TWI553071B - Hotline Masking Adhesive Composition and Hot Wire Masking Adhesive Sheet - Google Patents

Description

Heat shielding adhesive composition and heat shielding adhesive sheet

The present invention relates to a heat ray-shielding adhesive composition which can be used for adhering to a window glass or the like to efficiently shield a heat ray, and a heat ray-shielding adhesive sheet using the same.

In recent years, it has been demanded to reduce the load on air conditioners in terms of energy saving or global environmental problems. For example, it is required to provide a heat shield material that shields a hot wire from sunlight in a window of a house or a car, thereby suppressing an increase in temperature in a room or a car. There are various materials having heat shielding properties, and Patent Document 1 discloses an adhesive which imparts heat shielding properties and an adhesive sheet thereof. This adhesive sheet is characterized in that the heat-shielding adhesive is processed into a sheet shape, and has a feature that it can be processed into an arbitrary shape in advance and has reworkability secondary workability. However, the heat-shielding property of the heat-shielding adhesive sheet is not sufficient, and further improvement is desired.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Special Patent No. 10-8010

An object of the present invention is to provide a heat ray-shielding adhesive composition and a heat ray-shielding adhesive sheet which are improved in heat ray shielding properties as compared with the conventional heat ray-shielding adhesive sheet.

The inventors of the present invention conducted intensive studies to obtain a heat-shielding adhesive sheet in which heat ray shielding properties are greatly improved, and as a result, it has been found that metal fine particles including near-indium-doped indium oxide, near-infrared absorbing pigment, and dispersion can be obtained. The present invention is accomplished by obtaining a heat-shielding adhesive composition which can effectively shield the heat rays and a heat-shielding adhesive sheet which is processed into a sheet shape.

That is, the present invention relates to the following: "(1) A heat ray-shielding adhesive composition containing (A) metal fine particles, (B) an acrylic adhesive, (C) a dispersant, and (D) near-infrared absorption. (2) The heat shielding adhesive composition according to (1), wherein (A) the metal microparticles are selected from the group consisting of tin oxide, indium oxide, and zinc oxide; and (3) as (1) or (2) The heat shielding adhesive composition according to any one of the preceding claims, wherein (B) the ratio of the acrylic resin-based carboxyl group or the structural unit containing the acid anhydride-containing monomer is 1 to 1 of all monomer structural units in the polymer. (4) The heat ray-shielding adhesive composition according to any one of (1) to (3), wherein (B) the acrylic-based adhesive has a weight average molecular weight of from 100,000 to 1,200,000; The heat shielding adhesive composition according to any one of (1) to (4), wherein (D) a near-infrared absorbing pigment-based phthalocyanine-based compound, a naphthalocyanine-based compound, and/or a diimmonium-based compound (6) The heat ray-shielding adhesive composition according to (5), wherein (D) the near-infrared absorbing pigment system is a naphthalocyanine-based compound represented by the formula (1): [Chemical Formula 1] [In the formula (1), M represents a metal atom, a metal oxide, a metal hydroxide or 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 group. a group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfonylamino group; A represents a divalent crosslinking group, and Y represents a sulfonic acid group, a carboxyl group, and a residue of at least one hydrogen on the nitrogen atom of the amine group 1 to 2 Or removing at least one hydrogen residue on the nitrogen atom of the nitrogen-containing heterocyclic ring; m and n are 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) The heat shielding adhesive composition according to (6), wherein M in the formula (1) is VO, A is an alkylene group having 1 to 3 carbon atoms, and Y is an ortho-phenylene group which may have a substituent. (8) The heat ray-shielding adhesive composition of (6), wherein M in the formula (1) is Cu, A is an alkylene group having 1 to 3 carbon atoms, and Y may have (9) A heat ray-shielding adhesive sheet obtained by applying the heat ray-shielding adhesive composition according to any one of (1) to (8).

According to the present invention, there can be provided a heat ray-shielding adhesive sheet which is led by doping tin-doped indium oxide by using a dispersing agent. The heat-shielding adhesive composition in which the metal fine particles and the near-infrared absorbing pigment are dispersed in the acrylic adhesive is processed into a sheet shape, thereby further suppressing the heat line by comparison with the previous heat shielding adhesive sheet The temperature caused rises. Thereby, the temperature rise of the space of the house or the automobile can be suppressed, and the load of the air conditioner can be reduced, so that the present invention can contribute to the solution of energy saving or global environmental problems.

The present invention will be described in detail. The adhesive composition for forming a heat ray-shielding adhesive sheet of the present invention is characterized in that a metal microparticle containing a tin-doped indium oxide and a near-infrared absorbing pigment are dispersed in an acrylic adhesive using a dispersing agent, the adhesive The composition can also be processed into a sheet.

The metal microparticles used in the heat shielding adhesive composition are suitable for absorption of visible light and good absorption properties for light in the near-infrared to far-infrared region. Such metal fine particles can be exemplified by a conductive metal oxide having a plasma wavelength in the near-infrared region. Specifically, tin oxide, indium oxide, zinc oxide, tungsten oxide, chromium oxide, molybdenum oxide, or the like can be exemplified. Among them, tin oxide, indium oxide, and zinc oxide, which are particularly light-absorptive in the visible light region, are preferred.

Further, it is preferable to dope the third component for improving the electrical conductivity of the oxides. As a dopant for achieving the purpose, Sb, V, Nb, Ta, etc. may be selected with respect to tin oxide, and Zn, Al, Sn, Sb, Ga, Ge, etc. may be selected with respect to indium oxide, and may be relative to zinc oxide. Al, Ga, In, Sn, Sb, Nb, and the like are selected.

As a method of preparing metal microparticles, as long as the particle diameter is 100 nm The following is not particularly limited, and a known method such as a gas phase synthesis method or a liquid layer synthesis method can be used. For example, regarding the indium oxide fine particles, the method disclosed in Japanese Patent Laid-Open No. Hei 6-227815 can be used. That is, it is a method of neutralizing an aqueous solution containing a salt of a specific metal fine particle element by a base, filtering, washing the obtained precipitate, and heat-treating at a high temperature, thereby obtaining metal fine particles. Further, the tin oxide fine particles and the zinc oxide fine particles can be exemplified by Japanese Patent Laid-Open No. Hei 2-105875 and Japanese Patent Laid-Open No. Hei 6-234522, respectively.

As a method of dispersing metal fine particles into an organic solvent, the prior method can be used. That is, the metal fine particles and the organic solvent may be mixed at a specific ratio, and a dispersant, a surfactant, or the like may be added to the mixture as needed, and a sand mill, an attritor, a bead mill, a homogenizer, a roll mill, or the like may be used. Disperse the device to disperse the mixture.

The half-height width of the first main peak obtained by the XRD (X-ray diffraction) pattern of the metal microparticles of the present invention is 0.01 to 0.8°, and if the full width at half maximum is 0.01° or less, The diameter becomes large and it is difficult to ensure transparency. Further, if the full width at half maximum exceeds 0.8°, it is difficult to express sufficient heat shielding properties. Further, a preferred lower limit of the full width at half maximum of the metal fine particles is 0.1, preferably an upper limit of 0.8, a more preferred lower limit of 0.2, and a more preferred upper limit of 0.5.

The metal microparticles used in the present invention have a specific surface area of 5 to 200 m ³ /g as measured by a BET (Brunauer-Emmett-Teller) method, and more preferably 10 to 150 m ^{3 .} /g, especially preferably 10~100 m ³ /g. When the specific surface area measured by the BET method is less than 5 m ³ /g, since the primary particle diameter is large, in the case of a sheet or a film, a coating material, or a resin composition, there is a problem that the processed surface is not smooth. Further, there are disadvantages such as the inability to expect transparency and the like. On the other hand, in the case where the BET specific surface area is more than 200 m ³ /g, there is a problem that a special technique is required for the production, and sufficient crystallinity cannot be obtained, thereby impairing the heat ray shielding property. Further, the BET method is a method in which a molecule or ion having a known size is adsorbed on the surface of a powder particle, and the specific surface area of the sample is measured based on the amount.

The near-infrared absorbing dye is a general term for a pigment that absorbs near-infrared rays (wavelengths of about 780 to 2000 nm) closest to the visible region in infrared rays. Examples of the types of near-infrared absorbing pigments include azo, ammonium, and lanthanides. A cyanine system, a diammonium system, a dithiol metal complex system, a squaraine system, a phthalocyanine system, a naphthalocyanine system, or the like. From the viewpoint of improving durability, a phthalocyanine system, a naphthalocyanine system, and a diimonium system are preferred, and from the viewpoint of efficiently blocking the heat line, a naphthalocyanine system is preferred, and particularly preferably A compound represented by the above formula (1). In the above 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 system 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.

Specific examples of the metal atom in the above M include 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, and the like.

Examples of the metal oxide include VO, GeO, and the like. Examples of the metal hydroxide include Si(OH) ₂ , Cr(OH) ₂ , Sn(OH) ₂ , AlOH, and the like. Examples of the metal halide include SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, ZrCl, and AlCl. 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.

As the above, 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. A heat-shielding adhesive sheet made of a toluene dispersion of a naphthalocyanine-based compound of Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, or Bi, shielded by a heat line In the sex test, the temperature inside the box used in the test was lowered, and a good heat ray shielding effect was exhibited. Further, in particular, when a naphthalocyanine-based compound in which M is Cu is used, the temperature inside the cell is remarkably lowered, and an excellent heat ray blocking effect is exhibited, which is preferable. In the case of using a naphthalocyanine-based compound in which M is VO, the temperature inside the cell is also remarkably lowered, and an excellent heat ray blocking effect is exhibited, which is preferable.

X represents a lower alkyl group, a lower alkoxy group, a substituted amino group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, a sulfonic acid group or a sulfonylamino group. Examples of the cross-linking group of the A-type divalent group include an alkylene group having 1 to 3 carbon atoms, -CO ₂ -, -SO ₂ -, -SO ₂ NH(CH ₂ ) _a - (here, a represents 0~ 4), preferably an alkylene group having 1 to 3 carbon atoms, a being -SO ₂ NH- of 0, more preferably an alkylene group having 1 to 3 carbon atoms. Y represents a sulfonic acid group, a carboxyl group, a residue of at least one hydrogen on the nitrogen atom of the 1st to 2nd amino group, or a residue of at least one hydrogen on the nitrogen atom of the nitrogen-containing heterocyclic ring, and examples thereof include a carboxyl group. a sulfonic acid group, a phthalic acid imine group which may have a substituent, a piperazinyl group which may have a substituent, a piperidinyl group which may have a substituent, etc., preferably a carboxyl group, a sulfonic acid group, The phthalic acid imine group having a substituent may also be used, and more preferably an phthalimido group having a substituent. Further, Y is a substituent of a phthalimido group which may have a substituent, a piperazinyl group which may have a substituent, or a piperidinyl group which may have a substituent, and represents a hydrogen atom and a lower stage. The alkyl group, the lower alkoxy group, the substituted amine group, the nitro group, the halogen group, and the sulfonic acid group are preferably a hydrogen atom or a halogen group.

The substituted amino group in the present invention is not particularly limited, and examples thereof include an amine group substituted with a lower alkyl group. Further, the lower alkyl group and the lower alkoxy group each represent a linear or branched alkyl group having 1 to 4 carbon atoms and an alkoxy group. As a method of dispersing the near-infrared absorbing pigment into an organic solvent, the prior method can be used. That is, the near-infrared absorbing pigment and the organic solvent may be mixed at a specific ratio, and a dispersant, a surfactant, etc. may be added to the mixture as needed, and a sand mill, a grinder, a bead mill, a homogenizer, a roll mill may be used. The mixture is dispersed by a dispersing device such as a machine.

The heat ray-shielding adhesive sheet in which the metal microparticles and the near-infrared absorbing dye are dispersed or the heat-shielding adhesive sheet obtained by processing the composition into a sheet shape is attached to the window glass to block the sunlight. The hot wire component in the wavelength is used for the purpose, and therefore the first condition is that the weather resistance is good. Therefore, the adhesive resin used in the embodiment is preferably an acrylic copolymer-based adhesive resin having good weather resistance. Acrylic copolymer adhesives can usually be obtained by lowering the main monomer of the polymer with a lower glass transition point than the glass transition point. It is made by copolymerization of high comonomer.

Examples of the monomer which is a main component of the acrylic copolymer-based adhesive include an alkyl acrylate having a carbon number of 2 to 14 in an alkyl group having a lower glass transition point or a carbon number of 4 to 16 in an alkyl group. The alkyl acrylate may be used in combination with the main monomer with a glass transition point higher than that and may be copolymerized with the monomers.

As the alkyl acrylate monomer having a lower glass transition point, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid can be exemplified. Dibutyl ester, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, isostearyl acrylate, and the like.

Further, examples of the alkyl methacrylate monomer having a low glass transition point include 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.

Further, examples of the copolymerizable monomer include vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, and methyl acrylate.

In addition to the above monomers, in order to obtain the desired adhesive properties, (meth)acrylic acid, itaconic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid may also be used. Dimethylaminoethyl ester, acrylamide, methylol decylamine, dimethyl methacrylamide, glycidyl methacrylate, maleic anhydride or the like is used as a monomer having a functional group.

Further, regarding the molecular weight, in order to have a large influence on the dispersibility of the metal fine particles and the near-infrared absorbing pigment, the weight average molecular weight of the acrylic adhesive The amount is preferably from 100,000 to 1.2 million. More preferably 200,000 to 800,000.

The degree of crosslinking of the polymer material constituting the adhesive is not particularly limited depending on various conditions such as the type and combination of the adhesive (adhesive composition). The adhesive composition may also contain a plasticizer as needed. Examples of the plasticizer include esters such as phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipate, sebacate, phosphotriester or glycol ester. Alternatively, the oil, the liquid polyether, the liquid terpene, the other liquid resin, or the like may be used, or one of these may be used or a mixture of two or more of them may be used. Such a plasticizer is preferably one which is compatible with an adhesive. Further, in addition to the above plasticizer, the adhesive composition may contain various additives such as an ultraviolet absorber or an antioxidant as needed.

As the dispersing agent, representative are fatty acid salts (soap), α-sulfofatty acid ester salts (MES), alkylbenzenesulfonates (ABS), linear alkylbenzenesulfonates (LAS), and alkyl groups. Low-molecular anionic compound such as sulfate (AS), alkyl ether sulfate (AES), alkyl trisulfate; fatty acid ethanol decylamine, polyoxyethylene alkyl ether (AE), polyoxygen Low molecular nonionic compounds such as ethylene alkyl phenyl ether (APE), sorbitol, and sorbitan; alkyl trimethylammonium salts, dialkyl dimethyl ammonium chlorides, alkyl pyridinium chlorides, and the like a low molecular cationic compound; a low molecular amphoteric compound such as an alkanocarboxybetaine, a sulfobetaine or a lecithin; or a formalin polycondensate of a naphthalenesulfonate, a polystyrene sulfonate, Polyacrylate, copolymer salt of vinyl compound and carboxylic acid monomer, polymer aqueous dispersant represented by carboxymethyl cellulose, polyvinyl alcohol, etc.; polyalkyl acrylate partial alkyl ester, polyalkylene polyamine Polymer non-aqueous dispersant; A polymer cationic dispersant such as ethyl imine or an aminoalkyl methacrylate copolymer is used, but as long as it can be preferably used in the particles of the present invention, the form exemplified herein is not excluded. Other than the structure.

As a dispersing agent, if it has a specific name, it is as follows. That is, Flowlen DOPA-15B, Flowlen 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, Solmics 250 (manufactured by Lubrizol, Japan); EFKA 4008, EFKA 4009, EFKA 4010, EFKA 4015, EFKA 4046, EFKA 4047, EFKA 4060, EFKA 4080, EFKA 7462, EFKA 4020, EFKA 4050, EFKA 4055, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 6220, EFKA 6225, EFKA 6700, EFKA 6780, EFKA 6782 EFKA 8503 (manufactured by EFKA Additives); Ajisper PA111, Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PN411, FAMEX L-12 (manufactured by Ajinomoto Fine-Techno Co., Ltd.); TEXAPHOR-UV21, TEXAPHOR-UV61 (Cognis Japan) Co., Ltd. manufacturing); DisperBYK101, DisperBYK102, DisperBYK106, DisperBYK108, Disper BYK111, 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 (manufactured by BYK-Chemie Japan Co., Ltd.); Disparlon 1751N, Disparlon 1831, Disparlon 1850, Disparlon 1860, Disparlon 1934, Disparlon DA-400N, Disparlon DA-703-50, Disparlon DA-725, Disparlon DA-705, Disparlon DA-7301, Disparlon DN-900, Disparlon NS-5210, Disparlon NVI-8514L, HIPLAAD ED- 152, HIPLAAD ED-216, HIPLAAD ED-251, HIPLAAD ED-360 (Nanben Chemical Co., Ltd.); FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX- 750LL, Ftergent 212 P, Ftergent 220P, Ftergent 222F, Ftergent 228P, Ftergent 245F, Ftergent 245P, Ftergent 250, Ftergent 251, Ftergent 710FM, Ftergent 730FM, Ftergent 730LL, Ftergent 730LS, Ftergent 750DM, Ftergent 750FM (manufactured by Neos Co., Ltd.); AS-1100, AS-1800, AS-2000 (manufactured by Toagosei Co., Ltd.); Kaosera 2000, Kaosera 2100, KDH-154, MX-2045L, Homogenol L- 18. Homogenol L-95, Rheodol SP-010V, Rheodol SP-030V, Rheodol SP-L10, Rheodol SP-P10 (manufactured by Kao Co., Ltd.); Evan U103, Seanol DC902B, Noigen EA-167, Plysur fA219B, Plysur fAL (manufactured by First Industrial Pharmaceutical Co., Ltd.); Megafac F-477, Megafac 480SF, Megafac F-482, (manufactured by DIC Corporation); Sylface SAG503A, Dynol 604 (manufactured by Nissin Chemical Industry Co., Ltd.); SN sperse 2180, SN sperse 2190, SN leveler-S-906 (manufactured by San Nopco Co., Ltd.); S-386, S-420 (manufactured by AGC Seimi Chemical Co., Ltd.).

In general, the smaller the RED (Relative Energy Difference) of the metal fine particles and the dispersant, the better the dispersibility, and it is preferably a combination of 1.5 or less. As a dispersing agent having a RED of 1.5 or less with metal fine particles, there are mentioned DISPERBYK-116, DISPERBYK-142, DISPERBYK-145, DISPERBYK-163, DISPERBYK-2000, DSPERBYK-2155, BYK-P105, ANTI-TERRAU, EFKA- 4010, DOPA-17HF.

Using Hansen to consider the solubility parameter expressed by Equation 1 for the dispersive force, dipole interaction, and hydrogen bonding effect of Hildebrand's solubility parameter (δ), calculate δD (the effect of dispersive force generation; by using molecules London force or van der Waals generated by the formation of a dipole induced by a collision Known as the effect), δP (the effect of the polar interaction; the role of the permanent dipole produced by the molecule as the molecule in the case of the molecule), δH (the role of hydrogen bonding) ; indicates a specific interaction, such as the role of hydrogen bonding, acid/base bonding, and donor/acceptor bonding), and then using Equation 2 to calculate the interaction radius R0, the distance Ra between HSP, and according to the formula 3. R0 and Ra can calculate RED (Relative Energy Difference).

[Number 2] (R _a ) ² = 4 ( δ _D2 - δ _D1 ) ² + ( δ _P2 - δ _P1 ) ² + ( δ _H2 - δ _H1 ) ²

[Number 3] RED=R _a /R _o

The heat ray-shielding adhesive composition can be produced by a known method. For example, metal fine particles or a near-infrared absorbing pigment can be dispersed in a monomer which is a main component of an acrylic copolymer-based adhesive, and then a target heat-shielding adhesive composition can be obtained by polymerizing the same. Further, there is a method in which a dispersion of metal fine particles or a near-infrared absorbing dye is prepared in advance as in Patent Document 1, and the monomer is mixed and polymerized to obtain a target adhesive. Further, as a more convenient method, there is a method in which a target adhesive composition is obtained by mixing a dispersion of metal fine particles or a near-infrared absorbing pigment with a direct adhesive. Further, the metal fine particles and the near-infrared absorbing dye are mixed with a dispersing agent and dispersed in an adhesive, whereby an adhesive composition can also be obtained.

In the manufacture of the heat-shielding adhesive sheet, the method of applying the adhesive is not particularly limited, and a notch coater, a bar coater, a spin coater, a spray coater, a roll coater can be used. , gravure coater, knife coater or other various coating devices.

The dispersion ratio of the metal fine particles and the near-infrared absorbing dye to the monomer or the adhesive of the acrylic copolymer-based adhesive is determined by the coating thickness and the shielding property of the adhesive layer. The optical properties of the film coated with the heat ray-shielding adhesive are preferably such that the visible light transmittance is high and the solar light transmittance is low, and generally there is a proportional relationship between the two, and the optical performance is determined depending on which performance is emphasized.

The film coated with the heat-shielding adhesive is actually attached to the window glass of the building and the automobile, and the effects of summer and winter are respectively measured, and the following conclusions are obtained: in order to fully obtain the temperature reduction effect in summer, the solar transmittance It is preferably 80% or less, and in order to minimize the increase in lighting cost and heating cost in winter, the visible light transmittance is preferably 50% or more. Therefore, the optical property of the film coated with the heat ray-shielding adhesive is preferably a visible light transmittance of 50% or more and a solar energy transmittance of 80% or less.

In general, the coating thickness of the adhesive layer is usually 10 to 50 μm in consideration of the followability or adhesion to the adhesive surface and economy, and the amount of the heat-shielding fine particles is given in the range. Good (metal microparticles + near-infrared absorbing pigment): resin solids = 3:97~1:1 (weight ratio) range. The reason is that when the ratio of the heat shielding agent fine particles is less than this range, in order to obtain the desired heat ray shielding property, a film thickness of 50 μm or more is required, and conversely, when it is more than this range, it is visible. The light transmittance becomes too small. Further, the turbidity of the film must be such that it does not impair the transparency of the glass, and is preferably 8% or less, more preferably 3% or less.

[Examples]

The present invention will be specifically described by way of the following examples and comparative examples, but the present invention is not limited thereto.

Synthesis Example 1 (Metal Microparticles)

By dissolving 4.9 g of tin tetrachloride (SnCl ₄ ‧5H ₂ O) and 75.9 g of indium chloride (InCl ₃ ) in 4000 ml of water, 2% aqueous ammonia was added thereto over 58 minutes to bring the pH to 7.85. Thereby, the hydrate of tin oxide and indium oxide is coprecipitated. In the meantime, the liquid temperature was maintained at 5 °C. Then, the coprecipitate was washed, dried, and further calcined at 900 ° C for 2 hours to obtain tin (Indium Tin Oxide) fine powder (metal fine particles).

Synthesis Example 2 (near-infrared absorbing pigment)

By adding vanadium oxy 2,3-naphthalocyanine (manufactured by Aldrich Co., Ltd.) to 3.9 parts of polyphosphoric acid, 5.0 parts of phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.0 part of paraformaldehyde, at 140 After stirring at ° C for 8 hours, 300 parts of water was poured, and the precipitated solid was filtered to obtain 7.5 parts of a naphthalocyanine-based compound.

Production Example 1 (Metal Microparticle Dispersion)

To 7 ml of the toluene solution, 1.12 g of ITO synthetic particles obtained in Synthesis Example 1, 0.7 g of acetamidine acetone, and 0.175 g of dispersant DisperBYK140 were added, and the mixture was put into a batch type bead milling apparatus (TKfilmics Model 30-25, primix). (manufactured)) in the pulverization container. The crushed particles were zirconia particles having an average particle diameter of 30 μm, and filled to 35% of the volume of the pulverization container. The motor was set in such a manner that the rim rate became 6.8 m/s, and crushing was performed under the condition that the crushing time was 10 minutes. Further, the obtained dispersion (metal fine particle dispersion) was centrifuged at a number of revolutions of 5000 rpm for 15 minutes using a centrifugal separator (Himac CR18).

Production Example 2 (Near Infrared Absorbing Pigment Dispersion 1)

0.2 μg of the near-infrared absorbing pigment obtained in Synthesis Example 2 and 0.21 g of the dispersing agent DisperBYK 140 were added to 7 ml of the toluene solution, and the mixture was placed in a batch type bead milling apparatus (TKfilmics Model 30-25, manufactured by Primix). The inside of the crushing container. The crushed particles were zirconia particles having an average particle diameter of 30 μm and filled to 70% of the volume of the pulverization container. The motor was set in such a manner that the rim speed became 10 m/s, and crushing was performed under the condition that the crushing time was 30 minutes. Further, the obtained dispersion was subjected to centrifugation at a number of revolutions of 5000 rpm for 15 minutes using a centrifugal separator (Higashi Industrial Co., Ltd. Himac CR18) to obtain a near-infrared absorbing pigment dispersion liquid 1.

Production Example 3 (Near Infrared Absorbing Pigment Dispersion 2)

The near-infrared pigment dispersion liquid 2 was obtained in the same manner as in Production Example 2, except that the near-infrared absorbing dye obtained in Synthesis Example 2 was replaced with 2,3-naphthalocyanine (manufactured by Aldrich Co., Ltd.).

Synthesis Example 3 (Acrylic Adhesive A)

291 g of n-butyl acrylate as a monomer and 9 g of acrylic acid were dissolved in 366 g of toluene, 0.15 g of azobisisobutyronitrile was added, and the monomers were polymerized at 70 ° C for 6 hours under a nitrogen stream. Acrylic resin copolymer (weight average molecular weight: Mw = 320,000). Further, by diluting with toluene, an acrylic resin having a solid content fraction of 29.36% and a viscosity of 2700 mPas was obtained. Copolymer solution.

Manufacture of heat-shielding adhesives and heat-shielding adhesive sheets Example 1

100 parts by weight of the acrylic pressure-sensitive adhesive A obtained in Synthesis Example 3 (butyl acrylate: acrylic acid = 97:3), and the toluene dispersion liquid 144 containing tin oxide indium oxide (ITO) obtained in Production Example 1 was used. The mixture and the 14.7 parts by weight of the toluene dispersion liquid of the near-infrared absorbing dye obtained in Production Example 2 were mixed and dissolved to obtain a heat ray-shielding adhesive. Further, it was applied to a polyester film of a release sheet (manufactured by a polyxylene processor on one side) (manufactured by Lintec Co., Ltd., 3811 thickness: 38 μm) by a knurling coater, and dried. The heat-shielding adhesive sheet (thickness: 15 μm) was formed by covering the polyester film of the release sheet (manufactured by the lintec side with a polysiloxane treatment) (manufactured by Lintec Co., Ltd.) with a thickness of 38 μm. .

Example 2

A heat ray-shielding adhesive and a heat ray-shielding adhesive sheet were produced in the same manner as in Example 1 except that the toluene dispersion of the near-infrared absorbing dye was replaced with the Manufacturer of Production Example 3.

Comparative example 1

Except that the toluene dispersion of the near-infrared absorbing pigment was not mixed in Example 1, and 144 parts by weight of the toluene dispersion containing tin indium oxide (ITO) obtained in Production Example 1 and the weight of the acrylic adhesive A 100 were used. A heat ray-shielding adhesive sheet (having a thickness of 15 μm) was produced in the same manner as in Example 1 except for the parts.

Example 3

The heat shield properties of the heat ray-shielding adhesive sheets produced in Example 1, Example 2, and Comparative Example 1 were subjected to a heat ray shielding test by the method shown below. The results are shown in Table 1.

experiment method

Test environment: Prepare a test chamber with an outer temperature width of 150 mm × length 235 mm × height 110 mm with external temperature occlusion and air tightness. In the center of the top of the test chamber, infrared light (100 V, 250 W: Toshiba) Co., Ltd.) is placed at a height of 40 cm from the top of the test chamber to constitute a test device for evaluating heat shielding properties. Next, the heat-shielding adhesive sheet produced in the top portion of the test box was fixed by attaching the four corners of the tape. Further, the thermometer was placed at the center of the inside of the test chamber so as not to be in direct contact with the light. Thereafter, the lamp was turned on, the temperature was measured every 10 seconds, and the temperature in the test chamber after 30 minutes was measured. Furthermore, the above test chamber is placed in a room of about 25 °C. In this test, the temperature inside the box when the heat ray-shielding adhesive sheet produced in the comparative example was used and the temperature of the heat ray-shielding adhesive sheet using the present invention were compared, and the temperature inside the box using the heat ray-shielding adhesive sheet of the present invention was used. When lowered, the heat line shielding effect is improved. Further, the calculation method of the temperature difference in the tank was derived by subtracting the temperature inside the tank using the heat ray-shielding adhesive sheet of the present invention from the temperature inside the tank using the heat ray-shielding adhesive sheet produced in the comparative example.

As shown in Table 1, the temperature inside the box when the heat ray-shielding adhesive sheet produced in Comparative Example 1 was used was 72.5 °C. On the other hand, in the case where the heat ray-shielding adhesive sheets produced in Example 1 and Example 2 of the present invention were used, the in-tank temperatures were 68.4 ° C and 68.0 ° C, respectively. That is, the temperature inside the box of the heat ray-shielding adhesive sheet produced in Example 1 and Example 2 of the present invention was lower than that in the case of the heat ray-shielding adhesive sheet produced in the comparative example, respectively. °C, 4.5 °C. According to the results, it is understood that the heat ray shielding effect of the heat ray-shielding adhesive sheet of the present invention is improved.

[Industrial availability]

According to the present invention, the heat ray-shielding metal fine particles and the near-infrared absorbing pigment can be dispersed in the adhesive by using a dispersing agent, thereby suppressing the temperature rise caused by the heat line as compared with the conventional heat ray-shielding adhesive sheet. Accordingly, the present invention can suppress the temperature rise of the space of a house or a car, reduce the load of the air conditioner, and contribute to energy saving or global environmental problems.

Claims (6)

A heat ray-shielding adhesive composition comprising (A) metal fine particles, (B) an acrylic adhesive, (C) a dispersant, and (D) a near-infrared absorbing dye, wherein the (A) metal fine particles are represented by X The half-height width of the first main peak obtained by the diffraction pattern (XRD) is 0.01 to 0.8°, and the weight average molecular weight of the (B) acrylic adhesive is 100,000 to 1.2 million, and the above (D) near-infrared absorption A naphthalocyanine compound represented by the formula (1): [In the formula (1), M represents a metal atom, a metal oxide, a metal hydroxide or 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 group. a group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfonylamino group; A represents a divalent crosslinking group, and Y represents a sulfonic acid group, a carboxyl group, and a residue of at least one hydrogen on the nitrogen atom of the amine group 1 to 2 Or removing at least one hydrogen residue on the nitrogen atom of the nitrogen-containing heterocyclic ring; m and n are average values, and 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]. The heat shielding adhesive composition of claim 1, wherein the (A) metal microparticles are selected from the group consisting of tin oxide, indium oxide, and zinc oxide. The heat shielding adhesive composition according to any one of claims 1 to 2, wherein the ratio of the (B) acrylic adhesive-based carboxyl group or the structural unit of the acid-containing monomer is all monomer structural units in the polymer. 1 to 5% of the polymer. The heat shielding adhesive composition of claim 1, wherein M in the formula (1) is VO, A is an alkylene group having 1 to 3 carbon atoms, and Y is an o-benzonitrile having a substituent. Amine. The heat shielding adhesive composition according to claim 1, wherein M in the formula (1) is Cu, A is an alkylene group having 1 to 3 carbon atoms, and Y is an o-benzonitrile which may have a substituent. Amine. A heat ray-shielding adhesive sheet obtained by coating the heat ray-shielding adhesive composition according to any one of claims 1 to 5.