JP2013174690A - Heat-ray reflective member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-ray reflective member having a high transmittance and a high heat-ray shielding effect and being excellent in light resistance.SOLUTION: The present invention is a heat-ray reflective member 10 comprising a substrate 11, a heat-ray reflecting film 12 and an adhesive layer 13. The heat-ray reflecting film 12 has a transparent base material 12a and a cholesteric liquid crystal polymer layer 12b. The cholesteric liquid crystal polymer layer 12b is formed on one principal surface of the transparent base material 12a by polymerization of a liquid crystal compound having a polymerizable functional group with a chiral agent having a polymerizable functional group. The adhesive layer 13 is provided on the surface on which at least the cholesteric liquid crystal polymer layer 12b of the heat-ray reflecting film 12 is formed, the adhesive layer 13 bonding the substrate 11 and the heat-ray reflecting film 12. At least one of the layers located between the light incident surface and the cholesteric liquid crystal polymer layer 12b of the heat-ray reflective member 10 has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less and a water vapor transmittance of below 3.0 g/(m/day).

Description

  The present invention relates to a heat ray reflective member using a heat ray reflective film.

  From the viewpoint of preventing global warming and saving energy, it is widely practiced to cut the heat rays of sunlight (infrared rays) from building windows, show windows, automobile window surfaces, and the like to reduce the temperature. As the heat ray cutting material, a material using antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO) or the like (for example, see Patent Document 1), a material using a laminated film of a metal thin film (for example, Patent Document) 2), an infrared reflecting member using a cholesteric liquid crystal polymer (for example, see Patent Document 3), and the like have been proposed.

JP-A-9-156025 Japanese Patent Laid-Open No. 10-309767 JP-A-4-281403

  However, although the heat ray cut member using ATO or ITO as proposed in Patent Document 1 has an absorption band in the visible light region, the heat ray cut method is a heat ray absorption type, so it is used for glass or the like. May cause thermal cracking when used together.

  In addition, the heat ray cut member using the laminated film of the metal thin film as proposed in Patent Document 2 is a reflection type heat ray cut method, so the problem of causing the above thermal crack does not occur. When used in a building window or a show window, the electromagnetic wave is cut, and communication with a mobile phone or the like is impossible.

  On the other hand, since the infrared ray reflective film using the cholesteric liquid crystal polymer as proposed in Patent Document 3 is a reflection type heat ray cut method, the problem of causing the above-described thermal cracking does not occur, Since a non-metallic material is used, the problem that communication such as the above-described mobile phone cannot be performed does not occur. However, since this infrared reflective film uses an organic material, it has a problem that the light reflectance is lowered when exposed to light for a long time.

  The present invention has been made to solve the above-described problems, and provides a heat ray reflective member having high transmittance and high heat ray shielding effect and excellent in light resistance.

The heat ray reflective member of the present invention is a heat ray reflective member comprising a substrate, a heat ray reflective film disposed on one main surface of the substrate, and an adhesive layer, and the heat ray reflective film is a transparent substrate. And a cholesteric liquid crystal polymer layer, wherein the cholesteric liquid crystal polymer layer is formed on one main surface of the transparent substrate by polymerizing a liquid crystal compound having a polymerizable functional group and a chiral agent having a polymerizable functional group. The pressure-sensitive adhesive layer is formed on at least the surface of the heat ray reflective film on which the cholesteric liquid crystal polymer layer is formed, and bonds the substrate and the heat ray reflective film. At least one of the layers positioned between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less. , Water vapor transmission rate is smaller than a ^{3.0g / (m 2 · day)} .

  ADVANTAGE OF THE INVENTION According to this invention, it has a high transmittance | permeability and a high heat ray shielding effect, and can provide the heat ray reflective member excellent in light resistance.

FIG. 1 is a schematic cross-sectional view showing an example of the heat ray reflective member of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the heat ray reflective member of the present invention.

The heat ray reflective member of the present invention is a heat ray reflective member comprising a substrate, a heat ray reflective film disposed on one main surface of the substrate, and an adhesive layer, and the heat ray reflective film is a transparent substrate. And a cholesteric liquid crystal polymer layer, and the cholesteric liquid crystal polymer layer is formed on one main surface of the transparent substrate by polymerizing a liquid crystal compound having a polymerizable functional group and a chiral agent having a polymerizable functional group. The pressure-sensitive adhesive layer is provided on at least the surface of the heat ray reflective film on which the cholesteric liquid crystal polymer layer is formed, and bonds the substrate and the heat ray reflective film. At least one of the layers positioned between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less, or , Water vapor transmission rate is smaller than a ^{3.0g / (m 2 · day)} . Here, the light incident surface of the heat ray reflective member refers to the main surface of the heat ray reflective member on the substrate side. When the substrates are arranged on both main surfaces of the heat ray reflecting member, both main surfaces of the heat ray reflecting member can be light incident surfaces.

  By setting it as the said structure, this invention can have the high transmittance | permeability and the high heat ray shielding effect, and can provide the heat ray reflective member excellent in light resistance.

  Hereinafter, the heat ray reflective member of this invention is demonstrated based on drawing.

  FIG. 1 is a schematic cross-sectional view showing an example of the heat ray reflective member of the present invention. A heat ray reflective member 10 shown in FIG. 1 includes a substrate 11, a heat ray reflective film 12, and an adhesive layer 13. The heat ray reflective film 12 includes a transparent substrate 12a and a cholesteric liquid crystal polymer layer 12b. In FIG. 1, light is incident according to the arrow 14, and the main surface of the heat ray reflecting member 10 on the substrate 11 side becomes a light incident surface.

  FIG. 2 is a schematic cross-sectional view showing another example of the heat ray reflective member of the present invention. The heat ray reflective member 20 shown in FIG. 2 includes a heat ray reflective film 13 having a transparent base material 12a and a cholesteric liquid crystal polymer layer 12b disposed between two substrates 11. Each of the two substrates 11 and the heat ray reflective film 13 are bonded by an adhesive layer 13. In FIG. 2, light is incident according to the arrow 14a or 14b, and both main surfaces of the heat ray reflecting member 20 can be light incident surfaces.

<Board>
Glass, a transparent base material, etc. can be used for the board | substrate used for the heat ray reflective member of this invention.

  The glass that can be used for the substrate is not particularly limited as long as the transmittance does not decrease. For example, commercially available soda lime silicate glass can be used as the glass.

  The transparent substrate that can be used for the substrate is not particularly limited as long as the transmittance does not decrease. For example, polyester-based resins (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate-based resins, polyacrylic resins, and the like. Acid ester resins (for example, polymethyl methacrylate), alicyclic polyolefin resins, polystyrene resins (for example, polystyrene, acrylonitrile / styrene copolymers (AS resin), etc.), polyvinyl chloride resins, polyvinyl acetate A resin obtained by processing a resin such as a resin based on resin, a polyether sulfone resin, a cellulose resin (for example, diacetyl cellulose, triacetyl cellulose, etc.) or a norbornene resin into a film or sheet can be used. Examples of methods for processing the resin into a film or sheet include an extrusion molding method, a calender molding method, a compression molding method, an injection molding method, a method in which the resin is dissolved in a solvent, and the like. You may add additives, such as antioxidant, a flame retardant, a heat-resistant agent, a ultraviolet absorber, a slipping agent, an antistatic agent, to the said resin. The thickness of the transparent substrate is, for example, 10 to 500 μm.

When the substrate is disposed between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer, the substrate has a maximum transmittance of 7% or less, preferably 5% or less in a wavelength region of 380 nm or less, More preferably, the water vapor transmission rate is 3% or less and the water vapor transmission rate is smaller than 3.0 g / (m ² · day). In this case, the amount of light reaching the cholesteric liquid crystal polymer layer can be limited, and the exposure of the cholesteric liquid crystal polymer layer to air can be suppressed. As a result, the light resistance of the heat ray reflective member can be improved. The maximum transmittance can be adjusted using various ultraviolet absorbers, for example.

<Cholesteric liquid crystal polymer layer>
A cholesteric liquid crystal polymer can be obtained by adding a small amount of an optically active compound (chiral agent) to a nematic liquid crystal compound that is a rod-like molecule. This cholesteric liquid crystal polymer has a layered structure in which nematic liquid crystal compounds are stacked several times. Within this layer, the nematic liquid crystal compounds are arranged in a certain direction, and the layers are stacked such that the arrangement direction of the liquid crystal compounds is spiral. Therefore, the cholesteric liquid crystal polymer can selectively reflect only light of a specific wavelength according to the helical pitch.

  A normal cholesteric liquid crystal polymer is characterized in that the helical pitch changes with temperature, and the wavelength of reflected light changes. When a composition containing a liquid crystal compound having a polymerizable functional group and a chiral agent having a polymerizable functional group is made uniform in a liquid crystal state and then irradiated with active energy rays such as ultraviolet rays while maintaining the liquid crystal state It becomes possible to produce a layer (cholesteric liquid crystal polymer layer) containing a cholesteric liquid crystal polymer in which the alignment state of the liquid crystal compound is fixed semipermanently.

  The cholesteric liquid crystal polymer layer thus obtained can fix the reflection wavelength semipermanently without changing the wavelength of the light reflected by the temperature. In addition, since the cholesteric liquid crystal polymer layer has cholesteric liquid crystal optical rotation, when the rotation direction and wavelength of circularly polarized light are equal to the rotation direction of liquid crystal molecules and the helical pitch, the light is reflected without being transmitted. Normally, sunlight is synthesized from circularly polarized light of a right spiral and a left spiral. Therefore, a cholesteric liquid crystal polymer layer with a specific helical pitch using a chiral agent with a right-handed optical rotation and a cholesteric liquid crystal polymer layer with a specific helical pitch with a chiral agent with a left-handed optical rotation Can be made higher in reflectivity at the selective reflection wavelength.

  The cholesteric liquid crystal polymer layer constituting the heat ray reflective film used in the heat ray reflective member of the present invention is formed by polymerizing a liquid crystal compound having a polymerizable functional group and a chiral agent having a polymerizable functional group.

  Examples of the liquid crystal compound used in the formation of the cholesteric liquid crystal polymer layer in the present invention are described in Chapter 8 of “Basics and Applications of Liquid Crystals” (Shinichi Matsumoto, Ryo Kakuda City; Industrial Research Co., Ltd.). The known compounds can be used.

  Specific examples of the liquid crystal compound include, for example, WO95 / 22586 pamphlet, JP-A No. 2000-281629, JP-A No. 2001-233737, JP-A-2001-519317, JP-A-2002-533742, JP 2002-308832, JP 2002-265421, JP 2005-309255, JP 2005-263789, JP 2008-291218, JP 2008-242349, WO 2009/133290 The compounds described in No. pamphlet etc. can be mentioned.

  The liquid crystal compound preferably includes a high melting point liquid crystal compound and a low melting point liquid crystal compound. In this case, the difference between the melting point of the high melting point liquid crystal compound and the melting point of the low melting point liquid crystal compound is preferably 15 ° C. or higher and 30 ° C. or lower, and more preferably 20 ° C. or higher and 30 ° C. or lower. When the difference between the melting points is less than 15 ° C., the compatibility of the liquid crystal compound is lowered. As a result, the orientation of the cholesteric liquid crystal polymer layer is partly disturbed and haze may be increased. On the other hand, when the difference between the melting points exceeds 30 ° C., there may be a change in the light reflectance when the heat-resistant storage test is conducted at a temperature higher than the glass transition temperature of the transparent substrate.

  As the combination of the high melting point liquid crystal compound and the low melting point liquid crystal compound, commercially available products can be used. For example, trade names “PLC7700” (melting point: 90 ° C.) and “PLC8100” (melting point: 65 ° C.) manufactured by ADEKA. A combination of “PLC7700” (melting point 90 ° C.) and “PLC7500” (melting point 65 ° C.), trade names “UCL-017A” (melting point 96 ° C.) and “UCL-017” (melting point) 70 ° C) and the like.

  The liquid crystal compound preferably contains the high-melting-point liquid crystal compound in a total mass ratio of 90% by mass or less. When the ratio of the high-melting-point liquid crystal compound exceeds 90% by mass, the compatibility of the liquid crystal compound tends to be reduced. As a result, the orientation of the cholesteric liquid crystal polymer layer is partially disturbed, resulting in an increase in haze. There is.

  The melting point of the high melting point liquid crystal compound is preferably equal to or higher than the glass transition temperature of the transparent substrate. When the melting point of the liquid crystal compound is low, the compatibility and solubility with the chiral agent and the solvent are excellent. However, when the melting point is too low, the heat ray reflective film produced has poor heat resistance. Therefore, it is preferable that at least the melting point of the high melting point liquid crystal compound is equal to or higher than the glass transition temperature of the transparent substrate.

  Here, the melting point of the liquid crystal compound can be measured as follows. First, a liquid crystal compound is sandwiched between two slide glass plates. Then, while observing the slide glass with a microscope, the temperature of the slide glass is increased at a rate of 5 ° C./min, and the temperature at which the liquid crystal compound starts to melt is determined as the melting point.

  Moreover, the glass transition temperature of a transparent base material can be measured as follows. First, a sample piece of about 25 mm × 10 mm is prepared, heated in the range of 20 ° C. to 200 ° C., and measured for dynamic viscoelasticity at a frequency of 1 Hz using a dynamic viscoelasticity test measurement device “RSAII” manufactured by Rheometrics. To do. Then, the glass transition temperature is obtained from the value of the dynamic loss tangent tan δ calculated from the dynamic storage elastic modulus E ′ and the dynamic loss elastic modulus E ″ obtained from the measurement of the dynamic viscoelasticity.

  When three or more kinds of the above liquid crystal compounds are used, those having the maximum melting point are designated as high melting point liquid crystal compounds, and those having the minimum melting point are designated as low melting point liquid crystal compounds.

  The chiral agent used for forming the cholesteric liquid crystal polymer layer in the present invention is not particularly limited as long as it has good compatibility with the liquid crystal compound and can be dissolved in a solvent. A chiral agent having a polymerizable functional group can be used.

  Specific examples of the chiral agent include, for example, WO 98/00428 pamphlet, JP-T 9-506088, JP-T 10-509726, JP 2000-44451, JP 2000-506873. And compounds described in JP-A No. 2003-66214, JP-A No. 2003-313187, US Pat. No. 6,468,444, and the like. Moreover, as such a chiral agent, a commercial item can be used, for example, the brand name “S101”, “R811”, “CB15” manufactured by Merck; the brand name “PALIOCOLOR LC756” manufactured by BASF; ADEKA; For example, trade names “CNL715” and “CNL716” manufactured by the company are listed.

  The selective reflection wavelength of the cholesteric liquid crystal polymer layer can be controlled by adjusting the helical pitch. This helical pitch can be adjusted by adjusting the compounding amounts of the liquid crystal compound and the chiral agent. For example, when the concentration of the chiral agent is high, the twisting force of the spiral increases, so that the pitch of the spiral is reduced, and the selective reflection wavelength λ of the cholesteric liquid crystal polymer layer is shifted to the short wavelength side. Further, when the concentration of the chiral agent is low, the twisting force of the spiral is reduced, so that the pitch of the spiral is increased, and the selective reflection wavelength λ of the cholesteric liquid crystal polymer layer is shifted to the longer wavelength side. Therefore, the blending amount of the chiral agent is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.2 parts by mass with respect to 100 parts by mass in total of the at least two kinds of liquid crystal compounds and the chiral agent. More preferred is 7.0 parts by mass or less. When the blending amount of the chiral agent is 0.1 parts by mass or more and 10 parts by mass or less, the selective reflection wavelength of the obtained cholesteric liquid crystal polymer layer can be controlled in a long wavelength region.

  The selective reflection wavelength of the cholesteric liquid crystal polymer layer can be controlled by adjusting the blending amount of the chiral agent as described above. If this selective reflection wavelength is controlled in the near infrared region, a heat ray reflective film that has substantially no absorption in the visible light region, that is, is transparent in the visible light region and can selectively reflect light in the near infrared region. Can be obtained. It is preferable that the maximum reflectance wavelength of the heat ray reflective film in this invention exists in the range of 900-1800 nm.

  The thickness of the cholesteric liquid crystal polymer layer in the present invention is preferably 1.5 times or more and 4.0 times or less of the wavelength (maximum reflectance wavelength) that reflects incident light to the maximum, and is 1.7 times or more of the maximum reflectance wavelength. 0 times or less is more preferable. When the thickness of the cholesteric liquid crystal polymer layer is less than 1.5 times the maximum reflectance wavelength, it becomes difficult to maintain the orientation of the cholesteric liquid crystal polymer layer, and the light reflectance of the heat ray reflective film may be lowered. When the thickness of the cholesteric liquid crystal polymer layer exceeds 4.0 times the maximum reflectance wavelength, the orientation and light reflectance of the cholesteric liquid crystal polymer layer can be maintained well, but the thickness of the heat ray reflective film becomes too thick. There is. The thickness of the cholesteric liquid crystal polymer layer is, for example, from 0.5 μm to 20 μm, and preferably from 1 μm to 10 μm.

  The cholesteric liquid crystal polymer layer in the present invention is not limited to a single layer structure, and may have a multiple layer structure. In the case of a multi-layer structure, it is preferable that each layer has a different selective reflection wavelength because the wavelength region in which light is reflected can be easily controlled.

<Transparent substrate>
As a transparent base material which comprises the heat ray reflective film used for the heat ray reflective member of this invention, if it is formed with the material which has translucency, it will not specifically limit. Examples of the transparent substrate include polyester resins (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate resins, polyacrylate resins (eg, polymethyl methacrylate), alicyclic polyolefin resins, polystyrene. Resin (for example, polystyrene, acrylonitrile / styrene copolymer (AS resin), etc.), polyvinyl chloride resin, polyvinyl acetate resin, polyethersulfone resin, cellulose resin (for example, diacetyl cellulose, triacetyl cellulose) Etc.), a resin obtained by processing a resin such as a norbornene-based resin into a film shape or a sheet shape can be used. Examples of methods for processing the resin into a film or sheet include an extrusion molding method, a calender molding method, a compression molding method, an injection molding method, a method in which the resin is dissolved in a solvent, and the like. You may add additives, such as antioxidant, a flame retardant, a heat-resistant agent, a ultraviolet absorber, a slipping agent, an antistatic agent, to the said resin. Moreover, in order to improve the adhesiveness with the cholesteric liquid crystal polymer layer, the transparent substrate may be provided with a primer on its surface, or may be subjected to corona treatment or plasma treatment. The thickness of the transparent substrate is, for example, 10 to 500 μm.

When the transparent substrate is disposed between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer, the transparent substrate has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less, preferably It is preferable to use 5% or less, more preferably 3% or less, and a water vapor transmission rate smaller than 3.0 g / (m ² · day). In this case, the amount of light reaching the cholesteric liquid crystal polymer layer can be limited, and the exposure of the cholesteric liquid crystal polymer layer to air can be suppressed. As a result, the light resistance of the heat ray reflective member can be improved. The maximum transmittance can be adjusted using various ultraviolet absorbers, for example.

<Heat reflective film>
The heat ray reflective film used for the heat ray reflective member of the present invention can have, for example, a solar transmittance of 70% or more according to Japanese Industrial Standard (JIS) A5759, and a haze according to JIS K7105 of 2.0% or less, preferably 1 The light reflectance at the maximum reflectance wavelength can be 40% or more, preferably 45% or more. The heat ray reflective film having such characteristics has a high transmittance in the visible light region, a low haze, and a high light reflectance. Therefore, even if the reflection wavelength increases and the film thickness increases, the cholesteric liquid crystal polymer layer The disorder of the orientation does not occur. Moreover, it is preferable that the solar radiation transmittance | permeability of the heat ray reflective film in this invention is substantially the same as a board | substrate.

  Here, the solar radiation transmittance is calculated based on JIS A5759 by measuring the transmittance using an ultraviolet-visible near-infrared spectrophotometer “Ubest V-570 type” (manufactured by JASCO Corporation) in the range of 300 nm to 250 nm. The Further, haze can be measured using an ultraviolet-visible near-infrared spectrophotometer “Ubest V-570 type” (manufactured by JASCO Corporation) in the range of 380 nm to 780 nm based on JIS K7105. The light reflectance at the maximum reflectance wavelength is obtained by measuring the reflection spectrum using an ultraviolet-visible near-infrared spectrophotometer “Ubest V-570 type” (manufactured by JASCO Corporation) in the range of 350 nm to 2500 nm. Calculated from the reflection spectrum.

<Adhesive layer>
The adhesive layer used for the heat ray reflective member of this invention is arrange | positioned as an outermost layer of the said heat ray reflective film. The pressure-sensitive adhesive layer in the present invention is provided at least on the surface of the heat ray reflective film on which the cholesteric liquid crystal polymer layer is formed (hereinafter also referred to as a cholesteric liquid crystal polymer layer forming surface). Therefore, the substrate and the heat ray reflective film can be bonded without directly exposing the cholesteric liquid crystal polymer layer to air. Further, when an adhesive layer is provided on the surface opposite to the cholesteric liquid crystal polymer layer forming surface of the heat ray reflective film, the heat ray reflective film is disposed between the two substrates as shown in FIG. A heat ray reflective member can be provided.

  Examples of the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl acetate-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, phenol-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives. Can be mentioned.

When the pressure-sensitive adhesive layer is disposed between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer, the pressure-sensitive adhesive layer has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less, preferably It is preferable to use 5% or less, more preferably 3% or less, and a water vapor transmission rate smaller than 3.0 g / (m ² · day). In this case, the amount of light reaching the cholesteric liquid crystal polymer layer can be limited, and the exposure of the cholesteric liquid crystal polymer layer to air can be suppressed. As a result, the light resistance of the liquid crystal reflecting member can be improved. The maximum transmittance can be adjusted using, for example, various ultraviolet absorbers.

  Moreover, when producing the heat ray reflective member by which a heat ray reflective film is arrange | positioned between two board | substrates as shown in FIG. 2, as an adhesive layer provided in the transparent base material side of a heat ray reflective film, polyvinyl butyral resin is used. It is preferably an adhesive layer formed using (PVB), ethylene-vinyl acetate copolymer resin (EVA) or the like. In this case, the adhesiveness between the transparent base material and the substrate can be improved.

  Next, an example of the manufacturing method of the heat ray reflective member of this invention is demonstrated, referring FIG.

  First, two kinds of liquid crystal compounds having polymerizable functional groups having different melting points, a chiral agent having a polymerizable functional group, a polymerization initiator, and a surfactant, if necessary, orientation A coating solution for forming a cholesteric liquid crystal polymer layer is prepared by dissolving a regulator and the like in a solvent. And this coating liquid is apply | coated to the film form on one main surface of the transparent base material 12a, and it is made to dry. Thereafter, the obtained coating film is irradiated with, for example, ultraviolet rays to polymerize the liquid crystal compound and the chiral agent. Thereby, the heat ray reflective film 12 in which the cholesteric liquid crystal polymer layer 12b is formed on one main surface of the transparent substrate 12a is obtained.

  Next, the pressure-sensitive adhesive layer 13 is formed on the surface of the cholesteric liquid crystal polymer layer 12b opposite to the transparent substrate 12a side. And if the board | substrate 11 is bonded together on the exposed surface of this adhesive layer 13, the heat ray reflective member 10 shown in FIG. 1 will be obtained.

  In addition, after producing the heat ray reflective film 12, when not bonding to the board | substrate 11 immediately, it is good to provide a separator (not shown) on the adhesive layer 13 previously. In this case, since the separator may be peeled off immediately before the heat ray reflective film 12 is bonded to the substrate 11, contamination of the adhesive layer 13 can be prevented until just before the heat ray reflective film 12 is bonded to the substrate 11. As said separator, a plastic film, a rubber sheet, paper, cloth, a nonwoven fabric, a net | network, a foam sheet, metal foil etc. can be used, for example. The surface of the separator may be coated with a release agent such as silicone, long chain alkyl, or fluorine. Such a coated surface is preferably arranged so as to face the pressure-sensitive adhesive layer.

  The method for applying the coating solution is not particularly limited, for example, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, micro gravure coating, or gravure printing, screen printing, Printing methods such as offset printing and ink jet printing can be used.

  As said polymerization initiator, a photoinitiator is mentioned, for example. Examples of the photopolymerization initiator include benzoin alkyl ether initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, benzoylbenzoic acid, 3,3′-dimethyl Benzophenone initiators such as -4-methoxybenzophenone and polyvinylbenzophenone; α-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α ′ -Dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -pheny R] -2-morpholinopropane-1 and other aromatic ketone initiators; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Acylphosphine oxide-based initiators such as bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; benzyldimethyl ketal Aromatic ketal initiators such as: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxa Ton, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone initiators; benzyl and other benzyl initiators; benzoin and other benzoin initiators; 2-methyl-2-hydroxypropiophenone and the like α-ketol compounds; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; camphorquinone A halogenated ketone compound; an acyl phosphinoxide compound; an acyl phosphonate compound, and the like.

  As the photopolymerization initiator, commercially available photopolymerization initiators can also be used. For example, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) manufactured by Ciba Specialty Chemicals, Inc. 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1), Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), Irgacure® 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-on), Irgacure (registered trademark) 500, Irgacure (registered trademark) 1000, Irgacure (registered trademark) 1700, Irgacure (registered trademark) 1800, Irgacure (registered trademark) 1850; Darocur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by Merck & Co., Inc. ); N-1717 manufactured by Asahi Denka Kogyo Co., Ltd .; Bi, such as 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′-biimidazole manufactured by Kurokin Kasei Co., Ltd. Examples include imidazole compounds. These photopolymerization initiators may be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator is preferably 0.05 to 5 parts by mass with respect to a total of 100 parts by mass of the liquid crystal compound and the chiral agent.

There is no restriction | limiting in particular as said ultraviolet irradiation conditions, According to the objective, it can select suitably. The ultraviolet rays to be irradiated are, for example, 160 to 380 nm, and preferably 250 to 380 nm. The irradiation time is, for example, 0.1 to 600 seconds, and preferably 0.3 to 300 seconds. Examples of ultraviolet light sources include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights, etc.), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps, etc.), short arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, Mercury xenon lamp etc.) can be used. The quantity of ultraviolet light, for example, 200 to 600 mJ / cm ^2, preferably 300~500mJ / cm ^2.

  Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, methylene chloride, trichloroethylene, tetrachloroethylene, chlorobenzene, and orthodichlorobenzene; phenol, p-chlorophenol, and o-chlorophenol. , M-cresol, o-cresol, p-cresol, etc .; benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene and other aromatic hydrocarbons; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone , Cyclohexanone, cyclopentanone, 2-pyrrolidone, ketones such as N-methyl-2-pyrrolidone; esters such as ethyl acetate and butyl acetate; t-butyl alcohol, glycerin Alcohols such as ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; amides such as dimethylformamide, dimethylacetamide; acetonitrile, butyronitrile Nitriles such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like; carbon disulfide, ethyl cellosolve, butyl cellosolve and the like can be used. These solvents may be used alone or in combination of two or more.

  Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples. In addition, unless otherwise indicated, in the following, “part” means “part by mass”.

Example 1
<Preparation of heat ray reflective film>
First, as a transparent substrate, a polyethylene terephthalate (PET) film (trade name “U34”, manufactured by Toray Industries, Inc., thickness: 50 μm, glass transition temperature: 75 ° C.) having both surfaces easily treated with an acrylic resin was prepared. Next, the following materials were stirred and mixed to prepare a coating solution for forming a cholesteric liquid crystal polymer layer.

(1) Liquid crystal compound having a polymerizable functional group (manufactured by ADEKA, high melting point liquid crystal compound, trade name “PLC-7700”, melting point: 90 ° C.) 86.8 parts (2) Liquid crystal compound having a polymerizable functional group ( ADEKA, low melting point liquid crystal compound, trade name “PLC-8100”, melting point: 65 ° C.) 9.7 parts (3) chiral agent having a polymerizable functional group (trade name “CNL-715”, produced by ADEKA) 3.5 parts (4) Photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name “Irgacure 907”) 3.0 parts (5) Solvent (cyclohexanone) 412 parts

The coating liquid for forming the cholesteric liquid crystal polymer layer was applied onto a PET film using a micro gravure coater and dried at 100 ° C. to form a coating film. The coating film was cured by irradiating the coating film with ultraviolet rays (wavelength: maximum wavelength 365 nm, light source: high-pressure mercury lamp, light amount: 500 mJ / cm ² ) for 30 seconds. This produced the heat ray reflective film in which the cholesteric liquid crystal polymer layer (thickness: 2.1 micrometers) was formed on one main surface of a transparent base material.

<Production of adhesive tape>
First, a polyethylene terephthalate film (manufactured by Nakamoto Pax Co., Ltd., trade name “NS50MB”, thickness: 38 μm) (hereinafter referred to as a first release PET film) was prepared.

  Moreover, 1.25 parts of an ultraviolet absorber (manufactured by Wako Pure Chemical Industries, Ltd., benzophenone) is added to 100 parts of an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., trade name “SK Dyne 2094”, solid content: 25%), 0.27 parts by mass of a crosslinking agent (trade name “E-5XM”, manufactured by Soken Chemical Co., Ltd., solid content: 5%) was added and dispersed sufficiently to prepare a coating solution for forming an adhesive layer.

  And the said adhesive layer formation coating liquid was apply | coated on the surface by which the silicone process side of the said 1st peeling PET film was carried out so that the thickness after drying might be 25 micrometers, and the adhesive layer was formed. Further, a polyethylene terephthalate film (manufactured by Nakamoto Pax Co., Ltd., trade name “NS50A”) (hereinafter referred to as “second peeled PET film”) with a silicone treatment on one side was bonded to the upper surface of this pressure-sensitive adhesive layer, and Examples 1 adhesive tape was produced.

<Production of heat ray reflective member>
First, a float glass (manufactured by Nippon Sheet Glass Co., Ltd.) having a thickness of 3 mm was prepared as a substrate. Next, the second release PET film is peeled off from the pressure-sensitive adhesive tape to expose the surface of the pressure-sensitive adhesive layer, and the exposed surface of the pressure-sensitive adhesive layer is brought into contact with one main surface of the float glass. Bonding was performed at 5 MPa. Next, the first release PET film is peeled from the pressure-sensitive adhesive tape to expose the surface of the pressure-sensitive adhesive layer, and the exposed surface of the pressure-sensitive adhesive layer is the cholesteric liquid crystal polymer layer formed on one main surface of the transparent substrate. It was brought into contact with the exposed surface and bonded at 25 ° C. with a nip pressure of 0.5 MPa. Thereby, the heat ray reflective member of Example 1 with which the board | substrate and the heat ray reflective film were adhere | attached through the adhesive layer was produced.

(Example 2)
A heat ray reflective member of Example 2 was produced in the same manner as in Example 1 except that the float glass was changed to aluminum oxide vapor deposited PET (trade name “Barrier Rocks 1011HG”, thickness: 12 μm, manufactured by Toray Industries, Inc.).

(Example 3)
A heat ray reflective member of Example 3 was produced in the same manner as in Example 1 except that the float glass was changed to silicon oxide vapor-deposited PET (trade name “Techbarrier VX”, thickness: 12 μm, manufactured by Mitsubishi Plastics, Inc.). .

(Comparative Example 1)
A heat ray reflective member of Comparative Example 1 was produced in the same manner as in Example 1 except that the float glass was changed to aluminum oxide-deposited PET (trade name “Barrier Rocks 1011RG-CR”, thickness: 12 μm, manufactured by Toray Industries, Inc.). did.

(Comparative Example 2)
A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that no ultraviolet absorber (benzophenone) was used, and a heat ray reflective member in Comparative Example 2 was produced in the same manner as in Example 1.

  Regarding Examples 1 to 3 and Comparative Examples 1 and 2, the maximum transmittance and the water vapor transmission rate in a wavelength region of 380 nm or less of the layer located between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer, The solar radiation transmittance, the maximum reflectance wavelength, and the maximum reflectance of the heat ray reflective member were measured as follows. Moreover, the light resistance of each heat ray reflective member was evaluated as follows. Here, the light incident surface of the heat ray reflecting member is the main surface of the heat ray reflecting member on the substrate side.

[Maximum transmittance in a wavelength region of 380 nm or less of a layer positioned between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer]
In the said Example and comparative example, the layer located between the light-incidence surface of a heat ray reflective member and a cholesteric liquid crystal polymer layer is a board | substrate and an adhesive layer. Here, after bonding the substrate and the adhesive layer used in each Example and Comparative Example at 25 ° C. with a nip pressure of 0.5 Mpa, an ultraviolet-visible near-infrared spectrophotometer “Ubest” in the range of 380 nm to 780 nm. The maximum transmittance was measured using "V-570 type" (manufactured by JASCO Corporation). The maximum transmittance indicates whether or not light in a wavelength region of 380 nm or less can be transmitted. The lower the value, the less light is transmitted.

[Water vapor transmission rate of a layer located between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer]
After bonding the substrate and the pressure-sensitive adhesive layer used in each Example and Comparative Example at 25 ° C. with a nip pressure of 0.5 Mpa, water vapor permeates under an environment of a temperature of 40 ° C. and a relative humidity of 90% based on JIS K7129. Using a testing machine “PERMATRAN W (registered trademark) 3/33” (manufactured by MOCON), water vapor was permeated from the surface of the substrate on which the adhesive layer was not bonded, and the water vapor transmission rate was measured. The water vapor transmission rate indicates moisture resistance, and the lower the water vapor transmission rate, the higher the moisture resistance.

[Solar radiation transmittance]
Measure light transmittance using UV-visible near-infrared spectrophotometer “Ubest V-570” (manufactured by JASCO Corporation) in the range of 300 nm to 2500 nm with the main surface on the substrate side of the heat ray reflecting member as the light incident surface. The solar radiation transmittance was calculated based on JIS A 5759.

[Maximum reflectance wavelength and maximum reflectance]
The surface of the transparent substrate on which the cholesteric liquid crystal polymer layer was not formed was shaved with a sandpaper, and the surface was further painted black with an oil-based felt pen of black ink. The reflection spectrum of the heat ray reflective film treated in this manner was measured in the range of 350 nm to 2500 nm using an ultraviolet-visible near-infrared spectrophotometer “Ubest V-570 type” (manufactured by JASCO Corporation). From the obtained reflection spectrum, the maximum reflectance wavelength and the maximum reflectance of the heat ray reflective member were calculated. The maximum reflectance indicates the heat ray shielding effect, and the higher the value, the higher the heat ray shielding effect.

[Light resistance test]
Using a light resistance tester "Super Xenon Weather Meter SX-75" (manufactured by Suga Test Instruments Co., Ltd.) An irradiation test was performed in which xenon light was irradiated for 1000 hours at an illuminance of 60 W / m ² (energy density in the range of 300 to 400 nm), and the change rate of the maximum reflectance before and after storage was calculated based on the following formula. ΔR indicates the light resistance of the heat ray reflective member. The lower the value, the higher the light resistance. If ΔR is 0.5% or less, it can be determined that the light resistance is excellent.
ΔR (%) = | (Rsta (%) − Rend (%)) | / Rsta (%) × 100
In the above formula, Rsta (%) represents the maximum reflectance before the storage test, and Rend (%) represents the maximum reflectance after the 1000 hour storage test.

  The results are shown in Table 1.

As shown in Table 1, the layer located between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer has a maximum transmittance in a wavelength region of 380 nm or less of 7.0% or less, and a water vapor transmittance. Since the heat ray reflective members of Examples 1 to 3 having 3.0 g / (m ² · day) had a solar radiation transmittance of 85% or more and a maximum reflectance of 45% or more, high transmittance and It was confirmed that it has a high heat ray shielding effect. In addition, since the change rate ΔR of the maximum reflectance, which is an index of light resistance, was 0.5% or less, it was confirmed that even when exposed to light for a long time, the change rate of the reflectance was small and the light resistance was excellent. did it.

  The present invention has a high transmittance and a high heat ray shielding effect, and can provide a highly reliable heat ray reflective film even when exposed to light for a long time. By attaching the heat ray reflective film to a window, direct sunlight can be used. Heat rays can be effectively blocked, and even if exposed to sunlight for a long period of time, the cooling effect is enhanced without being deteriorated, and it is effective for energy saving and power saving.

DESCRIPTION OF SYMBOLS 10, 20 Heat ray reflective member 11 Substrate 12 Heat ray reflective film 12a Transparent base material 12b Cholesteric liquid crystal polymer layer 13 Adhesive layer

Claims (7)

A heat ray reflective member comprising a substrate, a heat ray reflective film disposed on one main surface of the substrate, and an adhesive layer,
The heat ray reflective film includes a transparent substrate and a cholesteric liquid crystal polymer layer,
The cholesteric liquid crystal polymer layer is formed on one main surface of the transparent substrate by polymerizing a liquid crystal compound having a polymerizable functional group and a chiral agent having a polymerizable functional group,
The pressure-sensitive adhesive layer is provided on at least the surface of the heat ray reflective film on which the cholesteric liquid crystal polymer layer is formed, and bonds the substrate and the heat ray reflective film.
At least one of the layers positioned between the light incident surface of the heat ray reflective member and the cholesteric liquid crystal polymer layer has a maximum transmittance of 7% or less in a wavelength region of 380 nm or less and a water vapor transmittance. Is less than 3.0 g / (m < ² > * day), The heat ray reflective member characterized by the above-mentioned.   The heat ray reflective member according to claim 1, wherein the pressure-sensitive adhesive layer and the substrate are further provided on a surface of the heat ray reflective film opposite to the surface on which the cholesteric liquid crystal polymer layer is formed.   The heat ray reflective member according to claim 1, wherein the substrate is glass or a transparent base material.   The heat ray reflective member according to any one of claims 1 to 3, wherein a maximum reflectance wavelength of the heat ray reflective film is in a range of 900 to 1800 nm.   The heat ray reflective member according to any one of claims 1 to 4, wherein a thickness of the cholesteric liquid crystal polymer layer is 1.5 times or more of a maximum reflectance wavelength. The liquid crystal compound used for forming the cholesteric liquid crystal polymer layer includes a high melting point liquid crystal compound and a low melting point liquid crystal compound,
The difference between the melting point of the high-melting-point liquid crystal compound and the melting point of the low-melting-point liquid crystal compound is in the range of 15 ° C. or higher and 30 ° C. or lower;
The heat ray reflective member according to claim 1, wherein a melting point of the high melting point liquid crystal compound is equal to or higher than a glass transition point of the transparent substrate.   The said liquid crystal compound is a heat ray reflective member of Claim 6 which contains the said high melting point liquid crystal compound in 90 mass% or less in the whole mass ratio.

Images