JP2003261361A - Interlayer film for laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an interlayer film for laminated glass which has excellent mechanical property, transparency, in particular, haze, thermal insulation and electromagnetic wave transmission and shows excellent resistance to penetration in the lapse of time when being fabricated into a laminated glass and to provide a laminated glass. <P>SOLUTION: In this interlayer film for laminated glass, a polyvinyl acetal resin, phillosilicate, plasticizer, adhesive power adjusting agent, ITO fine particle and dispersant are included and the ITO fine particle and laminar silicate are dispersed microscopically-uniformly. The laminated glass is also provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to transparency, heat shielding properties,
The present invention relates to an interlayer film for laminated glass, which is excellent in electromagnetic wave transparency, has an appropriate adhesive force with glass, and is also excellent in penetration resistance, and a laminated glass using the same.

[0002]

2. Description of the Related Art Conventionally, laminated glass is safe because there are few scattered glass fragments even if it is damaged by an external impact, and therefore it is safe to use it for window glass of vehicles such as automobiles, aircraft, buildings, etc. Widely used as etc. As the above-mentioned laminated glass, at least a pair of glasses, an intermediate film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized by a plasticizer is interposed, and those obtained by integration are generally used. ing. Further, Japanese Patent Application Laid-Open No. 2001-58853 discloses a technique of an intermediate film in which a layered silicate is finely dispersed in the film as an intermediate film having excellent strength, flexibility, transparency and the like. On the other hand, as laminated glass for automobiles and buildings, there is an increasing demand for laminated glass with excellent heat-shielding properties, which has not been emphasized so far, but conventional laminated glass as described above is superior in safety. However, there is a problem in that it has poor heat insulation.

Generally, among infrared rays, infrared rays having a wavelength of 780 nm or more have a small energy amount of about 10% as compared with ultraviolet rays, but have a large thermal action and are absorbed by a substance to cause a temperature rise. It is called a heat ray. Therefore, in order to enhance the heat shielding property, a method of blocking infrared rays entering from a windshield or a side glass of an automobile, a glass window or a glass door of a building has been studied, and for example, a metal or a metal oxide is deposited by vapor deposition or sputtering. Commercially available are heat-ray-cut glass and the like in which a coating layer such as the above is provided on the glass surface to impart heat-shielding properties.
Since the coating layer is weak against external scratches and has poor chemical resistance, for example, a method of laminating an intermediate film such as a plasticized polyvinyl butyral resin film to form a laminated glass has been adopted.

However, the heat ray-cutting glass laminated with an intermediate film such as the plasticized polyvinyl butyral resin film is expensive, and the multilayer coating is thick, so that the transparency (visible light transmittance) is lowered, and There has been a problem that the adhesiveness with the intermediate film is lowered and the intermediate film is peeled or whitened. In recent years, various communication devices such as amateur radio (3.5 MHz, 7 MHz) and emergency communication devices (10 MHz or less), VICS (vehicle information communication system, 2.5 GHz), ETC (toll road automatic toll collection) System, 5.8GHz, satellite broadcasting (12G)
However, the above multi-layer coating layers impede the transmission of electromagnetic waves and interfere with the communication functions of mobile phones, car navigation systems, garage openers, automatic toll collection systems, etc. There was a problem.
Further, a laminated glass in which a polyester film having a metal deposited thereon is laminated between interlayer films for laminated glass, instead of providing a heat shield layer on the glass surface, is disclosed in Japanese Examined Patent Publication No. 61-5209.
No. 3, Japanese Patent Laid-Open No. 64-36442, etc. However, the laminated glass disclosed above has a problem in adhesiveness between the plasticized polyvinyl butyral resin sheet and the polyester film, and not only peeling occurs at the interface but also insufficient electromagnetic wave transmission. It was

[0005]

An object of the present invention is to provide an interlayer film for laminated glass which has both strength and flexibility, good transparency, particularly good haze, and excellent heat shield properties without lowering electromagnetic wave permeability. And to provide a laminated glass using the interlayer film for laminated glass.

[0006]

The present invention is directed to a polyvinyl acetal resin, a layered silicate, a plasticizer, an adhesion control agent, I
An intermediate film containing TO (tin-doped indium oxide) fine particles and a dispersant, in which ITO fine particles and layered silicate are finely and uniformly dispersed.

In the present invention, ITO fine particles are used to improve the heat-shielding property, and the ITO fine particles are finely and uniformly dispersed in the film to improve transparency (particularly haze),
The heat shield property could be improved without lowering the electromagnetic wave permeability. Further, in the present invention, since a layered silicate is used and finely and uniformly dispersed in the film,
It was possible to achieve both strength and flexibility without lowering transparency (particularly haze).

The polyvinyl acetal resin used in the present invention is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol (PVA) resin with an aldehyde. The above PVA resin is usually obtained by saponifying polyvinyl acetate and has a saponification degree of 80 to 99.8 mol%.
Resins are commonly used. Further, the molecular weight and the molecular weight distribution of the polyacetal resin used in the present invention are not particularly limited, but in view of moldability, physical properties and the like, P as a raw material is used.
A VA resin having a polymerization degree of 200 to 3000 is preferably used, and a resin having a polymerization degree of 500 to 2000 is particularly preferably used. When the average degree of polymerization is less than 200, penetration resistance of the obtained laminated glass is lowered, and when the average degree of polymerization is more than 3000, the moldability of the resin film is deteriorated and the rigidity of the resin film is increased. Too much, resulting in poor processability.

The above aldehyde has 1 to 1 carbon atoms.
An aldehyde of 0 may be used, and may be appropriately selected and used according to the required performance, and if necessary, two or more kinds may be used in combination. Specific examples of the aldehyde include, for example, n-butyraldehyde, isobutyraldehyde,
n-valeraldehyde, 2-ethylbutyraldehyde,
n-hexyl aldehyde, n-octyl aldehyde, n
-Nonyl aldehyde, n-decyl aldehyde, formaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned. Aldehydes preferably used include n
-Butyraldehyde, n-hexyl aldehyde, n-valeraldehyde. Particularly preferred is butyraldehyde having 4 carbon atoms.

Particularly preferred polyvinyl acetal resins include polyvinyl butyral (PVB) resins acetalized with butyraldehyde. Further, these acetal resins may be blended in an appropriate combination in consideration of necessary physical properties. Also,
It is also possible to appropriately use a co-polyvinyl acetal resin in which two or more kinds of aldehydes are combined at the time of acetalization. The acetalization degree of the polyvinyl acetal resin used in the present invention is usually 40 to 85%, preferably 60 to 75%.

The layered silicate used in the present invention is a silicate mineral that has exchangeable cations between the layers of fine flaky crystals having a thickness of about 1 nm and is aggregated in layers by ionic bonds. In the present invention, the layered structure is peeled off by a chemical or physical means, and the flakes are uniformly dispersed in the transparent resin composition, thereby maintaining the transparency of the resin composition and In the material, the function as an inorganic filler, a filler, and a viscosity modifier can be exhibited.

The type of the layered silicate is not particularly limited, but in addition to smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, or swelling. Such as sex mica,
Both natural and synthetic compounds can be preferably used.

The shape of the layered silicate used in the present invention has an average length of 0.01 to 3 μm and a thickness of 0.001 to 1.
A material having a thickness of 1 μm and an aspect ratio of 20 to 500 is preferably used, more preferably an average length of 0.05 to 2 μm, a thickness of 0.01 to 0.5 μm, and an aspect ratio of 50 to 200.
The thing of is used.

The cation exchange capacity of the layered silicate used in the present invention is not particularly limited, but is 50 to 200 m.
It is preferably mol / 100 g. 50 mmol
When the amount is less than 100 g, the amounts of the plasticizer and the cationic surfactant intercalated between the crystal layers by ion exchange tend to be small, and as a result, the layered silicate may not be finely dispersed. On the other hand, 200 mmol / 1
When the amount exceeds 00 g, the interlaminar bond strength of the layered silicate becomes strong, the intercalation with the plasticizer and the cationic surfactant becomes insufficient, and it is difficult to finely disperse the layered silicate. There is.

The layered silicate may be used as it is,
A pre-organized layered silicate may be used, but it is preferable to use the layered silicate.
At this time, there is no problem even if the non-organized layered silicate is present in the organized layered silicate. The above-mentioned organically modified layered silicate is a layered silicate in which the layers of the layered silicate are organically treated with a cationic surfactant, and is dispersed more finely in the resin than the unorganized layered silicate. It is more preferably used because it is easily treated. As a cationic surfactant used for organizing, a quaternary ammonium salt,
Examples thereof include quaternary phosphonium salts, preferably having 8 carbon atoms.
A quaternary ammonium salt having at least one of the above alkyl chains is used. When the alkyl chain having 8 or more carbon atoms is not contained, the hydrophilicity of the alkylammonium ion is so strong that the layers of the layered silicate cannot be sufficiently depolarized. Examples of the quaternary ammonium salt having an alkyl chain having 8 or more carbon atoms include, for example, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, distearyl diamine. Examples thereof include benzyl ammonium salt.

The amount of the layered silicate added is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. If the amount is less than 0.05 parts by weight, the amount added is too small to achieve the desired physical properties,
If it is added in an amount of more than 20 parts by weight, the content of resin increases in the composite material and the transparency is decreased, haze is deteriorated, and physical properties such as impact resistance are deteriorated. A more preferable amount of layered silicate added is 0.5
~ 5 parts by weight.

It is necessary that the layered silicate be finely dispersed, and the degree of the dispersion is a layered silicate having a size of 1 μm or more which can be visually confirmed or by a scanning electron microscope (SEM) level. The presence of many is mechanical strength,
Especially, it is not preferable in terms of transparency. Preferred dispersion is 1
The amount of layered silicate or organized layered silicate having a size of μm or more is 10
The number is 10 or less per μm × 10 μm, and more preferably 5 or less.

The method of finely dispersing the layered silicate in the film is not particularly limited, but the layered silicate and the plasticizer are premixed to sufficiently swell the layer spacing of the layered silicate. It is particularly preferable to add these to the resin and knead. This is because by mixing the layered silicate and the plasticizer in advance, the layered silicate is swollen by the plasticizer and easily dispersed finely in the resin when mixed with the resin. In this case, a part of the plasticizer and the total amount of the layered silicate may be once mixed, and then the remaining amount of the plasticizer may be further added and mixed.

The plasticizer is not particularly limited as long as it has been conventionally used for interlayer films and polyvinyl acetal resins, and examples thereof include organic acids such as monobasic organic acid esters and polybasic organic acid esters. Ester-based plasticizers, organic phosphoric acid-based and organic phosphorous acid-based phosphoric acid-based plasticizers are used. As the monobasic organic acid ester plasticizer,
For example, glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol, and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid). ), Glycol-based esters obtained by reaction with a monobasic organic acid such as decyl acid, among which triethylene glycol-dicaproic acid ester, triethylene glycol-di-2-ethylbutyric acid ester, triethylene glycol. A monobasic organic acid ester of triethylene glycol such as di-n-octyl acid ester and triethylene glycol-di-2-ethylhexyl acid ester is preferably used. Examples of polybasic organic acid ester plasticizers include esters of polybasic organic acids such as adipic acid, sebacic acid, and azelaic acid with straight-chain or branched alcohols having 4 to 8 carbon atoms. , Among them, dibutyl sebacate ester,
Dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferably used. Examples of the organic phosphoric acid-based plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like. The above plasticizers may be used alone or in combination of two or more.

Particularly preferred specific examples of the plasticizer preferably used include, for example, triethylene glycol-dicaproic acid ester, triethylene glycol-di-2-ethylbutyric acid ester, triethylene glycol-di-n-octylic acid ester, Triethylene glycol-di-2-
Examples thereof include ethylhexyl acid ester. These plasticizers are used properly depending on the type of polyvinyl acetal resin in consideration of compatibility with the resin.

The addition amount of the plasticizer is preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. If it is less than 20 parts by weight, it is insufficient for finely dispersing the layered silicate, and the penetration resistance may decrease.
Further, if the plasticizer is added in excess of 100 parts by weight, bleed-out of the plasticizer may occur, the transparency and adhesiveness of the resin film may be deteriorated, and the optical strain of the obtained laminated glass may be increased. The preferred amount of plasticizer added is 3
It is 0 to 60 parts by weight.

Further, in the interlayer film for laminated glass of the present invention, at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts is used as an adhesive strength adjusting agent. The metal is not particularly limited, and examples thereof include sodium, potassium and magnesium. Examples of the acid that constitutes the salt include organic acids such as octylic acid, hexylic acid, butyric acid, acetic acid, and formic acid, and inorganic acids such as hydrochloric acid and nitric acid. Among them, salts of organic acids having 2 to 16 carbon atoms Is preferably used. More preferable metal salt is magnesium salt of carboxylic acid having 2 to 16 carbon atoms or potassium salt of carboxylic acid having 2 to 16 carbon atoms. The magnesium salt of carboxylic acid having 2 to 12 carbon atoms or the potassium salt of carboxylic acid having 2 to 12 carbon atoms is not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, and magnesium 2-ethylbutanoate. Potassium 2-ethylbutanoate, magnesium 2-hexanoate, 2-
Potassium ethylhexanoate and the like are preferably used, and these may be used alone or in combination of two or more kinds.

The addition amount of at least one metal salt selected from the group consisting of the above-mentioned alkali metal salts and alkaline earth metal salts is 0.0001 to 1.0 part by weight based on 100 parts by weight of the polyvinyl acetal resin. It is more preferably 0.01 to 0.2 parts by weight. If it is less than 0.0001 part by weight, the adhesive strength of the peripheral part will be reduced in a high humidity atmosphere, and if it exceeds 1.0 part by weight, the adhesive strength will be too low and the transparency of the film will be deteriorated. Occur.

In the present invention, ITO fine particles are used in order to impart a heat shielding property. As ITO fine particles,
It is not particularly limited as long as it is ITO fine particles which are obtained by doping indium oxide with tin and are usually used for imparting conductivity. As the particle size of the ITO fine particles, the average particle size of the primary particles is preferably 100 nm or less. If it exceeds 100 nm, the transparency may decrease.

The content of the ITO fine particles is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. When the content is less than 0.1 part by weight, the infrared ray shielding effect is difficult to be obtained and the heat shield property is deteriorated.
When it exceeds the weight part, the transmittance of visible light decreases and the haze also increases.

It is necessary that the ITO fine particles are finely and uniformly dispersed in the intermediate film, and if the ITO fine particle species are not finely and uniformly dispersed, the transparency (particularly haze) is lowered. As a dispersion state of the ITO fine particles in the intermediate film, it is preferable that the ITO fine particles are dispersed so that the average particle diameter is 80 nm or less and the number of particles of 100 nm or more is 1 particle / μm ² or less.

The method for dispersing the ITO fine particles in the resin is not particularly limited. Usually, the ITO fine particles are uniformly dispersed in a dispersion medium composed of an organic solvent and then dispersed in the resin. In the present invention, As the dispersion medium, it is preferable to disperse using a plasticizer of the same kind as the plasticizer used for the interlayer film.

In the present invention, a dispersant is used to finely and uniformly disperse the ITO fine particles in the resin. By using the dispersant, the ITO fine particles can be finely and uniformly dispersed in the film, and the haze of the film can be further improved. The dispersant may be added to the dispersion medium in advance and used, or may be added and used when the ITO fine particles are mixed with the resin.

As the dispersant, a sulfuric ester compound,
Examples of the dispersant generally used as a dispersant for inorganic fine particles include a phosphate ester compound, a carboxylate, a polyhydric alcohol type surfactant, and a compound having at least one or more carboxyl groups. Among these, a phosphate compound and a compound having at least one carboxyl group are preferably used as the dispersant. Examples of phosphoric acid ester compounds include alkyl phosphoric acid ester salts, polyoxyethylene alkylphenol ether phosphates, polyoxyethylene alkyl ether phosphoric acid, and the like. Further, as the compound having at least one or more carboxyl groups, a hydroxy acid,
Particularly, ricinoleic acid and polyricinoleic acid are preferably used.

The amount of the dispersant is preferably 0.001 to 5.0 parts by weight, more preferably 0.005 to 3.0 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin. If the amount of the dispersant is less than 0.001 part by weight, the effect of addition is hardly expected, and if it exceeds 5.0 parts by weight, foaming occurs during film formation and during the production of laminated glass, and the interlayer film and the glass are separated. The adhesive strength may be too high.

When the ITO fine particles are dispersed,
A dispersion aid other than the dispersant may be used, and examples of the dispersion aid include compounds having at least one carboxyl group excluding the above-mentioned ricinoleic acid and polyricinoleic acid, and chelating agents. The chelating agent is not particularly limited, and may be EDTA or β-
It is possible to use diketones and the like, but those having good compatibility with plasticizers and resins are preferable, and among the chelating agents, acetylacetone, benzoyltrifluoroacetone, and β-diketones such as dipivaloylmethane are preferable. , And more preferably, acetylacetone is preferably used. It is considered that the haze is improved by coordinating the chelating agent with the ITO fine particles to prevent aggregation of the ITO particles. The amount of the chelating agent added is preferably 0.001 to 2 parts by weight, more preferably 0.02 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin.
It is 1 to 1 part by weight. If the amount exceeds 2 parts by weight, foaming may occur during film formation or foaming during laminated glass production.
If it is less than 0.001 part, almost no effect can be expected.

Examples of the compound having one or more carboxyl groups excluding the above-mentioned ricinoleic acid and polyricinoleic acid include aliphatic carboxylic acid, aliphatic dicarboxylic acid, aromatic carboxylic acid, aromatic dicarboxylic acid, hydroxy acid and the like. Specifically, benzoic acid, phthalic acid, salicylic acid, etc. can be used. Among them, C2 to C18 aliphatic carboxylic acids and hydroxy acids are preferably used, and more preferably C2 to C10 aliphatic carboxylic acids. Specifically, acetic acid, propionic acid, n-butyric acid, 2-ethylbutyric acid,
Examples thereof include n-hexanoic acid, 2-ethylhexanoic acid and n-octanoic acid.

The amount of the compound having one or more carboxyl groups excluding the above-mentioned ricinoleic acid and polyricinoleic acid is 0.001 to 2 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin, and a more preferable addition amount. Is 0.
It is from 01 to 1 part by weight. If the amount exceeds 2 parts by weight, there is a risk of yellowing of the film or a decrease in the adhesive force between the glass and the film.
If it is less than 001 parts by weight, it is difficult to recognize the effect of addition.

In the interlayer film for laminated glass of the present invention, an antioxidant may be added, if necessary, within a range that does not impair the effects of the invention.
Additives such as an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, an adhesive strength adjusting agent, a moisture resistance agent, a heat ray reflecting agent, and a heat ray absorbing agent may be added.

The thickness of the interlayer film for laminated glass of the present invention is
Although not particularly limited, in consideration of the minimum penetration resistance and weather resistance required for the laminated glass, it is practically preferable that the thickness is 0.3 to 0.8 mm. In addition, the interlayer films for laminated glass of the present invention may be used together, or the interlayer film for laminated glass of the present invention and another interlayer film may be laminated and used, if necessary, such as improvement in penetration resistance.

The interlayer film of the present invention can be obtained by laminating the above-mentioned interlayer film for laminated glass and glass, but the glass is not particularly limited, and a commonly used transparent plate glass can be used. The glass may be ordinary glass, but 9
A heat ray absorbing glass that blocks infrared rays in the wavelength range of 00 nm to 1300 nm is preferable, and 900 nm to 1300 nm
The heat ray absorbing glass having a transmittance of 65% or less in all wavelength regions of is particularly preferable. The infrared ray blocking performance of ITO fine particles is greater than 1300 nm on the long wavelength side, and 900 nm to
Since it is relatively small in the wavelength range of 1300 nm, 900
By combining with glass that absorbs infrared rays in the wavelength range of 1 nm to 1300 nm, a wide range of infrared rays can be blocked and the heat shield effect can be enhanced. As the glass used as the laminated glass, so-called organic glass such as polycarbonate and polymethylmethacrylate having excellent transparency may be used in addition to the inorganic glass.

The method for obtaining the interlayer film for laminated glass of the present invention is not particularly limited, and includes polyvinyl acetal resin, layered silicate, plasticizer, adhesive strength adjusting agent, IT.
The O fine particles and the dispersant may be kneaded to form a film. At this time, it is particularly preferable that the layered silicate previously dispersed in the plasticizer is added to the resin and kneaded. By mixing the layered silicate and the plasticizer in advance, the layered silicate is swollen by the plasticizer, and the layers of the layered silicate are spread, so that the layered silicate easily becomes finely dispersed in the resin when mixed with the resin. Is. In this case, a part of the plasticizer and the total amount of the layered silicate may be once mixed, and then the remaining amount of the plasticizer may be further added and mixed. Further, as described above, it is preferable to add the ITO fine particles in a state of being dispersed in the dispersion medium in advance.

The apparatus for mixing the plasticizer and the layered silicate, the ITO fine particles, the plasticizer and the dispersant is not particularly limited,
A planetary stirring device, a wet mechanochemical device, a Henschel mixer, a homogenizer, an ultrasonic wave irradiator, etc. are generally used. Moreover, the apparatus used for kneading the polyvinyl acetal resin, the layered silicate, the plasticizer, the adhesiveness adjusting agent, the ITO fine particles and the dispersant is not limited, but an extruder, a plastograph, a kneader, a Banbury mixer, a calendar. A roll or the like can be used. In particular, it is preferable to use an extruder from the viewpoint of continuous production. The method for molding the interlayer film for laminated glass of the present invention is not particularly limited, and the film may be formed by an extrusion method, a calender method, a pressing method, or the like, but more preferably, an extrusion method in the same two axes. The haze can be further improved.

The laminated glass of the present invention has a haze of 1.0.
% Or less, the visible light transmittance is 70% or more, and the solar radiation transmittance is preferably 80% or less of the visible light transmittance. Here, visible light refers to light with a wavelength of 380 to 780 nm, and solar radiation transmitted light is light with a wavelength of 300 to 2500 nm. The haze of the laminated glass is 1.0% or less, and the visible light transmittance is 70.
% Or more, the transparency is excellent, and if the solar radiation transmittance (300 to 2500 nm) is 80% or less of the visible light transmittance, the transmittance of light in the infrared region on the longer wavelength side than visible light. It has excellent heat-shielding property because it decreases.

The laminated glass using the interlayer film for laminated glass of the present invention can be suitably used for windshields and side glasses of automobiles, glass parts of vehicles such as airplanes and trains, and architectural glass. Furthermore, by laminating it with another film, it can be used as a functional laminated glass such as a sound-insulating laminated glass having sound-insulating properties. Further, the interlayer film for laminated glass of the present invention can be applied as a damping material by laminating it with a rigid body other than glass, for example, a metal or an inorganic material.

(Function) Usually, an additive having a size equal to or larger than the wavelength of visible light, such as a bulk layered silicate, is added to a transparent resin such as an intermediate film in which a high visible light transmittance is essential. When added to, the additive strongly scatters visible light, which causes problems such as reduction in visible light transmittance and deterioration of haze. However, in the present invention,
As described above, when the layered silicate is dispersed in the resin, the layered silicate can be efficiently and finely dispersed by the plasticizer penetrating between the layers, so that the transparency is secured. Moreover, since it is not necessary to remove the plasticizer, an interlayer film for laminated glass having excellent physical properties can be easily obtained. In other words, while maintaining a high visible light transmittance, it is possible to modify the intermediate film (combining mechanical strength and strength and flexibility), which is the original purpose of adding an inorganic substance, and is excellent in transparency and mechanically. An interlayer film for laminated glass having both strength and flexibility can be obtained.

On the other hand, since the ITO fine particles which are transparent and have the ability to absorb infrared rays are finely dispersed in the intermediate film, an intermediate film having a heat shielding effect can be obtained while maintaining the transparency. Since the ITO fine particles are uniformly dispersed in the state of nano-scale ultrafine particles, they are sufficiently smaller than visible light and do not scatter, so that an intermediate film having excellent transparency, particularly a haze value, can be obtained. Furthermore, since the ITO fine particles are finely dispersed in the intermediate film in the form of ultrafine particles, heat ray reflection using heat-reflective glass or heat ray reflection PET, which has been conventionally used for heat-shielding intermediate films, by vapor deposition or coating. Unlike laminated glass, reflection in the communication wavelength band does not occur, and when it is made of laminated glass, it does not pose any problem for communication functions such as mobile phones, car navigation systems, and garage openers. Further, by using ITO ultrafine particles dispersed in a plasticizer in advance, it can be treated in the same manner as in the usual method for producing an intermediate film, and can be obtained in the same manner as in the past without impairing processability, workability, productivity and the like. .

As a secondary effect of the addition of the layered silicate, generally, the finer the layered silicate is dispersed in the resin, the mechanical properties of the thermoplastic resin-layered silicate composite. Strength, gas barrier property, and transparency are remarkably improved. This can be explained by the fact that the interfacial area between the layered silicate and the resin increases as the dispersion of the layered silicate increases. That is, since the molecular motion of the polymer is restricted at the interface between the resin and the inorganic crystal, the mechanical strength such as the elastic modulus of the polymer increases, and the more the degree of dispersion of the layered silicate is improved, the more efficiently the polymer strength is increased. Can be increased. In addition, since gas molecules are far more likely to diffuse in the resin layer as compared with inorganic substances, when the gas molecules diffuse in the composite material, they diffuse while circumventing the inorganic substances. Therefore, the higher the degree of dispersion of the layered silicate, the more efficiently the gas barrier can be improved. As described above, by compounding the ITO ultrafine particles and the layered silicate on the nanoscale, various functions can be given to the intermediate film.

[0044]

EXAMPLES The contents of the present invention will be described below based on Examples and Comparative Examples. Examples 1-9, Comparative Examples 1-4, 6-7 [Synthesis of polyvinyl butyral] 2890 g of pure water, P
275 g of VA resin (average degree of polymerization 1700, degree of saponification 99.2 mol%) was added and dissolved by heating. The temperature of the reaction system was adjusted to 15 ° C., 201 g of 35 wt% hydrochloric acid and 157 g of n-butyraldehyde were added, and this temperature was maintained to precipitate the reaction product. Then, the reaction system was kept at 60 ° C. for 3 hours to complete the reaction, washed with excess water to wash off unreacted n-butyraldehyde, and the hydrochloric acid catalyst was neutralized with an aqueous sodium hydroxide solution. After washing with water for 2 hours and drying, a PVB resin in white powder form was obtained. The average degree of butyralization of this resin was 68.5 mol%.

[Preparation of ITO Dispersion Plasticizer] 20 parts by weight of triethylene glycol-di-2-ethylhexylate was mixed with ITO powder (average particle diameter of primary particles: 30 nm).
1 part by weight was charged and ITO fine particles were dispersed in the plasticizer by a horizontal microbead mill using a phosphoric acid ester of nonylphenyl polyethylene oxide as a dispersant. Then, 0.1 part by weight of acetylacetone was added to the solution under stirring to prepare an ITO dispersion plasticizer.
The average particle diameter of the ITO fine particles of the dispersion plasticizer was 35 nm. [Preparation of Layered Silicate Dispersion Plasticizer] 20 parts by weight of triethylene glycol-di-2-ethylhexylate and 1 part by weight of swelling mica (trade name MAE, manufactured by Corp Chemical), a planetary type The mixture was mixed for 1 minute with a stirrer to obtain a pasty layered silicate dispersion plasticizer.

[Production of Intermediate Film for Laminated Glass] 100 parts by weight of the PVB resin obtained above, a predetermined amount of ITO dispersion plasticizer such that the amount of ITO fine particles is shown in Table 2, and the amount of layered silicate shown in Table 2 Of a layered silicate dispersion plasticizer such that the total amount of the plasticizer (triethylene glycol-di-2-ethylhexylate) is 40 parts by weight, In contrast, the magnesium content is 6
After sufficiently melting and kneading a predetermined amount of 2-ethyl magnesium butyrate to 0 ppm with a mixing roll, press molding is performed at 150 ° C. for 30 minutes using a press molding machine to obtain an intermediate film having an average film thickness of 0.76 mm. It was The average particle diameter of ITO fine particles in the film was 56 nm, and particles having a particle diameter of 100 nm or more were not observed. No layered silicate having a thickness of 1 μm or more was observed.

[Manufacture of Laminated Glass] The interlayer film for laminated glass obtained above is sandwiched from both ends by transparent float glass (length 30 cm × width 30 cm × thickness 2.5 mm), and this is placed in a rubber bag. After putting in and degassing at a vacuum degree of 20 torr for 20 minutes, it was transferred to an oven while being degassed, and further vacuum pressed while holding at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was heated in an autoclave at 135 ° C. under a pressure of 1.2 MPa.
Bonding was performed for 0 minutes to obtain a laminated glass.

Comparative Example 5 ITO having 5 parts by weight of ITO fine particles dispersed in 20 parts by weight of triethylene glycol-di-2-ethylhexylate
Example 1 was repeated except that a dispersion plasticizer was used. Comparative Example 8 Example 1 was repeated except that a layered silicate-dispersed plasticizer in which 23 parts by weight of layered silicate was dispersed in 20 parts by weight of triethylene glycol-di-2-ethylhexylate was used. Comparative Example 9 Using ITO, a normal interlayer film (average thickness of 0.76 mm) containing no layered silicate, one float glass used for producing a laminated glass is laminated and coated with a silver thin film and a metal oxide thin film. Laminated glass was produced as the heat ray reflective glass. Comparative Example 10 Two ordinary interlayer films (average thickness 0.38 mm) not containing ITO and layered silicate sandwiched a heat ray-reflective PET in which a silver thin film and a metal oxide thin film were laminated and coated, and further transparent from both ends. Laminated glass was created with float glass.

[Evaluation] The interlayer films for laminated glass and laminated glass obtained in the above Examples and Comparative Examples were evaluated as follows, and the results are summarized in Tables 2 and 3. 1) Optical characteristics Direct recording A spectrophotometer (“UV3100” manufactured by Shimadzu Corporation) was used to measure the transmittance of the laminated glass at 300 to 2500 nm, and JIS Z 8722 and JIS R3106 were used.
(1988), visible light transmittance (Tv) of 380 to 780 nm, and solar radiation transmittance (T of 300 to 2500 nm).
s) was calculated. 2) Haze The haze of the laminated glass was measured according to JIS K6714.

3) Dispersion state of ITO fine particles in the film After the ultrathin piece of the intermediate film was prepared, the dispersion state of the ITO fine particles was photographed and observed using a transmission electron microscope (TEM). The particle size of the ITO fine particles was the longest diameter of the ITO fine particles in the photograph obtained by the above photographing. Further, the particle size of all the ITO fine particles in the above-mentioned photographing range of 10 μm × 10 μm was measured, and the average particle size was obtained by volume conversion average.
Further, the number of fine particles having a particle diameter of 100 nm or more existing in the above photographing range was obtained, and the number per 1 μm ² was calculated. (1) Observation device, conditions-Transmission electron microscope: H-7100FA type (manufactured by Hitachi, Ltd.)-Acceleration voltage: 100 kV (2) Section preparation device-Ultramicrotome: EM-ULTRACUT-S (manufactured by Leica) ) ・ Freezing cutting system: REICHERT-NISSEI-FCS (manufactured by Leica) ・ Knife: DIATOME ULTRA CRYO DRY (manufactured by DIATOME) 4) Dispersion in layered silicate film Scanning using an interlayer film for laminated glass as a sample 10μm × 10μm at arbitrary position using scanning electron microscope (SEM)
The number of particles with a major axis of 1 μm or more is determined by observing the range
The number per μm ² was determined. (1) Observation device, conditions-Scanning electron microscope: S-3500N (manufactured by Hitachi, Ltd.)-Acceleration voltage: 15 KV

5) Electromagnetic wave transmission The reflection loss value (dB) in the range of 0.1 to 10 MHz by KEC method measurement (measurement of electromagnetic wave shielding effect in the near field).
On the other hand, a sample of 600 mm square is placed between a pair of transmitting and receiving antennas, and the radio wave from the radio wave signal generator is received by a spectrum analyzer (far field electromagnetic wave measuring method), and 2 to 26.5 GHz. Reflection loss ratio (d
B) was measured. The maximum value and the minimum value of the loss in the entire frequency range were obtained and used as an index of the electromagnetic wave shielding property. 6) Panmel laminated glass was adjusted by leaving it at a temperature of −18 ± 0.6 ° C. for 16 hours, and crushed with a hammer having a head of 0.45 kg until the glass particle size became 6 mm or less. . The degree of exposure of the film after the glass was partly peeled off was judged by a pre-graded limit sample, and the result was determined in accordance with Table 1 to obtain a Pammel value. The adhesiveness of the interlayer film to glass is evaluated by the Panmel value. The larger the Panmel value, the greater the adhesive force with the glass, and the smaller the adhesive value, the smaller the adhesive force. 7) Mechanical strength (tensile strength) Using a dumbbell No. 1 type test piece (JIS-K-6771), with a universal testing machine, temperature: 23 ° C, humidity: 50% R
A high-speed tensile test of the interlayer film was performed under the conditions of H and tensile speed: 200 mm / min. 8) Humidity resistance test Using a thermo-hygrostat, JIS R 3212 (199
2) A moisture resistance test of the laminated glass was conducted in accordance with "Automobile safety glass test method".

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

EFFECTS OF THE INVENTION According to the present invention, the layered silicate is finely dispersed in the polyvinyl acetal resin to achieve both strength and flexibility, and further, the ITO ultrafine particles are uniformly dispersed in the film to improve transparency. An interlayer film for laminated glass, which has excellent heat-shielding properties, good electromagnetic wave transparency, inexpensiveness, transparency, and particularly good haze, and whose adhesive strength can be adjusted,
Further, it is possible to provide a laminated glass using the intermediate film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/34 C08K 3/34 5/09 5/09 5/098 5/098 5/521 5/521 9 / 04 9/04 C08L 29/14 C08L 29/14 F term (reference) 4F071 AA30 AB18 AB26 AC09 AC15 AE04 AH07 AH19 BA09 BB03 BC01 BC10 BC17 4G061 AA02 AA03 AA04 AA20 AA21 AA29 BA02 CA02 CB03 CB19 DA38 CD46 CD02 CD18 CD02 CD18 CD18 DE098 DJ006 EF079 EG028 EG038 EH157 EW049 FB078 FD027 FD208 FD209 GT00

Claims (8)

[Claims] 1. A polyvinyl acetal resin, a layered silicate, a plasticizer, an adhesion control agent, ITO (tin-doped indium oxide) fine particles and a dispersant are contained, and the ITO fine particles and the layered silicate are finely and uniformly dispersed. An intermediate film characterized in that 2. Polyvinyl acetal resin 100 parts by weight, layered silicate 0.05 to 20 parts by weight, plasticizer 20 to 1
00 parts by weight, at least one or more kinds of metal salts selected from the group consisting of alkali metal salts and alkaline earth metal salts 0.0001 to 1.0 parts by weight, ITO fine particles 0.1 to 3.0
Parts by weight, and 0.001 to 5.0 parts by weight of the dispersant,
Furthermore, the layered silicate having a size of 1 μm or more is 100 μm
^The interlayer film for laminated glass according to claim 1, wherein the interlayer film is dispersed so that the number is 10 or less per ² . 3. The ITO fine particles in the film have an average particle size of 80.
The interlayer film for laminated glass according to claim 1 or 2, wherein the number of particles having a particle size of not more than 100 nm and not less than 100 nm is dispersed so as to be not more than 1 particle / μm ² . 4. The interlayer film for laminated glass according to claim 1, wherein the layered silicate is an organized layered silicate. 5. The laminated glass according to any one of claims 1 to 4, wherein the dispersant is at least one selected from the group consisting of a phosphoric acid ester system, ricinoleic acid and polyricinoleic acid. Intermediate film. 6. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin is a polyvinyl butyral resin. 7. A laminated glass using the interlayer film for laminated glass according to claim 1. 8. A haze of 1.0% or less, a visible light transmittance of 70% or more, and a solar radiation transmittance (300 nm to 2500 nm).
Is 80% or less of visible light transmittance, The laminated glass of Claim 7 characterized by the above-mentioned.