JP2014174214A - Heat ray control sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray control sheet excellent in elasticity.SOLUTION: A heat ray control sheet includes a light transmission part which has two or more grooves on one surface, and a heat ray absorption part formed on the groove. A tensile modulus of elasticity of the light transmission part is within a range of 300 to 2750 MPa.

Description

  The present invention relates to a heat ray control sheet having excellent bending resistance.

In recent years, as environmental problems such as global warming become more serious, countermeasures are being promoted worldwide. Among them, for the purpose of energy saving and CO ₂ reduction, attention is focused on a method for controlling the space temperature of a house, an automobile, or the like using a heat ray control sheet, and development of the heat ray control sheet is being promoted.
The heat ray control sheet selectively absorbs or transmits light in the infrared region (hereinafter sometimes referred to as “infrared ray” or “heat ray”) depending on the incident angle. This is a functional sheet that can adjust the incident heat dose.

As the heat ray control sheet, for example, as illustrated in FIG. 4, a plurality of groove portions 103 are formed in a straight line and in parallel in the light transmitting portion 101, and a heat ray absorbing portion 102 that absorbs heat rays is formed in the groove portion 103. Those having the above structure have been proposed (Patent Documents 1 and 2). By sticking the heat ray control sheet 100 having the above structure to the adherend 104 such as a window glass, the heat ray transmission sheet is selectively transmitted and blocked by using the change in the incident angle of light with respect to the heat ray control sheet 100. Can do.
Therefore, for example, in the case of using sunlight as a light source, the temperature rise in the interior of the vehicle or the interior of the vehicle is suppressed by reducing the intake of heat rays in the summer, and the interior of the vehicle or the interior of the vehicle by sufficiently capturing the heat rays in the winter. It is possible to suppress a temperature decrease such as.
In FIG. 4, the XY plane is the sheet surface of the heat ray control sheet, the X direction is the length direction, the Y direction is the width direction, and the Z direction is the thickness (groove depth) direction of the heat ray control sheet. Moreover, in FIG. 4, although the surface which has a heat ray absorption part among the sheet | seat surfaces of a heat ray control sheet is illustrated as an adherend side, the surface which has a heat ray absorption part is made into the adherend side. The same applies to the case.

In addition, since the heat ray control sheet has the above-described structure, the heat ray control sheet not only selectively transmits heat rays depending on the incident angle of light, but also may be visible light (hereinafter referred to as “visible light”). ) Can be efficiently performed.
The function of such a heat ray control sheet will be further described with reference to the drawings. FIG. 5 is an explanatory diagram for explaining a light transmission path in the heat ray control sheet according to the incident angle of light. 5 corresponds to a view of the heat ray control sheet 100 of FIG. 4 as viewed from the X direction, and is an aspect in which it is attached to the adherend 104. FIG. The light source L in FIG. 5 is the sun.
For example, when the solar altitude is high as in summer, as illustrated in FIG. 5A, the incident angle (θ ₁ ) of sunlight with respect to the sheet surface of the heat ray control sheet 100 becomes small, and the heat ray absorbing unit 102 Incidence of sunlight from the side of the. At this time, since visible light passes through the heat ray absorbing portion 102 and is taken into the room, it is possible to ensure daylighting, and heat rays that contribute to temperature rise in the room are included in the heat ray absorbing portion 102. Uptake into the room can be blocked by the heat ray absorbing particles.
For this reason, in summer indoors and the like, it is possible to secure illuminance using sunlight and to suppress an increase in indoor temperature.
On the other hand, when the solar altitude is low as in winter, the incident angle (θ ₂ ) of sunlight with respect to the sheet surface of the heat ray control sheet 100 increases as illustrated in FIG. That is, since the incident angle is an angle that is nearly perpendicular to the sheet surface of the heat ray control sheet 100, the sunlight incident on the light transmitting portion 101 is smaller than that in the summer illustrated in FIG. To increase. At this time, in the light transmission part 101, visible light and heat rays can be transmitted into the room.
For this reason, in winter and the like, it is possible to secure illuminance using sunlight and increase the room temperature.
Note that FIG. 5 shows a case where the surface having the heat ray absorbing portion among the sheet surfaces of the heat ray control sheet is on the light source side, but the same applies to the case where the sheet surface facing the surface is on the light source side.

JP 2010-259406 A Japanese Patent No. 4858269

Such a heat ray control sheet is required to have flexibility from the viewpoints of, for example, rollability in a roll shape during manufacture and conveyance, and workability when affixing to an adherend.
However, the conventional heat ray control sheet has a problem that it cannot be bent with a high curvature. In addition, there is a problem that material stress such as cracks occurs in the heat ray control sheet due to stress applied when bending.
Specifically, if the heat ray control sheet is bent in the width direction so that the surface including the heat ray absorption part is on the outer peripheral side, the light transmission part cannot be bent with a high curvature, and the heat ray absorption part It bends in the groove part which has. At this time, since stress due to bending is particularly concentrated on the bottom of the groove, there is a problem that cracks or the like are generated in the heat ray control sheet from the bottom of the groove.
In addition, due to the difference in bendability between the heat ray absorbing part and the light transmitting part, when the heat ray control sheet is bent in the above-described direction, stress is applied to the interface in the thickness direction between the heat ray absorbing part and the light transmitting part, and peeling occurs. May occur.
Further, even when the heat ray control sheet is bent in the width direction so that the surface including the heat ray absorbing portion is on the inner peripheral side, stress due to the bending is particularly concentrated on the bottom portion of the groove portion. Cracks are generated in the light transmission part between the side surfaces, and interface peeling occurs due to the cracks.
For this reason, the light incident on the gap generated by the interfacial separation is not absorbed by the heat ray absorbing portion, so that the function of the heat ray control sheet is impaired.

  This invention is made | formed in view of the said situation, and it aims at providing the heat ray | wire control sheet | seat excellent in the bending resistance.

  In order to solve the above problems, the present invention has a light transmission part having a plurality of grooves on one surface, and a heat ray absorption part formed in the groove, and the tensile elasticity modulus of the light transmission part is Provided is a heat ray control sheet characterized by being in the range of 300 MPa to 2750 MPa.

According to the present invention, since the light transmission part has a predetermined tensile elastic modulus, in the bent heat ray control sheet, it is possible to reduce stress concentration on the bottom part of the groove part, and the entire light transmission part can be reduced. It is possible to bend with a high curvature. Thereby, generation | occurrence | production of a crack etc. can be prevented in the said bottom part. Moreover, since stress concentration on the interface in the thickness direction between the light transmission part and the heat ray absorption part is alleviated, the occurrence of peeling at the interface can be prevented.
Thus, it becomes possible to improve the bending resistance of the heat ray control sheet.

  In this invention, there exists an effect that the heat ray | wire control sheet | seat excellent in bending resistance can be provided by making the tensile elasticity modulus of a light transmissive part into the predetermined range.

It is a schematic perspective view which shows an example of the heat ray | wire control sheet | seat of this invention. It is the schematic sectional drawing seen from the X direction of FIG. It is a schematic diagram which shows an example of the heat ray | wire control sheet | seat bent. It is a schematic diagram which shows an example of the conventional heat ray control sheet. It is explanatory drawing for demonstrating the permeation | transmission path | route of the light in the heat ray control sheet by the incident angle of light.

  Hereinafter, the heat ray control sheet of the present invention will be described in detail.

A. Heat ray control sheet The heat ray control sheet of this invention is demonstrated. The heat ray control sheet of the present invention has a light transmission part having a plurality of grooves on one surface and a heat ray absorption part formed in the groove part, and the tensile elastic modulus of the light transmission part is 300 MPa to 2750 MPa. It is characterized by being within the range.

The heat ray control sheet of the present invention will be described with reference to the drawings. FIG. 1 is a schematic perspective view showing an example of the heat ray control sheet of the present invention, and FIG. 2 is a schematic cross-sectional view (longitudinal cross-sectional view) seen from the X direction of FIG. In FIG. 1, the XY plane is the sheet surface of the heat ray control sheet, the X direction is the length direction of each part, the Y direction is the width direction of each part, and the Z direction is the thickness of the heat ray control sheet (the depth of the groove). A) direction.
As illustrated in FIGS. 1 and 2, the heat ray control sheet 10 of the present invention includes a light transmission part 1 having a plurality of groove parts 3 on one surface, and a heat ray absorption part 2 formed in the groove part 3. It has. Further, the light transmission part 1 has a tensile elastic modulus within a predetermined range.

The tensile elastic modulus in the present invention is measured using an ultra-micro hardness test system (trade name: Picodenter HM500, manufactured by Fisher Instruments Co., Ltd.). A specific measurement method is to use a test indenter (Vickers indenter, diamond regular square pyramid shape, maximum diameter 400 μm) of the ultra-micro hardness test system, load application speed (30 mN / sec), load time 5 seconds, The measurement was conducted by pressing the surface of the measurement site into the thickness direction to a depth of 3 μm under the condition of a creep time of 10 seconds.
In the following description, unless otherwise specified, the tensile modulus is measured by the above method.

The heat ray control sheet is usually required to have flexibility from the viewpoints of, for example, rollability in a roll shape at the time of manufacture and conveyance, and workability at the time of application to an adherend. However, the conventional heat ray control sheet has a problem that it cannot be bent with a high curvature. In addition, there is a problem that material stress such as cracks occurs in the heat ray control sheet due to stress applied when bending. In particular, when the direction of bending is the width direction of the heat ray control sheet, the heat ray control sheet tends to easily cause material destruction.
On the other hand, according to the present invention, it is possible to bend the heat ray control sheet without causing the above-mentioned problems by setting the tensile elastic modulus of the light transmitting portion within a predetermined range. That is, the heat ray control sheet of the present invention can have high bending resistance.
The reason why the heat ray control sheet of the present invention has high bending resistance will be described below with reference to the drawings together with the phenomenon that occurs when the conventional heat ray control sheet is bent.

FIG. 3 is a schematic diagram illustrating an example of a heat ray control sheet bent with the surface including the heat ray absorbing portion on the outer peripheral side. 3A illustrates a case where a conventional heat ray control sheet is bent, and FIG. 3B illustrates a case where the heat ray control sheet of the present invention is bent.
As illustrated in FIG. 3A, the conventional heat ray control sheet 100 is shown in the width direction (indicated by an arrow C1 in FIG. 3A) such that the surface including the heat ray absorbing portion 102 is on the outer peripheral side. (Light direction), the light transmitting part 101 having a large area ratio in the heat ray control sheet 100 has a high hardness and thus is difficult to bend. On the other hand, although the heat ray absorbing portion 102 and the groove portion 103 are bent, the stress due to the bending is concentrated on the bottom portion of the groove portion. This is presumably because the film thickness (T2 ′ in FIG. 3A) from the bottom of the groove 103 to the surface of the light transmitting part 101 not including the surface of the heat ray absorbing part 102 and the width of the groove 103 are small.
The greater the curvature at the time of bending, the greater the stress at the bottom of the groove 103. Therefore, the heat ray control sheet 100 generates crack A or the like starting from the bottom of the groove 103, and it is assumed that material destruction occurs. Is done.
Further, due to the difference in bendability between the heat ray absorbing portion 102 and the light transmitting portion 101, when the heat ray control sheet 100 is bent, stress is easily applied at the interface in the thickness direction between the heat ray absorbing portion 102 and the light transmitting portion 101. .
When the heat ray absorbing sheet 100 is bent with a desired curvature, the stress applied to the outer periphery of the bent heat ray absorbing sheet 100 (hereinafter, the stress applied to the outer periphery may be referred to as “tensile stress”) is light transmissive. It is assumed that it is concentrated on the interface in the thickness direction between the portion 101 and the heat ray absorbing portion 102. As described above, since the light transmitting portion 101 has high hardness and cannot bend following the curvature, the tensile stress is larger than the peeling force between the light transmitting portion 101 and the heat ray absorbing portion 102, and as a result. It is assumed that separation occurs at the interface and a gap B is formed.
For this reason, since the light which permeate | transmits the clearance gap B is not absorbed by the heat ray absorption part 102, the heat ray absorption rate of the said heat ray control sheet 100 may be impaired.
Furthermore, although not shown, the same problem occurs when the heat ray control sheet is bent so that the surface including the heat ray absorbing portion is on the inner peripheral side. That is, when the heat ray control sheet is bent in the width direction, tensile stress is concentrated on the light transmitting portion between the bottom of the groove and the outer peripheral surface, but the light transmitting portion has high hardness and follows the curvature. And cannot bend. For this reason, a crack etc. generate | occur | produce between a groove part and the outer peripheral side surface by tensile stress, and peeling will arise in the interface of the width direction of a groove part. Furthermore, peeling occurs at an interface in the thickness direction between the heat ray absorbing portion and the light transmitting portion, starting from the crack portion.

On the other hand, the present invention is characterized in that the light transmission part has a predetermined tensile elastic modulus. Thereby, as illustrated in FIG. 3B, the heat ray control sheet 10 is indicated by the arrow C <b> 2 in the width direction (the arrow C <b> 2 in FIG. 3B) so that the surface including the heat ray absorbing portion 2 is on the outer peripheral side. In the case of bending in the direction), the entire light transmitting portion 1 can be bent with a high curvature without stress being concentrated on the bottom of the groove portion 3. For this reason, it is possible to prevent cracks and the like from occurring at the bottom.
At this time, even if the heat ray absorbing part 2 in the groove part 3 has a high hardness, since the width and size of the heat ray absorbing part 2 are small, the hardness of the heat ray absorbing part 2 is the flexibility of the heat ray control sheet 10. Can be reduced. Furthermore, the difficulty of bending in the heat ray absorbing portion 2 can be compensated by the flexibility and followability of the light transmitting portion 2. Thereby, the tensile stress applied to the bent heat ray absorbing sheet 10 can be made smaller than the bonding force at the interface in the thickness direction of the light transmitting portion 1 and the heat ray absorbing portion 2, and the occurrence of peeling at the interface. Can be suppressed.
Although not shown, even when the heat ray control sheet of the present invention is bent in the width direction so that the surface including the heat ray absorbing portion is on the inner peripheral side, light transmission between the bottom of the groove and the outer peripheral surface is possible. Since the portion can follow the curvature, it is possible to prevent the occurrence of cracks due to tensile stress. For this reason, generation | occurrence | production of peeling in the interface of a light transmissive part and a heat ray absorption part can be suppressed.
Thus, the heat ray control sheet of the present invention can have high bending resistance.

The present invention includes at least a light transmission part having a groove part and a heat ray absorption part.
Hereinafter, each part is demonstrated about the heat ray | wire control sheet | seat of this invention.

1. Light transmissive part The light transmissive part in the present invention has a plurality of groove parts on one surface, and has a tensile elastic modulus in the range of 300 MPa to 2750 MPa.

  Note that the shape and the like of the groove part of the light transmission part are the same as the shape and the like of the heat ray absorbing part described in the section “2.

In the present invention, the tensile elastic modulus of the light transmitting portion is in the range of 300 MPa to 2750 MPa, preferably in the range of 300 MPa to 2250 MPa, and particularly preferably in the range of 300 MPa to 1750 MPa.
If it is smaller than the above range, the light transmission part does not have sufficient hardness to maintain the shape, so the heat ray control sheet may not be formed in a desired shape or may not be wound into a roll. . On the other hand, if it is larger than the above range, since it does not have flexibility and is difficult to bend, stress is concentrated on the bottom of the groove, and cracks occur in the light transmission part, or the heat ray absorption part and the light transmission part Peeling may occur at the interface in the thickness direction.

  As the material of the light transmission part, it is preferable that the light transmission part is an ionizing radiation curable resin capable of having a predetermined tensile elastic modulus. The ionizing radiation here refers to all ultraviolet rays (UV-A, UV-B, UV-C), visible light, γ-rays, X-rays, electron beams, active energy rays, and the like. Examples of the ionizing radiation curable resin include an ultraviolet curable resin, an electron beam curable resin, a visible light curable resin, a near infrared curable resin, and the like. Among them, an ultraviolet curable resin and an electron beam curable resin are included. Is preferably used.

As a preferable ultraviolet curable resin and electron beam curable resin in the present invention, an acrylic resin is particularly preferable. This is because the acrylic resin can be easily adjusted so that the tensile modulus after curing is within a predetermined range, and the tensile modulus after UV curing can be controlled by the number of functional groups. Moreover, since acrylic resin has high transparency, it can be used as a heat ray control sheet with high light transmittance.
Examples of the acrylic resin include oligomers or prepolymers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether urethane (meth) acrylate. And oligomers or prepolymers of caprolactone urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and phenol acrylate.
These acrylic resins may be used alone, or two or more of them may be used together and adjusted so that the tensile elasticity of the light transmission part after curing by ionizing radiation is within a predetermined range. Here, (meth) acrylate refers to acrylate or methacrylate.
Among them, in the present invention, monofunctional to trifunctional acrylates are preferable, and monofunctional to trifunctional aliphatic acrylates are particularly preferable. This is because a flexible three-dimensional structure is easily formed after curing with ionizing radiation.

  When polyfunctional urethane (meth) acrylate is used, a diluent such as monofunctional (meth) acrylate such as methyl (meth) acrylate can be used in combination depending on the purpose. The monofunctional (meth) acrylate may be used alone or in combination of two or more, or a low molecular weight polyfunctional (meth) acrylate may be used in combination. Moreover, as a diluent, coating property can also be ensured using said monomer.

The light transmission part may contain a weather resistance improving agent such as an ultraviolet absorber (UVA). The ultraviolet absorber may be inorganic or organic. Examples of inorganic ultraviolet absorbers include titanium oxide, cerium oxide, and zinc oxide. The average particle size (D ₅₀ ) of the inorganic ultraviolet absorber is preferably in the range of about ₅ nm to 120 nm. Moreover, as an organic type ultraviolet absorber, a benzotriazole type | system | group, a triazine type | system | group, a benzophenone type | system | group, a salicylate type | system | group, an acrylonitrile type | system | group, etc. can be used, for example, A triazine type is preferable. This is because the ultraviolet ray absorbing ability is high, and it is difficult to deteriorate against high energy such as ultraviolet rays.

  In addition to the above-mentioned materials, the light transmission part may include hard coat properties, light stabilizers, scratch-resistant fillers, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropes. You may contain additives, such as a property imparting agent, a coupling agent, a plasticizer, an antifoamer, and a filler.

The thickness of the light transmission part is appropriately selected according to the thickness of the target heat ray control sheet, the shape of the groove part, etc., and is preferably in the range of 10 μm to 300 μm, for example, 25 μm. It is preferably in the range of ˜250 μm, particularly preferably in the range of 50 μm to 200 μm.
If the thickness of the light transmission part is larger than the above range, light loss due to absorption of light incident on the light transmission part occurs, and the visibility of the heat ray control sheet formed according to the present invention decreases. There is a case. Moreover, when the thickness of the light transmission part is smaller than the above range, it may be difficult to form a groove part having a desired shape.
Note that the thickness of the light transmission portion is a portion indicated by T1 in FIG.

Further, in the light transmission part, the thickness from the bottom of the groove part to the surface of the light transmission part not having the groove part, that is, the thickness of the part indicated by T2 in FIG. 2 is in the range of 5 μm to 295 μm. It is preferable that it is within a range of 20 μm to 245 μm, and particularly preferably within a range of 45 μm to 195 μm.
By making the thickness of the light transmission part from the bottom of the groove part to the surface not having the groove part within the above range, even if stress is concentrated on the bottom part of the groove part when being bent, cracks and the like are generated. Can be prevented.
The bottom of the groove means the bottommost part of the flat surface when the bottom of the groove is a flat surface, and the bottommost part of the curved surface when the bottom of the groove is a curved surface. Further, the thickness of the light transmission part (T2 in FIG. 2) from the bottom of the groove part to the surface not having the groove part is subtracted from the entire thickness of the light transmission part (T1 in FIG. 2). The remainder is the depth of the groove, that is, the portion indicated by T3 in FIG.

Further, the refractive index of the light transmitting portion is appropriately adjusted according to the refractive index of the heat ray absorbing portion to be described later, but is preferably in the range of 1.40 to 1.80, for example. It is preferably in the range of 1.45 to 1.70, and particularly preferably in the range of 1.50 to 1.65.
The magnitude relationship between the refractive indexes of the heat ray absorbing portion and the light transmitting portion affects the visibility of the heat ray control sheet of the present invention. That is, when the refractive index difference between the heat ray absorbing part and the light transmitting part is large, a large deviation occurs in the emitted light between the visible light transmitted through the heat ray absorbing part and the light transmitting part and the visible light transmitted through the light transmitting part. At this time, the image reflected on the heat ray control sheet includes a plurality of stripes parallel to the vertical direction, and a rainbow-like blurred image (hereinafter referred to as “multiple image”) in which the color of the image is decomposed in the direction of the stripes. Therefore, the heat ray control sheet has low visibility.
On the other hand, by setting the refractive index of the light transmission part within the above range, it is possible to suppress the reflection and refraction of light at the interface with the heat ray absorption part, so that the heat ray absorption part and the light transmission part are transmitted. Thus, attenuation of visible light emitted can be suppressed. Thereby, it is possible to reduce the deviation of the emitted light between the visible ray transmitted through the heat ray absorbing portion and the light transmitting portion and the visible ray transmitted through the light transmitting portion, and to suppress the appearance of multiple images in the heat ray control sheet. Is possible.
In addition, as a measuring method of the refractive index of a light transmissive part, it can obtain by the measuring method of the refractive index prescribed | regulated to JISK7142. Specifically, it can be measured by an Abbe refractometer (manufactured by Atago Co., Ltd.) using a sodium light source with a measurement wavelength of 589 nm under the condition of a temperature of 23 ° C. Hereinafter, the refractive index in this invention shall be measured by the above-mentioned method.

In addition, the visible light transmittance of the light transmitting portion is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.
Since the light transmission part has the above-described visible light transmittance, it is possible to suppress the occurrence of light loss due to absorption of the light incident on the light transmission part, and to improve the visibility of the heat ray control sheet. Can do.
The visible light transmittance was measured using a spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation, JIS K 0115 compliant product) and a Toyobo PET film (product number: Cosmo Shine A4300, thickness). This is confirmed by measuring a light transmission part having a thickness of 10 μm formed on a thickness of 100 μm within a measurement wavelength range of 380 nm to 780 nm.

The method for forming the light transmitting portion is not particularly limited as long as the thickness of the light transmitting portion is within a desired range and a plurality of groove portions can be formed.
Specifically, by applying the light transmitting part forming composition composed of the light transmitting part material described above to the shaping plate having a convex part, the formed light transmitting part forming coating film is crosslinked and cured, The light transmission part can be formed by peeling the shaped plate.
Moreover, when using a base material, after forming the light transmission part formation coating film on a base material, a shaping plate may be pressed and the said light transmission part formation coating film may be bridge | crosslinked and hardened. The base material and the shaping plate may be arranged so as to face each other, and the composition for forming a light transmission part may be injected between them and crosslinked and cured.
Furthermore, as another method, a light-transmitting portion-forming coating film formed separately may be loaded on the shaping plate or bonded.
The shaped plate has a plurality of convex portions on the surface, and the shape and size of the convex portions are usually the same as the shape of the groove portions. Further, the shape of the shaping plate is not particularly limited, and examples thereof include a plate shape and a roll shape.

  The viscosity of the composition for forming a light transmission part is not particularly limited as long as it has a viscosity that can be used in a coating method described later, and is preferably in the range of, for example, about 500 Cps to 5000 Cps. In addition, although the said composition for light transmissive part formation does not contain a solvent normally, in order to acquire coating property, you may dissolve the material of the light transmissive part mentioned above in the solvent etc. .

  The method for applying the light transmitting portion forming composition is not particularly limited as long as it is a method capable of forming a light transmitting portion forming coating film having a uniform film thickness. As such a coating method, for example, a spin coating method, a die coating method, a dip coating method, a bar coating method, a gravure printing method, a screen printing method, or the like can be used.

As a curing method of the composition for forming a light transmission part, curing by irradiation with ionizing radiation as described above is preferable, and ultraviolet rays or electron beams are preferably used from the viewpoint of practicality.
Moreover, about hardening conditions etc., it can set suitably according to the kind of composition for light transmissive part formation.

2. Heat ray absorbing portion The heat ray absorbing portion in the present invention is formed in the groove portion. That is, the shapes of the heat ray absorbing portion and the groove portion are basically the same.

  The tensile elastic modulus of the heat-absorbing part in the present invention varies depending on the type of material such as the heat-absorbing particles used, and may be larger or smaller than the tensile elastic modulus of the light transmitting part described above. Of these, a larger size is preferred. Specifically, the pressure is preferably in the range of 100 MPa to 5000 MPa, more preferably in the range of 200 MPa to 4000 MPa, and particularly preferably in the range of 300 MPa to 3000 MPa. If the tensile modulus of the heat-absorbing part is larger than the above range, the elongation rate may be deteriorated and breakage may occur easily. On the other hand, if it is smaller than the above range, the shape may not be restored after bending.

  The heat ray absorbing part in the present invention contains heat ray absorbing particles as a heat ray absorbent. Hereinafter, the heat ray absorbing particles will be described.

(1) Heat-absorbing particles The heat-absorbing particles may transmit visible light and absorb heat rays, that is, particles having absorption characteristics in the infrared region and transmission properties in the visible region. That's fine. It is preferable that the visible light transmittance is 50% or more, particularly 60% or more, particularly 70% or more. Moreover, as an infrared absorptivity, it is preferable that it is 50% or more, for example, it is preferable that it is 60% or more especially, and it is especially preferable that it is 70% or more.
Note that the visible light transmittance is obtained by adding a composition for forming a heat ray absorbing portion in which 5% by mass of heat ray absorbing particles are contained in 95% by mass of a binder resin used in Examples described later, and the total amount is 100% by mass. A spun PET film (trade name: Cosmo Shine A4300, thickness 100 μm) is applied at a film thickness of 1 μm, and a spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation, JIS K 0115 compliant product) is used. The average value of the visible light transmittance at each wavelength when measured within the measurement wavelength range of 380 nm to 780 nm.
Moreover, the said infrared absorptivity is the average value of the infrared absorptivity in each wavelength when it measures within the measurement wavelength of 780 nm-2500 nm using the sample and measuring method similar to the measurement of the visible light transmittance mentioned above. is there.

Moreover, it is preferable that the said heat ray absorption particle is a material which can form the heat ray absorption part which has a desired tensile elasticity modulus.
As such heat ray absorbing particles, for example, inorganic nanoparticles can be used. Specifically, antimony tin oxide (ATO), indium tin oxide (ITO), lanthanum hexaboride (LaB ₆ ), Aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, cerium hexaboride, anhydrous zinc antimonate and copper sulfide, or a mixture thereof can be used. Among these, it is preferable to use antimony tin oxide (ATO), indium tin oxide (ITO), lanthanum hexaboride (LaB ₆ ), or a mixture thereof.
Moreover, although the said heat ray absorption particle | grains may be transparent and may not be transparent, it is preferable that it is transparent.

The heat ray absorbing particles are preferably nano fine particles. The average particle diameter (D ₅₀ ) is, for example, preferably in the range of 10 nm to 200 nm, more preferably in the range of 20 nm to 150 nm, and particularly in the range of 30 nm to 100 nm. Is preferred.
When the average particle diameter of the heat ray absorbing particles is larger than the above range, haze is generated and the transparency of the heat ray control sheet of the present invention may be lowered. Moreover, when smaller than the said range, a heat ray cannot fully be absorbed and the function as a heat ray control sheet may be inferior.
In addition, the said average particle diameter is the value calculated | required by observing the particle | grains of a heat ray absorption particle with an electron microscope, and arithmetic mean.

Moreover, it is preferable that the particle size distribution of the heat ray absorbing particles has a broad particle size distribution width and is broad. In particular, it is preferable that the particle size distribution width is wide and broad, and among the particle size distributions of the heat-absorbing particles, the particle size D _{90 that} is 90% cumulative from the fine particle side of the cumulative particle size distribution is not in the visible light region. This is because haze occurs and the heat ray control sheet of the present invention may not have transparency.
The particle size distribution of the heat absorbing particles, measured using the measuring method described later, from the microparticles side of cumulative particle size distribution, the particle size of cumulative 10% and D _10, the particle size of cumulative 90% was D _{90 when,} it is preferable that _{D 90} of at 25nm or more 400nm or less, preferably, is preferably 50nm or more 200nm or less. The ratio (D ₉₀ / D ₁₀ ) between the cumulative particle size D _{10 of} 10% and the cumulative particle size D _{90 of} 90% (D ₉₀ / D ₁₀ ) is preferably in the range of 2 to 400, and more preferably in the range of 3 to 200. It is preferably within the range, and particularly preferably within the range of 4 to 100.
When the value of D ₉₀ / D ₁₀ of the particle size distribution of the heat-absorbing particles is within the above range, the particle size distribution width is widened, and heat rays having a wider wavelength range can be absorbed. The particle size distribution is a value obtained from measurement by a particle size distribution meter.

(2) Other materials It is preferable that the heat ray absorption part in this invention has binder resin at least other than the heat ray absorption particle mentioned above.
The binder resin in the heat ray absorbing portion is not particularly limited as long as it is a material that can form a heat ray absorbing portion having a desired tensile elastic modulus and can be cured by irradiation with ionizing radiation. The ionizing radiation is the same as that described in the section “1. Light transmission part” described above.
The binder resin material is preferably an ionizing radiation curable resin polymerized mainly with a monomer, oligomer, prepolymer or polymer having a radical polymerizable active group in the structure, and the ionizing radiation curable resin. Examples of the resin include an ultraviolet curable resin, an electron beam curable resin, a visible light curable resin, and a near infrared curable resin. In the present invention, it is particularly preferable to use an ultraviolet curable resin and an electron beam curable resin. Specifically, reactive oligomers such as epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, polythiol, vinyl pyrrolidone, 2-ethylhexyl acrylate, β-hydroxy acrylate, tetrahydrofurfuryl acrylate, etc. And reactive monomers.

  The binder resin preferably contains a photoinitiator. This is because the binder resin can be cured by irradiation with ionizing radiation such as ultraviolet rays having a wavelength of 300 nm to 400 nm. The photoinitiator can be appropriately selected according to the type of ionizing radiation to be irradiated. For example, a ketone or acetophenone photoinitiator, specifically, Sandley 1000, Darocur 1163, Darocur 1173, Irgacure 183, Irgacure 651, or the like is used. be able to. In addition, as a content rate of the said photoinitiator, it can adjust suitably according to the quantity of binder resin, For example, in the range of about 0.1 mass part-5 mass parts with respect to 100 mass parts of binder resin. It is preferable that

  The binder resin in the heat ray absorbing portion preferably has a small refractive index of light in the visible light region. This is because the heat ray absorbing particles described above have a large refractive index of light in the visible light region, and thus the refractive index of the entire heat ray absorbing portion can be adjusted by reducing the refractive index of the binder resin.

  As a content rate of the binder resin in the said heat ray absorption part, it is preferable to exist in the range of 40 mass%-98 mass% with respect to the total mass (100 mass%) of a heat ray absorption part, Especially, 50 mass%- It is preferably within the range of 95% by mass. If the binder resin content is higher than the above range, the concentration of the heat-absorbing particles may become thin and heat rays may not be sufficiently absorbed. On the other hand, if the binder resin content is lower than the above range, the adhesiveness to the light transmission part may be poor. There is.

  Moreover, the said heat ray absorption part can have a photoinitiator, a ultraviolet absorber, and a light stabilizer other than the heat ray absorption particle | grains and binder resin which were mentioned above.

(3) Heat ray absorption part It is preferable that the heat ray absorption part in this invention has desired visible ray transmittance and infrared rays absorptivity.
The specific visible light transmittance and infrared absorptance of the heat ray absorbing portion are the same as those described in the above-mentioned section “(1) Heat ray absorbing particles”, and thus description thereof is omitted here.

  Moreover, it is preferable that a heat ray absorption part has a desired refractive index with respect to visible light, and it is preferable that it is a thing close | similar to the refractive index with respect to visible light in a light transmissive part especially. Specifically, it is preferably within the range of 1.40 to 1.80, more preferably within the range of 1.45 to 1.70, and particularly within the range of 1.50 to 1.65. Preferably there is. When the refractive index with respect to visible light of the heat ray absorbing portion is within the above range, the difference in refractive index with the light transmitting portion is reduced, and a heat ray control sheet with high visibility in which the appearance of multiple images is suppressed can be obtained. .

Since the heat ray absorbing portion in the present invention is formed by filling the material of the heat ray absorbing portion described above in the groove portion in the light transmitting portion, the heat ray absorbing portion is usually the same shape as the shape of the groove portion. Become.
Examples of the longitudinal cross-sectional shape of the heat ray absorbing portion include a triangle, a square, a rectangle, a trapezoid, and a shape having four curved sides. Moreover, according to the shape of a groove part, the corner | angular part of the said heat ray absorption part may have a curved surface, and the side surface of the said heat ray absorption part may be a curve instead of a straight line.
In addition, the shape of the heat ray absorbing portion viewed from the sheet surface is not particularly limited, and may be, for example, a straight shape or a curved shape. Furthermore, arrangement | positioning of the said heat ray absorption part seen from the sheet | seat surface of the heat ray | wire control sheet | seat of this invention is not specifically limited, You may arrange | position in parallel and may arrange in parallel. , May be randomly arranged in the other direction. As a heat ray absorption part seen from the sheet | seat surface of the heat ray | wire control sheet | seat of this invention, what is arrange | positioned in parallel at linear form is suitable.

  The height of the heat ray absorbing part is equal to the depth of the groove part. That is, it is the same as the contents described in the above-mentioned section “1.

The width of the heat ray absorbing part is preferably in the range of 5 μm to 50 μm, more preferably in the range of 7 μm to 45 μm, and particularly preferably in the range of 10 μm to 40 μm.
When the width | variety of a heat ray absorption part is larger than the said range, visible light may become difficult to permeate | transmit as the heat ray absorption part and the heat ray control sheet whole.
Moreover, depending on the magnitude | size of the tensile elasticity modulus of a heat ray absorption part, when bending the said heat ray control sheet, it may be unable to bend with a high curvature in a heat ray absorption part. At this time, if the width of the heat ray absorbing portion is larger than the above range, it becomes more difficult to bend, and a greater stress is concentrated on the groove portion, which may easily cause cracks. Moreover, peeling may easily occur at the interface in the thickness direction with the light transmission portion. On the other hand, if it is smaller than the above range, the height of the heat ray absorbing portion may not be within the above range, or the heat ray absorbing portion may not have a desired infrared absorption rate. In addition, the width | variety of the said heat ray absorption part is a part shown by W in FIG.

  The length of the heat ray absorbing portion is appropriately selected according to the desired size of the heat ray control sheet. In addition, the length of the said heat ray absorption part means the length extended in the X direction in FIG.

The pitch width of the heat ray absorbing portion is preferably in the range of 30 μm to 200 μm, more preferably in the range of 40 μm to 150 μm, and particularly preferably in the range of 50 μm to 100 μm.
When the pitch width of the heat ray absorbing part is larger than the above range, light having a large incident angle is difficult to enter the heat ray absorbing part, and the heat ray may not be sufficiently absorbed. On the other hand, if it is smaller than the above range, it is difficult to transmit visible light in the light transmitting portion, or the bending difficulty in the heat ray absorbing portion cannot be sufficiently compensated for by the flexibility and followability of the light transmitting portion, and heat ray absorption Separation may occur at the interface in the thickness direction between the portion and the light transmitting portion. In addition, the pitch width of the said heat ray absorption part is a part shown by P in FIG.

  As a formation method of the said heat ray absorption part, it can form, for example by filling the groove part of a light transmissive part with the composition for heat ray absorption part formation containing the material of the heat ray absorption part mentioned above.

  The viscosity of the composition for forming a heat ray absorbing portion may be a viscosity that can be used in a coating method described later. Specifically, the viscosity is preferably in the range of about 100 Cps to 20000 Cps, more preferably in the range of about 250 Cps to 10000 Cps, and particularly preferably in the range of about 500 Cps to 5000 Cps. If the viscosity of the composition for forming a heat ray absorbing part is higher than the above range, the coating method described later may not be used. Moreover, when lower than the said range, the shape after apply | coating the composition for heat ray absorption part formation and making it harden | cure may not be able to be hold | maintained.

The method for applying the composition for forming a heat ray absorbing portion is not particularly limited as long as it is a method capable of sufficiently filling at least the groove portion with the composition for forming a heat ray absorbing portion. As a specific coating method, a wiping method, a coating method, a dry laminating method, an extrusion laminating method, or the like can be used. Among them, the coating method is preferable from the viewpoint of productivity, the precision of the coated film, and the like. As the coating method, applicator coating, Miya bar coating, wire bar coating, gravure coating, die coating and the like can be used.
Further, when the composition for forming a heat ray absorbing part is applied, an excessive amount of the composition for forming a heat ray absorbing part flowing out from the groove part to the surface of the light transmitting part may be removed by scraping with a squeegee or the like. Good.

  As a curing method of the composition for forming a heat ray absorbing portion, curing by irradiation with ionizing radiation is preferable. The type of ionizing radiation is the same as that described in the above-mentioned section “1. Light transmission part”, and thus the description thereof is omitted here. Moreover, about the hardening conditions etc. of the composition for heat ray absorption part formation, it can set suitably according to the kind of composition for heat ray absorption part formation, and the kind of ionizing radiation to be used.

3. Other Configurations The heat ray control sheet of the present invention has at least the light transmission part and the heat ray absorption part described above, but has other parts as long as it does not hinder the flexibility of the heat ray control sheet. May be. Hereinafter, the site | part assumed in this invention is demonstrated.

(1) Base material The heat ray | wire control sheet | seat of this invention may have the base material which can hold | maintain the shape of the whole heat ray | wire control sheet | seat.
The substrate is not particularly limited as long as it has light permeability and does not adversely affect the visibility of the heat ray control sheet. As such a substrate, a sheet-like or film-like one made of a transparent resin can be used, and among them, a film-like substrate (hereinafter sometimes referred to as a film substrate) is preferably used. It is done.

  The film substrate may be any material as long as it has transparency to light in the visible light region and has strength to support the light transmission part, the heat ray absorption part, and the scattering layer. For example, polyethylene terephthalate, polycarbonate, Resin films such as polyester, polyurethane, polyvinyl alcohol, polycarbonate, vinyl chloride, fluororesin, and rubber can be used. Of these, polyethylene terephthalate and polycarbonate resin films are preferred in terms of transparency and strength. Moreover, the said film base material may contain antioxidant, a ultraviolet absorber, etc.

  In addition, the said base material may perform the surface treatment etc. to the single side | surface or both surfaces as needed. As the above-mentioned surface treatment, surface treatment by an oxidation method such as corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone ultraviolet irradiation treatment, and surface treatment by an uneven method such as a sand blast method or a solvent treatment method. Chemical surface treatment or the like can be used.

  The thickness of the substrate can be appropriately selected depending on the purpose of use, but it is usually preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm. If the substrate is too thin, curls and wrinkles are likely to occur, and the heat ray control sheet of the present invention may not have the desired strength.

  The tensile modulus of the base material can be set in a range that is not too small as compared with the tensile modulus of elasticity of the light transmission part and the heat ray absorbing part. For example, it is preferably within the range of 100 MPa to 5000 MPa, more preferably within the range of 200 MPa to 4000 MPa, and particularly preferably within the range of 300 MPa to 3000 MPa.

(2) Adhesive layer The heat ray control sheet of the present invention may have an adhesive layer in order to adhere to an adherend such as a window glass.
The material of the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited as long as it has light weather resistance. For example, acrylic, urethane, silicon, rubber-based pressure-sensitive adhesives can be used. Among them, it is preferable to use an acrylic pressure-sensitive adhesive mainly composed of a polymer or copolymer of an acrylic monomer such as acrylic acid ester or methacrylic acid ester as a material having light weather resistance, and in particular, n-butyl acrylate. It is preferable to use 2-ethylhexyl acrylate or the like.

Moreover, it is preferable that the said adhesion layer contains the ultraviolet absorber. It is because the light weather resistance of an adhesion layer can be improved by containing a ultraviolet absorber.
The ultraviolet absorber may be either inorganic or organic, and an ultraviolet absorber having a reactive group in the molecule can also be used. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type, a salicylate type, an acrylonitrile type etc. can be mentioned preferably, for example. Of these, triazines are preferable because they have a high ability to absorb ultraviolet rays and do not easily deteriorate even with high energy such as ultraviolet rays.

  As content of the ultraviolet absorber in the said adhesion layer, it is preferable to exist in the range of 0.1 mass part-25 mass parts with respect to 100 mass parts of adhesives, Especially the range of 1 mass part-25 mass parts is preferable. It is preferably within the range, and particularly preferably within the range of 3 parts by mass to 20 parts by mass.

Moreover, the said adhesion layer may contain the light stabilizer etc. This is because the weather resistance of the adhesive layer can be improved.
The light stabilizer is preferably a hindered amine light stabilizer or the like, and may have a reactive group in the molecule. Examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1,2 , 2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1- Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine and the like.

  As content of the light stabilizer in the said adhesion layer, it is preferable to exist in the range of 0.05 mass part-7 mass parts with respect to 100 mass parts of adhesives, Especially 0.5 mass part-5 mass parts are preferable. It is more preferable to be within the range, and it is particularly preferable to be within the range of 1 part by mass to 5 parts by mass.

  The formation position of the said adhesion layer can be suitably selected according to the usage aspect of the heat ray | wire control sheet | seat of this invention. For example, when the heat ray control sheet is used for internal application, it is preferably formed on the surface of the light transmission part including the surface of the heat ray absorption part. On the other hand, when using the said heat ray | wire control sheet | seat for external sticking, it is preferable to form on a base material. The thickness of the adhesive layer is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 75 μm.

The pressure-sensitive adhesive layer is prepared by, for example, diluting the above-mentioned material of the pressure-sensitive adhesive layer with a solvent such as ethyl acetate or toluene to prepare a coating solution having a solid content of 20% by mass to 60% by mass, and applying the coating solution to a release sheet or the like It can form by sticking to the surface which has at least one of a light transmissive part or a heat ray absorption part.
In the above-described forming method, as a method of applying the coating solution for the adhesive layer, for example, a knife coater, a comma coater, a gravure coater, a roll coater or the like can be used. In the case of using the coating method, the coating amount of the material of the adhesive layer is in the range of ^10g / ^{m 2 ~30g} / m 2 is preferable in dry weight. This is because by setting the amount of the adhesive layer material to be applied within the above range, sufficient adhesion to the adherend can be obtained, and the adhesive layer does not protrude during processing.

(3) Release layer When the heat ray | wire control sheet | seat of this invention has an adhesion layer, you may have a release layer on the adhesion layer.
This is because by having the release layer, dust or the like can be prevented from adhering to the adhesive layer, and deterioration of the visibility of the heat ray control sheet due to dirt can be prevented. In addition, in the case where the heat ray control sheet of the present invention is formed into a roll shape, it is possible to prevent the occurrence of unwinding failure such as roughening of the adhesive surface during unwinding.

  The material used for the release layer is not particularly limited as long as it is generally used. Specific examples include acrylic and methacrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl chloride resins, cellulose resins, silicone resins, chlorinated rubber, casein, various surfactants, metal oxides, and the like. Or what mixed 2 or more types can be used.

(4) Protective layer It is preferable that the heat ray | wire control sheet | seat of this invention has a protective layer from viewpoints, such as a weather resistance and scratch resistance. Examples of the protective layer include a weather resistant layer, a hard coat layer, a weather resistant hard coat layer, and a self-cleaning layer.

As a material for the protective layer, an ionizing radiation curable resin is preferably used. The ionizing radiation curable resin can be appropriately selected from a polymerizable oligomer or prepolymer, and among them, a polyfunctional polymerizable oligomer or prepolymer is preferably used. Examples of the polymerizable oligomer or prepolymer include oligomers and prepolymers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether urethane (meth) acrylate. And caprolactone-based urethane (meth) acrylate, polyester (meth) acrylate-based, polyether (meth) acrylate-based oligomers and prepolymers, etc., in particular, polyfunctional urethane (meth) acrylate-based It is preferable in terms of achieving both hard coat properties, and the molecular weight is preferably about 1000 to 5000.
Here, (meth) acrylate refers to acrylate or methacrylate.

  In addition to the above polyfunctional polymerizable oligomer, the ionizing radiation curable resin includes a caprolactone urethane (meth) acrylate obtained by a reaction of a caprolactone polyol, an organic isocyanate and a hydroxy acrylate, and a polybutadiene oligomer side. A polymer urethane (meth) acrylate such as a highly hydrophobic polybutadiene (meth) acrylate having a (meth) acrylate group in the chain can be used in combination. It is because the weather resistance of a protective layer can be improved by using together. Among these, it is preferable to use a caprolactone-based material in combination.

When a polyfunctional urethane (meth) acrylate is used as the material for the protective layer, a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate is used for the purpose of adjusting the viscosity. Can be used in combination. The monofunctional (meth) acrylate may be used alone or in combination of two or more, or a low molecular weight polyfunctional (meth) acrylate may be used in combination. Moreover, as a diluent, applicability | paintability can also be ensured using said monomer.
The protective layer material may contain an ultraviolet absorber, a light stabilizer, a scratch-resistant filler such as silica particles, a silicate compound, and the like. In addition, about the specific ultraviolet absorber and light stabilizer, the same kind as what was mentioned above can be used.

  The thickness of the protective layer is preferably in the range of 0.1 μm to 20 μm, more preferably in the range of 0.5 μm to 10 μm, and particularly preferably in the range of 1 μm to 8 μm. .

  The tensile elastic modulus of the protective layer is preferably the same as the tensile elastic modulus of the light transmitting portion described above. The specific tensile elastic modulus is preferably within the range described in the section “1.

As a method for forming the protective layer, for example, a coating solution obtained by diluting the above-described protective layer material with a desired solvent may be prepared, and the coating solution may be applied to the surface of the heat ray control sheet.
In the above-described forming method, as a method for applying the coating solution for the protective layer, for example, an applicator coat, a beer bar coat, a wire bar coat, a gravure coater, a die coater, or the like can be used.

  The position where the protective layer is disposed is appropriately selected according to the application mode of the heat ray control sheet of the present invention, and when the heat ray control sheet of the present invention is attached to the adherend, It arrange | positions so that it may become the outermost layer of the said heat ray control sheet | seat with respect to a to-be-adhered body.

(5) Others In addition to the above-described portions, for example, a flattening layer, a scattering layer, and the like may be provided on the surfaces of the heat ray absorbing portion and the light transmitting portion. This is because it is possible to suppress the occurrence of the light diffraction phenomenon and the light interference phenomenon in the heat ray control sheet, and to prevent the visibility from being lowered due to the appearance of multiple images. Moreover, you may have a photocatalyst layer for the purpose of control of an air chamber.

4). Heat ray control sheet The heat ray control sheet of the present invention is a heat ray control part in the bending resistance evaluation test (cylindrical mandrel method) based on JIS K 5600-5-1 and the occurrence of cracks and the like in the heat ray control sheet. The minimum value ( _Rmin ) of the diameter of the cylindrical mandrel when there is no occurrence of peeling at the interface in the thickness direction between the light transmitting portion and the light transmitting portion is preferably 1.5 mm or more, and more preferably 3 mm or more. preferable.
When the minimum value (R _min ) of the diameter of the cylindrical mandrel is in the above range, when the heat ray control sheet is bent in the step of attaching to an adherend such as glass, interfacial debonding and cracks in the groove, etc. It can be affixed without causing material destruction, and can exhibit desired light transmittance and heat ray absorption.
In addition, when the heat ray control sheet is made into a roll body, even if a thin core material is used, it can be wound without causing material destruction, and the entire roll diameter can be wound without becoming too large. The length can be increased. Therefore, there exists an advantage that it becomes easy to handle the said roll body in a conveyance process, a manufacturing line, etc.
In the above-described test method for the heat ray control sheet of the present invention, the upper limit of the minimum diameter (R _min ) of the cylindrical mandrel is not particularly limited as long as no material destruction or peeling occurs during winding. However, it is preferably 20 mm or less. This is because when the R _min exceeds 20 mm, the roll diameter becomes relatively large when winding the heat ray control sheet having a desired length, and efficiency such as transportability, workability, and productivity may be lowered.

In the heat ray control sheet of the present invention, the surface of the light transmission part including the heat ray absorption part may have flatness or may have irregularities, but preferably has flatness.
When the surface has irregularities, the region where the light incident surface or light exit surface is flat and the region where the light incident surface or light exit surface is concave or convex are the respective incident surfaces or light exit surfaces. There is a bias in the diffusion of light. For this reason, the emitted light amount is biased, and the light diffraction phenomenon and the interference phenomenon are induced by the biased light amount, and a multiple image appears on the heat ray control sheet. That is, the visibility of the heat ray control sheet may be reduced.
In order to suppress a decrease in visibility, the average surface roughness (Ra) of the surface of the heat ray control sheet of the present invention is preferably in the range of 0.1 nm to 100 nm, and in particular, 0.1 nm to 20 nm. It is preferable that it is in the range of 0.1 nm to 10 nm.
In addition, the said average surface roughness (Ra) was measured in the measurement environment of 23 degreeC according to prescription | regulation of JISB0601 2001, and it computed with the following method.

(Calculation method of average surface roughness (Ra))
Only the reference length is extracted from the roughness curve in the direction of the average line, the X-axis is taken in the direction of the average line of the extracted portion, the Y-axis is taken in the direction of the vertical magnification, and the roughness curve is expressed as y = f (x) The value obtained by the following equation (1) was expressed in micrometers (μm).

The heat ray control sheet preferably has a small difference in the refractive index of light in the visible light region at the interface between the heat ray absorbing part and the light transmitting part. By making the difference in the refractive index of visible light between the heat ray absorbing part and the light transmitting part small, it is possible to suppress the occurrence of multiple reflections of visible light at the interface and to form a heat ray control sheet that hardly produces multiple images. Because you can.
The difference in refractive index between the heat ray absorbing portion and the light transmitting portion in the present invention is preferably 0.025 or less, and particularly preferably 0.015 or less.

  Moreover, it is preferable that the heat ray | wire control sheet | seat of this invention has a low haze value, for example, it is preferable that it is 20% or less, Especially it is preferable that it is 10% or less, It is especially preferable that it is 5% or less. When the haze value is higher than the above range, transparency of the heat ray control sheet is low, and visibility may be lowered when the heat ray control sheet is attached to an adherend such as a window glass. In addition, the said haze value is confirmed by measuring according to JISK7136.

As a use mode of the heat ray control sheet of the present invention, it can also be used as “for internal application” to be applied to the inside of the adherend, that is, the indoor side, and can also be applied to the outside of the adherend, that is, the outdoor side. It can also be used as an “outside paste”.
In addition, the heat ray control sheet is attached to the adherend so that the sheet surface including the surface of the heat ray absorbing portion becomes the light incident surface in any of the usage modes of “inner bonding” or “outer bonding”. Alternatively, the surface facing the sheet surface including the surface of the heat ray absorbing portion may be attached to the adherend so as to be the light incident surface.

5. Manufacturing method As a manufacturing method of the heat ray control sheet of the present invention, as long as it is a method capable of forming an aspect having a light transmission part having a plurality of grooves on one surface and a heat ray absorption part formed in the groove, It is not particularly limited.
As an example of the manufacturing method, a composition for forming a light transmission part is applied to a shaping plate having a convex part that is an inverted shape of a groove part, and cured by irradiation with ionizing radiation or the like to form a light transmission part having a groove part. Subsequently, a method of forming the heat ray absorbing portion by filling the groove portion with the composition for forming the heat ray absorbing portion and curing it by irradiation with ionizing radiation or the like can be mentioned. In addition, since the formation method of each part is the same as the content demonstrated in the item of each part mentioned above, description here is abbreviate | omitted.

6). Applications Since the heat ray control sheet of the present invention can control the rise and fall of the indoor temperature while ensuring the daylight according to the incident angle of light from the light source, for example, buildings, houses, trains, cars, buses It can be used by being attached to a window glass, an opening, or the like of a vehicle such as a vehicle, an airplane, or a ship.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
(Formation of light transmission part)
First, a continuous belt-shaped transparent biaxially stretched PET film (manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was prepared as a substrate. On one surface of the base material, a liquid composition for forming a light transmitting part A having the following composition was applied and cured by ultraviolet irradiation. The thickness of the coating film after curing was 100 μm.

<Light transmission part forming composition A>
・ Urethane acrylate (manufactured by Daicel-Sitec)… 99% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

  Next, a roll in which a convex shaped plate is linearly connected in the circumferential direction is pressed against the coating film formed on the substrate, and the coating film is cured by ultraviolet irradiation with a mercury lamp, and light having grooves A transmission part was formed. The obtained grooves had a wedge-shaped cross section with a pitch width of 78 μm, a depth of 63 μm, a lower bottom width of 24 μm, and an upper and lower width of 28 μm.

(Formation of heat ray absorption part)
A composition for forming a heat ray absorbing portion having the following composition was applied to the surface of a light transmitting portion having a groove. Then, the composition applied to the region other than the groove portion was scraped off using an iron doctor blade, so that the heat ray absorbing portion forming composition was filled only in the groove portion.
Subsequently, ultraviolet rays were irradiated with a mercury lamp, and the composition for forming a heat ray absorbing part was crosslinked and cured to obtain a heat ray absorbing part.

<Composition of composition for forming heat-absorbing part>
・ Transparent acrylic UV-curable prepolymer comprising a mixed solution of urethane acrylate (manufactured by Daicel-Cytik) and dipentaerythritol acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.): 78 parts by mass
・ ATO nanoparticles (average particle size 100 nm) 20% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 2% by mass

(Formation of protective layer)
Subsequently, in order to fill the groove portion of about 2 μm, the above-described composition A for forming a light transmitting portion was applied to the surface of the light transmitting portion having the heat ray absorbing portion using an applicator. The coating film was irradiated with ultraviolet rays, crosslinked and cured to form a smooth protective layer (Ra = 0.12 nm), and an intended heat ray control sheet was obtained.

[Example 2]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmission part forming composition B having the following composition was used.

<Light transmission part forming composition B>
・ Urethane acrylate (manufactured by Daicel-Sitec)… 95% by mass
・ Dipentaerythritol acrylate oligomer (made by Shin-Nakamura Chemical Co., Ltd.) 4% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 3]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition C having the following composition was used.

<Light transmission part forming composition C>
・ Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 79% by mass
・ Propoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 4]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition D having the following composition was used.

<Light transmission part forming composition D>
・ Urethane acrylate (manufactured by Daicel-Cytik)… 90% by mass
・ Dipentaerythritol acrylate oligomer (made by Shin-Nakamura Chemical Co., Ltd.) 9% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 5]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmission part forming composition E having the following composition was used.

<Light transmission part forming composition E>
・ Urethane acrylate (manufactured by Daicel-Sitec)… 80% by mass
・ Dipentaerythritol acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.) 19% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 6]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition F having the following composition was used.

<Light transmission part forming composition F>
・ Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.): 59% by mass
・ Propoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.): 40% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 7]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmission part forming composition G having the following composition was used.

<Light transmission part forming composition G>
・ Urethane acrylate (manufactured by Daicel-Sitec) 70% by mass
・ Dipentaerythritol acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.): 29% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Example 8]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmission part forming composition H having the following composition was used.

<Light transmission part forming composition H>
・ Urethane acrylate (manufactured by Daicel-Scitic)… 60% by mass
・ Dipentaerythritol acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.): 39% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Comparative Example 1]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition I having the following composition was used.

<Light transmission part forming composition I>
・ Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20% by mass
・ Propoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 79% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Comparative Example 2]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition J having the following composition was used.

<Light transmission part forming composition J>
・ Urethane acrylate (manufactured by Daicel-Cytik) 50% by mass
・ Dipentaerythritol acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.): 49% by mass
1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1% by mass

[Comparative Example 3]
A heat ray control sheet was produced in the same manner as in Example 1 except that the light transmitting part forming composition K having the following composition was used.

<Light transmission part forming composition K>
・ High-strength silicone rubber (KE-555 manufactured by Shin-Etsu Silicone Co., Ltd.) ... 100% by mass

[Evaluation]
(Measurement of tensile modulus)
The heat ray control sheets of Examples 1 to 8 and Comparative Examples 1 to 3 were cut into 5 mm × 20 mm samples, cross-sectioned with a sharp blade and resin-embedded, and then surfaced with a surface polishing machine.
While expanding the cross section of the sample with a microscope, a test indenter was pushed into the light transmitting portion using a Picodenter HM500 (manufactured by Fisher Instruments Co., Ltd.), and the tensile elastic modulus at 23 ° C. was measured. The test indenter was pushed in under the following conditions.

(Test indentation conditions)
-Load application speed: 30 mN / sec
・ Loading time: 5 seconds ・ Creep time: 10 seconds ・ Maximum indentation depth: 3 μm depth from the surface of the light transmitting part in the thickness direction

(Bending resistance evaluation test)
About the heat ray | wire control sheet | seat of Examples 1-8 and Comparative Examples 1-3, the bending resistance evaluation test was done according to JISK5600-5-1. Specifically, a cylindrical mandrel (diameter R = 1.5 mm to 20 mm) is arranged on the substrate side so as to be parallel to the heat ray control part of the heat ray control sheet, and the heat ray control sheet is orthogonal to the heat ray absorption part. Bent in the direction. A cylindrical shape that does not cause the above problems by checking whether a material destruction such as cracks has occurred in the heat ray control sheet and whether the interface in the thickness direction between the heat ray absorbing part and the light transmitting part is peeled off. The minimum value (R _min ) of the mandrel diameter was determined.
The evaluation results are shown in Table 1.

In the heat ray control sheets of Examples 1 to 8, the tensile modulus of the light transmitting part is in the range of 300 MPa to 2750 MPa, so that the crack (R) of the cylindrical mandrel has a diameter (R) of 20 mm or less, and cracks. And no interfacial peeling occurred.
On the other hand, in the heat ray control sheets of Comparative Examples 1 and 2, when the diameter (R) of the cylindrical mandrel was bent with a diameter smaller than 20 mm, cracks, interfacial peeling, and the like occurred.
Moreover, in Comparative Example 3, the tensile elastic modulus of the light transmission part was less than 300 MPa, and it was difficult to form a light transmission part having a groove part. For this reason, the obtained heat ray control sheet cannot be wound up because it does not have sufficient hardness to maintain its shape, and it has not been possible to measure the bending resistance.

DESCRIPTION OF SYMBOLS 1 ... Light transmission part 2 ... Heat ray absorption part 3 ... Groove part 10 ... Heat ray control sheet

Claims (1)

  It has a light transmission part having a plurality of grooves on one surface, and a heat ray absorption part formed in the groove, and the tensile elastic modulus of the light transmission part is in the range of 300 MPa to 2750 MPa. Heat ray control sheet.

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