WO2010095349A1 - Composition adhésive sensible à la pression absorbant le proche infra-rouge - Google Patents

Composition adhésive sensible à la pression absorbant le proche infra-rouge Download PDF

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Publication number
WO2010095349A1
WO2010095349A1 PCT/JP2010/000266 JP2010000266W WO2010095349A1 WO 2010095349 A1 WO2010095349 A1 WO 2010095349A1 JP 2010000266 W JP2010000266 W JP 2010000266W WO 2010095349 A1 WO2010095349 A1 WO 2010095349A1
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group
infrared absorbing
adhesive composition
resin
dye
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PCT/JP2010/000266
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English (en)
Japanese (ja)
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張替尊子
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株式会社日本触媒
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Priority claimed from JP2009038476A external-priority patent/JP2010018773A/ja
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Publication of WO2010095349A1 publication Critical patent/WO2010095349A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • 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]
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • 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

Definitions

  • the present invention relates to a near-infrared absorbing pressure-sensitive adhesive composition, a near-infrared absorbing material containing the near-infrared-absorbing pressure-sensitive adhesive composition, and an optical filter for a thin display using the near-infrared absorbing pressure-sensitive adhesive composition or the near-infrared absorbing material. And so on.
  • the present invention is a near-infrared absorbing adhesive composition excellent in transparency in the visible region and durability of infrared absorbing ability, a near-infrared absorbing material containing the near-infrared absorbing adhesive composition, and the near-infrared absorbing adhesive
  • the present invention relates to an optical filter for an optical semiconductor element using an agent composition or a near-infrared absorbing material, an optical filter for a thin display using the near-infrared absorbing adhesive composition or a near-infrared absorbing material, and the like.
  • a thin liquid crystal display applicable to a large screen and a thin display such as PDP (Plasma Display Panel) have been attracting attention.
  • the thin display generates near infrared rays having a wavelength of 800 nm to 1100 nm.
  • this near infrared ray causes malfunction of the remote control for home appliances.
  • the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Therefore, there is a demand for a near-infrared absorbing material that has a high near-infrared absorbing ability and high transparency in the visible region.
  • cyanine dyes polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes or inorganic oxide particles are used as near infrared absorbing dyes that absorb near infrared rays.
  • diimonium dyes are frequently used because they have a high near-infrared absorption ability and high transparency in the visible light region (see, for example, Patent Documents 1, 2, and 3).
  • the PDP generates a discharge in a rare gas, particularly a gas mainly composed of neon, enclosed in the panel, and R, G, B provided in the cells inside the panel by vacuum ultraviolet rays generated at that time.
  • the phosphor is made to emit light. Therefore, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted during this light emission process. It is necessary to shield this electromagnetic wave. Further, an antireflection film and an antiglare film (antiglare film) are also required to suppress reflected light.
  • an optical filter for plasma display is generally produced by laminating a near-infrared absorbing film, an electromagnetic wave shielding film and an antireflection film on glass or a shock absorbing material as a support. Such an optical filter for plasma display is placed on the front side of the PDP. Such an optical filter for plasma display may be used by being directly bonded onto glass or a shock absorbing material as a support using an adhesive or a pressure-sensitive adhesive.
  • Patent Document 4 JP 2003-96040 A Japanese Unexamined Patent Publication No. 2000-80071 JP 2005-325292 A Japanese Patent No. 3621322 International Publication WO2008 / 026786
  • Diimonium-based dyes may be inferior in durability, and lowering of near-infrared absorption ability and coloring can be a serious problem when used in optical semiconductor devices and display applications.
  • a resin having a low glass transition point (Tg) such as an adhesive resin, the dye is severely deteriorated.
  • JP-A-2005-325292 discloses a diimonium dye having improved durability by introducing a halogen atom into the alkyl group of the diimonium cation.
  • the near-infrared cut-off filter using the diimonium dye and the high Tg binder resin shows improved durability as compared with the conventional diimonium dye.
  • the durability tends to be insufficient when combined with a rapidly degrading low Tg adhesive resin.
  • WO2008 / 026786 durability of the dye in the pressure-sensitive adhesive composition is improved by appropriately limiting the diimonium dye.
  • a technique capable of improving the durability of the diimonium dye in the pressure-sensitive adhesive resin has been found from a viewpoint different from the invention of International Publication WO2008 / 026786.
  • An object of the present invention is to provide a near-infrared absorbing adhesive composition useful for producing a near-infrared absorbing material having high transparency in the visible region and high durability of near-infrared absorbing ability. Furthermore, an object of the present invention is to provide a near-infrared absorbing material, an optical filter for an optical semiconductor element, an optical filter for a thin display, and a thin display using the composition.
  • the present inventors diligently studied to improve the durability of the diimonium dye in the adhesive resin. As a result, it was found that a near-infrared absorbing pressure-sensitive adhesive composition excellent in the durability of a dye can be obtained by using a dispersion in which a diimonium dye is dispersed. Moreover, it discovered that the near-infrared absorption adhesive composition excellent in durability of a pigment
  • the present invention relating to the composition contains a resin (B) in which a dispersion (A) in which a diimonium dye is dispersed in a composition containing a solvent (D) is mixed, and the glass transition temperature is 0 ° C. or lower.
  • the near-infrared absorbing adhesive composition contains a resin (B) in which a dispersion (A) in which a diimonium dye is dispersed in a composition containing a solvent (D) is mixed, and the glass transition temperature is 0 ° C. or lower.
  • the near-infrared absorbing adhesive composition is 0 ° C. or lower.
  • the dimonium dye is in an associated state.
  • composition containing an aggregate (X) of a diimonium dye, a solvent (D), and a resin (B) having a glass transition temperature of 0 ° C. or lower. is there.
  • Still another invention according to the composition includes a liquid (C) containing a particulate dimonium dye and a solvent (D), and a resin (B) having a glass transition temperature of 0 ° C. or lower. It is an infrared ray absorbing pressure-sensitive adhesive composition, wherein the solubility of the dimonium dye in the solvent (D) is 5% by mass or less.
  • the diimonium dye is a compound having a diimonium cation represented by the following formula (1) described below.
  • the diimonium anion of the diimonium dye is a hexafluorophosphate ion.
  • At least one of R 1 to R 8 is a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, 3 to 12 cycloalkyl groups, or a cycloalkyl ring optionally substituted [C 3-12 cycloalkyl-C 1-10 alkyl group].
  • At least one of R 1 to R 8 is an organic group represented by the following formula (2).
  • the organic group represented by the above formula (2) is a cyclohexylmethyl group.
  • R 1 to R 8 are cyclohexylmethyl groups.
  • At least one of R 1 to R 8 is an organic group represented by the following formula (3).
  • the organic group represented by the above formula (3) is a 3-fluoropropyl group.
  • R 1 to R 8 are 3-fluoropropyl groups.
  • At least one of R 1 to R 8 is a branched alkyl group having 3 to 12 carbon atoms.
  • the branched alkyl group is an isobutyl group.
  • the acid value of the resin (B) is 0 or more and 300 or less.
  • the calculated solubility parameter of the resin (B) is 10.2 or less.
  • the resin (B) is a polymer obtained by copolymerizing the following monomers (1a) to (3a) in the following ratio.
  • the near infrared absorbing pressure-sensitive adhesive composition may further contain a phthalocyanine dye.
  • the near-infrared absorbing adhesive composition is diluted with a diluting solvent (E) in which the solubility of the dimonium dye is 5% by mass or less.
  • E diluting solvent
  • the near-infrared absorbing material according to the present invention includes any one of the above near-infrared absorbing adhesive compositions.
  • the near-infrared absorbing material is formed by laminating one of the above near-infrared absorbing adhesive compositions on a transparent substrate.
  • the transparent substrate is glass, PET film, easy-adhesive PET film, TAC film, antireflection film or electromagnetic wave shielding film.
  • the thin display optical filter according to the present invention uses any one of the above near-infrared absorbing materials.
  • the optical filter for an optical semiconductor element uses any one of the above near-infrared absorbing materials.
  • the thin display according to the present invention uses any one of the above near infrared absorbing pressure-sensitive adhesive compositions, any one of the above near infrared absorbing materials, or the above optical filter.
  • the near-infrared absorbing material using the near-infrared absorbing adhesive composition of the present invention can maintain the near-infrared absorbing ability of the pigment for a long period of time. Therefore, when this near-infrared absorbing pressure-sensitive adhesive composition is used for the production of an optical filter for an optical semiconductor element or a thin display, it becomes possible to make the optical filter thin and simplify the optical filter manufacturing process.
  • FIG. 1 is the transmission spectrum of a dispersion containing IRG-022 particles.
  • FIG. 2 is a transmission spectrum of a MEK solution of IRG-022.
  • FIG. 3 is the transmission spectrum of a dispersion containing IRG-023 particles.
  • FIG. 4 is a transmission spectrum of a MEK solution of IRG-023.
  • FIG. 5 is a transmission spectrum of Example 1 before the test, after the heat resistance test, and after the light resistance test.
  • FIG. 6 is a transmission spectrum of Example 2 before the test, after the heat resistance test, and after the light resistance test.
  • FIG. 7 is a transmission spectrum of Comparative Example 1 before the test, after the heat resistance test, and after the light resistance test.
  • FIG. 1 is the transmission spectrum of a dispersion containing IRG-022 particles.
  • FIG. 2 is a transmission spectrum of a MEK solution of IRG-022.
  • FIG. 3 is the transmission spectrum of a dispersion containing IRG-023 particles.
  • FIG. 8 is a graph showing the molar extinction coefficient at each concentration when the dispersion (a) is diluted with ethyl acetate.
  • FIG. 9 is a graph showing the molar extinction coefficient at each concentration when the dispersion (b) is diluted with toluene.
  • FIG. 10 is a graph showing the molar extinction coefficient at each concentration when the dispersion (c) is diluted with toluene.
  • FIG. 11 is a graph showing the molar extinction coefficient of a liquid obtained by diluting dimonium salt (c) with methylene chloride to a concentration of 10 mg / L.
  • FIG. 12 is a graph showing the molar extinction coefficient at each concentration when the dispersion (d) is diluted with toluene.
  • FIG. 13 is a transmission spectrum of the near-infrared absorbing adhesive composition Aa1 according to Experimental Example 1.
  • FIG. 14 is a transmission spectrum of the specimen Z1 according to Experimental Example 1.
  • FIG. 15 is a transmission spectrum of the near-infrared absorbing adhesive composition Az2 according to Experimental Example 2.
  • FIG. 16 is a transmission spectrum of the specimen Z2 according to Experimental Example 2.
  • Diimonium dye diimonium salt
  • the dispersion (A) described later is used.
  • the durability of the diimonium salt is improved.
  • the diimonium dye is in an associated state. That is, preferably, the diimonium dye is dispersed in the aggregate (X). Details of the aggregate (X) will be described later. As will be described later, the diimonium salt forming the aggregate (X) is excellent in durability.
  • the near-infrared absorbing pressure-sensitive adhesive composition using this dispersion (A) was found to be excellent in durability even though it was present in the pressure-sensitive adhesive resin (B). Furthermore, it has been found that the durability can be further improved by using the diimonium salt in the dispersion (A) as the aggregate (X).
  • the diimonium dye is in the same dispersion state as in the dispersion (A) even in the near-infrared absorbing adhesive composition. Furthermore, in view of the good results, it can be said that at least a part of the diimonium dye is in an associated state even in the near-infrared absorbing adhesive composition.
  • the diimonium dye used in the present invention is preferably used as a dispersion (A) dispersed in a composition containing a solvent (D). Dispersion (A) helps to form aggregates (X).
  • the dispersion (A) is, for example, a dispersion in which a diimonium dye is dispersed in a solvent (D).
  • the dispersion (A) may contain other components such as a resin and a dispersant in addition to the solvent (D).
  • the diimonium dye may be dispersed in the solvent (D) or in a component other than the solvent (D) such as a resin. From the viewpoint of dispersion stability, in the dispersion (A), the diimonium dye is preferably dispersed in the solvent (D). In the dispersion (A), the diimonium dye is dispersed without dissolving in the composition containing the solvent (D).
  • the dispersion (A) is a dispersion in which a diimonium dye is dispersed. It is preferred that the diimonium dye and the solvent (D) are selected so that they can be dispersed.
  • the diimonium dye is dispersed in the near-infrared absorbing adhesive composition.
  • the diimonium salt is dispersed in an associated state in the dispersion (A). More preferably, the diimonium salt is dispersed in an associated state in the near-infrared absorbing adhesive composition.
  • Dispersion in this application is a concept including “meeting”. That is, “dispersion” as used in the present application includes dispersion in an associated state (aggregate (X)).
  • diimonium dye having a diimonium cation represented by the following formula (1) is exemplified.
  • diimmonium dyes as represented by the following formula (1S) and the diimmonium cation represented by the formula (1), diimmonium anion Z - consists of.
  • R 1 to R 8 each represents an atom or a group that may be the same or different.
  • R 1 to R 8 in the formula (1) are not particularly limited as long as they can form the aggregate (X).
  • R 1 to R 8 may each independently be a hydrogen atom, a halogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkyl group having 1 to 22 carbon atoms having a substituent. From the viewpoint of forming an association state, preferably, all of R 1 to R 8 are organic groups which may be the same or different.
  • R 1 to R 8 is the following (1x), (2x), or (3x).
  • (1x) A linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.
  • (2x) a cycloalkyl group having 3 to 12 carbon atoms.
  • (3x) The cycloalkyl ring may be substituted [C 3-12 cycloalkyl-C 1-10 alkyl group].
  • R 1 to R 8 are all the same. From the viewpoint of easily obtaining an association state, it is preferable that R 1 to R 8 are all the same and are (1x), (2x), or (3x).
  • alkyl group having 1 to 10 carbon atoms in the above (1x) methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group Group, n-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n -Hexyl group and the like are exemplified.
  • branched alkyl groups having 3 to 6 carbon atoms such as an iso-propyl group, an iso-butyl group, and an iso-amyl group, are preferable from the viewpoint of obtaining a molecular sequence necessary for forming an aggregate.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms in (2x) above include a cyclopentyl group and a cyclohexyl group.
  • Examples of the substituent for substituting the cycloalkyl ring in (3x) above include an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, an alkyl halide, a halogen atom, and the like.
  • the cycloalkyl ring in (3x) above is not substituted.
  • the [C 3-12 cycloalkyl-C 1-10 alkyl group] in the above (3x) is an organic compound represented by the following formula (2). Based on.
  • R 9 represents a linear or branched alkyl group having 1 to 10 carbon atoms, and m represents an integer of 3 to 12 inclusive.
  • R 1 to R 8 are all the same from the viewpoint that the cation structure is symmetric and an association state is easily obtained.
  • the carbon number of R 9 is more preferably 1 or more and 4 or less.
  • m is preferably 5 or more and 8 or less, and more preferably 5 or more and 6 or less. Such a carbon number range contributes to an increase in the intermolecular interaction necessary for the association.
  • a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclohexylmethyl group, a 2-cyclohexylpropyl group, a 3-cyclohexylpropyl group, and a 4-cyclohexylbutyl group are preferable, and a cyclopentylmethyl group and a cyclohexylmethyl group are more preferable.
  • a cyclohexylmethyl group is preferable.
  • the cycloalkyl ring in the above formula (2) may or may not have a substituent.
  • this substituent include at least one selected from the group consisting of an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogenated alkyl group, and a halogen. More preferably, the cycloalkyl ring in the above formula (2) does not have a substituent.
  • R 1 to R 8 are cyclohexylmethyl groups. That is, a diimonium salt represented by the following formula (2S) is particularly preferable.
  • a linear or branched alkyl group having 1 to 10 carbon atoms substituted with a halogen atom includes a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, 2,2,2- Trihalogenoethyl group, 3-halogenopropyl group, 3,3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4 Examples thereof include alkyl halides such as 4-trihalogenobutyl group, 5-halogenopentyl group, 5,5-dihalogenopentyl group, and 5,5,5-trihalogenopentyl group.
  • a monohalogenated alkyl group represented by the following general formula (3) is preferable.
  • n represents an integer of 1 to 9
  • X represents a halogen atom.
  • n is more preferably 1 or more and 4 or less.
  • X is more preferably a fluorine atom.
  • Preferable specific examples include 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group and 5-fluoropentyl group, and 3-fluoropropyl group is particularly preferable.
  • R 1 to R 8 are 3-fluoropropyl groups. That is, a diimonium salt represented by the following formula (3S) is particularly preferable.
  • the diimonium salt compound represented by the general formula (2S) and the diimonium salt compound represented by the general formula (3S) are both novel compounds. These dimonium salt compounds form an aggregate (X), are excellent in heat resistance and moisture resistance in the pressure-sensitive adhesive composition, and have a high near-infrared absorbing ability.
  • Examples of the halogen atom constituting R 1 to R 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 to R 8 include linear, branched and alicyclic alkyl groups having 1 to 10 carbon atoms.
  • alkyl group examples include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-amyl group, isoamyl group, Examples include 1-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, and the like.
  • R 1 to R 8 include 4,4,4-trifluorobutyl group, 2,2,2-trifluoroethyl group and perfluorobutyl group.
  • R 1 to R 8 may all be the same or different from each other. In these, the above-mentioned branched alkyl group is more preferable.
  • R 1 to R 8 may be a linear or branched alkyl group having 3 to 5 carbon atoms.
  • R 1 to R 8 may be an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-amyl group, or an isoamyl group.
  • the aforementioned branched alkyl group is particularly preferred.
  • Examples of the substituent that can be bonded to the alkyl group of R 1 to R 8 include cyano group; hydroxyl group; halogen atom such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, n-propoxy group, n
  • An alkoxy group having 1 to 6 carbon atoms such as butoxy group; alkoxy having 2 to 8 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group, etc.
  • Alkoxy group methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, etc., alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms; allyloxy group; phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group 6-12 carbon atoms such as Aryloxy group; alkoxycarbonyl group having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, C2-C7 alkylcarbonyloxy groups such as n-propylcarbonyloxy group and n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group
  • the kind of anion in the dimonium dye is not particularly limited. This dimonium anion is necessary to neutralize the dimonium cation represented by the general formula (1).
  • halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion; perchlorate ion; periodate ion; tetrafluoroborate ion; hexafluorophosphate ion; hexafluoroantimonate ion; trifluoro Lomethanesulfonate ion; Toluenesulfonate ion; Bis (trifluoromethanesulfone) imide ion; Tetrakis (pentafluorophenyl) borate ion; Tris (trifluoromethanesulfone) methide ion, etc.
  • fluorine ion, chlorine ion, bromine ion, iodine Inorganic anions such as halogen ions such as ions; perchlorate ions; periodate ions; tetrafluoroborate ions; hexafluorophosphate ions; hexafluoroantimonate ions
  • hexafluorophosphate ions are preferred.
  • the diimonium dye of the present invention preferably has a form in which two anions are bonded to one diimonium cation.
  • a salt of the preferable diimonium cation and the preferable diimonium anion is preferably used as the diimonium dye.
  • the diimonium salt according to the present invention is excellent in heat resistance, moist heat resistance and light resistance in combination with the resin (B) having a glass transition temperature (Tg) of 0 ° C. or less, and may have good haze.
  • an amino compound represented by the following formula (4) is obtained by an Ullmann reaction and a reduction reaction.
  • an iodide corresponding to the above R 1 to R 8 and an alkali metal carbonate as a deiodizing agent are added in a polar solvent such as NMP or DMF, and 30 ° C. or more and 150 ° C. or less, preferably Is reacted at 70 ° C. or higher and 120 ° C. or lower to obtain an alkyl-substituted product represented by the following formula (5).
  • R 1 to R 8 are all cyclohexylalkyl groups
  • a cyclohexylalkane iodide is used as the corresponding iodide.
  • R 1 to R 8 are all cyclohexylmethyl groups
  • cyclohexylmethyl iodide is used as the corresponding iodide.
  • all of R 1 to R 8 are fluoroalkyl groups
  • a fluoroalkane iodide is used as the corresponding iodide.
  • R 1 to R 8 are all 3-fluoropropyl groups
  • 1-iodo-3-fluoropropane is used as the corresponding iodide.
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • R 1 to R 8 are two or more different substituents, the iodides in the number of moles corresponding to the number of the respective organic groups are sequentially reacted, or these are simultaneously added and reacted.
  • R 1 to R 8 are a cyclohexylmethyl group and other organic groups, a mole number of cyclohexylalkane iodide (cyclohexylmethyl iodide) corresponding to the number of substituents is added and reacted.
  • iodide for example, fluoroalkane iodide; iodoalkane; alkoxyiodide; benzene iodide; phenyl-1-iodoalkane such as benzyl iodide and phenethyl iodide
  • iodide for example, fluoroalkane iodide; iodoalkane; alkoxyiodide; benzene iodide; phenyl-1-iodoalkane such as benzyl iodide and phenethyl iodide
  • a silver salt of an anion Z ⁇ corresponding to the alkyl-substituted product represented by the above formula (5) is 30 ° C. or more and 150 ° C. or less, preferably 40 ° C. or more and 80 ° C. in an organic solvent such as NMP, DMF, or acetonitrile.
  • an organic solvent such as NMP, DMF, or acetonitrile.
  • R 1 to R 8 have the same meaning as described above.
  • the diimonium dye according to the present invention forms an aggregate (X) in which a plurality of molecules represented by the formula (1S) are associated.
  • This aggregate (X) is considered to be a molecular assembly formed by several to several tens of molecules.
  • the aggregate (X) When the aggregate (X) is diluted to 100 mg / L with toluene, the aggregate (X) exhibits absorption in a wavelength region of 750 nm to 1300 nm, and has a maximum absorption wavelength in a wavelength region of 1110 nm to 1250 nm.
  • the maximum absorption wavelength when the aggregate (X) is formed has an absorption spectrum different from that in the dissolved state (for example, Photographic Science and Engineering, Vol. 18, No. 323-335 ( 1974)). In general, the absorption band in the associated state moves to the longer wavelength side than the dissolved state.
  • a diimonium salt compound generally exhibits a maximum absorption wavelength between 1050 nm and 1095 nm in a dissolved state, but when an aggregate (X) is formed, the maximum absorption wavelength is shifted to the longer wavelength side from 15 nm to 200 nm. .
  • the aggregate (X) when the aggregate (X) is diluted to 100 mg / L with toluene, it exhibits a maximum absorption wavelength in the range of 1110 nm to 1250 nm. Note that if the amount of change due to the shift is too large, near infrared absorption near 900 nm or more and 1100 nm or less may be insufficient. From this viewpoint, the amount of change in the shift of ⁇ max when measured after being diluted to 100 mg / L with toluene is preferably 15 nm or more and 100 nm or less.
  • the measurement conditions for measuring the shift change amount are, for example, the following [Measurement method 1] for the aggregate (X) and the following [Measurement method 2] for the dissolved state.
  • the absorption wavelength region and the maximum absorption wavelength of the aggregate (X) of the diimonium dye according to the present invention can be measured, for example, by the following [Measurement method 1].
  • the dimonium salt compound is determined based on the absorbance measured in a suspended or suspended state (dispersed state) as particles having a concentration of at least 50 mg / L and not less than 0.001 ⁇ m and not more than 10 ⁇ m in a dispersion medium. This particle size is measured by a Microtrac particle size analyzer. Specifically, 0.5 parts by weight of a diimonium salt compound, 9.5 parts by weight of toluene, and 70 parts by weight of zirconia beads having a particle diameter of 0.3 mm were placed in a 50 ml glass container and shaken with a paint shaker for 2 hours. The zirconia beads are filtered off to obtain liquid L1.
  • the liquid L1 is diluted with toluene so that the concentration of the diimonium salt compound is 100 mg / L, and a diimonium salt dispersion L2 is obtained.
  • the absorbance of this dispersion L2 is measured with a spectrophotometer.
  • a spectrophotometer As this spectrophotometer, UV-3100 (manufactured by Shimadzu Corporation) can be used.
  • the dilution concentration (100 mg / L) may be appropriately changed as long as the dimonium salt is not dissolved.
  • the maximum absorption wavelength of the dimonium salt compound in a dissolved state can be measured, for example, by the following [Measurement Method 2].
  • the dispersion L2 obtained by the above [Measuring method 1] is further diluted with toluene, and the solution at the time when the solution is dissolved is used. Whether or not it is in a dissolved state can be comprehensively determined by shifting ⁇ max to the short wavelength side or narrowing the half width. If the solution is not dissolved even when diluted to about 5 mg / L with toluene, dilute with methylene chloride instead of toluene. This solution is measured with a spectrophotometer. As this spectrophotometer, UV-3100 (manufactured by Shimadzu Corporation) can be used.
  • the dispersion medium may be other than toluene.
  • examples of the dispersion medium include ethyl acetate, butyl acetate and methylcyclohexane.
  • the diimonium salt compound may be in a dispersed state as a crystal, not as an aggregate.
  • a steep absorption band having a half width smaller than that in the crystal dispersion state is shown.
  • the half-value width is a width of a wavelength region showing an absorbance that is half of the absorbance at the maximum absorption wavelength.
  • the amount of change in the maximum absorption wavelength relative to the dissolved state is large.
  • ⁇ max under a condition diluted to 100 mg / L with toluene shifts to a longer wavelength side than 1250 nm.
  • the molar extinction coefficient at the maximum absorption wavelength is less than 40,000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 .
  • the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ) is an extinction coefficient when the concentration is 1 mol / L and the optical path length is 1 cm.
  • the molar extinction coefficient at this maximum absorption wavelength is 70000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
  • the near-infrared absorption ability is inferior compared with the association state.
  • the determination of whether the diimonium salt compound is in an associated state or a dissolved state is made by comparing the absorption spectrum measured in the dispersion (dispersed state) with the absorption spectrum measured in the dissolved state.
  • the maximum absorption wavelength and the shift amount of the maximum absorption wavelength can be performed.
  • the determination of whether the diimonium salt compound is in an associated state or a crystal dispersed state is made by comparing the maximum absorption wavelength of the absorption spectrum measured in the dispersed state and its molar extinction coefficient.
  • Preferred diimonium dyes can be obtained, for example, by the above production method.
  • Commercially available diimonium dyes include trade name “CIR-1085” manufactured by Nippon Carlit Co., Ltd., trade name “CIR-1085F” manufactured by Nippon Carlit Co., Ltd., and trade name “KAYASORB IRG-022” manufactured by Nippon Kayaku Co., Ltd. ", Trade name” KAYASORB IRG-023 "manufactured by Nippon Kayaku Co., Ltd., and the like.
  • “KAYASORB IRG-022” and “KAYASORB IRG-023” are also simply referred to as “IRG-022” and “IRG-023”, respectively.
  • the diimonium dye is preferably in a form that is easily dispersed in the solvent (D).
  • the diimonium dye is refined by pulverization or the like.
  • the miniaturization method both wet and dry methods can be adopted.
  • a wet micronization method a bead mill or ball mill, micronization by liquid flow, or micronization using laser or ultrasonic waves can be employed.
  • a dry refinement method a ball mill, an attritor, a roll mill or an air stream can be used. More preferably, a method of pulverizing a diimonium dye using particles such as zirconia beads and glass beads may be employed.
  • a liquid is prepared by mixing a diimonium dye, a solvent (D) having a solubility of 5% by mass or less of the diimonium dye, and zirconia beads.
  • a method of separating zirconia beads after shaking is a method of separating zirconia beads after shaking.
  • the diimonium dye is used by being dispersed in a composition containing the solvent (D).
  • the diimonium dye is used by being dispersed in the solvent (D).
  • the solvent (D) is preferably a poor solvent for the diimonium dye used.
  • a solvent in which the diimonium dye used has a solubility of 5% by mass or less is preferable. A method for measuring this solubility will be described later.
  • solvent (D) examples include toluene, xylene, ethyl acetate, butyl acetate, methylcyclohexane and the like, and toluene and ethyl acetate are particularly preferable.
  • Dispersion (A) The dispersion (A) is a liquid in which the diimonium dye is dispersed in a composition containing the solvent (D).
  • the dispersion (A) is formed by mixing a diimonium dye and a dispersion medium.
  • the dispersion medium include a resin in addition to the solvent (D).
  • the dispersion medium may be a mixture of the solvent (D) and another compound.
  • the dispersion medium includes a solvent (D).
  • the dispersion means a state in which particles of about 0.001 ⁇ m to 10 ⁇ m (10 ⁇ 9 m to 10 ⁇ 5 m) are suspended or suspended in the composition containing the solvent (D).
  • the diimonium dye is in an associated state. That is, in the dispersion (A), it is preferable that the diimonium dye is the aggregate (X).
  • Examples of the dispersion (A) in which the diimonium dye is in an associated state include a dispersion (a), a dispersion (b), a dispersion (c), and a dispersion (d) obtained in Synthesis Examples described later.
  • Examples of the dispersing device include a bead mill, a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill, and a bead mill is preferable.
  • Examples of the dispersing device that can be used in the present invention include those described in JP-A-52-92716 and International Publication No. 88/074794. Among these, a vertical or horizontal medium dispersion device is preferable.
  • a dispersion medium may not be used, but it is preferably carried out in the presence of the dispersion medium.
  • Examples of the dispersion medium include water and various organic solvents.
  • an organic solvent is preferable, and toluene, ethyl acetate, and the like are particularly preferable.
  • a surfactant may be used as the dispersion medium.
  • the surfactant include an anionic surfactant, an anionic polymer, a nonionic surfactant, and a cationic surfactant. In this way, the dispersion (A) can be obtained.
  • the liquid (C) in the present application is a concept including the dispersion (A).
  • the liquid (C) is obtained by mixing a particulate diimonium dye and a solvent (D) having a solubility of the diimonium dye of 5% by mass or less.
  • the liquid (C) may contain a component (third component) other than the solvent (D) and the diimonium dye.
  • dye becomes easy to disperse
  • the method for measuring the solubility is as described later.
  • a diluting solvent (E) may be used separately from the solvent (D).
  • a dispersant may be added for the purpose of improving the dispersibility of the diimonium dye dispersion.
  • the dispersant include an anionic, cationic or nonionic surfactant and a polymeric dispersant.
  • the diimonium salt In the dispersion (A) or the liquid (C), depending on the concentration of the diimonium salt, all of them may form an aggregate (X), or a part of the aggregate (X). It may be formed.
  • a part of the dimonium salt is an aggregate (X)
  • the other dimonium salt may be in a dissolved state and / or a crystal dispersion state.
  • the maximum absorption wavelength is 1110 nm or more and 1250 nm or less
  • the molar extinction coefficient at the maximum absorption wavelength is 70000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
  • the diimonium salt is an aggregate (X).
  • a diimonium salt that is an aggregate when diluted to 100 mg / L with toluene is also considered to be an aggregate when diluted to a concentration higher than 100 mg / L with toluene.
  • the dimonium salt that is an aggregate is diluted with this dispersion medium S to a concentration higher than B (mg / L). In some cases, it is considered an association.
  • ⁇ max of the dispersion (A) or liquid (C) using the solvent S1 as a dispersion medium is further added to the dispersion (A) or liquid (C) by further adding the solvent S1. It is preferably larger than ⁇ max of the diluted diluent (long wavelength). In this case, it is considered that ⁇ max is shifted because the diimonium salt is dissolved in the diluted body.
  • this solvent S1 the same thing as the said solvent (D) is illustrated.
  • a diimonium salt when used as a near-infrared absorbing composition for a PDP filter or the like, a substituent is often devised so that the diimonium salt is in a dissolved state from the viewpoint of haze or the like.
  • the durability of the diimonium dye in the near-infrared absorbing composition tends to decrease.
  • the pressure-sensitive adhesive resin (B) the durability of the diimonium dye is greatly reduced.
  • the diimonium dye when used in a crystal dispersion state, the dispersion stability is poor and the crystal becomes coarse. In this case, the half width is large and the extinction coefficient at the maximum absorption wavelength is low. For this reason, sufficient near-infrared absorptivity cannot be obtained, and light is scattered due to the coarseness of crystals, and white turbidity is likely to occur.
  • the diimonium dye is an aggregate (X)
  • a so-called aggregate band is formed, and a steep absorption band having a small half width is obtained.
  • the aggregate (X) has a high extinction coefficient at the maximum absorption wavelength and has an excellent near infrared absorption ability.
  • This aggregate (X) is considered to be an aggregate (molecular aggregate) formed by several to several tens of molecules. Therefore, light scattering is not strong and the transparency is excellent.
  • an aminium salt compound is produced. This aminium salt compound has an absorption in the visible light region (near 480 nm) and exhibits a yellow color, so that the appearance of the near-infrared absorbing material is deteriorated.
  • the aggregate (X) is a molecular assembly, it is stabilized by the interaction between molecules, and an aminium salt compound is hardly generated.
  • the dissolved state is a state dispersed in a single molecule, it is not stabilized by the interaction between molecules. Therefore, in the dissolved state, compared to the aggregate (X), the diimonium dye is easily decomposed and an aminium salt compound is easily generated. For these reasons, it is considered that the aggregate (X) is excellent in heat resistance, moisture resistance and light resistance even in the pressure-sensitive adhesive resin (B).
  • Resin (B) The resin (B) according to the present invention is not particularly limited as long as the glass transition temperature is 0 ° C. or lower.
  • the resin (B) according to the present invention has adhesiveness. This tackiness enables direct adhesion between the near-infrared absorbing pressure-sensitive adhesive composition and the adherend.
  • the near-infrared absorbing pressure-sensitive adhesive composition and the adherend can be bonded without interposing an adhesive.
  • this resin (B) is also referred to as an adhesive resin (B).
  • the glass transition temperature of the adhesive resin (B) is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and more preferably ⁇ 20 ° C. or lower. More preferably, it is ⁇ 30 ° C. or lower. When it is higher than 0 ° C., the tackiness may be insufficient.
  • the glass transition temperature can also be obtained by determining the maximum temperature of the loss tangent (tan ⁇ ) by a differential scanning calorimeter (Dynamic Scanning Calorimeter) or dynamic viscoelasticity measurement.
  • Means the calculated glass transition temperature obtained by The monomer used for the polymerization of the resin (B) is not particularly limited as long as the calculated glass transition temperature Tg calculated using the Fox formula represented by the following formula satisfies a predetermined value.
  • 1 / (Tg + 273) ⁇ [Wi / (Tgi + 273)]: Fox formula Tg (° C.): calculated glass transition temperature
  • Wi weight fraction of each monomer Tgi (° C.): single weight of each monomer component Glass transition temperature of coalescence
  • the adhesive resin (B) is generally copolymerized with a carboxyl group-containing monomer such as acrylic acid for the purpose of improving the adhesion to the adherend and increasing the adhesive strength.
  • a carboxyl group-containing monomer such as acrylic acid
  • the acid value of the resin (B) is preferably 300 or less, more preferably 100 or less, and still more preferably 80 or less.
  • the acid value of the pressure-sensitive adhesive resin (B) is preferably 0 or more, more preferably 5 or more, and still more preferably 10 or more.
  • “Acid value” refers to the amount of mg of potassium hydroxide required to neutralize 1 g of the adhesive resin.
  • reaction 1 when the transparent base material mentioned later is glass, it is estimated that the following (Reaction 1) has occurred in the glass surface (interface of glass and a near-infrared absorption adhesive composition layer). It is believed that Na + ions in the glass emerge on the glass surface by diffusion. The Na + ions react with present in the near-infrared absorbing pressure-sensitive adhesive composition H 2 O (or H 2 O which is attached to the glass surface prior to application of the adhesive composition) and NaOH generates considered It is done. (Reaction 1) Na + + H 2 O ⁇ NaOH + H + (to the inside of the glass)
  • This NaOH degrades the diimonium salt.
  • this carboxyl group traps Na + . It is considered that this trap suppresses the generation of NaOH and suppresses the deterioration of the diimonium salt.
  • the reaction 1 is likely to occur because a large amount of H 2 O is present. Therefore, in particular, from the viewpoint of heat and humidity resistance, the acid value is preferably large. Specifically, as described above, 0 or more is preferable, 5 or more is more preferable, and 10 or more is more preferable.
  • the acid value of the resin (B) is excessively high, the solubility of the diimonium salt in the resin (B) increases and the aggregate (X) tends to decrease. Therefore, from the viewpoint of heat resistance for evaluating durability at high temperatures, the acid value is preferably small. Specifically, as described above, 300 or less is preferable, 100 or less is more preferable, and 80 or less is preferable. Further preferred.
  • the calculated solubility parameter is a value calculated by the method described on pages 147 to 154 of “POLYMER ENGINEERING AND SCIENCE” (1974, Vol. 14, No. 2). The method is outlined below.
  • the solubility parameter ( ⁇ ) of the homopolymer is calculated by the following formula based on the evaporation energy ( ⁇ ei) and molar volume ( ⁇ vi) of the structural unit forming the polymer.
  • ⁇ ( ⁇ ei / ⁇ vi) 1/2
  • ⁇ ei Evaporation energy of i component atom or atomic group
  • ⁇ vi Molar volume of i component atom or atomic group
  • the solubility parameter of the copolymer is obtained by multiplying the evaporation energy of each constituent monomer constituting the copolymer by the mole fraction ( ⁇ Ei) and adding it to the molar volume of each constituent monomer. Calculated by multiplying by the mole fraction and adding together ( ⁇ Vi) and taking the 1/2 power.
  • the adhesive resin (B) may be a copolymer.
  • the pressure-sensitive adhesive resin (B) is preferably a copolymer of a monomer containing a functional group and another compound. Furthermore, from the viewpoint of the durability of the diimonium dye, the pressure-sensitive adhesive resin (B) is a (meth) acryl having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic ring alkyl group. A copolymer obtained by copolymerizing 5 to 40% by mass of an acid ester is preferable.
  • the resin (B) is a resin obtained by copolymerizing the following monomers (p1) to (p3).
  • P1 (meth) acrylic acid ester (p2) functional group-containing monomer having an alkyl group having 1 to 12 carbon atoms (P3)
  • P3 Other copolymerizable monomers
  • the preferable ratio of the monomer is 60% by mass or more and 99.9% by mass or less of (meth) acrylic acid ester of (p1), and 0.1% by mass or more and 20% by mass of the functional group-containing monomer of (p2).
  • the other copolymerizable monomer (p3) is 0% by mass or more and 30% by mass or less. More preferably, the ratio of the functional group-containing monomer (p2) is 0.1% by mass or more and 10% by mass or less.
  • the alkyl group in the monomer (p1) is a linear, branched or alicyclic alkyl group.
  • Examples of (meth) acrylic acid ester of (p1) above are 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, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-nonyl ( Examples include meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, and n-dodecyl (meth) acrylate.
  • the functional group-containing monomer (p2) is preferably a hydroxyl group or carboxyl group-containing monomer, more preferably a hydroxyl group or carboxyl group-containing (meth) acrylic monomer.
  • a carboxyl group-containing (meth) acrylic monomer is preferable.
  • the carboxyl group of the carboxyl group-containing (meth) acryl monomer serves as a crosslinking point. Therefore, the adhesiveness can be adjusted by the blending amount of the carboxyl group-containing (meth) acrylic monomer.
  • the carboxyl group of the carboxyl group-containing (meth) acrylic monomer contributes to the improvement of durability. Details of this reason are as described above.
  • carboxyl group-containing (meth) acrylic monomer acrylic acid and methacrylic acid are preferably used.
  • the hydroxyl group-containing (meth) acrylic monomer examples include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
  • the hydroxyl group of the hydroxyl group-containing (meth) acrylic monomer can be a crosslinking point. Therefore, the hydroxyl group-containing (meth) acrylic monomer contributes to the adjustment of the adhesive properties.
  • the ratio of the hydroxyl group-containing (meth) acrylic monomer is particularly preferably 0.1% by mass or more and 10% by mass or less based on the total amount of the monomers.
  • benzyl (meth) acrylate As other copolymerizable monomers of the above (p3), benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Examples include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • (p3) examples include (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate; ⁇ -methylstyrene, vinyltoluene, styrene, etc.
  • Styrene monomers represented by: vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid; monoalkyl ester of fumaric acid; dialkyl ester of fumaric acid; maleic acid; Dialkyl ester of maleic acid; itaconic acid; monoalkyl ester of itaconic acid; dialkyl ester of itaconic acid; (meth) acrylonitrile; vinyl chloride; vinylidene chloride; vinyl acetate; Nirupirijin; vinyl carbazole and the like.
  • monomers having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group, and a fluoroalkyl group may be copolymerized within a range that does not impair the object of the present invention.
  • More preferred adhesive resin (B) is a resin obtained by copolymerizing the following (m1) to (m4).
  • (M1) A (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group.
  • (M2) A (meth) acrylic acid ester having an alkyl group. However, this alkyl group is linear or branched, and the alkyl group has 1 to 10 carbon atoms.
  • M3 Functional group-containing monomer (m4) Other copolymerizable monomers.
  • a preferable ratio of the monomer is 5% by mass or more and 40% by mass or less of (meth) acrylic acid ester of (m1), and (meth) acrylic acid ester of (m2). Is from 60% by mass to 95% by mass, the functional group-containing monomer of (m3) is from 0.1% by mass to 20% by mass, and the other monomer of (m4) is from 0% by mass to 20% by mass. % Or less.
  • Examples of the (meth) acrylic ester of (m1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth).
  • Examples of the (m) acrylic acid ester of (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) Examples include acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, and the like.
  • Examples of the monomer (m3) include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
  • Examples of the monomer (m4) include (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; ⁇ -methylstyrene, vinyltoluene, Styrenic monomers typified by styrene and the like; vinyl ether monomers typified by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like; fumaric acid; monoalkyl ester of fumaric acid; dialkyl ester of fumaric acid; maleic acid; Monoalkyl ester of maleic acid; dialkyl ester of maleic acid; itaconic acid; monoalkyl ester of itaconic acid; dialkyl ester of itaconic acid; (meth) acrylonitrile; vinyl chloride; vinylidene chloride; vinyl acetate; Emission
  • monomers having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group, and a fluoroalkyl group may be copolymerized within a range that does not impair the object of the present invention.
  • Peroxide-based initiators include peroxyesters such as perbutyl O and perhexyl O (both manufactured by NOF); peroxydicarbonates such as PERROYL L and PEROIL O (both manufactured by NOF); Diacyl peroxides such as BW and Nyper BMT (both made by NOF); Peroxyketals such as perhexa 3M and perhexa MC (both made by NOF); perbutyl P, park mill D (both made by NOF) And hydroperoxides such as Park Mill P and Permenter H (both manufactured by NOF Corporation).
  • the azo initiator include ABN-E, ABN-R, and ABN-V (all manufactured by Nippon Hydrazine Kogyo).
  • a chain transfer agent may be used as necessary.
  • the chain transfer agent is not particularly limited, and thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, and mercaptoethanol can be used.
  • the polymerization of the pressure-sensitive adhesive resin (B) may be performed without a solvent or in an organic solvent.
  • aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone; other known organics
  • MEK methyl ethyl ketone
  • organic solvents are preferred. From the viewpoint of the stability of the dispersion, an organic solvent having a diimonium dye solubility of 5% by mass or less is preferred.
  • the pressure-sensitive adhesive resin (B) may be composed of a single composition, or may be a polymer alloy or polymer blend in which polymers having different compositions are combined.
  • 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-6, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Co., Ltd.) and the like can be used.
  • the polyfunctional monomer include LIGHT EG EG, LIGHT SEL 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 (all manufactured by NOF Corporation), Trigonox 17-40MB, Parkadox 12-XL25 (all manufactured by Explosive Akzo), and the like.
  • polyfunctional chain transfer agent pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) or the like can be used.
  • Near-infrared-absorbing pressure-sensitive adhesive composition The near-infrared-absorbing pressure-sensitive adhesive composition of the present invention is excellent in sustainability of near-infrared absorptivity because it uses a dimonium dye dispersed therein. Moreover, this near-infrared absorption adhesive composition is excellent in transparency in the visible region. Since the near-infrared absorbing adhesive composition of the present invention contains an adhesive resin, it can be easily adhered to an adherend.
  • This near-infrared absorbing pressure-sensitive adhesive composition can be excellent in haze even though the diimonium dye is a pigment dispersion.
  • the near-infrared absorbing adhesive composition has a haze of 5 or less, more preferably 3 or less. This haze is measured by the method shown by the below-mentioned Example.
  • near infrared absorbing dyes may be added to the near infrared absorbing pressure-sensitive adhesive composition of the present invention.
  • Other near infrared absorbing dyes that can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like. Can be mentioned.
  • Preferred other dyes are dyes that can exhibit a quencher effect with respect to the diimonium dye.
  • the quencher effect is an effect of deexciting an active molecule in an excited state.
  • other dyes having an effect of de-exciting and stabilizing diimonium dye molecules, diimonium anions or diimonium cations are preferred.
  • a phthalocyanine dye is preferable as the other dye.
  • a dye or a metal dithiol complex dye having a maximum absorption wavelength of 800 to 950 nm is preferably used in combination.
  • near infrared rays of 800 to 1100 nm can be effectively absorbed. From the viewpoint of obtaining a near-infrared absorbing pressure-sensitive adhesive composition having good durability, it is particularly preferable to use a phthalocyanine dye in combination.
  • the phthalocyanine compound that can be used in the present invention is not particularly limited as long as it has excellent near-infrared absorption ability, and a known phthalocyanine compound can be used.
  • Preferable phthalocyanine compounds include compounds represented by the following formula (A) or compounds represented by the following formula (I).
  • a 1 to A 16 represent functional groups.
  • a 1 to A 16 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, or an optionally substituted carbon atom having 1 to 20 carbon atoms.
  • Alkyl groups optionally substituted alkoxy groups having 1 to 20 carbon atoms, optionally substituted aryl groups having 6 to 20 carbon atoms, optionally substituted carbon atoms 6 to 20 Aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, and optionally substituted carbon atoms 1-20 alkylthio group, optionally substituted arylthio group having 6-20 carbon atoms, optionally substituted aralkylthio group having 7-20 carbon atoms, substituted An optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl having 7 to 20 carbon atoms A sulfonyl group, an optionally substituted acyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy
  • the functional groups of A 1 to A 16 may be the same or different, and may be the same or different in the same type, and the functional groups may be connected via a linking group.
  • M 1 represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal.
  • the “acyl group” has the same definition as that described on page 17 of the third edition of the Dictionary of Science and Technology Terms published by the Nikkan Kogyo Shimbun.
  • a group from which a group has been removed is a group represented by the formula: RCO— (where R is an aliphatic group, an alicyclic group or an aromatic group).
  • examples of the halogen atom of the functional groups A 1 to A 16 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. It is not limited to.
  • Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, 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, etc.
  • an alkoxy group is mentioned, it is not limited to these.
  • Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group.
  • Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, a phenoxy group and a naphthoxy group.
  • Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group and a diphenylmethyloxy group, but are not limited thereto.
  • Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, etc.
  • Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group, but are not limited thereto.
  • Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzylthio group, phenethylthio group, diphenylmethylthio group and the like.
  • Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc.
  • Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups.
  • Examples of the optionally substituted arylsulfonyl group having 6 to 20 carbon atoms include, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group.
  • Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto.
  • Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight-chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups.
  • Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group.
  • Examples of the optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups.
  • Examples of the optionally substituted aralkyloxycarbonyl group having 8 to 20 carbon atoms include benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like, but are not limited thereto. .
  • Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, an n-octyl carbonyloxy group, etc.
  • the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted includes a benzoyloxy group, but is not limited thereto.
  • Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group.
  • Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.
  • the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group of the functional groups A 1 to A 16 An arylsulfonyl group, an aralkylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an aralkylcarbonyloxy group or a heterocyclic group
  • substituents present in these functional groups A 1 to A 16 for example, halogen atoms, acyl groups, alkyl groups, phenyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro
  • the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups A 1 to A 16 are as follows: Hydrogen atom; linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, cyclohexyl group, etc.
  • Alkyl group aryl group such as phenyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso- Butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexyl Linear, branched or cyclic alkylcarbonyl groups such as carbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group and n-octylcarbonyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; benzyl Examples thereof include, but are not limited
  • substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.
  • Examples of the divalent metal as the metal M 1 include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and 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 are not limited thereto.
  • Examples of trivalent substituted metal atoms include Al—F, Al—Cl, Al—Br, Al—I, Fe—Cl, Ga—F, Ga—Cl, Ga—I, Ga—Br, and In—F.
  • Examples of tetravalent substituted metal atoms 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 ) 2 , Ge (R 1 ) 2 , Si (R 1 ) 2 , Sn (R 1 ) 2 , Ti (R 1 ) 2 ⁇ R 1 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, Ti (OR 2) 2,
  • B 1 to B 24 represent functional groups.
  • Each of B 1 to B 24 is any of the functional groups represented by A 1 to A 16 in the above formula (a).
  • the functional groups of B 1 to B 24 may be the same type or different types, and may be the same or different in the same type, and the functional groups may be linked via a linking group.
  • M 2 represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal.
  • Examples of M 2 are the same as the examples of M 1 in the above formula (a), but are not limited thereto.
  • EEX COLOR IR-10A trade names EEX COLOR IR-12, EEX COLOR IR-14, EEX COLOR IR-906, EEX COLOR IR-910, TX-EX-820 And TX-EX-915 (both manufactured by Nippon Shokubai).
  • a cyanine dye may be used in combination as a near infrared absorbing dye.
  • the cyanine dye is not particularly limited as long as it has an excellent near-infrared absorbing ability, but a salt composed of an indolium cation or a benzothiazolium cation and a counter anion can be preferably used.
  • a salt composed of an indolium cation or a benzothiazolium cation and a counter anion can be preferably used.
  • the indolium cation or benzothiazolium cation cations represented by the above formulas (a) to (i) can be preferably used, but are not limited thereto.
  • the counter anion of the indolium cation or benzothiazolium cation is not particularly limited, and chloride ion, bromide ion, iodide ion, perchlorate ion, nitrate ion, benzenesulfonate ion, p-toluenesulfonic acid Ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid Acid ion, oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion,
  • ADS812MI counter anion is an iodide ion
  • ADS780MT Counter anion is an iodide ion
  • AS0712 S0712 manufactured by FEW Chemical Co.
  • Counter anion is hexafluorophosphate ion
  • S0726 manufactured by FEW Chemical Co.
  • Counter anion is chloride ion
  • ADS780MT As cyanine-based dye containing a cation represented by the above general formula (d), ADS780MT manufactured by American Dye Source Co.
  • the blending amount of the diimonium dye of the present invention, or the total blending amount of the diimonium dye of the present invention and other near-infrared absorbing dyes can be appropriately selected depending on the type and use of the dye.
  • the blending amount is preferably 0.01 to 10% by mass, more preferably 0. 1 to 5% by mass.
  • the total amount of these dyes is preferably 0.01 to 10% by mass, more preferably 0.1%, based on the solid content of the resin. ⁇ 5% by mass.
  • the blending amount is less than 0.01% by mass, there is a possibility that sufficient near infrared absorption ability cannot be achieved. Conversely, when it exceeds 10 mass%, the effect corresponding to addition cannot be acquired and it is not economical, and conversely, transparency in the visible region may be impaired.
  • the near-infrared absorbing adhesive composition of the present invention is characterized by transparency in the visible region, durability of near-infrared absorbing ability, and good adhesiveness.
  • a dye that absorbs visible light may be added to the near-infrared absorbing adhesive composition of the present invention.
  • dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complex, squarylium, azurenium, diphenylmethane, triphenylmethane, oxazine, and azine.
  • dye such as a system and a diketopyrrolopyrrole type
  • the near-infrared absorbing adhesive composition of the present invention is used as an optical filter for PDP, it is preferable to use a visible absorbing dye having a maximum absorption wavelength of 550 to 650 nm in order to absorb unnecessary neon light emission.
  • the type of the dye that absorbs neon light emission is not particularly limited, and a cyanine dye and a tetraazaporphyrin dye can be used.
  • Adeka Arcles TY-102 Adeka Arcles TY-14 (Asahi Denka Kogyo Co., Ltd.), Adeka Arcles TY-15 (Asahi Denka Kogyo Co., Ltd.), TAP-2 ( Yamada Chemical Industries), TAP-18 (Yamada Chemical Industries), TAP-45 (Yamada Chemical Industries), NK-5451 (Hayashibara Biochemical Laboratories), NK-5532 (Hayashibara Biochemical Laboratories) ), NK-5450 (produced by Hayashibara Biochemical Laboratories), and the like.
  • the addition amount of the dye for absorbing neon emission varies depending on the kind of the dye, but it is preferable to add so that the transmittance at the maximum absorption wavelength is about 20 to 80%.
  • a visible light absorbing dye for toning may be added.
  • coloring pigment 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 (Ciba) ⁇ Specialty Chemicals), Orazole Black CN (Ciba Specialty Chemicals), Orasol Yellow 2GLN (Ciba Specialty Chemicals), Orazole Yellow 2RLN (Ciba Specialty Chemicals), Microlith DPP Red BK (manufactured by Ciba Specialty Chemicals) and the like.
  • the near-infrared absorbing pressure-sensitive adhesive composition of the present invention may contain one or more diluent solvents (E), additives, and curing agents as long as the performance is not lost.
  • the dilution solvent (E) can facilitate coating of the near-infrared absorbing pressure-sensitive adhesive composition.
  • the dilution solvent (E) that can be contained in the near-infrared absorbing pressure-sensitive adhesive composition is not limited, and examples thereof include aliphatic systems such as cyclohexane and methylcyclohexane; aromatic systems such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • Ketone type such as ethyl acetate and butyl acetate; nitrile type such as acetonitrile; alcohol type such as methanol, ethanol and isopropyl alcohol; ether type such as tetrahydrofuran and dibutyl ether; butyl cellosolve, propylene glycol n-propyl ether, propylene glycol glycol ethers such as n-butyl ether and propylene glycol monomethyl ether acetate; amides such as formamide and N, N-dimethylformamide; methylene chloride, chloroform and the like Androgenic system or the like can be used. These solvents may be used alone or in combination.
  • a solvent having a solubility of 5% by mass or less with respect to the diimonium dye used it is preferable to use a solvent having a solubility of 5% by mass or less with respect to the diimonium dye used.
  • a solvent having a solubility of the dimonium dye exceeding 5% by mass is used, the dimonium dispersion may be dissolved.
  • the solubility of the dimonium dye is measured by the following method. First, five kinds of samples having a content of diimonium dye of 0.01% by mass, 0.1% by mass, 1.0% by mass, 2.0% by mass and 5.0% by mass were prepared, respectively. Sonic agitate. Next, it is confirmed whether or not there is a residue for each sample. The residue is confirmed by visually observing whether there is a residue on the filter paper after filtration. Solubility is determined by the presence or absence of residues. When no residue is confirmed in the 5.0% by mass sample (and other samples), it is determined that “the solubility is 5% by mass or more”.
  • a solvent having a boiling point of 100 ° C. or less such as ethyl acetate is suitable as the diluting solvent (E).
  • a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, butyl acetate or the like is suitable as the diluting solvent (E).
  • a solvent having a boiling point of 150 to 200 ° C. such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether acetate, etc. Is preferred.
  • diluting solvent (E) examples include toluene, ethyl acetate, butyl acetate and methylcyclohexane. From the viewpoint of the durability of the diimonium dye, the dilution solvent (E) is preferably the same as the solvent (D). ⁇ ⁇ ⁇ ⁇ From this viewpoint, toluene and ethyl acetate are particularly preferable as the diluting solvent (E).
  • the viscosity of the near-infrared absorbing pressure-sensitive adhesive composition is appropriately selected depending on the type of the coating machine, but in the case of coating by a small-diameter gravure kiss reverse method such as a micro gravure coater, 1 to 1000 mPa ⁇ In the case of coating by an extrusion method such as s or a die coater, 100 to 10,000 mPa ⁇ s is generally used.
  • the solid content of the near-infrared absorbing adhesive composition is adjusted according to the viscosity of the paint.
  • additives that are used in resin compositions that form films, coating films, and the like can be used.
  • additives include dispersants, leveling agents, antifoaming agents, viscosity modifiers, matting agents, tackifiers, antistatic agents, antioxidants, UV absorbers, light stabilizers, quenchers, curing agents, A blocking agent etc. are mentioned.
  • an isocyanate compound, a thiol compound, an epoxy compound, an amine compound, an imine compound, an oxazoline compound, a silane coupling agent, a UV curing agent, and the like can be used as the curing agent.
  • the near-infrared absorbing adhesive composition of the present invention is a near-infrared absorbing material for optical, agricultural, architectural or vehicle use, an image recording material such as photosensitive paper, an information recording material such as an optical disc, and a dye-sensitized type. It can be used for a solar cell such as a solar cell, a photosensitive material using a semiconductor laser beam or the like as a light source, and an eye strain prevention material.
  • the near infrared absorbing pressure-sensitive adhesive composition of the present invention is particularly preferably used in the form of a film or a sheet.
  • the near-infrared absorbing material according to the present invention includes the near-infrared absorbing adhesive composition.
  • the near-infrared absorbing material of the present invention may be a film obtained by forming the near-infrared absorbing adhesive composition into a film, and a coating film containing the near-infrared absorbing adhesive composition is laminated on a transparent substrate. It may be what you did.
  • the transparent substrate is generally usable as an optical material and is not particularly limited as long as it is substantially transparent.
  • Specific examples include glass; olefin polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl polymers such as vinyl acetate and vinyl halides; polyesters such as PET; polycarbonate and butyral.
  • examples thereof include polyvinyl acetals such as resins; polyaryl ether resins; lactone ring-containing resin films.
  • the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, and coating such as an anchor coating agent and a primer. May be applied.
  • the base resin constituting the transparent base material can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, and the like.
  • the transparent substrate is formed into a film or a sheet using a known method such as injection molding, T-die molding, calendar molding, compression molding, or a method of casting by melting in an organic solvent.
  • the base material constituting the transparent base material may be unstretched or stretched, and may be laminated with another base material.
  • a PET film As a transparent substrate for obtaining a near infrared ray absorbing film by a coating method, a PET film is preferable, and a PET film subjected to an easy adhesion treatment is particularly preferable.
  • a PET film As a transparent substrate for obtaining a near infrared ray absorbing film by a coating method, a PET film is preferable, and a PET film subjected to an easy adhesion treatment is particularly preferable.
  • Cosmo Shine A4300 manufactured by Toyobo
  • Lumirror U34 manufactured by Toray
  • Melinex 705 manufactured by Teijin DuPont
  • Functional films such as a TAC (triacetylcellulose) film, an antireflection film, an antiglare film, an impact absorbing film, an electromagnetic wave shielding film, and an ultraviolet absorbing film can also be used as the transparent substrate.
  • TAC triacetylcellulose
  • the transparent substrate is preferably a film.
  • glass PET film, lactone ring-containing resin film, easy-adhesive PET film, TAC film, antireflection film and electromagnetic wave shielding film are preferably used as the transparent substrate.
  • an inorganic base material such as glass is used as the transparent base material, a material having a small alkali component is preferable from the viewpoint of durability of the near-infrared absorbing dye.
  • the thickness of the near-infrared absorbing material of the present invention is generally about 0.1 ⁇ m to 10 mm, but is appropriately determined according to the purpose. Further, the content of the near-infrared absorbing dye contained in the near-infrared absorbing material is also appropriately determined according to the purpose.
  • the method for producing the near-infrared absorbing material of the present invention is not particularly limited.
  • the following method can be used.
  • III a method of coating the near-infrared absorbing adhesive composition according to the present invention on the transparent substrate, etc. It is.
  • the near-infrared absorbing pressure-sensitive adhesive composition according to the present invention is usually used as a resin powder or pellet. Examples thereof include a method of adding, heating to 150 to 350 ° C. and dissolving, followed by molding to produce a resin plate, and a method of forming a film (resin plate) with an extruder.
  • the near-infrared absorbing pressure-sensitive adhesive composition according to the present invention and a monomer or oligomer are cast polymerized in the presence of a polymerization catalyst, and the mixture is injected into a mold and reacted to be cured. Or by pouring into a mold and solidifying until a hard product is formed in the mold.
  • Many resins can be molded in this process. Specific examples of such resins include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like.
  • the casting method by bulk polymerization of methyl methacrylate which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable.
  • known radical thermal polymerization initiators can be used, and examples thereof include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. .
  • the amount used is generally 0.01 to 5% by mass relative to the total amount of the mixture.
  • the heating temperature in the thermal polymerization is generally 40 to 200 ° C., and the polymerization time is generally about 30 minutes to 8 hours.
  • a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be used.
  • a method of coating the near-infrared absorbing material of the present invention on a transparent substrate a paint in which the near-infrared absorbing adhesive composition of the present invention is fixed to fine particles, and the fine particles are dispersed are used. There is a method of coating on a transparent substrate.
  • a known coating machine When applying the near-infrared absorbing adhesive composition to the substrate, a known coating machine can be used. Examples thereof include knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters and bar coaters.
  • knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters and bar coaters.
  • the substrate Prior to coating, the substrate may be surface treated by a known method such as corona discharge treatment or plasma treatment.
  • a drying / curing method a known method such as hot air, far-infrared ray or UV curing can be used. You may wind up with a well-known protective film after drying and hardening.
  • the drying method is not particularly limited, and hot air drying or far infrared drying can be used.
  • the drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If the substrate is a PET film, the general drying temperature is 50 to 150 ° C. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild.
  • the near-infrared-absorbing pressure-sensitive adhesive composition of the present invention can be a constituent material of an excellent optical filter having high transparency in the visible region and high near-infrared absorption ability.
  • the near-infrared absorbing pressure-sensitive adhesive composition of the present invention has higher durability, especially heat resistance and light resistance than conventional near-infrared absorbing materials, so that appearance and near-infrared absorbing ability are maintained even during long-term storage and use.
  • the near-infrared absorbing adhesive composition of the present invention can be easily formed into a sheet or film, it is effective for thin displays and optical semiconductor elements.
  • the near-infrared absorbing adhesive composition of the present invention can also be used in filters and films that need to cut infrared rays, such as agricultural films, heat insulating films, sunglasses, optical recording materials, and the like.
  • the near-infrared absorbing adhesive composition of the present invention is suitable for an optical filter.
  • This optical filter is formed using the near-infrared absorbing material.
  • This optical filter is suitable as an optical filter for an optical semiconductor element or an optical filter for a thin display.
  • Such an optical filter has a total light transmittance in the visible region of 40% or more, preferably 50% or more, more preferably 60% or more, and a transmittance of near infrared light having a wavelength of 800 to 1100 nm is preferably 30% or less. Is 15% or less, more preferably 5% or less.
  • the optical filter of the present invention includes an electromagnetic wave shielding layer, an antireflection layer, a glare prevention (antiglare) layer, a scratch prevention layer, and color adjustment.
  • a support such as a layer or glass may be provided.
  • each layer of the optical filter may be arbitrarily selected.
  • an optical filter that preferably combines at least one of an antireflection layer and an antiglare layer and at least two layers of a near-infrared absorbing layer is preferable, and more preferably at least 3 that further combines an electromagnetic wave shielding layer.
  • An optical filter having a layer is preferable.
  • the antireflection layer or the glare prevention layer is the outermost layer on the human side.
  • the stacking order between the near infrared absorbing layer and the electromagnetic wave shielding layer is arbitrary.
  • other layers such as a damage prevention layer, a color adjustment layer, a shock absorption layer, a support body, and a transparent base material, may be inserted between the three layers.
  • an antireflection layer or an antiglare layer on the outermost layer on the human side in order to make the optical filter for thin display easier to see the screen.
  • the antireflection layer is for suppressing reflection of the surface and preventing reflection of external light such as a fluorescent lamp on the surface.
  • the antireflection layer consists of a single layer of a resin with a different refractive index, such as an acrylic resin or a fluororesin, when it is made of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide.
  • it may be composed of multi-layers, and as a manufacturing method in the former case, there is a method of forming an antireflection coating on a transparent substrate in the form of a single layer or a multilayer using vapor deposition or sputtering. is there.
  • a knife coater such as a comma coater, a fountain coater such as a slot coater and a lip coater, a gravure coater, a flow coater, a spray coater, and a bar coater are used.
  • a bar coater such as a comma coater, a fountain coater such as a slot coater and a lip coater, a gravure coater, a flow coater, a spray coater, and a bar coater are used.
  • the glare-preventing layer is formed by converting fine powders of silica, melamine resin, acrylic resin, etc. into ink, applying it on any layer of the filter of the present invention by a conventionally known coating method, and curing it by heat or photocuring. Is done.
  • An antiglare-treated film may be attached on the filter.
  • the scratch-preventing layer is a coating solution prepared by dissolving or dispersing an acrylate such as urethane acrylate, epoxy acrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent by a conventionally known coating method, and any of the filters of the present invention. On this layer, it is formed by coating, drying and photocuring.
  • An optical filter having an antireflection layer or an antiglare layer and a near infrared absorbing layer is provided with a layer made of the near infrared absorbing adhesive composition or the near infrared absorbing material of the present invention on the back surface of the antireflection film or the antiglare film. Obtained by laminating.
  • the near-infrared absorbing layer according to the present invention in the form of a film and the antireflection film or the anti-glare film may be directly bonded together, or the near-infrared absorbing adhesive composition of the present invention in solution may be used. You may apply
  • a near-infrared absorbing layer is provided on the back surface of the antireflection film or the antiglare film, it is preferable to use an ultraviolet absorbing film as a transparent substrate in order to suppress deterioration of the pigment due to ultraviolet rays.
  • the near infrared ray absorbing pressure-sensitive adhesive composition of the present invention has adhesiveness. Therefore, when the near-infrared absorbing layer and another layer are bonded, a pressure-sensitive adhesive or an adhesive may be unnecessary.
  • a near-infrared absorption layer is a layer containing the near-infrared absorption adhesive composition of this invention.
  • the plasma display optical filter is preferably provided with an electromagnetic wave shielding layer in order to remove electromagnetic waves generated from the panel.
  • the electromagnetic wave shielding layer is a film in which a metal mesh is patterned on a film by etching, printing, etc., or a film in which a metal is deposited on a fiber mesh and embedded in a resin. used.
  • An optical filter having two layers of a near-infrared absorbing layer and an electromagnetic wave shielding layer can be obtained by combining an electromagnetic wave prevention material and a near-infrared absorbing adhesive composition.
  • the film form of the near-infrared absorbing adhesive composition of the present invention and the electromagnetic wave shielding film may be laminated, or the solution of the near-infrared absorbing adhesive composition of the present invention is used as an electromagnetic wave shielding film. You may apply directly.
  • the near-infrared absorption adhesive composition of this invention can also be used.
  • the near-infrared absorption adhesive composition of this invention can also be used.
  • an optical filter having three layers of a near-infrared absorbing layer, a reflection or anti-glare layer and an electromagnetic wave shielding layer a near-infrared absorbing film comprising the near-infrared absorbing adhesive composition of the present invention, a reflection or anti-glare film, an electromagnetic wave A laminate of three shielding films can be used.
  • an optical filter having a structure in which a near-infrared absorbing film made of the near-infrared absorbing adhesive composition of the present invention is sandwiched between a reflection or glare-preventing film and an electromagnetic wave shielding film is preferable.
  • this optical filter is laminated
  • a preferable optical filter is an optical filter in which a near-infrared absorbing adhesive layer comprising the near-infrared absorbing adhesive composition of the present invention is bonded to a composite film including an electromagnetic wave shielding layer and a reflection or glare-preventing layer on a single film. It is.
  • the optical filter for thin display of the present invention may be installed away from the display device or may be directly attached to the display device.
  • an optical filter that does not use glass is preferable.
  • the present invention relating to a thin display is a thin display comprising the near-infrared absorbing adhesive composition of the present invention, the near-infrared absorbing material of the present invention, or the optical filter of the present invention.
  • a thin display in which an optical filter is directly bonded to the display body can provide clearer image quality.
  • the optical filter is directly attached, it is preferable to use tempered glass as the display glass or an optical filter provided with a shock absorbing layer.
  • rubber such as styrene butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber, polymethyl acrylate
  • examples include polyacrylic acid alkyl esters such as ethyl polyacrylate and butyl polyacrylate, and these may be used alone, or further added with piccolite, polyvale, rosin ester, etc. as a tackifier. It may be used.
  • an adhesive having an impact absorbing ability can be used, but it is not limited to this. Without using an adhesive, the optical filter of the present invention may be attached to the display device by utilizing the adhesiveness of the near-infrared absorbing layer.
  • this adhesive layer is usually 5 to 2000 ⁇ m, preferably 10 to 1000 ⁇ m.
  • a release film is provided on the surface of the pressure-sensitive adhesive layer, and this release film protects the pressure-sensitive adhesive layer and prevents dust from adhering to the pressure-sensitive adhesive layer until the optical filter is attached to the surface of the thin display. Also good.
  • a non-adhesive part is formed by forming a part where the adhesive layer is not provided or by sandwiching a non-adhesive film between the adhesive layer at the edge of the filter and the release film. If the part is a peeling start part, the work at the time of sticking is easy.
  • the impact absorbing layer is for protecting the display device from external impacts. It is preferably used in an optical filter that does not use a support.
  • the shock absorbing material ethylene-vinyl acetate copolymer, acrylic polymer, polyvinyl chloride, urethane-based, silicon-based resin as disclosed in JP-A Nos. 2004-246365 and 2004-264416 are disclosed. However, it is not limited to these.
  • the methods for evaluating near-infrared absorptivity, heat resistance, light resistance and acid value are as follows.
  • the dye residual ratio (%) was measured in the evaluation of heat resistance and light resistance.
  • the absorbance at ⁇ max after the test is A1 (%) and the absorbance at ⁇ max before the test is B1 (%)
  • the dye residual ratio P1 (%) is calculated by the following equation.
  • P1 (A1 / B1) ⁇ 100
  • the absorbance is obtained by the following formula when the transmittance is T (%).
  • Absorbance ⁇ log (T / 100)
  • Production Example 1 As monomers, 2-ethylhexyl acrylate (264.6 g), butyl acrylate (150 g), cyclohexyl methacrylate (180 g) and 2-hydroxyethyl acrylate (5.4 g) were weighed and mixed thoroughly to obtain a polymerizable monomer mixture ( 1) was obtained.
  • the internal temperature of the flask was raised to 95 ° C., and a polymerization initiator, Niper BMT-K40 (0.15 g), was charged into the flask to initiate the polymerization reaction. 30 minutes after charging the polymerization initiator, the dropping of the dropping mixture (1) from the dropping funnel was started. The dropping mixture (1) was dropped evenly over 90 minutes. After completion of the dropwise addition of the mixture for dripping (1), the mixture was aged for 6 hours while maintaining the reflux temperature while appropriately diluting with ethyl acetate as the viscosity increased.
  • a polymerization initiator Niper BMT-K40 (0.15 g
  • the reaction solution is diluted with ethyl acetate so that the nonvolatile content is about 45%, and resin (1) having a calculated glass transition temperature (Tg) of ⁇ 35 ° C. and a calculated solubility parameter of 8.99 is obtained. Obtained.
  • This resin (1) was an adhesive resin.
  • the weight average molecular weight (Mw) of the resin (1) was 420,000, and the acid value of the resin (1) was 0.
  • Production Example 2 486 g of butyl acrylate, 108.6 g of methyl methacrylate and 5.4 g of 2-hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture (2).
  • a resin (2) as an adhesive resin was obtained in the same manner as in Production Example 1 except that the polymerizable monomer mixture (2) was used in place of the polymerizable monomer mixture (1).
  • Resin (2) has a calculated glass transition temperature (Tg) of ⁇ 35.6 ° C., a calculated solubility parameter of 9.84, a weight average molecular weight (Mw) of 640,000, and an acid value of 0. there were.
  • Production Example 3 570.6 g of butyl acrylate, 24 g of acrylic acid and 5.4 g of 2-hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture (3).
  • a resin (3) as an adhesive resin was obtained in the same manner as in Production Example 1 except that the polymerizable monomer mixture (3) was used in place of the polymerizable monomer mixture (1).
  • Resin (3) has a calculated glass transition temperature (Tg) of ⁇ 50 ° C., a calculated solubility parameter of 9.95, a weight average molecular weight (Mw) of 820,000, and an acid value of 31.2. there were.
  • Dispersion Synthesis Example 1 0.5 g of IRG-022 (Nippon Kayaku Co., Ltd. diimonium dye), 9.5 g of toluene, and 25 g of zirconia beads (particle size 300 ⁇ m, manufactured by Nikkato Co., Ltd.) are placed in a 50 ml screw tube, and the mixture is shaken for 2 hours. After shaking, the zirconia beads were filtered off to prepare a dispersion (1) containing IRG-022 particles. Dispersion (1) was injected into a 0.025 mm flow cell (manufactured by GL Science), and this was measured by an ultraviolet-visible absorption spectrum to obtain a transmission spectrum of dispersion (1).
  • IRG-022 Nippon Kayaku Co., Ltd. diimonium dye
  • zirconia beads particle size 300 ⁇ m, manufactured by Nikkato Co., Ltd.
  • the absorption spectrum of the MEK solution of IRG-022 is shown in FIG. This absorption spectrum was obtained by dissolving IRG-022 in a predetermined amount of methyl ethyl ketone and confirming that there was no insoluble matter, and then measuring the absorption spectrum.
  • UV-3700 manufactured by Shimadzu Corporation
  • a quartz cell having an optical path length of 10 mm was used as a measurement cell.
  • Dispersion synthesis example 2 A dispersion (2) was obtained in the same manner as in Synthesis Example 1, except that IRG-023 (Nippon Kayaku Co., Ltd. diimonium dye) was used instead of IRG-022. This dispersion (2) is a liquid containing IRG-023 particles. Dispersion (2) was injected into a 0.025 mm flow cell (GL Science Co., Ltd.), and this was measured by UV-visible absorption spectrum to obtain a transmission spectrum of dispersion (2). For the measurement of the spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used. The resulting spectrum is shown in FIG.
  • the absorption spectrum of the MEK solution of IRG-023 is shown in FIG. This absorption spectrum was obtained by dissolving IRG-023 in a predetermined amount of methyl ethyl ketone and confirming that there was no insoluble matter, and then measuring the absorption spectrum.
  • UV-3700 manufactured by Shimadzu Corporation
  • a quartz cell having an optical path length of 10 mm was used as a measurement cell.
  • Dispersion Synthesis Example 3 A dispersion (3) was obtained in the same manner as in Synthesis Example 1, except that CIR-1085F (a diimonium dye manufactured by Nippon Carlit Co., Ltd.) was used instead of IRG-022. This dispersion (3) is a liquid containing CIR-1085F particles.
  • CIR-1085F a diimonium dye manufactured by Nippon Carlit Co., Ltd.
  • Example 1 Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in toluene to prepare a crosslinking agent solution 1 having a solid content of 2.75%. Di-n-butyltin dilaurate, which is a crosslinking accelerator, was dissolved in toluene to prepare a crosslinking accelerator solution 1 having a solid content of 1%. The resin (1) obtained in Production Example 1, the dispersion (1) obtained in Synthesis Example 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed at a solid weight ratio of 100/1 / 0.25 /.
  • the near-infrared absorbing pressure-sensitive adhesive composition A1 was coated on an easy-adhesion-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300) with an applicator. The thickness at the time of coating was set so that the thickness of the pressure-sensitive adhesive composition layer after drying was 25 ⁇ m. Subsequently, it was dried in a hot air circulating oven at 100 ° C. for 2 minutes. A release film (silicone-treated PET film) was laminated to the layer made of the pressure-sensitive adhesive composition A1, and then cured at 23 ° C. for 7 days to obtain a near-infrared absorbing material B1.
  • this near-infrared absorbing material B1 was attached to a glass plate to obtain a test body according to Example 1. About this test body, near-infrared transmittance, heat resistance, and light resistance were evaluated. The evaluation results are shown in Table 1 below.
  • Example 2 A test body according to Example 2 was obtained in the same manner as in Example 1 except that the dispersion (2) was used instead of the dispersion (1). About this test body, near-infrared transmittance, heat resistance, and light resistance were evaluated. The evaluation results are shown in Table 1 below.
  • Example 3 A test body according to Example 3 was obtained in the same manner as in Example 1 except that the dispersion (3) was used instead of the dispersion (1). About this test body, near-infrared transmittance, heat resistance, and light resistance were evaluated. The evaluation results are shown in Table 1 below.
  • Example 4 Toluene was added to “e-ex color IR-10A” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to adjust the IR-10A solution so that “e-ex color IR-10A” was 5% by mass.
  • the resin (1) obtained in Production Example 1 the dispersion (1) obtained in Synthesis Example 1, the IR-10A solution, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed at a weight ratio of 100/1. /1/0.25/0.05 It mixed so that it might become solid content, and it diluted with toluene so that it might become 25%, and near-infrared absorption adhesive composition A5 was obtained.
  • This solid content weight ratio is expressed in the order of (resin (1) / dispersion (1) / IR-10A solution / crosslinking agent solution 1 / crosslinking accelerator solution 1).
  • a test body according to Example 4 was obtained in the same manner as in Example 1 except that the near-infrared absorbing adhesive composition A5 was used in place of the near-infrared absorbing adhesive composition A1.
  • This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 below.
  • Example 5 A test body according to Example 5 was obtained in the same manner as in Example 1 except that the resin (2) obtained in Production Example 2 was used in place of the resin (1). This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 below.
  • Example 6 A test body according to Example 6 was obtained in the same manner as in Example 1 except that the resin (3) obtained in Production Example 3 was used in place of the resin (1). This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 below.
  • Example 7 A test body according to Example 7 was obtained in the same manner as in Example 1 except that toluene as the diluent solvent (E) was changed to methyl ethyl ketone. This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 below.
  • the solid content weight ratio is expressed in the order of (resin (1) / diimonium solution 2 / crosslinking agent solution 1 / crosslinking accelerator solution 1).
  • a test specimen Th2 according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the near-infrared absorbing adhesive composition A4 was used instead of the near-infrared absorbing adhesive composition A1. Evaluation similar to Example 1 was performed about this test body Th2. The evaluation results are shown in Table 1 below.
  • methyl ethyl ketone is represented as “MEK”.
  • the solubility of IRG-022 in toluene is 0.1% by mass or less, the solubility of IRG-023 in toluene is 0.1% by mass or less, and the solubility of IRG-022 in methyl ethyl ketone is 5% by mass or more.
  • the solubility of IRG-023 in methyl ethyl ketone was 5% by mass or more, and the solubility of CIR-1085F in toluene was 0.01% by mass or less.
  • the transmission spectrum of the specimen of Example 1 is shown in FIG. FIG. 5 shows transmission spectra before the test, after the heat resistance test, and after the light resistance test.
  • the transmission spectrum of the specimen of Example 2 is shown in FIG. FIG. 6 shows transmission spectra before the test, after the heat resistance test, and after the light resistance test.
  • the transmission spectrum of the test sample of Comparative Example 1 is shown in FIG. FIG. 7 shows transmission spectra before the test, after the heat resistance test, and after the light resistance test.
  • the evaluation method in the second experimental example is as follows.
  • the dye residual ratio (%) was measured in the evaluation of heat resistance, moist heat resistance and light resistance. This measurement method is the same as in [First Experimental Example].
  • Production Example 1a As monomers, weigh 2-ethylhexyl acrylate (360.6 g), butyl acrylate (60 g), cyclohexyl methacrylate (156 g), acrylic acid (18 g) and 2-hydroxyethyl acrylate (5.4 g) and mix well. A polymerizable monomer mixture (1a) was obtained.
  • the internal temperature of the flask was raised to 95 ° C., and a polymerization initiator, Niper BMT-K40 (0.15 g), was charged into the flask to initiate the polymerization reaction. 30 minutes after charging the polymerization initiator, the dropping of the dropping mixture (1a) from the dropping funnel was started. The dropping mixture (1a) was dropped evenly over 90 minutes. After completion of the dropwise addition of the mixture for dropping (1a), the mixture was aged for 6 hours while maintaining the reflux temperature while appropriately diluting with ethyl acetate as the viscosity increased.
  • a polymerization initiator Niper BMT-K40 (0.15 g
  • the reaction solution is diluted with ethyl acetate so that the nonvolatile content is about 45%, a resin (1a) having a calculated glass transition temperature (Tg) of ⁇ 38.5 ° C. and a calculated solubility parameter of 9.08.
  • This resin (1a) was an adhesive resin.
  • the weight average molecular weight (Mw) of the resin (1a) was 430,000, and the acid value of the resin (1a) was 23.4.
  • Production Example 2a 312 g of 2-ethylhexyl acrylate, 132 g of butyl acrylate, 120 g of cyclohexyl methacrylate, and 36 g of acrylic acid were weighed and mixed thoroughly to obtain a polymerizable monomer mixture (2a).
  • a resin (2a) as an adhesive resin was obtained in the same manner as in Production Example 1a except that the polymerizable monomer mixture (2a) was used in place of the polymerizable monomer mixture (1a).
  • the resin (2a) has a calculated glass transition temperature (Tg) of ⁇ 39.9 ° C., a calculated solubility parameter of 9.31, a weight average molecular weight (Mw) of 510,000, and an acid value of 46. It was 8.
  • Production Example 3a Resin (3a) was obtained in the same manner as in Production Example 1. This resin (3a) is the same as the resin (1).
  • Production Example 4a 507.6 g of butyl acrylate, 90.6 g of methyl methacrylate, and 1.8 g of 2-hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture (4a).
  • a resin (4a) as an adhesive resin was obtained in the same manner as in Production Example 1a except that the polymerizable monomer mixture (4a) was used in place of the polymerizable monomer mixture (1a).
  • the resin (4a) has a calculated glass transition temperature (Tg) of ⁇ 40.0 ° C., a calculated solubility parameter of 9.80, a weight average molecular weight (Mw) of 680,000, and an acid value of 0. there were.
  • Production Example 5a 502.9 g of butyl acrylate, 31.1 g of methyl methacrylate, 48 g of acrylic acid, and 18 g of 2-hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture (5a). .
  • a resin (5a) as an adhesive resin was obtained in the same manner as in Production Example 1a except that the polymerizable monomer mixture (5a) was used in place of the polymerizable monomer mixture (1a).
  • the resin (5a) has a calculated glass transition temperature (Tg) of ⁇ 40.9 ° C., a calculated solubility parameter of 10.19, a weight average molecular weight (Mw) of 1.28 million, and an acid value of 62. 3.
  • Production Example 6a 495.1 g of butyl acrylate, 74.9 g of methyl methacrylate, and 30 g of 2-hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture (6a).
  • a resin (6a) as an adhesive resin was obtained in the same manner as in Production Example 1a except that the polymerizable monomer mixture (6a) was used in place of the polymerizable monomer mixture (1a).
  • the resin (6a) has a calculated glass transition temperature (Tg) of ⁇ 40.9 ° C., a calculated solubility parameter of 10.00, a weight average molecular weight (Mw) of 950,000, and an acid value of 0. there were.
  • Synthesis Example 1a 100 parts by weight of DMF, 10 parts by weight of N, N, N ′, N′-tetrakis- (p-aminophenyl) -p-phenylenediamine, 63 parts by weight of cyclohexylmethyl iodide and 30 parts by weight of potassium carbonate And reacted at 120 ° C. for 10 hours.
  • this reaction solution was added to 500 parts by mass of water, and the resulting precipitate was filtered, washed with 500 parts by mass of methyl alcohol, dried at 100 ° C., and 24.1 parts of N, N, N ′. , N′-tetrakis- ⁇ p-di (cyclohexylmethyl) aminophenyl ⁇ -p-phenylenediamine was obtained.
  • N, N, N ′, N′-tetrakis- ⁇ p-di (cyclohexylmethyl) aminophenyl ⁇ -p-phenylenediamine 200 parts by weight of DMF and 7.9 parts by weight of hexa Silver fluorophosphate was added and reacted at 60 ° C. for 3 hours, and the resulting silver was filtered off.
  • this diimonium salt is also referred to as diimonium salt (a).
  • the solubility of the diimonium salt (a) in ethyl acetate was 0.01% by mass or less.
  • a 0.5 parts by mass of dimonium salt (a), 9.5 parts by mass of ethyl acetate and 70 parts by mass of zirconia beads (particle size: 0.3 mm) were placed in a 50 ml glass container and shaken for 2 hours with a paint shaker. Thereafter, the zirconia beads were separated by filtration and the pigment concentration was adjusted to 2% by mass to obtain a liquid dispersion (a).
  • the dispersion (a) was diluted with ethyl acetate so that the concentration of the dimonium salt (a) was 100 mg / L, 50 mg / L, 10 mg / L, and 5 mg / L, respectively.
  • a spectrum obtained by measuring the absorbance of each of these four types of dilutions and converting it to a molar extinction coefficient is shown in FIG.
  • the maximum absorption wavelength ( ⁇ max) of this 100 mg / L diluted solution was 1093 nm.
  • the molar extinction coefficient at ⁇ max of this 100 mg / L diluted solution was 75300 (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ).
  • the maximum absorption wavelength ( ⁇ max) when the diimonium salt is an aggregate is different from that when the dispersion medium is toluene.
  • the dispersion (a) In consideration of the fact that the diimonium dye is in the associated state in the dispersion (b) (described later) in which the diimonium salt is the same as the dispersion (a) and the dispersion medium is toluene, the dispersion (a) However, the diimonium salt (a) is considered to be an aggregate.
  • Synthesis Example 2a A liquid dispersion (b) was obtained in the same manner as in Synthesis Example 1a except that the dispersion solvent was changed from ethyl acetate to toluene.
  • the solubility of the diimonium salt (a) in toluene was 0.01% by mass or less.
  • the dispersion (b) was diluted with toluene so that the concentration of the dimonium salt (a) was 100 mg / L, 50 mg / L, 20 mg / L, and 5 mg / L, respectively.
  • FIG. 9 shows a spectrum obtained by measuring the absorbance of each of these four types of diluted solutions and converting them to molar extinction coefficients.
  • the maximum absorption wavelength ( ⁇ max) of this 100 mg / L diluted solution was 1119 nm. Further, the molar extinction coefficient at ⁇ max of this diluted solution of 100 mg / L was 103634 (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ), which was 70000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
  • the diimonium salt (a) was in an associated state at a concentration (100 mg / L) lower than that of the dispersion (b). Therefore, the diimonium dye (a) is considered to be in an associated state even in the dispersion (b) having a higher dilution concentration with toluene.
  • Synthesis Example 3a Instead of 63 parts by mass of cyclohexylmethyl iodide used in Synthesis Example 1a, the same mole number of 1-iodo-3-fluoropropane was used as in Synthesis Example 1a. , N, N ′, N′-tetrakis- ⁇ p-di (3-fluoropropyl) aminophenyl ⁇ -p-phenylenediimonium was obtained.
  • this diimonium salt is also referred to as diimonium salt (c).
  • a liquid dispersion (c) was obtained in the same manner as in Synthesis Example 2a except that this dimonium salt (c) was used. The solubility of the diimonium salt (c) in toluene was 0.01% by mass or less.
  • the dispersion (c) was diluted with toluene so that the concentration of the dimonium salt (c) was 100 mg / L, 50 mg / L, 20 mg / L, and 5 mg / L, respectively.
  • FIG. 10 shows a spectrum obtained by measuring the absorbance of each of these four types of diluted solutions and converting them to molar extinction coefficients.
  • the maximum absorption wavelength ( ⁇ max) of this 100 mg / L diluted solution was 1120 nm.
  • the molar extinction coefficient at ⁇ max of the diluted solution of 100 mg / L was 83775 (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ), which was 70000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
  • the diimonium salt (c) was in an associated state at a concentration (100 mg / L) lower than that of the dispersion (c). Therefore, it is considered that the diimonium dye (c) is in an associated state even in the dispersion (c) having a higher dilution concentration with toluene.
  • FIG. 11 shows a spectrum obtained by measuring the absorbance of the diluted product (c) and converting it to a molar extinction coefficient.
  • the maximum absorption wavelength ( ⁇ max) of this diluted body (c) was 1050 nm, which was a value smaller than 1120 nm.
  • Synthesis Example 4a Hexafluorophosphoric acid-N, N, N ′ was prepared in the same manner as in Synthesis Example 1a except that isobutyl iodide having the same mole number was used instead of 63 parts by mass of cyclohexylmethyl iodide used in Synthesis Example 1a. , N′-Tetrakis- ⁇ p-di (isobutyl) aminophenyl ⁇ -p-phenylenediimonium was obtained.
  • this diimonium salt is also referred to as diimonium salt (d).
  • a liquid dispersion (d) was obtained in the same manner as in Synthesis Example 2a except that this dimonium salt (d) was used.
  • the solubility of the diimonium salt (d) in toluene was 0.01% by mass or less.
  • the dispersion (d) was diluted with toluene so that the concentration of the dimonium salt (d) was 100 mg / L, 50 mg / L, 20 mg / L, and 5 mg / L, respectively.
  • FIG. 12 shows a spectrum obtained by measuring the absorbance of each of these four types of dilutions and converting them to molar extinction coefficients.
  • the maximum absorption wavelength ( ⁇ max) of this 100 mg / L diluted solution was 1220 nm.
  • the molar extinction coefficient at ⁇ max of this 100 mg / L diluted solution was 11293 (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ), which was 70000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
  • the diimonium salt (d) was in an associated state at a concentration (100 mg / L) lower than that of the dispersion (d). Therefore, it is considered that the diimonium dye (d) is in an associated state even in the dispersion (d) having a higher dilution concentration with toluene.
  • ⁇ max The maximum absorption wavelength ( ⁇ max) of this diluted body (d) was 1081 nm, which was a value smaller than 1220 nm.
  • Example 1a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in ethyl acetate to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • the resin (1a) obtained in Production Example 1a, the dispersion (a) obtained in Synthesis Example 1a, and the crosslinking agent solution 1 are mixed so that the solid content weight ratio is 100 / 1.0 / 0.5. And it diluted with ethyl acetate so that solid content might be 25%, and near-infrared absorption adhesive composition Aa1 was obtained.
  • this solid content weight ratio is described in the order of (resin (1a) / dispersion (a) / crosslinking agent solution 1).
  • the near-infrared absorbing pressure-sensitive adhesive composition Aa1 was coated on an easy-adhesion-treated PET film (Toyobo Co., Ltd., Cosmo Shine A4300) with an applicator. The thickness at the time of coating was set so that the thickness of the pressure-sensitive adhesive composition layer after drying was 25 ⁇ m. Subsequently, it was dried in a hot air circulating oven at 100 ° C. for 2 minutes. A release film (silicone-treated PET film) was laminated to the layer made of the pressure-sensitive adhesive composition Aa1, and then cured at 23 ° C. for 7 days to obtain a near-infrared absorbing material Ba1.
  • this near-infrared absorbing material Ba1 was attached to a glass plate to obtain a test specimen Z1 according to Example 1a.
  • this test body Z1 the heat test, the moist heat test, and the light resistance test were done. The evaluation results are shown in Table 4 below.
  • Example 2a Toluene was added to “e-ex color IR-14” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to adjust the IR-14 solution so that “e-ex color IR-14” was 5% by mass.
  • toluene is added to “e-ex color TX-EX-820” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, so that “e-ex color TX-EX-820” is 5% by mass, so that TX-EX- 820 solution was prepared.
  • the resin (1a) obtained in Production Example 1a, the dispersion (a) obtained in Synthesis Example 1a, the IR-14 solution, the TX-EX-820 solution, and the crosslinking agent solution 1 were mixed at a solid content weight ratio of 100. /1.1/0.35/0.17/0.5, and the mixture was diluted with ethyl acetate so that the solid content was 25% to obtain a near-infrared absorbing adhesive composition Aa2. .
  • the solid content weight ratio is expressed in the order of (resin (1a) / dispersion (a) / IR-14 solution / TX-EX-820 solution / crosslinking agent solution 1).
  • Example 2a A test body according to Example 2a was obtained in the same manner as Example 1a except that near-infrared absorbing adhesive composition Aa2 was used instead of near-infrared absorbing adhesive composition Aa1. The test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 4 below.
  • Example 3a Toluene was added to “e-ex color IR-14” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to prepare an IR-14 solution so that “e-ex color IR-14” was 5% by mass.
  • the resin (1a) obtained in Production Example 1a, the dispersion (b) obtained in Synthesis Example 2a, the IR-14 solution and the crosslinking agent solution 1 were mixed at a solids weight ratio of 100 / 1.3 / 0.7.
  • the mixture was mixed so as to be /0.25, and diluted with toluene so that the solid content was 25%, to obtain a near-infrared absorbing adhesive composition Aa3.
  • Example 3a The solid content weight ratio is expressed in the order of (resin (1a) / dispersion (b) / IR-14 solution / crosslinking agent solution 1).
  • a test body according to Example 3a was obtained in the same manner as Example 1a, except that near-infrared absorbing adhesive composition Aa3 was used instead of near-infrared absorbing adhesive composition Aa1.
  • the test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 4 below.
  • Example 4a A test body according to Example 4a was obtained in the same manner as in Example 2a except that the resin (2a) obtained in Production Example 2a was used instead of the resin (1a). The test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 4 below.
  • Example 5a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in ethyl acetate to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • Di-n-butyltin dilaurate which is a crosslinking accelerator, was dissolved in ethyl acetate to prepare a crosslinking accelerator solution 2 having a solid content of 1%.
  • the resin (3a) obtained in Production Example 3a, the dispersion (a) obtained in Synthesis Example 1a, the cross-linking agent solution 1 and the cross-linking accelerator solution 2 are 100 / 1.0 / 0.
  • Example 5a It mixed so that it might become 5 / 0.05, and it diluted with ethyl acetate so that solid content might be 25%, and the near-infrared absorption adhesive composition Aa5 which concerns on Example 5a was obtained.
  • the solid content weight ratio is expressed in the order of (resin (3a) / dispersion (a) / crosslinking agent solution 1 / crosslinking accelerator solution 2).
  • a test body according to Example 5a was obtained in the same manner as Example 1a except that this near-infrared absorbing adhesive composition Aa5 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 4 below.
  • Example 6a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in ethyl acetate to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • Di-n-butyltin dilaurate which is a crosslinking accelerator, was dissolved in ethyl acetate to prepare a crosslinking accelerator solution 2 having a solid content of 1%.
  • the resin (4a) obtained in Production Example 4a, the dispersion (a) obtained in Synthesis Example 1a, the cross-linking agent solution 1 and the cross-linking accelerator solution 2 are 100 / 1.0 / 0.
  • Example 6a It mixed so that it might become 5 / 0.05, and it diluted with ethyl acetate so that solid content might be 25%, and the near-infrared absorption adhesive composition Aa6 which concerns on Example 6a was obtained.
  • this solid content weight ratio is described in the order of (resin (4a) / dispersion (a) / crosslinking agent solution 1 / crosslinking accelerator solution 2).
  • a test body according to Example 6a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Aa6 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 4 below.
  • Example 7a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in toluene to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • the resin (1a) obtained in Production Example 1a, the dispersion (c) obtained in Synthesis Example 3a, and the crosslinking agent solution 1 are mixed so that the solid content weight ratio is 100 / 1.3 / 0.5. And it diluted with toluene so that solid content might be 25%, and near-infrared absorption adhesive composition Aa7 was obtained.
  • this solid content weight ratio is described in the order of (resin (1a) / dispersion (c) / crosslinking agent solution 1).
  • Example 7a A test body according to Example 7a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Aa7 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was subjected to a heat resistance test, a moist heat resistance test, and a light resistance test. The evaluation results are shown in Table 4 below.
  • Example 8a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in toluene to prepare a crosslinking agent solution 1 having a solid content of 2.75%. Di-n-butyltin dilaurate, which is a crosslinking accelerator, was dissolved in toluene to prepare a crosslinking accelerator solution 1 having a solid content of 1%.
  • the resin (3a) obtained in Production Example 3a, the dispersion (c) obtained in Synthesis Example 3a, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 are 100 / 1.3 / 0.
  • Example 8a A test body according to Example 8a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Aa8 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was subjected to a heat resistance test, a moist heat resistance test, and a light resistance test. The evaluation results are shown in Table 5 below.
  • Example 9a A test body according to Example 9a was obtained in the same manner as in Example 7a except that the resin (5a) obtained in Production Example 5a was used instead of the resin (1a). The test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 5 below.
  • Example 10a Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in toluene to prepare a crosslinking agent solution 1 having a solid content of 2.75%.
  • Di-n-butyltin dilaurate which is a crosslinking accelerator, was dissolved in toluene to prepare a crosslinking accelerator solution 1 having a solid content of 1%.
  • the resin (6a) obtained in Production Example 6a, the dispersion (c) obtained in Synthesis Example 3a, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 are 100 / 1.3 / 0.
  • Example 10a A test body according to Example 10a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Aa10 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was subjected to a heat resistance test, a moist heat resistance test, and a light resistance test. The evaluation results are shown in Table 5 below.
  • Example 11a Toluene was added to “e-ex color IR-10A” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to adjust the IR-10A solution so that “e-ex color IR-10A” was 5% by mass.
  • the resin (3a) obtained in Production Example 3a, the dispersion (d) obtained in Synthesis Example 4a, the IR-10A solution, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed at a solid content weight ratio of 100/1.
  • Example 11a A test body according to Example 11a was obtained in the same manner as Example 1a, except that near-infrared absorbing adhesive composition Aa11 was used instead of near-infrared absorbing adhesive composition Aa1. The test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 5 below.
  • Example 12a Toluene was added to “e-ex color IR-14” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to adjust the IR-14 solution so that “e-ex color IR-14” was 5% by mass.
  • the resin (1a) obtained in Production Example 1a, the dispersion (d) obtained in Synthesis Example 4a, the IR-14 solution and the crosslinking agent solution 1 were mixed at a solids weight ratio of 100 / 1.0 / 1.0.
  • the mixture was mixed so as to be /0.25, and diluted with toluene so that the solid content was 25%, to obtain a near-infrared absorbing adhesive composition Aa12.
  • Example 12a The solid content weight ratio is expressed in the order of (resin (1a) / dispersion (d) / IR-14 solution / crosslinking agent solution 1).
  • a test body according to Example 12a was obtained in the same manner as Example 1a, except that near-infrared absorbing adhesive composition Aa12 was used instead of near-infrared absorbing adhesive composition Aa1.
  • the test body was evaluated in the same manner as in Example 1a. The evaluation results are shown in Table 5 below.
  • Example 13a Toluene was added to “e-ex color IR-14” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine dye, to adjust the IR-14 solution so that “e-ex color IR-14” was 5% by mass.
  • the resin (3a) obtained in Production Example 3a, the dispersion (2) obtained in Synthesis Example 2, the IR-14 solution, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 were mixed at a solids weight ratio of 100 / It mixed so that it might become 2.0 / 0.45 / 0.25 / 0.05, and it diluted with toluene so that solid content might be 25%, and near-infrared absorption adhesive composition Aa13 was obtained.
  • the solid content weight ratio is expressed in the order of (resin (3a) / dispersion (2) / IR-14 solution / crosslinking agent solution 1 / crosslinking accelerator solution 1).
  • Example 13a A test body according to Example 13a was obtained in the same manner as in Example 1a, except that this near-infrared absorbing adhesive composition Aa13 was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the test body was subjected to a heat resistance test, a moist heat resistance test, and a light resistance test. The evaluation results are shown in Table 6 below.
  • a test body T1 according to Comparative Example 1a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Ah1a was used in place of the near-infrared absorbing adhesive composition Aa1.
  • this test body T1 the heat resistance test, the heat-and-moisture resistance test, and the light resistance test were done. The evaluation results are shown in Table 6 below.
  • a specimen T2 according to Comparative Example 2a was obtained in the same manner as in Example 1a except that this near-infrared absorbing adhesive composition Ah2a was used instead of the near-infrared absorbing adhesive composition Aa1.
  • the specimen T2 was subjected to a heat test, a moist heat test and a light resistance test. The evaluation results are shown in Table 6 below.
  • Example 1 When the near-infrared absorbing adhesive composition Aa1 obtained in Example 1a was put in a cell having an inner diameter of 0.1 mm and measured for a transmission spectrum, ⁇ max was 1123 nm. The transmission spectrum of this composition Aa1 is shown in FIG. Moreover, when the transmission spectrum was measured about the said test body Z1 obtained by affixing the said near-infrared absorber Ba1 on a glass plate, (lambda) max was 1169 nm. The transmission spectrum of this specimen Z1 is shown in FIG.
  • Example 8 Synthesis of polymerizable polysiloxane (M-1) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 parts of tetramethoxysilane, 23.6 parts of ⁇ -methacryloxypropyltrimethoxysilane, water 19.0 parts, 30.0 parts of methanol, and 5.0 parts of Amberlyst 15 (trade name: cation exchange resin manufactured by Organo) were added and stirred at 65 ° C. for 2 hours for reaction.
  • Amberlyst 15 trade name: cation exchange resin manufactured by Organo
  • the ratio of inorganic fine particles to organic polymer in the organic polymer composite inorganic fine particles was 70/30. This ratio is a weight ratio.
  • the average particle diameter of the obtained organic polymer composite inorganic fine particles was 23.9 nm.
  • the ratio of the inorganic fine particles to the organic polymer in the organic polymer composite inorganic fine particles was determined by conducting an elemental analysis on the organic polymer composite fine particle dispersion dried at 130 ° C. for 24 hours under a pressure of 1.33 ⁇ 10 kPa, and calculating the ash content. It calculated
  • the average particle size was determined by photographing particles with a transmission electron microscope using a solution obtained by diluting 1 part of the organic polymer composite inorganic fine particle dispersion (S-1) with 99 parts of n-butyl acetate. The diameter of the particles was read and the average was determined as the average particle diameter.
  • Antireflective film 8 parts of dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) and 2 parts of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed and a solution dissolved in 40 parts of methyl ethyl ketone was prepared.
  • a photopolymerization initiator Irgacure 907, manufactured by Ciba Geigy Co., Ltd.
  • the hard coat layer coating solution was applied to a 188 ⁇ m thick polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) using a bar coater to obtain a coating layer h.
  • the coating layer h was dried at 100 ° C. for 15 minutes and then cured by irradiating with 200 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp to form a hard coat layer having a thickness of 5 ⁇ m.
  • the above low refractive index coating solution was applied using a bar coater to form an antireflection film on the polyethylene terephthalate film.
  • the surface opposite to the antireflection film side of the film was roughened with steel wool. Black ink was applied to the roughened surface.
  • the specular reflection spectrum of the surface on the antireflection film side at an incident angle of 5 ° is measured using an ultraviolet-visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the wavelength at which the reflectance shows the minimum value and the reflectance at that wavelength. (Minimum reflectance) was determined.
  • UV-3100 ultraviolet-visible spectrophotometer
  • Minimum reflectance was 0.45%.
  • the near-infrared absorbing adhesive composition A1 obtained in Example 1 was coated and dried in the same manner as in Example 1 to obtain an optical filter 1.
  • the near-infrared transmittance, total light transmittance, heat resistance, moist heat resistance, light resistance, crack resistance and solvent resistance of the optical filter 1 were good.
  • Example 9 An optical filter 2 was obtained in the same manner as in Example 8, except that the near-infrared absorbing adhesive composition Aa7 obtained in Example 7a was used instead of the near-infrared absorbing adhesive composition A1.
  • the optical filter 2 had good near-infrared transmittance, total light transmittance, heat resistance, heat and humidity resistance, light resistance, crack resistance and solvent resistance.
  • the near-infrared-absorbing pressure-sensitive adhesive composition of the present invention is useful as an optical filter for thin displays because it has a long-infrared-absorbing ability and high transparency in the visible region, and is excellent in heat resistance, moist heat resistance and light resistance. is there. It can also be used as an optical information recording material.

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Abstract

La présente invention concerne une composition adhésive sensible à la pression absorbant le proche infra-rouge qui contient une dispersion (A) mélangée à celle-ci et qui contient une résine (B) ayant une température de transition vitreuse inférieure ou égale à 0 °C, ladite dispersion (A) étant une dispersion préparée en dispersant une matière colorante de type diimonium dans une composition contenant un solvant (D). De plus, la composition adhésive sensible à la pression peut être diluée avec un solvant diluant (E). La composition adhésive sensible à la pression peut en outre contenir une matière colorante qui n'est pas de type diimonium. Il est préférable que l'indice d'acidité de la résine (B) se trouve dans la plage allant de 0 à 300. Il est préférable que le paramètre calculé de solubilité de la résine (B) soit inférieur ou égal à 10,2. La composition adhésive sensible à la pression est appropriée pour une utilisation dans des filtres optiques pour panneaux d'affichage plats ; des filtres optiques pour éléments photo-semi-conducteurs ; des panneaux d'affichage plats ; et ainsi de suite.
PCT/JP2010/000266 2009-02-20 2010-01-19 Composition adhésive sensible à la pression absorbant le proche infra-rouge WO2010095349A1 (fr)

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WO2014168189A1 (fr) * 2013-04-10 2014-10-16 旭硝子株式会社 Filtre bloquant l'infrarouge
WO2015186685A1 (fr) * 2014-06-05 2015-12-10 Dic株式会社 Film adhésif protecteur, dispositif d'affichage d'images et terminal électronique portatif

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WO2015186685A1 (fr) * 2014-06-05 2015-12-10 Dic株式会社 Film adhésif protecteur, dispositif d'affichage d'images et terminal électronique portatif
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