WO2013065662A1 - Heat ray shielding adhesive composition and heat ray shielding adhesive sheet - Google Patents

Heat ray shielding adhesive composition and heat ray shielding adhesive sheet Download PDF

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Publication number
WO2013065662A1
WO2013065662A1 PCT/JP2012/077972 JP2012077972W WO2013065662A1 WO 2013065662 A1 WO2013065662 A1 WO 2013065662A1 JP 2012077972 W JP2012077972 W JP 2012077972W WO 2013065662 A1 WO2013065662 A1 WO 2013065662A1
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Prior art keywords
heat ray
group
sensitive adhesive
shielding
pressure
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PCT/JP2012/077972
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French (fr)
Japanese (ja)
Inventor
貴大 樋下田
高明 倉田
高橋　知宏
達治 有福
幸広 原
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日本化薬株式会社
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Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to CN201280048422.5A priority Critical patent/CN103842463B/en
Priority to KR1020147007116A priority patent/KR20140095459A/en
Priority to JP2013541774A priority patent/JP6194250B2/en
Publication of WO2013065662A1 publication Critical patent/WO2013065662A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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 heat ray-shielding pressure-sensitive adhesive composition that can be used by being attached to a window glass or the like and can efficiently shield heat rays, and a heat ray-shielding pressure-sensitive adhesive sheet using the same.
  • Patent Literature 1 discloses a pressure-sensitive adhesive imparted with heat ray shielding properties and an adhesive sheet thereof.
  • This pressure-sensitive adhesive sheet is obtained by processing a pressure-sensitive adhesive having heat ray shielding properties into a sheet shape, and can be processed into an arbitrary shape in advance and has reworkability that enables re-stretching.
  • the pressure-sensitive adhesive sheet imparted with the heat ray shielding property is insufficient in the heat shielding property, and further improvement is desired.
  • the heat-ray-shielding pressure-sensitive adhesive composition capable of efficiently shielding heat rays and a heat-ray-shielding pressure-sensitive adhesive sheet obtained by processing the same into a sheet, thereby completing the present invention.
  • the present invention “(1) (A) Metal fine particles, (B) Acrylic adhesive, (C) Dispersant, and (D) Heat ray-shielding adhesive composition containing near-infrared absorbing dye, (2) (A) The heat ray shielding pressure-sensitive adhesive composition according to (1), wherein the metal fine particles are a kind of metal fine particles selected from the group consisting of tin oxide, indium oxide, and zinc oxide, (3) (B) The acrylic pressure-sensitive adhesive is a polymer in which the proportion of structural units of a carboxy group or an acid anhydride-containing monomer is 1 to 5% of the total monomer structural units in the polymer ( 1) or the heat ray shielding adhesive composition according to any one of (2), (4) (B) The heat ray shielding adhesive composition according to any one of (1) to (3), wherein the acrylic adhesive has a weight average molecular weight of 100,000 to 1,200,000, (5) (D) The heat ray according to any one of (1) to (4), wherein the near-infrared absorbing dye is a
  • M represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, or a hydrogen atom
  • X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen atom. Represents a group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group.
  • A is a divalent bridging group
  • Y is a sulfonic acid group, a carboxy group, a residue obtained by removing at least one of the hydrogen atoms on the nitrogen atom of the primary or secondary amino group, or a nitrogen atom of a heterocyclic ring containing nitrogen Represents a residue excluding at least one of the above hydrogens.
  • m and n are both average values, m and n are each 0 or more and 12 or less, and the sum of m and n is 0 or more and 12 or less.
  • M in formula (1) is VO
  • A is an alkylene group having 1 to 3 carbon atoms
  • Y is a phthalimide group which may have a substituent.
  • Adhesive composition, (8) M in formula (1) is Cu, A is an alkylene group having 1 to 3 carbon atoms, and Y is a phthalimide group which may have a substituent.
  • Adhesive composition, (9) It is related with the heat ray shielding adhesive sheet formed by apply
  • a heat ray-shielding pressure-sensitive adhesive composition in which metal fine particles including tin-doped indium oxide and a near-infrared absorbing dye are dispersed in an acrylic pressure-sensitive adhesive using a dispersant is processed into a sheet shape.
  • the heat ray shielding adhesive sheet which can suppress the temperature rise by a heat ray more can be provided.
  • the present invention can contribute to energy saving and the solution of global environmental problems.
  • the pressure-sensitive adhesive composition for forming a heat ray-shielding pressure-sensitive adhesive sheet according to the present invention is characterized in that metal fine particles including tin-doped indium oxide and a near-infrared absorbing dye are dispersed in an acrylic pressure-sensitive adhesive using a dispersant.
  • the pressure-sensitive adhesive composition can be processed into a sheet shape.
  • the metal fine particles used in the heat ray-shielding pressure-sensitive adhesive composition are suitable for those having low absorption of visible light and having good absorption characteristics for light in the near infrared to far infrared region.
  • the electroconductive metal oxide which has a plasma wavelength in a near-infrared region is mentioned.
  • Specific examples include tin oxide, indium oxide, zinc oxide, tungsten oxide, chromium oxide, and molybdenum oxide. Of these, tin oxide, indium oxide, and zinc oxide, which have a small light absorption property particularly in the visible light region, are preferable.
  • the third component in order to improve the electrical conductivity of these oxides.
  • Sb, V, Nb, Ta, etc. are selected for tin oxide, Zn, Al, Sn, Sb, Ga, Ge, etc. are selected for indium oxide, and zinc oxide is used.
  • Al, Ga, In, Sn, Sb, Nb or the like is selected.
  • the method for producing metal fine particles is not particularly limited as long as a particle size of 100 nm or less is obtained, and known methods such as a gas phase synthesis method and a liquid layer synthesis method can be used.
  • indium oxide fine particles the method disclosed in JP-A-6-227815 can be used. That is, this is a method of obtaining metal fine particles by neutralizing an aqueous solution of a salt containing a specific metal fine particle element with an alkali, filtering and washing the obtained precipitate, and heat-treating it at a high temperature.
  • JP-A-2-105875 and JP-A-6-234522 can be exemplified.
  • Conventional methods can be used as a method for dispersing the metal fine particles in the organic solvent. That is, metal fine particles and an organic solvent are mixed at a predetermined ratio, and a dispersant, a surfactant, etc. are added to this mixture as necessary, and the mixture is used using a dispersing device such as a sand mill, attritor, ball mill, homogenizer, roll mill, etc. Can be dispersed.
  • a dispersing device such as a sand mill, attritor, ball mill, homogenizer, roll mill, etc.
  • the half width of the first main peak obtained by the XRD pattern is 0.01 to 0.8 °, and when the half width is 0.01 ° or less, the primary particle diameter becomes large. Therefore, it is difficult to ensure transparency. Moreover, when the half width exceeds 0.8 °, it is difficult to develop sufficient heat shielding properties.
  • the metal fine particles have a preferred lower limit of the half width of 0.1 °, a preferred upper limit of more than 0.8 °, a preferred lower limit of 0.2, and a more preferred upper limit of 0.5 °.
  • the specific surface area of the metal fine particles used in the present invention measured by the BET method is preferably 5 to 200 m 3 / g, more preferably 10 to 150 m 3 / g, and particularly preferably 10 to 100 m 3 / g. is there.
  • Those having a specific surface area of less than 5 m 3 / g by the BET method have a large primary particle size, and therefore, when a sheet, film, paint or resin composition is used, the finished surface may not be smooth. Furthermore, there is a risk that disadvantages such as the inability to expect transparency can occur.
  • the BET method is a method in which a specific surface area of a sample is measured based on the amount of molecules and ions having a known size adsorbed on the powder particle surface.
  • Near-infrared absorbing dye is a generic term for dyes that absorb the near infrared ray (wavelength of about 780 to 2000 nm) that is the closest to the visible region, and the types of near-infrared absorbing dyes are azo, aminium, and anthra Examples include quinone, cyanine, diimonium, dithiol metal complex, squarylium, phthalocyanine, and naphthalocyanine.
  • M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide.
  • M means that the naphthalocyanine ring in the formula (1) has a so-called central metal.
  • M is a hydrogen atom, it means that the naphthalocyanine ring does not have a central metal.
  • metal atom in M include, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd,
  • Examples include Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi.
  • Examples of the metal oxide include VO and GeO.
  • Examples of the metal hydroxide include Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2 , AlOH and the like.
  • As the metal halide for example, SiCl 2, VCl, VCl 2 , VOCl, FeCl, GaCl, ZrCl, AlCl , and the like.
  • metal atoms such as Fe, Co, Cu, Ni, Zn, Al, and V
  • metal oxides such as VO
  • metal hydroxides such as AlOH, and the like are preferable, and Cu and VO are more preferable.
  • the M is Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag. , Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi
  • a heat-shielding adhesive sheet prepared using a toluene dispersion of a naphthalocyanine-based compound In the property test, the temperature inside the box used for the test was lowered, and a good heat ray shielding effect was shown.
  • naphthalocyanine-based compound in which M is Cu when used, the temperature in the box is remarkably reduced, and an excellent heat ray heat shielding effect is exhibited, which is preferable.
  • a naphthalocyanine-based compound in which M is VO is also preferable because it significantly reduces the temperature in the box and exhibits an excellent heat-ray heat shielding effect.
  • X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group or a sulfonamide group.
  • A is a divalent bridging group, for example, an alkylene group having 1 to 3 carbon atoms, —CO 2 —, —SO 2 —, —SO 2 NH (CH 2 ) a — (where a represents 0 to 4).
  • an alkylene group having 1 to 3 carbon atoms, —SO 2 NH— in which a is 0 is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.
  • Y represents a sulfonic acid group, a carboxy group, a residue excluding at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or at least one hydrogen on the nitrogen atom of the heterocyclic ring containing nitrogen.
  • the phthalimide group which may have a carboxy group, a sulfonic acid group and a substituent is preferable, and a phthalimide group which may have a substituent is more preferable.
  • Y is a phthalimide group that may have a substituent, a piperazino group that may have a substituent, or a piperidino group that may have a substituent
  • the substituent may be a hydrogen atom or a lower alkyl group.
  • the substituted amino group is not particularly limited, and examples thereof include an amino group substituted with a lower alkyl group.
  • the lower alkyl group and the lower alkoxy group refer to a linear or branched alkyl group having 1 to 4 carbon atoms and an alkoxy group, respectively.
  • a conventional method can be used as a method of dispersing the near-infrared absorbing dye in an organic solvent. That is, a near-infrared absorbing dye and an organic solvent are mixed in a predetermined ratio, and a dispersant, a surfactant, etc. are added to this mixture as necessary, and a dispersing device such as a sand mill, an attritor, a ball mill, a homogenizer, or a roll mill is added. Can be used to disperse the mixture.
  • the heat ray-shielding pressure-sensitive adhesive composition in which the metal fine particles and the near-infrared absorbing dye are dispersed and the heat ray-shielding pressure-sensitive adhesive sheet obtained by processing this composition into a sheet shape are attached to the window glass, and are included in the wavelength included in sunlight. Therefore, the first condition is that the weather resistance is good. Therefore, the pressure-sensitive adhesive resin used in this embodiment is preferably an acrylic copolymer pressure-sensitive adhesive resin with good weather resistance.
  • the acrylic copolymer-based pressure-sensitive adhesive can be usually produced by copolymerization of a main monomer having a low glass transition point and a comonomer having a high glass transition point.
  • the main component of the acrylic copolymer pressure-sensitive adhesive is an acrylic acid alkyl ester having a low glass transition point and an alkyl group having 2 to 14 carbon atoms, or a methacrylic acid alkyl ester having an alkyl group having 4 to 16 carbon atoms.
  • a monomer having a glass transition point higher than them and copolymerizable therewith is used together with the main monomer.
  • acrylic acid alkyl ester monomers having a low glass transition point examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, n-butyl actylate, isobutyl acrylate, secondary butyl acrylate, acrylic acid 2 -Ethylhexyl, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate and the like.
  • methacrylic acid alkyl ester monomer having a low glass transition point examples include 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.
  • examples of the copolymerizable monomer include vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, and the like.
  • Amide, methylol acrylamide, dimethylacrylamide, glycidyl methacrylate, maleic anhydride and the like are also used.
  • the acrylic adhesive preferably has a weight average molecular weight of 100,000 to 1,200,000. More preferably, it is 200,000 to 800,000.
  • the degree of crosslinking of the polymer material constituting the pressure-sensitive adhesive varies depending on various conditions such as the type and composition of the pressure-sensitive adhesive (pressure-sensitive adhesive composition), and is not particularly limited.
  • the pressure-sensitive adhesive composition may contain a plasticizer.
  • esters such as phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid ester, sebacic acid ester, phosphoric acid triester or glycol ester, process oil, liquid polyether, liquid polyterpene, Other liquid resin etc. are mentioned, Among these, 1 type or 2 types or more can be mixed and used.
  • a plasticizer is preferably one having good compatibility with the pressure-sensitive adhesive.
  • the adhesive composition can contain various additives, such as a ultraviolet absorber or antioxidant, as needed, in addition to the plasticizer.
  • Dispersants include fatty acid salts (soap), ⁇ -sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chlorides, alkylpyridinium chlorides, alkylcarboxyl betaines, sulfobetas Low molecular amphoteric compounds such as styrene and lecithin
  • Dispersants with a RED of 1.5 or less with fine metal particles include DISPERBYK-116, DISPERBYK-142, DISPERBYK-145, DISPERBYK-163, DISPERBYK-2000, DSPERBYK-2155, BYK-P105, ANTI-TERRA U, And EFKA-4010 and DOPA-17HF.
  • the heat ray shielding adhesive composition can be produced by a known method.
  • the target heat ray-shielding pressure-sensitive adhesive composition can be obtained by dispersing metal fine particles or near-infrared absorbing dyes in a monomer that is a main component of an acrylic copolymer-based pressure-sensitive adhesive and then polymerizing it.
  • Patent Document 1 there is a method in which a dispersion liquid of metal fine particles or near infrared absorbing dye is prepared in advance, mixed with a monomer, and then polymerized and then a desired pressure-sensitive adhesive is obtained.
  • a method of obtaining a desired pressure-sensitive adhesive composition by directly mixing a dispersion of metal fine particles or a near-infrared absorbing dye with a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition can also be obtained by mixing metal fine particles and a near-infrared absorbing dye with a dispersant and dispersing the mixture in the pressure-sensitive adhesive.
  • the method of applying the pressure-sensitive adhesive is not particularly limited, but use of a comma coater, bar coater, spin coater, spray coater, roll coater, gravure coater, knife coater or other various coating apparatuses Is possible.
  • the dispersion ratio of the metal fine particles and the near-infrared absorbing dye to the monomer of the acrylic copolymer adhesive or the adhesive is determined by the coating thickness of the adhesive layer and the shielding performance.
  • the ideal optical performance of a film coated with a heat-shielding pressure-sensitive adhesive is high in visible light transmittance and low in solar radiation transmittance. The optical performance is determined depending on whether or not to do so.
  • the optical characteristics of the film coated with the heat ray-shielding pressure-sensitive adhesive are preferably such that the visible light transmittance is 50% or more and the solar radiation transmittance is 80% or less.
  • the coating thickness of the pressure-sensitive adhesive layer is usually 10 to 50 ⁇ m in consideration of the followability to the adherend surface, adhesive strength and economy, but the fine particles that give the above-mentioned heat ray shielding properties within this range
  • Synthesis example 1 (metal fine particles) 5.9 g of stannic chloride (SnCl 4 .5H 2 O) and 75.9 g of indium chloride (InCl 3 ) are dissolved in 4000 ml of water, to which 2% aqueous ammonia is added over 58 minutes, and the pH is finally adjusted. In this case, a hydrate of tin oxide and indium oxide was coprecipitated to 7.85. During this time, the liquid temperature was maintained at 5 ° C. Next, the coprecipitate was washed and dried, and further calcined at 900 ° C. for 2 hours to obtain tin-containing indium oxide (ITO) fine powder (metal fine particles).
  • ITO indium oxide
  • Synthesis Example 2 Near-infrared absorbing dye
  • 3.9 parts of vanadyl 2,3-naphthalocyanine (Aldrich) 5.0 parts of phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 part of paraformaldehyde are added and stirred at 140 ° C. for 8 hours. Then, it was poured into 300 parts of water, and the precipitated solid was filtered to obtain 7.5 parts of a naphthalocyanine compound.
  • dye dispersion liquid 1 was obtained by centrifuging the obtained dispersion for 15 minutes at 5000 rpm with a centrifuge (Hitachi Koki Co., Ltd. Himac CR18).
  • Production Example 3 (Near-infrared absorbing dye dispersion 2) A near-infrared pigment dispersion 2 was obtained in the same manner as in Production Example 2 except that the near-infrared absorbing pigment obtained in Synthesis Example 2 was replaced with 2,3-naphthalocyanine (manufactured by Aldrich).
  • ITO tin-containing indium oxide
  • Production Example 14.7 parts by weight of the toluene dispersion of the near-infrared absorbing dye obtained in 2 was mixed and dissolved in a uniform manner to obtain a heat ray shielding adhesive.
  • this is a release sheet polyester film (silicone treatment on one side) (manufactured by Lintec) 3811 (thickness: 38 ⁇ m), coated with a comma coater and dried, release sheet polyester film (one side coated with silicone) (manufactured by Lintec) 3801 (thickness: 38 ⁇ m) to produce a heat ray shielding adhesive sheet (thickness: 15 ⁇ m).
  • Example 2 A heat ray-shielding pressure-sensitive adhesive and a heat ray-shielding pressure-sensitive adhesive sheet were produced in the same manner as in Example 1, except that the toluene dispersion of the near-infrared absorbing dye was changed to that produced in Production Example 3.
  • Example 1 144 parts by weight of the toluene dispersion of tin-containing indium oxide (ITO) obtained in Production Example 1 and 100 parts by weight of acrylic adhesive A were used without mixing the toluene dispersion of the near infrared absorbing dye.
  • a heat ray shielding adhesive sheet (thickness: 15 ⁇ m) was prepared in the same manner as Example 1 except for the above.
  • Example 3 A heat ray shielding test was conducted on the heat ray shielding adhesive sheets produced in Example 1, Example 2 and Comparative Example 1 by the method shown below. The results are shown in Table 1.
  • Test method Test environment A test box having an inner diameter width of 150 mm, a length of 235 mm, and a height of 110 mm and having an outside air-blocking property and airtightness is prepared. Co., Ltd.) was installed at a height of 40 cm from the ceiling of the test box to constitute a test apparatus for evaluating thermal insulation. Next, the heat ray shielding adhesive sheet produced in the ceiling part of the test box was installed, and the four sides were fixed with tape. In addition, a thermometer was installed in the center of the test box so that the light from the lamp was not directly applied.
  • the lamp was turned on, the temperature was measured every 10 seconds, and the temperature in the test box after 30 minutes was measured.
  • the test box was installed in a room at about 25 ° C.
  • the temperature inside the box when the heat ray shielding adhesive sheet prepared in the comparative example and the heat ray shielding adhesive sheet of the present invention were used was compared, and the temperature inside the box using the heat ray shielding adhesive sheet of the present invention was low. In this case, the heat ray shielding effect is improved.
  • the calculation method of the temperature difference in a box is guide
  • the temperature in the box when using the heat ray shielding adhesive sheet produced in Comparative Example 1 was 72.5 ° C.
  • the temperature in the box at the time of using the heat ray shielding adhesive sheet produced in Example 1 and Example 2 of the present invention was 68.4 ° C. and 68.0 ° C., respectively. That is, the temperature in the box of the heat ray shielding adhesive sheet produced in Example 1 and Example 2 of the present invention was 4.1 ° C. and 4.5 ° C., respectively, than the temperature in the box of the heat ray shielding adhesive sheet produced in the comparative example. °C was low. From this result, it became clear that the heat ray shielding adhesive sheet of the present invention has an improved heat ray shielding effect.
  • heat ray-shielding metal fine particles and near-infrared absorbing dye are dispersed in a pressure-sensitive adhesive using a dispersant, thereby suppressing a temperature rise due to heat rays as compared with a conventional heat-ray-shielding pressure-sensitive adhesive sheet.
  • this invention can suppress the temperature rise of the space of a house or a motor vehicle, can reduce the load of an air-conditioning apparatus, and can contribute to energy saving and a global environmental problem.

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Abstract

[Problem] To efficiently shield heat rays not only in the infrared region but also in the near-infrared region. [Solution] The present invention provides: a heat ray shielding adhesive composition which contains (A) fine metal particles, (B) an acrylic adhesive, (C) a dispersant and (D) a near-infrared absorbing dye; and a heat ray shielding adhesive sheet which uses the heat ray shielding adhesive composition.

Description

熱線遮蔽性粘着剤組成物および熱線遮蔽性粘着シートHeat ray shielding adhesive composition and heat ray shielding adhesive sheet
　本発明は、窓ガラス等に貼着して用いられ、熱線を効率的に遮蔽できる熱線遮蔽性粘着剤組成物およびこれを用いた熱線遮蔽性粘着シートに関するものである。 The present invention relates to a heat ray-shielding pressure-sensitive adhesive composition that can be used by being attached to a window glass or the like and can efficiently shield heat rays, and a heat ray-shielding pressure-sensitive adhesive sheet using the same.
　近年、省エネルギーや地球環境問題の観点から、空調機器の負荷を軽減することが求められている。例えば、住宅や自動車の分野では太陽光からの熱線を遮蔽できる熱線遮蔽性材料を窓ガラスへ付与し、室内や車内の温度上昇を抑えることが求められている。熱線遮蔽性を有する材料は様々あるが、特許文献１では、熱線遮蔽性を付与した粘着剤およびその粘着シートが開示されている。この粘着シートは熱線遮蔽性を付与した粘着剤をシート状に加工したものであり、事前に任意の形状に加工出来ること、張り直しが可能なリワーク性を有することを特徴に持つ。しかしながら、この熱線遮蔽性を付与した粘着シートは、熱遮断性が不十分であり、更なる改善が希求されている。 In recent years, it has been required to reduce the load on air conditioning equipment from the viewpoint of energy saving and global environmental problems. For example, in the field of houses and automobiles, it is required to apply a heat ray shielding material capable of shielding heat rays from sunlight to the window glass to suppress the temperature rise in the room or in the vehicle. Although there are various materials having heat ray shielding properties, Patent Literature 1 discloses a pressure-sensitive adhesive imparted with heat ray shielding properties and an adhesive sheet thereof. This pressure-sensitive adhesive sheet is obtained by processing a pressure-sensitive adhesive having heat ray shielding properties into a sheet shape, and can be processed into an arbitrary shape in advance and has reworkability that enables re-stretching. However, the pressure-sensitive adhesive sheet imparted with the heat ray shielding property is insufficient in the heat shielding property, and further improvement is desired.
特願平１０－８０１０号Japanese Patent Application No.10-8010
　従来の熱線遮蔽性粘着シートに比べ、熱線遮蔽性が大幅に改善された熱線遮蔽性粘着剤組成物と熱線遮蔽性粘着シートを提供することが本発明の課題である。 It is an object of the present invention to provide a heat ray-shielding pressure-sensitive adhesive composition and a heat ray-shielding pressure-sensitive adhesive sheet that have significantly improved heat ray-shielding properties compared to conventional heat ray-shielding pressure-sensitive adhesive sheets.
　本発明者らは、熱線遮蔽性が大幅に改善された熱線遮蔽性粘着シートを得るために鋭意検討した結果、錫ドープ酸化インジウムをはじめとする金属微粒子と近赤外吸収色素と分散剤と粘着剤とを含むことにより、効率的に熱線を遮蔽できる熱線遮蔽性粘着剤組成物およびこれをシート状に加工した熱線遮蔽性粘着シートを得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to obtain a heat ray-shielding pressure-sensitive adhesive sheet having greatly improved heat ray-shielding properties, the present inventors have found that metal fine particles including tin-doped indium oxide, near-infrared absorbing dyes, dispersants and pressure-sensitive adhesives. The heat-ray-shielding pressure-sensitive adhesive composition capable of efficiently shielding heat rays and a heat-ray-shielding pressure-sensitive adhesive sheet obtained by processing the same into a sheet, thereby completing the present invention. .
　すなわち、本発明は、
「（１）（Ａ）金属微粒子、（Ｂ）アクリル系粘着剤、（Ｃ）分散剤、及び（Ｄ）近赤外吸収色素を含有する熱線遮蔽性粘着剤組成物、
（２）（Ａ）金属微粒子が酸化スズ、酸化インジウム、酸化亜鉛の群から選ばれる一種の金属微粒子であることを特徴とする（１）に記載の熱線遮蔽性粘着剤組成物、
（３）（Ｂ）アクリル系粘着剤が、カルボキシ基、もしくは酸無水物含有モノマーの構造単位の割合がポリマー中の全モノマー構造単位の１～５％であるポリマーであることを特徴とする（１）または（２）の何れか一項に記載の熱線遮蔽性粘着剤組成物、
（４）（Ｂ）アクリル系粘着剤の重量平均分子量が１０万～１２０万であることを特徴とする（１）から（３）の何れか一項に記載の熱線遮蔽性粘着剤組成物、
（５）（Ｄ）近赤外吸収色素がフタロシアニン系化合物、ナフタロシアニン系化合物、及び／又はジイモニウム系化合物であることを特徴とする（１）乃至（４）の何れか一項に記載の熱線遮蔽性粘着剤組成物、
（６）（Ｄ）近赤外吸収色素が式（１）で示されるナフタロシアニン系化合物である（５）に記載の熱線遮蔽性粘着剤組成物、 That is, the present invention
“(1) (A) Metal fine particles, (B) Acrylic adhesive, (C) Dispersant, and (D) Heat ray-shielding adhesive composition containing near-infrared absorbing dye,
(2) (A) The heat ray shielding pressure-sensitive adhesive composition according to (1), wherein the metal fine particles are a kind of metal fine particles selected from the group consisting of tin oxide, indium oxide, and zinc oxide,
(3) (B) The acrylic pressure-sensitive adhesive is a polymer in which the proportion of structural units of a carboxy group or an acid anhydride-containing monomer is 1 to 5% of the total monomer structural units in the polymer ( 1) or the heat ray shielding adhesive composition according to any one of (2),
(4) (B) The heat ray shielding adhesive composition according to any one of (1) to (3), wherein the acrylic adhesive has a weight average molecular weight of 100,000 to 1,200,000,
(5) (D) The heat ray according to any one of (1) to (4), wherein the near-infrared absorbing dye is a phthalocyanine compound, a naphthalocyanine compound, and / or a diimonium compound. Shielding adhesive composition,
(6) (D) The heat ray-shielding pressure-sensitive adhesive composition according to (5), wherein the near-infrared absorbing dye is a naphthalocyanine compound represented by the formula (1),
Figure JPOXMLDOC01-appb-C000002
 ［式（１）中、Ｍは金属原子、金属酸化物、金属水酸化物、若しくは金属ハロゲン化物、又は水素原子を表し、Ｘは低級アルキル基、低級アルコキシ基、置換アミノ基、ニトロ基、ハロゲン基、ヒドロキシ基、カルボキシ基、スルホン酸基、スルホンアミド基を表す。Ａは二価の架橋基を、Ｙはスルホン酸基、カルボキシ基、第１～２級アミノ基の窒素原子上の水素の少なくとも１つを除いた残基、又は窒素を含む複素環の窒素原子上の水素の少なくとも１つを除いた残基を表す。ｍ及びｎはいずれも平均値であり、ｍ、ｎはそれぞれ０以上１２以下、かつ、ｍとｎとの和は０以上１２以下である。］
（７）式（１）中のＭはＶＯであり、Ａは炭素数１～３のアルキレン基であり、Ｙは置換基を有してもよいフタルイミド基である（６）に記載の熱線遮蔽性粘着剤組成物、
（８）式（１）中のＭはＣｕであり、Ａは炭素数１～３のアルキレン基であり、Ｙは置換基を有してもよいフタルイミド基である（６）に記載の熱線遮蔽性粘着剤組成物、
（９）（１）乃至（８）の何れか一項に記載の熱線遮蔽性粘着剤組成物を塗布してなる熱線遮蔽性粘着シート」に関する。
Figure JPOXMLDOC01-appb-C000002
 [In the formula (1), M represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, or a hydrogen atom, and X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen atom. Represents a group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group. A is a divalent bridging group, Y is a sulfonic acid group, a carboxy group, a residue obtained by removing at least one of the hydrogen atoms on the nitrogen atom of the primary or secondary amino group, or a nitrogen atom of a heterocyclic ring containing nitrogen Represents a residue excluding at least one of the above hydrogens. m and n are both average values, m and n are each 0 or more and 12 or less, and the sum of m and n is 0 or more and 12 or less. ]
(7) M in formula (1) is VO, A is an alkylene group having 1 to 3 carbon atoms, and Y is a phthalimide group which may have a substituent. Adhesive composition,
(8) M in formula (1) is Cu, A is an alkylene group having 1 to 3 carbon atoms, and Y is a phthalimide group which may have a substituent. Adhesive composition,
(9) It is related with the heat ray shielding adhesive sheet formed by apply | coating the heat ray shielding adhesive composition as described in any one of (1) thru | or (8).
　本発明によれば、錫ドープ酸化インジウムをはじめとする金属微粒子と近赤外吸収色素を分散剤を用いてアクリル系粘着剤に分散させた熱線遮蔽性粘着剤組成物をシート状に加工することにより、従来の熱線遮蔽性粘着シートと比較して、熱線による温度上昇をより抑えることができる熱線遮蔽性粘着シートを提供できる。これにより住宅や自動車の空間の温度上昇を抑えることができ、空調機器の負荷を軽減できるため、本発明は省エネルギーや地球環境問題の解決に貢献できる。 According to the present invention, a heat ray-shielding pressure-sensitive adhesive composition in which metal fine particles including tin-doped indium oxide and a near-infrared absorbing dye are dispersed in an acrylic pressure-sensitive adhesive using a dispersant is processed into a sheet shape. Thereby, compared with the conventional heat ray shielding adhesive sheet, the heat ray shielding adhesive sheet which can suppress the temperature rise by a heat ray more can be provided. Thereby, the temperature rise of the space of a house or a car can be suppressed, and the load on the air conditioner can be reduced. Therefore, the present invention can contribute to energy saving and the solution of global environmental problems.
　本発明を詳細に説明する。本発明の熱線遮蔽性粘着シート形成用の粘着剤組成物は、錫ドープ酸化インジウムをはじめとする金属微粒子と近赤外吸収色素を分散剤を用いてアクリル系粘着剤へ分散させることを特徴とし、この粘着剤組成物はシート状に加工することもできる。 The present invention will be described in detail. The pressure-sensitive adhesive composition for forming a heat ray-shielding pressure-sensitive adhesive sheet according to the present invention is characterized in that metal fine particles including tin-doped indium oxide and a near-infrared absorbing dye are dispersed in an acrylic pressure-sensitive adhesive using a dispersant. The pressure-sensitive adhesive composition can be processed into a sheet shape.
　熱線遮蔽性粘着剤組成物に用いる金属微粒子は、可視光の吸収が小さく、近赤外から遠赤外域の光に対しては良好な吸収特性を有しているものが適している。そのようなものとして、近赤外域にプラズマ波長を持っている電気伝導性の金属酸化物が挙げられる。具体的には、酸化スズ、酸化インジウム、酸化亜鉛、酸化タングステン、酸化クロム、酸化モリブデン等を例示することができる。このうち、特に可視光領域に光吸収性が小さい酸化スズ、酸化インジウム、酸化亜鉛が好適である。 The metal fine particles used in the heat ray-shielding pressure-sensitive adhesive composition are suitable for those having low absorption of visible light and having good absorption characteristics for light in the near infrared to far infrared region. As such a thing, the electroconductive metal oxide which has a plasma wavelength in a near-infrared region is mentioned. Specific examples include tin oxide, indium oxide, zinc oxide, tungsten oxide, chromium oxide, and molybdenum oxide. Of these, tin oxide, indium oxide, and zinc oxide, which have a small light absorption property particularly in the visible light region, are preferable.
　また、これらの酸化物の電気導電性を向上させるために第三成分をドープすることは、大変好ましい。このためのドーパントとしては、酸化スズに対してはＳｂ，Ｖ，Ｎｂ，Ｔａ等が選ばれ、酸化インジウムに対してはＺｎ，Ａｌ，Ｓｎ，Ｓｂ，Ｇａ，Ｇｅ等が選ばれ、酸化亜鉛に対しては、Ａｌ，Ｇａ，Ｉｎ，Ｓｎ，Ｓｂ，Ｎｂ等が選ばれる。 Also, it is very preferable to dope the third component in order to improve the electrical conductivity of these oxides. As the dopant for this, Sb, V, Nb, Ta, etc. are selected for tin oxide, Zn, Al, Sn, Sb, Ga, Ge, etc. are selected for indium oxide, and zinc oxide is used. For this, Al, Ga, In, Sn, Sb, Nb or the like is selected.
　金属微粒子の製法は、粒径が１００ｎｍ以下のものが得られれば特に制限はなく、気相合成法、液層合成法等の公知の方法を使用することができる。例えば酸化インジウム微粒子については、特開平６－２２７８１５に開示されている方法によることができる。すなわち、特定の金属微粒子元素を含んだ塩の水溶液をアルカリにより中和し、得られた沈殿物をろ過、洗浄し、高温で加熱処理することにより金属微粒子を得る方法である。また、酸化スズ微粒子、酸化亜鉛微粒子については、それぞれ特開平２－１０５８７５、特開平６－２３４５２２を例示することができる。 The method for producing metal fine particles is not particularly limited as long as a particle size of 100 nm or less is obtained, and known methods such as a gas phase synthesis method and a liquid layer synthesis method can be used. For example, for indium oxide fine particles, the method disclosed in JP-A-6-227815 can be used. That is, this is a method of obtaining metal fine particles by neutralizing an aqueous solution of a salt containing a specific metal fine particle element with an alkali, filtering and washing the obtained precipitate, and heat-treating it at a high temperature. As for the tin oxide fine particles and the zinc oxide fine particles, JP-A-2-105875 and JP-A-6-234522 can be exemplified.
　金属微粒子を有機溶媒へ分散する方法としては従来の方法を用いることができる。すなわち、金属微粒子と有機溶剤を所定比率に混合し、この混合物に必要に応じて分散剤、界面活性剤等を添加し、サンドミル、アトライター、ボールミル、ホモジナイザー、ロールミル等の分散装置を用いて混合物を分散することができる。 Conventional methods can be used as a method for dispersing the metal fine particles in the organic solvent. That is, metal fine particles and an organic solvent are mixed at a predetermined ratio, and a dispersant, a surfactant, etc. are added to this mixture as necessary, and the mixture is used using a dispersing device such as a sand mill, attritor, ball mill, homogenizer, roll mill, etc. Can be dispersed.
　本発明の金属微粒子は、ＸＲＤパターンにより得られる第一主ピークの半値幅が、０．０１～０．８°であり、半値幅が０．０１°以下であると、一次粒子径が大きくなるため透明性を確保することが難しい。また、半値幅が０．８°を超えると十分な遮熱性を発現することが難しい。また、上記金属微粒子は、半値幅の好ましい下限が０．１°、好ましい上限が０．８°より好ましい下限が０．２、より好ましい上限が０．５°である。 In the metal fine particles of the present invention, the half width of the first main peak obtained by the XRD pattern is 0.01 to 0.8 °, and when the half width is 0.01 ° or less, the primary particle diameter becomes large. Therefore, it is difficult to ensure transparency. Moreover, when the half width exceeds 0.8 °, it is difficult to develop sufficient heat shielding properties. The metal fine particles have a preferred lower limit of the half width of 0.1 °, a preferred upper limit of more than 0.8 °, a preferred lower limit of 0.2, and a more preferred upper limit of 0.5 °.
　本発明で用いられる金属微粒子の、ＢＥＴ法で測定した比表面積は５～２００ｍ３／ｇであると好ましく、より好ましくは１０～１５０ｍ３／ｇであり、特に好ましくは１０～１００ｍ３／ｇである。ＢＥＴ法による比表面積が５ｍ３／ｇより小さいものは、一次粒子径が大きいため、シートやフィルム、塗料、樹脂組成物にした場合に仕上がり表面が平滑でない恐れがある。さらには、透明性が期待できないなどのデメリットが生じる恐れがある。一方で、ＢＥＴ比表面積が２００ｍ３／ｇより大きいものは、製造に特殊な技術が必要となり、また十分な結晶化度を得られず、熱線遮蔽性が損なわれる恐れがある。なお、ＢＥＴ法は、紛体粒子表面に大きさのわかった分子やイオンを吸着させて、その量から試料の比表面積を測定する方法である。 The specific surface area of the metal fine particles used in the present invention measured by the BET method is preferably 5 to 200 m 3 / g, more preferably 10 to 150 m 3 / g, and particularly preferably 10 to 100 m 3 / g. is there. Those having a specific surface area of less than 5 m 3 / g by the BET method have a large primary particle size, and therefore, when a sheet, film, paint or resin composition is used, the finished surface may not be smooth. Furthermore, there is a risk that disadvantages such as the inability to expect transparency can occur. On the other hand, when the BET specific surface area is larger than 200 m 3 / g, a special technique is required for production, and sufficient crystallinity cannot be obtained, which may impair heat ray shielding. The BET method is a method in which a specific surface area of a sample is measured based on the amount of molecules and ions having a known size adsorbed on the powder particle surface.
　近赤外吸収色素とは、赤外線の中でも可視領域に最も近い近赤外線（波長約７８０～２０００ｎｍ）を吸収する色素の総称であり、近赤外吸収色素の種類としてはアゾ系、アミニウム系、アンスラキノン系、シアニン系、ジイモニウム系、ジチオール金属錯体系、スクアリリウム系、フタロシアニン系、ナフタロシアニン系等が挙げられる。耐久性を高くする観点からフタロシアニン系、ナフタロシアニン系、ジイモニウム系が好ましく、かつ熱線を効率良く遮断する観点からナフタロシアニン系であることが好ましく、前記式（１）で表される化合物が特に好ましい。前記式（１）において、Ｍは水素原子、金属原子、金属酸化物、金属水酸化物、又は金属ハロゲン化物を表す。Ｍが水素原子以外である場合、該Ｍは式（１）におけるナフタロシアニン環がいわゆる中心金属を有することを意味する。又、Ｍが水素原子である場合、該ナフタロシアニン環は中心金属を有しないことを意味する。 Near-infrared absorbing dye is a generic term for dyes that absorb the near infrared ray (wavelength of about 780 to 2000 nm) that is the closest to the visible region, and the types of near-infrared absorbing dyes are azo, aminium, and anthra Examples include quinone, cyanine, diimonium, dithiol metal complex, squarylium, phthalocyanine, and naphthalocyanine. From the viewpoint of increasing durability, phthalocyanine-based, naphthalocyanine-based, and diimonium-based are preferable, and from the viewpoint of efficiently blocking heat rays, naphthalocyanine-based is preferable, and the compound represented by the formula (1) is particularly preferable. . In the formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide. When M is other than a hydrogen atom, the M means that the naphthalocyanine ring in the formula (1) has a so-called central metal. Further, when M is a hydrogen atom, it means that the naphthalocyanine ring does not have a central metal.
　前記Ｍにおける金属原子の具体例としては例えば、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ等が挙げられる。 Specific examples of the metal atom in M include, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Examples include Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi.
　金属酸化物としてはＶＯ、ＧｅＯ等が挙げられる。金属水酸化物としては例えば、Ｓｉ（ＯＨ）２、Ｃｒ（ＯＨ）２、Ｓｎ（ＯＨ）２、ＡｌＯＨ等が挙げられる。金属ハロゲン化物としては例えば、ＳｉＣｌ２、ＶＣｌ、ＶＣｌ２、ＶＯＣｌ、ＦｅＣｌ、ＧａＣｌ、ＺｒＣｌ、ＡｌＣｌ等が挙げられる。これらの中でもＦｅ、Ｃｏ、Ｃｕ、Ｎｉ、Ｚｎ、Ａｌ、Ｖ等の金属原子、ＶＯ等の金属酸化物、ＡｌＯＨ等の金属水酸化物等が好ましく、Ｃｕ、ＶＯがより好ましい。 Examples of the metal oxide include VO and GeO. Examples of the metal hydroxide include Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2 , AlOH and the like. As the metal halide, for example, SiCl 2, VCl, VCl 2 , VOCl, FeCl, GaCl, ZrCl, AlCl , and the like. Among these, metal atoms such as Fe, Co, Cu, Ni, Zn, Al, and V, metal oxides such as VO, metal hydroxides such as AlOH, and the like are preferable, and Cu and VO are more preferable.
　前記ＭがＬｉ、Ｎａ、Ｋ、Ｍｇ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉであるナフタロシアニン系化合物のトルエン分散液を用い作製された熱線遮蔽性粘着シートは、熱線遮蔽性試験において、試験に用いた箱の箱内温度を低下させ、良好な熱線遮蔽性効果を示した。また、特にＭがＣｕであるナフタロシアニン系化合物を用いた場合、箱内温度を顕著に低下させ、優れた熱線遮熱性効果を示し、好ましい。ＭがＶＯであるナフタロシアニン系化合物を用いた場合も、箱内温度を顕著に低下させ、優れた熱線遮熱性効果を示し、好ましい。 The M is Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag. , Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi A heat-shielding adhesive sheet prepared using a toluene dispersion of a naphthalocyanine-based compound In the property test, the temperature inside the box used for the test was lowered, and a good heat ray shielding effect was shown. In particular, when a naphthalocyanine-based compound in which M is Cu is used, the temperature in the box is remarkably reduced, and an excellent heat ray heat shielding effect is exhibited, which is preferable. A naphthalocyanine-based compound in which M is VO is also preferable because it significantly reduces the temperature in the box and exhibits an excellent heat-ray heat shielding effect.
　Ｘは低級アルキル基、低級アルコキシ基、置換アミノ基、ニトロ基、ハロゲン基、ヒドロキシ基、カルボキシ基、スルホン酸基またはスルホンアミド基であることを示す。Ａは二価の架橋基であり、例えば炭素数１～３のアルキレン基、－ＣＯ２－、－ＳＯ２－、－ＳＯ２ＮＨ（ＣＨ２）ａ－（ここで、ａは０～４を表す）が挙げられるが、炭素数１～３のアルキレン基、aが０である－ＳＯ２ＮＨ－であることが好まく、炭素数１～３のアルキレン基がより好ましい。Ｙは、スルホン酸基、カルボキシ基、第１～２級アミノ基の窒素原子上の水素の少なくとも１つを除いた残基、又は窒素を含む複素環の窒素原子上の水素の少なくとも１つを除いた残基を表し、例えば、カルボキシ基、スルホン酸基、置換基を有してもよいフタルイミド基、置換基を有してもよいピペラジノ基、置換基を有してもよいピペリジノ基等が挙げられるが、カルボキシ基、スルホン酸基、置換基を有してもよいフタルイミド基が好ましく、置換基を有してもよいフタルイミド基がより好ましい。なお、Ｙが置換基を有してもよいフタルイミド基、置換基を有してもよいピペラジノ基、置換基を有してもよいピペリジノ基であるときの置換基としては水素原子、低級アルキル基、低級アルコキシ基、置換アミノ基、ニトロ基、ハロゲン基、スルホン酸基を示し、水素原子、ハロゲン基であることが好ましい。 X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group or a sulfonamide group. A is a divalent bridging group, for example, an alkylene group having 1 to 3 carbon atoms, —CO 2 —, —SO 2 —, —SO 2 NH (CH 2 ) a — (where a represents 0 to 4). And an alkylene group having 1 to 3 carbon atoms, —SO 2 NH— in which a is 0 is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. Y represents a sulfonic acid group, a carboxy group, a residue excluding at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or at least one hydrogen on the nitrogen atom of the heterocyclic ring containing nitrogen. Represents a removed residue, such as a carboxy group, a sulfonic acid group, a phthalimide group which may have a substituent, a piperazino group which may have a substituent, a piperidino group which may have a substituent, etc. The phthalimide group which may have a carboxy group, a sulfonic acid group and a substituent is preferable, and a phthalimide group which may have a substituent is more preferable. In addition, when Y is a phthalimide group that may have a substituent, a piperazino group that may have a substituent, or a piperidino group that may have a substituent, the substituent may be a hydrogen atom or a lower alkyl group. , A lower alkoxy group, a substituted amino group, a nitro group, a halogen group and a sulfonic acid group, preferably a hydrogen atom or a halogen group.
　本発明において置換アミノ基は特に限定されないが、例えば低級アルキル基で置換したアミノ基が含まれる。また、低級アルキル基、低級アルコキシ基は、それぞれ直鎖状または分岐状の炭素数１～４のアルキル基及びアルコキシ基を指す。近赤外吸収色素を有機溶媒へ分散する方法としては従来の方法を用いることができる。すなわち、近赤外吸収色素と有機溶剤を所定比率に混合し、この混合物に必要に応じて分散剤、界面活性剤等を添加し、サンドミル、アトライター、ボールミル、ホモジナイザー、ロールミル等の分散装置を用いて混合物を分散することができる。 In the present invention, the substituted amino group is not particularly limited, and examples thereof include an amino group substituted with a lower alkyl group. The lower alkyl group and the lower alkoxy group refer to a linear or branched alkyl group having 1 to 4 carbon atoms and an alkoxy group, respectively. A conventional method can be used as a method of dispersing the near-infrared absorbing dye in an organic solvent. That is, a near-infrared absorbing dye and an organic solvent are mixed in a predetermined ratio, and a dispersant, a surfactant, etc. are added to this mixture as necessary, and a dispersing device such as a sand mill, an attritor, a ball mill, a homogenizer, or a roll mill is added. Can be used to disperse the mixture.
　金属微粒子と近赤外吸色素が分散された熱線遮蔽性粘着剤組成物やこの組成物をシート状に加工した熱線遮蔽性粘着シートは、窓ガラスに貼付し、太陽光に含まれる波長のうちの熱線成分を遮断する目的に使用するため、耐候性の良いことが第一の条件である。したがって、この実施の形態に用いる粘着樹脂は、耐候性の良いアクリル共重合体系粘着樹脂であることが好ましい。アクリル共重合体系粘着剤は、通常、ポリマーのガラス転移点が低い主モノマーとガラス転移点が高いコモノマーの共重合により作ることができる。 The heat ray-shielding pressure-sensitive adhesive composition in which the metal fine particles and the near-infrared absorbing dye are dispersed and the heat ray-shielding pressure-sensitive adhesive sheet obtained by processing this composition into a sheet shape are attached to the window glass, and are included in the wavelength included in sunlight. Therefore, the first condition is that the weather resistance is good. Therefore, the pressure-sensitive adhesive resin used in this embodiment is preferably an acrylic copolymer pressure-sensitive adhesive resin with good weather resistance. The acrylic copolymer-based pressure-sensitive adhesive can be usually produced by copolymerization of a main monomer having a low glass transition point and a comonomer having a high glass transition point.
　アクリル共重合体系粘着剤の主成分となるモノマーとしては、ガラス転移点が低くアルキル基の炭素数が２～１４のアクリル酸アルキルエステルまたはアルキル基の炭素数が４乃至１６のメタアクリル酸アルキルエステルが挙げられ、ガラス転移点がそれらより高く、それらと共重合可能なモノマーが主モノマーと共に使用される。 The main component of the acrylic copolymer pressure-sensitive adhesive is an acrylic acid alkyl ester having a low glass transition point and an alkyl group having 2 to 14 carbon atoms, or a methacrylic acid alkyl ester having an alkyl group having 4 to 16 carbon atoms. A monomer having a glass transition point higher than them and copolymerizable therewith is used together with the main monomer.
　ガラス転移点が低いアクリル酸アルキルエステルモノマーとしては、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸イソプロピル、アクリル酸メトキシエチル、アクチル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸セカンダリーブチル、アクリル酸２－エチルヘキシル、アクリル酸ｎ－オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸イソステアリル等を例示することができる。 Examples of acrylic acid alkyl ester monomers having a low glass transition point include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, n-butyl actylate, isobutyl acrylate, secondary butyl acrylate, acrylic acid 2 -Ethylhexyl, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate and the like.
　また、ガラス転移点の低いメタアクリル酸アルキルエステルモノマーとしては、メタアクリル酸２－エチルヘキシル、メタアクリル酸ｎ－オクチル、メタアクリル酸ｎ－ラウリル等を例示することができる。 Examples of the methacrylic acid alkyl ester monomer having a low glass transition point include 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.
　また、共重合可能モノマーとしては、酢酸ビニル、アクリロニトリル、アクリルアマイド、スチレン、メタアクリル酸メチル、アクリル酸メチル等を例示することができる。 Further, examples of the copolymerizable monomer include vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, and the like.
　前記モノマー以外に所要の粘着性能を得るために、官能基含有モノマーとして（メタ）アクリル酸、イタコン酸、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、アクリルアマイド、メチロールアクリルアマイド、ジメチルアクリルアミド、グリシジリルメタアクリレート、無水マレイン酸等も使用される。 In order to obtain the required adhesion performance in addition to the above monomers, (meth) acrylic acid, itaconic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, acrylic as functional group-containing monomers Amide, methylol acrylamide, dimethylacrylamide, glycidyl methacrylate, maleic anhydride and the like are also used.
　また、分子量については金属微粒子と近赤外吸収色素の分散性に大きく影響するため、アクリル系粘着剤の重量平均分子量が１０万～１２０万であることが好ましい。より好ましくは２０万～８０万である。 In addition, since the molecular weight greatly affects the dispersibility of the metal fine particles and the near-infrared absorbing dye, the acrylic adhesive preferably has a weight average molecular weight of 100,000 to 1,200,000. More preferably, it is 200,000 to 800,000.
　粘着剤を構成する高分子材料の架橋度は、粘着剤（粘着剤組成物）の種類、組成等の諸条件により異なり、特に限定されない。必要に応じ粘着剤組成物は可塑剤を含んでもよい。この可塑剤としてはフタル酸エステル、トリメリット酸エステル、ピロメリット酸エステル、アジピン酸エステル、セバシン酸エステル、リン酸トリエステル又はグリコールエステル等のエステル類や、プロセスオイル、液状ポリエーテル、液状ポリテルペン、その他の液状樹脂等が挙げられ、これらのうちの１種又は２種以上を混合して用いることができる。このような可塑剤は、粘着剤との相溶性が良いものであるのが好ましい。また、粘着剤組成物は、前記可塑剤の他、必要に応じ、例えば、紫外線吸収剤又は酸化防止剤等の各種添加剤を含むことができる。 The degree of crosslinking of the polymer material constituting the pressure-sensitive adhesive varies depending on various conditions such as the type and composition of the pressure-sensitive adhesive (pressure-sensitive adhesive composition), and is not particularly limited. If necessary, the pressure-sensitive adhesive composition may contain a plasticizer. As this plasticizer, esters such as phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid ester, sebacic acid ester, phosphoric acid triester or glycol ester, process oil, liquid polyether, liquid polyterpene, Other liquid resin etc. are mentioned, Among these, 1 type or 2 types or more can be mixed and used. Such a plasticizer is preferably one having good compatibility with the pressure-sensitive adhesive. Moreover, the adhesive composition can contain various additives, such as a ultraviolet absorber or antioxidant, as needed, in addition to the plasticizer.
　分散剤としては、脂肪酸塩（石けん）、α－スルホ脂肪酸エステル塩（ＭＥＳ）、アルキルベンゼンスルホン酸塩（ＡＢＳ）、直鎖アルキルベンゼンスルホン酸塩（ＬＡＳ）、アルキル硫酸塩（ＡＳ）、アルキルエーテル硫酸エステル塩（ＡＥＳ）、アルキル硫酸トリエタノールといった低分子陰イオン性（アニオン性）化合物、脂肪酸エタノールアミド、ポリオキシエチレンアルキルエーテル（ＡＥ）、ポリオキシエチレンアルキルフェニルエーテル（ＡＰＥ）、ソルビトール、ソルビタンといった低分子非イオン系化合物、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウムクロリド、アルキルピリジニウムクロリド、といった低分子陽イオン性（カチオン性）化合物、アルキルカルボキシルベタイン、スルホベタイン、レシチンといった低分子両性系化合物や、ナフタレンスルホン酸塩のホルマリン縮合物、ポリスチレンスルホン酸塩、ポリアクリル酸塩、ビニル化合物とカルボン酸系単量体の共重合体塩、カルボキシメチルセルロース、ポリビニルアルコールなどに代表される高分子水系分散剤、ポリアクリル酸部分アルキルエステル、ポリアルキレンポリアミンといった高分子非水系分散剤、ポリエチレンイミン、アミノアルキルメタクリレート共重合体といった高分子カチオン系分散剤が代表的なものであるが、本発明の粒子に好適に適用されるものであれば、ここに例示したような形態のもの以外の構造を有するものを排除しない。 Dispersants include fatty acid salts (soap), α-sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chlorides, alkylpyridinium chlorides, alkylcarboxyl betaines, sulfobetas Low molecular amphoteric compounds such as styrene and lecithin, formalin condensate of naphthalene sulfonate, polystyrene sulfonate, polyacrylate, copolymer salt of vinyl compound and carboxylic acid monomer, carboxymethyl cellulose, polyvinyl alcohol Typical examples are polymeric water-based dispersants such as polyacrylic acid partial alkyl esters and polyalkylene polyamines, and polymer cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers. However, as long as it can be suitably applied to the particles of the present invention, those having a structure other than the ones exemplified here are not excluded.
　分散剤として、具体的名称を挙げると次のようなものが知られている。即ち、フローレンＤＯＰＡ－１５Ｂ、フローレンＤＯＰＡ－１７（共栄社化学株式会社製）、ソルプラスＡＸ５、ソルプラスＴＸ５、ソルスパース９０００、ソルスパース１２０００、ソルスパース１７０００、ソルスパース２００００、ソルスパース２１０００、ソルスパース２４０００、ソルスパース２６０００、ソルスパース２７０００、ソルスパース２８０００、ソルスパース３２０００、ソルスパース３５１００、ソルスパース５４０００、ソルシックス２５０、（日本ルーブリゾール株式会社製）、ＥＦＫＡ４００８、ＥＦＫＡ４００９、ＥＦＫＡ４０１０、ＥＦＫＡ４０１５、ＥＦＫＡ４０４６、ＥＦＫＡ４０４７、ＥＦＫＡ４０６０、ＥＦＫＡ４０８０、ＥＦＫＡ７４６２、ＥＦＫＡ４０２０、ＥＦＫＡ４０５０、ＥＦＫＡ４０５５、ＥＦＫＡ４４００、ＥＦＫＡ４４０１、ＥＦＫＡ４４０２、ＥＦＫＡ４４０３、ＥＦＫＡ４３００、ＥＦＫＡ４３３０、ＥＦＫＡ４３４０、ＥＦＫＡ６２２０、ＥＦＫＡ６２２５、ＥＦＫＡ６７００、ＥＦＫＡ６７８０、ＥＦＫＡ６７８２、ＥＦＫＡ８５０３（エフカアディディブズ社製）、アジスパーＰＡ１１１、アジスパーＰＢ７１１、アジスパーＰＢ８２１、アジスパーＰＢ８２２、アジスパーＰＮ４１１、フェイメックスＬ－１２（味の素ファインテクノ株式会社製）、ＴＥＸＡＰＨＯＲ－ＵＶ２１、ＴＥＸＡＰＨＯＲ－ＵＶ６１（コグニスジャパン株式会社製）、ＤｉｓｐｅｒＢＹＫ１０１、ＤｉｓｐｅｒＢＹＫ１０２、ＤｉｓｐｅｒＢＹＫ１０６、ＤｉｓｐｅｒＢＹＫ１０８、ＤｉｓｐｅｒＢＹＫ１１１、ＤｉｓｐｅｒＢＹＫ１１６、ＤｉｓｐｅｒＢＹＫ１３０、ＤｉｓｐｅｒＢＹＫ１４０、ＤｉｓｐｅｒＢＹＫ１４２、ＤｉｓｐｅｒＢＹＫ１４５、ＤｉｓｐｅｒＢＹＫ１６１、ＤｉｓｐｅｒＢＹＫ１６２、ＤｉｓｐｅｒＢＹＫ１６３、ＤｉｓｐｅｒＢＹＫ１６４、ＤｉｓｐｅｒＢＹＫ１６６、ＤｉｓｐｅｒＢＹＫ１６７、ＤｉｓｐｅｒＢＹＫ１６８、ＤｉｓｐｅｒＢＹＫ１７０、ＤｉｓｐｅｒＢＹＫ１７１、ＤｉｓｐｅｒＢＹＫ１７４、ＤｉｓｐｅｒＢＹＫ１８０、ＤｉｓｐｅｒＢＹＫ１８２、ＤｉｓｐｅｒＢＹＫ１９２、ＤｉｓｐｅｒＢＹＫ１９３、ＤｉｓｐｅｒＢＹＫ２０００、ＤｉｓｐｅｒＢＹＫ２００１、ＤｉｓｐｅｒＢＹＫ２０２０、ＤｉｓｐｅｒＢＹＫ２０２５、ＤｉｓｐｅｒＢＹＫ２０５０、ＤｉｓｐｅｒＢＹＫ２０７０、ＤｉｓｐｅｒＢＹＫ２１５５、ＤｉｓｐｅｒＢＹＫ２１６４、ＢＹＫ２２０Ｓ、ＢＹＫ３００、ＢＹＫ３０６、ＢＹＫ３２０、ＢＹＫ３２２、ＢＹＫ３２５、ＢＹＫ３３０、ＢＹＫ３４０、ＢＹＫ３５０、ＢＹＫ３７７、ＢＹＫ３７８、ＢＹＫ３８０Ｎ、ＢＹＫ４１０、ＢＹＫ４２５、ＢＹＫ４３０（ビックケミー・ジャパン株式会社製）、ディスパロン１７５１Ｎ、ディスパロン１８３１、ディスパロン１８５０、ディスパロン１８６０、ディスパロン１９３４、ディスパロンＤＡ－４００Ｎ、ディスパロンＤＡ－７０３－５０、ディスパロンＤＡ－７２５、ディスパロンＤＡ－７０５、ディスパロンＤＡ－７３０１、ディスパロンＤＮ－９００、ディスパロンＮＳ－５２１０、ディスパロンＮＶＩ－８５１４Ｌ、ヒップラードＥＤ－１５２、ヒップラードＥＤ－２１６、ヒップラードＥＤ－２５１、ヒップラードＥＤ－３６０（楠本化成株式会社）、ＦＴＸ－２０７Ｓ、ＦＴＸ－２１２Ｐ、ＦＴＸ－２２０Ｐ、ＦＴＸ－２２０Ｓ、ＦＴＸ－２２８Ｐ、ＦＴＸ－７１０ＬＬ、ＦＴＸ－７５０ＬＬ、フタージェント２１２Ｐ、フタージェント２２０Ｐ、フタージェント２２２Ｆ、フタージェント２２８Ｐ、フタージェント２４５Ｆ、フタージェント２４５Ｐ、フタージェント２５０、フタージェント２５１、フタージェント７１０ＦＭ、フタージェント７３０ＦＭ、フタージェント７３０ＬＬ、フタージェント７３０ＬＳ、フタージェント７５０ＤＭ、フタージェント７５０ＦＭ（株式会社ネオス製）、ＡＳ－１１００、ＡＳ－１８００、ＡＳ－２０００（東亞合成株式会社製）、カオーセラ２０００、カオーセラ２１００、ＫＤＨ－１５４、ＭＸ－２０４５Ｌ、ホモゲノールＬ－１８、ホモゲノールＬ－９５、レオドールＳＰ－０１０Ｖ、レオドールＳＰ－０３０Ｖ、レオドールＳＰ－Ｌ１０、レオドールＳＰ－Ｐ１０（花王株式会社製）、エバンＵ１０３、シアノールＤＣ９０２Ｂ、ノイゲンＥＡ－１６７、ブライサーフＡ２１９Ｂ、ブライサーフＡＬ（第一工業製薬株式会社製）、メガファックＦ－４７７、メガファック４８０ＳＦ、メガファックＦ－４８２、（ＤＩＣ株式会社製）、シルフェイスＳＡＧ５０３Ａ、ダイノール６０４（日信化学工業株式会社製）、ＳＮスパーズ２１８０、ＳＮスパーズ２１９０、ＳＮレベラーＳ－９０６（サンノプコ株式会社製）、Ｓ－３８６、Ｓ－４２０（ＡＧＣセイミケミカル株式会社製）といったものが例示できる。 The following are known as specific dispersants. That is, Floren DOPA-15B, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solplus AX5, Solplus TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 54000, Sol Six 250, (manufactured by Nippon Lubrizol Corporation), EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA4080, EFKA4080, EFKA4080, EFKA4080, EFKA4080 055, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782, EFKA8503, EFKA8503, EFKA8503 Famex L-12 (manufactured by Ajinomoto Fine Techno Co., Ltd.), TEXAPHOR-UV21, TEXAPHOR-UV61 (manufactured by Cognis Japan Co., Ltd.), DisperBYK101, DisperBYK102, DisperBYK106, DisperBYK108, DisperBYK111, Dispe BYK116, DisperBYK130, DisperBYK140, DisperBYK142, DisperBYK145, DisperBYK161, DisperBYK162, DisperBYK163, DisperBYK164, DisperBYK166, DisperBYK167, DisperBYK168, DisperBYK170, DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070, DisperBY K2155, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK380N, BYK410, BYK425, BYK Spa, BYK425, BYK425, SPA , Disparon 1860, Disparon 1934, Disparon DA-400N, Disparon DA-703-50, Disparon DA-725, Disparon DA-705, Disparon DA-7301, Disparon DN-900, Disparon NS-5210, Disparon NVI-8514L, Hip Lard ED-152, Hip Lard D-216, Hiprad ED-251, Hiprad ED-360 (Enomoto Kasei Co., Ltd.), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL, Aftergent 212P, Aftergent 220P, Aftergent 222F, Aftergent 228P, Aftergent 245F, Aftergent 245P, Aftergent 250, Aftergent 251, Aftergent 710FM, Aftergent 730FM, Aftergent 730LL, Aftergent 730LS, Aftergent 750DM, Aftergent 750FM (manufactured by Neos Co., Ltd.), AS-1100, AS-1800, AS-2000 (manufactured by Toagosei Co., Ltd.), Kaosela 200 Kaosela 2100, KDH-154, MX-2045L, Homogenol L-18, Homogenol L-95, Rheodor SP-010V, Rheodor SP-030V, Rheodor SP-L10, Rheodor SP-P10 (manufactured by Kao Corporation), Evan U103 , Cyanol DC902B, Neugen EA-167, BRYSURF A219B, BRYSURF AL (Daiichi Kogyo Seiyaku Co., Ltd.), Megafuck F-477, MegaFuck 480SF, MegaFuck F-482, (DIC Corporation), Sil Face SAG503A, Dinol 604 (Nisshin Chemical Co., Ltd.), SN Spurs 2180, SN Spurs 2190, SN Leveler S-906 (San Nopco), S-386, S-420 (AGC Seimi Chemical Co., Ltd.) Toi Can be illustrated.
　一般的に、金属微粒子と分散剤のＲＥＤ（Ｒｅｌａｔｉｖｅ　Ｅｎｅｌｇｙ　Ｄｉｆｆｅｒｅｎｃｅ）は小さいほど分散性は良く、１．５以下となる組み合わせが好ましい。金属微粒子とのＲＥＤが１．５以下となる分散剤としては、ＤＩＳＰＥＲＢＹＫ－１１６、ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、ＤＩＳＰＥＲＢＹＫ－１６３、ＤＩＳＰＥＲＢＹＫ－２０００、ＤＳＰＥＲＢＹＫ―２１５５、ＢＹＫ－Ｐ１０５、ＡＮＴＩ－ＴＥＲＲＡ　Ｕ、ＥＦＫＡ－４０１０、ＤＯＰＡ－１７ＨＦがあげられる。 In general, the smaller the RED (relative energy difference) of the metal fine particles and the dispersant, the better the dispersibility, and a combination of 1.5 or less is preferable. Dispersants with a RED of 1.5 or less with fine metal particles include DISPERBYK-116, DISPERBYK-142, DISPERBYK-145, DISPERBYK-163, DISPERBYK-2000, DSPERBYK-2155, BYK-P105, ANTI-TERRA U, And EFKA-4010 and DOPA-17HF.
　Ｈａｎｓｅｎが、Ｈｉｌｄｅｂｒａｎｄの溶解度パラメーター（δ）に関与している分散力、双極子相互作用、水素結合の効果を考慮して提案した数式１に示される溶解度パラメータを用いて、δＤ（分散力による寄与；分子衝突により誘導される双極子の形成によって生じるロンドン力又はファンデルワールス力による寄与として知られている。）、δＰ（極性相互作用による寄与；分子が溶液中に存在する場合に対象とする分子が発生する永久双極子による寄与を意味する。）、δＨ（水素結合による寄与；特定の相互作用を表し、例えば水素結合、酸／塩基結合及びドナー／アクセプター結合による寄与を表す。）を計算し、さらに数式２を用いて相互作用半径Ｒ０、ＨＳＰ間距離Ｒａを計算し、数式３、Ｒ０、Ｒａから、ＲＥＤ（Ｒｅｌａｔｉｖｅ　Ｅｎｅｌｇｙ　Ｄｉｆｆｅｒｅｎｃｅ）を算出することができる。 Hansen's proposed solubility parameter shown in Equation 1 in consideration of the dispersion force, dipole interaction, and hydrogen bond effects involved in the Hildebrand solubility parameter (δ), δD (contribution by dispersion force) Known as the contribution from London or van der Waals forces caused by the formation of dipoles induced by molecular collisions), δP (contributions from polar interactions; targeted when molecules are present in solution ΔH (contribution by hydrogen bond; represents a specific interaction, for example, contribution by hydrogen bond, acid / base bond and donor / acceptor bond) is calculated. Furthermore, the interaction radius R0 and the HSP distance Ra are calculated using Equation 2, and from Equation 3, R0 and Ra, RED (R lative Enelgy Difference) can be calculated.
Figure JPOXMLDOC01-appb-M000003
Figure JPOXMLDOC01-appb-M000003
Figure JPOXMLDOC01-appb-M000004
Figure JPOXMLDOC01-appb-M000004
Figure JPOXMLDOC01-appb-M000005
Figure JPOXMLDOC01-appb-M000005
　熱線遮蔽性粘着剤組成物は公知の方法で作製することができる。例えば、金属微粒子や近赤外吸収色素をアクリル共重合体系粘着剤の主成分となるモノマーへ分散し、次いでこれを重合することで目的の熱線遮蔽性粘着剤組成物を得ることが出来る。また、特許文献１のように予め金属微粒子や近赤外吸収色素の分散液を作製し、モノマーと混合したのち重合させることにより目的の粘着剤を得る方法がある。さらにより簡便な方法としては、金属微粒子や近赤外吸収色素の分散液を直接粘着剤と混合することにより目的の粘着剤組成物を得る方法がある。また、金属微粒子と近赤外吸収色素を分散剤と混合し、これを粘着剤へ分散させることによっても粘着剤組成物が得られる。 The heat ray shielding adhesive composition can be produced by a known method. For example, the target heat ray-shielding pressure-sensitive adhesive composition can be obtained by dispersing metal fine particles or near-infrared absorbing dyes in a monomer that is a main component of an acrylic copolymer-based pressure-sensitive adhesive and then polymerizing it. In addition, as disclosed in Patent Document 1, there is a method in which a dispersion liquid of metal fine particles or near infrared absorbing dye is prepared in advance, mixed with a monomer, and then polymerized and then a desired pressure-sensitive adhesive is obtained. As a simpler method, there is a method of obtaining a desired pressure-sensitive adhesive composition by directly mixing a dispersion of metal fine particles or a near-infrared absorbing dye with a pressure-sensitive adhesive. The pressure-sensitive adhesive composition can also be obtained by mixing metal fine particles and a near-infrared absorbing dye with a dispersant and dispersing the mixture in the pressure-sensitive adhesive.
　熱線遮蔽性粘着シートの製造において、粘着剤の塗布の方法は特に限定されないが、コンマコーター、バーコーター、スピンコーター、スプレーコーター、ロールコーター、グラビアコーター、ナイフコーター又はその他の各種のコーティング装置の使用が可能である。 In the production of the heat ray-shielding pressure-sensitive adhesive sheet, the method of applying the pressure-sensitive adhesive is not particularly limited, but use of a comma coater, bar coater, spin coater, spray coater, roll coater, gravure coater, knife coater or other various coating apparatuses Is possible.
　アクリル共重合体系粘着剤のモノマーあるいは粘着剤に対する金属微粒子と近赤外吸収色素の分散割合は、粘着層の塗工厚と遮蔽性能により決定される。熱線遮蔽性粘着剤を塗工したフィルムの光学性能としては、可視光透過率が高く、日射透過率が低いものが理想的であるが、一般には両者は比例関係にあり、どちらの性能を重視するかにより光学性能を決定することになる。 The dispersion ratio of the metal fine particles and the near-infrared absorbing dye to the monomer of the acrylic copolymer adhesive or the adhesive is determined by the coating thickness of the adhesive layer and the shielding performance. The ideal optical performance of a film coated with a heat-shielding pressure-sensitive adhesive is high in visible light transmittance and low in solar radiation transmittance. The optical performance is determined depending on whether or not to do so.
　この熱線遮蔽性粘着剤を塗工したフィルムを実際に建物および自動車の窓ガラスに貼付し、夏季および冬季の効果をそれぞれ測定したところ、夏季の温度低減効果を十分得るためには、日射透過率は８０％以下とするのが良く、照明コスト並びに冬季の暖房コストの上昇を最小限にするためには、可視光透過率は５０％以上とするのが良いとの結論に達した。したがって、熱線遮蔽性粘着剤を塗工したフィルムの光学特性は、可視光透過率は５０％以上でかつ日射透過率は８０％以下とするのが好ましい。 A film coated with this heat-shielding pressure-sensitive adhesive was actually applied to window glass of buildings and automobiles, and the effects in summer and winter were measured. It has been concluded that the visible light transmittance should be 50% or more in order to minimize the increase in lighting costs and heating costs in winter. Therefore, the optical characteristics of the film coated with the heat ray-shielding pressure-sensitive adhesive are preferably such that the visible light transmittance is 50% or more and the solar radiation transmittance is 80% or less.
　一般に、粘着層の塗工厚は、被接着面への追従性や粘着力および経済性を考慮して通常１０～５０μｍの厚みが採用されるが、この範囲で上記の熱線遮蔽性を与える微粒子の量として、（金属微粒子＋近赤外吸収色素）：樹脂固形分＝３：９７～１：１（重量比）の範囲が好適である。熱線遮蔽剤微粒子の割合がこれより少ない場合は、必要な熱線遮蔽性を得るには５０μｍ以上の膜厚が必要になり、反対に、これより多い場合は、可視光透過率が小さくなり過ぎるからである。さらに、フィルムのヘイズ値は、ガラスの透明性を損なわないものとする必要があり、８％以下とするのが良く、より好ましくは３％以下とするのが良い。 In general, the coating thickness of the pressure-sensitive adhesive layer is usually 10 to 50 μm in consideration of the followability to the adherend surface, adhesive strength and economy, but the fine particles that give the above-mentioned heat ray shielding properties within this range The amount of (metal fine particles + near infrared absorbing dye): resin solid content = 3: 97 to 1: 1 (weight ratio) is preferable. If the proportion of the heat ray shielding fine particles is smaller than this, a film thickness of 50 μm or more is required to obtain the necessary heat ray shielding properties. On the other hand, if the proportion is larger than this, the visible light transmittance becomes too small. It is. Furthermore, the haze value of the film needs to be such that the transparency of the glass is not impaired, and should be 8% or less, more preferably 3% or less.
　本発明を下記実施例、および比較例を挙げて具体的に説明するが、本発明はこれらに限定されるものではない。 The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited thereto.
合成例１（金属微粒子）
　塩化第２スズ（ＳｎＣｌ４・５Ｈ２Ｏ）５．９ｇ及び塩化インジウム（ＩｎＣｌ３）７５．９ｇを水４０００ｍｌに溶解し、これに２％アンモニア水を５８分かけて添加し、ｐＨを最終的に７．８５とすることにより酸化スズおよび酸化インジウムの水和物を共沈させた。この間、液温は５℃を維持するようにした。次いで、該共沈物を洗浄後乾燥、更に９００℃にて２時間焼成し、スズ含有酸化インジウム（ＩＴＯ）微粉末（金属微粒子）を得た。 Synthesis example 1 (metal fine particles)
5.9 g of stannic chloride (SnCl 4 .5H 2 O) and 75.9 g of indium chloride (InCl 3 ) are dissolved in 4000 ml of water, to which 2% aqueous ammonia is added over 58 minutes, and the pH is finally adjusted. In this case, a hydrate of tin oxide and indium oxide was coprecipitated to 7.85. During this time, the liquid temperature was maintained at 5 ° C. Next, the coprecipitate was washed and dried, and further calcined at 900 ° C. for 2 hours to obtain tin-containing indium oxide (ITO) fine powder (metal fine particles).
合成例２（近赤外吸収色素）
　ポリリン酸４０部にバナジル２，３－ナフタロシアニン（Ａｌｄｒｉｃｈ社製）３．９部、フタルイミド（東京化成工業社製）５．０部、パラホルムアルデヒド１．０部を加え、１４０℃で８時間撹拌した後、水３００部に注ぎ、析出した固体をろ過することによりナフタロシアニン系化合物を７．５部得た。 Synthesis Example 2 (Near-infrared absorbing dye)
To 40 parts of polyphosphoric acid, 3.9 parts of vanadyl 2,3-naphthalocyanine (Aldrich), 5.0 parts of phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 part of paraformaldehyde are added and stirred at 140 ° C. for 8 hours. Then, it was poured into 300 parts of water, and the precipitated solid was filtered to obtain 7.5 parts of a naphthalocyanine compound.
製造例１（金属微粒子分散液）
　トルエン溶液７ｍｌに合成例１で得たＩＴＯ合成粒子１．１２ｇ、アセチルアセトン０．７ｇ、分散剤ＤｉｓｐｅｒＢＹＫ１４０を０．１７５ｇ加え、バッチ式ビーズミリング装置（Ｔ．Ｋ．フィルミックス３０－２５型、プライミクス（株）製）の粉砕容器に投入した。解砕ビーズには平均粒径が３０μｍのジルコニアビーズを用い、粉砕容器体積の３５％充填まで充填した。解砕は周速が６．８ｍ／ｓとなるようモーターを設定し、解砕時間は１０分の条件で行った。また、得られた分散体（金属微粒子分散液）を遠心分離機（日立工機株式会社　Ｈｉｍａｃ　ＣＲ１８）を用いて回転数５０００ｒｐｍで１５分間遠心処理を行った。 Production Example 1 (Metal fine particle dispersion)
To 7 ml of toluene solution, 1.12 g of the ITO synthetic particles obtained in Synthesis Example 1, 0.7 g of acetylacetone, and 0.175 g of dispersant DispersBYK140 were added, and a batch type bead milling apparatus (TK Fillmix 30-25 type, Primix ( The product was put into a crushing container manufactured by Co., Ltd. Zirconia beads having an average particle size of 30 μm were used as the crushing beads, and the crushing beads were filled up to 35% of the grinding container volume. The crushing was performed under the condition that the motor was set so that the peripheral speed was 6.8 m / s and the crushing time was 10 minutes. Further, the obtained dispersion (metal fine particle dispersion) was centrifuged for 15 minutes at a rotational speed of 5000 rpm using a centrifuge (Hitachi Koki Co., Ltd. Himac CR18).
製造例２（近赤外線吸収色素分散液１）
　トルエン溶液７ｍｌに合成例２で得た近赤外吸収色素０．２１ｇ、分散剤ＤｉｓｐｅｒＢＹＫ１４０を０．２１ｇ加え、バッチ式ビーズミリング装置（Ｔ．Ｋ．フィルミックス３０－２５型、プライミクス（株）製）の粉砕容器に投入した。解砕ビーズには平均粒径が３０μｍのジルコニアビーズを用い、粉砕容器体積の７０％充填まで充填した。解砕は周速が１０ｍ／ｓとなるようモーターを設定し、解砕時間は３０分の条件で行った。また、得られた分散体を遠心分離機（日立工機株式会社　Ｈｉｍａｃ　ＣＲ１８）を用いて回転数５０００ｒｐｍで１５分間遠心処理を行うことにより、近赤外吸収色素分散液１を得た。 Production Example 2 (Near-infrared absorbing dye dispersion 1)
Add 0.21 g of the near-infrared absorbing dye obtained in Synthesis Example 2 and 0.21 g of the dispersing agent DisperBYK140 to 7 ml of the toluene solution, and use a batch type bead milling apparatus (TK Fillmix 30-25, manufactured by Primix Co., Ltd.) ). Zirconia beads having an average particle diameter of 30 μm were used as the crushing beads, and the crushing beads were filled up to 70% of the crushing vessel volume. The crushing was performed under the condition that the motor was set so that the peripheral speed was 10 m / s and the crushing time was 30 minutes. Moreover, the near-infrared absorption pigment | dye dispersion liquid 1 was obtained by centrifuging the obtained dispersion for 15 minutes at 5000 rpm with a centrifuge (Hitachi Koki Co., Ltd. Himac CR18).
製造例３（近赤外吸収色素分散液２）
　合成例２で得た近赤外吸収色素を２，３-ナフタロシアニン（Ａｌｄｒｉｃｈ社製）に替える以外は製造例２と同様にして近赤外色素分散液２を得た。 Production Example 3 (Near-infrared absorbing dye dispersion 2)
A near-infrared pigment dispersion 2 was obtained in the same manner as in Production Example 2 except that the near-infrared absorbing pigment obtained in Synthesis Example 2 was replaced with 2,3-naphthalocyanine (manufactured by Aldrich).
合成例３（アクリル系粘着剤Ａ）
　モノマーとしてのアクリル酸ｎ－ブチル２９１ｇとアクリル酸９ｇをトルエン３６６ｇに溶解し、アゾビスイソブチロニトリル０．１５ｇを添加して、窒素気流下において７０℃で６時間これらのモノマーを重合してアクリル樹脂共重合体（重量平均分子量：Ｍｗ＝３２万）を得た。さらにトルエンで希釈し、固形分率２９．３６％、粘度２７００ｍＰａｓのアクリル樹脂共重合体溶液を得た。 Synthesis example 3 (acrylic adhesive A)
291 g of n-butyl acrylate and 9 g of acrylic acid as monomers are dissolved in 366 g of toluene, 0.15 g of azobisisobutyronitrile is added, and these monomers are polymerized at 70 ° C. for 6 hours under a nitrogen stream. An acrylic resin copolymer (weight average molecular weight: Mw = 320,000) was obtained. Further, the resultant was diluted with toluene to obtain an acrylic resin copolymer solution having a solid content of 29.36% and a viscosity of 2700 mPas.
熱線遮蔽性粘着剤及び熱線遮蔽性粘着シートの作製
実施例１
　合成例３で得たアクリル系粘着剤Ａ　１００重量部（アクリル酸ブチル：アクリル酸＝９７：３）、製造例１で得たスズ含有酸化インジウム（ＩＴＯ）のトルエン分散液　１４４重量部、製造例２で得た近赤外吸収色素のトルエン分散液　１４．７重量部を均一になるように混合溶解し、熱線遮蔽性粘着剤を得た。また、これを離型シートのポリエステルフィルム（片面側にシリコーン処理を施したもの）（リンテック社製 
３８１１　厚さ：３８μｍ）上にコンマコーターで塗布して乾燥し、離型シートのポリエステルフィルム（片面側にシリコーン処理を施したもの）（リンテック社製 
３８０１　厚さ：３８μｍ）で覆うことにより熱線遮蔽性粘着シート（厚さ：１５μｍ）を作製した。 Production Example 1 of heat ray shielding adhesive and heat ray shielding adhesive sheet
100 parts by weight of acrylic adhesive A obtained in Synthesis Example 3 (butyl acrylate: acrylic acid = 97: 3), 144 parts by weight of toluene dispersion of tin-containing indium oxide (ITO) obtained in Production Example 1, Production Example 14.7 parts by weight of the toluene dispersion of the near-infrared absorbing dye obtained in 2 was mixed and dissolved in a uniform manner to obtain a heat ray shielding adhesive. In addition, this is a release sheet polyester film (silicone treatment on one side) (manufactured by Lintec)
3811 (thickness: 38 μm), coated with a comma coater and dried, release sheet polyester film (one side coated with silicone) (manufactured by Lintec)
3801 (thickness: 38 μm) to produce a heat ray shielding adhesive sheet (thickness: 15 μm).
実施例２
　近赤外吸収色素のトルエン分散液を製造例３で作製したものに替える以外は実施例１と同様にして熱線遮蔽性粘着剤および熱線遮蔽性粘着シートを作製した。 Example 2
A heat ray-shielding pressure-sensitive adhesive and a heat ray-shielding pressure-sensitive adhesive sheet were produced in the same manner as in Example 1, except that the toluene dispersion of the near-infrared absorbing dye was changed to that produced in Production Example 3.
比較例１
　実施例１において近赤外吸収色素のトルエン分散液を混合せず、製造例１で得たスズ含有酸化インジウム（ＩＴＯ）のトルエン分散液　１４４重量部とアクリル系粘着剤Ａ　１００重量部を使用した以外は実施例1と同様にして熱線遮蔽性粘着シート（厚さ：１５μｍ）を作製した。 Comparative Example 1
In Example 1, 144 parts by weight of the toluene dispersion of tin-containing indium oxide (ITO) obtained in Production Example 1 and 100 parts by weight of acrylic adhesive A were used without mixing the toluene dispersion of the near infrared absorbing dye. A heat ray shielding adhesive sheet (thickness: 15 μm) was prepared in the same manner as Example 1 except for the above.
実施例３
　実施例１、実施例２および比較例１で作製した熱線遮蔽性粘着シートを下記に示す方法で熱線遮蔽性試験を実施した。その結果を表１に示す。
試験方法
　試験環境：内径幅１５０ｍｍ×長さ２３５ｍｍ×高さ１１０ｍｍの外気温遮断性と気密性とを有する試験箱を準備し、この試験箱の天井中央部に赤外ランプ（１００Ｖ、２５０Ｗ：東芝株式会社）を前記試験箱天井部から高さ４０ｃｍの位置に設置し、遮熱性評価用試験装置を構成した。次に試験箱天井部分に作製した熱線遮蔽性粘着シートを設置し、四方をテープで貼り付け固定した。また、この試験箱内部の中央部に、ランプの光が直接当たらないよう、温度計を設置した。その後、ランプを点灯し、温度を１０秒ごとに測定し、３０分後の試験箱内温度を測定した。なお、上記試験箱は２５℃程度の部屋に設置した。この試験において比較例で作成した熱線遮蔽性粘着シートと本発明の熱線遮蔽性粘着シートを用いた時の箱内温度を比較し、本発明の熱線遮蔽性粘着シートを用いた箱内温度が低ければ、熱線遮蔽効果が向上していることになる。なお、箱内温度差の計算方法は比較例で作製した熱線遮蔽性粘着シートを用いた箱内温度から本発明の熱線遮蔽性粘着シートを用いた箱内温度を差し引くことにより導かれる。 Example 3
A heat ray shielding test was conducted on the heat ray shielding adhesive sheets produced in Example 1, Example 2 and Comparative Example 1 by the method shown below. The results are shown in Table 1.
Test method Test environment: A test box having an inner diameter width of 150 mm, a length of 235 mm, and a height of 110 mm and having an outside air-blocking property and airtightness is prepared. Co., Ltd.) was installed at a height of 40 cm from the ceiling of the test box to constitute a test apparatus for evaluating thermal insulation. Next, the heat ray shielding adhesive sheet produced in the ceiling part of the test box was installed, and the four sides were fixed with tape. In addition, a thermometer was installed in the center of the test box so that the light from the lamp was not directly applied. Thereafter, the lamp was turned on, the temperature was measured every 10 seconds, and the temperature in the test box after 30 minutes was measured. The test box was installed in a room at about 25 ° C. In this test, the temperature inside the box when the heat ray shielding adhesive sheet prepared in the comparative example and the heat ray shielding adhesive sheet of the present invention were used was compared, and the temperature inside the box using the heat ray shielding adhesive sheet of the present invention was low. In this case, the heat ray shielding effect is improved. In addition, the calculation method of the temperature difference in a box is guide | induced by subtracting the temperature in a box using the heat ray shielding adhesive sheet of this invention from the temperature in a box using the heat ray shielding adhesive sheet produced by the comparative example.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表１に示したように、比較例１で作製した熱線遮蔽性粘着シートを用いた際の箱内温度は７２．５℃であった。一方、本発明の実施例１、実施例２で作製した熱線遮蔽性粘着シートを用いた際の箱内温度はそれぞれ６８．４℃、６８．０℃であった。つまり、本発明の実施例１、実施例２で作製した熱線遮蔽性粘着シートの箱内温度は比較例で作製した熱線遮蔽性粘着シートの箱内温度よりもそれぞれ４．１℃、４．５℃低かった。この結果から、本発明の熱線遮蔽性粘着シートは熱線遮蔽効果が向上していることが明らかになった。 As shown in Table 1, the temperature in the box when using the heat ray shielding adhesive sheet produced in Comparative Example 1 was 72.5 ° C. On the other hand, the temperature in the box at the time of using the heat ray shielding adhesive sheet produced in Example 1 and Example 2 of the present invention was 68.4 ° C. and 68.0 ° C., respectively. That is, the temperature in the box of the heat ray shielding adhesive sheet produced in Example 1 and Example 2 of the present invention was 4.1 ° C. and 4.5 ° C., respectively, than the temperature in the box of the heat ray shielding adhesive sheet produced in the comparative example. ℃ was low. From this result, it became clear that the heat ray shielding adhesive sheet of the present invention has an improved heat ray shielding effect.
　本発明は、熱線遮蔽性金属微粒子と近赤外吸収色素を、分散剤を用いて粘着剤に分散させることにより、従来の熱線遮蔽性粘着シートと比較して、熱線による温度上昇を抑えることができる。これにより本発明は住宅や自動車の空間の温度上昇を抑え、空調機器の負荷を軽減し、省エネルギーや地球環境問題に貢献できる。 In the present invention, heat ray-shielding metal fine particles and near-infrared absorbing dye are dispersed in a pressure-sensitive adhesive using a dispersant, thereby suppressing a temperature rise due to heat rays as compared with a conventional heat-ray-shielding pressure-sensitive adhesive sheet. it can. Thereby, this invention can suppress the temperature rise of the space of a house or a motor vehicle, can reduce the load of an air-conditioning apparatus, and can contribute to energy saving and a global environmental problem.

Claims (9)

  1. 　（Ａ）金属微粒子、（Ｂ）アクリル系粘着剤、（Ｃ）分散剤、及び（Ｄ）近赤外吸収色素を含有する熱線遮蔽性粘着剤組成物。 A heat ray-shielding pressure-sensitive adhesive composition containing (A) metal fine particles, (B) an acrylic pressure-sensitive adhesive, (C) a dispersant, and (D) a near-infrared absorbing dye.
  2. 　（Ａ）金属微粒子が酸化スズ、酸化インジウム、酸化亜鉛の群から選ばれる一種の金属微粒子であることを特徴とする請求項１に記載の熱線遮蔽性粘着剤組成物。 (A) The heat ray-shielding pressure-sensitive adhesive composition according to claim 1, wherein the metal fine particles are a kind of metal fine particles selected from the group consisting of tin oxide, indium oxide and zinc oxide.
  3. 　（Ｂ）アクリル系粘着剤が、カルボキシ基、もしくは酸無水物含有モノマーの構造単位の割合がポリマー中の全モノマー構造単位の１～５％であるポリマーであることを特徴とする請求項１または２の何れか一項に記載の熱線遮蔽性粘着剤組成物。 (B) The acrylic pressure-sensitive adhesive is a polymer in which the proportion of structural units of a carboxy group or an acid anhydride-containing monomer is 1 to 5% of the total monomer structural units in the polymer. The heat ray shielding adhesive composition as described in any one of 2.
  4. 　（Ｂ）アクリル系粘着剤の重量平均分子量が１０万～１２０万であることを特徴とする請求項１から３の何れか一項に記載の熱線遮蔽性粘着剤組成物。 (B) The heat ray-shielding pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the acrylic pressure-sensitive adhesive has a weight average molecular weight of 100,000 to 1,200,000.
  5. 　（Ｄ）近赤外吸収色素がフタロシアニン系化合物、ナフタロシアニン系化合物、及び／又はジイモニウム系化合物であることを特徴とする請求項１乃至４の何れか一項に記載の熱線遮蔽性粘着剤組成物。 (D) The near-infrared absorbing dye is a phthalocyanine compound, a naphthalocyanine compound, and / or a diimonium compound, The heat ray-shielding pressure-sensitive adhesive composition according to any one of claims 1 to 4 object.
  6. 　（Ｄ）近赤外吸収色素が式（１）で示されるナフタロシアニン系化合物である請求項５に記載の熱線遮蔽性粘着剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）中、Ｍは金属原子、金属酸化物、金属水酸化物、若しくは金属ハロゲン化物、又は水素原子を表し、Ｘは低級アルキル基、低級アルコキシ基、置換アミノ基、ニトロ基、ハロゲン基、ヒドロキシ基、カルボキシ基、スルホン酸基、スルホンアミド基を表す。Ａは二価の架橋基を、Ｙはスルホン酸基、カルボキシ基、第１～２級アミノ基の窒素原子上の水素の少なくとも１つを除いた残基、又は窒素を含む複素環の窒素原子上の水素の少なくとも１つを除いた残基を表す。ｍ及びｎはいずれも平均値であり、ｍ、ｎはそれぞれ０以上１２以下、かつ、ｍとｎとの和は０以上１２以下である。］     (D) The heat ray-shielding pressure-sensitive adhesive composition according to claim 5, wherein the near-infrared absorbing dye is a naphthalocyanine compound represented by the formula (1).
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (1), M represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, or a hydrogen atom, and X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen atom. Represents a group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group. A is a divalent bridging group, Y is a sulfonic acid group, a carboxy group, a residue obtained by removing at least one of the hydrogen atoms on the nitrogen atom of the primary or secondary amino group, or a nitrogen atom of a heterocyclic ring containing nitrogen Represents a residue excluding at least one of the above hydrogens. m and n are both average values, m and n are each 0 or more and 12 or less, and the sum of m and n is 0 or more and 12 or less. ]
  7. 式（１）中のＭはＶＯであり、Ａは炭素数１～３のアルキレン基であり、Ｙは置換基を有してもよいフタルイミド基である請求項６に記載の熱線遮蔽性粘着剤組成物。 7. The heat ray-shielding pressure-sensitive adhesive according to claim 6, wherein M in the formula (1) is VO, A is an alkylene group having 1 to 3 carbon atoms, and Y is a phthalimide group which may have a substituent. Composition.
  8. 式（１）中のＭはＣｕであり、Ａは炭素数１～３のアルキレン基であり、Ｙは置換基を有してもよいフタルイミド基である請求項６に記載の熱線遮蔽性粘着剤組成物。 7. The heat ray-shielding pressure-sensitive adhesive according to claim 6, wherein M in the formula (1) is Cu, A is an alkylene group having 1 to 3 carbon atoms, and Y is a phthalimide group which may have a substituent. Composition.
  9. 請求項１乃至８の何れか一項に記載の熱線遮蔽性粘着剤組成物を塗布してなる熱線遮蔽性粘着シート。 The heat ray shielding adhesive sheet formed by apply | coating the heat ray shielding adhesive composition as described in any one of Claims 1 thru | or 8.
PCT/JP2012/077972 2011-11-01 2012-10-30 Heat ray shielding adhesive composition and heat ray shielding adhesive sheet WO2013065662A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9903988B2 (en) 2012-12-11 2018-02-27 3M Innovative Properties Company Stabilized infrared absorbing dispersions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08281860A (en) * 1995-04-11 1996-10-29 Sumitomo Osaka Cement Co Ltd Heat ray shielding film
JPH09208918A (en) * 1996-01-30 1997-08-12 Kureha Chem Ind Co Ltd Acrylic resin composition
JP2005146143A (en) * 2003-11-17 2005-06-09 Seed Co Ltd Ultraviolet-curing heat-ray-shielding hard coat composition
JP2006257223A (en) * 2005-03-16 2006-09-28 Lintec Corp Adhesive composition
WO2011024787A1 (en) * 2009-08-24 2011-03-03 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH108010A (en) * 1996-06-28 1998-01-13 Sumitomo Osaka Cement Co Ltd Heat ray blocking tacky agent, its production and heat ray blocking transparent sheet
JP2004067923A (en) * 2002-08-08 2004-03-04 Mitsui Chemicals Inc Film for awning

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08281860A (en) * 1995-04-11 1996-10-29 Sumitomo Osaka Cement Co Ltd Heat ray shielding film
JPH09208918A (en) * 1996-01-30 1997-08-12 Kureha Chem Ind Co Ltd Acrylic resin composition
JP2005146143A (en) * 2003-11-17 2005-06-09 Seed Co Ltd Ultraviolet-curing heat-ray-shielding hard coat composition
JP2006257223A (en) * 2005-03-16 2006-09-28 Lintec Corp Adhesive composition
WO2011024787A1 (en) * 2009-08-24 2011-03-03 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9903988B2 (en) 2012-12-11 2018-02-27 3M Innovative Properties Company Stabilized infrared absorbing dispersions
US10895673B2 (en) 2012-12-11 2021-01-19 3M Innovative Properties Company Stabilized infrared absorbing dispersions

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