JPH0343219B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an interlayer film for laminated glass. Laminated glass, which is widely used in the windows of various types of transportation such as automobiles and aircraft, and buildings, is usually made by laminating two sheets of glass together with an interlayer film made of plasticized polyvinyl acetal resin interposed therebetween. It is used. The laminated glass described above is not easily damaged due to the fact that even if the glass breaks when an impact is applied to it, the interlayer film interposed between the glasses does not easily break and has the ability to absorb the impact. Objects do not penetrate easily, and the glass bonded by the interlayer film remains attached to the interlayer film even after it is broken, so its fragments do not scatter, making it easier to transport. No significant harm will be caused to the human body inside the engine or building. However, in order to more safely protect the human body from external impacts, and from the above-mentioned circumstances, it has become a social demand to further improve the penetration resistance of laminated safety glass by improving the interlayer film used. ing. For this reason, for example, it is known that an interlayer film contains an alkali metal or alkaline earth metal carboxylate and a modified silicone oil as a penetration resistance increasing agent, and two pieces of glass are bonded together through the interlayer film. There is. However, the above-mentioned conventional interlayer film is
There was a drawback that the manufacturing temperature conditions for the resulting laminated glass were limited to a narrow range. In view of the current state of laminated glass and interlayer films, the present invention provides an interlayer film for laminated glass that can produce laminated glass having high penetration resistance that can be put to practical use over a wide processing temperature range. It was made for the purpose of However, the gist of the invention is that a plasticized polyvinyl acetal resin contains a magnesium salt of a linear monocarboxylic acid and a modified silicone oil in a blending ratio that satisfies formula (1). Intermediate film. (1) 3.9≦Y/X+0.24C≦4.5 and 0.05≦Y/X (Y is the number of parts by weight of modified silicone oil based on 100 parts by weight of polyvinyl acetal resin, C is the total number of carbon atoms in the carboxylate salt and represents an integer from 8 to 18). A wide variety of conventionally known plasticized polyvinyl acetal resins can be used as the plasticized polyvinyl acetal resin in the present invention, such as polyvinyl butyral resin and triethylene glycol-2-ethyl butyrate, triethylene glycol di-2-ethylhexoate, or dibutyl sebacate. A resin composition containing a plasticizer is used. The degree of butyralization of the polyvinyl butyral resin is preferably 55 to 80 mol%, and the amount of plasticizer is 20 to 60 parts by weight per 100 parts by weight of the polyvinyl butyral resin.
Parts by weight are preferred. Known methods may be used to form the above-mentioned plasticized polyvinyl acetal resin into an interlayer film, such as extrusion molding into a sheet using an extruder or molding into a sheet using a heating roll. Methods etc. may be adopted as appropriate. Next, in the present invention, the magnesium salt of a linear monocarboxylic acid applied to the above-mentioned interlayer film is a compound having a total carbon number of 8 to 18, and preferably has the general formula (k, k': integers of 2 to 7) are used, and more preferably, each of k and k' is 5.
~7 magnesium salts are used. In the present invention, examples of the modified silicone oil applied to the interlayer film together with the monocarboxylic acid salt include ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, amine-modified silicone oil, etc. Oils are generally viscous liquids obtained by reacting polysiloxanes with compounds to be modified. In the present invention, formula (2) (n, m are positive integers x of 30 or less, y are positive integers of 20 or less) Ether-modified silicone oil represented by formula (3) (n, m are positive integers of 30 or less) Epoxy-modified silicone oil or formula 4 (n, m are positive integers of 30 or less) An ester-modified silicone oil represented by the following is particularly preferably used. Furthermore, each modified silicone oil represented by the above general formula is represented by the structural formula of a block copolymer, but in the present invention, one represented by the structural formula of a random copolymer is also used. Also used in the same way. Further, in the present invention, the blending ratio of the magnesium salt of a linear monocarboxylic acid and the modified silicone oil applied to the above-mentioned interlayer film is set as shown in the above-mentioned formula (1). In other words, the blending ratio of the carboxylate and the silicone oil needs to be changed depending on the number of carbon atoms in the carboxylate. Specifically, the smaller the number of carbon atoms in the carboxylate, the greater the amount of silicone oil used. However, as the number of carbon atoms in the carboxylate increases, the amount of silicone oil needs to be reduced. In addition, the amount of the above carboxylate used is usually 0.005 to 100 parts by weight of polyvinyl acetal resin.
The amount is 0.5 parts by weight, preferably 0.01 to 0.2 parts by weight. The amount of the above modified silicone oil used is usually 0.0005 parts by weight per 100 parts by weight of polyvinyl acetal resin.
~0.75 parts by weight, preferably 0.001 to 0.3 parts by weight. The reason for this is that the object of the present invention can be achieved within the range of the amount used, and if the amount used is too large, the quality of the resulting laminated glass, such as transparency, tends to deteriorate. The interlayer film of the present invention is obtained by incorporating the above-mentioned carboxylic acid salt and modified silicone oil into the above-mentioned plasticized polyvinyl acetal resin. A preferred method for incorporating the polyvinyl acetal resin is to manufacture an interlayer film from a mixture of a plasticizer mixture in which a carboxylic acid salt and a modified silicone oil are mixed in advance and a polyvinyl acetal resin according to the above-mentioned molding method. Can be mentioned. Therefore, as a method for manufacturing laminated glass from glass and the plasticized polyvinyl acetal resin interlayer film of the present invention containing a carboxylic acid salt and modified silicone oil, a conventional method for manufacturing laminated glass can be used. For example, after sandwiching the interlayer film between two glass plates and preliminarily bonding them at an appropriate temperature and pressure,
An example of this method is to bond the glass and the interlayer film by holding the glass under treatment conditions of Kg/cm ² for 10 to 60 minutes to obtain a laminated glass. The interlayer film for laminated glass of the present invention is constructed as described above, and is made of plasticized polyvinyl acetal resin,
Since the magnesium salt of a linear monocarboxylic acid and the modified silicone oil are contained or attached in a blending ratio that satisfies the above formula (1), it can be used practically over a wide range of laminated glass processing temperature conditions. Therefore, a laminated glass having high penetration resistance can be obtained. In other words, if the interlayer film of the present invention is used, during the production of laminated glass, when a laminate in which the interlayer film is sandwiched between glass plates is heated and pressurized to form a laminated glass, the penetration resistance strength will change due to changes in heating temperature. The quality of laminated glass has never varied,
It is possible to obtain laminated glass with stable quality. Next, examples of the present invention will be described. The physical properties in the examples were measured using the following test methods. 1. Penetration resistance The prepared laminated glass is held horizontally by a support frame of 30 cm x 30 cm, and a 2.26 kg steel ball is freely dropped from above the laminated glass to the center of the test piece at a temperature of 20°C. The height of the falling ball is defined as the distance from the glass surface of the steel ball when the laminated glass prevents the steel ball from penetrating in 50% of the tests in which the height of the steel ball is gradually increased. Therefore, the larger the numerical value of the falling ball height, the higher the penetration resistance strength. 2. Adhesion to glass The laminated glass was adjusted by leaving it at a temperature of -18°C ± 0.6°C for 16 hours, and was crushed by hitting it with a hammer with a head weighing 0.45 kg until the particle size of the glass became 6 mm or less. After the glass has peeled off, the degree of exposure of the film is determined using pre-graded limit samples.
The results were expressed as pummel values according to Table 1.

[Table] Examples 1 to 6 100 parts by weight of polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., trade name: ESLETSUKU) having a degree of butyralization of 65 mol %, residual vinyl alcohol 24.5 %, and residual vinyl acetate 0.5 mol % was prepared. Separately, 40 parts by weight of triethylene glycol di-2-ethyl butyrate was prepared as a plasticizer, and the general formula Ether-modified silicone oil represented by (n, m=15, x=4) and general formula (k=2 to 7) and a magnesium salt of a carboxylic acid shown in Table 2 are mixed with the above plasticizer in the weight parts shown in Table 2 to prepare a plasticizer mixture. After adding and mixing the above plasticizer mixture to the above polyvinyl butyral resin, kneading with a roll at 70°C and applying a pressure of 30 kg/cm ² at a temperature of 140°C to obtain a thickness.
A 0.76 mm plasticized polyvinyl butyral resin interlayer film was obtained. The interlayer film obtained in this way was cut into appropriate sizes and left in a constant temperature and humidity chamber to adjust the moisture content to 0.47% by weight, and the interlayer film was cut to a thickness of 2.5%.
Sandwiched between two mm glass plates at 100℃, 120℃, 140℃
℃ or 160℃ autoclave temperature, 10Kg/
The laminated glass was obtained by keeping it under the pressure of ^cm2 for 20 minutes. As shown in Table 3, the penetration strength of these laminated glasses was consistently high regardless of the temperature of the autoclave. In addition, in all Examples, the pummel values of the laminated glasses obtained under each autoclave temperature condition of 100 to 160°C were measured, and all of them were 6 or more, indicating that the interlayer film of the present invention has sufficient adhesion to glass. It was shown that it has.

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[Table] Comparative Examples 1 and 2 The same modified silicone oil used in each example (Comparative Example 1) or the same carboxylic acid salt used in Example 4 (Comparative Example 2) was used as a penetration strength increasing agent. An interlayer film and a laminated glass were produced in the same manner as in the example except that the amounts shown in Table 4 were used individually, and their physical properties were measured. The penetration resistance strength was strongly influenced by the temperature of the autoclave (Table 5), and in all of the comparative examples, there were cases where the pummel value was less than 6. Comparative Examples 3 to 10 Intermediate films and composites were prepared in the same manner as in Examples, except that the same modified silicone oil as in Examples and the amounts of monocarboxylic acid magnesium salts shown in Table 4 as shown in Table 4 were used as penetration resistance strength increasing agents. Glass was manufactured and its physical properties were measured. In addition, in Comparative Examples 4 to 6, magnesium salts of branched carboxylic acids were used, in Comparative Examples 3 and 10, carboxylic acid salts having a total number of carbon atoms outside the range of 8 to 18 were used, and in Comparative Examples 7 to 9, examples were used in this order. The same magnesium salt used in Examples 2, 4, and 6 was used, but a mixture with a blending ratio of modified silicone oil that did not satisfy the above formula (1) was used. As shown in Table 5, the penetration strength was strongly affected by the temperature of the autoclave, and the strength of the laminated glass produced at 100°C or 160°C was extremely low. Furthermore, in all of the comparative examples, there were cases where the pummel value was less than 6.

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Claims (1)

[Scope of Claims] 1. A laminated glass characterized in that a plasticized polyvinyl acetal resin contains a magnesium salt of a linear monocarboxylic acid and a modified silicone oil in a blending ratio that satisfies formula (1). interlayer film. (1) 3.9≦Y/X+0.24C≦4.5 and 0.05≦Y/X (Y is the number of parts by weight of modified silicone oil based on 100 parts by weight of polyvinyl acetal resin, (C is the total number of carbon atoms in the carboxylate and represents an integer from 8 to 18.) 2. For laminated glass according to item 1, wherein the modified silicone oil is represented by formula (2). Intermediate film. (n and m are positive integers of 30 or less, and x and y are positive integers of 20 or less.) 3. The interlayer film for laminated glass according to item 1 or 2, wherein C is an integer of 14 to 18.