JP6155600B2 - Transparent resin laminate, method for producing the same, and primer layer forming primer layer having a heat ray shielding function - Google Patents

Description

  The present invention relates to a transparent resin laminate, a method for producing the same, and a primer solution for forming a primer layer having a heat ray shielding function. Further, heat ray shielding fine particles and adhesion imparting are provided on at least one surface of a transparent resin substrate. Resin and a transparent resin laminate in which a primer layer having a heat ray shielding function containing a (meth) acrylic resin is laminated, and a silicone resin layer is laminated on the primer layer having the heat ray shielding function, and a method for producing the same And a primer solution for forming the primer layer having the heat ray shielding function.

  Transparent resin base materials such as polycarbonate resin are lightweight and excellent in transparency, impact resistance, and the like, and thus are used as window materials for vehicles and buildings as members that replace glass. However, since the transparent resin base material is inferior in mechanical properties such as scratch resistance and weather resistance as compared with glass, it is required to improve surface properties.

  As a means for improving the mechanical properties of the surface of the transparent resin substrate, a method of coating the surface of the substrate with a thermosetting resin such as polyorganosiloxane (silicone) or melamine or a polyfunctional acrylic A method of laminating a photocurable resin has been proposed. Among them, a method of laminating a silicone resin is applied in glazing applications for vehicles that require high weather resistance and wear resistance.

  However, the silicone resin has poor adhesion to the transparent resin substrate and has been a big problem in the past. In order to solve the problem, usually, by interposing an acrylic resin layer between the silicone resin layer and the transparent resin substrate, the adhesion between the silicone resin layer and the transparent resin substrate is improved, A method of modifying the surface of the transparent resin substrate has been adopted.

  On the other hand, near-infrared rays that pass through window materials such as the vehicles and buildings described above and enter the vehicle and the interior of the vehicle cause excessive increases in the temperature of the interior and the interior of the vehicle. In order to eliminate the excessive temperature rise, provision of a transparent resin laminate having a heat ray shielding function for suppressing the temperature rise is strongly demanded as the window material described above.

As a method for meeting such a demand, there is a method of blending a material having a heat ray shielding function into the transparent resin substrate itself. For example, in Patent Documents 1 and 2, a heat ray shielding material in which a polycarbonate resin, a poly (meth) acrylic resin, a polyethylene resin, a polyester resin, a polystyrene resin, or a vinyl chloride resin is blended with a phthalocyanine compound that is a material having a heat ray shielding function. Is disclosed.
Patent Documents 3, 4 and 5 disclose heat ray shielding materials in which a polycarbonate resin is compounded with tungsten oxide or hexaboride.
On the other hand, in Patent Document 6, a methyl methacrylate resin in which composite tungsten oxide fine particles are dispersed is applied to the surface of a transparent resin base material, thermally cured to laminate a heat ray shielding layer, and a silicone resin coating is applied thereon. A heat ray shielding material in which a silicone resin layer is laminated by applying and thermosetting is disclosed.

Patent Document 1: Japanese Patent Application Laid-Open No. 06-240146 Patent Document 2: Japanese Patent Application Laid-Open No. 06-264050 Patent Document 3: Japanese Patent Application Laid-Open No. 2005-179504 Patent Document 4: Japanese Patent Application Laid-Open No. 2007-212213 Patent Document 5: Japanese Patent Application Laid-Open No. 2007-212213 Japanese Patent Laid-Open No. 2008-044609 Patent Document 6: Japanese Patent Laid-Open No. 2009-256413

  However, according to the study by the present inventors, in the methods of Patent Documents 1 and 2, in order to obtain a sufficient heat ray shielding function, a large amount of phthalocyanine compound must be blended into the transparent resin substrate. However, blending a large amount of the phthalocyanine compound causes a decrease in heat resistance of the transparent resin base material, resulting in coloring problems and insufficient weather resistance.

  On the other hand, the techniques disclosed in Patent Documents 3, 4, and 5 can impart sufficient heat ray shielding characteristics to the transparent resin substrate with a small amount of addition. Furthermore, there are many facilities involved in the production of a transparent resin substrate having a heat ray shielding function. Therefore, it is a manufacturing method with good cost performance when producing transparent resin substrates in large quantities. However, in order to respond precisely to customer specifications regarding the optical characteristics and mechanical characteristics of the transparent resin base material having heat ray shielding, it is required to produce a variety of products in small quantities. However, with the techniques disclosed in Patent Documents 3, 4, and 5, when trying to meet the customer specifications, adjustment of a large number of facilities involved is required. After all, this technology is not suitable for high-mix low-volume production.

Patent Document 6 discloses that a primer layer having a heat ray shielding function is obtained by applying a methyl methacrylate resin in which composite tungsten oxide fine particles are dispersed to the surface of a transparent resin base material and thermally curing the resin. A silicone resin coating material is applied onto the layer and thermally cured to produce a heat ray shielding transparent covering material in which the silicone resin layer is laminated. According to the manufacturing method, since it is sufficient to study the primer layer having the heat ray shielding function in order to respond precisely to customer specifications, it is possible to flexibly respond to the demand for high-mix low-volume production.
However, according to the study by the present inventors, the transparent resin base material having a heat ray shielding function proposed in Patent Document 6 has excellent heat ray shielding characteristics and can flexibly cope with a variety of small-quantity production. However, there are problems in optical characteristics and mechanical characteristics. Specifically, the haze value, which is a problem on the optical properties of the transparent resin substrate having a heat ray shielding function, and the adhesion between the transparent resin substrate and the silicone-based resin layer, which are issues on the mechanical properties. I left a challenge.
That is, when forming a primer layer having a heat ray shielding function, if the drying temperature is high, the adhesion between the primer layer having the heat ray shielding function and the silicone resin layer is deteriorated. On the other hand, when the drying temperature is low, the haze value of the produced transparent resin laminate having a heat ray shielding function is increased and the design properties are impaired. After all, since it is difficult to achieve both optical properties and mechanical properties, it has been difficult to produce a transparent resin laminate having the desired quality.

  The present invention has been made under the above-described circumstances, and the problem to be solved is a primer solution for producing a transparent resin laminate, and it is widely dried to maintain excellent productivity. Under a temperature range, a transparent resin laminate having a primer layer having a low heat haze function with a low haze value, excellent design and good adhesion to a silicone resin layer, and a method for producing the same, and the heat ray shielding It is to provide a primer solution for forming a primer layer having a function.

  The present inventors have intensively studied to solve the above problems. As a result, by adding a silane compound having a predetermined structure to the primer solution, it has an excellent heat ray shielding function, low haze, excellent design, and good adhesion between the primer layer and the silicone resin layer. It was found that a transparent resin laminate could be obtained, and the present invention was completed.

That is, the first invention for solving the above problem is
At least one surface of the transparent resin base material is laminated with a primer layer having a heat ray shielding function containing fine particles having a heat ray shielding function, an adhesion imparting agent, a dispersant, and a (meth) acrylic resin. A transparent resin laminate in which a silicone resin layer is laminated on the primer layer having the heat ray shielding function,
The fine particles having a heat ray shielding function are selected from the general formula M _y WO _Z (where M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu). One or more elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and a composite tungsten oxide fine particle having a hexagonal crystal structure,
The dispersant is an acrylic dispersant having a group containing an amine as a functional group, having a molecular weight Mw of 2000 to 200000, and an amine value of 5 to 100 mgKOH / g, and the amount of the dispersant added is the composite tungsten oxide 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the product fine particles,
The adhesion-imparting agent is isocyanate propyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- It is at least one selected from methacryloxypropyltriethoxysilane and vinyltriethoxysilane, and the addition amount of the adhesion-imparting agent is 0.1 to 30 parts by weight with respect to 100 parts by weight of the acrylic resin. It is a transparent resin laminate characterized by being.
The second invention is
The transparent resin laminate according to the first aspect, wherein the amount of the fine particles having a heat ray shielding function is 1 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin.
The third invention is
The transparent resin laminate according to the first or second invention, wherein the heat ray shielding fine particles are fine particles having an average particle diameter of 1 nm to 800 nm.
The fourth invention is:
The transparent resin laminate according to any one of the first to third inventions, wherein the primer layer having a heat ray shielding function has a thickness of 1 μm to 20 μm.
The fifth invention is:
The thickness of the silicone resin layer is 1 μm to 20 μm. The transparent resin laminate according to any one of the first to fourth inventions .
The sixth invention is:
The transparent resin laminate according to any one of the first to fifth inventions, wherein the transparent resin base material is a polycarbonate resin.
The seventh invention
The transparent resin laminate according to any one of the first to sixth inventions , wherein a haze when the visible light transmittance of the transparent resin laminate is set to 50% or more is 5% or less. A transparent resin laminate.
The eighth invention
A primer solution for forming a primer layer having a heat ray shielding function in the transparent resin laminate according to any one of the first to seventh inventions ,
It has the heat ray shielding function characterized by including the said heat ray shielding microparticles | fine-particles, the said adhesiveness imparting agent, the said (meth) acrylic-type resin, the organic solvent with a boiling point of 120 degrees C or less, and the said acrylic dispersing agent. A primer solution for forming a primer layer.
The ninth invention
On at least one surface of the transparent resin substrate, the heat ray shielding fine particles, the adhesion-imparting agent, the (meth) acrylic resin, an organic solvent having a boiling point of 120 ° C. or less, and the acrylic dispersant. , A first step of applying a primer solution containing and heat-curing at a temperature of 90 ° C. to 140 ° C. to form a primer layer having a heat ray shielding function;
8. The method according to claim 1 , further comprising a second step in which a coating liquid containing the silicone resin is applied on the primer layer having the heat ray shielding function and thermally cured. It is a manufacturing method of a transparent resin laminated body.

  The transparent resin laminate according to the present invention can be easily manufactured while maintaining excellent productivity, has an excellent heat ray shielding function, has a low haze and is excellent in design, and includes a primer layer and a silicone resin layer. Adhesion was also good. According to the method for producing a transparent resin laminate of the present invention, a transparent resin laminate having an excellent heat ray shielding function, low haze, excellent design, and good adhesion between a primer layer and a silicone-based resin layer. The body could be easily manufactured while maintaining excellent productivity under a wide drying temperature range of 90 ° C to 140 ° C. In addition, the primer solution according to the present invention is applied on a transparent resin base material to form a primer layer, and a silicone resin layer is provided thereon, so that it has an excellent heat ray shielding function, has a low haze, and has a design property. A transparent resin laminate with excellent adhesion and good adhesion between the primer layer and the silicone-based resin layer in a wide drying temperature range of 80 ° C. to 140 ° C. while maintaining excellent productivity. Was made.

The transparent resin laminate according to the present invention has a fine particle (A) having a heat ray shielding function, an adhesion imparting agent (B), and a (meth) acrylic resin (C) on at least one surface of a transparent resin substrate. Is a transparent resin laminate in which a primer layer containing a heat ray-shielding function is laminated and a silicone-based resin (D) layer is further laminated thereon.
In the transparent resin laminate, the primer layer having a heat ray shielding function is for forming a heat ray shielding film containing fine particles (A) having a heat ray shielding function, an adhesion-imparting agent (B), and a (meth) acrylic resin (C). The primer solution is applied to a transparent resin substrate and cured.
Furthermore, the primer solution for forming the heat ray shielding film has an adhesion imparting agent (B) in a fine particle dispersion having a heat ray shielding function (may be referred to as “heat ray shielding fine particle-containing dispersion” in the present invention), It can be obtained by adding and mixing (meth) acrylic resin (C).
Hereinafter, embodiments of the present invention will be described in detail in the order of [1] dispersion containing heat ray shielding fine particles, [2] primer solution for forming a primer layer having a heat ray shielding function, and [3] transparent resin laminate. To do.

[1] Heat ray shielding fine particle-containing dispersion The heat ray shielding fine particle-containing dispersion according to the present invention includes (1) fine particles having a heat ray shielding function, (2) a dispersant, (3) an organic solvent, and (4) heat ray shielding fine particles. It demonstrates in detail in order of the manufacturing method of a containing dispersion liquid.

(1) Fine particles having a heat ray shielding function The fine particles having a heat ray shielding function used in the dispersion containing the heat ray shielding fine particles according to the present invention are composite tungsten oxide fine particles.
Since the composite tungsten oxide fine particles absorb a large amount of light in the near infrared region, particularly a wavelength of 1000 nm or more, the transmitted color tone often has a blue color tone.
The composite tungsten oxide fine particles have a general formula MyWO _Z (where M is one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu). Element, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and preferably has a hexagonal crystal structure.

  The particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding film. For example, when the heat ray shielding film is used for applications requiring transparency, the composite tungsten oxide fine particles preferably have a dispersed particle diameter of 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle size smaller than 40 nm, light is not completely blocked by scattering, and visibility in the visible light region is maintained, and at the same time, transparency is efficiently maintained. Because you can.

  When the heat ray shielding film or the heat ray shielding laminated transparent base material according to the present invention is applied to an application in which the transparency in the visible light region is particularly important, such as an automobile windshield, the scattering by the composite tungsten oxide fine particles is further performed. It is preferable to consider the reduction. When importance is attached to the scattering reduction, the dispersed particle diameter of the composite tungsten oxide fine particles is 30 nm or less, preferably 25 nm or less.

This is because if the composite tungsten oxide fine particles have a small dispersed particle diameter, light scattering in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. This is because, by reducing the scattering of the light, it is possible to avoid a situation in which the heat ray shielding film has an appearance like a frosted glass when strong light is irradiated and the clear transparency is lost. This is because when the dispersed particle diameter of the composite tungsten oxide fine particles is 40 nm or less, the geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. This is because, in the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is decreased. Furthermore, it is preferable that the dispersed tungsten oxide fine particles have a dispersed particle diameter of 25 nm or less because the scattered light is extremely reduced.
As described above, from the viewpoint of avoiding light scattering, it is preferable that the dispersed tungsten oxide fine particles have a small dispersed particle diameter. On the other hand, if the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, industrial production is easy.

  Regarding the composite tungsten oxide fine particles described above, <1-1> component of composite tungsten oxide fine particles, <1-2> method for producing composite tungsten oxide fine particles, <1-3> surface-coated composite tungsten oxide This will be further described in the order of fine particles.

<1-1> Components of Composite Tungsten Oxide Fine Particles Examples of components of preferable composite tungsten oxide fine particles include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ etc. can be mentioned. However, if the values of y and z are within the above ranges, useful heat ray shielding characteristics can be obtained. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Moreover, about the range of Z, 2.2 <= z <= 3.0 is preferable. This is because the same mechanism works as the above-described tungsten oxide material represented by WO _x in the composite tungsten oxide material represented by MyWO _Z , and the above-described element is also obtained when z ≦ 3.0. This is because free electrons are supplied by adding M. However, from the viewpoint of optical characteristics, 2.45 ≦ z ≦ 3.00 is more preferable.

<1-2> Manufacturing Method of Composite Tungsten Oxide Fine Particles Composite tungsten oxide fine particles represented by the general formula M _Y WO _Z are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. Can do.
First, the tungsten compound starting material will be described.
The tungsten compound starting material is dried after dissolving tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder or tungsten hexachloride powder in alcohol. Tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or Starting material of tungsten compound containing at least one element selected from tungsten compound powder obtained by drying ammonium tungstate aqueous solution and metallic tungsten powder, and further containing element M in elemental form or compound form It is preferable that

  Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material in the form of a solution, and the tungsten compound starting material containing the element M is water, an organic solvent, or the like. It is preferable that it is soluble in a solvent. Examples include tungstate, chloride, nitrate, sulfate, oxalate, oxide, carbonate, hydroxide, etc. containing element M, but are not limited to these and are in solution form Is preferable.

Next, heat treatment in an inert gas atmosphere or a reducing gas atmosphere will be described.
First, the heat treatment conditions in an inert gas atmosphere are preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has a sufficient near-infrared absorbing power and is efficient as heat ray shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used.
As the heat treatment conditions in the reducing atmosphere, the starting material is first heat-treated at 100 ° C. or more and 650 ° C. or less in the reducing gas atmosphere, and then the temperature of 650 ° C. or more and 1200 ° C. or less in the inert gas atmosphere. It is better to heat-treat with. The reducing gas at this time is not particularly limited, but H ₂ is preferable. Then, when H ₂ is used as the reducing gas, the composition of the reducing atmosphere, for example, Ar, preferably mixed with 0.1% or more by volume of H ₂ in an inert gas such as N _2, More preferably, 0.2% or more is mixed. H ₂ can be advanced efficiently reduced if more than 0.1% by volume.
The starting material powder reduced with hydrogen contains a Magneli phase and exhibits good heat ray shielding properties. Therefore, even in this state, it can be used as heat ray shielding fine particles.

<1-3> Surface-coated composite tungsten oxide fine particles The composite tungsten oxide fine particles according to the present invention are surface-treated, and are compounds containing at least one selected from Si, Ti, Zr, and Al, preferably oxides. It is preferable from the viewpoint of improving the weather resistance. In order to perform the surface treatment, a known surface treatment may be performed using an organic compound containing one or more selected from Si, Ti, Zr, and Al. For example, the composite tungsten oxide fine particles according to the present invention and an organosilicon compound may be mixed and subjected to a hydrolysis treatment.

Further, from the viewpoint of improving the optical properties of the heat ray shielding film described later, the powder color of the composite tungsten oxide fine particles is the L ^* a ^* b ^* color system recommended by the International Lighting Commission (CIE) ( In the powder color in JISZ8729-2004), it is desirable to satisfy the conditions that L ^* is 25 to 80, a ^* is -10 to 10, and b ^* is -15 to 15. By using the composite tungsten oxide fine particles having the powder color, a heat ray shielding film having excellent optical properties can be obtained.

(2) Dispersant The dispersant according to the present invention comprises the composite tungsten oxide fine particles according to the present invention in a heat ray shielding fine particle-containing dispersion, and in a primer solution for forming a primer layer having a heat ray shielding function to be described later. Exhibits a function of uniformly dispersing in a primer layer having a heat ray shielding function to be described later.
The dispersant according to the present invention is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, prevent aggregation of the composite tungsten oxide fine particles, and have an effect of uniformly dispersing the fine particles even in the heat ray shielding fine particle-containing dispersion.

  Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group, and acrylic dispersants having an amine-containing group as a functional group. The dispersant having a functional group containing an amine is preferably one having a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Moreover, in the dispersing agent which has a carboxyl group, the thing of molecular weight Mw2000-200000 and an acid value of 1-50 mgKOH / g is preferable.

  The addition amount of the dispersant is desirably in the range of 10 parts by weight to 1000 parts by weight, and more preferably in the range of 30 parts by weight to 400 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. If the added amount of the dispersant is in the above range, the composite tungsten oxide fine particles are contained in the heat ray shielding fine particle-containing dispersion, in the primer solution for forming a primer layer having a heat ray shielding function described later, and further described in the heat ray shielding described later. This is because the properties of the primer layer having the heat ray shielding function are not adversely affected while being uniformly dispersed in the primer layer having the function.

(3) Organic solvent The organic solvent according to the present invention is not limited as long as it can dissolve the above-described dispersant and can uniformly disperse the fine particles having a heat ray shielding function and does not dissolve the transparent resin substrate. However, in view of the removal efficiency from the primer layer having the heat ray shielding function during the heat curing step in forming the heat ray shielding film described later, the boiling point is preferably 120 ° C. or lower.
Specific examples include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol.

The amount of the organic solvent added is desirably in the range of 100 to 3000 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. If the amount of the organic solvent is 100 parts by weight or more, the dispersibility of the heat ray shielding fine particles in the heat ray shielding fine particle dispersion can be ensured. On the other hand, when the amount of the organic solvent is 3000 parts by weight or less, it is possible to avoid an excess of the organic solvent contained in the primer solution and to avoid a situation in which the organic solvent to be removed becomes excessive.
Moreover, the primer liquid for primer layer formation which has the heat ray shielding function which concerns on this invention is manufactured by adding the acrylic resin and adhesiveness imparting agent which are mentioned later to the heat ray shielding fine particle containing dispersion liquid which concerns on this invention. Therefore, it should be noted that the organic solvent does not dissolve the transparent base resin as described above. This is to avoid a situation in which the organic solvent erodes the transparent base resin during the formation of the primer layer having a heat ray shielding function and leads to defects in the appearance of the transparent resin laminate.

(4) Manufacturing method of heat ray shielding fine particle-containing dispersion The heat ray shielding fine particle-containing dispersion according to the present invention is obtained by adding and mixing the above-described fine particles having a heat ray shielding function, a dispersing agent and an organic solvent, a bead mill, a ball mill, a sand mill, It can manufacture by applying the general method used when dispersing microparticles | fine-particles, such as an ultrasonic homogenizer.
The concentration of fine particles having a heat ray shielding function contained in the heat ray shielding fine particle-containing dispersion is preferably 50% by mass or less. When the amount is 50% by mass or less, aggregation of fine particles hardly occurs, dispersion is easy, and a sudden increase in viscosity can be avoided, and handling is easy.

[2] Primer solution for forming a primer layer having a heat ray shielding function The primer solution for forming a primer layer having a heat ray shielding function according to the present invention includes the above-described dispersion containing a heat ray shielding fine particle, an adhesion-imparting agent, and an acrylic resin. A solution containing a resin.
The heat ray shielding fine particle-containing dispersion is as described above.
Here, (1) acrylic resin and (2) adhesion imparting agent will be described in this order, and (3) a method for producing a primer solution for forming a primer layer having a heat ray shielding function will be described.

(1) Acrylic resin The acrylic resin that can be used in the primer solution for forming a primer layer having a heat ray shielding function according to the present invention is excellent in adhesion between the transparent resin substrate and the silicone resin. Anything can be used as long as it is not particularly limited.
However, in the primer solution for forming a primer layer having a heat ray shielding function according to the present invention, a thermosetting acrylic resin is desirable. Specifically, in consideration of the dispersibility of the composite tungsten oxide fine particles, the transparency of the material itself, processability, durability, etc., it is obtained by polymerizing an alkyl acrylate monomer or an alkyl methacrylate monomer (meth). Acrylic resin is desirable.

  These monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These can be polymerized alone or in combination.

  As the other copolymerizable monomer, acrylic acid, methacrylic acid or derivatives thereof are preferably used particularly in terms of durability such as adhesion or weather resistance. Specifically, acrylic acid, methacrylic acid, acrylic amide, and methacrylic amide can also be used.

  In addition, the acrylic resin that can be used for the primer layer having a heat ray shielding function according to the present invention is prepolymerized and dissolved in an organic solvent in a primer solution for forming a primer layer having a heat ray shielding function, or Any of those in which the above-described monomer is polymerized by heat treatment during the formation of the primer layer having a heat ray shielding function, or those in which the polymerized resin and monomer are mixed and the monomer is polymerized by heat treatment can be used.

  The ratio of the acrylic resin contained in the primer solution for forming the primer layer having the heat ray shielding function and the fine particles having the heat ray shielding function according to the present invention has a heat ray shielding function with respect to 100 parts by weight of the acrylic resin. The amount of fine particles added is preferably 1 to 100 parts by weight. More preferably, it is 5-70 weight part. If the addition amount of the heat ray shielding fine particles is 1 part by weight or more, a desired heat ray shielding function can be secured to the transparent resin laminate, which is preferable. On the other hand, if it is 100 parts by weight or less, the viscosity of the primer layer forming coating solution having a heat ray shielding function is remarkably high, and it is possible to avoid a situation where it is difficult to apply the coating solution to the transparent resin substrate.

(2) Adhesion imparting agent The adhesion imparting agent according to the present invention is formed on a primer layer having a heat ray shielding function laminated on at least one surface of a transparent resin substrate, and a primer layer having the heat ray shielding function. It is added to the primer solution for the purpose of improving the interlayer adhesion with the silicone resin layer.
From the standpoint of interlayer adhesion between the primer layer having a heat ray shielding function and the silicone-based resin layer, an epoxy crosslinking agent, various silane compounds, and other compounds having an equivalent effect should be used as the adhesion-imparting agent. Is also possible.

Nevertheless, the present inventors have at least one alkoxy group and at least one organic functional group selected from an amino group, an epoxy group, an isocyanate group, a mercapto group, a vinyl group, an acryloxy group, and a methacryloxy group. The inventors have found a silane compound having at least one and have arrived at a configuration in which these silane compounds are added to the primer solution as an adhesion-imparting agent.
And the primer liquid which concerns on this invention which has the said structure has a low haze in the primer layer which has the heat ray shielding function in the transparent resin laminated body which concerns on this invention in the wide drying temperature range of temperature 90 degreeC-140 degreeC. It can be formed as a primer layer having excellent design properties and good adhesion to the silicone resin layer and having an excellent heat ray shielding function. That is, in addition to ensuring interlayer adhesion between the primer layer having a heat ray shielding function and the silicone-based resin layer, it is possible to achieve suppression of haze value in the primer layer having a heat ray shielding function while maintaining excellent productivity. .

Specific examples of the adhesion imparting agent include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltrimethoxysilane. Ethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acrylic Roxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Toxisilane, γ-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ- Isocyanatopropyltriethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate in which isocyanate groups are bonded, tris (3-triethoxysilylpropyl) isocyanurate, 4-trimeth Xylylpropyloxy-2-hydroxybenzophenone, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyl Dimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-methacryloxypropylmethyl Dimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminop Pills methyl diethoxy silane, N- and (2-aminoethyl) aminopropyl methyl dimethoxy silane, it can be cited those hydrolytic polycondensate.
For example, isocyanate propyl triethoxysilane (trade name: KBE9007, Shin-Etsu Chemical Co., Ltd.) can be exemplified.

  It is preferable that the addition amount of the said adhesion imparting agent (B) is 0.1-30 weight part with respect to 100 weight part of acrylic resin mentioned above. More preferably, it is 0.5 to 15 parts by weight. If the addition amount of the adhesion-imparting agent (B) is 0.1 parts by weight or more, the adhesion between the primer layer having a heat ray shielding function and the silicone resin layer is sufficient, which is preferable. On the other hand, if the addition amount of the adhesion-imparting agent (B) is 30 parts by weight or less, the composite tungsten oxide fine particles can be prevented from forming aggregates in the primer layer having a heat ray shielding function, and the resulting transparent laminate It is preferable because the haze value of the body can be suppressed and the design can be maintained.

(3) Method for producing primer solution for forming primer layer having heat ray shielding function Primer solution for forming a primer layer having a heat ray shielding function according to the present invention includes a heat ray shielding fine particle-containing dispersion, a solution containing an acrylic resin, And it can manufacture by adding and mixing an adhesion imparting agent. The mixing method is not particularly limited as long as it is a method capable of uniformly mixing the heat ray shielding fine particle-containing dispersion, the solution containing the acrylic resin, and the adhesion imparting agent. For example, a stirring and mixing method or an ultrasonic mixing method can be used.

  In addition, an organic ultraviolet absorber, an inorganic ultraviolet absorber, a hindered amine system for the purpose of improving the durability and strength of the transparent resin laminate described later to a primer solution for forming a primer layer having the heat ray shielding function, if desired. A light stabilizer, an antioxidant, a color tone adjusting agent, and the like may be added and mixed.

[3] Transparent resin laminate As described above, the transparent resin laminate according to the present invention includes a primer layer having a heat ray shielding function laminated on at least one surface of a transparent resin substrate, and a primer having the heat ray shielding function. And a silicone-based resin layer formed on the layer.
Here, (1) a transparent resin substrate, (2) a primer layer having a heat ray shielding function, (3) a silicone-based resin layer will be described in this order, and (4) a method for producing a transparent resin laminate will be described.

(1) Transparent resin substrate The transparent resin substrate of the transparent resin laminate according to the present invention can be used as long as it is a transparent resin substrate having a high light transmittance in the visible light region, and is not particularly limited. .
Specifically, polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, polyester resin, polyacetal resin, polysulfone resin, polyether sulfone resin, polyvinyl chloride resin, polyvinylidene chloride resin, epoxy resin, unsaturated polyester resin, polyurethane Examples thereof include resins, diallyl phthalate resins, diethylene glycol bisallyl carbonate resins, acetyl cellulose resins, sulfur-containing urethane resins, and crosslinked (meth) acrylic resins. In particular, a polycarbonate resin is preferable from the viewpoint of excellent mechanical strength, heat resistance, and durability.

(2) Primer layer having a heat ray shielding function The primer layer having a heat ray shielding function of the transparent resin laminate according to the present invention uses a primer solution for forming a primer layer having a heat ray shielding function according to the present invention described above. It is a primer layer having a heat ray shielding function laminated on at least one surface of a transparent resin substrate.
The primer solution for forming a primer layer having a heat ray shielding function is as already described. Moreover, the lamination | stacking method of the primer layer which has a heat ray shielding function on a transparent resin base material is mentioned later.

(3) Silicone resin The silicone resin of the transparent resin laminate according to the present invention is a silicon compound having a polysiloxane bond, and includes, for example, an inorganic silane compound and / or a polyorganosiloxane compound as a main component. Mention may be made of silicone-based resins forming a hard coat layer.

The inorganic silane compound, the polyorganosiloxane compound, or a mixed system thereof, for example, hydrolyzes an alkoxysilane compound represented by (Formula 1) using a catalyst such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. Can be obtained by polycondensation.
R1 _n Si (OR2) _4-n ... (Formula 1)
[However, R1 in the above general formula is a non-hydrolyzable group, and is an alkyl group, a substituted alkyl group (substituent: halogen atom, epoxy group, (meth) acryloyloxy group etc.), alkenyl group, aryl group or Aralkyl group, R2 is a lower alkyl group, and n is an integer of 0 or 1-3. When there are a plurality of R1s and OR2s, the plurality of R1s may be the same or different, and the plurality of OR2s may be the same or different. ]
In this case, an inorganic silane-based binder can be obtained by hydrolyzing a compound of n = 0, that is, tetraalkoxysilane, and a polyorganosiloxane-based binder or a mixture of an inorganic silane-based and a polyorganosiloxane-based can be obtained by partial hydrolysis. A system binder is obtained. On the other hand, since a compound with n = 1 to 3 has a non-hydrolyzable group, a polyorganosiloxane-based binder can be obtained by partial or complete hydrolysis. In the above case, an appropriate organic solvent may be used for the purpose of controlling the hydrolysis reaction.

  Examples of the alkoxysilane compound represented by the above (formula 1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra -Sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyl Trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloylio Examples include cyclopropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane, and trivinylethoxysilane. .

(4) Production method of transparent resin laminate The transparent resin laminate according to the present invention is prepared by applying a primer solution for forming a primer layer having a heat ray shielding function according to the present invention to at least one surface of a transparent resin substrate. After laminating a primer layer having a heat ray shielding function by applying and thermosetting, a coating solution made of a silicone resin is further applied on the primer layer having the heat ray shielding function, and the silicone resin layer is thermally cured. It can be manufactured by laminating.
Hereinafter, <4-1> a method for laminating a primer layer having a heat ray shielding function and <4-2> a method for laminating a silicone resin layer will be described in this order.

<4-1> Laminating method of primer layer having heat ray shielding function The primer layer forming primer solution having the heat ray shielding function described above is coated with a bar coating method, a spray coating method, a roll coating method, a dip coating method, a spin coating method, or the like. It apply | coats on a transparent resin base material by an appropriate method. Next, the coating layer on the transparent resin substrate is dried by heating at 90 ° C. to 140 ° C. for 10 minutes to 3 hours to obtain a primer layer having a heat ray shielding function by a method of thermosetting the acrylic resin. .
This will be examined from the adhesion between the primer layer and the silicone resin film described later. When the drying temperature is 80 ° C. or higher, a primer layer in which the acrylic resin is sufficiently thermoset can be formed. On the other hand, when the drying temperature is less than 150 ° C., the adhesion between the primer layer having a heat ray shielding function and the silicone resin film can be secured. From this viewpoint, a more preferable drying temperature is in the range of 80 ° C to 140 ° C.
Further, considering the design properties of the primer layer, if the drying temperature is 90 ° C. or higher, a low haze value can be secured in the primer layer. Then, when the viewpoint of the said design property is also added, the most preferable drying temperature is the range of 90-140 degreeC.
The preferred drying time is 20 minutes to 2 hours, most preferably 30 minutes to 1 hour 30 minutes.
By the drying treatment, the organic solvent in the primer solution for forming the primer layer having the heat ray shielding function is removed, and the acrylic resin monomer in the primer solution for forming the primer layer having the heat ray shielding function is polymerized.

Further, the thickness of the primer layer having a heat ray shielding function is not particularly limited, but is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.
If the film thickness is 1 μm or more, in order to obtain desired heat ray shielding characteristics in the transparent resin laminate according to the present invention, the compounding amount of the composite tungsten oxide fine particles that should be present in the primer layer having the heat ray shielding function is excessive. This is because the primer layer having the heat ray shielding function can exhibit sufficient adhesion strength as a primer layer. On the other hand, if the film thickness is 20 μm or less, an increase in haze value can be suppressed, and a situation in which the upper silicone resin layer is easily cracked or peeled due to curing shrinkage of the primer layer having the heat ray shielding function is avoided. I can do it.

<4-2> Method for Laminating Silicone Resin Layer The silicone resin layer is prepared by applying a coating solution composed of a silicone resin by an appropriate method such as a bar coating method, a spray coating method, a roll coating method, a dip coating method, or a spin coating method. It can apply | coat and can laminate | stack by the method of heating a coating layer for 10 to 2 hours from room temperature-150 degreeC, and hardening the said silicone type resin. The lower limit temperature, heating time, and heating atmosphere (including vacuum) are not particularly limited as long as the solvent evaporates and the coating layer (coating film) is cured.

  Although there are variations depending on the type of silicone resin used, a more preferred heating time is in the range of 80 to 140 ° C., most preferably in the range of 110 to 130 ° C., and a more preferred heating time is 20 minutes to 2 hours, Most preferably, it is 30 minutes to 1 hour 30 minutes. The film thickness of the silicone resin layer is not particularly limited, but is preferably 1 to 20 μm, particularly preferably 1 to 10 μm. If the thickness of the silicone resin layer is within this range, the silicone resin layer may crack due to the stress generated during thermosetting, or the adhesion between the silicone resin layer and the substrate may be reduced. Thus, a silicone resin layer having sufficient wear resistance and adhesion can be obtained.

  In addition, for the purpose of improving the durability and strength of the transparent resin laminate to the coating liquid comprising the above-described silicone resin, an organic ultraviolet absorber, an inorganic ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, A color adjusting agent, colloidal silica or the like may be added and mixed.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail, referring an Example, this invention is not restrict | limited at all by the following example.

Example 1
<Manufacture of dispersion containing heat ray shielding fine particles>
An acrylic dispersant (amine value 44 mgKOH / amine) having 100 parts by weight of Cs _0.33 WO ₃ particles, which are fine particles having a heat ray shielding function, 500 parts by weight of methyl isobutyl ketone as an organic solvent and an amine-containing group as a functional group g) 50 parts by weight were added to obtain a mixture. The mixture was charged into a medium stirring mill, and a heat ray shielding fine particle-containing dispersion liquid according to Example 1 was produced in which Cs _0.33 WO ₃ particles were pulverized and dispersed. At this time, the dispersed particle diameter of the Cs _0.33 WO ₃ fine particles in the dispersion containing the heat ray shielding fine particles was 21 nm, and the Cs _0.33 WO ₃ fine particle content was 18.5 wt%. The dispersed particle size of Cs _0.33 WO ₃ fine particles was measured with a Nikkiso Microtrac particle size distribution meter.

<Manufacture of primer solution for forming primer layer with heat ray shielding function>
Momentive PH-91 was prepared as a coating liquid containing an acrylic resin.
As an adhesion-imparting agent, isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-9007 /) B-1 was prepared.
Then, a solution containing the acrylic resin according to Example 1, the dispersion containing the heat ray shielding fine particles according to Example 1, and the isocyanate propyltriethoxysilane which is an adhesion-imparting agent were added to the acrylic resin: Cs _0.33 WO ₃ fine particles. : Adhesiveness imparting agent = 100 parts by weight: 5.75 parts by weight: 5 parts by weight. And the primer liquid for primer layer formation which has the heat ray shielding function which concerns on Example 1 by mixing the solution containing a heat ray shielding fine particle, the solution containing acrylic resin, and the adhesiveness imparting agent uniformly was manufactured.

<Manufacture of heat transparent resin laminate (lamination of primer layer having heat ray shielding function)>
The primer solution according to Example 1 was dip coated on the surface of three polycarbonate resin plates. Then, the three polycarbonate resin plates were dried for 1 hour at temperatures of 85 ° C., 115 ° C., 120 ° C., 125 ° C. and 130 ° C., respectively, and a primer layer having a heat ray shielding function was laminated. The film thickness of the primer layer having the heat ray shielding function was 8.5 μm.

<Manufacture of heat transparent resin laminate (lamination of silicone resin layer)>
Momentive Tosguard 510 was prepared as a coating solution containing a silicone resin.
A coating liquid containing a silicone resin is dip coated on the primer layer having the heat ray shielding function according to the above three types of Example 1, and the silicone resin layer is laminated by drying at 120 ° C. for 1 hour. Three types of transparent resin laminates according to No. 1 were produced. The film thicknesses of the three types of silicone resin layers were all 5.2 μm.

<Evaluation of heat-transparent resin laminate (optical properties)>
Optical properties of the three types of transparent resin laminates obtained in Example 1 were evaluated: visible light transmittance T (unit:%), solar transmittance ST (unit:%), and haze H (unit:%). did. The visible light transmittance T (unit:%) and solar radiation transmittance ST (unit:%) were evaluated using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), and haze H (unit:%). Was evaluated according to JISK7136 using a haze meter (manufactured by Murakami Color Research Laboratory). The evaluation results are shown in Table 1.

<Evaluation of heat-transparent resin laminate (mechanical properties)>
Mechanical properties (adhesiveness) of the obtained three types of transparent resin laminates were evaluated.
Specifically, when the laminated coating film is made of 100 grids with a 1 mm interval with a cutter knife, Nichiban adhesive tape (trade name cello tape (registered trademark)) is pressure-bonded, and then peeled off strongly vertically, Evaluation was based on the number X of the grids remaining without peeling off the coating film. The evaluation results are indicated by X / 100. The evaluation results are shown in Table 1.

(Example 2)
Addition amount of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-9007 /) B-1 as an adhesion imparting agent was changed to acrylic resin: Cs _0.33 WO ₃ fine particles: adhesion imparting agent = 100 parts by weight: 5.75 parts by weight: A primer solution for forming a primer layer having a heat ray shielding function according to Example 2 was prepared in the same manner as in Example 1 except that the mixture was formulated to be 0.1 parts by weight. Manufactured.
Using the primer solution according to Example 2, three types of transparent resin laminates according to Example 2 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates produced in Example 2 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Example 3)
Addition amount of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-9007 /) B-1 as an adhesion imparting agent was changed to acrylic resin: Cs _0.33 WO ₃ fine particles: adhesion imparting agent = 100 parts by weight: 5.75 parts by weight: A primer solution for forming a primer layer having a heat ray shielding function according to Example 3 was produced in the same manner as in Example 1 except that the mixture was blended so as to be 30 parts by weight. .
Using the primer solution according to Example 3, three types of transparent resin laminates according to Example 3 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to the manufactured Example 3 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Example 4
A primer having a heat ray shielding function according to Example 4 in the same manner as in Example 1 except that the adhesion-imparting agent was replaced with γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-903) B-2. A primer solution for layer formation was produced.
Using the primer solution according to Example 4, three types of transparent resin laminates according to Example 4 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to the manufactured Example 4 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Example 5)
Except that the adhesion-imparting agent was replaced with γ-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-403) B-3, the heat ray shielding function according to Example 5 was performed in the same manner as in Example 1. A primer solution for forming a primer layer was prepared.
Using the primer solution according to Example 5, three types of transparent resin laminates according to Example 5 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates produced in Example 5 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Example 6)
A primer having a heat ray shielding function according to Example 6 in the same manner as in Example 1 except that the adhesion-imparting agent was replaced with γ-mercaptopropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-803) B-4. A primer solution for layer formation was produced.
Using the primer solution according to Example 6, three types of transparent resin laminates according to Example 6 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates produced in Example 6 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Example 7)
Except for replacing the adhesion-imparting agent with γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-5103) B-5, the heat ray shielding function according to Example 7 is provided in the same manner as in Example 1. A primer solution for forming a primer layer was produced.
Using the primer solution according to Example 7, three types of transparent resin laminates according to Example 7 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Example 7 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Example 8)
Except that the adhesiveness-imparting agent is replaced with γ-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-503) B-6, the heat ray shielding function according to Example 8 is provided in the same manner as in Example 1. A primer solution for forming a primer layer was produced.
Using the primer solution according to Example 8, three types of transparent resin laminates according to Example 8 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates produced in Example 8 were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Example 9
For primer layer formation having a heat ray shielding function according to Example 9 in the same manner as in Example 1 except that the adhesiveness imparting agent is replaced with vinyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-1003) B-7. A primer solution was prepared.
Using the primer solution according to Example 9, three types of transparent resin laminates according to Example 9 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Example 9 manufactured were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that the adhesion-imparting agent was not added and the mixture was blended such that acrylic resin: Cs _0.33 WO ₃ fine particles = 100 parts by weight: 5.75 parts by weight. A primer solution for forming a primer layer having a heat ray shielding function according to Comparative Example 1 was produced.
Using the primer solution according to Comparative Example 1, three types of transparent resin laminates according to Comparative Example 1 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 1 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 2)
Addition amount of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-9007 /) B-1 as an adhesion imparting agent was changed to acrylic resin: Cs _0.33 WO ₃ fine particles: adhesion imparting agent = 100 parts by weight: 5.75 parts by weight: A primer solution for forming a primer layer having a heat ray shielding function according to Comparative Example 2 was prepared in the same manner as in Example 1 except that the mixture was formulated to be 0.05 parts by weight. Manufactured.
Using the primer solution according to Comparative Example 2, three types of transparent resin laminates according to Comparative Example 2 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 2 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 3)
Addition amount of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-9007 /) B-1 as an adhesion imparting agent was changed to acrylic resin: Cs _0.33 WO ₃ fine particles: adhesion imparting agent = 100 parts by weight: 5.75 parts by weight: A primer solution for forming a primer layer having a heat ray shielding function according to Comparative Example 3 was produced in the same manner as in Example 1 except that the mixture was formulated to be 35 parts by weight. .
Using the primer solution according to Comparative Example 3, three types of transparent resin laminates according to Comparative Example 3 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 3 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 4)
The primer for forming a primer layer having a heat ray shielding function according to Comparative Example 4 was used in the same manner as in Example 1 except that the adhesion-imparting agent was replaced with tetraethoxysilane (manufactured by Shin-Etsu Chemical: KBE-04) B-8. A primer solution was produced.
Using the primer solution according to Comparative Example 4, three types of transparent resin laminates according to Comparative Example 4 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 4 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 5)
The primer layer formation which has the heat ray shielding function which concerns on the comparative example 5 is carried out similarly to Example 1 except having replaced the adhesive imparting agent with the isocyanate type crosslinking agent (Asahi Kasei Co., Ltd. product: MF-K60X) B-9. A primer solution was prepared.
Using the primer solution according to Comparative Example 5, three types of transparent resin laminates according to Comparative Example 5 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 5 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 6)
A primer layer having a heat ray shielding function according to Comparative Example 6 in the same manner as in Example 1 except that the adhesion-imparting agent is replaced with an epoxy-based crosslinking agent (manufactured by Soken Chemical Co., Ltd .: E-AX) B-10. A primer solution for formation was produced.
Using the primer solution according to Comparative Example 6, three types of transparent resin laminates according to Comparative Example 6 were produced in the same manner as in Example 1.
The optical properties and mechanical properties of the three types of transparent resin laminates according to Comparative Example 6 produced were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Claims (9)

At least one surface of the transparent resin base material is laminated with a primer layer having a heat ray shielding function containing fine particles having a heat ray shielding function, an adhesion imparting agent, a dispersant, and a (meth) acrylic resin. A transparent resin laminate in which a silicone resin layer is laminated on the primer layer having the heat ray shielding function,
The fine particles having a heat ray shielding function are selected from the general formula M _y WO _Z (where M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu). One or more elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and a composite tungsten oxide fine particle having a hexagonal crystal structure,
The dispersant is an acrylic dispersant having a group containing an amine as a functional group, having a molecular weight Mw of 2000 to 200000, and an amine value of 5 to 100 mgKOH / g, and the amount of the dispersant added is the composite tungsten oxide 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the product fine particles,
The adhesion-imparting agent is isocyanate propyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- It is at least one selected from methacryloxypropyltriethoxysilane and vinyltriethoxysilane, and the addition amount of the adhesion-imparting agent is 0.1 to 30 parts by weight with respect to 100 parts by weight of the acrylic resin. A transparent resin laminate. The transparent resin laminate according to claim 1 , wherein the amount of the fine particles having a heat ray shielding function is 1 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin. The transparent resin laminate according to claim 1 , wherein the heat ray shielding fine particles are fine particles having an average particle diameter of 1 nm to 800 nm. The transparent resin laminate according to any one of claims 1 to 3, wherein the primer layer having a heat ray shielding function has a thickness of 1 µm to 20 µm. The transparent resin laminate according to any one of claims 1 to 4, wherein the silicone resin layer has a thickness of 1 µm to 20 µm. The said transparent resin base material is polycarbonate resin, The transparent resin laminated body in any one of Claims 1-5 characterized by the above-mentioned . It is a transparent resin laminated body in any one of Claims 1-6, Comprising: Haze when the visible light transmittance | permeability of the said transparent resin laminated body is set to 50% or more is 5% or less, It is characterized by the above-mentioned. Transparent resin laminate. A primer solution for forming a primer layer having a heat ray shielding function in the transparent resin laminate according to claim 1 ,
It has the heat ray shielding function characterized by including the said heat ray shielding microparticles | fine-particles, the said adhesiveness imparting agent, the said (meth) acrylic-type resin, the organic solvent with a boiling point of 120 degrees C or less, and the said acrylic dispersing agent. Primer solution for primer layer formation. On at least one surface of the transparent resin substrate, the heat ray shielding fine particles, the adhesion-imparting agent, the (meth) acrylic resin, an organic solvent having a boiling point of 120 ° C. or less, and the acrylic dispersant. , A first step of applying a primer solution containing and heat-curing at a temperature of 90 ° C. to 140 ° C. to form a primer layer having a heat ray shielding function;
The transparent resin according to claim 1 , further comprising a second step of applying a coating liquid containing the silicone resin on the primer layer having the heat ray shielding function and thermally curing the coating liquid. A manufacturing method of a layered product.