JPS6337052B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an interlayer film for laminated glass, and more specifically, when used as an interlayer film, it has excellent adhesive workability between the interlayer film and a glass plate, and has good light resistance and penetration resistance at low temperatures. The present invention aims to provide an improved interlayer film for laminated glass. The use of plasticized polyvinyl butyral membranes as interlayer films for bonding safety laminated glass is widely known, and plasticized polyvinyl butyral membranes are now widely used in safety glass for automobiles, aircraft, and architecture. It's being used. However, this plasticized polyvinyl butyral film has a property (hereinafter referred to as self-adhesion) that the film sticks to each other when it is rolled up after film formation because the film surface has extremely strong adhesiveness at room temperature, which prevents such adhesion. For this purpose, the membrane surface is embossed and an anti-blocking agent such as bicarbonate of soda is sprayed. Therefore, when adhering a polyvinyl butyral film and glass, there is a problem in that a washing process and a drying process must be performed in advance to remove the anti-blocking agent. In view of the above-mentioned drawbacks of conventional interlayer films for laminated glass, the present inventors have conducted intensive research on resin compositions containing vinyl chloride resin, which is a general-purpose resin, and have determined the adhesion required for interlayer films for laminated glass. We have now invented a new interlayer film for laminated glass that has excellent workability, weather resistance, and penetration resistance at low temperatures. That is, the present inventors have developed a thermoplastic resin obtained by copolymerizing vinyl chloride, glycidyl methacrylate, and at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. The interlayer film created by adding the agent in this way has low self-adhesion, and furthermore, when a fatty acid plasticizer is used as the plasticizer, the interlayer film becomes more stable at low temperatures than when other plasticizers are used. It was discovered that although the penetration resistance of the steel sheet was improved, there was still room for further improvement in terms of weather resistance. The present inventors conducted further research and discovered that an interlayer film with good weather resistance could be obtained by adding a fatty acid plasticizer and other specific plasticizers to the copolymer, thereby completing the present invention. It is something. That is, the gist of the present invention is to add a fatty acid-based thermoplastic resin to a thermoplastic resin obtained by copolymerizing vinyl chloride, glycidyl methacrylate, and at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. a plasticizer;
A phthalic acid plasticizer or a phosphoric acid plasticizer is added to the thermoplastic resin, and the thermoplastic resin has a vinyl chloride content of 80 to 80%.
An intermediate for laminated glass characterized by containing 98.5% by weight of glycidyl methacrylate, 1 to 10% by weight of glycidyl methacrylate, and 0.5 to 10% by weight of a monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. Exists in the membrane. The content of glycidyl methacrylate in the thermoplastic resin copolymer used in the present invention is 1% by weight to 10% by weight. If a copolymer containing 1% by weight or less of the monomer is used as a raw material, the adhesion between the resulting interlayer film and the glass plate will be insufficient, which is not preferable. Furthermore, if 10% by weight or more of the copolymer is used as a raw material, the resulting interlayer film will be hard and have a high softening temperature, which is unfavorable for bonding work with glass plates. Further, the content of the monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers is 0.5% by weight or more and 10% by weight or less. It is not preferable to use a copolymer containing 0.5% by weight or less of the monomer as a raw material because the resulting safety laminated glass will lack puncture resistance. When using a copolymer in an amount of 10% by weight or more, the yield during polymerization may decrease or transparency may deteriorate, which is not preferable. Suspension polymerization, emulsion polymerization, and solution polymerization can be used to carry out polymerization using the raw materials used in the present invention, but suspension polymerization is preferable from the viewpoint of thermal stability and economic efficiency. Next, the ethylene hydrocarbons used in the present invention include ethylene, propylene, and isobutylene. Vinyl fatty acids include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, and vinyl palmitate. Acrylic esters include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, and cetyl vinyl ether. When forming the copolymer used in the present invention into a film, a plasticizer is mixed in advance. Among the plasticizers to be blended, fatty acid plasticizers include dioctyl adipate, butyl diglycol adipate, dioctyl azelate, dibutyl sebacate, and diisodecyl adipate, and phthalic acid plasticizers include dioctyl phthalate, dibutyl phthalate, Diisobutyl phthalate, butylbenzyl phthalate, dilauryl phthalate, and diheptyl phthalate are mentioned, and examples of phosphoric acid plasticizers include tricylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trischloroethyl phosphate, and tris. Examples include chloroethyl phosphite and tributyl phosphate, and dioctyl adipate, diethylhexyl phthalate, and trischloroethyl phosphate are preferred in terms of compatibility with the above copolymer and other plasticizers. The interlayer film of the present invention is characterized in that these fatty acid plasticizers and a phthalic acid plasticizer or a phosphoric acid plasticizer are added to the copolymer, and the three types of plasticizers are They may be used in combination at the same time, and in some cases, epoxy derivatives, polyester derivatives, etc., which are generally called plasticizers for polyvinyl chloride, may be added. The amount of fatty acid plasticizer added is 20 to 60 parts by weight, especially 20 to 50 parts by weight, per 100 parts by weight of the thermoplastic resin copolymer.
Parts by weight (hereinafter "parts by weight" will simply be referred to as "parts") are preferred, and phthalic acid plasticizers and phosphoric acid plasticizers are each preferably 5 to 40 parts, particularly 10 to 20 parts, and the total amount of these plasticizers added The amount is preferably 20 to 60 parts per 100 parts of the thermoplastic resin copolymer. In either case, if the amount of plasticizer is too large, the mechanical strength of the interlayer film, such as penetration resistance, will be reduced, and if it is too small, the plasticity, weather resistance, etc. will be reduced. The interlayer film of the present invention is prepared by processing the above-mentioned copolymer with the above-mentioned plasticizer and, if necessary, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, etc., using a known processing method, such as calender rolling. The film can be formed by a method such as a method, an extrusion sheet casting method, or an inflation method. In order to use this resin film as an interlayer film to produce a safety laminated glass, the interlayer film may be placed between glasses and melted and bonded under heat and pressure. In this case, the heating temperature is preferably 80 to 200°C, usually 100 to 180°C. The pressure may be the pressure necessary to maintain close contact between the interlayer film and the glass plate, and to remove air bubbles at the interface and within the interlayer film layer, and is preferably from 5 to 15 kg/cm ² .
For heat-compression bonding, conventional bonding devices used for plasticized polyvinyl butyral films, such as a hot press molding machine, a pressure roll with a heating furnace, and a hydraulic or pneumatic autoclave, can be used. Since the interlayer film for laminated glass of the present invention has the above-mentioned structure, it can be provided at a low price, and when it is formed as an interlayer film, the films do not exhibit stickiness to each other at room temperature, so spraying an anti-adhesive agent is not required. without the need for
It has excellent adhesion workability between the interlayer film and safety laminated glass, and has sufficient adhesion with laminated glass.
The weather resistance is also good, and furthermore, the puncture resistance of the laminated glass made using the interlayer film of the present invention is also good, especially at low temperatures. Next, examples of the present invention will be described. Physical property measurement method 1 Penetration resistance An interlayer film with a thickness of 0.76 m/m is 30.5 cm x 30.5 cm thick.
A laminated glass is obtained by sandwiching it between 2.5 m/m plate glass and heating and pressurizing it. After leaving it in an atmosphere of 0℃ or 20℃, a 2.26 kg steel ball is dropped into the center of this laminated glass, and the steel ball is placed in the laminated glass. The height at which the percentage of penetration through the glass was 50% was measured. 2 Weather resistance An interlayer film with a thickness of 0.76 m/m is sandwiched between glass sheets with a thickness of 2.5 m/m, and a laminated glass is obtained by heating and pressing.
Measured in accordance with R-3212 "Test Methods for Automotive Safety Glass". That is, a 750±50W quartz glass mercury lamp was used as the light source, and the laminated glass was placed at a distance of 230m/m from the light source in an apparatus maintained at 45±5℃, and the light transmittance at each time shown in Table 1 was calculated. It was measured using a spectrophotometer, and the degree of coloring of the laminated glass was visually determined. 3 Adhesion Adjust the laminated glass by leaving it at a temperature of -18°C ± 0.6°C for 16 ± 4 hours, and after the glass peels off by hitting it with a hammer, the degree of exposure of the film is judged using a pre-graded limit sample. The results were expressed as Pummel values according to Table 1.

[Table] Examples Example 1 Vinyl chloride 92.5%, glycidyl methacrylate
100 parts of a copolymer with an average degree of polymerization of 900 consisting of 2.5% ethylene and 5.0%, 30 parts of a fatty acid plasticizer (dioctyl adipate, "DOA" manufactured by Sekisui Chemical Co., Ltd.),
10 parts of phthalic acid plasticizer (diethylhexyl phthalate, "DOP" manufactured by Sekisui Chemical Co., Ltd.), 3 parts of heat stabilizer (manufactured by Sankyoki Gosei Co., Ltd.), and 0.3 parts of ultraviolet absorber ("Tinuvin 326" manufactured by Ciba Geigy) , 0.3 parts of antioxidant (BHT manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added, and 110
The mixture was thoroughly kneaded using two rolls heated to 0.degree. C. to obtain a non-adhesive sheet with a thickness of 0.76 m/m. This resin sheet was sandwiched between two glass plates, left in an atmosphere at 70°C for about 10 minutes, and then passed between rubber rollers at 70-75°C for preliminary adhesion at a surface pressure of 3 kg/cm. Thereafter, it was heated for 20 minutes in a pneumatic autoclave at 150°C - 13 kg/cm to completely adhere, and a laminated glass was obtained. The physical properties of the laminated glass were as shown in Table 2. Example 2 An interlayer film was made using the same resin and additives as in Example 1, except that 20 parts each of the same fatty acid plasticizer and phthalic acid plasticizer as used in Example 1 were used. A laminated glass was obtained under the same conditions as in Example 1. The physical properties of the laminated glass were as shown in Table 2. Example 3 The same conditions as in Example 1 were used, except that 30 parts of the same fatty acid plasticizer as in Example 1 and 10 parts of a phosphoric acid plasticizer (tricylenyl phosphate, "TXP" manufactured by Daihachi Kagaku Co., Ltd.) were used. A laminated glass was obtained. The physical properties of the laminated glass were as shown in Table 2. Example 4 Same conditions as Example 1 except that 30 parts of the same fatty acid plasticizer as in Example 1 and 10 parts of phosphoric acid plasticizer (trischloroethyl phosphate, "CLP" manufactured by Daihachi Kagaku Co., Ltd.) were used. The laminated glass was obtained below. The physical properties of the laminated glass were as shown in Table 2. Comparative Example Comparative Example 1 A laminated glass was obtained under the same conditions as in Example 1 except that 40 parts of the same fatty acid plasticizer as in Example 1 was used as the plasticizer. The physical properties of the laminated glass were as shown in Table 2. Comparative Example 2 A laminated glass was obtained under the same conditions as in Example 1, except that 40 parts of the same phthalic acid plasticizer used in Example 1 was used as the plasticizer. The physical properties of the laminated glass were as shown in Table 2.

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Claims (1)

[Scope of Claims] 1 A thermoplastic resin obtained by copolymerizing vinyl chloride, glycidyl methacrylate, and at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers; The thermoplastic resin contains 80 to 98.5% by weight of vinyl chloride, 1 to 10% by weight of glycidyl methacrylate, and carbonized ethylene. Monomer selected from hydrogen, fatty acid vinyl, acrylic ester, and vinyl ether from 0.5 to
An interlayer film for laminated glass characterized by containing 10% by weight. 2. The interlayer film according to item 1, wherein the fatty acid plasticizer is dioctyl adipate. 3. The interlayer film according to item 1 or 2, wherein the phthalic acid plasticizer is diethylhexyl phthalate. 4. The interlayer film according to any one of items 1 to 3, wherein the phosphoric acid plasticizer is trichloroethyl phosphate.