JP2016093892A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate suitable for a window laminating application having excellent scratch resistance and excellent weather resistance even when making a protection layer thin for exhibiting solar radiation shielding property and heat resistance at high level.SOLUTION: There is provided a laminate having at least heat ray reflection layer and a hard coat layer on a single side surface of a substrate in this order from a substrate side, the heat ray reflection layer has a metal thin film and a metal oxide thin film, the hard coat layer contains a crosslinked resin (A) having one or more kind of polar groups selected for a phosphate group, a sulfonate group and an amide group and an inorganic particle (B), and the content of the inorganic particle is 40 to 60 mass% based on 100 mass% of the total component contained in the hard coat layer.SELECTED DRAWING: None

Description

  The present invention relates to a laminate.

  2. Description of the Related Art Conventionally, a laminate in which a heat ray reflective layer in which metal thin films / metal oxide thin films are alternately laminated on a glass of an opening of a house / building, for example, a window, and a protective layer are sequentially formed has been used. These laminated bodies can suppress the inflow of solar heat (near infrared) from the outside to the room and the outflow of heating heat (far infrared gland) from the room to the outside by the infrared reflective function of the metal thin film. , Energy saving effect can be obtained throughout the year. Furthermore, by laminating a metal oxide thin film with a high refractive index, the transparency is improved and the appearance visibility is secured, and by laminating a protective layer, the metal thin film and the metal oxide thin film are protected, and the scratch resistance and weather resistance. Sex is expressed.

  As the above-mentioned laminate, for example, after alternately laminating metal thin films such as gold, silver, and copper and metal oxide films on a transparent polymer film, the heat ray shielding performance is obtained by further laminating silicon oxide or acrylic resin as a protective layer. The transparent laminated body which has is proposed (refer patent document 1).

JP 2012-135888 A

  In the transparent laminate described in Patent Document 1, a material containing silicon oxide or acrylic resin is used for the protective layer in order to obtain a transparent laminate suitable for window pasting that has both high solar shielding properties and high heat insulation properties. The modified emissivity (infrared absorptance) of the protective layer is reduced by reducing the thickness of the protective layer. However, the present inventor has shown that the silicon oxide or acrylic resin used in the protective layer exhibits scratch resistance and weather resistance at a level sufficient for window pasting when it is thinned to reduce the modified emissivity. I found a problem that I could not do. That is, when the protective layer is made thin, a transparent laminate having a low correction emissivity and excellent solar radiation shielding properties and heat insulation properties can be obtained, while the scratch resistance and weather resistance are reduced. It was.

  Therefore, in view of such problems, the present invention is a window pasting application that has excellent scratch resistance and excellent weather resistance even when the protective layer is thinned to express solar radiation shielding and heat insulation at a high level. It is intended to provide a suitable laminate.

The present invention employs the following means in order to solve such problems.
(1) At least a heat ray reflective layer and a hard coat layer are laminated in this order from the substrate side on one side of the substrate, the heat ray reflective layer has a metal thin film and a metal oxide thin film, and the hard coat layer is phosphorus It contains a crosslinked resin (A) having at least one polar group selected from the group consisting of an acid group, a sulfonic acid group and an amide group, and inorganic particles (B), and the content of the inorganic particles (B) is A laminate characterized by 40 to 60% by mass with respect to 100% by mass of all components contained in the hard coat layer;
(2) The laminate of (1), wherein the crosslinked resin (A) is a crosslinked resin containing a phosphate group,
(3) The laminate according to (1) or (2), wherein the inorganic particles (B) are silica.
(4) The laminate according to (3), wherein the silica is not subjected to a hydrophobic treatment,
(5) The thickness of the hard coat layer is 0.5 to 1.5 μm, and the infrared reflectance at a wavelength of 5.5 to 15 μm is 50% or more (1) to (4) Any laminate of.

  According to the present invention, even when the protective layer is thinned to achieve high levels of solar shading and heat insulating properties, the laminate is suitable for window pasting applications having excellent scratch resistance and excellent weather resistance. Can be obtained.

  The laminate of the present invention is a laminate in which at least a heat ray reflective layer and a hard coat layer are laminated in this order from the substrate side on one side of the substrate, and the heat ray reflective layer has a metal thin film and a metal oxide thin film. The hard coat layer includes a crosslinked resin (A) having at least one polar group selected from the group consisting of a phosphoric acid group, a sulfonic acid group, and an amide group, and inorganic particles (B), and the inorganic particles Content of (B) is 40-60 mass% with respect to 100 mass% of all the components contained in a hard-coat layer.

  The substrate used in the present invention is not particularly limited as long as it has excellent visible light transmission performance and weather resistance. However, when used for window pasting applications, it has flexibility and excellent handleability. It is preferable that the synthetic resin is included. Here, the synthetic resin is preferably, for example, polyethylene terephthalate, polycarbonate, acrylic, nylon, or the like, and is required when forming a heat ray reflective layer (hereinafter referred to as a heat ray reflective layer) composed of a metal thin film and a metal oxide thin film. In view of heat resistance, cost, etc., polyethylene terephthalate is more preferable. In addition, from the viewpoint of improving the adhesion between the substrate and the heat ray reflective layer, an easy adhesion layer is provided on the surface of the substrate on which the heat ray reflective layer is laminated, or surface treatment such as corona treatment, plasma treatment, saponification, etc. It is preferable to apply. Here, examples of the resin used for the easy adhesion layer include a polyester resin, an acrylic resin, and a urethane resin. Although there is no restriction | limiting in particular about the thickness of this base material, It is preferable that it is 10-150 micrometers when the handleability at the time of using mechanical strength, heat resistance, and a window sticking use is considered. By setting the thickness to 10 μm or more, generation of wrinkles due to thermal shrinkage can be suppressed in the surface treatment process of the base material and the formation process of the metal layer and metal oxide layer, and the window breakage prevention performance and crime prevention Performance and the like can be imparted. On the other hand, by making the thickness 150 μm or less, the amount of necessary materials can be reduced, leading to a reduction in the environmental burden, and making the workability when constructing the laminated body to a window or the like better. Can do.

Next, the heat ray reflective layer is a laminate of a metal thin film and a metal oxide thin film on a substrate,
As the simplest configuration, a configuration in which a metal oxide thin film is laminated on one of upper and lower surfaces of a metal thin film can be exemplified. Alternatively, a metal thin film and a metal oxide thin film may be alternately stacked to have a three-layer structure of metal oxide thin film / metal thin film / metal oxide thin film.
By adopting this configuration, it is possible to suppress visible light interface reflection between the metal thin film and the hard coat layer, or between the metal thin film and the substrate, and to improve the visible light transmission performance. Further, the heat ray reflective layer is composed of (I) metal oxide thin film / metal thin film / metal oxide thin film / metal thin film / metal oxide thin film, or (II) metal oxide thin film / metal thin film / metal oxide. The seven-layer structure of thin film / metal thin film / metal oxide thin film / metal thin film / metal oxide thin film can improve the infrared light reflection performance in addition to the improvement of the visible light transmission performance. Generally, as the number of layers is increased, there is a tendency to obtain a laminate excellent in visible light transmission performance and infrared reflection performance, but from the viewpoint of balance between improvement in performance and handleability of the laminate, the laminate of the present invention. The number of layers possessed by is preferably 7 or less as the upper limit.

  The metal thin film used in the present invention is not particularly limited as long as it is excellent in infrared reflection performance. For example, silver, gold, platinum, copper, aluminum and the like are preferable, and particularly excellent in infrared reflection performance. It is preferable that silver is a main component. Here, the above-mentioned main component means that the silver content contained in the metal thin film exceeds 50 mass% when all the components of the metal thin film are 100 mass%, and the silver content is 90%. It is preferable that it is mass% or more. Furthermore, it is also preferable to use an alloy in which at least one kind of palladium, bismuth, nickel, niobium, magnesium, zinc or the like is added in addition to the above-described metal for the purpose of improving the corrosion resistance of silver. Among these metals, it is particularly preferable to contain gold and / or palladium from the viewpoint of achieving both infrared reflection performance and corrosion resistance. Further, the content of gold and / or palladium is not particularly limited, but from the viewpoint of corrosion resistance and cost, when all the components of the metal thin film are 100% by mass, the total number of gold atoms and palladium atoms is 2 to 2. It is preferable to contain 5 mass%. If it is less, the effect of suppressing silver corrosion cannot be obtained. On the other hand, if the amount is too large, an improvement effect commensurate with the cost increase cannot be obtained only by an increase in cost. Although there is no restriction | limiting in particular about the thickness of a metal thin film, It is preferable to select suitably in the range of 5-20 nm in view of the required infrared reflective performance and visible light transmission performance. If the thickness is thin, the visible light transmission performance is excellent, but the infrared reflection performance is degraded. On the other hand, if it is too thick, the visible light transmission performance is lowered, the amount of metal used is increased, and this is not economically preferable.

  Next, for the metal oxide thin film used in the present invention, it is preferable to use a metal oxide having a high refractive index at a wavelength of 500 nm from the viewpoint of reducing visible light interface reflection and improving visible light transmission performance. Specific examples include oxides such as titanium, niobium, zinc, tin, indium, and zirconium. One or more of these metal oxides are preferably selected and used. The thickness of the metal oxide thin film is preferably 10 nm or more, and more preferably 30 nm or more. On the other hand, the upper limit is preferably 100 nm or less, and more preferably 60 nm or less. By setting the thickness of the metal oxide thin film to 10 nm or more, it is possible to suppress the reflection of visible light and obtain a laminate having excellent visible light transmission performance. On the other hand, even if the thickness of the metal oxide thin film exceeds 100 nm, not only the material cost increases but also the visible light transmission performance cannot be further improved.

  In addition, the metal oxide thin film sufficiently contains oxygen from the viewpoint of improving the visible light transmission and improving the adhesion between the metal thin film and the metal oxide thin film and improving the durability of the laminate. It is preferable that However, if the metal oxide thin film is formed in an oxygen-rich atmosphere so that the metal oxide thin film contains sufficient oxygen, the metal thin film underlying the metal oxide thin film is oxidized. As a result, the infrared reflecting performance of the laminate tends to decrease. Therefore, when forming a metal oxide layer sufficiently containing oxygen, a barrier layer is formed between the metal thin film and the metal oxide thin film so as to suppress oxidation of the underlying metal thin film. preferable. Here, the barrier layer is a layer having a lower oxygen content than the metal oxide thin film, and a volume-based flow rate (hereinafter referred to as a flow rate) in the atmosphere when forming the barrier layer is 2%. It can be obtained by setting it to 5% or less. Note that the flow rate in the atmosphere when forming the metal oxide thin film is preferably more than 5% and 15% or less, and from the viewpoint of making oxygen contained in the metal oxide thin film more sufficient, the lower limit is It is more preferably 10% or more, and further preferably 15% or more.

  Further, the thickness of the barrier layer is preferably 1 nm or more, and more preferably 2 nm or more. When the thickness of the barrier layer is 1 nm or more, oxidation of the metal thin film is suppressed when the metal oxide thin film is formed, and a laminate that is more excellent in infrared reflection performance can be obtained. By making the thickness of the barrier layer 2 nm or more, the above effect becomes more remarkable. On the other hand, the upper limit is preferably 10 nm or less, more preferably 8 nm or less, still more preferably 6 nm or less, and particularly preferably 4 nm or less. By setting the thickness of the barrier layer to 10 nm or less, a laminate superior in visible light transmission performance can be obtained. This tendency becomes more prominent as the barrier layer becomes thinner. The thickness of the metal thin film, metal oxide thin film, and barrier layer can be analyzed by appropriately using a known method such as a transmission electron microscope (TEM) or an optical film thickness meter. These metal thin films, metal oxide thin films, and barrier layers can be formed by vapor deposition methods such as vacuum deposition, sputtering, and ion plating, but there are a wide variety of materials that can be formed. It is preferable to use a sputtering method by which a quality film can be obtained.

Next, the hard coat layer used in the present invention has a function of protecting the metal thin film and the metal oxide thin film, that is, a protective layer, which is one kind selected from the group consisting of a phosphoric acid group, a sulfonic acid group, and an amide group. It is essential to include the crosslinked resin (A) having the above polar group. The cross-linked resin (A) is selected from the group consisting of monofunctional, bifunctional, and polyfunctional acrylates, methacrylates, urethane acrylates, epoxy acrylates, and the like, and a phosphoric acid group, a sulfonic acid group, and an amide group. One or more polar groups are introduced. As a method of obtaining a crosslinked resin (A) by introducing a polar group into the crosslinked resin, an acrylic acid derivative or a methacrylic acid derivative having a polar group such as phosphoric acid, amide, or sulfonic acid is mixed with the crosslinked resin, and ultraviolet rays or electron beams are mixed. The method of irradiating electromagnetic waves, such as, is mentioned. As the above-mentioned acrylic acid derivative and methacrylic acid derivative, those having a phosphoric acid group are preferable, and examples thereof include hydrogen phosphate = bis [2- (methacryloyloxy) ethyl] and 2- [methacryloyloxy] ethyl phosphate. be able to. A metal oxide thin film that is a base of the hard coat layer by including in the hard coat layer a cross-linked resin (A) having at least one polar group selected from the group consisting of a phosphoric acid group, a sulfonic acid group, and an amide group It is possible to improve the adhesion to the surface and improve the scratch resistance and weather resistance. Here, from the viewpoint of more prominently obtaining the effects described above, the crosslinked resin (A) is preferably a crosslinked resin containing a phosphate group.
In addition, the crosslinked resin used in the present invention is mainly composed of a polyfunctional urethane acrylate having high hardness and excellent extensibility from the viewpoint of further improving the scratch resistance and flexibility required for a window pasting film, and curing at the time of crosslinking. From the viewpoint of reducing shrinkage and suppressing curling, it is preferable to use one or more selected from the group consisting of bifunctional acrylates, methacrylates, urethane acrylates and epoxy acrylates. Here, the main component means that the content of the polyfunctional urethane acrylate contained in the hard coat layer exceeds 50% by mass when the total mass of the crosslinked resin (A) is 100% by mass.

In addition, the hard coat layer of the present invention must contain 40 to 60% by mass of inorganic particles (B) when all components contained in the hard coat layer are 100% by mass.
Window pasting film repeats thermal expansion and contraction due to the effects of solar heat in the daytime and the difference in temperature between day and night, so if the thermal expansion coefficient of the hard coat layer and the underlying metal oxide thin film differ greatly, metal oxidation will occur. The adhesion between the physical thin film and the hard coat layer decreases with time, causing a problem that cracks and peeling occur in the hard coat layer, resulting in a laminate having poor weather resistance. Therefore, it is necessary to add the inorganic particles (B) to the crosslinked resin (A) that is an organic substance so that the thermal expansion coefficient of the hard coat layer is close to that of the metal oxide thin film that is an inorganic substance. When the addition amount of the inorganic particles (B) is less than 40% by mass, the thermal expansion coefficient of the hard coat layer is increased and the above-described effects cannot be obtained. On the other hand, when it exceeds 60% by mass, the amount of the crosslinked resin (A) in the hard coat layer is decreased, the hardness of the hard coat layer is lowered, and the scratch resistance is lowered. The lower limit of the added amount of the inorganic particles (B) is more preferably 45% by mass or more, and the upper limit is more preferably 55% by mass or less. By making the addition amount of the inorganic particles (B) in the above-described range, a laminate excellent in the balance of scratch resistance and weather resistance can be obtained.

  The inorganic particles (B) used in the present invention are preferably oxide particles containing at least one element of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Examples of the oxide of the particles described above include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, antimony oxide, cerium oxide, and the like. These oxides of particles can be used alone or in combination of two or more. Of these oxide particles, it is preferable to use an oxide of silicon, and more preferable to use silica in order to develop durability as a laminate.

  Furthermore, these inorganic particles (B) are not subjected to surface treatment, so that the adhesion between the hard coat layer and the metal oxide thin film as the base is improved, and the scratch resistance and weather resistance are improved. preferable. In addition, the surface treatment mentioned here means hydrophobic treatment with a silane coupling agent or the like. By using inorganic particles that have not been subjected to hydrophobic treatment, the adhesion between the crosslinked resin (A) and the inorganic particles (B) is improved, and the weather resistance is further improved.

  Further, the hard coat layer may have a single layer structure, but may be formed of two or more different layers. For example, a two-layer structure including a layer composed of a crosslinked resin not containing a polar group and inorganic particles (B), a crosslinked resin containing a polar group (A) and inorganic particles (B) may be used. However, in this case, it is preferable to form a layer of a crosslinked resin (A) containing a polar group and an inorganic particle (B) in a layer in contact with the metal oxide thin film from the viewpoint of improving adhesion.

  The thickness of the hard coat layer is preferably 0.5 to 1.5 μm. By setting the thickness of the hard coat layer to 0.5 μm or more, the scratch resistance of the laminate can be further improved, and by setting the thickness of the hard coat layer to 1.5 μm or less, the infrared absorption amount of the hard coat layer Can be further reduced, and the infrared reflection performance of the laminate can be further improved. Furthermore, in order to improve the infrared reflectance of the laminate, the type of the crosslinked resin used for the crosslinked resin (A) is appropriately selected, and the infrared reflectance at a wavelength of 5.5 to 15 μm, which is the infrared absorption peak of the crosslinked resin. Is preferably 50% or more in order to increase the infrared reflectance of the laminate. Here, from the viewpoint of obtaining a laminate having excellent scratch resistance and high infrared reflectance, the hard coat layer has an infrared reflectance of 0.5 to 1.5 μm and a wavelength of 5.5 to 15 μm. Is more preferably 50% or more.

  The hard coat layer is formed by applying a resin solution using a gravure coating method, reverse roll coating method, roll coating method, dip coating method, etc., drying, and then irradiating with ultraviolet rays, electron beams, etc. can do.

  Next, an undercoat layer may be formed between the substrate and the heat ray reflective layer. By forming the undercoat layer, the adhesion between the base material and the heat ray reflective layer is improved, and corrosion of the metal thin film can be suppressed, which is preferable. As the material for forming the undercoat layer, a resin is preferable, and a material having high transparency and durability is preferable. For example, an acrylic resin, a urethane resin, a fluorine resin, a silicone resin, or the like can be used alone or a mixture thereof. These undercoat layers are coated with a resin-containing solution by a known technique such as a gravure coating method, reverse roll coating method, roll coating method, dip coating method, etc., dried, and then, if necessary, ultraviolet rays, electron beams, etc. Can be formed by irradiating and curing. The thickness of the undercoat layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, it is preferably 5 μm or less, and more preferably 3 μm or less. By setting the thickness of the undercoat layer to 0.5 μm or more, the substrate surface can be coated more uniformly, and the scratch resistance can be sufficiently improved. On the other hand, handling property can be improved more by making the thickness of an undercoat layer into 5 micrometers or less.

  In addition, the laminated body of this invention can be affixed on a window glass etc. by providing an adhesion layer in the surface on the opposite side to the surface where the thermal warfare reflection layer and hard-coat layer of a base material are laminated | stacked.

  Hereinafter, the present invention will be described more specifically with reference to examples. The production method of the test specimen for evaluation used for the measurement of the characteristic values shown in the examples and the measurement / calculation method of the characteristic values are as follows.

A. Preparation of test specimen for evaluation (1) The laminate is cut into a 50 mm square.
(2) An adhesive layer is formed on the surface opposite to the surface on which the hard coat layer of the film cut in the above (1) is formed.
(3) Next, it is bonded to a 3 mm thick float glass through the adhesive layer formed in the item (2).

B. Scratch resistance (1) Measuring method:
i) The surface of the specimen is reciprocated 50 times with steel wool (Bonster # 0000, manufactured by Nippon Steel Wool Co., Ltd.) using a Gakushin type friction tester (for example, RT-200 manufactured by Daiei Kagaku Seisakusho Co., Ltd.). In addition, a friction element: 30 mm × 10 mm and a load: 500 g. ii) Visually confirm the surface of the test specimen after evaluation.
(2) Judgment criteria “：”: occurrence of flaws of 5 or less / 10 mm), “◯”: occurrence of flaws of 10 or less / 10 mm, “x”: occurrence of flaws of 11 or more / 10 mm
C. Weather resistance (1) Standard: Conforms to JIS A5759-2008 (2) Measurement method:
i) Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), irradiate ultraviolet rays from the glass surface side of the specimen. The irradiation conditions are as described in Table 10 of JIS A5759 (black panel temperature 63 ° C., relative humidity 50%, radiation intensity 255 W / m ² , water spraying for 18 minutes during 120 minutes irradiation), irradiation time 1000 hours, 2000 Time.
(3) Criteria:
“◎”: Hard coat layer peeling and no crack after 2000 hour test, “◯”: Hard coat layer peeling and no crack after 1000 hour test, “×”: Hard coat in 1000 hours or less Layer peeling or cracking.

D. Far-infrared reflectance (thermal insulation)
(1) Standard: based on JIS R3106-1998 (2) Measurement method:
i) Using a spectrophotometer “IR Prestige-21 (manufactured by Shimadzu Corporation)” and a specular reflection measurement unit “SRM-8000A (manufactured by Shimadzu Corporation)”, spectral reflection of a test specimen for evaluation having a wavelength of 5 to 25 μm. Measure the rate. An Al vapor deposition mirror is used for the standard plate.
ii) Extract the spectral reflectance at the selected wavelengths of the numbers λ1 (wavelength 5.5 μm) to λ30 (wavelength 50 μm) described in Appendix 3 of the JIS text from the spectral reflectance. In addition, the value of (lambda) 24 (wavelength 23.3 micrometers) is used for the reflectance of (lambda) 25 (wavelength 25.2 micrometers)-(lambda) 30 (wavelength 50 micrometers).
iii) Multiply the extracted spectral reflectance by the standard reflectance of the Al vapor deposition mirror described in Appendix 3 of the JIS text to obtain the reflectance of the evaluation specimen at the selected wavelength of λ1 to λ30.
iV) The average value of the reflectance is defined as the far-infrared reflectance.
(3) Measurement conditions: Wavelength range “5 to 25 μm”, avodis coefficient “Happ-Genzel”, integration count “20 times”, resolution “4.0 cm −1”.

E. Solar heat acquisition rate (sunlight shielding)
(1) Standard: based on JIS R3106-1998 (2) Measurement method:
i) Using a spectrophotometer “UV-3150 (manufactured by Shimadzu Corporation)”, the spectral transmittance and spectral reflectance of the test specimen for evaluation at a wavelength of 300 to 2500 nm are measured at 1 nm intervals. ii) After multiplying the transmittance / reflectance by the weight coefficient described in Appendix 2 of the JIS text, the total value is calculated to be the solar transmittance / reflectance (%). iii) The solar heat acquisition rate is calculated using the calculation formula in 8.4 of the JIS text.
(3) Measurement conditions: scan speed “high speed”, resolution capability “10 nm”.

[Example 1]
An acrylic hard coating agent “Ray Queen” (registered trademark, the same applies hereinafter) RQ-5105 (manufactured by Mitsubishi Rayon Co., Ltd.) was applied to one side of a 50 μm thick PET film, dried, and then irradiated with UV to a thickness of 3 μm. A thick undercoat layer was formed to provide a base material for the laminate. Next, a 40 nm thick first metal oxide thin film was formed on the undercoat layer of the base material using a sputtering target material having a metal composition of tin: zinc = 65 mass%: 35 mass%. (The sputtering gas is argon: oxygen = 90%: 10% (flow rate ratio)). Subsequently, a metal thin film having a thickness of 16 nm was formed on the first metal oxide thin film using a sputtering target material containing 3% by mass of gold in silver (sputtering gas is argon = 100%). . Further, a barrier layer having a thickness of 2 nm was formed using the same sputtering target material as the first metal oxide thin film (sputtering gas was argon: oxygen = 98%: 2% (flow rate ratio)), and metal The thin film was masked. Next, a second-layer metal oxide thin film having a thickness of 50 nm is formed on the barrier layer using the same sputtering target material as the first-layer metal oxide thin film (sputtering gas is argon: oxygen = 90%: 10% (flow rate ratio)) On the PET film, heat ray reflection formed of the first metal oxide thin film / metal thin film / barrier layer / second metal oxide thin film was formed.

  Next, an acrylic hard coat agent was applied on the heat ray reflective layer, dried, and then irradiated with UV to form a hard coat layer having a thickness of about 0.7 μm to obtain a laminate.

  In addition, about the acrylic hard coat agent which is a hard-coat layer, 6 functional urethane acrylate: 2 functional acrylate = 80 mass%: 50 mass% of crosslinked resin which consists of 20 mass%, 2 mass% of methacrylic acid derivatives which have a phosphate group Silica (with hydrophobic treatment) 40% by mass and polymerization initiator 8% by mass diluted with an equal amount of solvent were used.

  [Example 2] The composition of the hard coating agent was changed to 40% by mass of a crosslinked resin, 2% by mass of a methacrylic acid derivative having a phosphoric acid group, 50% by mass of silica (with hydrophobic treatment) and 8% by mass of a polymerization initiator. Except for the above, a laminate was obtained in the same manner as in Example 1.

  [Example 3] The composition of the hard coat agent was changed to 30% by mass of a crosslinked resin, 2% by mass of a methacrylic acid derivative having a phosphoric acid group, 60% by mass of silica (with hydrophobic treatment) and 8% by mass of a polymerization initiator. Except for the above, a laminate was obtained in the same manner as in Example 1.

  [Example 4] A laminate was obtained in the same manner as in Example 1 except that the silica used in the hard coating agent was changed to "no hydrophobic treatment".

  [Example 5] A laminate was obtained in the same manner as in Example 3 except that the silica used in the hard coating agent was changed to "no hydrophobic treatment".

  [Comparative Example 1] A laminate in the same manner as in Example 1 except that the composition of the hard coat agent was changed to 52% by mass of the crosslinked resin, 40% by mass of silica (with hydrophobic treatment) and 8% by mass of the polymerization initiator. Got.

  [Comparative Example 2] Example 1 except that the composition of the hard coat agent was changed to 20% by mass of a crosslinked resin, 2% by mass of a methacrylic acid derivative, 70% by mass of silica (with hydrophobic treatment) and 8% by mass of a polymerization initiator. A laminate was obtained in the same manner as above.

  [Comparative Example 3] Example 1 except that the composition of the hard coating agent was changed to 60% by mass of a crosslinked resin, 2% by mass of a methacrylic acid derivative, 30% by mass of silica (with hydrophobic treatment) and 8% by mass of a polymerization initiator. A laminate was obtained in the same manner as above.

  About each test body of Examples 1-5 and Comparative Examples 1 and 2, the results of measuring scratch resistance, weather resistance, far-infrared gland reflectivity, and solar heat gain using the measurement method described above are shown in Table 1 and It shows in Table 2.

  In Examples 1, 2, and 3 in which a crosslinked resin (A) having a phosphoric acid group was used in the hard coat layer and silica was added in an amount of 40, 50, or 60% by mass as inorganic particles (B), all of Examples 1, 2, and 3 were scratch resistant and weather resistant It was excellent and the judgment was “◯” or more. Further, it was confirmed that Examples 4 and 5 using silica not subjected to hydrophobic treatment further improved the scratch resistance and weather resistance. Furthermore, the far-infrared reflectance, which is an index of heat insulation, and the solar radiation acquisition rate, which is an index of solar radiation shielding property, were good values in all the test specimens.

  On the other hand, Comparative Example 1 using a cross-linked resin having no phosphate group in the hard coat layer was inferior in adhesion to the base, and both the scratch resistance and weather resistance were judged as “x”. In Comparative Example 2 in which 70% by mass of silica was added as the inorganic particles (B), the weather resistance was judged as “◯”, but the hardness of the hard coat layer was low and the scratch resistance was “x”. . Further, Comparative Example 3 in which 30% by mass of silica was added as the inorganic particles (B) was excellent in scratch resistance, but the difference in thermal expansion coefficient between the hard coat layer and the base was large, so that the hard coat was tested by a weather resistance test. Peeling / cracking of the layer occurred and the judgment was “x”.

  Since the laminated body of the present invention has high levels of solar shading and heat insulation, and is excellent in scratch resistance and weather resistance, it can be suitably used for window glass in houses and buildings.

Claims (5)

On one side of the substrate, at least the heat ray reflective layer and the hard coat layer are laminated in this order from the substrate side,
The heat ray reflective layer has a metal thin film and a metal oxide thin film,
The hard coat layer includes a crosslinked resin (A) having at least one polar group selected from the group consisting of a phosphoric acid group, a sulfonic acid group, and an amide group, and inorganic particles (B); and
Content of the said inorganic particle (B) is 40-60 mass% with respect to 100 mass% of all the components contained in a hard-coat layer, The laminated body characterized by the above-mentioned. The laminate according to claim 1, wherein the crosslinked resin (A) is a crosslinked resin containing a phosphate group. The laminate according to claim 1 or 2, wherein the inorganic particles (B) are silica. The laminate according to claim 3, wherein the silica is not subjected to a hydrophobic treatment. The hard coat layer has a thickness of 0.5 to 1.5 μm, and
The laminate according to any one of claims 1 to 4, wherein an infrared reflectance at a wavelength of 5.5 to 15 µm is 50% or more.