JP6156786B2 - Heat ray shielding material - Google Patents

Description

  The present invention relates to a laminated glass, a resin translucent plate, and a window that are suitably used for automobiles, railway vehicles, aircraft, ships, buildings, etc. by effectively shielding light having a wavelength in the near infrared region, for example. The present invention relates to a heat ray shielding material constituting an adhesive film for glass.

  Sunlight consists of ultraviolet rays, visible rays, and near infrared rays called heat rays, and the energy ratio thereof is 5% for ultraviolet rays, 45% for visible rays, and 50% for near infrared rays. In recent years, in order to cut the heat rays (infrared rays) from sunlight for the purpose of reducing greenhouse gases and conserving energy, conventional thermal barrier thin films have been applied to the glass surfaces of vehicles such as automobiles, railways, houses, and buildings. It is widely used. Examples of the general shape of the heat shielding thin film include a film coated with a resin composition containing a heat ray shielding agent. In such films, inorganic fine particles such as antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO) have been used as heat ray absorbents. These are excellent in the heat ray shielding rate and visible light transmittance, but the absorption in the near infrared region tends to gradually increase from the wavelength of about 800 nm as the wavelength becomes longer, so that the wavelength is shorter than 800 nm. Specifically, light in the near infrared region of 700 to 800 nm cannot be shielded.

  In recent years, one example of a move to reduce greenhouse gases is that the California Air Resources Board (CARB) in the United States has reduced the amount of carbon dioxide emitted from automobiles to reduce greenhouse gases. The proposed example can be given. More specifically, the CARB is a so-called cool car regulation that regulates the heat energy that permeates through the laminated glass and flows into the automobile, reduces the fuel consumed by the air conditioning equipment, and improves the fuel efficiency of the automobile. We are considering introduction. Such cool car regulations require that the total solar transmittance (Trs) of laminated glass used in automobiles be 40% or less in FY2016. Furthermore, the visible light transmittance is required to be 70% or more. Such a movement is expected to spread not only in the United States but worldwide.

  In general, it may be possible to increase the amount of an inorganic heat ray shielding agent such as ATO or ITO, but as described above, the absorption in the near-infrared region of ATO and ITO gradually increases from a wavelength of about 800 nm. Because it is a tendency to increase, if the amount of ATO or ITO is simply increased to reduce the total solar transmittance and light is further absorbed at a wavelength of 800 to 1000 nm, the content must be doubled than before. Don't be. In such a case, since these ATO and ITO are conductors in automobiles, communication between the inside and outside of the laminated glass, that is, communication between the car navigation system and the ETC, etc. with the outside of the automobile is hindered, and malfunctions such as malfunctioning are not expected. The At present, other problems can be solved by using a tungsten oxide / cesium-based compound, but there is a problem in terms of workability.

  As one of the measures for realizing a heat ray cut film with a higher heat ray shielding rate, it has an absorption peak in the wavelength region of 800 to 1000 nm, and absorbs light with a wavelength of 750 to 1100 nm well. Organic compounds have been proposed (see, for example, Patent Document 1).

  However, even with these organic compounds, if the light transmittance in the visible region is not high, the quality of the product will be deteriorated. In addition, since such organic compounds tend to suddenly decrease the absorption at wavelengths away from the peak, ATO and ITO cannot absorb, and the ability to absorb light of 700 to 800 nm with high solar radiation intensity is poor. . And the light in such a wavelength region is light with a wavelength that is easy for humans to feel as heat, and even if the near-infrared light as a whole has a high absorptivity, a person who has been exposed to light in such a wavelength region in the vehicle or Feeling hot or hot indoors will still set the temperature of the air-conditioning equipment low, leading to fuel and power consumption.

  That is, at present, it is expected that an organic compound having a high light transmittance in the visible region and having a peak in the wavelength region of 700 to 800 nm as described above is provided.

JP 2012-31176 A

  The present invention pays attention to such inconveniences, and an object of the present invention is to provide a heat ray shielding material that has high light transmittance in the visible region and can effectively improve the shielding of light in the near infrared region.

  In order to achieve such an object, the present invention provides the following means (1) to (11).

  (1): A heat ray shielding material comprising a phthalocyanine compound represented by the following chemical formula 1.

Ｘ１〜Ｘ４は、全て水素原子である。Ｘ１〜Ｘ４が水素原子の場合は、Ｙ１とＹ２、Ｙ３とＹ４、Ｙ５とＹ６、Ｙ７とＹ８の組み合わせにおいて、一方は水素原子を表し、一方は下記一般式で表されるフェニルチオ基を表す。

X1 to X4 are all hydrogen atoms . When X1 to X4 are hydrogen atoms, in the combination of Y1 and Y2, Y3 and Y4, Y5 and Y6, Y7 and Y8, one represents a hydrogen atom, and one represents a phenylthio group represented by the following general formula.

ここで、Ｒは炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を表し、ｎは１〜５の整数を表す。Ｍは２価の金属原子、金属酸化物を表す。

Here, R represents an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 5 . M represents a divalent metal atom or metal oxide.

  (2) The heat ray shielding material according to claim 1, wherein M represents vanadyl.

  (3) The heat ray shielding material according to (1) or (2), wherein the phthalocyanine compound is contained in a sheet-like resin.

(4): The amount of the phthalocyanine compound is 0.0005 to 20 parts by mass with respect to 100 parts by mass of the resin. (5): The sheet-like resin is flexible. The heat ray shielding material according to (3) or (4), which is used as an intermediate film of laminated glass.

  (6): The heat ray shielding material according to (3) or (4), wherein the sheet-like resin has flexibility and is used as a film adhered to glass.

  (7): The heat ray shielding material according to (3) or (4), wherein the sheet-like resin is a hard material having shape retention.

  (8) The heat ray shielding material according to any one of (1) to (7), wherein the phthalocyanine compound has an absorption maximum in a wavelength range of 700 to 800 nm.

  (9) The heat ray shielding material according to any one of (1) to (8), which contains fine particles of antimony-doped tin oxide or tin-doped indium oxide.

  (10): The heat ray shielding material according to any one of (1) to (9), wherein an organic compound having an absorption maximum in a wavelength range of 800 to 1100 nm is contained.

(11) The heat ray shielding material according to (10), wherein the organic compound is another phthalocyanine compound different from the phthalocyanine compound.
(12): In the combination of Y1 and Y2, Y3 and Y4, Y5 and Y6, Y7 and Y8, one is a hydrogen atom, and one is represented by the following chemical formula (1), (2), The heat ray shielding material according to (3), (4), (5), (6), (7), (8), (9), (10) or (11).

  ADVANTAGE OF THE INVENTION According to this invention, the heat ray shielding material which has the high transmittance | permeability of the light of visible region, and can improve the shielding of the light of a near infrared region effectively can be provided.

The graph which shows the light absorbency of the compound example which concerns on one Embodiment of this invention. Same as above. Same as above. Same as above. Explanatory drawing which concerns on 2nd embodiment of this invention. FIG. 6 is a schematic cross-sectional view according to FIG. 5. Explanatory drawing which concerns on 3rd embodiment of this invention. The typical structure explanatory view concerning the embodiment. Other typical composition explanatory views concerning the embodiment. The graph which shows the transmittance | permeability of the heat ray shielding material which concerns on material Example 1-2. The graph which shows the transmittance | permeability of the heat ray shielding material which concerns on material comparative example 1-1. The figure which shows the transmittance | permeability and reflectance of a material Example and a material comparative example as a table | surface. The graph which shows the transmittance | permeability of the heat ray shielding material which concerns on material Example 2-1. The graph which shows the transmittance | permeability of the heat ray shielding material which concerns on material Example 2-2. The graph which shows the transmittance | permeability of the heat ray shielding material which concerns on the material comparative example 2-1. The other figure which shows the transmittance | permeability and reflectance of a material Example and a material comparative example as a table | surface.

<First embodiment>
Hereinafter, a first embodiment of the present invention will be described.

  (1): Chemical formula 1:

Ｘ１〜Ｘ４は水素原子、ハロゲン原子、又は炭素原子数２〜５のハロゲノアルコキシ基を表す。Ｘ１〜Ｘ４が水素原子の場合は、Ｙ１とＹ２、Ｙ３とＹ４、Ｙ５とＹ６、Ｙ７とＹ８の組み合わせにおいて一方は水素原子を表し、一方は下記一般式で表されるフェニルチオ基を表す。

X1 to X4 represent a hydrogen atom, a halogen atom, or a halogenoalkoxy group having 2 to 5 carbon atoms. When X1 to X4 are hydrogen atoms, one of the combinations of Y1 and Y2, Y3 and Y4, Y5 and Y6, and Y7 and Y8 represents a hydrogen atom, and one represents a phenylthio group represented by the following general formula.

ここで、Ｒは炭素原子数１〜４のアルキル基、炭素原子数１〜４アルコキシ基を表し、ｎは１〜５の整数を表す。Ｘ１〜Ｘ４がハロゲン原子の場合は、Ｙ１〜Ｙ８は炭素原子数１〜８の直鎖、分岐、又は環状のアルコキシ基を表す。Ｍは２価の金属原子、金属酸化物を表す。

Here, R represents an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 5. When X1 to X4 are halogen atoms, Y1 to Y8 represent a linear, branched, or cyclic alkoxy group having 1 to 8 carbon atoms. M represents a divalent metal atom or metal oxide.

  Hereinafter, the phthalocyanine compound represented by Formula 1 will be described.

  First, in the chemical formula 1, X1 to X4 may be the same or different, and the phenylthio groups represented by the general formula in Y1 to Y4 may be the same or different. Good.

  The “halogenoalkoxy group having 2 to 5 carbon atoms” in the chemical formula 1 means 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoro-1-propyloxy group, 2, Examples include 2,3,3,4,4,5,5-octafluoro-1-pentyloxy group.

  The “alkyl group having 1 to 4 carbon atoms” in the chemical formula 1 is a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group.

  The “C 1-4 alkoxy group” in the above chemical formulas 1 and 2 is a linear or branched alkoxy group having 1 to 4 carbon atoms. Specific examples include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a sec-butyloxy group, a tert-butyloxy group, and an isobutyloxy group.

  Examples of the divalent metal atom represented by “M” in Chemical Formula 1 include vanadyl, copper, nickel, palladium, cobalt, and zinc. The most preferable one is vanadyl.

  And the said phthalocyanine compound used for the heat ray shielding material of this invention has the absorption maximum in the wavelength range of 700-800 nm, It is characterized by the above-mentioned.

  Specific examples thereof include compounds represented by the following chemical formula 3 and the following chemical formulas 4-1 to 4-4. In Examples described later, the compound represented by Chemical Formula 3 is referred to as Pc-01. A mixture of any of compounds represented by chemical formulas 4-1 to 4-4 and a plurality thereof is referred to as Pc-02.

これらのようなものであれば、近赤外領域のうちでこれまで十分に吸収し得なかった７００ｎｍ〜８００ｎｍの波長領域に吸収極大を有し有効に吸収することで、従来の化合物を増加させるよりもより有効に熱線を遮蔽することができる。

If it is such, it will increase the number of conventional compounds by having an absorption maximum in the wavelength region of 700 nm to 800 nm that could not be sufficiently absorbed so far in the near infrared region, and effectively absorbing it. It is possible to shield the heat rays more effectively than the above.

  Moreover, the heat ray shielding material according to the present embodiment is used in combination with an organic compound having an absorption maximum in a wavelength region longer than 800 nm, thereby further improving the heat ray shielding ability. Here, examples of “an organic compound having an absorption maximum in the wavelength range of 800 to 1100 nm” and “another phthalocyanine compound” include, for example, Compound Example 1 to Compound Example 6 below.

これら６つの化合物例のうち化合物例１、化合物例３、化合物例４及び化合物例５は、図１乃至図４に示す分光特性を有している。そしてこれら６つの化合物例のλｍａｘはそれぞれ８７５ｎｍ、８９４ｎｍ、９０９ｎｍ、９６２ｎｍ、９７８ｎｍ、８３０ｎｍである。

Of these six compound examples, Compound Example 1, Compound Example 3, Compound Example 4 and Compound Example 5 have the spectral characteristics shown in FIGS. Λmax of these six compound examples is 875 nm, 894 nm, 909 nm, 962 nm, 978 nm, and 830 nm, respectively.

<Second embodiment>
In the present embodiment, as shown in FIG. 5, an example in which the heat ray shielding material shown in the first embodiment is applied to the intermediate film 10 of the laminated glass 1 used in the automobile C will be described. In this automobile C, a laminated glass 1 according to this embodiment is applied to a windshield C1, a door glass C2, and a rear glass (not shown).

  As shown in FIG. 6, the laminated glass 1 has a structure in which an intermediate film 10 is disposed between two glass bodies 11.

  The glass body 11 depends on the use location such as the front glass C1, the rear glass, or the door glass C2. Examples thereof include inorganic glasses such as heat ray reflective glass and multilayer glass, and organic glasses such as polycarbonate plates and polymethyl methacrylate plates. These glasses may be colored glasses. The shape of the glass may be appropriately selected depending on the shape of the automobile C and the like, and may be a flat surface or a curved shape. Further, the thickness of the glass is preferably 0.5 mm or more and 5 mm or less in consideration of normally required penetration resistance.

  Although the intermediate film 10 is a single layer in the drawing, the intermediate film 10 may be a single-layer intermediate film 10 or an intermediate film 10 having a multilayer structure. In this intermediate film 10, 0.0005 to 20 parts by mass of the phthalocyanine compound according to the above embodiment is mixed in 100 parts by mass of the intermediate film resin in the intermediate film resin. In addition to the phthalocyanine compound, the intermediate film 10 also contains fine particles of antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO).

  The resin for the interlayer film is not particularly limited as long as the resin has flexibility and stretchability, but is not limited to polyvinyl alcohol resin, plasticized polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer. Examples thereof include a resin, a polyurethane resin, and a polyurethane resin containing a sulfur element. Especially, since various ions other than the phthalocyanine compound can be introduced in a hydrated state, a water-soluble polymer such as a polyvinyl alcohol resin is preferable. The interlayer film 10 further includes an antioxidant, a deterioration preventing agent, a thermal stabilizer, a dimensional stabilizer, a metal salt for adjusting the adhesive force, and an adhesive force adjusting member as long as the effect of the present embodiment, that is, the heat ray shielding effect is not impaired. Silicone oil, silane coupling agent for adjusting adhesive force, antiblocking agent, pigment, dye, colorant, light diffusing agent, light diffusing particle, antistatic agent, effective for whitening prevention by moisture absorption of interlayer film 10 Inorganic fine particles, surfactants for dispersing fine particle additives, chelating agents for trapping free metal ions, adsorbents for preventing migration of low-molecular compounds in the intermediate film 10, plasticizers Contains organic solvents, plasticizers and additives for adjusting the polarity of organic solvents, tackifiers, crystal nucleating agents, cross-linking agents, and flame retardants to prevent haze rise due to crystallization of interlayer resin It may be.

  In the laminated glass 1, in addition to the glass body 11 and the intermediate film 10, one or more layers can be additionally provided. Examples of the layer to be added include a primer layer for enhancing the adhesive force between the glass body 11 and the intermediate film 10, an ultraviolet absorbing layer containing an ultraviolet absorber, and a difficulty for preventing the laminated glass 1 from burning. Examples include a fuel layer, a decorative layer on which various patterns and characters are printed, a polyester film layer for improving penetration resistance, a hard coat layer, a dielectric layer, a deposited metal layer, a polarizing plate layer, and the like. Moreover, most of harmful ultraviolet rays can be shielded by including an ultraviolet absorber in the intermediate film 10. Examples of the ultraviolet absorber include organic ultraviolet absorbers and inorganic fine particles that absorb ultraviolet rays, such as zinc oxide fine particles, titanium oxide fine particles, and cerium oxide fine particles.

  By setting it as the above structures, the intermediate film 10 for the laminated glasses 1 which concerns on this embodiment has a strong solar radiation intensity, and the wavelength of 700-800 nm which was not able to fully shield with existing ATO and ITO. It has a feature that it selectively absorbs a region and has a high visible light transmittance. As a result, the temperature rise inside the laminated glass 1, that is, the automobile C can be effectively suppressed by shielding the heat rays more than before without increasing the amount of ATO and ITO as compared with the conventional case. Moreover, since the increase of ATO and ITO is avoided, it does not interfere with the communication of the car navigation system and ETC system which are mounted on the vehicle. As a result, it is possible to comply with cool car regulations previously proposed in the United States or similar regulations outside the United States.

  In particular, in the present embodiment, by using other phthalocyanine compounds as shown in the above chemical formulas 5 to 10 and ATO and ITO which have been used for the interlayer film 10 for the laminated glass 1 in the past, 800 to 1000 nm By effectively shielding light in the wavelength region and light in the wavelength region of 1000 nm or more, the laminated glass 1 that can further reduce the total solar transmittance and suppress the temperature rise in the vehicle is realized.

<Third embodiment>
In the second embodiment, the heat ray shielding material having flexibility and stretchability, which is applied as the intermediate film 10 of the laminated glass 1 of the automobile C, is disclosed. Of course, the heat ray shielding material according to the present invention is the laminated glass 1. The intermediate film 10 is not limited to this, and a film-like resin material or a hard resin material having shape retention may be used.

  FIG. 7 illustrates the vicinity of a terrace of a house as an example to which the heat ray shielding material according to the present embodiment is applied. In the same figure, like a normal house, a mode in which a terrace roof T installed as a protection against rain and sun is installed at the upper part of the window W which is the entrance of the house is illustrated.

  The terrace roof T includes a column T1 standing outdoors, a roof frame T2 attached to the column T1 and a part of the building, and a transparent or translucent resin board fixed to the roof frame T2. 2. The resin board 2 is firmly held by the roof frame T2 by being sandwiched by the roof frame T2 from above and below. Further, the terrace roof T is provided with a rain gutter provided over the roof frame T2 and the support column T1, but detailed description thereof is omitted.

  The window W has a normal form provided in the building, and is a rectangular frame-shaped sash W1 attached to the opening of the building, and a window frame W2 that can slide and slide in the sash W1. And a window glass 3 attached to the window frame W2.

  Therefore, in this embodiment, while the resin board 2 of the terrace roof T has the heat ray shielding plate 20 according to this embodiment, the window glass 3 is the heat ray shield according to this embodiment. It has a film 30.

  As shown in FIG. 8, the resin boat includes a transparent plate 21 made of, for example, a transparent resin material disposed on the front and back and the middle, and a heat ray shielding plate 20 disposed between the transparent plates 21.

  The heat ray shielding plate 20 is obtained by mixing a phthalocyanine compound by melt kneading with a hard resin having shape retention property as in the above embodiment. Here, the resin material constituting the transparent plate 21 and the heat ray shielding plate 20 may be the same material or different materials. Examples of the hard resin having a shape-retaining property include various existing resin materials such as an acrylic resin, a polycarbonate resin, a polypropylene resin, and an ABS resin.

  As shown in FIG. 9, the window glass 3 includes a glass main body 31 made of a glass material that can be used for a normal window glass 3, and a heat ray shielding film 30 attached to, for example, the outdoor side or the indoor side of the glass main body 31. have. The heat ray shielding film 30 includes a film layer 32 in which a phthalocyanine compound is mixed in a resin material having flexibility as described above or appropriately coated, and an adhesive for closely attaching the film layer 32 to the crow body. Layer 33. Various resin materials can be considered as the resin material that can form the film layer 32. Examples of the resin material include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC). Mention may be made of plastic films. The pressure-sensitive adhesive layer 33 only needs to be made of a pressure-sensitive adhesive that can transmit light in the visible region as in the case of the glass body 31. Of course, the aspect of mixing the phthalocyanine compound according to the present embodiment is not hindered as described above. As an example of the pressure-sensitive adhesive, various existing pressure-sensitive adhesives such as a hot-melt pressure-sensitive adhesive made of an acrylic polymer or a styrene-based polymer and a solvent-based pressure-sensitive adhesive can be applied.

  Also in the present embodiment, the heat ray shielding plate 20 and the heat ray shielding film 30 are prepared by mixing ATO and ITO in the same manner as the intermediate film 10 of the second embodiment, in addition to the phthalocyanine compound. Needless to say, other various compounds may be mixed in the same manner as in the intermediate film 10 or a special layer having a different function may coexist.

  Even in such a case, as in the above embodiment, it is possible to reduce the total solar transmittance by effectively shielding near-infrared light and obtain the same effect as in the above embodiment.

  Although the embodiment of the present invention has been described above, the specific configuration of each unit is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.

  For example, although the aspect which applied this invention to the laminated glass of an automobile, the terrace roof, and the window glass was disclosed in the said embodiment, of course, you may apply to a ship, an aircraft, and another vehicle. Moreover, specific aspects, such as a dimension and shape of a heat ray shielding material, are not limited to the thing of the said embodiment, The thing of various aspects including an existing thing is applicable.

  In addition, the specific configuration of each part is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.

  Hereinafter, material examples of the present invention, specifically, material example 1 in which the above phthalocyanine compound is included in an interlayer film of laminated glass, and the phthalocyanine compound are contained in a resin formed into a sheet on the glass surface. The material example 2 will be described. Here, the present invention is not limited by these material examples.

<Material Example 1>
In a 100 ml beaker, 4.00 g of polyvinyl butyral, 1.04 g of triethylene glycol bis (2-ethylhexoate), 0.38 g of ATO fine particle MEK dispersion (ATO content 29.5%), phthalocyanine compound Pc-02 1 mg and 80 ml of THF were charged, and this mixture was stirred at room temperature for 1 hour to completely dissolve polyvinyl butyral in THF. Next, this solution was poured into a Teflon (registered trademark) coating vat (158 mm × 120 mm × 25 mm), allowed to stand at room temperature for 1 day, and then dried at 40 ° C. for 5 hours to obtain a polyvinyl butyral interlayer film. The obtained interlayer film was cut out to a size of 40 mm × 40 mm, and sandwiched between a glass plate of 40 mm × 40 mm having a thickness of 2 mm and two glass plates of the same size having a thickness of 1.0 mm. Further, it was sandwiched between two rubber plates and then two stainless steel plates, and crimped using a small vise. Next, the polyvinyl chloride containing ATO fine particles and the phthalocyanine compound Pc-02 was put in a vacuum dryer together with the small vise in the pressure-bonded state, deaerated at room temperature under reduced pressure for 1 hour, and then heat-pressed at 90 ° C. for 2 hours. A laminated glass having a butyral interlayer film, ie, material example 2-1, was obtained.

  The transmission spectrum, transmittance, and reflectance of the obtained laminated glass were measured with a spectrophotometer (manufactured by JASCO: V-570). The transmittance spectral chart is shown in FIG. 10, and the transmittance and reflectance data are shown as a table in FIG. Further, the values of visible light transmittance, visible light reflectance (380 nm to 780 nm), solar transmittance, and solar reflectance (300 nm to 2500 nm) were measured in accordance with JIS 3107 (1998) standards.

  Except that the phthalocyanine compound Pc-02 was not used, all operations were carried out in the same manner as in the Examples to obtain Material Comparative Example 1-1 which was a laminated glass having a polyvinyl butyral interlayer film containing ATO fine particles.

  The transmission spectrum, transmittance, and reflectance of the obtained laminated glass were measured with a spectrophotometer (manufactured by JASCO: V-570). The transmittance spectral chart is shown in FIG. 11, and the transmittance and reflectance data are shown as a table in FIG. Further, the values of visible light transmittance, visible light reflectance (380 nm to 780 nm), solar transmittance, and solar reflectance (300 nm to 2500 nm) were measured in accordance with JIS 3107 (1998) standards.

<Material Example 2>
Polymethyl methacrylate (hereinafter referred to as PMMA) 7.5g, chlorobenzene 15.3g, toluene 6g, ethyl acetate 6.3g and acetone 5.5g were mixed to obtain a PMMA preparation solution. In a solution obtained by diluting 1 g of this preparation solution with 0.6 mL of toluene and 0.6 mL of chloroform, 12 mg of a phthalocyanine compound Pc-01 having the following structural formula is dissolved, and the resulting solution is an ITO made of a glass plate on which ITO is deposited. The layer was spin-coated and dried to form a phthalocyanine compound-containing layer. Let the heat ray shielding material in which the said phthalocyanine type compound containing layer was formed be material Example 2-1.

  The transmission spectrum, transmittance, and reflectance of the obtained material example 2-1 were measured with a spectrophotometer (manufactured by JASCO: V-570). A spectral chart of transmittance is shown in FIG. The values of visible light transmittance, visible light reflectance (380 nm to 780 nm), solar transmittance, and solar reflectance (300 nm to 2500 nm) are measured in accordance with the standard of JIS A 5759, and the transmittance and reflectance are measured. These data are shown as a table in FIG.

  When preparing the coating solution, the coating solution was obtained in the same manner as in Example 1 except that 10 mg of Pc-02 formed from the mixture of the following structural formula was dissolved by changing the phthalocyanine compound to Pc-01. Material Example 2-2 was prepared. The transmittance chart according to the obtained material example 2-2 is shown in FIG. Further, the transmittance and reflectance data are shown as a table in FIG.

  Comparative Example 2-1 was obtained in the same manner as in Example 1 except that the phthalocyanine compound was not added in Example 2-1. The transmittance chart of the obtained heat ray shielding material is shown in FIG. 3, and the transmittance and reflectance data are shown in Table 1.

  As is clear from the material example 1 and the material example 2 shown above, each of the material examples 1-2, 2-1 and 2-2 is compared with the material comparative examples 1-1 and 2-1, respectively. Thus, the visible light transmittance is kept high so that there is no fading. Specifically, in FIG. 12, the visible light transmittance of material example 1-2 shows a high value of 70% or more, and in FIG. 16, the visible light transmittances of material examples 2-1 and 2-2 are shown. A high value of 80% or more is shown. In particular, in each of the above-described material examples, an extreme value with low transmittance appears in the wavelength region of 700 nm to 800 nm, whereas in the material comparative example 1, the same extreme value does not appear in the wavelength region. That is, as shown in FIGS. 12 and 16, the existence of the extreme values according to the material example 1-2, the material example 2-1 and the material example 2-2 shown in FIGS. It is clear that the solar absorptance is a cause of clearly higher values than those of the material comparative example 1-1 and the material comparative example 2-1.

  In addition, although the above extreme values all appear as steep curves, the absorption rate of solar radiation is greatly increased because light having a wavelength of 700 nm to 800 nm, which is considered to be strong in solar radiation, is applied to each of the above materials. It is thought that it originates in the compound which concerns on an example shielding effectively. As a result, it has been clarified that each of the material examples can provide a heat ray shielding material capable of effectively shielding heat rays while maintaining a high visible light transmittance.

  In addition, the extreme value is represented by a steep curve, which means that light having a wavelength in the vicinity of 700 nm to 800 nm that is intensely irradiated in the solar radiation by using a plurality of compounds having different wavelengths at which the extreme value is indicated. The possibility of more effective absorption is also suggested.

  Here, in FIG. 10, FIG. 13 and FIG. 14, the decrease in the transmittance of 1000 nm or more is considered to be due to ITO deposited on the glass. When it sees, it is clear that the heat ray shielding material which concerns on the said embodiment can shield a heat ray more effectively, avoiding increasing the amount of ITO etc. which are used as a heat ray shielding agent from before.

  Furthermore, the extreme value is represented by a steep curve, and it can be seen that the transmittance of 800 nm to 1000 nm, which is actually strong in solar radiation, does not decrease so much. That is, by using together with another compound having a wavelength of 800 nm to 1000 nm at which the extreme value is shown, the light of the wavelength around 900 nm that is strongly irradiated in the solar radiation is absorbed more effectively, and the heat ray shielding has a further effect. The possibility of providing material is also suggested.

  The present invention is for a laminated glass, a resin translucent plate, and a window glass that are suitably used for automobiles, railway vehicles, aircraft, ships, buildings, etc. by effectively shielding light having a wavelength in the near infrared region. It can utilize as a heat ray shielding material which comprises a sticking film.

10 ... Heat ray shielding material (intermediate film)
20 ... Heat ray shielding material, resin (heat ray shielding plate)
30 ... Film (heat shielding film)

Claims (12)

A heat ray shielding material comprising a phthalocyanine compound represented by the following chemical formula 1.

(X1 to X4 are all hydrogen atoms . In the combination of Y1 and Y2, Y3 and Y4, Y5 and Y6, Y7 and Y8, one represents a hydrogen atom, and one represents a phenylthio group represented by the following general formula. Represents.)

(Here, R represents an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, n represents an integer of 1 to 5. M represents a divalent metal atom or metal oxide. Represents.) The heat ray shielding material according to claim 1, wherein M represents vanadyl. The heat ray shielding material according to claim 1 or 2, wherein the phthalocyanine compound is contained in a sheet-like resin. The heat ray shielding material according to claim 3 , wherein the amount of the phthalocyanine compound is 0.0005 to 20 parts by mass with respect to 100 parts by mass of the resin. The heat ray shielding material according to claim 3 or 4, wherein the sheet-like resin has flexibility and is used as an intermediate film of laminated glass. The heat ray shielding material according to claim 3 or 4, wherein the sheet-like resin is flexible and is used as a film adhered to glass. The heat ray shielding material according to claim 3 or 4, wherein the sheet-like resin is a hard material having shape retention. The heat ray shielding material according to claim 1, 2, 3, 4, 5 or 6, which contains fine particles of antimony-doped tin oxide or tin-doped indium oxide. The heat ray shielding material according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the phthalocyanine compound has an absorption maximum in a wavelength range of 700 to 800 nm. The heat ray shielding material according to claim 1, further comprising an organic compound having an absorption maximum in a wavelength range of 800 to 1100 nm. The heat ray shielding material according to claim 10, wherein the organic compound is another phthalocyanine compound different from the phthalocyanine compound. In the combination of Y1 and Y2, Y3 and Y4, Y5 and Y6, Y7 and Y8, one is a hydrogen atom, and one is represented by the following chemical formulas: 1, 2, 3, 4, 5, The heat ray shielding material according to 6, 7, 8, 9, 10 or 11.

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