JP4507854B2 - Transparent synthetic resin laminate - Google Patents

Description

  The present invention relates to a transparent synthetic resin laminate used as a protective surface or protective shield for self-defense, security, etc., and particularly relates to a transparent synthetic resin laminate excellent in impact resistance (elasticity resistance).

Conventionally, protective surfaces or shields have been used to protect the body from stones in the case of violent incidents, gunshots, etc., and these protective surfaces and shields are laminated with an acrylic resin plate and a polycarbonate resin plate. The laminated body that is thermoformed into a flat shape or a curved shape is used.
JP 2001-355999 A

  However, the laminate of the acrylic resin plate and the polycarbonate resin plate described above has insufficient impact resistance against a stone or a handgun, and there is a problem that the acrylic resin plate is broken and scattered by a strong impact. Further improvement was desired in terms of sex. In the laminated body, the impact resistance is improved by increasing the thickness of the acrylic resin plate or the polycarbonate resin plate, but naturally the weight increases and it is not suitable for use as a protective shield or a protective surface.

  The present invention has been made in view of the above-described problems, and has an object of providing a transparent synthetic resin laminate that is excellent in impact resistance against stones, pistols, and the like and is used for protective surfaces, protective shields, and the like. .

  As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved by laminating a polyester resin layer on a laminate of an acrylic resin plate and a polycarbonate resin plate. Is. That is, the present invention provides a polyester resin layer having a thickness of 300 μm or more on a laminate in which an acrylic resin plate having a thickness of 10 to 13 mm and a polycarbonate resin plate having a thickness of 6 to 8 mm are laminated via an adhesive layer. The gist is a transparent synthetic resin laminate characterized by being laminated on the acrylic resin plate side.

  The transparent synthetic resin laminate of the present invention has a thickness of 300 μm or more on a laminate in which an acrylic resin plate having a thickness of 10 to 13 mm and a polycarbonate resin plate having a thickness of 6 to 8 mm are laminated via an adhesive layer. The polyester resin layer is laminated on the acrylic resin plate side, and has excellent impact resistance against throwing stones or pistols. For example, the bullets of the handgun Tokarev do not penetrate, and the acrylic resin plate breaks and scatters. Without being effective in terms of safety.

  Examples of the acrylic resin used in the present invention include various acrylic resins such as polymethyl methacrylate and copolymers mainly composed of methyl methacrylate. Examples of other monomers copolymerizable with methyl methacrylate include alkyl methacrylates having an alkyl group having 2 to 8 carbon atoms such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, Examples include alkyl acrylates having an alkyl group having 1 to 8 carbon atoms such as propyl acrylate, butyl acrylate, octyl acrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, styrene, glycidyl methacrylate, glycidyl acrylate, and mixtures thereof. It is done.

  The molecular weight of the acrylic resin is 100,000 to 1,200,000, preferably 500,000 to 1,000,000 in terms of weight average molecular weight. When the weight average molecular weight is less than 100,000, it is not preferable to mold the resin laminate into a curved shape because bubbles are likely to be generated in the molded product and the transparency is deteriorated. If the weight average molecular weight exceeds 1,200,000, it is not preferable because it becomes difficult to form a curved shape.

  The acrylic resin may appropriately contain various conventionally known additives such as an ultraviolet absorber, an antioxidant, a flame retardant, and a colorant. Moreover, the impact resistance of an acrylic resin board can also be improved by containing a rubber component by a conventionally known method.

  The acrylic resin plate used in the present invention is produced by a conventionally known method such as a casting polymerization method using the above acrylic resin.

  The polycarbonate resin used in the present invention is produced, for example, by a phosgene method based on a reaction between a dihydric phenol and phosgene or a transesterification method based on a reaction between a divalent phenol and a carbonic acid diester. As the dihydric phenol, it is preferable to use bisphenols, particularly 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Moreover, it is preferable to use diphenyl carbonate as the carbonic acid diester.

  The molecular weight of the polycarbonate resin is 20000 to 30000, preferably 24000 to 27000 in terms of viscosity average molecular weight. When the molecular weight is less than 20000, impact resistance strength, that is, resistance to a handgun is lowered, and when the resin laminate is molded into a curved shape, a large number of bubbles are generated in the molded product, and the transparency is deteriorated. Absent. When the molecular weight exceeds 30000, it is not preferable because thermoforming into a curved shape becomes difficult.

  The polycarbonate resin plate is manufactured by extruding the polycarbonate resin.

  The acrylic resin plate and the polycarbonate resin plate are laminated via an adhesive layer. The adhesive layer has a transparent and film-like form such as thermoplastic polyurethane, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and is melted at 80 ° C. to 200 ° C. Any material that can be bonded can be used.

  Thermoplastic polyurethane has transparency, and is a reaction product of a non-yellowing isocyanate, either a polyether polyol or a polyester polyol, and a chain extender. The thickness of the adhesive layer of this thermoplastic polyurethane is selected in the range of 0.05 to 5.0 mm, preferably 0.5 to 3.0 mm. If the thickness is less than 0.05 mm, it is too thin to make uniform adhesion to the resin plate difficult, and the impact absorption performance and internal stress relaxation performance are deteriorated. On the other hand, when the thickness exceeds 5.0 mm, it is not preferable since the impact absorption performance and the internal stress relaxation performance cannot be expected, and the increase in weight and cost are uneconomical.

  The polyester resin used in the present invention is a polymer obtained by condensation polymerization from a dicarboxylic acid and a diol. As the dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, The diol is represented by ethylene glycol, trimethylene glycol, tetramethylene glycol, cyclohexanedimethanol, polyalkylene glycol, bisphenol A ethylene oxide adduct, and the like. Specific polyester resins include polymethylene terephthalate, polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-p-oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, and the like. Can do. Of course, these polyesters may be homopolymers or copolymers, and as copolymerization components, for example, diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, bisphenol A ethylene oxide adduct, Dicarboxylic acid components such as dimer acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are used. Moreover, a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, and an antistatic agent may be blended as long as the effects of the present invention are not impaired.

  The polyester resin layer of the present invention comprises the polyester resin film and an adhesive layer laminated on the film. This polyester resin film is obtained by known extrusion molding or the like. The polyester resin film is preferably biaxially oriented in terms of mechanical strength, dimensional stability, and the like. The term “biaxially oriented” refers to a pattern showing a biaxially oriented pattern by wide-angle X-ray diffraction. For example, unstretched, that is, a polyester resin film before crystal orientation is completed is 2 in the longitudinal direction and the width direction, respectively. The film is stretched about 5 to 5.0 times, and then crystal orientation is completed by heat treatment.

  The production of the transparent synthetic resin laminate of the present invention will be described. First, in order to obtain a flat laminate of an acrylic resin plate and a polycarbonate resin plate, these resin plates are stacked through an adhesive layer and integrated with a hot press, or heated in a degassed state in an air bag. Then, after the temporary adhesion, lamination and integration are performed by a method such as heating and pressurizing with an autoclave. In order to obtain a curved shape, the flat laminate obtained as described above is heat-softened in a hot air oven or the like, pressed against a mold, and formed into a desired curved shape. The transparent synthetic resin laminate of the present invention can be obtained by laminating the polyester resin layer on the laminate of the acrylic resin plate and the polycarbonate resin plate thus obtained. The polyester resin layer is laminated on the acrylic resin plate side of the laminate of the acrylic resin plate and the polycarbonate resin plate. Or you may laminate | stack on both surfaces of the laminated body of an acrylic resin board and a polycarbonate resin board.

  In the transparent synthetic resin laminate, it is necessary that the acrylic resin plate has a thickness of 10 to 13 mm, the polycarbonate resin plate has a thickness of 6 to 8 mm, and the polyester resin layer has a thickness of 300 μm or more. When the thickness of the acrylic resin plate is less than 10 mm, the impact resistance (elasticity resistance) to the handgun is insufficient and the bullet penetrates easily. In this case, in order to give sufficient elasticity resistance, it is necessary to increase the thickness of the polycarbonate resin plate, which is too heavy for use as a protective surface or a protective shield, or difficult to form in a curved shape. A problem occurs. Further, when the thickness of the acrylic resin plate exceeds 13 mm, although the resistance to elasticity is improved, there is a problem that it is too heavy or difficult to form into a curved shape. On the other hand, when the thickness of the polycarbonate resin plate is less than 6 mm, the elasticity resistance is insufficient, and when the thickness exceeds 8 mm, there is a problem that it becomes heavy and curve forming becomes difficult. Further, when the thickness of the polyester resin layer is less than 300 μm, it is insufficient for improving impact resistance (elasticity resistance).

  As described above, as the polyester resin film, a biaxially stretched film is used. However, it is generally difficult to biaxially stretch a polyester resin film having a thickness exceeding 250 μm, and 300 μm used in the present invention. In order to obtain the above polyester resin layer, it can be obtained by laminating two or more polyester resin films with an adhesive or a pressure-sensitive adhesive. In this case, any laminated structure may be used as long as the total thickness is 300 μm or more. For example, three or more polyester resin films may be laminated. For the lamination of the polyester film, one having excellent transparency is selected from known adhesives and pressure-sensitive adhesives. The polyester resin film used for the surface layer may be subjected to a hard coat treatment, a vapor deposition treatment, or the like.

  The obtained transparent synthetic resin laminate is used as a protective shield or a protective surface with a handle, a rubber winding for protecting the surroundings, etc., as necessary. At this time, the acrylic resin plate side is used so as to be the bullet side.

  Examples of the present invention will be described together with comparative examples. A trade name “Sumipex 000” (manufactured by Sumitomo Chemical Co., Ltd.) was prepared as an acrylic resin plate, and a trade name “Polyca Ace” (manufactured by Tsutsunaka Plastic Industry) was prepared as a polycarbonate resin plate.

  In addition, an acrylic pressure-sensitive adhesive is applied to a 125 μm thick polyester resin film (“Teijin Tetron Film HS” manufactured by Teijin DuPont Films) by gravure coating so that the film thickness becomes 15 μm. The polyester resin film was bonded. An acrylic pressure-sensitive adhesive was further applied to the laminated film so that the film thickness was 35 μm to prepare a polyester resin layer having a total thickness of 300 μm.

<Examples 1-2 and Comparative Examples 1-2>
The acrylic resin plate and the polycarbonate resin plate having the thicknesses shown in Table 1 were laminated and integrated by hot pressing using thermoplastic polyurethane having non-yellowing isocyanate and polycarbonate diol (polyester diol) as main reaction components as an adhesive layer. . A transparent synthetic resin laminate was obtained by laminating the polyester resin layer on the acrylic resin plate side of the laminate at room temperature with a pressure roll.

  In this transparent synthetic resin laminate (size 400 × 400 mm), H. P. White Laboratory, Inc. Then, the elastic resistance was evaluated from a distance of 5 m using a handgun Tokarev. Five bullets were fired on one specimen. The incident angle of the bullet, the landing location, the presence / absence of penetration, etc. were in accordance with NIJ standards. In the case where one of the five bullets did not penetrate the specimen, it was marked as ◯. The results are shown in Table 1.

<Comparative Example 3>
An acrylic pressure-sensitive adhesive was applied to a polyester resin film having a thickness of 175 μm by a transfer method so as to have a film thickness of 25 μm to prepare a polyester resin layer having a total thickness of 200 μm. A transparent synthetic resin laminate is obtained by laminating the above-mentioned polyester resin layer having a thickness of 200 μm to the laminate of the acrylic resin and the polycarbonate resin plate used in Example 1 with a pressure roll. The elastic resistance was evaluated.

Claims (1)

  A polyester resin layer having a thickness of 300 μm or more is placed on the acrylic resin plate side on a laminate in which an acrylic resin plate having a thickness of 10 to 13 mm and a polycarbonate resin plate having a thickness of 6 to 8 mm are laminated via an adhesive layer. A transparent synthetic resin laminate characterized by being laminated.