JP2001089202A - Sunlight shielding laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sunlight shielding laminated glass improved in sunlight shielding function and having high transmissive performance to visible ray region. SOLUTION: The sunlight shielding laminated glass is formed by interposing an intermediate layer having the sunlight shielding function between 2 glass sheets. The intermediate layers is formed from an intermediate film composed of an adding liquid, which is prepared by dispersing at least one kind of hexaborate fine particle selected from a group composed of LaB6, CeB6, PrB6, NdB6, GdB6, TbB6, DyB6, HoB6, YB6, SmB6, EuB6, ErB6, TmB6, YbB6, LuB6, (La, Ce)B6, SrB6 and CaB6 and if necessary, ITO fine particle and/or ATO fine particle in a plasticizer, and a vinyl resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass for shielding sunlight, which is used as safety glass for vehicles such as automobiles and window glass of buildings.

[0002]

2. Description of the Related Art A conventional safety glass for an automobile or the like has a solar light shielding film interposed between glass sheets to block solar energy from the glass, thereby reducing a cooling load and a feeling of heat and heat of a person. Proposed.

As a conventional safety glass for automobiles and the like
Is inserted from the glass by sandwiching the solar shading film between the glass sheets.
Cuts off solar energy and reduces the cooling load and the heat and heat of people.
Those aimed at reduction have been proposed. For example, JP-A-8
According to -217500, such a laminated glass is
An acid having a fine particle size of 0.1 μm or less is placed between a pair of glass sheets.
Heat shielding metallic acid composed of tin oxide or indium oxide
Is formed by interposing a soft resin layer containing
You. Also, JP-A-8-259279 discloses at least
Between two glass sheets, Sn, Ti, Si, Zn,
Zr, Fe, Al, Cr, Co, Ce, In, Ni, A
g, Cu, Pt, Mn, Ta, W, V, Mo metal, acid
Or nitride, sulfide or Sb or F dope or
Is a composite that has an intermediate layer in which these composites are dispersed.
Laminated glass is disclosed. Further, JP-A-4-160
No. 04 discloses TiO₂, ZrO₂, SnO₂, In ₂
O₂Ultra-fine particles consisting of organosilicon or organosilicon
The glass component of the compound is interposed between the transparent plate members.
Window glass for automobiles. Even better
Japanese Patent Laid-Open No. 10-297945 discloses at least two sheets.
An intermediate layer consisting of three layers
The second intermediate layer among the intermediate layers is Sn, Ti, S
i, Zn, Zr, Fe, Al, Cr, Co, In, N
i, Ag, Cu, Pt, Mn, Ta, W, V, Mo gold
Metal, oxide, nitride, sulfide or Sb or F dope
Or a composite thereof, and a first layer and a third layer
Describes a laminated glass in which the intermediate layer is a resin layer.

[0004]

However, the laminated glass according to the prior art described in these publications does not have a sufficient sunshade function and visible light transmission performance, and improvements have been demanded. An object of the present invention is to provide a solar-shielded laminated glass having an enhanced solar-shielding function and having high transmission performance in the visible light region.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted various studies on an intermediate film interposed between two glass sheets or an intermediate layer comprising the intermediate film and the solar radiation shielding film. Attention was focused on hexaboride fine particles having a large amount of free electrons, which were converted to ultrafine particles.
An additive liquid is prepared by dispersing the additive liquid in a plasticizer together with TO or ATO fine particles. The vinyl resin composition obtained by adding the additive liquid to a vinyl resin is formed into a sheet to form an intermediate film. The intermediate film formed in the form of a sheet is sandwiched between sheet glasses, or two sheets of glass coated with a coating liquid having a solar shading function on the inside, or one sheet glass and a coating liquid having a solar shading function are coated on the inside A plasticizer is added to two sheets of glass on which a solar shading film is formed, or an interlayer formed as described above between one sheet of glass and another normal sheet of glass, or a vinyl resin. By producing a laminated glass for solar shading by sandwiching a conventional interlayer formed into a sheet into an intermediate layer, the laminated glass for solar shading has a transmittance maximum in the visible light region. , And have completed the present invention have found to have a minimum transmittance expressing strong absorption in the near infrared region.

That is, a date according to the first embodiment of the present invention.
Laminated glass for solar shading is an intermediate layer that has a solar shading function
Of solar radiation between two glass sheets
Glass, wherein the intermediate layer is LaB₆, CeB₆,
PrB₆, NdB₆, GdB ₆, TbB₆, DyB₆,
HoB₆, YB₆, SmB₆, EuB₆, ErB₆, T
mB₆, YbB₆, LuB₆, (La, Ce) B₆, S
rB₆And CaB₆Selected from the group consisting of
Addition of one type of hexaboride fine particles dispersed in a plasticizer
Formed by an intermediate film composed of a liquid and a vinyl resin
It is characterized by the following.

[0007] The laminated glass for solar shading according to the second embodiment of the present invention comprises an intermediate layer having a solar shading function.
A solar-shielding laminated glass interposed between two glass sheets, wherein the intermediate layer is composed of LaB ₆ , CeB ₆ , Pr
B ₆ , NdB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , Ho
B ₆ , YB ₆ , SmB ₆ , EuB ₆ , ErB ₆ , TmB
_{6, YbB 6, LuB 6,} (La, Ce) B 6, SrB
₆ and CaB _6, formed by an intermediate film comprising a vinyl resin and an additive liquid in which at least one type of hexaboride fine particles selected from the group consisting of ₆ and CaB ₆ and ITO fine particles and / or ATO fine particles are dispersed in a plasticizer. Wherein the weight ratio of the hexaboride fine particles to the ITO fine particles and / or ATO fine particles is in the range of 0.1: 99.9 to 90:10. It is assumed that.

[0008] In the first and second embodiments of the present invention, the plasticizer is triethylene glycol-di-2-ethylbutyrate.

Further, the solar radiation according to the third embodiment of the present invention.
Laminated glass for shielding has an intermediate layer that has a solar radiation shielding function.
Solar-shielding interlocking gas interposed between two glass sheets
A lath, wherein the intermediate layer has at least one plate glass.
Formed on the surface located inside the₆, Ce
B₆, PrB₆, NdB₆, GdB₆, TbB₆, Dy
B₆, HoB₆, YB₆, SmB₆, EuB₆, ErB
₆, TmB₆, YbB ₆, LuB₆, (La, Ce) B
₆, SrB₆And CaB₆Selected from the group consisting of
At least one type of hexaboride fine particles as a solar radiation shielding component
A solar shading film formed by applying a coating solution containing
Contains vinyl resin interposed between the two glass sheets
Characterized by being formed by an intermediate film
You.

[0010] Furthermore, a laminated glass for solar radiation according to a fourth embodiment of the present invention is a laminated glass for solar radiation wherein an intermediate layer having a solar radiation shielding function is interposed between two glass sheets. The layer is formed on a surface located on the inside of at least one of the sheet glass, and LaB ₆ ,
CeB ₆ , PrB ₆ , NdB ₆ , GdB ₆ , TbB ₆ ,
DyB ₆ , HoB ₆ , YB ₆ , SmB ₆ , EuB ₆ , E
rB ₆ , TmB ₆ , YbB ₆ , LuB ₆ , (La, C
at least one hexaboride particles selected from the group consisting of _e) B 6, SrB ₆ and CaB _6, a coating solution containing as a solar radiation shielding component and one or more of ITO fine particles and the ATO fine particles was applied And an intermediate film containing a vinyl-based resin interposed between the two glass sheets.

In the third and fourth embodiments of the present invention, it is preferable that the intermediate film has a solar shading function.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the form of the intermediate layer includes the following. An intermediate film consisting of only a vinyl-based resin composition obtained by adding an additive liquid in which a solar-shielding component is dispersed in a plasticizer to a vinyl-based resin while interposing the two glass plates in close contact with each other between two glass plates. layer. A solar shading film formed by applying a coating liquid formed by adding a binder to an additional liquid in which a solar shading component is dispersed in a plasticizer, which is formed on a surface located inside at least one of the plate glasses, and two sheets And an intermediate film made of the vinyl resin composition and interposed between and adhered to the glass sheets. A solar shading film formed by applying a coating liquid formed by adding a binder to an additional liquid in which a solar shading component is dispersed in a plasticizer, which is formed on a surface located inside at least one of the plate glasses, and two sheets An intermediate layer composed of a conventional interlayer formed by adding a plasticizer to a vinyl resin interposed between and adhered to the sheet glass.

Next, the additive liquid used for the solar-shielding laminated glass of the present invention includes fine particles of hexaboride, fine particles of hexaboride and fine particles of ITO (tin-containing indium oxide), fine particles of hexaboride and fine particles of ATO (antimony) as a solar-shielding component. Containing tin oxide) or hexaboride fine particles and ITO
It is produced by uniformly dispersing fine particles and ATO fine particles in a mixture of a plasticizer and a solvent.

The fine particles of hexaboride used in the present invention include lanthanum hexaboride (LaB ₆ ), cerium hexaboride (CeB ₆ ), and praseodymium hexaboride (PrB).
₆ ), neodymium hexaboride (NdB ₆ ), gadolinium hexaboride (GdB ₆ ), terbium hexaboride (Tb)
B ₆ ), dysprosium hexaboride (DyB ₆ ), holmium hexaboride (HoB ₆ ), yttrium hexaboride (YB ₆ ), samarium hexaboride (SmB ₆ ), europium hexaboride (EuB ₆ ) , Erbium hexaboride (E
rB ₆ ), thulium hexaboride (TmB ₆ ), ytterbium hexaboride (YbB ₆ ), lutetium hexaboride (Lu)
B ₆ ), lanthanum cerium hexaboride ((La, Ce) B
₆ ), strontium hexaboride (SrB ₆ ), calcium hexaboride (CaB ₆ ) fine particles, or fine particles of a mixture thereof, and the like.

It is preferable that the surface of the hexaboride fine particles used in the present invention is not oxidized, but usually the surface is often slightly oxidized. Is inevitable to some extent. However, even in that case, there is no effect on the effectiveness of expressing the solar shading effect.

Further, these hexaboride fine particles have a higher solar radiation shielding effect as the crystal perfection is higher. However, even if the hexaboride fine particles have low crystallinity and cause a broad diffraction peak in X-ray diffraction, If the basic bond inside the fine particles is composed of the bond between each metal and boron, the solar radiation shielding effect can be exhibited.

These hexaboride fine particles are powders colored in gray black, brown black, green black or the like, and have a particle size sufficiently smaller than the wavelength of visible light and dispersed in an intermediate film or a solar shading film. In the above, visible light transmission occurs in the intermediate film or the solar shading film, but the infrared light shading ability can be maintained sufficiently strong. Although the reason for this has not been elucidated in detail, the amount of free electrons in these fine particles is large, and the absorption energy of the indirect interband transition by free electrons inside and on the surface of the fine particles is exactly in the vicinity of the visible to near infrared. In addition, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.
According to experiments, in a film in which these fine particles are sufficiently fine and uniformly dispersed, the transmittance has a maximum value between wavelengths of 400 nm to 700 nm, and a wavelength of 700 nm to 1800 nm.
It is observed that the difference between the maximum value and the minimum value of the transmittance is 15 points or more. Considering that the wavelength of visible light is 380 nm to 780 nm and that the visibility is a bell shape with a peak around 550 nm, such a film effectively transmits visible light and effectively reflects and absorbs other heat rays. I do.

Next, the ITO fine particles and the ATO fine particles used in combination with the hexaboride fine particles in the present invention hardly reflect or absorb light in the visible light region, and have a reflection or absorption derived from plasma resonance in a region of 1000 nm or more. Large absorption. These transmission profiles decrease rightward toward the longer wavelength side in the near infrared region.

On the other hand, the transmission profile of hexaboride is 1
It has a bottom near 000 nm and gradually rises to the right on the longer wavelength side. For this reason, it is possible to shield sunlight rays in the near infrared region without reducing the visible light transmittance by using hexaboride and ITO or ATO in combination, and the ITO fine particles and the ATO fine particles can be used alone or in combination. The solar shading characteristics can be improved as compared with the case of using together.

In addition, the hexaboride has a very high solar shading ability per unit weight, and exhibits its effect with a usage of 1/10 or less as compared with ITO or ATO. More ITO
When used together with ATO or ATO, only the solar shading property can be further improved while maintaining a constant visible light transmittance, so that the cost can be reduced. Further, since the usage amount of all the fine particles can be greatly reduced, it is possible to improve the wear strength and weather resistance of the intermediate film and the solar shading film.

Further, since the hexaboride has an absorption in the visible light region when the amount of use is increased, the absorption in the visible light region can be freely controlled by controlling the amount of addition, and the application of brightness adjustment, privacy protection, etc. Can also.

The particle size of the hexaboride fine particles used is preferably 200 nm or less, more preferably 100 nm or less. This is because the fine particles or the aggregated coarse particles having an average particle diameter larger than 200 nm serve as a light scattering source of the formed intermediate film or the intermediate layer formed of the applied solar shading film, and the intermediate layer becomes cloudy.

The ITO fine particles and the ATO fine particles are also preferably 200 nm or less, more preferably 100 nm or less for the same reason as described above.

The weight ratio of hexaboride fine particles to ITO fine particles and / or ATO fine particles is 0.1: 9.
It is preferably in the range of 9.9 to 90:10, and if the amount of the hexaboride fine particles is smaller than this weight ratio range, the usage of all the fine particles cannot be reduced so much, the cost reduction effect is small, and the solar shading property is small. Also gets worse. On the other hand, even if the amount of the hexaboride fine particles is larger than the above-mentioned weight ratio range, the solar shading property is deteriorated.

The method of dispersing the fine particles in the solvent can be arbitrarily selected as long as the fine particles are uniformly dispersed in the solvent. Examples of the method include a bead mill, a ball mill, a sand mill, and an ultrasonic dispersion method. By dispersing the fine particles in a solvent, an intermediate film or an additive for a solar shading film used as the solar shading laminated glass of the present invention is produced.

The solvent for adding and dispersing the fine particles in the additive solution is not particularly limited, and may be used under the conditions for forming an intermediate film or a solar shading film, or when preparing a vinyl resin composition. It can be selected according to the vinyl resin to be used and the like, for example, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-2-ethylhexyl adipate, diisodecyl adipate, epoxy fatty acid monoester, triethylene glycol-diethyl Plasticizers such as -2-ethyl butyrate, triethylene glycol-di-2-ethylhexoate, dibutyl sebacate and dibutyl sebacate; and alcohols, ethers, esters,
Various common organic solvents such as ketones can also be used. If necessary, the pH may be adjusted by adding an acid or an alkali.

In preparing the vinyl resin composition, the following plasticizers, various surfactants, and cups may be used in order to further improve the dispersion stability when the fine particles are contained in the vinyl resin. It is also possible to add a ring agent and the like.

The plasticizer added to the vinyl resin is not particularly restricted but includes, for example, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-2-ethylhexyl adipate, diisodecyl adipate, and monoester triethylene fatty acid. Glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, dibutyl sebacate, dibutyl sebacate, and the like are included.

The vinyl resin used when preparing the vinyl resin composition using the additive solution prepared as described above includes, for example, polyvinyl butyral, polyvinyl chloride, and vinyl chloride-ethylene copolymer. Coalescing,
Vinyl chloride-ethylene-glycidyl methacrylate copolymer, vinyl chloride-ethylene-glycidyl acrylate copolymer, vinyl chloride-glycidyl methacrylate copolymer, vinyl chloride-glycidyl acrylate copolymer,
Examples thereof include polyvinylidene chloride, a vinylidene chloride-acrylonitrile copolymer, a polyvinyl acetate ethylene-vinyl acetate copolymer, a polyvinyl acetal-polyvinyl butyral mixture, and the like. Particularly, polyvinyl butyral is preferable.

Next, a known method is used for forming the intermediate film according to the present invention. For example, a calender roll method, an extrusion method, a casting method, an inflation method and the like can be used. In particular, when an interlayer made of a vinyl-based resin composition is used as the interlayer for solar radiation-shielded laminated glass of the present invention, the vinyl-based resin composition is obtained by adding the additive liquid to a vinyl-based resin, kneading the mixture, and uniformly dispersing the fine particles. The vinyl resin composition thus prepared can be formed into a sheet. When the vinyl resin composition is formed into a sheet, a heat stabilizer, an antioxidant, and the like may be added as necessary, and an adhesive force modifier (eg, a metal salt) may be added to enhance the sheet penetration. You may mix.

Further, a coating liquid obtained by dispersing hexaboride fine particles as a solar radiation shielding component in a binder such as ethyl silicate is coated on at least one of the two glass sheets constituting the laminated glass for solar radiation shielding. A solar shading film is formed by coating, or a coating solution obtained by dispersing hexaboride fine particles as a solar shading component and at least one of ITO fine particles and ATO fine particles in the binder is applied. A conventional interlayer or a sheet-like interlayer made of the vinyl-based resin composition is formed by adding a plasticizer to a vinyl resin between the two glass sheets and then softening and liquefying the resultant into a sheet. It is also possible to form a laminated glass for solar shading by interposing and closely contacting.

As described above, according to the present invention, a vinyl resin prepared by adding an additive solution containing hexaboride fine particles as a solar shading component to a vinyl resin, further adding a plasticizer, and uniformly dispersing the vinyl resin. A laminated glass is produced using an intermediate film obtained by molding the composition into a sheet shape, or a coating solution obtained by adding a binder to the additive solution is applied to at least one surface of two plate glasses located on the inner side. Forming a solar-shielding film by using an intermediate film made of the vinyl resin composition or a laminated glass using a conventional intermediate film, thereby eliminating the need for high-cost physical film-forming methods and complicated processes. It is possible to provide a laminated glass for solar shading which has a function and has a high transmission performance in a visible light region.

Further, as a solar shading component, an additive liquid prepared by using a combination of hexaboride fine particles having strong absorption in the near infrared region and ATO fine particles and / or ITO fine particles is added to a vinyl resin, followed by further plasticization. A laminated glass is produced using an interlayer formed by sheeting a vinyl-based resin composition prepared by adding and uniformly dispersing a vinyl resin composition, or a coating solution obtained by adding a binder to the above-mentioned additive solution is used. ATO or the like by forming a solar radiation shielding film by applying to at least one surface located inside one of the sheet glass to form a laminated glass using an intermediate film made of the vinyl resin composition or a conventional intermediate film. The solar shading characteristics are improved as compared with the use of individual fine particles of ITO alone or in combination.
It is also possible to reduce the use amount of the TO fine particles and reduce the material cost.

[0034]

EXAMPLES Examples of the present invention will be described below together with comparative examples.

Example 1 LaB ₆ having an average particle size of 67 nm
Fine particles 20 g, diacetone alcohol (DAA) 50
g, triethylene glycol - di-2-ethyl butyrate 20g, water and a dispersing agent mixed with an appropriate amount, and mixing 100 hours in a ball mill containing zirconia balls having a diameter of 4 mm, the intermediate layer additive liquid LaB ₆ fine particles are dispersed 100g
Was prepared (Solution A).

On the other hand, ITO fine particles 20 having an average particle size of 80 nm
g, 70 g of triethylene glycol-di-2-ethyl butyrate, water and a suitable amount of a dispersing agent, and ball milling using a zirconia ball having a diameter of 4 mm for 100 hours to obtain 100 g of an additive liquid for an intermediate film in which ITO fine particles are dispersed. Was prepared (Solution B).

Addition solution for an intermediate film prepared by mixing Solution A and Solution B was added to polyvinyl butyral, and triethylene glycol-di-2-ethylbutyrate was added as a plasticizer to give an ITO concentration of 0.61% by weight. %, LaB ₆ concentration is zero.
A vinyl resin composition was prepared so that the concentration of 0038% by weight and the concentration of polyvinyl butyral became 70% by weight.

This vinyl resin composition is kneaded with a roll.
Into a 0.76 mm thick sheet to form an interlayer
Was. This intermediate film is transparent float glass with a thickness of 2.5 mm.
Sandwiched between two pieces of paper and heated to 80 ° C. for temporary bonding
After, 140 ° C, 14kg / cm ²By autoclave
The main bonding was performed to produce a laminated glass.

The spectral characteristics of the laminated glass thus produced were measured using a spectrophotometer manufactured by Hitachi, Ltd.
Insolation transmittance according to 106, JIS R 32
The visible light transmittance was calculated according to No. 11, and the results are shown in Table 1.

The Pummel value of the produced laminated glass was measured in the following manner. As a result, the Pummel value was 5, and the adhesion between the plate glass and the interlayer film was sufficient. Pummel test: After keeping the laminated glass at -18 ° C. for at least 1 hour and keeping it at a constant temperature, the laminated glass was subjected to a hammer (head portion is 1 lb.) crushing tester, and the particle diameter of the adhered glass was at most 6 mm.
Crushed until below. Shake off the broken glass pieces, divide the exposed part of the interlayer film into 0-8 ranks,
It was determined that the lower the degree of exposure, the larger the value. This is a test method for determining whether or not the adhesion between the sheet glass and the intermediate film is within a predetermined range, and the value is desirably in the range of 3 to 6. If it is 1 or less, it is easy to peel off, while if it is 8 or more, the penetration resistance becomes small.

(Examples 2 to 5) A vinyl resin composition was prepared from solution A, solution B, polyvinyl butyral, and triethylene glycol di-2-ethyl butyrate so as to have the composition shown in Table 1. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Example 6 A vinyl resin composition was prepared from solution A, polybierbutyral, and triethylene glycol-di-2-ethyl butyrate so as to have the composition shown in Table 1. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Comparative Example 1 A vinyl resin composition was prepared from Solution B, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate so as to have the composition shown in Table 1. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Next, changes in the composition and optical characteristics of Comparative Example 1 and Examples 1 to 5 are shown in FIG. By trace amount added LaB ₆ fine particles than 1, without lowering the visible light transmittance in comparison with the characteristics of the conventional ITO, it is possible to further reduce the solar radiation transmittance and the time ITO fine amount It turns out that it can be reduced significantly. For example, comparing the Comparative Example 1 and Example 2, LaB by the addition 1.38 wt% relative to the ₆ particles all particles in the intermediate layer, while solar transmittance visible light transmittance was maintained at 78% Can be reduced by 3 points or more, and the amount of ITO added can be reduced to half or less. This and improve the solar radiation shielding properties in slight amount of LaB ₆ fine particles from further and reduce costs was clear that performed simultaneously.

(Comparative Example 2) 20 g of ATO fine particles having an average particle size of 55 nm, 70 g of triethylene glycol di-2-ethyl butyrate, water and a suitable amount of a dispersant were mixed, and the mixture was used for 100 hours using zirconia balls having a diameter of 4 mm. The mixture was mixed with a ball mill to prepare 100 g of an intermediate film additive liquid in which ATO fine particles were dispersed (Solution C).

Solution C, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate were prepared into a vinyl resin composition so as to have the composition shown in Table 1. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

(Examples 7 to 10) A vinyl resin composition was prepared from the solutions A, C, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate so as to have the composition shown in Table 1. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Next, changes in the composition and optical characteristics of Comparative Example 2 and Examples 7 to 10 are shown in FIG. By going to trace amount added LaB ₆ fine particles than 2, without lowering the visible light transmittance in comparison with the characteristic of the conventional ATO, it becomes possible to further reduce the solar transmittance. At this time, it was found that the amount of ATO fine particles could be significantly reduced. For example, comparing with Comparative Example 2 and Example 8, by the addition 10.71% by weight relative to the total particles in the intermediate layer the LaB ₆ fine particles, while the visible light transmittance was maintained at 78%, a solar radiation transmittance Rate can be reduced by about 2 points, and ATO
It was found that the addition amount could be reduced by 60% or more.

Example 11 CeB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, 20 g of triethylene glycol-di-2-ethyl butyrate, water and a dispersant are mixed in appropriate amounts, and ball-mixed with zirconia balls having a diameter of 4 mm for 100 hours to obtain an additive solution for an intermediate film in which CeB ₆ fine particles are dispersed. 100g
Was prepared (D solution).

Liquid D, Liquid B, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Example 12 PrB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, 20 g of triethylene glycol-di-2-ethyl butyrate, water and a dispersant are mixed in appropriate amounts, and ball milled using zirconia balls having a diameter of 4 mm for 100 hours to obtain an additive solution for an intermediate film in which PrB ₆ fine particles are dispersed. 100g
Was prepared (Solution E).

Solution E, Solution B, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

(Example 13) NdB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, 20 g of triethylene glycol-di-2-ethyl butyrate, water and a dispersant are mixed in an appropriate amount, and the mixture is ball-milled using zirconia balls having a diameter of 4 mm for 100 hours to obtain an additive for an intermediate film in which NdB ₆ fine particles are dispersed. 100g
Was prepared (Solution F).

The solutions F, C, polyvinyl butyral, and triethylene glycol di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

(Example 14) GdB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, triethylene glycol - di-2-ethyl butyrate 20g, water and a dispersing agent mixed with an appropriate amount, and mixing 100 hours in a ball mill containing zirconia balls having a diameter of 4 mm, the intermediate layer additive liquid GdB ₆ fine particles are dispersed 100g
Was prepared (G solution).

Solution G, Solution C, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Example 15 YB _{6 having an} average particle size of 85 nm
Fine particles 20 g, diacetone alcohol (DAA) 50
g, triethylene glycol - di-2-ethyl butyrate 20g, water and a dispersing agent mixed with an appropriate amount, and mixing 100 hours in a ball mill containing zirconia balls having a diameter of 4 mm, the intermediate layer additive liquid YB ₆ fine particles are dispersed 100 g was prepared (H solution).

The liquids H, B, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

(Example 16) SmB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, triethylene glycol - di-2-ethyl butyrate 20g, water and a dispersing agent mixed with an appropriate amount, and mixing 100 hours in a ball mill containing zirconia balls having a diameter of 4 mm, the intermediate layer additive liquid SmB ₆ fine particles are dispersed 100g
Was prepared (Solution I).

Solution I, Solution C, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate are shown in Table 1.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

Example 17 EuB having an average particle size of 85 nm
₆ Fine particles 20 g, diacetone alcohol (DAA) 50
g, 20 g of triethylene glycol-di-2-ethyl butyrate, water and a dispersant are mixed in appropriate amounts, and ball milled using zirconia balls having a diameter of 4 mm for 100 hours to obtain an additive solution for an intermediate film in which EuB ₆ fine particles are dispersed. 100g
Was prepared (Solution J).

Table 1 shows solutions J, C, polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate.
A vinyl resin composition was prepared so as to have the following composition. This was used to produce an intermediate film in the same manner as in Example 1 to produce the intended laminated glass. Table 1 also shows the optical characteristics of the laminated glass.

[0063]

[Table 1]

Example 18 Ethyl silicate 40 having an average degree of polymerization of 4 to 5 mer (manufactured by Tama Chemical Industry Co., Ltd .:
(Trade name), ethanol 27 g, 5% hydrochloric acid aqueous solution 8 g, and water 5 g, an ethyl silicate solution was well mixed and stirred to prepare an ethyl silicate mixed solution 50 g (liquid K).

[0065] mixing the liquids A and B and K solution, and further diluted with diacetone alcohol, ITO concentration of 7.25 wt%, LaB ₆ concentration of 0.045 wt%, SiO ₂ concentration of 2.5 A coating solution for a solar shading film was prepared so as to have a weight%. 15 g of this coating solution was applied to a thickness of 2.5 m using a spin coater.
m, and placed in a 180 ° C. electric furnace and heated for 30 minutes to prepare a solar shading glass having a solar shading film formed on the float glass.

The solar shading glass and the float glass having a thickness of 2.5 mm were sandwiched between a 0.76 mm polyvinyl butyral film for an interlayer so that the solar shading film faced inward, and a normal laminated glass manufacturing method was performed. Therefore, a laminated glass was produced by heating and pressing.

The spectral characteristics of the laminated glass thus produced were measured in the same manner as in Example 1, and the solar transmittance and visible light transmittance were calculated. In addition, the prepared laminated glass was subjected to the same Pummel test as in Example 1 and the Pummel value was measured. As a result, the Pummel value was 5, and the adhesion between the plate glass and the interlayer film was sufficient.

(Examples 19 to 22) The solution A, the solution B and the solution K were mixed and further diluted with diacetone alcohol to prepare a coating solution for a solar shading film so as to have the composition shown in Table 2. Using this coating liquid, a solar shading glass was produced in the same manner as in Example 18, and a target laminated glass was produced using this. Table 2 also shows the optical characteristics of the laminated glass.

Example 23 A solution and a K solution were mixed, and further diluted with diacetone alcohol to prepare a coating solution for a solar shading film so as to have a composition shown in Table 2. Using this coating liquid, a solar shading glass was produced in the same manner as in Example 18, and a target laminated glass was produced using this. Table 2 also shows the optical characteristics of the laminated glass.

[0070] (Example 24) were mixed liquids A and B and K solution, and further diluted with diacetone alcohol, ITO concentration of 3.63 wt%, LaB ₆ concentration of 0.023 wt%, SiO ₂ A coating solution for a solar shading film was prepared so that the concentration was 1.25% by weight. 15 g of this coating solution was applied on a float glass having a thickness of 2.5 mm with a spin coater, placed in an electric furnace at 180 ° C., and heated for 30 minutes to form a solar shading film on the float glass to form a solar shading glass. Produced.

[0071] On the other hand polyvinyl butyral as vinyl resin liquids A and B, triethylene glycol as a plasticizer - mixed di-2-ethyl butyrate, ITO concentration of 0.18 wt%, LaB ₆ concentration is zero. 0025% by weight,
A vinyl-based resin composition was prepared such that the polyvinyl butyral concentration was 70% by weight, and an intermediate film was formed in the same manner as in Example 1.

The solar shading glass and a thickness of 2.5 m
m of float glass was heated and pressed in accordance with a normal laminated glass manufacturing method by sandwiching the intermediate film with the solar shading film facing inward, to produce a laminated glass. Table 2 also shows the optical characteristics of the laminated glass.

The Pummel value of the produced laminated glass was measured. As a result, the Pummel value was 5, and the adhesion between the plate glass and the interlayer film was sufficient.

[0074] (Example 25) were mixed liquid A and K solution, further diluted with diacetone alcohol, LaB ₆ concentration of 0.24 wt%, the solar radiation as SiO ₂ concentration of 1.25 wt% A coating solution for a shielding film was prepared. This coating liquid 15
g on a 2.5 mm thick float glass with a spin coater, and placed in a 180 ° C. electric furnace and heated for 30 minutes.
A solar shading film was formed on the float glass to produce a solar shading glass.

[0075] On the other hand polyvinyl butyral as vinyl resin liquids A and B, triethylene glycol as a plasticizer - mixed di-2-ethyl butyrate, ITO concentration of 0.19 wt%, LaB ₆ concentration is zero. 0025% by weight,
A vinyl-based resin composition was prepared so that the polyvinyl butyral concentration was 70% by weight, and a sheet-like interlayer film formed in the same manner as in Example 1 was produced.

The solar shading glass and a thickness of 2.5 m
Then, the intermediate film was sandwiched between the glass and the float glass of m in such a manner that the solar shading film faced inward, and heated and pressed in accordance with a normal laminated glass manufacturing method to produce a laminated glass. Table 2 also shows the optical characteristics of the laminated glass.

[0077]

[Table 2]

As shown in the above examples, in a laminated glass in which an interlayer for laminated glass is interposed between two sheet glasses, a simple method can be used without using an expensive physical film forming method. Boride fine particles, if desired ITO
A coating solution using an intermediate film formed from a vinyl-based resin composition prepared by adding an additive solution containing fine particles and / or ATO fine particles to a vinyl-based resin, or adding a binder to the additive solution Is applied to the surface facing the inside of the plate glass to form a solar shading film, and then by interposing the intermediate film or a conventional intermediate film, has a solar shading function, and has a high transmission performance in the visible light region. It has become possible to produce a solar-shielded laminated glass having the same.

[0079]

As described above, according to the present invention, in a solar-shielding laminated glass having an intermediate layer interposed between two sheet glasses, hexaboride fine particles and, if desired, ITO fine particles and / or An intermediate film formed from a vinyl-based resin composition prepared by adding an additive solution containing ATO fine particles to a vinyl-based resin, or a coating solution obtained by adding the additive solution to a binder faces the inside of the plate glass. After forming a solar shading film by applying to the surface, by interposing the interlayer or a conventional interlayer, having a solar shading function, and a solar shading laminated glass having a high transmission performance in the visible light region, It has become possible to manufacture the semiconductor device very easily by a simple method without using an expensive physical film forming method.

[Brief description of the drawings]

FIG. 1 is a graph showing changes in the concentration of ITO fine particles and optical characteristics in Comparative Example 1 and Examples 1 to 5.

FIG. 2 shows ATO in Comparative Example 2 and Examples 7 to 10.
FIG. 4 is a graph showing changes in the concentration of fine particles and optical characteristics.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyo Yabuki 3-18-5, China, Ichikawa, Chiba Prefecture Sumitomo Metal Mining Co., Ltd. Central Research Laboratory (72) Inventor Hiromitsu Takeda 3-18, China, Ichikawa, Chiba −5 Sumitomo Metal Mining Co., Ltd. Central Research Laboratory (72) Inventor Kenji Adachi 3-18-5 China, Ichikawa City, Chiba Pref. Sumitomo Metal Mining Co., Ltd. Central Research Laboratory (72) Inventor Takashi Muromachi Michio Chuo-ku, Osaka City, Osaka 3-5-11, Nippon Sheet Glass Co., Ltd. F-term (reference) 4G061 AA09 AA20 BA01 BA02 CB05 CB12 CB19 CD02 CD18

Claims (7)

[Claims] 1. An intermediate layer having a solar shading function comprising two plates
A solar-shielded laminated glass that is interposed between glass
Thus, the intermediate layer is LaB₆, CeB₆, PrB₆,
NdB₆, GdB₆, TbB₆, DyB₆, HoB₆,
YB₆, SmB₆, EuB₆, ErB₆, TmB₆, Y
bB₆, LuB₆, (La, Ce) B ₆, SrB₆And
And CaB₆At least one member selected from the group consisting of
An additive liquid in which hexaboride fine particles are dispersed in a plasticizer;
It is characterized by being formed by an intermediate film consisting of
Laminated glass for solar shading. 2. An intermediate layer having a solar shading function comprising two plates
A solar-shielded laminated glass that is interposed between glass
Thus, the intermediate layer is LaB₆, CeB₆, PrB₆,
NdB₆, GdB₆, TbB₆, DyB₆, HoB₆,
YB₆, SmB₆, EuB₆, ErB₆, TmB₆, Y
bB₆, LuB₆, (La, Ce) B ₆, SrB₆And
And CaB₆At least one member selected from the group consisting of
Hexaboride fine particles, and ITO fine particles and / or
Is an additive liquid in which ATO fine particles are dispersed in a plasticizer;
It is characterized by being formed by an intermediate film consisting of
Laminated glass for solar shading. 3. The weight ratio of said hexaboride fine particles to said ITO fine particles and / or ATO fine particles is 0.1:
3. The laminated glass for solar shading according to claim 2, wherein the range is 99.9 to 90:10. 4. The laminated glass for solar shading according to claim 1, wherein the plasticizer is triethylene glycol-di-2-ethyl butyrate. 5. A solar-shielded laminated glass in which an intermediate layer having a solar-shielding function is interposed between two glass sheets, wherein the intermediate layer is formed on a surface located inside at least one of the glass sheets, And LaB ₆ , CeB ₆ , P
rB ₆ , NdB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , H
oB ₆ , YB ₆ , SmB ₆ , EuB ₆ , ErB ₆ , Tm
B ₆ , YbB ₆ , LuB ₆ , (La, Ce) B ₆ , Sr
A solar shading film formed by applying a coating solution containing at least one type of hexaboride fine particles selected from the group consisting of B ₆ and CaB ₆ as a solar shading component, and interposed between the two sheet glasses; A laminated glass for shielding sunlight, characterized by being formed of an interlayer containing a vinyl resin. 6. A solar-shielded laminated glass in which an intermediate layer having a solar-shielding function is interposed between two glass sheets, wherein the intermediate layer is formed on a surface located inside at least one of the glass sheets, And LaB ₆ , CeB ₆ , P
rB ₆ , NdB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , H
oB ₆ , YB ₆ , SmB ₆ , EuB ₆ , ErB ₆ , Tm
B ₆ , YbB ₆ , LuB ₆ , (La, Ce) B ₆ , Sr
At least one type of hexaboride fine particles selected from the group consisting of B ₆ and CaB ₆ , ITO fine particles and AT
A solar-shielding film formed by applying a coating solution containing at least one of the O fine particles as a solar-shielding component, and an intermediate film containing a vinyl-based resin interposed between the two glass sheets; A laminated glass for shielding sunlight. 7. The laminated glass for solar shading according to claim 5, wherein the intermediate film has a solar shading function.