JP2018135232A - Infrared shielding member, transparent substrate with infrared shielding member and method for producing transparent substrate with infrared shielding member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared shielding member which has low infrared transmittance and is excellent in chemical resistance and wear resistance.SOLUTION: The infrared shielding member is provided which has an infrared shielding layer and a barrier layer laminated on the infrared shielding layer, and in which: the infrared shielding layer includes a binder component and ITO (Indium Tin Oxide) particles dispersed into the binder component; the binder component contains a resin such as an epoxy resin and a hydrolyzate of silicon alkoxide; a content of the hydrolyzate of the silicon alkoxide of the binder component is in the range of 30 mass% or more and 60 mass% or less; the barrier layer contains a resin having the same skeleton as a resin contained in the binder component and a hydrolyzate of the same silicon alkoxide as a hydrolyzate of the silicon alkoxide contained in the binder component; and a content of the hydrolyzate of the silicon alkoxide of the barrier layer is in the range of 5 mass% or more and 30 mass% or less and is a smaller amount than the content of the hydrolyzate of the silicon alkoxide of the binder component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an infrared shielding member, a transparent substrate with an infrared shielding member, and a method for producing a transparent substrate with an infrared shielding member.

  Transparent substrates such as window glass used in automobiles and buildings generally tend to transmit infrared rays that serve as heat sources. For this reason, in an automobile or a building, an infrared shielding member is disposed on the transparent substrate, and the infrared ray in the light irradiated on the transparent substrate is shielded, and the temperature rise in the automobile or building is accompanied by the temperature rise. Reducing the cooling load has been studied.

  As an infrared shielding member, a film in which tin-doped indium oxide particles (ITO particles) are dispersed in a binder component is known. The ITO particles have an action of absorbing infrared rays. As the binder component, an inorganic material, an organic material, or a mixture thereof is used.

For example, in Patent Document 1, as a binder component of an infrared cut-off film (infrared shielding member), (1) an alkoxide of Si, Al, Zr or Ti and / or a partial hydrolyzate thereof, (2) water and / or It describes the use of an organic resin soluble or dispersible in alcohol, or (3) a mixture of (1) and (2).
Patent Document 2 discloses an infrared shielding layer having a layer thickness of 100 to 1500 nm, in which ITO fine particles having an average primary particle diameter of 100 nm or less are dispersed in a matrix (binder component) containing silicon oxide and titanium oxide. Describes a glass plate with an infrared shielding layer having a surface of a glass substrate.

JP-A-7-70482 JP 2008-24577 A

  It is preferable that the infrared shielding member used for the transparent base material of a motor vehicle or a building can shield infrared rays stably over a long period of time. In particular, since the infrared shielding member used for the transparent base material of an automobile or a building may come into contact with a detergent during cleaning, high chemical resistance is required. However, the ITO particles used in the infrared shielding member have low chemical resistance, and when they come into contact with chemicals such as acid and alkali, the infrared absorption ability may be lowered. For this reason, as described in Patent Documents 1 and 2, a film in which ITO particles are dispersed in a binder component may have insufficient chemical resistance. In addition, the infrared shielding member used for the transparent base material of automobiles and buildings is also required to have high wear resistance so that the surface is not consumed due to friction during cleaning.

  The present invention has been made in view of the above-described circumstances, and has an infrared shielding member, a transparent substrate with an infrared shielding member, and a transparent substrate with an infrared shielding member, which have low infrared transmittance and excellent chemical resistance and wear resistance. It is in providing the manufacturing method of.

  In order to solve the above problems, an infrared shielding member of the present invention includes an infrared shielding layer and a barrier layer laminated on the infrared shielding layer, and the infrared shielding layer includes a binder component and the binder. Tin-doped indium oxide particles dispersed in a component, wherein the binder component is at least one resin selected from the group consisting of an epoxy resin, a (meth) acrylic resin, an epoxy (meth) acrylic resin, a fluororesin, and silicon An alkoxide hydrolyzate, wherein the silicon alkoxide hydrolyzate content of the binder component is in the range of 30% by mass to 60% by mass, and the barrier layer is contained in the binder component. A resin having the same skeleton as the resin and the hydrolyzate of the silicon alkoxide contained in the binder component A hydrolyzate of the silicon alkoxide of the binder component, wherein the content of the hydrolyzate of the silicon alkoxide in the barrier layer is in the range of 5% by mass to 30% by mass. It is characterized by being less than the content of.

  According to the infrared shielding member of the present invention configured as described above, the binder component and the barrier layer of the infrared shielding layer contain a resin having the same skeleton and a hydrolyzate of the same silicon alkoxide, The infrared shielding layer and the barrier layer have high adhesion, and the infrared shielding layer and the barrier layer are difficult to peel off, and the thickness of the barrier layer is likely to be uniform. When the infrared shielding layer and the barrier layer are difficult to peel off, the chemical resistance is improved because the chemical does not easily enter the gap between the infrared shielding layer and the barrier layer. Further, when the thickness of the barrier layer is uniform, the strength of the barrier layer surface is increased, so that the wear resistance is improved.

  Furthermore, the content of the hydrolyzate of silicon alkoxide as the binder component of the infrared shielding layer is in the range of 30% by mass to 60% by mass, and the content of the hydrolyzate of silicon alkoxide in the barrier layer is 5% by mass to 30%. Since the amount is less than the mass% and less than the content of the hydrolyzate of silicon alkoxide as a binder component, chemical resistance and wear resistance are further improved. The reason for this is considered to be that the content of the hydrolyzate of silicon alkoxide in the barrier layer is 5% by mass or more, and the hardness of the barrier layer surface is high. The content of the hydrolyzate of the silicon alkoxide in the barrier layer is in the range of 30% by mass or less and less than the content of the hydrolyzate of the silicon alkoxide as the binder component. Because it contains more resin than it is, it is easily deformed. For this reason, even when a load is applied to the surface of the barrier layer, the adhesion between the infrared shielding layer and the barrier layer is high, and peeling between the infrared shielding layer and the barrier layer and wear of the barrier layer are less likely to occur. This is considered to be because the entry of chemicals from the gap between the layer and the barrier layer is suppressed.

Here, in the infrared shielding member of the present invention, it is preferable that the average primary particle diameter of the tin-doped indium oxide particles is 100 nm or less.
In this case, since the average primary particle diameter of tin-doped indium oxide particles (ITO particles) is 100 nm or less, scattering of visible light by the ITO particles hardly occurs, and infrared absorption by the ITO particles is maintained while maintaining high visible light transmittance. Efficiency can be increased.

Moreover, in the infrared shielding member of this invention, it is preferable that the contact angle with the water of the said barrier layer is 70 degree | times or more.
In this case, the barrier layer has a high water repellency such as a contact angle with water of 70 degrees or more, so that the chemical resistance to an aqueous drug is improved.

  The transparent substrate with an infrared shielding member of the present invention has a transparent substrate and the above-described infrared shielding member disposed on at least one surface of the transparent substrate, and the infrared shielding of the infrared shielding member on the surface of the transparent substrate. It is characterized in that the layers are arranged in contact with each other.

  According to the transparent substrate with an infrared shielding member of the present invention having such a configuration, since the above-described infrared shielding member is used on the surface of the transparent substrate, it is excellent in chemical resistance and wear resistance.

  The method for producing a transparent substrate with an infrared shielding member of the present invention is a method for producing the above-described transparent substrate with an infrared shielding member, which is a soluble epoxy resin, a soluble (meth) acrylic resin, a soluble epoxy (meth) acrylic resin, or a soluble fluorine. At least one soluble resin selected from the group consisting of resins, a hydrolyzate of silicon alkoxide, tin-doped indium oxide particles, and a solvent, and the solid content of the soluble resin and the hydrolyzate of the silicon alkoxide A coating solution for forming an infrared shielding layer in which the solid content of the hydrolyzate of silicon alkoxide with respect to the total amount of the solid content is in the range of 30% by mass to 60% by mass, and the same skeleton as the soluble resin A soluble resin having a hydrolyzate of silicon alkoxide identical to the hydrolyzate of silicon alkoxide, The solid content of the hydrolyzate of the silicon alkoxide is 5% by mass or more and 30% by mass with respect to the total content of the solids content of the soluble resin and the solids content of the hydrolyzate of the silicon alkoxide. At least one of a transparent substrate and a step of preparing a barrier layer-forming coating solution having an amount less than the content of the hydrolyzate of the silicon alkoxide in the infrared shielding layer-forming coating solution in the following range: Applying the infrared shielding layer forming coating liquid on the surface, drying to form an infrared shielding layer, and applying the barrier layer forming coating liquid to the surface of the infrared shielding layer; And a barrier layer forming step of forming a barrier layer by drying.

  According to the method for producing a transparent substrate with an infrared shielding member of the present invention having such a configuration, since the coating liquid for forming the barrier layer is applied to the surface of the infrared shielding layer and heated, the infrared shielding layer and An infrared shielding member that is in close contact with the barrier layer can be formed.

  According to the present invention, it is possible to provide an infrared shielding member having a low infrared transmittance, excellent chemical resistance and wear resistance, a transparent substrate with an infrared shielding member, and a method for producing a transparent substrate with an infrared shielding member. .

It is sectional drawing of the transparent base | substrate with an infrared shielding member provided with the infrared shielding member which is one Embodiment of this invention.

Embodiments of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view of a transparent substrate with an infrared shielding member provided with an infrared shielding member according to an embodiment of the present invention.
The transparent substrate 1 with an infrared shielding member includes a transparent substrate 10 and an infrared shielding member 20 disposed on one surface (the upper surface in FIG. 1) of the transparent substrate 10. The infrared shielding member 20 includes an infrared shielding layer 30 and a barrier layer 40 laminated on the infrared shielding layer 30. The infrared shielding member 20 is disposed so that the infrared shielding layer 30 of the infrared shielding member 20 is in contact with the surface of the transparent substrate 10.

  Examples of the material of the transparent substrate 10 include glass and glass substitute resin. Examples of the glass substitute resin include polycarbonate (PC) resin and acrylic resin. There is no restriction | limiting in particular in the shape of the transparent base | substrate 10, It can be set as arbitrary shapes, such as plate shape, a sheet form, and a film form.

  The infrared shielding layer 30 of the infrared shielding member 20 absorbs infrared rays in the light irradiated on the infrared shielding member 20 and shields the infrared rays from entering the transparent substrate 10. The infrared shielding layer 30 preferably has a thickness in the range of 1 μm to 4 μm. When the thickness of the infrared shielding layer 30 is 1 μm or more, the infrared absorption efficiency is improved, and the infrared transmittance of the infrared shielding member 20 is lowered. On the other hand, when the thickness of the infrared shielding layer 30 is 4 μm or less, a reduction in visible light transmittance is suppressed.

  The infrared shielding layer 30 of the infrared shielding member 20 includes a binder component 31 and ITO particles (tin-doped indium oxide particles) 32 dispersed in the binder component 31.

  The binder component 31 contains at least one resin selected from the group consisting of an epoxy resin, a (meth) acrylic resin, an epoxy (meth) acrylic resin, and a fluororesin, and a hydrolyzate of silicon alkoxide.

The epoxy resin is a polymer compound having an epoxy group as a skeleton. The (meth) acrylic resin includes a methacrylic resin and an acrylic resin. The (meth) acrylic resin is a polymer compound having a (meth) acryloyl group as a skeleton. The epoxy (meth) acrylic resin is a polymer compound having an epoxy group and a (meth) acryloyl group as a skeleton. A fluororesin is a polymer compound having a hydrocarbon group substituted with fluorine as a skeleton.
There is no restriction | limiting in particular in the molecular structure of an epoxy resin, a (meth) acrylic resin, an epoxy (meth) acrylic resin, and a fluororesin, A well-known thing can be used. When the binder component 31 has a high content of epoxy resin, (meth) acrylic resin, and epoxy (meth) acrylic resin, the strength of the infrared shielding layer 30 tends to increase. The fluororesin is highly effective in increasing the water repellency of the infrared shielding layer 30. The fluororesin is preferably used in combination with any of an epoxy resin, a (meth) acrylic resin, and an epoxy (meth) acrylic resin.

The silicon alkoxide hydrolyzate contained in the binder component 31 is preferably a hydrolyzed silicon alkoxide represented by the following general formula (1).
General formula (1):
R ¹ _x Si (OR ² ) _4-x

In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group (eg, methyl group, ethyl group, propyl group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group), aryl group (eg, phenyl group). , Tolyl group, xylyl group, biphenyl group, naphthyl group) and aralkyl group (for example, benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group). R ² represents an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, or a propyl group). x represents an integer of 0 to 3.

  Examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like. . These silicon alkoxides may be used alone or in combination of two or more.

The content of the hydrolyzate of silicon alkoxide of the binder component 31 is in the range of 30% by mass to 60% by mass. That is, the ratio of the hydrolyzate of the silicon alkoxide of the binder component 31 and the resin is 30:70 to 40:60 in terms of mass ratio.
If the content of the hydrolyzate of silicon alkoxide is too small, the hardness of the infrared shielding layer 30 is lowered, and the shape stability of the infrared shielding member 20 may be lowered. If the content of the hydrolyzate of silicon alkoxide is too large, the hardness of the infrared shielding layer 30 becomes too high and becomes brittle, and the shape stability of the infrared shielding member 20 may be lowered.

  In the infrared shielding member 20 of the present embodiment, the ITO particles 32 have an average primary particle diameter of 100 nm or less. If the average primary particle diameter of the ITO particles 32 becomes too large, visible light is likely to be scattered, and the visible light permeability may be reduced. For this reason, in the infrared shielding member 20 of this embodiment, the average primary particle diameter of the ITO particles 32 is 100 nm or less. In addition, the ITO particle | grains 32 can use the well-known thing utilized as an infrared absorber. The average primary particle diameter of the ITO particles 32 is preferably 5 nm or more.

The content of the ITO particles 32 in the infrared shielding layer 30 is preferably in the range of 10/90 or more and 50/50 or less as the mass ratio of the binder component 31 and the ITO particles 32 (ITO particles 32 / binder component 31).
When the content of the ITO particles 32 is 10/90 or more, the infrared absorption efficiency of the infrared shielding layer 30 is improved, and the infrared transmittance of the infrared shielding member 20 is lowered. Further, when the content of the ITO particles 32 is 50/50 or less, the ITO particles 32 are difficult to touch the outside, and the chemical resistance of the infrared shielding member 20 is improved.

  The barrier layer 40 of the infrared shielding member 20 protects the infrared shielding layer 30 and improves chemical resistance and wear resistance. The thickness of the barrier layer 40 is preferably in the range of 1 μm to 5 μm. When the thickness of the barrier layer 40 is 1 μm or more, chemical resistance is improved. On the other hand, when the thickness of the barrier layer 40 is 5 μm or less, a decrease in visible light transmittance is suppressed.

  In the infrared shielding member 20 of the present embodiment, the barrier layer 40 has a contact angle with water of 70 degrees or more. If the contact angle of the barrier layer 40 with water becomes too low, water may easily enter between the infrared shielding layer 30 and the barrier layer 40, and the chemical resistance against an aqueous drug may be reduced. For this reason, in the infrared shielding member 20 of this embodiment, the contact angle with the water of the barrier layer 40 is 70 degrees or more.

The barrier layer 40 contains a resin having the same skeleton as the resin contained in the binder component 31 and a silicon alkoxide hydrolyzate identical to the silicon alkoxide hydrolyzate contained in the binder component 31.
Having the same skeleton means that the skeleton (group or element) specifying the resin is common.
For example, when the resin contained in the binder component 31 is an epoxy resin, the barrier layer 40 contains a resin having an epoxy group (epoxy resin). However, components other than the epoxy group need not be common. Specifically, the epoxy resin contained in the binder component 31 and the epoxy resin contained in the barrier layer 40 may have different constituent elements and molecular weights other than the epoxy group. Moreover, when the resin contained in the binder component 31 is a (meth) acrylic resin, the barrier layer 40 contains a resin ((meth) acrylic resin) having a (meth) acryloyl group. However, components other than the (meth) acryloyl group need not be common. Furthermore, when the resin contained in the binder component 31 is an epoxy (meth) acrylic resin, the barrier layer 40 contains a resin having an epoxy group and a (meth) acryloyl group (epoxy (meth) acrylic resin). However, constituent elements other than the epoxy group and the (meth) acryloyl group do not need to be shared. Furthermore, when the resin contained in the binder component 31 is a fluororesin, the barrier layer 40 contains a resin having a fluorine atom (fluororesin). However, the constituent elements of the fluorine atom need not be common.

  The barrier layer 40 has a silicon alkoxide hydrolyzate content in the range of 5% by mass to 30% by mass, and is smaller than the silicon alkoxide hydrolyzate content of the binder component 31.

Next, the manufacturing method of the transparent base | substrate with an infrared shielding member which concerns on this embodiment is demonstrated.
The method for producing a transparent substrate with an infrared shielding member according to the present embodiment includes a step of preparing an infrared shielding layer forming coating solution and a barrier layer forming coating solution, an infrared shielding layer forming step, and a barrier layer forming step. Prepare.

  The coating liquid for forming an infrared shielding layer contains a soluble resin, a hydrolyzate of silicon alkoxide, ITO particles, and a solvent. The soluble resin is a resin that is soluble in a solvent. The soluble resin is at least one soluble resin selected from the group consisting of a soluble epoxy resin, a soluble (meth) acrylic resin, a soluble epoxy (meth) acrylic resin, and a soluble fluororesin. When two or more soluble resins are used, two or more resins having the same skeleton may be used in combination, or two or more resins having different skeletons may be used in combination. A solvent will not be restrict | limited especially if soluble resin melt | dissolves. As the solvent, for example, monohydric alcohol, ketone, glycol ether, glycol ether acetate can be used. Examples of monohydric alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and tert-butyl alcohol. Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. An example of a glycol ether is ethylene glycol monoethyl ether. An example of glycol ether acetate is propylene glycol monomethyl ether acetate.

  The coating solution for forming the infrared shielding layer has a solid content of hydrolyzate of silicon alkoxide of 30 mass with respect to the total amount of solid content of soluble resin and hydrolyzate of silicon alkoxide. % Or more and 60% by mass or less. In addition, the content of the ITO particles in the coating liquid for forming the infrared shielding layer is the content of the ITO particles relative to the total amount (the binder component content) of the solid content of the soluble resin and the solid content of the hydrolyzate of silicon alkoxide. The mass ratio of the quantity (ITO particle content / binder component content) is preferably in the range of 10/90 to 50/50. In the coating liquid for forming an infrared shielding layer, the solid content means an amount remaining as a solid content when the coating liquid for forming an infrared shielding layer is dried. Therefore, by drying the coating liquid for forming the infrared shielding layer, the hydrolyzate of silicon alkoxide and the solid material of the soluble resin are contained, and the content of hydrolyzate of silicon alkoxide is 30% by mass or more and 60% by mass. An infrared shielding layer containing a binder component in the following range and ITO particles can be formed.

The coating solution for forming an infrared shielding layer can be prepared, for example, as follows.
Silicon alkoxide, water, catalyst, and organic solvent are mixed. The obtained liquid mixture is heated to produce a hydrolyzate of silicon alkoxide to obtain a silicon alkoxide hydrolyzate-containing liquid. Examples of the catalyst include inorganic acids such as hydrochloric acid, nitric acid and phosphoric acid, and organics such as formic acid, oxalic acid and acetic acid. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more types. A monohydric alcohol can be used as the organic solvent.

  Next, the obtained silicon alkoxide hydrolyzate-containing liquid and a soluble resin are mixed to obtain a binder component-containing liquid. As the soluble resin, a known resin used for coating can be used. For example, as a soluble epoxy resin, EPICLON HP-4700, EPICLON HP-4710, EPICLON HP-6000, EPICLON 850, EPICLON EXA-4700 manufactured by DIC Corporation, NC-3000 manufactured by Nippon Kayaku Co., Ltd. may be used. it can. Moreover, as a soluble acrylic resin, DIC Corporation Acridic A-9585 and Acridic WXU-880 can be used. As the soluble epoxy-acrylic resin, BAEM-50 manufactured by KSM Co., Ltd. can be used. As the soluble fluororesin, Lumiflon LF200 manufactured by Asahi Glass Co., Ltd. or Obligard SS0054 manufactured by AGC Co-Tech Co., Ltd. can be used.

Next, the obtained binder component-containing liquid and the ITO dispersion liquid are mixed. The ITO dispersion liquid is a dispersion liquid in which ITO powder is dispersed in a solvent. As the solvent for the ITO dispersion liquid, a solvent having compatibility with the solvent for the binder component-containing liquid is preferably used.
Then, an appropriate amount of a solvent is added to the mixture so that the obtained mixture of the binder component-containing liquid and the ITO dispersion liquid has a viscosity suitable for coating.

  The coating solution for forming a barrier layer includes a resin having the same skeleton as the soluble resin contained in the coating solution for forming an infrared shielding layer, a hydrolyzate of silicon alkoxide identical to the hydrolyzate of silicon alkoxide, and a solvent. The coating solution for forming the barrier layer has a silicon alkoxide hydrolyzate content of 5% by mass or more and 30% by mass or less based on the total amount of the solids content of the soluble resin and the hydrolyzate of silicon alkoxide. The amount is less than the solid content of the hydrolyzate of silicon alkoxide in the above-described coating solution for forming an infrared shielding layer. In the barrier layer forming coating solution, the solid content means an amount remaining as a solid content when the barrier layer forming coating solution is dried. Therefore, by drying this barrier layer forming coating solution, it contains a hydrolyzate of silicon alkoxide and a solid material of a soluble resin, and the content of hydrolyzate of silicon alkoxide is 5% by mass or more and 30% by mass or less. In this range, a barrier layer having an amount smaller than the content of the hydrolyzate of silicon alkoxide as a binder component of the infrared shielding layer can be formed.

  The coating liquid for forming the barrier layer is obtained, for example, by mixing a silicon alkoxide hydrolyzate-containing liquid and a soluble resin to obtain a mixed liquid. Then, an appropriate amount of a solvent is added to the mixture so that the obtained mixture has a viscosity suitable for application.

  In the infrared shielding layer forming step, an infrared shielding layer forming coating solution is applied to at least one surface of the transparent substrate and dried to form an infrared shielding layer. As a coating method of the coating liquid for forming the infrared shielding layer, a known method such as a dipping method, a printing method, a spraying method, a spin coating method, a roll coating method, a meniscus coating method, or a die coating method can be used. For the drying, a known drying method such as heat drying or vacuum drying can be used. The drying time is appropriately selected according to the type of solvent and the coating amount of the coating solution for forming the infrared shielding layer. In the infrared shielding layer forming step, it is not necessary to dry until the solvent of the coating solution for forming the infrared shielding layer is completely removed. That is, in the next barrier layer forming step, when the barrier layer forming coating solution is applied, the infrared shielding layer may be dried to such an extent that the shape of the layer can be maintained.

  In the barrier layer forming step, a barrier layer forming coating solution is applied to the surface of the infrared shielding layer formed in the infrared shielding layer forming step and dried to form a barrier layer. The coating method and the drying method of the barrier layer forming coating solution are the same as in the infrared shielding layer forming step. In the barrier layer forming step, drying is performed until the solvent of the barrier layer forming coating solution is completely removed.

  In addition, after forming the barrier layer, in order to improve the adhesion between the infrared shielding layer and the barrier layer, a firing step of further firing the infrared shielding layer and the barrier layer may be performed. The firing temperature and firing time are appropriately selected according to conditions such as the thickness of the infrared shielding layer and the barrier layer, the material of the resin contained in the infrared shielding layer and the barrier layer, and the like.

  According to the transparent substrate 1 with an infrared shielding member of the present embodiment configured as described above, the binder component 31 of the infrared shielding layer 30 and the barrier layer 40 have the same skeleton and the same silicon alkoxide. Therefore, chemical resistance and wear resistance are improved. Further, the silicon alkoxide hydrolyzate content of the binder component 31 of the infrared shielding layer 30 is in the range of 30% by mass to 60% by mass, and the silicon alkoxide hydrolyzate content of the barrier layer 40 is 5% by mass. % To 30% by mass and less than the content of the hydrolyzate of the silicon alkoxide of the binder component 31, the chemical resistance and wear resistance are further improved.

  Further, in the transparent substrate 1 with the infrared shielding member according to the present embodiment, since the average primary particle diameter of the ITO particles 32 of the infrared shielding member 20 is 100 nm or less, the visible light is hardly scattered by the ITO particles. The infrared absorption efficiency by the ITO particles can be increased while maintaining a high visible light transmittance.

  Furthermore, in the transparent substrate 1 with an infrared shielding member according to the present embodiment, the barrier layer 40 has a contact angle with water of 70 degrees or more and high water repellency, so that the chemical resistance to aqueous chemicals is improved. .

  Further, according to the method for producing a transparent substrate with an infrared shielding member of the present invention, since the coating liquid for forming the barrier layer is applied to the surface of the infrared shielding layer and heated, the infrared shielding layer and the barrier layer are strong. An intimate infrared shielding member can be formed.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.

  Below, the result of the evaluation test which evaluated the effect of the infrared shielding member which concerns on this invention is demonstrated.

In this example, the following materials were prepared as silicon alkoxide, soluble resin, and ITO powder.
[Silicon alkoxide]
TEOS: Tetraethoxysilane TMOS: Tetramethoxysilane PTMS: Phenyltrimethoxysilane [soluble resin]
Epoxy resin A: EPICLON HP-4700, manufactured by DIC Corporation Epoxy resin B: EPICLON HP-4710, manufactured by DIC Corporation Epoxy resin C: EPICLON HP-6000, manufactured by DIC Corporation Epoxy resin D: NC-3000, Nippon Kayaku Epoxy resin E: EPICLON 850, manufactured by DIC Corporation Epoxy resin F: EPICLON EXA-4700, manufactured by DIC Corporation Acrylic resin A: Acridic A-9585, manufactured by DIC Corporation Acrylic resin B: Acrydic WXU-880 DIC Corporation Epoxy Acrylate: BAEM-50, KS Corporation Fluoropolymer A: Lumiflon LF200, Asahi Glass Co., Ltd. Fluororesin B: Obligard PS214, AGC Co-Tech Co., Ltd. [ TO powder]
Average primary particle size: 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 50 nm

<Invention Example 1>
(1) Preparation of Infrared Shielding Film Forming Coating Solution To 1 part by mass of TEOS, 1.2 parts by mass of water, 0.02 parts by mass of formic acid, and 2.0 parts by mass of IPA (isopropyl alcohol) as an organic solvent are added. To obtain a mixed solution. The obtained mixed liquid was heated to a temperature of 55 ° C. and stirred for 1 hour to hydrolyze the silicon alkoxide to obtain a silicon alkoxide hydrolyzate-containing liquid.

  The resulting silicon alkoxide hydrolyzate-containing liquid and epoxy resin B were mixed to obtain a binder component-containing liquid. The mixing ratio of the silicon alkoxide hydrolyzate-containing liquid and the epoxy resin B is such that the silicon alkoxide hydrolyzate content is 35 with respect to the total content of the silicon alkoxide hydrolyzate and the epoxy resin B (binder component content). The ratio by which the content of the epoxy resin B was 65% by mass was 65% by mass.

The obtained binder component-containing liquid and the previously prepared ITO dispersion were mixed so that the mass ratio of the ITO powder and the binder component was 30/70 (= ITO powder / binder component).
The ITO dispersion was prepared by dispersing ITO powder having an average primary particle diameter of 20 nm in MEK (methyl ethyl ketone). In order to make the obtained mixture into a viscosity suitable for coating, MEK was added to the mixture little by little with stirring to prepare a coating solution for forming an infrared shielding film.

(2) Preparation of coating solution for forming barrier layer Silicon alkoxide hydrolyzate-containing solution obtained in the same manner as in (1) above and epoxy resin B were mixed. The mixing ratio of the silicon alkoxide hydrolyzate-containing liquid and the epoxy resin B is such that the silicon alkoxide hydrolyzate content is 10% by mass with respect to the total solid content of the silicon alkoxide hydrolyzate and the epoxy resin B. The content of the epoxy resin B was 90% by mass.
In order to make the obtained mixture have a viscosity suitable for coating, MEK (methyl ethyl ketone) was added to the mixture little by little with stirring to prepare a coating solution for forming a barrier layer.

(3) Production of Soda Lime Glass Substrate with Infrared Shielding Member A soda lime glass substrate 1.1 mmt was prepared as a visible light transmissive substrate. The infrared shielding film forming agent prepared in (1) above was applied to the surface of the soda lime glass substrate, and the resulting coating film was dried at 130 ° C. for 10 minutes to form an infrared shielding film. Next, the barrier film forming agent prepared in (2) above was applied to the surface of the infrared shielding film. The obtained coating film was dried at a temperature of 130 ° C. for 30 minutes and further baked at a temperature of 180 ° C. for 5 minutes to form a barrier film. Thus, a soda lime glass substrate with an infrared shielding member in which a soda lime glass substrate, an infrared shielding layer, and a barrier layer were formed in this order was produced.

<Invention Examples 2 to 11 and Comparative Examples 1 to 6>
In the preparation of the coating liquid for forming the infrared shielding film of Example 1 of the present invention, the materials described in Table 1 below were used as the silicon alkoxide, the resin and the ITO powder, and the silicon alkoxide hydrolyzate and the resin were contained. The amount and the ratio of ITO powder / binder component were the values described in Table 1 below. (2) In the preparation of the coating solution for forming the barrier layer, the use of the materials described in Table 1 below as the silicon alkoxide and resin, the content of the silicon alkoxide hydrolyzate and the resin are shown in Table 1 below. It was set as the value described in. Except for the above, a soda-lime glass substrate with an infrared shielding member was produced in the same manner as in Invention Example 1.

<Evaluation>
About the soda lime glass substrate with an infrared shielding member produced in Invention Examples 1 to 11 and Comparative Examples 1 to 6, the thickness of the infrared shielding layer and the barrier layer, the contact angle of the barrier layer with water, visible light (wavelength 450 nm) ) And near-infrared (wavelength 1300 nm) transmittance, chemical resistance and abrasion resistance were measured by the following methods. The results are shown in Table 2.

[Thickness of infrared shielding layer and barrier layer]
The thickness of the infrared shielding layer and the barrier layer was measured by cross-sectional observation with a scanning electron microscope (SU-8000 manufactured by Hitachi High-Technologies Corporation).

[Contact angle of the barrier layer with water]
The contact angle between the barrier layer and water was measured by a droplet method using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., Drop Master DM-700). Ion exchange water was dropped on the surface of the barrier layer of the soda lime glass substrate with an infrared shielding member, and the contact angle after 1000 msec was determined by the θ / 2 method. The amount of water dropped was 2 μL, and the measurement temperature was room temperature (22 ± 4 ° C.).

[Transmittance of visible light (wavelength 450 nm) and near infrared light (wavelength 1300 nm)]
Visible light and near-infrared transmittances were measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) according to the method described in JIS R 3216-1998.

[chemical resistance]
The chemical resistance was evaluated by the transmittance of near infrared rays after the soda lime glass substrate with an infrared shielding member was immersed in a 1N-HCl aqueous solution and a 1N-NaCl aqueous solution.
(Near-infrared transmittance after immersion in 1N-HCl aqueous solution)
The soda lime glass substrate with an infrared shielding member was immersed in a 1N-HCl aqueous solution (liquid temperature: 23 ° C.) for 6 hours. After soaking, the soda lime glass substrate with an infrared shielding member was taken out of the aqueous HCl solution, thoroughly washed with pure water, and then dried. About the soda lime glass substrate with an infrared shielding member after drying, the transmittance | permeability of near infrared rays was measured by said method.

(Near-infrared transmittance after immersion in 1N-NaCl aqueous solution)
The soda lime glass substrate with an infrared shielding member was immersed in a 1N-NaCl aqueous solution (liquid temperature: 23 ° C.) for 6 hours. After the immersion, the soda lime glass substrate with an infrared shielding member was taken out from the NaCl aqueous solution, thoroughly washed with pure water, and then dried. About the soda lime glass substrate with an infrared shielding member after drying, the transmittance | permeability of near infrared rays was measured by said method.

[Abrasion resistance]
Abrasion resistance was reciprocated 20 times while sliding at a strength of about 100 g / cm ² with steel wool # 0000 on the surface of the barrier layer of the soda lime glass substrate with an infrared shielding member. Evaluation was based on the presence or absence of scratches. The presence or absence of scratches on the surface of the barrier layer was confirmed by observing a range of 1 cm × 1 cm using visual observation and a stereomicroscope (magnification 50 times). When there is no scratch on both the visual microscope and the stereomicroscope, it is “excellent”, and when no scratch is confirmed by visual inspection, it is “good” when there are three or less scratches of 10 μm or less on the stereomicroscope. Although it was confirmed that the scratch was confirmed with a stereomicroscope and there were 5 or less scratches of 50 μm or less with a stereomicroscope, it was judged as “good”, and when it was confirmed with both a visual microscope and a stereomicroscope, it was judged as “bad”.

  The silicon alkoxide hydrolyzate contained in the binder component of the infrared shielding layer and the barrier layer are the same, the resins have the same skeleton, and the silicon alkoxide hydrolyzate contained in the infrared shielding layer and the barrier layer Inventive Examples 1 to 11 whose amounts are within the scope of the present invention all had high chemical resistance and wear resistance.

On the other hand, in Comparative Example 1 in which the content of the silicon alkoxide hydrolyzate in the barrier layer is less than the range of the present invention, the chemical resistance and the wear resistance were lowered. This is presumably because the hardness of the barrier layer was too low and the adhesion between the infrared shielding layer and the barrier layer was lowered. In Comparative Example 2 in which the content of the silicon alkoxide hydrolyzate in the barrier layer was larger than the range of the present invention, chemical resistance and wear resistance were lowered. This is presumably because the hardness of the barrier layer was too high and the adhesion between the infrared shielding layer and the barrier layer was lowered.
In Comparative Example 3 in which the types of silicon alkoxides in the infrared shielding layer and the barrier layer were different, the chemical resistance was lowered. This is presumably because the adhesion between the infrared shielding layer and the barrier layer was lowered. In Comparative Example 4 in which the types of the resin for the infrared shielding layer and the barrier layer were different, the chemical resistance and the wear resistance were lowered. This is presumably because the adhesion between the infrared shielding layer and the barrier layer was lowered. In Comparative Example 5 in which the content of the silicon alkoxide hydrolyzate in the infrared shielding layer was less than the range of the present invention, chemical resistance and wear resistance were lowered. This is presumably because the hardness of the infrared shielding layer was too low and the adhesion between the infrared shielding layer and the barrier layer was lowered. In Comparative Example 6 in which the content of the silicon alkoxide hydrolyzate in the infrared shielding layer was larger than the range of the present invention, chemical resistance and wear resistance were lowered. This is presumably because the hardness of the infrared shielding layer was too high and the adhesion between the infrared shielding layer and the barrier layer was lowered.

DESCRIPTION OF SYMBOLS 1 Transparent base | substrate with an infrared shielding member 10 Transparent base | substrate 20 Infrared shielding member 30 Infrared shielding layer 31 Binder component 32 ITO particle (tin dope indium oxide particle)
40 Barrier layer

Claims (5)

An infrared shielding layer, and a barrier layer laminated on the infrared shielding layer,
The infrared shielding layer includes a binder component and tin-doped indium oxide particles dispersed in the binder component;
The binder component contains at least one resin selected from the group consisting of an epoxy resin, a (meth) acrylic resin, an epoxy (meth) acrylic resin, and a fluororesin, and a hydrolyzate of silicon alkoxide, The content of the hydrolyzate of the silicon alkoxide is in the range of 30% by mass to 60% by mass,
The barrier layer contains a resin having the same skeleton as the resin contained in the binder component, and a silicon alkoxide hydrolyzate identical to the silicon alkoxide hydrolyzate contained in the binder component. The content of the hydrolyzate of the silicon alkoxide in the barrier layer is in the range of 5% by mass to 30% by mass and less than the content of the hydrolyzate of the silicon alkoxide of the binder component. An infrared shielding member characterized by that.   The infrared shielding member according to claim 1, wherein an average primary particle diameter of the tin-doped indium oxide particles is 100 nm or less.   The infrared shielding member according to claim 1, wherein a contact angle of the barrier layer with water is 70 degrees or more. A transparent substrate, and the infrared shielding member according to any one of claims 1 to 3 disposed on at least one surface of the transparent substrate,
A transparent substrate with an infrared shielding member, wherein the infrared shielding layer of the infrared shielding member is in contact with the surface of the transparent substrate. A method for producing a transparent substrate with an infrared shielding member according to claim 4,
At least one soluble resin selected from the group consisting of a soluble epoxy resin, a soluble (meth) acrylic resin, a soluble epoxy (meth) acrylic resin, and a soluble fluororesin, a hydrolyzate of silicon alkoxide, tin-doped indium oxide particles, and a solvent The solid content of the hydrolyzate of the silicon alkoxide with respect to the total amount of the solid content of the soluble resin and the solid content of the hydrolyzate of the silicon alkoxide is 30% by mass to 60% by mass. A coating solution for forming an infrared shielding layer in the following range;
A soluble resin having the same skeleton as the soluble resin, a hydrolyzate of the same silicon alkoxide as the hydrolyzate of the silicon alkoxide, and a solvent, and a solid content of the soluble resin and hydrolysis of the silicon alkoxide The solid content of the hydrolyzate of the silicon alkoxide with respect to the total solid content of the product is in the range of 5% by mass to 30% by mass, and the silicon alkoxide in the coating liquid for forming the infrared shielding layer Preparing a coating solution for forming a barrier layer that is less than the content of the hydrolyzate;
An infrared shielding layer forming step of applying the infrared shielding layer forming coating solution on at least one surface of the transparent substrate, and drying to form an infrared shielding layer; and
A barrier layer forming step of applying the barrier layer forming coating solution on the surface of the infrared shielding layer and drying to form a barrier layer; and
A method for producing a transparent substrate with an infrared shielding member, comprising:

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