 5/crosslinking agent solution 1/crosslinking accelerator solution 1] . [0273]
A near infrared ray absorbent material A7 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition A7 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The evaluation results on this test sample are shown in the following Table 1. [0274]
(Comparative Example 1)
The resin (Ia) , the diimonium dye solution 1, and the phthalocyanine dye solution 1 were mixed such that the weight ratio on the solid content basis became 100/2.8/2.5 to give a near infrared ray absorbing composition Bl. This weight ratio is represented in the order of: [resin (Ia) /diimonium dye solution 1/phthalocyanine dye solution 1] . [0275] A near infrared ray absorbent material Bl was obtained in a similar manner to Example 1 except that the near infrared ray absorbing composition Bl was used in place of the near infrared ray absorbing composition Al. This near infrared ray absorbent material Bl was employed as a test sample. Similar evaluation to Example 1 was made on this test sample. The evaluation results are shown in the following Table 1. [0276] (Comparative Example 2)
The resin (2a) and the diimonium dye solution 2 were mixed such that the weight ratio on the solid content basis became 100/1.88 to obtain a near infrared ray absorbing composition B2. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2]. [0277]
A near infrared ray absorbent material B2 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing composition B2 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was made on this test sample. The evaluation results are shown in the following Table 1.
[0278] (Comparative Example 3)
The resin (2a) , the diimonium dye solution 2, the phthalocyanine dye 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed such that the weight ratio on the solid content basis became
100/1.88/1.1/0.25/0.05 to give a near infrared ray absorbing pressure sensitive adhesive composition B3. This weight ratio is represented in the order of: [resin (2a) /diimonium dye solution 2/phthalocyanine dye 1/crosslinking agent solution
1/crosslinking accelerator solution 1] .
[0279]
A near infrared ray absorbent material B3 and the test sample were obtained in a similar manner to Example 3 except that the near infrared ray absorbing pressure sensitive adhesive composition B3 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition A3. Similar evaluation to Example 3 was carried out on this test sample. The visible-near infrared ray absorption spectrum of this test sample before and after the heat resistance test is shown in Fig. 3. Further, the evaluation results are shown in the following Table 1.
[0280]
The salt for a near infrared ray absorbing composition added in each Example is listed in the column of "Salt Dissolved in Additive Solution" in the following Table 1.
O
Table 1 Specifications and Evaluation Results of Examples and Comparative Examples σ
H OO (D M
Figure imgf000127_0001
[0282] (Example 8)
1. Synthesis of Polymer!zable Polysiloxane (M-I)
To a 300-ml four-necked flask equipped with an agitator, a thermometer and a condenser tube were placed 144.5 parts of tetramethoxysilane, 23.6 parts of γ-methacryloxypropyltrimethoxysilane, 19.0 parts of water, 30.0 parts of methanol and 5.0 parts of Amberlist 15 (trade name : cation exchange resin manufactured by ORGANO CORPORATION) , which are agitated at 65 °C for 2 hrs to allow them to react. After cooling the reaction mixture to room temperature, a distillation column, and a condenser tube and an outlet which were connected to this distillation column were attached in place of the condenser tube. The internal temperature of the flask was raised to about 80° C under a normal pressure over 2 hrs, and the same temperature was kept until the outflow of methanol ceased. Further, the pressure was kept at 2.67 x 10 kPa and the temperature was kept at 9O0C until the outflow of methanol ceased to further proceed the reaction. After cooling to room temperature again, Amberlist 15 was filtered of to obtain a polymerizable polysiloxane (M-I) having a number average molecular weight of 1,800. [0283]
2. Synthesis of Organic Polymer (P-I)
To a 1-liter flask equipped with an agitator, a drip opening, a thermometer, a condenser tube and a N2 gas feed port was charged 260 parts of n-butyl acetate as an organic solvent.
Thereto was fed a N2 gas, and the internal temperature was raised to 110 "C by heating while stirring. Subsequently, a solution prepared by mixing 12 parts of the polymerizable polysiloxane (M-I) , 19 parts of tert-butyl methacrylate, 94 parts of butyl acrylate, 67 parts of 2-hydroxyethyl methacrylate, 48 parts of perfluorooctylethyl methacrylate (LIGHT-ESTER FM-IO8, manufactured by Kyoeisha Chemical Co., Ltd.) and 2.5 parts of 2, 2' -azobis- (2-methylbutyronitrile) was added dropwise from the drip opening over 3 hrs . Also after completing the dropwise addition, the mixture was kept to be stirred at the same temperature for additional 1 hour. Thereafter, 0.1 parts of tert-butylperoxy-2-ethylhexanoate was added twice at a 30 min interval, followed by further heating for 2 hrs to perform copolymerization. This copolymerization yielded a solution of an organic polymer (P-I) dissolved in n-butyl acetate. Thus obtained solution had a solid content of 48.2%. This organic polymer (P-I) had a number average molecular weight of 12,000, and a weight average molecular weight of 27,000. [0284]
3. Synthesis of Dispersion of Organic Polymer-Complexed Inorganic Fine Particles (S-I)
To a 500-ml four-necked flask equipped with an agitator, two drip openings (drip opening α and drip opening β) and a thermometer were charged 200 parts of n-butyl acetate and 500 parts of methanol, and the internal temperature was regulated to 40 °C. Subsequently, while stirring the mixture in the flask, a stock solution A was added dropwise from the drip opening α over 2 hrs, and at the same time, a stock solution B was add dropwise from the drip opening β over 2 hrs. The stock solution A is a mixture of 10 parts of the organic polymer (P-I) solution in n-butyl acetate, 30 parts of tetramethoxysilane and 5 parts of n-butyl acetate. The stock solution B is a mixture of 5 parts of 25% aqueous ammonia, 10 parts of deionized water, and 15 parts of methanol. [ 0285 ]
After adding the stock solution A and the stock solution B dropwise, a distillation column and a condenser tube and an outlet which were connected to this distillation column were attached in place of the condenser tube. Under a pressure of 40 kPa, the internal temperature of the flask was raised to 1000C, and ammonia, methanol and n-butyl acetate were distilled off until the solid content reached to 30%. Following this distillation, a dispersion (S-I) in which organic polymer-complexed inorganic fine particle were dispersed in n-butyl acetate was obtained. In this dispersion (S-I) , the proportion (inorganic fine particle/organic polymer) of the inorganic fine particles to the organic polymer in the organic polymer-complexed inorganic fine particle was 70/30. This proportion is a ratio on the weight basis. Thus obtained organic polymer-complexed inorganic fine particles had a mean particle size of 23.9 nm. The proportion of the organic polymer to the inorganic fine particles in the organic polymer-complexed inorganic fine particle was determined by performing an elemental analysis of the dispersion of the organic polymer-complexed fine particles under a pressure of 1.33 x 10 kPa at 1300C for 24 hrs, and calculating the ash content in terms of the content of the organic polymer-complexed inorganic fine particle. Moreover, for determining the mean particle size, a solution prepared by diluting 1 part of the dispersion of the organic polymer-complexed inorganic fine particles (S-I) in 99 parts of n-butyl acetate was used to take a transmission electron micrograph of the particles. The diameter of arbitrary 100 particles was measured, and the average of the diameters was defined as the mean particle size.
[0286] 4. Reflection Film
A mixture prepared by mixing 8 parts of dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) with 2 parts of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was dissolved in 40 parts of methyl ethyl ketone to obtain a solution Fl. To this solution Fl was added a solution F2 to prepare a hard coat layer coating liquid Hl. The solution F2 is a solution including 0.5 parts of a photopolymerization initiator (IRGACURE907, manufactured by Ciba Specialty Chemicals Co. in 2 parts of methyl ethyl ketone . [0287] Nine parts of the dispersion of the organic polymer-complexed inorganic fine particles (S-I), 0.3 parts of Desmodule N3200 (trade name, isocyanate curing agent, manufactured by Sumika Bayer Urethane Co., Ltd.), 0.003 parts of di-n-butyltin dilaurate, and 110 parts of methyl isobutyl ketone were mixed to prepare a low-refractive index layer coating liquid Tl.
[0288]
The hard coat layer coating liquid Hl was applied on a polyethylene terephthalate film having a thickness of 188 μm (COSMOSHINE A4300, manufactured by Toyobo Co., Ltd.,) using a bar coater to obtain a coated layer h. After drying the layer h at 100° C for 15 min, an ultraviolet ray of 200 mJ/cm2 was irradiated with a high-pressure mercury arc lamp to allow the layer h to be cured. Following this curing, a hard coat layer having a film thickness of 5 μm was formed. On this hard coat layer was applied a low-refractive index coating liquid Tl using a bar coater. This application yielded an antireflection film
Rl having an antireflection film provided on the polyethylene terephthalate film. This antireflection film is constructed with the coated layer h, and a low-refractive index layer formed adjacent to this coated layer h. This low-refractive index layer is formed by curing a low-refractive index coating liquid Tl.
[0289]
The surface of the film Rl opposite to the antireflection film was roughened with steel wool, and to this roughened face was applied a black ink. Next, a specular reflection spectrum of the face on the antireflection film side was measured at an incidence angle of 5° using an ultraviolet visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) . From this measurement, a wavelength at which a minimum reflectance was attained, and the reflectance at the wavelength were determined. The wavelength at which a minimum reflectance was attained was 550 nm, and the reflectance at this wavelength was 0.45%. [0290]
5. Optical Filter
The near infrared ray absorbing composition A6 obtained in Example 6 was applied on the back face side of the antireflection film Rl and dried, in a similar manner to Example 6 to obtain an optical filter 1. The optical filter 1 exhibited favorable near infrared ray transmittance, transmittance of entire rays of light, heat resistance, crack resistance, and solvent resistance. [0291] In Production Examples 1 to 16, Examples 9 to 26, and Comparative Examples 4 and 5, the evaluation method of the near infrared ray absorptivity, the heat resistance, the resistance to moist heat and the acid value are as in the following.
[0292] (Evaluation 4) Evaluation of Near Infrared Ray Absorptivity (Near Infrared Ray Transmittance)
Using UV-3700 (manufactured by Shimadzu Corporation) , a transmission spectrum of the test sample at 350 to 1250 nm was determined. The near infrared ray absorptivity was evaluated based on the transmittance at a wavelength of 1000 nm. In the following Table 3, the transmittance at a wavelength of 1000 nm is shown in the column of "1000 nm transmittance". In the following Table 3, the evaluation results before performing the heat resistance test and the test of resistance to moist heat are shown in the column of "initial".
[0293]
(Evaluation 5) Evaluation of Heat Resistance The test sample was stood still in a 1000C incubator with constant temperature and humidity for 120 hrs, and the transmission spectrum of 350 to 1250 nm before and after the test was determined. Upon determination of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used. Based on thus obtained transmission spectra before and after the test, alteration of the transmittance at a wavelength of 1000 nm was evaluated. Also, the color difference was calculated from thus obtained transmission spectra before and after the test to evaluate the alteration of b*. [0294]
(Evaluation 6) Evaluation of Resistance to Moist Heat The test sample was stood still in a 800C, 95% RH incubator with constant temperature and humidity for 120 hrs, and the transmission spectrum of 350 to 1250 nm before and after the test was determined. Upon determination of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used. Based on thus obtained transmission spectra before and after the test, alteration of the transmittance at a wavelength of 1000 nm was evaluated. Also, the color difference was calculated from thus obtained transmission spectra before and after the test to evaluate the alteration of b*. [0295]
(Evaluation 7) Measurement of Acid Value
0.5 g of the pressure sensitive adhesive resin solution was precisely weighed to which 50 g of toluene was added, and the resin was uniformly dissolved. Thereto was added two to three drops of a phenolphthalein/alcohol solution as an indicator, titration with a 0.1 N potassium hydroxide/alcohol solution was carried out. The endpoint was specified when the reddish color of the liquid disappeared in about 30 sec. The acid value was determined from the titer and the solid content of the resin. The acid value is represented by mg of potassium hydroxide required for neutralization of 1 g of the resin solid content.
[0296] Production Example 1:
2-Ethylhexyl acrylate (458.5 g) , ethyl acrylate (40 g) and hydroxyethyl acrylate (1.5 g) were weighed as the polymerizable monomer, and sufficiently mixed to obtain a polymerizable monomer mixture.
[0297]
To a flask equipped with a thermometer, an agitator, an inert gas inlet tube, a reflux condenser and a dropping funnel were charged 50% by weight of this polymerizable monomer mixture, and ethyl acetate (162 g) . A polymerizable monomer mixture for dropwise addition including 50% by weight of the polymerizable monomer mixture, ethyl acetate (13 g) , and NYPER BMT-K40 (0.13 g, manufactured by NOF Corporation) as a polymerization initiator was placed in a dropping funnel and mixed well. [0298]
The internal temperature of the flask was elevated to 90° C while allowing a nitrogen gas to be circulated at 20 ml/min. NYPER BMT-K40 (0.13 g) that is a polymerization initiator was charged to the flask, whereby the polymerization reaction was initiated. Ten minutes after charging the polymerization initiator, the dropwise addition of the polymerizable monomer mixture for dropwise addition charged in the dropping funnel was started. The polymerizable monomer mixture for dropwise addition was uniformly added dropwise over 90 min. After completing the dropwise addition, aging was carried out for 6 hrs while diluting the mixture with ethyl acetate ad libitum to meet elevation of the viscosity, and while maintaining the reflux temperature. [0299]
After completing the reaction, the reaction mixture was diluted with ethyl acetate such that the non-volatile matter accounted for about 40% to give a pressure sensitive adhesive resin (1) having a calculated glass transition temperature (Tg) of-66.7°C, and a calculated solubility parameter of 9.30. Thus obtained pressure sensitive adhesive resin (1) had a weight average molecular weight (Mw) and an acid value of 600,000 and 0, respectively. Specifications and evaluation results of Production Example 1 are shown in the following Table 2. [0300] Production Examples 2 to 16:
Production Examples 2 to 16 were similar to Production Example 1 except that the employed composition of the polymerizable monomer mixture was as shown in Table 2. According to these Production Examples 2 to 16, the pressure sensitive adhesive resins (2) to (16) were obtained. The calculated Tg, the calculated solubility parameter, Mw and the acid value of thus resulting pressure sensitive adhesive resins are shown in the following Table 2. [0301]
The "composition" in Table 2 represents % by weight of each monomer based on total weight of the monomer mixture. In Table 2, 2EHA represents 2-ethylhexyl acrylate (Tg: -70 'C); BA represents n-butyl acrylate (Tg: -55°C); EA represents ethyl acrylate (Tg: -22°C); MA represents methyl acrylate (Tg: -9°C); MMA represents methyl methacrylate (Tg: 105 'C) ; CHMA represents cyclohexyl methacrylate (Tg: 83°C); CHA represents cyclohexyl acrylate (Tg: 19°C); BzA represents benzyl acrylate (Tg: β°C); IBA represents isobornyl acrylate (Tg: 94 'C); HEA represents hydroxyethyl acrylate (Tg: -150C) ; and AA represents acrylic acid (Tg: 1060C) . [0302] Example 9 : "CIR-1085F" (manufactured by Japan Carlit Co., Ltd.) having a bis (trifluoromethanesulfonyl) imide anion and having a maximum absorption wavelength in the acetone solution of 1049 ran, as the diimonium dye, was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 5%. Further, CoronateL-55E (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.) as a crosslinking agent, and di-n-butyltin dilaurate as a crosslinking accelerator were dissolved in methyl ethyl ketone, respectively to prepare a crosslinking agent solution Ia having a solid content of 1%, and a crosslinking accelerator solution Ia having a solid content of 1%. The pressure sensitive adhesive resin (1) , the diimonium solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia obtained in Production Example 1 were mixed such that the weight ratio on the solid content basis became 100/1.88/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition Cl. This weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (1) /diimonium solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] . [0303]
The near infrared ray absorbing pressure sensitive adhesive composition Cl was applied on an easy-adhesion treated PET film (manufactured by Toyobo Co., Ltd., COSMOSHINE A4300) with an applicator. The coating thickness was defined such that the thickness after drying became 25 μm. Then, the film was dried in a 100 "C hot-air circulating oven for 2 min. After pasting a releasable film (PET film subjected to a silicon treatment) on the layer composed of this near infrared ray absorbing pressure sensitive adhesive composition Cl, it was left to stand at 230C for two days to obtain a near infrared ray absorbent material Cl. After peeling the releasable film, this near infrared ray absorbent material Cl was pasted on a glass plate to give a test sample according to Example 9. Evaluation of the near infrared ray transmittance, heat resistance and the resistance to moist heat was made on this test sample. The visible-near infrared absorption spectrum of this test sample is shown in Fig. 4, and the evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat on the test sample are shown in Table 3.
[0304] Examples 10 to 24:
The near infrared ray absorbing pressure sensitive adhesive compositions C2 to C16, the near infrared ray absorbent materials C2 to Clβ, and the test samples according to Examples 10 to 24 were obtained in a similar manner to Example 9 except that the pressure sensitive adhesive resin (1) was changed to the pressure sensitive adhesive resins (2) to (16). Similar evaluation to Example 9 was made on these test samples. Specifications and the evaluation results of Examples 10 to 24 are shown in the following Table 3.
[0305] Example 25:
"EXCOLOR IR-IOA" (manufactured by Nippon Shokubai Co., Ltd. ) that is a phthalocyanine dye was dissolved in methyl ethyl ketone to prepare a phthalocyanine solution 1 having a solid content of 5%. The pressure sensitive adhesive resin (11) obtained in Production Example 11, the diimonium solution 1, the phthalocyanine solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.88/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition C17. The weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (11) /diimonium solution 1/phthalocyanine solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] . The test sample according to Example 25 was obtained in a similar manner to Example 9 except that the near infrared ray absorbing pressure sensitive adhesive composition C17 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition Cl. Similar evaluation to Example 9 was made on this test sample. The visible-near infrared absorption spectrum of the test sample according to Example 25 is shown in the following Fig. 5. The evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample according to Example 25 are shown in the following Table 3.
[0306] Comparative Example 4 :
"CIR-1085" (manufactured by Japan Carlit Co. , Ltd. ) having a bis (trifluoromethanesulfonyl) imide anion and having a maximum absorption wavelength in the acetone solution of 1073 ran, as the diimonium dye, was used. This "CIR-1085" was dissolved in methyl ethyl ketone to prepare a diimonium solution 2 having a solid content of 5%. The pressure sensitive adhesive resin (8) obtained in Production Example 8, the diimonium solution 2, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition Dl. The weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (8) /diimonium solution 2/ crosslinking agent solution la/crosslinking accelerator solution Ia] . The test samples according to the near infrared ray absorbent material Dl and the Comparative Example 4 were obtained in a similar manner to Example 9 except that this near infrared ray absorbing pressure sensitive adhesive composition Dl was used in place of the near infrared ray absorbing pressure sensitive adhesive composition Cl. Similar evaluation to Example 9 was made on the test sample. The visible-near infrared absorption spectrum of the test sample according to Comparative Example 4 is shown in Fig. 6. The evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample according to Comparative Example 4 are shown in the following Table 3.
[0307] Comparative Example 5: The pressure sensitive adhesive resin (8) obtained in Production Example 8, the diimonium solution 2, the phthalocyanine solution 1, the crosslinking agent solution Ia and the crosslinking accelerator solution Ia were mixed such that the weight ratio on the solid content basis became 100/1.1/1.1/0.3/0.05 to prepare a near infrared ray absorbing pressure sensitive adhesive composition D2. The weight ratio on the solid content basis is represented in the order of: [pressure sensitive adhesive resin (8) /diimonium solution 2/phthalocyanine solution 1/crosslinking agent solution la/crosslinking accelerator solution Ia] . The near infrared ray absorbent material D2 and the test samples according to the Comparative Example 5 were obtained in a similar manner to Example 9 except that the near infrared ray absorbing pressure sensitive adhesive composition D2 was used in place of the near infrared ray absorbing pressure sensitive adhesive composition D2. Similar evaluation to Example 9 was made on this test sample . The evaluation results of the near infrared ray transmittance, the heat resistance and the resistance to moist heat of the test sample are shown in the following Table 3.
O ω σ O
OO
CD
K)
Figure imgf000142_0001
2EHA: 2- thylhexyl Acrylate Tg -70 * C CHA: Cyclohexyl Acrylate Tg 19 * C BA: n-Butyl Acrylate (Tg -55 * C) BzA: Benzyl Acrylate (Tg 6 ° C)
EA: Ethyl Acrylate (Tg -22 # C) IBA: Isobornyl Acrylate (Tg 94 ° C)
MA: Methyl Acrylate (Tg -9 ' C) HEA: Hydroxyethyl Acrylate (Tg -15 ' C)
MMA: Methyl Methacrylate (Tg 105 * C) AA: Acrylic Acid (Tg 106 ° C) CHMA: Cyclohexyl Methacrylate (Tg 83 ° C)
[0309] [Table 3]
Table 3 Specifications and Evaluation Results of Examples and Comparative Examples
Figure imgf000143_0001
parts y weg t assumng t e so content o t e aggutnant resn as 100 parts by weg t. [ 0310 ]
From Table 3, it is revealed that the near infrared ray absorbent materials of the present invention Cl to C17 according to Examples 9 to 25 are excellent in durability since they exhibited less alteration of the transmittance at 1000 nm and b* in the heat resistance test and the test of resistance to moist heat. In contrast, the near infrared ray absorbent materials Dl and D2 of Comparative Examples 4 and 5 in which a dye having, a maximum absorption wavelength in the acetone solution exceeding 1060 nm was used as the diimonium dye are inferior in durability, exhibiting alterations of the transmittance at 1000 nm and b* in the heat resistance test and the test of resistance to moist heat .
[0311] Example 26:
The near infrared ray absorbing pressure sensitive adhesive composition Cl obtained in Example 9 was applied on the back face side of the antireflection film Rl obtained in Example 8, and dried, in a similar manner to Example 9 to obtain an optical filter 2. The optical filter 2 exhibited favorable near infrared ray transmittance, transmittance of entire rays of light, heat resistance, crack resistance, and solvent resistance.
[0312] Example 27: To the pressure sensitive adhesive resin (14) obtained in the above Production Example 14 of the present invention concerning a pressure sensitive adhesive composition were mixed the diimonium dye solution 2 obtained in Example 3 of the present invention concerning a salt, the phthalocyanine dye solution 1 obtained in Example 1, the additive solution 1 obtained in Example 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 obtained in Example 5 such that the weight ratio on the solid content basis became 100/1.88/0.7/0.3/0.27/0.14 to prepare a near infrared ray absorbing pressure sensitive adhesive composition El. This weight ratio is represented in the order of: [pressure sensitive adhesive resin (14) /diimonium dye solution 2/phthalocyanine dye solution 1/additive solution 1/crosslinking agent solution 1/crosslinking accelerator solution 1] . Using this near infrared ray absorbing pressure sensitive adhesive composition El, the near infrared ray absorbent material according to Example 27 and the test sample were obtained in a similar manner to Example 9. Similar evaluation to Example 9 was made on this test sample. The visible-near infrared absorption spectrum of the test sample according to Example 27 before and after the heat resistance test is shown in the following Fig. 7. The evaluation results of the heat resistance and the resistance to moist heat of this test sample are shown in the following Table 4.
[0313] [Table 4]
Table 4 Evaluation Results of Example
Figure imgf000146_0001
[ 0314 ]
From Table 4, it is revealed that the near infrared ray absorbent material according to Example 27 is excellent in durability since they exhibited less alteration of the transmittance at 1000 nm and b* in the heat resistance test and the test of resistance to moist heat. [Industrial Applicability] [0315]
The near infrared ray absorbing composition of the present invention is useful as an optical filter for thin displays since it has high near infrared ray absorptivity and transparency in the visible region, and is excellent in the heat resistance and the resistance to moist heat. Further, it can be also used as an optical recording material. In addition, the near infrared ray absorbing pressure sensitive adhesive composition of the present invention is useful as an optical filter for thin displays since it has high near infrared ray absorptivity and transparency in the visible region, and is excellent in the heat resistance and the resistance to moist heat. Further, it can be also used as an optical recording material.

Claims

1. A salt for a near infrared ray absorbing composition comprising an anion represented by the following formula (1) , formula (2), formula (3) or formula (4), but not substantially having near infrared ray absorptivity per se: [Chem. 28]
Figure imgf000148_0001
[Chem. 29]
Figure imgf000148_0002
[Chem. 30]
RgS03 " O)
[Chem. 31]
R'Fm (4) in the formula (1) and the formula (3), Ra, Rb and Rg each represent a fluoroalkyl group which may be the same or different; in the formula (2) , Rc represents a fluoroalkylene group; and in the formula (4), m represents an integer of from 1 to 6.
2. The salt for a near infrared ray absorbing composition according to claim 1 wherein the anion is at least one selected from the group consisting of the following (al) , (a2) , (a3) and (a4) : (al) an anion represented by the above formula (1) wherein Ra and Rb is a perfluoroalkyl group having 1 to 10 carbon atoms; (a2) an anion represented by the above formula (2) wherein Rc is a perfluoroalkylene group having 1 to 10 carbon atoms;
(a3) an anion represented by the above formula (3) wherein Rg is a perfluoroalkyl group having 1 to 10 carbon atoms; and
(a4) an anion represented by the above formula (4) wherein
Rx is selected from the group consisting of phosphorus, antimony, arsenic, boron and tin.
3. The salt for a near infrared ray absorbing composition according to claim 1 or 2 wherein the counter cation of the salt comprising the anion represented by the formula (1) , the formula (2) , the formula (3) or the formula (4) is an alkali metal cation.
4. A near infrared ray absorbing composition comprising a near infrared ray absorbing dye, a resin and the salt according to any one of claims 1 to 3.
5. The near infrared ray absorbing composition according to claim 4 wherein the near infrared ray absorbing dye is at least one selected from the group consisting of a diimonium dye, a phthalocyanine dye, a cyanine dye, a squarylium dye and a dithiol metal complex dye.
6. The near infrared ray absorbing composition according to claim 5 wherein at least one of the near infrared ray absorbing dye is a diimonium dye comprising a diimonium cation represented by the following formula (5) , and at least one anion selected from the group consisting of the following formula (6) , formula (7), formula (8) and formula (9) . [Chem. 32]
Figure imgf000150_0001
[Chem. 33]
Figure imgf000151_0001
[Chem . 34 ]
Figure imgf000151_0002
[Chem. 35 ]
RjSO3 " (8)
[Chem . 36]
RkF n " O)
in the formula (5), R1 to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms having a substituent; in the formula (6), Rd and Re each represent a fluoroalkyl group which may be the same or different; in the formula (7) , Rf represents a fluoroalkylene group; in the formula (8), Rj represents a perfluoroalkyl group having 1 to 10 carbon atoms; in the formula (9), Rk represents at least one selected from the group consisting of phosphorus, antimony, arsenic, boron and tin; and n represents an integer of from 1 to 6.
7. The near infrared ray absorbing composition according to any one of claims 4 to 6 wherein the diimonium dye has a maximum absorption wavelength in the acetone solution of 1000 to 1060 nm.
8. The near infrared ray absorbing composition according to any one of claims 4 to 7 wherein the resin has a glass transition temperature of equal to or lower than 850C.
9. The near infrared ray absorbing composition according to any one of claims 4 to 8 wherein the resin has a glass transition temperature of equal to or lower than -20 "C.
10. The near infrared ray absorbing composition according to claim 9 wherein the resin has a calculated solubility parameter of equal to or less than 9.80.
11. A near infrared ray absorbent material comprising the near infrared ray absorbing composition according to any one of claims 4 to 10.
12. A near infrared ray absorbent material comprising the near infrared ray absorbing composition according to any one of claims 4 to 10 laminated on a transparent substrate.
13. The near infrared ray absorbent material according to claim 12 wherein the transparent substrate is glass, a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film or an electromagnetic wave shielding film.
14. An optical filter for thin displays wherein the near infrared ray absorbent material according to claim 12 or 13 is used.
15. An optical filter for optical semiconductor elements wherein the near infrared ray absorbent material according to claim 12 or 13 is used.
16. A thin display wherein the near infrared ray absorbing composition according to any one of claims 4 to 10, the near infrared ray absorbent material according to any one of claims 11 to 13, or the optical filter according to claim 14 is used.
17. A near infrared ray absorbing pressure sensitive adhesive composition comprising: a diimonium dye (A) having a maximum absorption wavelength in the acetone solution of ,1000 to 1060 nm; and a resin (B) having a calculated glass transition temperature of equal to or lower than -20° C.
18. A near infrared ray absorbing pressure sensitive adhesive composition according to claim 17 wherein the diimonium dye comprises a diimonium cation represented by the following formula (10) , and an anion represented by the following formula (11) or (12). [Chem. 37]
Figure imgf000154_0001
[Chem. 38]
Figure imgf000154_0002
[Chem. 39]
Figure imgf000154_0003
in the formula (10) , R9 to R16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent. In the formula (11), RL and RM each represent a fluoroalkyl group which may be the same or different. Further, in the formula (12), RN represents a fluoroalkylene group.
19. The near infrared ray absorbing pressure sensitive adhesive composition according to claim 17 or 18 wherein the resin (B) has an acid value of equal to or less than 25.
20. The near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 19 wherein the resin (B) has a calculated solubility parameter of equal to or less than 9.80.
21. The near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 20 wherein the resin (B) is a polymer produced by copolymerization of the monomers represented in the following (1) to (3) at the following proportions:
(1) a (meth) acrylate ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic alkyl group; 0.05 to 40% by weight; (2) a (meth) acrylate ester having a linear, or branched alkyl group having 1 to 10 carbon atoms; 60 to 95% by weight; and
(3) other copolymerizable monomer; 0 to 30% by weight.
22. The near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 21 wherein the resin (B) is a polymer produced by copolymerization of a (meth) acrylate ester and other monomer, and wherein this
(meth) acrylate ester has an alkyl group including an aromatic ring.
23. The near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 22 further comprising a phthalocyanine dye.
24. A near infrared ray absorbent material comprising the near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 23.
25. The near infrared ray absorbent material according to claim
24 wherein the near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 23 is laminated on a transparent substrate.
26. The near infrared ray absorbent material according to claim
25 wherein the transparent substrate is a glass, a PET film, a PET film with an easy-adhesion layer, a TAC film, an antireflection film or an electromagnetic wave shielding film.
27. An optical filter for thin displays wherein the near infrared ray absorbent material according to any one of claims 24 to 26 is used.
28. An optical filter for optical semiconductor elements wherein the near infrared ray absorbent material according to any one of claims 24 to 26 is used.
29. A thin display wherein the near infrared ray absorbing pressure sensitive adhesive composition according to any one of claims 17 to 23, the near infrared ray absorbent material according to any one of claims 24 to 26, or the optical filter according to claim 27 is used.
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