JP2012240905A - Interlayer for laminated glass having heat ray shielding property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass having excellent transparency, heat ray shielding properties and light resistance.SOLUTION: The interlayer for laminated glass has a layer comprising a thermoplastic resin composition containing hydrothermally treated heat ray shielding fine particles obtained by a method including the following steps (a) and (b): the step (a) is a step of dry-grinding and/or wet-grinding crystalline heat ray shielding fine particles having a primary particle diameter of 5-100 nm; and the step (b) is a step in which the heat ray shielding fine particles ground by the step (a) are dispersed in water and then heated at 200-320°C.

Description

  The present invention relates to an interlayer film for laminated glass that is excellent in transparency, heat ray shielding properties and light resistance. Moreover, it is related with the manufacturing method and the laminated glass using the same.

  Laminated glass is widely used for vehicles such as automobiles, window glass for buildings, etc., for improving safety such as prevention of glass scattering. Examples of such laminated glass include those in which an interlayer film for laminated glass made of, for example, plasticized polyvinyl butyral resin is interposed between at least one pair of glass plates and the two are bonded to each other. However, when a normal interlayer film for laminated glass is used, there is a problem that near infrared rays (heat rays) having a large thermal effect cannot be shielded, and it has been demanded to impart heat ray shielding properties.

  For the purpose of imparting heat ray shielding properties, an interlayer film for laminated glass is proposed in which fine particles having heat ray absorption performance such as tin-doped indium oxide (ITO) fine particles and antimony-doped tin oxide (ATO) fine particles are contained in a matrix resin. ing. Laminated glass using such an interlayer film for laminated glass not only can impart heat ray shielding to ordinary laminated glass, but also has excellent electromagnetic wave permeability compared to so-called heat ray reflective laminated glass.

  Laminated glass using an interlayer film for laminated glass containing heat ray shielding fine particles having such heat ray absorbing performance has better weather resistance and longer resistance than the case of containing an organic compound having the same heat ray shielding performance. The heat ray shielding property stable for a period can be exhibited. However, when the laminated glass is exposed to high energy rays such as UV light for a long time, the visible light transmittance of the laminated glass is reduced due to deterioration of the matrix resin due to photocatalytic activation of the surface of the heat ray shielding fine particles, or alteration of the fine particles themselves. Yellowing or the like may be caused, which may cause a serious problem in safety particularly when used for a vehicle.

  As a technique for suppressing deterioration due to such heat ray shielding fine particles, a technique of surface treatment with a metal alkoxide, a coupling agent, or the like is known (see Patent Documents 1 to 3). By using such surface-treated heat ray shielding fine particles, deterioration of the matrix resin and alteration of the heat ray shielding fine particles can be suppressed. However, since such surface treatment depends on the surface reactivity of the fine particles, depending on the fine particles, the treatment method may not be changed, or the surface treatment itself may not be performed. to differ greatly. In addition, metal alkoxides and coupling agents used as surface treatment agents are generally expensive, and have potential problems such as increased processing costs. Furthermore, even if the surface-treated fine particles are subjected to a pulverization treatment in order to improve the dispersibility of the fine particles in the matrix resin, the effect is sufficiently obtained by exposing the active surface that has not been treated. There was concern that it would not develop.

JP 2000-016841 A JP 2001-240769 A International Publication No. 2005/118503 Pamphlet

The present invention has been made to solve the above-described problems, and an object thereof is to provide an interlayer film for laminated glass that is excellent in transparency, heat ray shielding properties, and light resistance. Moreover, this invention aims at providing the manufacturing method of the said intermediate film for laminated glasses, and the laminated glass using the said intermediate film for laminated glasses.

As a result of intensive studies on the above problems, it was found that the surface activity of the heat-shielding fine particles was due to the fact that the crystal structure of the fine particles was destroyed during pulverization for micronization, and became amorphous. By using the heat ray shielding fine particles having a reduced quality part, an interlayer film for laminated glass having excellent transparency, heat ray shielding property and light resistance has been provided. Specifically, it has a layer made of a thermoplastic resin composition containing the heat ray shielding fine particles using hydrothermally treated heat ray shielding fine particles obtained by a method including the following steps (a) and (b). This was achieved by using an interlayer film for laminated glass.
(A) Step: Dry pulverization and / or wet pulverization of crystalline heat ray shielding fine particles having a primary particle size of 5 to 100 nm (b) Step: Heat ray shielding fine particles pulverized in step (a) in water Step of heating at 200 to 320 ° C. after dispersion

  Examples of the heat ray shielding fine particles include tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, lanthanum hexaboride, cerium hexaboride, anhydrous zinc antimonate and It is preferably at least one kind of fine particles selected from the group consisting of copper sulfide, more preferably anhydrous zinc antimonate fine particles.

  In view of the above problems, from the viewpoint of improving transparency, in the interlayer film for laminated glass, the heat-shielding fine particles subjected to hydrothermal treatment have secondary aggregates having an average particle diameter of 200 nm or less, and the secondary aggregates are heated. It is preferably in a state of being dispersed inside the layer made of the plastic resin composition. Moreover, it is preferable to use a polyvinyl acetal type-resin as a thermoplastic resin in the layer which consists of a thermoplastic resin composition containing the heat-ray shielding fine particle hydrothermally treated from a viewpoint of the adhesive improvement to glass.

  In addition, from the viewpoint of improving the light resistance, in the interlayer film for laminated glass, a thermoplastic containing an ultraviolet absorber on both sides of a layer made of a thermoplastic resin composition containing hydrothermally-treated heat ray shielding fine particles. It is preferable that the layer which consists of a resin composition is arrange | positioned.

  Moreover, the said subject is also solved by providing the laminated glass provided with the said intermediate film for laminated glasses, ie, the laminated glass which adhere | attaches a some glass plate to this intermediate film for laminated glasses.

  In addition, the method for producing the interlayer film for laminated glass preferably includes a step of melt-kneading the hydrothermally-treated heat ray shielding fine particles and the thermoplastic resin to form a film.

  The interlayer film for laminated glass of the present invention is excellent in transparency, heat ray shielding properties and light resistance. Therefore, the laminated glass excellent in transparency, heat ray shielding property, and light resistance can be provided by using the said intermediate film for laminated glasses.

Hereinafter, embodiments of the present invention will be described. In the following description, specific materials (compounds and the like) may be exemplified as materials that exhibit a specific function, but the present invention is not limited to an embodiment using such materials. The exemplified materials are 1 unless otherwise specified.
A seed may be used independently and two or more sorts may be used together.

The interlayer film for laminated glass of the present invention has a layer made of a thermoplastic resin composition containing hydrothermally treated heat ray shielding fine particles obtained by a method including the following steps (a) and (b).
(A) Step: Dry pulverization and / or wet pulverization of crystalline heat ray shielding fine particles having a primary particle size of 5 to 100 nm (b) Step: Heat ray shielding fine particles pulverized in step (a) in water Step of heating at 200 to 320 ° C. after dispersion

[Heat-treated heat ray shielding fine particles]
Examples of the heat ray shielding fine particles provided for the step (a) of the present invention include tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, lanthanum hexaboride, It is preferably at least one fine particle selected from the group consisting of cerium hexaboride, anhydrous zinc antimonate and copper sulfide. Among these, anhydrous zinc antimonate fine particles are more preferable from the viewpoint of both cost and heat ray shielding properties.

  The crystalline heat ray shielding fine particles used in the step (a) of the present invention are fine particles having a primary particle diameter of 5 to 100 nm, preferably 8 to 70 nm, and more preferably 10 to 50 nm. In the production of the heat ray shielding fine particles, a secondary aggregate having a particle diameter of about 1 to 100 μm is often formed when the powder is formed by baking or drying. Here, the primary particle diameter is the long diameter of the particle measured by a transmission electron microscope, and the particle diameter of the secondary aggregate is, for example, a particle size distribution measuring device by centrifugal sedimentation method, laser diffraction method, or dynamic light scattering method It is an average particle diameter measured by the above. A composition obtained by combining a secondary aggregate having such a large particle size with a thermoplastic resin described later tends to have low transparency.

  For this reason, in the step (a) of the present invention, crystalline heat ray shielding fine particles having a primary particle diameter of 5 to 100 nm are dry-ground and / or wet-ground. In this step, the particle size of the secondary aggregate of the heat ray shielding fine particles is preferably pulverized to about 20 to 200 nm, so that when the heat ray shielding fine particles are combined with a thermoplastic resin described later, higher transparency is obtained. It becomes possible to express.

As the dry pulverization method, a known method such as an impact pulverizer such as a hammer mill or a pin mill, a grinding pulverizer such as a pulverizer, or an airflow pulverizer such as a jet mill can be employed. Wet pulverization is more effective for refining secondary aggregates. As the wet pulverization method, after preparing the slurry by dispersing the heat ray shielding fine particles in a dispersion medium such as water, a known method such as a bead mill, a sand mill, an attritor, a disper, a ball mill, or a paint shaker may be employed. it can.
1-80 mass% is preferable as a solid content concentration, and 10-60 mass% is more preferable as the slurry used for wet grinding.
For wet pulverization, beads having a diameter of about 0.03 to 10 mm such as alumina, zirconia, and glass are preferably used.
The wet pulverization is performed for 1 to 1000 hours, and the secondary aggregate can be refined to a particle size of about 20 to 200 nm. In addition, performing the wet pulverization after the dry pulverization is more effective for refining the secondary aggregate.

In the heat ray shielding fine particles pulverized by the dry pulverization and / or wet pulverization in the step (a), an amorphous portion is generated near the surface of the heat ray shielding fine particles due to the impact of the pulverization. The volume fraction of the amorphous part in the heat-shielding fine particles subjected to pulverization varies depending on the pulverization method and pulverization conditions, but is generally 10 to 70% by volume.

The volume fraction of the amorphous part is calculated by the following method. When the transmission ray electron microscope observation of the cross section of the heat-shielding fine particles subjected to the pulverization process is performed, the crystalline portion connecting the crystal lattice image to the central portion of the heat-ray shielding fine particles and the crystal lattice image are not formed around the crystalline portion. An amorphous part is observed. For any 30 heat-ray shielding fine particles (primary particles), a circle-equivalent diameter R _c is calculated from the area of the crystalline portion, an average of 30 is calculated, and then a volume V _c converted to a sphere is obtained. Further, for the 30 heat-ray shielding fine particles (primary particles), the equivalent circle diameter R _{(a + c)} is similarly calculated from the combined area of the crystalline portion and the amorphous portion, and the average of 30 particles is calculated. Then, the volume V _{(a + c)} converted to a sphere is obtained. The volume fraction of the amorphous part is calculated as (V _{(a + c)} −V _c ) / V _{(a + c)} × 100 (volume%).

  In the step (b) of the present invention, the heat ray shielding fine particles pulverized in the step (a) are dispersed in water and then heated at 200 to 320 ° C. Hereinafter, this process is referred to as hydrothermal treatment. The advantage of hydrothermal treatment is the recrystallization of the amorphous part while maintaining the particle size of the crystalline heat-ray shielding fine particles in which the amorphous part is generated near the particle surface by the pulverization process while maintaining the particle size. The surface modification is possible.

  The aqueous dispersion of heat ray shielding fine particles to be subjected to hydrothermal treatment is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 70% by mass as the content of the heat ray shielding fine particles. Hereinafter, it is more preferably 50% by mass or less.

  The temperature of the hydrothermal treatment is 200 to 320 ° C. When the temperature of the hydrothermal treatment is less than 200 ° C., it is not preferable because crystallization of the amorphous part does not occur or hardly occurs. On the other hand, when it exceeds 320 degreeC, it is industrially difficult. The hydrothermal treatment temperature is preferably 205 to 280 ° C, more preferably 210 to 250 ° C.

  In the hydrothermal treatment, the time maintained at 200 to 320 ° C. is preferably 5 minutes to 100 hours. When the holding time is less than 5 minutes, crystallization of the amorphous part does not occur or hardly occurs, which is not preferable. On the other hand, even if it is maintained for more than 100 hours, the crystallization of the amorphous part does not proceed or hardly proceeds further, which is not preferable from the viewpoint of productivity. The time maintained at 200 to 320 ° C. is more preferably 1 to 60 hours, and further preferably 2 to 20 hours.

  The apparatus for performing the hydrothermal treatment is not particularly limited as long as it has pressure resistance in the presence of high-temperature and high-pressure hot water, and a container made of a material such as stainless steel, titanium, nickel alloy, or cocoon is preferably used.

  The hydrothermally-treated heat ray shielding fine particles obtained by the above-described method are obtained in the form of an aqueous dispersion, and are used as a dispersion of an organic solvent, a dispersion of a plasticizer, or a dispersion of a mixture of a plasticizer and an organic solvent. be able to.

  In order to obtain a dispersion of the organic solvent, the heat-ray shielding fine particles that have been hydrothermally treated with an additive such as an alkali component, an acid component, or a surfactant can be stabilized as necessary.

Alkali components used include alkali metal hydroxides such as lithium, sodium and potassium, alkaline earth metal hydroxides such as calcium, magnesium and strontium, ammonia, ethylamine, triethylamine, isopropylamine and n-propylamine. , Diisopropylamine, diisobutylamine, dibutylamine, dipropylamine, diamylamine, tributylamine, tripropylamine, triamylamine, n-
Examples thereof include alkylamines such as octylamine and n-dodecylamine, aromatic amines such as benzylamine, alkanolamines such as monoethanolamine and triethanolamine, and quaternary ammonium hydroxides.

  As the acid component used, oxycarboxylic acids (hydroxycarboxylic acids) such as lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, and mandelic acid can be suitably used. Formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, etc. Can also be used.

  As the surfactant to be used, any of anionic, cationic and nonionic surfactants can be used. However, nitrogen-containing polyoxyethylene derivatives having amino groups and anionic surfactants having acid groups Is desirable.

  Although it does not specifically limit as a nitrogen-containing type polyoxyethylene derivative which has an amino group, NOMIN (registered trademark) L-201, L-202, L-207, F-202, F-203, manufactured by NOF Corporation, F-205, F-210, F-215, O-205, S-202, S-204, S-210, S-215, S-220, T2-202, T2-206, T2-210, T2- 230, T2-260, DT-203, DT-208 and the like.

  Although it does not specifically limit as an anionic surfactant which has an acid group, What has a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group is preferable, and what has a phosphoric acid group is the most preferable especially. Examples of the anionic surfactant having a phosphate group include Disperbyk (registered trademark) -102, 103, 106, 110, 111, 142, 163, and 180 manufactured by Big Chemie Japan.

  These additives are used in an addition amount of about 1.0 to 50% by mass with respect to the solid content of the heat ray shielding fine particles.

  Examples of the organic solvent used in the dispersion of the heat-shielded fine particles subjected to hydrothermal treatment include aliphatic hydrocarbons such as mineral spirits, aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, 1-propanol, and 2-propanol. , Alcohols such as 1-butanol, 2-butanol and cyclohexanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate, isobutyl acetate and amyl acetate, ethyl cellosolve , Butyl cellosolve, carbitol, butyl carbitol, ether alcohols such as methoxypropanol, methoxybutanol, cellosolve acetate, butyl cellosolve, carbitol acetate, methoxybutyl acetate, methoxypropano Ether esters such as acetates and the like.

Moreover, organic ester plasticizer is mentioned as a plasticizer used for the dispersion liquid of the heat ray shielding microparticles | fine-particles hydrothermally treated. The organic ester plasticizer is not particularly limited, but triethylene glycol di (2-ethylbutyrate), triethylene glycol di (2-ethylhexanoate), triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, oligoethylene glycol di (2-ethylhexanoate), triethylene glycol di-isononanoate, triethylene glycol di (2- Propylhexanoate), dipropylene glycol benzoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di (2-ethylbutyrate), 1,3-propylene glycol Di (2-ethylbutyrate), 1,4-butylene glycol di (2-ethylbutyrate), 1,2-butylene glycol di (2-ethylbutyrate), diethylene glycol di (2-ethylbutyrate), diethylene glycol Di (2-ethylhexanoate), dipropylene glycol di (2-ethylbutyrate), triethylene glycol di (2-ethylpentanoate), tetraethylene glycol di (2-ethylbutyrate), diethylene glycol dicapri , Tetraethylene glycol di (2-ethylhexanoate), dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, di (2-butoxyethyl) adipate, di (2-butoxyethyl) adipate 2 Butoxyethoxyethyl), di (2-ethylhexyl) adipate, di (2-butoxyethyl) sebacate, di (2-ethylhexyl) sebacate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate, phthalate Examples include di (2-ethylhexyl) acid, trioctyl trimetate, tris (2-ethylhexyl) phosphate, diisononylcyclohexane dicarboxylate, and the like.

  The aqueous dispersion of heat-treated heat-shielding fine particles obtained by the steps (a) and (b) of the present invention is converted into the organic solvent, the plasticizer or a mixture of the plasticizer and the organic solvent by a known solvent substitution method. (Solvent) can be substituted.

  The water dispersion, or the organic solvent dispersion, plasticizer dispersion or mixture dispersion of plasticizer and organic solvent obtained therefrom is preferably 1% by mass or more, more preferably 10%, as the content of the heat ray shielding fine particles. It is at least mass%, more preferably at least 20 mass%, preferably at most 70 mass%, more preferably at most 50 mass%.

  The heat-ray-shielding fine particles that have been subjected to hydrothermal treatment can be further improved in dispersibility and light resistance by surface treatment with a metal alkoxide or a coupling agent. In this case, an organosilicon compound having a hydrolyzable substituent is particularly preferably used because of easy treatment.

[Interlayer film for laminated glass]
In the present invention, in the interlayer film for laminated glass, heat constituting a layer made of a thermoplastic resin composition containing hydrothermally treated heat ray shielding fine particles or a layer made of a thermoplastic resin composition containing an ultraviolet absorber described later The plastic resin is not particularly limited. For example, polyvinyl acetal resin, polyurethane resin, acrylic resin, block copolymer rubber, α-olefin-vinyl ester copolymer and a modified product thereof, ethylene- Examples include acrylic acid copolymers, ionomers, polyamide resins, and polyester resins.

  Examples of the α-olefin in the α-olefin-vinyl ester copolymer include ethylene, 1-butene, 1-pentene, and the like. Among these, ethylene is preferably used. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate and the like. Among these, vinyl acetate is preferably used.

  In the interlayer film for laminated glass of the present invention, a polyvinyl acetal resin is suitable as the thermoplastic resin constituting the layer made of the thermoplastic resin composition containing the heat-ray shielding fine particles subjected to hydrothermal treatment, and the polyvinyl butyral resin is More preferred. In addition, as the thermoplastic resin constituting the layer made of a thermoplastic resin composition containing an ultraviolet absorber described later in the interlayer film for laminated glass of the present invention, a polyvinyl acetal resin is suitable, and a polyvinyl butyral resin is used. More preferred. When the thermoplastic resin is a polyvinyl acetal-based resin, the thermoplastic resin composition containing it preferably further contains a plasticizer.

  As said polyvinyl acetal type-resin, the thing of 40-90 mol% of acetalization degree is preferable. If the degree of acetalization is less than 40 mol%, the water absorption is high, which is not preferable. On the other hand, if the degree of acetalization exceeds 90 mol%, a long reaction time is required for obtaining a polyvinyl acetal resin, which may be undesirable in the process. More preferably, it is 60-85 mol%, More preferably, it is 65-80 mol% from a water-resistant viewpoint.

  Although there is no restriction | limiting in particular in the kind of said plasticizer, For example, 1 type, or 2 or more types of the above-mentioned plasticizer group is mentioned.

  The addition amount of the plasticizer is preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin. If it is less than 20 parts by mass, the resulting interlayer film for laminated glass or the laminated glass using it may have insufficient impact resistance. Conversely, if it exceeds 100 parts by mass, the plasticizer bleeds out, The transparency of the obtained interlayer film for laminated glass and the laminated glass using the same may decrease, or the adhesion between the glass and the interlayer film for laminated glass may be impaired.

  In the interlayer film for laminated glass of the present invention, the layer composed of the thermoplastic resin composition containing the heat-ray-shielding fine particles subjected to hydrothermal treatment is used in combination with 100 parts by mass of the heat-ray-shielding fine particles or a plasticizer. When doing, it is preferable to contain 0.001-2 mass part with respect to 100 mass parts of total amounts of a thermoplastic resin and a plasticizer. If the content of the heat-ray shielding fine particles subjected to hydrothermal treatment is less than 0.001 part by mass, the expected heat-ray shielding effect may not be obtained. More preferably, it is 0.002 mass part or more, More preferably, it is 0.005 mass part or more. Moreover, when content of the heat ray shielding microparticles | fine-particles hydrothermally processed exceeds 2 mass parts, there exists a possibility that transparency of the laminated glass obtained may be impaired. More preferably, it is 1.5 mass parts or less, More preferably, it is 1 mass part or less.

  In order to obtain a transparent interlayer film for laminated glass in the present invention, hydrothermally treated heat ray shielding fine particles have secondary aggregates having an average particle size of 200 nm or less, and the secondary aggregates are thermoplastic resin compositions. It is preferable to be in a state of being dispersed inside the layer made of a material. The method for obtaining such a state is not particularly limited. For example, it can be achieved by compounding with a thermoplastic resin in the state of a dispersion in which heat ray shielding fine particles are stabilized using a dispersant described later. The dispersion is not particularly limited and may be any of the above-mentioned aqueous dispersion, organic solvent dispersion, plasticizer dispersion, or a mixture dispersion of a plasticizer and an organic solvent, and a plasticizer is added to the thermoplastic resin composition. When it is contained, it is preferably combined with the thermoplastic resin in the state of a plasticizer dispersion or a mixture dispersion of a plasticizer and an organic solvent.

  Although it does not specifically limit as said dispersing agent, An alkylamine type dispersing agent and a phosphate ester type dispersing agent are used suitably. These dispersants have a relatively good affinity with the hydrothermally-treated heat ray shielding fine particles, and an excellent dispersion stabilizing effect can be expected.

  The alkylamine dispersant is not particularly limited, but an alkylamine dispersant having a secondary or tertiary amino group is preferable from the viewpoint of suppressing deterioration when combined with a thermoplastic resin. Examples of such alkylamine dispersants include triethylamine, diisopropylamine, diisobutylamine, dibutylamine, dipropylamine, diamylamine, tributylamine, tripropylamine, triamylamine and the like. These may be used alone or in combination of two or more.

  The phosphate ester dispersant is not particularly limited, and monobasic acid or dibasic acid phosphate esters are preferably used. Examples include Disperbyk (registered trademark) -102, 103, 106, 110, 111, 142, 163, 180, and the like. These may be used alone or in combination of two or more.

The alkylamine dispersant and the phosphate ester dispersant may be used alone, but it is preferable to use a combination of the alkylamine dispersant and the phosphate ester dispersant. By combining both dispersants, an even higher dispersion stabilizing effect can be obtained.

  In the layer made of the thermoplastic resin composition containing the heat-ray-shielding fine particles subjected to hydrothermal treatment, the amount of the dispersing agent added is based on 100 parts by mass of the thermoplastic resin constituting the layer or when a plasticizer is used in combination. Is preferably 0.0001 to 3 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the plasticizer. If it is less than 0.0001 part by mass, the dispersion stability of the heat ray shielding fine particles may be lowered. More preferably, it is 0.0002 mass part or more. Moreover, when it exceeds 3 mass parts, there exists a possibility that problems, such as degradation of resin and the adhesive force fall with glass by the bleed-out of an additive, may arise. More preferably, it is 2 parts by mass or less.

  The interlayer film for laminated glass of the present invention may consist only of a layer made of the thermoplastic resin composition containing the hydrothermally treated heat ray shielding fine particles, but in addition to the layer made of the thermoplastic resin composition. In addition, a layer made of a thermoplastic resin composition containing an ultraviolet absorber may be included. In this case, heat containing an ultraviolet absorber on both sides of a layer made of a thermoplastic resin composition containing the hydrothermally treated heat ray shielding fine particles (hereinafter sometimes referred to as a first resin composition layer). A layer made of a plastic resin composition (hereinafter sometimes referred to as a second resin composition layer) is preferably disposed. By having the second resin composition layer, it is possible to more effectively suppress deterioration of the resin in the first resin composition layer and alteration of the heat-ray shielding fine particles that have been subjected to hydrothermal treatment. In addition, it may include a structure in which another layer is disposed between the first resin composition layer and the second resin composition layer, and two or more second resin composition layers may be included. The types of the ultraviolet absorber and the thermoplastic resin included may be the same or different.

  Moreover, in the intermediate film for laminated glasses which has a 1st resin composition layer and a 2nd resin composition layer, sound insulation can also be provided by making a 1st resin composition layer into a soft layer. In order to make the first resin composition layer a soft layer, for example, the polyvinyl acetal resin contained in the first resin composition layer contains a vinyl acetate unit amount of 5 to 8 mol% and a vinyl alcohol unit amount of 22 mol. %, And the polyvinyl acetal resin contained in the second resin composition layer preferably has a vinyl acetate unit amount of 0.1 to 11 mol% and a vinyl alcohol unit amount of 25 to 34 mol%. In this case, it is also preferable that the difference between the plasticizer content in the first resin composition layer and the plasticizer content in the second resin composition layer is 5% by mass or more. The interlayer film for laminated glass having such a sound insulating property is a 1st mode (179 Hz) damping performance at 10 ° C. measured according to ISO 16940 in a laminated glass produced by sandwiching it with two pieces of glass having a thickness of 2 mm. Is preferably 10% or more, and the damping performance in the 1st mode (128 Hz) at 20 ° C. is preferably 22% or more.

  In the interlayer film for laminated glass of the present invention, in addition to the thermoplastic resin and the hydrothermally treated heat ray shielding fine particles, various additives as required within a range not inhibiting the effect of the invention, for example, an adhesive force adjusting agent, Antioxidants, stabilizers, lubricants, flame retardants, processing aids, antistatic agents, colorants, heat ray reflective agents, impact resistance aids, fillers, moisture resistance agents, and the like may be added.

As a method for producing the interlayer film for laminated glass of the present invention, a known method can be employed. From the viewpoint of productivity and the like, it is preferable to manufacture by a melt molding method in which hydrothermally treated heat ray shielding fine particles and a thermoplastic resin are melt kneaded and molded. Here, the melt kneading means kneading in which at least the thermoplastic resin is melted. The specific method of melt kneading is not particularly limited, and examples thereof include a method using a known melt kneading apparatus such as a single screw extruder, a twin screw extruder, a brabender, an open roll, and a kneader. After melt-kneading, it is preferably formed into a film. There are no particular restrictions on the specific method for forming the film, and it can be formed into a film by directly attaching a T-die to the melt-kneading device, or once a pellet of the thermoplastic resin composition is produced. Then, it may be separately formed into a film. The film thickness of the molded film is not particularly limited, but in consideration of the minimum penetration resistance and weather resistance required for laminated glass, it is preferably 0.2 to 1.2 mm, more preferably 0.8. 3 to 1.0 mm.

  The interlayer film for laminated glass of the present invention is excellent in transparency, heat ray shielding properties and light resistance. Therefore, the laminated glass obtained by laminating this with glass can be widely used as window materials for buildings, vehicles, aircraft, ships, and the like. Examples of vehicles in which laminated glass is used include automobiles and trains. In automobiles, the laminated glass of the present invention can be used as a windshield, side glass, rear glass, roof glass, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, each evaluation value was measured and calculated according to the following method.

[Visible light transmittance and solar radiation transmittance]
Using a spectrophotometer “SolidSpec-3700” manufactured by Shimadzu Corporation, transmittance of the wavelength region of 280 to 2500 nm was measured for the produced laminated glass. Based on this value, a visible light transmittance (%) of 380 to 780 nm was determined according to JIS R3106. Moreover, the solar radiation transmittance (%) of 300-2500 nm was calculated | required using the weight value coefficient of JISR3106.

[Light resistance]
For the light resistance evaluation, a light resistance tester “Due Panel Light Control Weather Meter FDP” manufactured by Suga Test Instruments Co., Ltd. was used. U with a strength of 30 W / m ² for the produced laminated glass
V light was irradiated for 200 hours, and the difference (ΔT) in visible light transmittance before and after irradiation was calculated and used as an index of light resistance.

[Haze]
Using a turbidimeter “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd., the haze (%) was measured according to JIS K7105 for the produced laminated glass.

[Average particle diameter of secondary aggregate dispersed in the layer made of thermoplastic resin composition]
Using a transmission electron microscope (TEM) “H-800NA” manufactured by Hitachi High-Technologies Corporation, a photograph of a cross section of the layer made of the thermoplastic resin composition (PVB composition) was taken. From the photograph, 50 secondary aggregates of heat ray shielding fine particles dispersed inside the layer were arbitrarily selected, the major axis of each was measured, and the average value thereof was taken as the average particle diameter (nm). However, secondary aggregates having a major axis of less than 5 nm were excluded from the measurement because they were indistinguishable from photographic contrast spots.

[Reference Example 1]
110 kg of antimony trioxide (manufactured by Mikuni Seiren Co., Ltd. (currently Yamanaka Sangyo Co., Ltd.)) was dispersed in 1364 kg of water, and then 182 kg of 35% by mass hydrogen peroxide and 594 g of 87% by mass formic acid were added. The mixture was heated to 100 ° C. and reacted for 2 hours to obtain an antimony pentoxide sol. The obtained sol had a specific gravity of 1.174, pH of 1.44, a viscosity of 1.8 mPa · s, and a Sb ₂ O ₅ concentration of 16
. The primary particle diameter (major axis) was 10 to 20 nm by observation with a transmission electron microscope (JEM-1010 manufactured by JEOL Ltd.), and the specific surface area was 57.0 m ² / g by BET method.
After 334 kg of the obtained antimony pentoxide sol was diluted with pure water so that the Sb ₂ O ₅ concentration was 13.3 mass%, basic zinc carbonate (manufactured by Sakai Chemical Industry Co., Ltd., 3ZnCO ₃ .4Zn)
(OH) ₂ , containing 70% by mass in terms of ZnO) 16.9 kg was added and stirred for 6 hours to obtain a slurry. This slurry was 3.1% by mass in terms of ZnO and 12.7 in terms of Sb ₂ O _5.
Including each mass%, the molar ratio of ZnO / Sb ₂ O ₅ was 0.97. This slurry was dried with a spray dryer to obtain a dry powder. The result of the X-ray diffraction measurement of this dried powder coincided with the peak of hydrous antimony pentoxide (Sb ₂ O ₅ / xH ₂ O).
A mixed gas (0.47 as a partial pressure ratio of water vapor / nitrogen gas) obtained by charging 72 kg of this dry powder into a 450 mmφ fluidized tank and bubbling air through a warm bath at 85 ° C. at 24 Nm ³ / hr It introduce | transduced into the fluidized tank and baked at 480 degreeC for 4 hours. The obtained powder was dark blue and coincided with the peak of anhydrous zinc antimonate (ZnSb ₂ O ₆ ) as a result of X-ray analysis measurement. The primary powder was observed by a transmission electron microscope (JEM-1010 manufactured by JEOL Ltd.). The particle diameter (major axis) was 10 to 20 nm, and the specific surface area by the BET method was 56.9 m ² / g. Moreover, what press-molded this powder at 300 kg / cm < ² > showed the electroconductivity of 150 ohm * cm of specific resistance. Further, as a result of measuring the reflectance with a spectrophotometer using an integrating sphere (UV-3150, manufactured by Shimadzu Corporation) from a wavelength of 250 nm to 2500 nm, the resulting powder showed a decrease in reflectance at 800 to 2500 nm. It was confirmed that it absorbs infrared light and has heat ray shielding properties.
After the anhydrous zinc antimonate powder was pulverized with a pin disc mill, 84 kg of the powder and 320 kg of water were added to a 20 liter wet pulverizer (LMK-20 type pulverizer manufactured by Ashizawa Co., Ltd.), and glass beads (0. Wet pulverization was performed at 3 mmφ) for 20 hours to obtain an aqueous sol. The pH of this aqueous sol was 6.6. This aqueous sol was passed through a column packed with 50 liters of a cation exchange resin at a liquid passing speed of SV = 12 to perform cation exchange. Next, an anion exchange was performed by passing the solution through a column packed with 50 liters of anion exchange resin at a liquid passing rate of SV = 12. The pH of the sol after cation / anion exchange was 3.1. 400 g of diisopropylamine was added to this aqueous sol, and this aqueous sol was concentrated to 258 kg using an ultrafiltration apparatus.
The obtained anhydrous zinc antimonate aqueous sol is dark blue with transparency, specific gravity 1.353, pH 6.9, viscosity 2.8 mPa · s, conductivity 409 μs / cm, ZnSb ₂ O ₆ concentration 30.6% by mass Met. The particle diameter of the anhydrous zinc antimonate contained in this sol is 10 to 20 nm in primary particle diameter (major diameter) observed by a transmission electron microscope (JEM-1010 manufactured by JEOL Ltd.), and the dynamic light scattering particle size distribution. The particle diameter of the secondary aggregate, which is the average particle diameter of the light intensity distribution measured with a measuring machine (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.), was 87 nm. The specific surface area of the dried sol by the BET method was 63.9 m ² / g, and the particle diameter calculated from the specific surface area was 15 nm.

Example 1
[Preparation of hydrothermally treated heat ray shielding fine particles]
The anhydrous zinc antimonate aqueous sol obtained in Reference Example 1 was diluted with pure water so that the ZnSb ₂ O ₆ concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). Then, the liquid temperature was raised to 200 ° C. over 2.0 hours, held at 200 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 2 hours.
The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure and replaced with a methanol solvent to produce hydrothermally treated anhydrous zinc antimonate methanol dispersion d0 (concentration 60.5% by mass). did. As a result of observing a cross section of 30 arbitrary hydrothermally treated anhydrous zinc antimonate fine particles (primary particles) contained in the dispersion liquid with a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.), a crystalline portion The average of the equivalent circle diameter R _c was 14.5 nm, and the average equivalent circle diameter R _{(a + c)} of the combined area of the crystalline portion and the amorphous portion was 16.2 nm. The volume fraction of the amorphous part of the obtained hydrothermally treated anhydrous zinc antimonate fine particles was calculated to be 29% by volume.

[Production of interlayer film for laminated glass]
The hydrothermally-treated anhydrous zinc antimonate methanol dispersion d0 (concentration 60.5% by mass) 0.27 g and “Disp” manufactured by BYK Japan Japan as a phosphate ester dispersant
erbyk-102 ”0.16 g, triethylene glycol di (2-ethylhexanoate) (hereinafter abbreviated as 3G8) 15.2 g as a plasticizer, 0.14 g of“ Tinuvin 328 ”manufactured by Ciba Japan as an ultraviolet absorber, adhesion A dispersion obtained by mixing 0.08 g of a 25 mass% aqueous solution of a mixture of magnesium acetate and potassium acetate (mixing mass ratio: 2/1) as a force adjusting agent was prepared as polyvinyl butyral (hereinafter also abbreviated as PVB) (raw material PVA). The viscosity average polymerization degree 1700, the degree of acetalization 70 mol%, the vinyl alcohol unit amount 29 mol%, and the vinyl acetate unit amount 1 mol%) were added to 40 g and mixed. This mixture is kneaded at 170 ° C. using a lab plast mill, and then press-molded at 140 ° C. for 5 minutes using a press machine to form a PVB composition containing hydrothermally-treated anhydrous zinc antimonate fine particles. A 0.76 mm single-layer interlayer film for laminated glass was produced. Table 2 shows the constitution of the interlayer film for laminated glass and the average particle diameter of secondary aggregates dispersed in the layer made of the PVB composition.

[Production and evaluation of laminated glass]
The obtained interlayer film for laminated glass was sandwiched between two pieces of 2 mm-thick glass (Saint Gobain, Planilux Clear), and then held at 140 ° C. under reduced pressure for 90 minutes to produce a laminated glass. . The obtained laminated glass was evaluated by the above method. The results are shown in Table 3.

(Example 2)
The anhydrous zinc antimonate aqueous sol obtained in Reference Example 1 was diluted with pure water so that the ZnSb ₂ O ₆ concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). The solution was heated to 220 ° C. over 2.0 hours, held at 220 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 3 hours. The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol has a pH of 7.2, and the particle size of the secondary aggregate is determined by measurement using a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). It was 86 nm.
The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure and replaced with methanol solvent to obtain hydrothermally treated anhydrous zinc antimonate methanol dispersion d1. The obtained hydrothermally treated anhydrous zinc antimonate methanol dispersion d1 contains 61.1% by mass of ZnSb ₂ O ₆ , and the pH of the solution obtained by mixing water and the dispersion at 1: 1 (mass ratio) is 6. 1. The particle diameter of the secondary aggregate was 80 nm as measured by a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). As a result of observing a cross section of 30 arbitrary hydrothermally treated anhydrous zinc antimonate fine particles (primary particles) contained in the dispersion liquid with a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.), a crystalline portion the average of the equivalent circle diameter R _c is a 16.8 nm, the average of the crystalline portion and amorphous portion and a circle equivalent diameter of the total area of the R _{(a + c)} was 18.1 nm. The volume fraction of the amorphous part of the obtained hydrothermally treated anhydrous zinc antimonate fine particles was calculated to be 20% by volume.

[Production of interlayer film for laminated glass and production and evaluation of laminated glass]
In Example 1, instead of hydrothermally treated anhydrous zinc antimonate methanol dispersion d0, 0.26 g of hydrothermally treated anhydrous zinc antimonate methanol dispersion d1 obtained above was used in the same manner as in Example 1. Thus, an interlayer film for laminated glass and a laminated glass were produced. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

(Example 3)
In Example 2, the amount of hydrothermally treated anhydrous zinc antimonate methanol dispersion d1 (concentration 61.1% by mass) was changed to 1.31 g, and the amount of “Disperbyk-102” manufactured by BYK Japan KK was changed. A thickness of 0.16 m comprising a PVB composition containing hydrothermally treated anhydrous zinc antimonate fine particles in the same manner as in Example 2 except that the amount was changed to 0.8 g.
A single-layer sheet of m was prepared, and this sheet was cut into 20 cm × 20 cm to form a layer x.
Next, 15.2 g of 3G8, 0.14 g of “Tinuvin 328” manufactured by Ciba Japan as an ultraviolet absorber, and 25 mass of a mixture of magnesium acetate and potassium acetate (mixing mass ratio: 2/1) as an adhesion modifier. % Aqueous solution 0.08 g was added to and mixed with 40 g of the same PVB used in Example 1, and thereafter, in the same manner as in Example 1, a single layer sheet made of PVB composition having a thickness of 0.3 mm was prepared. It produced and cut out this sheet | seat into 20 cm x 20 cm, and was set as the layer y.
Furthermore, the produced layer x was sandwiched between two layers y to form an interlayer film for laminated glass, and thereafter, a laminated glass was produced in the same manner as in Example 1. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

Example 4
1.31 g of anhydrous zinc antimonate methanol dispersion d1 (concentration 61.1 mass%) prepared by the method described in Example 2 and hydrothermally treated at 220 ° C., and Big Chemie Japan (as phosphate ester dispersant) "Disperbyk-102" 0.8 g, 3G8 19.9 g as a plasticizer, "Tinuvin 328" manufactured by Ciba Japan as an ultraviolet absorber, 0.14 g, a mixture of magnesium acetate and potassium acetate as an adhesion modifier A dispersion obtained by mixing 0.08 g of a 25 mass% aqueous solution having a (mixing mass ratio: 2/1) was mixed with PVB (raw material PVA viscosity average polymerization degree 1700, acetalization degree 74 mol%, vinyl alcohol unit amount. 19 mol%, vinyl acetate unit amount 7 mol%) was added to 35.3 g and mixed. This mixture is kneaded at 100 ° C. using a lab plast mill, and then press molded at 140 ° C. for 5 minutes using a press machine, thereby comprising a PVB composition containing hydrothermally treated anhydrous zinc antimonate fine particles. A 0.16 mm single-layer sheet was prepared, and this sheet was cut into 20 cm × 20 cm to form a layer x.
Next, the layer y similar to the layer y in Example 3 was produced.
Furthermore, the produced layer x was sandwiched between two layers y to form an interlayer film for laminated glass, and thereafter, a laminated glass was produced in the same manner as in Example 1. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.
Moreover, as a result of evaluating the damping performance of the 1st mode (179 Hz) at 10 ° C. according to ISO 16940, the laminated glass was found to have a damping performance of 11%. Further, the damping performance in the 1st mode (128 Hz) at 20 ° C. was 23%.

(Comparative Example 1)
An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1 except that the hydrothermally treated anhydrous zinc antimonate methanol dispersion (d0) was not used. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

(Comparative Example 2)
The anhydrous zinc antimonate aqueous sol obtained in Reference Example 1 was concentrated while blowing methanol vapor under normal pressure and replaced with a methanol solvent to obtain an anhydrous zinc antimonate methanol dispersion cd0 that was not hydrothermally treated. The obtained hydrothermally-treated anhydrous zinc antimonate methanol dispersion cd0 contains 60.9% by mass of ZnSb ₂ O ₆ and is a mixture of water and the dispersion at a ratio of 1: 1 (mass ratio). The pH was 7.1, and the particle size of the secondary aggregate was 87 nm as measured by a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). As a result of observing the cross section of 30 arbitrary anhydrous zinc antimonate fine particles (primary particles) contained in the dispersion liquid with a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.), the circular portion of the crystalline portion The average converted diameter R _c was 11.4 nm, and the average circle converted diameter R _{(a + c)} of the combined area of the crystalline portion and the amorphous portion was 14.2 nm. The volume fraction of the amorphous part of the obtained anhydrous zinc antimonate fine particles was calculated to be 48% by volume.

[Production of interlayer film for laminated glass and production and evaluation of laminated glass]
In Example 1, except that 0.26 g of anhydrous zinc antimonate methanol dispersion cd0 not subjected to hydrothermal treatment obtained above was used instead of hydrothermally treated anhydrous zinc antimonate methanol dispersion d0. In the same manner as in Example 1, an interlayer film for laminated glass and a laminated glass were produced. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

(Comparative Example 3)
The anhydrous zinc antimonate aqueous sol obtained in Reference Example 1 was diluted with pure water so that the ZnSb ₂ O ₆ concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). Then, the temperature was raised to 150 ° C. over 2.0 hours, held at 150 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 2 hours. The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol has a pH of 7.3, and the particle size of the secondary aggregate is measured by a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). It was 84 nm.
The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure and replaced with methanol solvent to obtain hydrothermally treated anhydrous zinc antimonate methanol dispersion cd1. The obtained hydrothermally treated anhydrous zinc antimonate methanol dispersion cd1 contains 60.8% by mass of ZnSb ₂ O ₆ , and the pH of the solution prepared by mixing water and the dispersion at 1: 1 (mass ratio) is 6. 8. The particle diameter of the secondary aggregate was 84 nm as measured by a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). As a result of observing the cross section of 30 arbitrary hydrothermally treated anhydrous zinc antimonate fine particles (primary particles) contained in the dispersion liquid with a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.), a crystalline portion the average of the equivalent circle diameter R _c is a 11.7 nm, the average of the crystalline portion and amorphous portion and a circle equivalent diameter of the total area of the R _{(a + c)} was 14.2 nm. The volume fraction of the amorphous part of the obtained hydrothermally treated anhydrous zinc antimonate fine particles was calculated to be 44% by volume.

[Production of interlayer film for laminated glass and production and evaluation of laminated glass]
In Example 1, instead of hydrothermally treated anhydrous zinc antimonate methanol dispersion d0, 0.26 g of hydrothermally treated anhydrous zinc antimonate methanol dispersion cd1 obtained above was used in the same manner as in Example 1. Thus, an interlayer film for laminated glass and a laminated glass were produced. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

(Comparative Example 4)
The anhydrous zinc antimonate aqueous sol obtained in Reference Example 1 was diluted with pure water so that the ZnSb ₂ O ₆ concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). The solution was heated to 180 ° C. over 2.0 hours, held at 180 ° C. for 5 hours, and then subjected to hydrothermal treatment to cool to room temperature over 3 hours. The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol has a pH of 7.6, and the particle size of the secondary aggregate is measured by a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). It was 75 nm.
The obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure and replaced with methanol solvent to obtain hydrothermally treated anhydrous zinc antimonate methanol dispersion cd2. The obtained hydrothermally treated anhydrous zinc antimonate methanol dispersion cd2 contains 49.2% by mass of ZnSb ₂ O ₆ , and the pH of the solution prepared by mixing water and the dispersion at 1: 1 (mass ratio) is 6. 1. The particle diameter of the secondary aggregate was 75 nm as measured with a dynamic light scattering particle size distribution analyzer (submicron particle analyzer N5 manufactured by Beckman Coulter, Inc.). As a result of observing a cross section of 30 arbitrary hydrothermally treated anhydrous zinc antimonate fine particles (primary particles) contained in the dispersion liquid with a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.), a crystalline portion the average of the equivalent circle diameter R _c is a 11.9Nm, average crystalline portion and amorphous portion and a circle equivalent diameter of the total area of the R _{(a + c)} was 14.1 nm. The volume fraction of the amorphous part of the obtained hydrothermally treated anhydrous zinc antimonate fine particles was calculated to be 40% by volume.

[Production of interlayer film for laminated glass and production and evaluation of laminated glass]
In Example 1, instead of hydrothermally treated anhydrous zinc antimonate methanol dispersion d0, 0.33 g of hydrothermally treated anhydrous zinc antimonate methanol dispersion cd2 obtained above was used in the same manner as in Example 1. Thus, an interlayer film for laminated glass and a laminated glass were produced. The obtained laminated glass was evaluated by the above method. The above results are shown in Tables 1-3.

From the results shown in Table 3, the laminated glass (Examples 1 to 4) using the interlayer film for laminated glass of the present invention has low solar radiation transmittance while maintaining high visible light transmittance, and is irradiated with high energy rays. It turns out that there is little degradation of.
On the other hand, when the heat ray shielding fine particles are not contained (Comparative Example 1), the heat ray shielding performance is not sufficient. When the heat ray shielding fine particles are not hydrothermally treated (Comparative Example 2), the performance degradation under high energy ray irradiation is remarkable. Further, even when the heat ray shielding fine particles are subjected to hydrothermal treatment, when the treatment temperature is low (Comparative Examples 3 and 4), the crystallization of the amorphous part hardly occurs (see Table 1), and the high energy ray is caused. It is impossible to suppress the performance degradation.

  ADVANTAGE OF THE INVENTION According to this invention, the intermediate film for laminated glasses excellent in transparency, heat ray shielding property, and light resistance can be provided. Laminated glass using the interlayer film for laminated glass can be suitably used for, for example, automotive windshield, side glass, rear glass, roof glass, glass parts of vehicles such as aircraft and trains, architectural glass, etc. By suppressing the rise, it is possible to reduce the use of excessive cooling equipment and enable environmentally friendly space design.

Claims (8)

An interlayer film for laminated glass having a layer comprising a thermoplastic resin composition containing hydrothermally treated heat ray shielding fine particles obtained by a method comprising the following steps (a) and (b).
(A) Step: Dry pulverization and / or wet pulverization of crystalline heat ray shielding fine particles having a primary particle size of 5 to 100 nm (b) Step: Heat ray shielding fine particles pulverized in step (a) in water Step of heating at 200 to 320 ° C. after dispersion The heat ray shielding fine particles are tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, lanthanum hexaboride, cerium hexaboride, anhydrous zinc antimonate, and sulfide. The interlayer film for laminated glass according to claim 1, which is at least one kind of fine particles selected from the group consisting of copper. The interlayer film for laminated glass according to claim 1, wherein the heat ray shielding fine particles are anhydrous zinc antimonate fine particles. The hydrothermally-treated heat ray shielding fine particles have secondary aggregates having an average particle diameter of 200 nm or less, and the secondary aggregates are in a state of being dispersed inside a layer made of the thermoplastic resin composition. Item 4. The interlayer film for laminated glass according to any one of Items 1 to 3. The interlayer film for laminated glass according to any one of claims 1 to 4, wherein the thermoplastic resin in the layer made of the thermoplastic resin composition is a polyvinyl acetal resin. The layer which consists of a thermoplastic resin composition containing a ultraviolet absorber is arrange | positioned on both sides of the layer which consists of the thermoplastic resin composition containing the said heat-heat-shielding microparticles | fine-particles hydrothermally treated. An interlayer film for laminated glass according to any one of the above. Laminated glass comprising the interlayer film for laminated glass according to claim 1. The method for producing an interlayer film for laminated glass according to any one of claims 1 to 6, comprising a step of melt-kneading the hydrothermally treated heat ray shielding fine particles and a thermoplastic resin, and forming the film into a film. A method for producing an interlayer film for laminated glass.