JP5897641B2 - Laminated glass interlayer film and laminated glass - Google Patents

Description

  The present invention relates to an interlayer film for laminated glass that is excellent in transparency, heat shielding properties, and weather resistance, and does not cause whitening due to moisture absorption, and a laminated glass using the interlayer film.

  Conventionally, laminated glass has been widely used as a window glass for vehicles such as automobiles, aircraft, buildings, etc., even if it is damaged by an external impact, it is safe with few glass fragments scattered. ing. As the laminated glass, a glass obtained by integrating an interlayer film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer between at least a pair of glass plates is used. ing.

However, such a laminated glass is excellent in safety, but has a problem that it is inferior in heat shielding and moisture resistance.
As the glass having a heat shielding function, for example, a heat ray cut glass is commercially available. This heat ray cut glass is obtained by applying a metal / metal oxide multi-layer coating on the surface of a glass plate by metal deposition, sputtering or the like for the purpose of directly blocking sunlight. However, since this multilayer coating is weak against external scratches and inferior in chemical resistance, for example, a method of laminating an intermediate film made of plasticized polyvinyl butyral resin or the like to form a laminated glass has been adopted.

  However, the heat ray cut glass on which the intermediate film made of the above-mentioned plasticized polyvinyl butyral resin or the like is laminated is expensive. Since the multilayer coating is thick, transparency (visible light transmittance) is lowered. There is a problem in that the adhesiveness of the film is lowered, peeling of the interlayer film or whitening occurs, or the transmission of electromagnetic waves is hindered and the communication functions of a mobile phone, a car navigation system, a garage opener, etc. are hindered.

  As other laminated glass having heat shielding performance, for example, Patent Document 1 (Japanese Patent Publication No. 61-52093), Patent Document 2 (Japanese Patent Laid-Open No. 64-36442), and the like include a plasticized polyvinyl butyral resin sheet. In the meantime, a laminated glass in which a metal-deposited polyester film is laminated has been proposed. However, this laminated glass has a problem in the adhesion between the plasticized polyvinyl butyral resin sheet and the polyester film, and there are problems such as not only peeling at the interface but also insufficient electromagnetic wave permeability. It was.

  Moreover, in this kind of laminated glass, although the above basic performance is good and excellent in safety, there is a problem that moisture resistance is inferior. That is, when the laminated glass is placed in a high humidity atmosphere, the intermediate film is in direct contact with the ambient air at the periphery of the laminated glass, causing a problem that the intermediate film at the peripheral portion is whitened. Especially in automobile side glass and windshields with exposed edges, high quality in moisture resistance has been demanded along with the open edge, etc. Glass and the like had a problem in this respect.

Japanese Patent Publication No. 61-52093 JP-A 64-36442

  In view of the above, the present invention has excellent basic performance such as transparency and weather resistance, is excellent in heat shielding properties, and even when placed in a humid atmosphere, whitening is performed on the peripheral edge of the laminated glass. It is an object of the present invention to provide an interlayer film for laminated glass suitable for obtaining a laminated glass with little occurrence, and a laminated glass using the interlayer film for laminated glass.

  The present invention is an interlayer film for laminated glass made of a plasticized polyvinyl acetal resin, and when the laminated glass is used, the laminated glass has a visible light transmittance Tv at a wavelength of 380 to 780 nm of 75% or more, 340 to Under an environment where solar transmittance Ts at 1800 nm is 60% or less, haze H is 1.0% or less, and electromagnetic wave shielding performance ΔdB at 10 to 2000 MHz is 10 dB or less, and at 80 ° C. and relative humidity 95%. The interlayer film for laminated glass has a whitening distance from the edge of the laminated glass of 7 mm or less when left for 2 weeks.

  Since the interlayer film for laminated glass of the present invention has the above-described configuration, it has excellent transparency, weather resistance, and penetration resistance, as well as excellent heat shielding properties, electromagnetic wave permeability, and adhesion to glass. Demonstrate. Furthermore, since the interlayer film for laminated glass of the present invention is excellent in moisture resistance, whitening hardly occurs in the peripheral portion even when placed under high humidity, and it is suitably used for window glass of vehicles, buildings, etc. It is done.

  The present invention is described in detail below.

  Since the laminated glass produced using the interlayer film for laminated glass of the present invention has the properties as described above, it is excellent in transparency, heat shielding properties and weather resistance, and is not easily whitened by moisture absorption. When the interlayer film for laminated glass of the present invention is used as laminated glass, if the Tv of the laminated glass is less than 75%, the transparency becomes small, which is not preferable in practical use. When Ts of the laminated glass exceeds 60%, the heat shielding property becomes insufficient. When H of the laminated glass exceeds 1.0%, the transparency is small, which is not preferable for practical use. When ΔdB of the laminated glass exceeds 10 dB, the electromagnetic wave permeability becomes insufficient. Further, when the whitening distance from the edge of the laminated glass exceeds 7 mm when left in an environment of 80 ° C. and relative humidity of 95% for 2 weeks, the moisture resistance becomes insufficient.

  The interlayer film for laminated glass of the present invention is made of a plasticized polyvinyl acetal resin. It does not specifically limit as a polyvinyl acetal resin used for the said plasticization polyvinyl acetal resin, The thing of the kind conventionally used as resin for interlayer films for safety glass can be used, for example, butyralization degree 60-75 mol%, polymerization degree 800-3000 polyvinyl butyral or the like is preferably used.

The plasticized polyvinyl acetal resin used in the interlayer film for laminated glass according to the present invention is obtained by plasticizing a polyvinyl acetal resin with a plasticizer.
The plasticizer is not particularly limited, and all of the plasticizers that have been presented so far can be used. For example, triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol -Di-2-ethylbutyrate (3GH), dihexyl adipate (DHA), tetraethylene glycol-di-heptanoate (4G7), tetraethylene glycol-di-2-ethylhexanoate (4GO), etc. are preferably used. . These may be used alone or in combination of two or more.

In the interlayer film for laminated glass of the present invention, the content of the plasticizer is preferably 20 to 60 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin.
If the content of the plasticizer is less than 20 parts by weight relative to 100 parts by weight of the polyvinyl acetal resin, the impact resistance of the interlayer film for laminated glass obtained may be lowered. If it exceeds 60 parts by weight, the plasticizer may bleed out and the adhesive force may be reduced.

  In the interlayer film for laminated glass of the present invention, the plasticized polyvinyl acetal resin preferably contains metal oxide fine particles having a heat ray cutting function. By including the metal oxide fine particles having a heat ray cutting function, the obtained interlayer film for laminated glass has excellent heat shielding properties, excellent optical properties such as haze transmittance, and good electromagnetic waves. It will have transparency.

  The metal oxide fine particles having a heat ray cutting function used for the interlayer film for laminated glass of the present invention are one or more metals selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, and aluminum-doped zinc oxide. An oxide is preferable.

  In the interlayer film for laminated glass of the present invention, the content of the metal oxide fine particles is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. If the content is less than 0.1 parts by weight, the infrared cut effect may be difficult to achieve. If it exceeds 3.0 parts by weight, the transmittance of visible light may decrease.

  In the interlayer film for laminated glass of the present invention, it is preferable that the metal oxide fine particles are uniformly dispersed in the plasticized polyvinyl acetal resin. When the metal oxide fine particles are uniformly dispersed in the film, the heat insulating property of the obtained interlayer film for laminated glass becomes high throughout the film.

  The method for dispersing the metal oxide fine particles in the polyvinyl acetal resin is not particularly limited, but a method of adding a dispersion in which the metal oxide fine particles are dispersed in a plasticizer with a dispersant to the polyvinyl acetal resin is preferable. . By the above method, the metal oxide fine particles are uniformly dispersed in the film.

The dispersant is not particularly limited, and any commercially available dispersant may be used as long as it is soluble in the plasticizer and has good dispersibility, and examples thereof include castor oil fatty acid, phosphate ester, polycarboxylic acid and the like. These may be used alone or in combination of two or more.
By including the dispersant, the resulting interlayer film for laminated glass has a high degree of moisture resistance.
Further, in order to further improve the moisture resistance, a dispersant may be added afterwards.

  In the interlayer film for laminated glass of the present invention, the method for dispersing the metal oxide fine particles in the plasticizer is not particularly limited. However, the plasticizer, the dispersant and the metal oxide fine particles are mixed to disperse the general paint. It can disperse | distribute with apparatuses, such as a sand mill, a ball mill, a homogenizer, an attritor, a high-speed rotation stirring apparatus, an ultrasonic dispersion apparatus, used for a mixing | blending.

  Further, the dispersion obtained by dispersing the metal oxide fine particles obtained by the above method is directly added to the plasticized polyvinyl acetal resin so that the ratio of the metal oxide fine particles contained in the interlayer film for laminated glass is in the above range. Alternatively, it may be added in advance to the plasticizer and then mixed with the polyvinyl acetal resin.

In addition, the interlayer film for laminated glass of the present invention may contain an adhesion adjusting agent as necessary.
As said adhesive force regulator, an organic metal or an inorganic acid alkali metal salt, alkaline-earth metal salt, etc. are used suitably, for example.
It does not specifically limit as said alkali metal salt and alkaline-earth metal salt, For example, salts, such as potassium, sodium, magnesium, are mentioned. The organic acid is not particularly limited, and examples thereof include carboxylic acids such as octylic acid, hexyl acid, butyric acid, acetic acid, and formic acid. It does not specifically limit as said inorganic acid, For example, hydrochloric acid, nitric acid, etc. are mentioned. These adhesive strength modifiers may be used alone or in combination of two or more.

Among the alkali metal salts and alkaline earth metal salts of organic acids or inorganic acids, alkali metal salts of organic acids having 2 to 16 carbon atoms and alkaline earth metal salts of organic acids having 2 to 16 carbon atoms are preferable. More preferably, it is a magnesium salt of a carboxylic acid having 2 to 16 carbon atoms.
The magnesium salt of a carboxylic acid having 2 to 16 carbon atoms is not particularly limited, and examples thereof include magnesium acetate, magnesium propionate, magnesium 2-ethylbutanoate, and magnesium 2-ethylhexanoate. These may be used alone or in combination of two or more.

  As for content of the said adhesive force regulator, 0.001-0.5 weight part is preferable with respect to 100 weight part of polyvinyl acetal resins. If it is less than 0.001 part by weight, the adhesive strength of the peripheral part may decrease in a high humidity atmosphere. If it exceeds 0.5 parts by weight, the adhesive strength of the interlayer film for laminated glass obtained becomes too low, and the transparency of the film may be lost. The content of the adhesive strength modifier is more preferably 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin.

Moreover, you may use together the modified silicone oil currently disclosed by Japanese Patent Publication No.55-29950 as an adhesive force regulator.
The modified silicone oil is generally a viscous liquid obtained by reacting a compound to be modified with polysiloxane. The modified silicone oil is not particularly limited, and examples thereof include ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, and amine-modified silicone oil. These may be used alone or in combination of two or more.

  The content of the modified silicone oil is preferably 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. If it exceeds 0.5 parts by weight, the adhesive force between the obtained interlayer film for laminated glass and the glass becomes too low, and peeling, foaming and the like occur. More preferably, it is 0.02-0.2 weight part.

  In the interlayer film for laminated glass of the present invention, as other additives, an antioxidant for preventing deterioration due to heat in the extruder, an ultraviolet absorber for improving weather resistance and light resistance, various stabilizers, etc. 1 type (s) or 2 or more types may be added.

  The antioxidant is not particularly limited, and examples thereof include phenol-based products such as trade name “Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd. and trade name “Irganox 1010” manufactured by Ciba Geigy. These may be used alone or in combination of two or more.

  The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole-based products such as trade names “Tinuvin P”, “Tinuvin 320”, “Tinuvin 326”, and “Tinuvin 328” manufactured by Ciba Geigy. These may be used alone or in combination of two or more.

  The method for molding the interlayer film for laminated glass of the present invention is not particularly limited. For example, the polyvinyl acetal resin, the plasticizer, the metal oxide fine particles, the dispersant, and various additions added as necessary. After mixing with an agent and kneading it uniformly, the film may be formed into a sheet by an extrusion method, a calendering method, a pressing method, a casting method, an inflation method, or the like.

  The total film thickness of the interlayer film for laminated glass of the present invention is not particularly limited. However, in consideration of the minimum penetration resistance and weather resistance required for laminated glass, practically 0.3 mm It is preferable that it is -0.8mm.

Since the interlayer film for laminated glass of the present invention has the above-described configuration, it is excellent in transparency, heat shielding properties, electromagnetic wave permeability, light resistance and the like, and has good adhesion force adjustment with glass. Furthermore, whitening due to moisture absorption hardly occurs.
The present invention 2 is a laminated glass formed by integrating the interlayer film for laminated glass of the present invention 1 between at least one pair of glass plates.

  The method for producing the laminated glass of the present invention 2 is not particularly limited. For example, the interlayer film for laminated glass of the present invention 1 is sandwiched between two transparent glass plates, and this is placed in a rubber bag and sucked under reduced pressure. Pre-bonding at a temperature of about 70 to 110 ° C., and then performing main bonding at a temperature of about 120 to 150 ° C. and a pressure of about 1 to 1.5 MPa using an autoclave to obtain a desired laminated glass Can do.

  It does not specifically limit as said glass plate, For example, various inorganic glass plates, such as float plate glass, polished plate glass, type | mold plate glass, netted glass, wire-containing glass, colored plate glass, etc. are mentioned. These may be used alone or in combination of two or more.

  In addition, the interlayer film for laminated glass of the present invention 1 may be sandwiched between organic glass other than inorganic glass, that is, a transparent body having high rigidity. As said transparent body, what consists of polycarbonate resin etc. are mentioned, for example.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
As the polyvinyl acetal resin, a polyvinyl butyral resin having a butyralization degree of 68 mol%, a residual acetylation degree of 1 mol%, a residual vinyl alcohol of 31 mol%, and an average polymerization degree of 1700 was used.
100 parts by weight of this polyvinyl butyral resin, 40 parts by weight of triethylene glycol di-2-ethylhexanoate as a plasticizer, and tin-doped indium oxide (ITO) in the interlayer film have a content of 1.0% by weight. Then, 50 ppm of magnesium acetate, an ultraviolet absorber, and an antioxidant were added as an adhesive strength adjusting agent, and the mixture was supplied to a mixing roll and kneaded. The kneaded product obtained by kneading was press molded at 150 ° C. for 30 minutes with a press molding machine to obtain an intermediate film having a thickness of about 0.8 mm. At this time, 0.4 part by weight of Prisurf A212E (Daiichi Kogyo Seiyaku Co., Ltd.) was contained as a dispersant. This interlayer film was adjusted in a constant temperature and humidity chamber so that the water content was 0.3 to 0.5%, sandwiched between two 2.4 mm thick float glass sheets, and preliminarily bonded by a roll method. Subsequently, it pressure-bonded by the pressure of 1.2 MPa with the 140 degreeC autoclave, and the laminated glass was obtained.

The performance of the obtained laminated glass was evaluated by the following method, and the results are shown in Table 1.
1) Moisture resistance The laminated glass was placed in an environment of 80 ° C. and a relative humidity of 95% for 2 weeks, and immediately after taking out, the whitening state of the edge was confirmed. The whitening distance from the periphery of the laminated glass was measured and evaluated.

2) Optical characteristics Using a spectrophotometer (manufactured by Shimadzu Corporation, UV3100), the transmittance of the laminated glass at 340 to 1800 nm was measured. The visible light transmittance Tv of ˜780 nm and the solar radiation transmittance Ts of 340 to 1800 nm were evaluated.

3) Haze H
The measurement was performed according to JIS K 6714.
4) Electromagnetic wave transmittance Based on KEC method measurement (electromagnetic wave shielding effect test), the reflection loss value (dB) in the range of 10 to 2000 MHz is measured in comparison with a normal float glass single plate having a thickness of 3 mm, and the above The maximum difference in the frequency range was evaluated as ΔdBmax.

5) Pummel value The adhesion of the interlayer film to the glass was evaluated by the pummel value. The details of the test method are as follows.
The laminated glass was adjusted by allowing it to stand at a temperature of −18 ° C. ± 0.6 ° C. for 16 hours, and this was crushed with a hammer having a head of 0.45 kg until the particle size of the glass became 6 mm or less. Next, the degree of exposure of the film after partial peeling of the glass was determined using a pre-graded limit sample, and the result was expressed as a Pummel value according to the determination criteria shown in Table 1. In addition, the larger the Pummel value, the larger the adhesive force between the interlayer film and the glass, and the smaller the Pummel value, the smaller the adhesive force between the interlayer film and the glass.

Example 2
A laminated glass was obtained by forming a film in the same manner as in Example 1 except that Dispersant Price Surf A212E was added so that the content thereof was 0.8 parts by weight. Moreover, it evaluated by said evaluation method using this laminated glass. The evaluation results are shown in Table 2.

Example 3
A laminated glass was obtained in the same manner as in Example 1 except that antimony-doped tin oxide (ATO) was used instead of ITO. Moreover, it evaluated by said evaluation method using this laminated glass. The evaluation results are shown in Table 2.

Comparative Example 1
In the production of the intermediate film, a laminated glass was obtained by forming a film by the same method as in Example 1 except that ITO was not added. Moreover, it evaluated by said evaluation method using this laminated glass. The evaluation results are shown in Table 2.

Comparative Example 2
In Example 1, an interlayer film was produced without adding ITO, and laminated glass was obtained using glass on which ITO was vapor-deposited instead of transparent float plate glass. Moreover, it evaluated by said evaluation method using this laminated glass. The evaluation results are shown in Table 2.

Comparative Example 3
In Example 1, an intermediate film having a film thickness of 0.38 mm was manufactured without adding ITO, and a 50 μm-thick polyester film having ITO deposited thereon was sandwiched between the two intermediate films. Laminated glass was obtained using as an interlayer film. Moreover, it evaluated by said evaluation method using this laminated glass. The evaluation results are shown in Table 2.

  From Table 2, the laminated glass produced in Examples 1 to 3 has excellent transparency and heat shielding properties, good electromagnetic wave permeability, and excellent moisture resistance that hardly causes whitening even when placed in a high humidity environment. It was what had. On the other hand, the laminated glass produced in Comparative Example 1 had poor moisture resistance. The laminated glass produced in Comparative Examples 2 and 3 had poor electromagnetic wave permeability and poor moisture resistance.

Claims (3)

An interlayer film for laminated glass made of plasticized polyvinyl acetal resin,
The plasticized polyvinyl acetal resin is obtained by plasticizing a polyvinyl acetal resin with a plasticizer,
The plasticized polyvinyl acetal resin contains metal oxide fine particles having a heat ray cutting function,
When a laminated glass is formed by sandwiching an intermediate film between two 2.4 mm thick float glass sheets, the laminated glass has a visible light transmittance Tv of 75% or more at a wavelength of 380 to 780 nm and 340 to 1800 nm. The solar radiation transmittance Ts is 60% or less, the haze H is 1.0% or less, and the electromagnetic wave shielding performance ΔdB at 10 to 2000 MHz is 10 dB or less. When left for a week, the whitening distance from the edge of the laminated glass is 7 mm or less,
The separate and phosphoric acid ester plasticizer, as bond strength control agent, see contains a magnesium salt of a carboxylic acid having 2 to 16 carbon atoms,
An interlayer film for laminated glass , wherein the plasticizer plasticizing the polyvinyl acetal resin is triethylene glycol di-2-ethylhexanoate . Metal oxide fine particles having a heat-ray shielding function, according to claim 1, wherein the tin-doped indium oxide, at least one metal oxide selected from antimony-doped tin oxide and the group consisting of aluminum-doped zinc oxide Interlayer film for laminated glass. A laminated glass comprising an interlayer film for laminated glass according to claim 1 or 2 interposed between at least one pair of glass plates and integrated.