TW201213127A - Method for producing transparent resin laminate, molded body and resin laminate - Google Patents

Abstract

An intermediate layer of a crystalline resin and a surface layer are formed, said surface layer being formed, on at least one surface of the intermediate layer, from a crystalline resin that has a higher melt flow rate and a shorter relaxation time in comparison to those of the crystalline resin that constitutes the intermediate layer. The intermediate layer and/or the surface layer contains a metallocene type ethylene-a-olefin copolymer that is produced using a metallocene catalyst. A master sheet (2) is formed by cooling laminated sheets that are obtained by extruding the crystalline resins in a molten state, and the master sheet (2) is heat-treated at a temperature not lower than the crystallization temperature but not higher than the melting point, so that a transparent resin laminate (3) is produced.

Description

201213127 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a method for producing a transparent resin laminate, a molded body, and a resin laminate. [Prior Art] Since the crystalline resin represented by polypropylene has high crystallinity (crystallinity, crystallization rate, spherulite size, etc.), it is not transparent in the usual film forming method. In the case of a film or a sheet of a resin, for example, as disclosed in the document ι (Japanese Patent No. 3725955), a large amount of fine crystals are produced by an additive formulation (nucleating agent) to inhibit polymerization of spherulite growth. The method of object design. For example, a rapid cooling method using a belt type process as disclosed in the document 2 (Japanese Patent No. 4237275) can be cited as a method of expressing the transparency. In the rapid cooling method of the (four) type process, in the film forming step of maintaining the low temperature band and the roll and rapidly cooling, the polypropylene is rapidly cooled, and the growth of the crystal is received by the rapid cooling method. It is possible to achieve low crystallization and fine spheroidization by suppression, and it is possible to achieve transparency of a degree or more without adding a nucleating agent. Moreover, it is not disclosed in Japanese Patent Laid-Open Publication No. Hei 2-6-297876. In the case of the polypropylene-based resin sheet, by adding a specific linear low-density poly-bending rapid cooling in the polypropylene material, the transparency is high and the transparency of the nucleating agent disclosed in the literature 1 is added.盥 盥 盥 屮浐妲 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 Further, since the polypropylene is originally a crystalline resin, the viscosity is drastically lowered near the melting point, and it is difficult to form a hot melt. The addition of the nucleating agent increases the degree of crystallinity and further reduces the range of thermoformability, and thermoforming becomes more difficult. . Further, in the film-formed process or the water-cooling method, the film of the rapid cooling process of the film formation in the literature 2 forms a large number of spherulites in the vicinity of the surface of the sheet, and the presence of the spherulites causes a decrease in transparency. Further, as disclosed in Document 3, it is expected that polypropylene has a specific straight-bonded low-density polyethylene, and it is expected to improve its transparency. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a transparent resin laminate having improved transparency, a molded article, and a resin laminate. According to the efforts of the inventors of the present invention, it has been found that the crystal formed by the rapid cooling thereafter is changed by controlling the stress at the time of extrusion of the resin. The present invention has been completed based on this finding. The method for producing a transparent resin laminate according to the present invention is characterized in that it comprises an intermediate layer formed of a crystalline resin and a surface formed of the crystalline resin on the one to seven sides of the one layer. The manufacturing method of the transparent resin laminated body is a translucent fish opening Q... and the crystallizing tree of the above surface layer is opened up; 4 is asked to 禺 0 0 a. Λ/Γ. s, ·, α day Compared with the Japanese resin, the melt flow rate (Melt Flow Rate, 无 thousand.. „ is not MFR) is larger, and the hesitation time is shorter. At least any of the crystalline resin resins forming the above intermediate layer includes the use of ^ A metallocene system 158273.doc 201213127 produced by the above-mentioned surface layer of a crystalline dendritic metal catalyst. The ethylene-α-anthracene hydrocarbon copolymer forms a crystalline resin of the above intermediate layer and a crystalline resin forming the above surface layer. Each of the present invention is preferably melted, extruded, and cooled in a state in which the laminate is in a sheet form to form a resin laminate, and the resin laminate is heat-treated at a temperature equal to or higher than the crystallization temperature and not higher than the melting point. : The middle of the above The layer has an isotactic pentad fraction of 80% by mass or more and 99.5% by mass or less of 85% or more and 99% or less, MFR of 〇.5 g/1〇min or more and 5 〇g/1 of the claw.丙烯 The following propylene-based resin (a) and 〇·5 mass% or more and 2〇 mass% or less are produced using a metallocene catalyst, and have a density of 898 kg/m3 or more and 913 kg/m3 or less and an MFR of 0.5 g/ Further, in the present invention, it is preferable to form a metallocene-based ethylene-α-olefin copolymer having a thickness of not less than 〇min and not more than 6 〇g/1〇min. In the present invention, it is preferably configured to form a crystal of the intermediate layer and the surface layer. Further, in the present invention, the metallocene-based ethylene-α-olefin copolymer is preferably a linear low-density polyethylene. In the present invention, it is preferably set to be a propylene resin. In the following configuration, the intermediate layer is provided on both surfaces of the base material layer formed of the crystalline resin, and the surface layer is provided on the surface of the intermediate layer. Preferably, the base layer is configured to form the base. The crystalline resin of the material layer is a propylene resin. The molded article is characterized in that it has an intermediate layer formed of a crystalline resin and is provided on at least one surface of the intermediate layer: a surface layer formed of a crystalline resin, and the surface layer is crucible Compared with the crystalline resin forming the above intermediate layer, the melting flow 158273.doc 201213127 Melt Flow Rate (hereinafter referred to as ^^1^) is larger, and the relaxation time is shorter, forming the middle At least one of the crystalline resin of the layer and the crystalline resin forming the surface layer contains a metallocene-based ethylene-α-olefin copolymer produced by using a metallocene catalyst, and the crystalline resin forming the intermediate layer is The crystalline resin forming the surface layer is formed into a sheet shape in a molten state and rapidly cooled, and the obtained resin laminated body is thermoformed at a temperature equal to or higher than the crystallization temperature and not higher than the melting point. The resin laminate disclosed in the present invention is characterized in that it is formed by heat treatment to form a transparent resin laminate, and has an intermediate layer formed of a crystalline resin and is provided on at least one side of the ten layers. Further, the surface layer formed of the crystalline resin, the crystalline resin of the intermediate layer contains an isotactic pentad fraction of 85% by mass or more and 99.5% by mass or less and 85% or more. /. In the following, the MFR is 〇_5 g/1 〇min or more, and the propylene-based resin (a) having a particle size of 5 〇g/i 〇 or less is produced by using a metallocene catalyst, and 0.5% by mass or more and 2% by mass or less. The metallocene ethylene-α-olefin copolymer (b) having a density of 898 kg/m3 or more and 913 kg/m3 or less and an MFR of 0.5 g/l〇min or more and 6·〇g/1〇min or less, the above surface The crystalline resin of the layer has a larger mfr and a shorter relaxation time than the crystalline resin forming the intermediate layer. Further, in the present invention, it is preferable to provide a configuration in which the intermediate layer ' is provided on both surfaces of a base material layer formed of a crystalline resin, and the surface layer is provided on both surfaces of the intermediate layer. In the present invention, an intermediate layer of a crystalline resin is formed, and a molten flow is formed on the surface J of the intermediate layer by a crystalline resin which forms the intermediate layer. 158273.doc 201213127 The rate is larger and the time is shorter. The crystalline resin forms a surface layer. Further, at least one of the intermediate layer and the surface layer contains a pentylene-based ethylene-CC·smoke copolymer produced by using a metallocene catalyst. Therefore, the stress applied in the sheet-like extrusion is relaxed by the surface layer, and the residual stress which causes the formation of spherulites which are likely to be generated at a certain depth from the surface is lowered. However, the reduction of residual stress alone does not completely inhibit the generation of spherulites. Therefore, by containing a metallocene-based ethylene-α-olefin copolymer at a position where the depth of spherulites is generated, the formation and growth of spherulites are suppressed, and the amount of spherulites is reduced. And the size of the spherulites also becomes smaller. Therefore, the scattering of light by spherulites is reduced to improve transparency (reduce turbidity). Further, the respective crystalline resins are extruded in a molten state and cooled in a state in which the laminate is in a sheet form to form a resin laminated body. The resin laminated body is heat-treated at a temperature equal to or higher than the crystallization temperature and not higher than the melting point. In the heat treatment of the rapid cooling fin, the crystal is crystallized in a state of maintaining a fine high-order structure in the resin laminate having a good crystallinity obtained by cooling, so that there is no damage, and the sheet can be formed well. In the form of a transparent resin laminate having a high transparency. [Embodiment] Hereinafter, a method for producing a transparent resin laminate according to an embodiment of the present invention will be described with reference to Fig. 1 . In the present embodiment, a polypropylene-based sheet-like transparent resin laminate is described as a transparent resin laminate. However, the present invention is not limited thereto, and various crystalline resins other than polypropylene may be used. , also 158273.doc 201213127 Heat can be formed into a container or the like as an object. [Configuration of Manufacturing Apparatus] In Fig. 1, the manufacturing apparatus 1 includes a whole sheet forming apparatus 1 that melts and kneads a raw material resin in a sheet form and rapidly cools it, and opens the entire sheet. The heat treatment device 2 of the transparent resin laminate 3 is produced by heat-treating the entire sheet 2 (see FIG. 2) which is a resin laminate. Here, the entire sheet 2 will be described in detail below. As shown in Fig. 2, the entire sheet 2 has two three-layer structures in which the surface layer 2B is provided on both sides of the sheet-like intermediate layer 2A. The whole web forming apparatus 10 is provided with a τ die extrusion apparatus 1 and a cooling extrusion apparatus 110. The 模 die extrusion apparatus 100 is provided with an extruder 1〇1 and a butting die 1〇2. As the extruder 101, for example, a single-shaft extruder or a multi-axis extruder or the like can be used. The extruder 101 is provided with a plurality of inter-layers 2A corresponding to the entire web 2 and corresponding to the surface layer 23. The T-die 102 is detachably attached to the front end of each extruder 1〇1, and the slick resin 2 which is extruded from the extruder 1〇1 is formed in a state in which the laminate is formed into a sheet shape. For example, a hanger type die, a slit die, etc. can be exemplified. Further, if the T die 102 is a mold capable of forming a multilayer sheet, it is not limited to a hanger type die and a slit die. The configuration in which the molten raw material resin is laminated, for example, a feed block method or a multi-manifold die method can be exemplified. The cooling and rubbing device 11 of the entire web forming device 10 will be formed into a sheet shape by using a stencil mold. The molten resin 2C_ which is formed is cooled and formed into a whole sheet 2 by cooling. The cooling and weaving device 11 is provided with a cooling roll 111 and a second cooling roll as shown in Fig. 1 and Fig. 2, 158273.doc 201213127 112, a third cooling roll 113, a fourth cooling roll 114, a cooling endless belt 115, a cooling water spray nozzle 116, a water tank 117, a suction roll 118, and a peeling roll 119. The first cooling roll 111, the second cooling roll 112, The third cooling roll 113 and the fourth cooling roll 114 are rotatably journalled and have excellent thermal conductivity. The metal roll "and at least one of the first cooling roll 111, the third cooling roll 113, and the fourth cooling roll 114 is coupled to a rotary drive mechanism (not shown) and is rotated by a rotary drive mechanism Further, in terms of the durability of the cooling endless belt 115, the first cooling roller 111, the second cooling roller 112, the third cooling roller 113, and the fourth cooling roller 114 are preferably of a smaller diameter. Large, practically, the diameter is designed to be 100 to 1 500 mm. The outer surface of the first cooling roll 11i is covered with an elastic material 111. As the ejection member, for example, Nitrile Butadiene Rubber can be used. , NBR), gas rubber, polyoxyalkylene rubber, EPDM (Ethy) ene_

Propylene_DleneM〇n〇mer, ethylene propylene diene copolymer) and the like. . The elastic material 111A has a good surface pressure for elastic deformation. For example, the hardness (measured according to the method of JIS K 6301A) is 80 degrees or less and the thickness is about 10 mm. "The cold portion roller 112 is a metal surface having a surface roughness (based on the surface roughness I of the definition and expression of JIS 〇 〇6〇1 "surface roughness.") Roller (mirror cooling roll). In the second cooling, inside. P 'In order to adjust the temperature of the surface, a cooling mechanism such as a water-cooled type is not included. The reason is that if the second cooling chain is 158273. Doc 201213127

Mm' has a total surface roughness (Rmax) of more than 0.3, and the gloss or transparency of the film 2 is reduced. The second cooling roll 丨12 is formed by sandwiching the intermediate layer 2B and the surface layer 2Β which are melt-extruded from the τ die 102 via the metal cooling endless belt 115 formed of stainless steel or the like to the first cooling roll!方式 Between the way the configuration. The cooling endless belt 115 is formed in an endless belt shape by, for example, stainless steel, carbon steel, titanium alloy or the like, and is wound around the first cooling roll 丨丨, the third cold part roll 113, and the fourth cooling ship 14. The cooling is formed by an endless belt ιι 5

The surface roughness (Rmax) of the outer peripheral surface, that is, the surface in contact with the intermediate layer 2A and the surface layer 2B which are melt-extruded from the T-die 102 is a mirror surface of 〇 3 μm or less. Further, the third cooling roller 113 and the fourth cooling roller 114 can perform temperature adjustment of the cooling endless belt 115 by internally providing a cooling mechanism such as a water-cooling type. The cooling water spray nozzle 116 is located below the second cooling roller 112 in the vertical direction, and is disposed in a state in which the cooling water U6A is sprayed on the back surface of the cooling endless belt 115. The cooling water spray nozzle 116 rapidly cools the cooling endless belt 115 by spraying the cooling water 116, and also presses the intermediate layer 2A which is surface-bonded by the first cooling roll lu and the second cooling roll 112. The surface layer 2B is rapidly cooled. The water tank 117 is formed in a box shape having an open upper surface, and is disposed so as to cover the entire lower surface of the second cooling roll 112, and recovers the cooling water 116A sprayed on the back surface of the cooling endless belt 115. The water tank 117 is provided with a drain port 117 排出 for discharging the recovered water 1丨7A from the lower side of the water tank π 7 . 158273.doc 201213127 The suction roll Π 8 is provided on the side surface of the second cooling sheet 113 side of the second cooling pattern 112 so as to be in contact with the cooling endless belt 11 5 . The suction roll 11 8 is for removing excess cooling water adhering to the back surface of the cooling endless belt u 5 . The peeling roller 119 is disposed such that the intermediate layer 2A and the surface layer 2B are guided to the third cooling roll 113 and the cooling endless belt 115, and the entire sheet 2 after the cooling is completed is peeled off from the cooling endless belt 1丨5. By. Further, the peeling roller 119 may be disposed such that the entire sheet 2 is pressed against the third cooling roller 113 side, but is preferably disposed to be spaced apart from the third cooling sheet 113 as shown, and is not connected. The entire piece 2. The heat treatment apparatus 20 of the manufacturing apparatus 1 includes a preheating apparatus 21, a heat treatment apparatus main body 220, and a cooling apparatus 230. The preheating device 210 warms up the entire web 2 formed by the entire web forming apparatus 1 to be preheated. The preheating device 210 includes a first preheating roller 211, a second preheating roller 212, and a third preheating roller 213 as shown in Fig. i. For the first preheating roller 211, the second preheating roller 212, and the third preheating roller 213, for example, a material having excellent thermal conductivity such as metal can be used. The first preheating roller 211, the second preheating roller 212, and the third preheating roller 213 are provided with a temperature adjustment mechanism (not shown) such as a vapor heating type that can adjust the temperature of the surface. Further, the temperature adjustment mechanism is not limited to being directly provided in each of the preheating rollers 211 to 213_, and may be formed as a roller for preheating or preheating by a preheating device provided outside. Composition. In addition, the preheating device 210 is not limited to the configuration in which the three preheating rollers 158273.doc -12·201213127 211 to 213 are disposed, and the configuration or use of one or a plurality of preheating rollers may be provided. The configuration of the endless belt or the like can be arbitrarily configured to preheat the entire sheet 2. The heat treatment apparatus main body 220 of the heat treatment apparatus 20 moves the entire sheet 2 preheated by the preheating apparatus 210 while being heated. The heat treatment apparatus main body 220 includes a first heating roller κι, a second heating roller 222, a third heating roller 223, a fourth heating roller 224, a rubber roller 225 as a pressure roller, a guide roller 226, and a metal heating endless belt. 227 and a drive mechanism not shown. Further, the first heating roller 221, the second heating roller 222, the third heating roller 223, the fourth heating roller 224, and the guide roller 226 can be made of a material having excellent thermal conductivity such as metal. Further, in terms of the durability of the metal heating endless belt 227, the first heating roller 221, the second heating roller 222, the third heating roller 223, and the fourth heating roller 224 preferably have a large diameter. It is particularly practical to design the diameter to be 100 to 15 mm. The first heating roller 221, the second heating roller 222, the third heating roller=and the fourth heating rib 4 are provided with a temperature adjustment mechanism (not shown) such as a helium gas heating type that can adjust the temperature of the surface. . In addition, the temperature adjustment mechanism 'is not limited to the configuration directly provided in each of the heating rollers 221 to 224' may be formed as a heating-only rotation or a heating device provided by an external heating device, and The condition of the second heating is above the crystallization temperature of the entire sheet 2 and the melamine metal rL is, for example, the entire sheet 2 comprising the above-mentioned propylene resin (4)' surface hydrocarbon copolymer (8), which is the entire sheet 2-A It is a condition of 120 C or more and does not reach the melting point. 158273.doc • 13- 201213127 Further, the drive mechanism is coupled to at least one of the first heating roller 221, the second heating roller 222, and the second heating roller 223. Further, the drive mechanism rotates at least one of the connected first heating report 221, second heating roller 222, and third heating report 223 by driving. The heating endless belt 227 is formed into an endless belt shape by, for example, stainless steel, carbon steel, titanium alloy or the like. Further, the thickness dimension can be arbitrarily set, and is preferably 0.3 mm or more in terms of strength. Further, the 8-inch heating endless belt 227 is erected on the first heating roller 221, the second heating roller 222, and the third heating roller 223, and is rotationally moved by the driving mechanism. Further, the drive mechanism performs drive control such that the moving speed of the heating endless belt 227 is substantially the same as the moving speed of the cooling endless belt 115 that is rotationally moved by the driving mechanism of the cooling and pressing device 11G. The outer circumferential surface of the fourth heating roller 224 faces the outer circumferential surface of the heating endless belt 227, and is disposed in a state in which the outer surfaces of the first heating roller 221 and the second heating roller 222 are tangentially intersected. The fourth heating roller 224 is rotatably disposed between the outer circumferential surface of the fourth heating roller 224 and the outer circumferential surface of the heating endless belt 227 by introducing the entire sheet 2 preheated by the preheating device 2 10 . . The rubber roller 225 is opposed to the outer circumferential surface of the heating endless belt 227 which is stretched in a state of being wound around the first heating roller 221. Further, the rubber roller 225 is formed with a cushioning material (not shown) formed at least on the outer peripheral surface. The cushioning material may use the same material as the second cooling roller 112 which cools the pressing device 11''. Further, the rubber roller 225 may be formed by coating a cushioning material over substantially the entire outer peripheral surface, or may be substantially formed of a cushioning material, such as I58273.doc •14-201213127. Moreover, the rubber knee roller 225 squeezing and splicing the entire sheet 2 from the preheating device 21 to the outer peripheral surface 1 of the heating endless belt 227, and the rubber 225 is passed through the preheated whole sheet 2 and The heating endless belt 227 is disposed in a state in which the first twisting light 221 is in contact with each other. Further, the entire sheet 2 is moved in a state of being in close contact with the heating endless belt 227. Then, the fourth heating roller 224 is pressed and held, and the outer circumferential surface of the zero guide roller 226 is opposed to the outer circumferential surface of the heating endless belt 227. The sheet-like transparent resin laminate 3 that is heated and extruded between the heating endless belt 227 and the fourth heating roller 224 is disposed to be rotatably disposed. In other words, the guide roller 226 is disposed on the downstream side of the downstream side in the moving direction of the transparent resin laminated body 3, that is, on the downstream side of the manufacturing, and is disposed on the downstream side of the fourth heating roller 224. By this, the transparent resin laminated body 3 obtained by heating and pressing between the heating endless belt 227 and the fourth heating roll 224 is peeled off from the outer peripheral surface of the fourth heating roll 224, and is self-heating. The outer circumferential surface of the endless belt 227 is guided to be peeled off. The cooling device 230 of the heat treatment apparatus 20 cools the transparent resin laminate 3 which has been heat-treated by the heat treatment apparatus body 220. The cooling device 230 has a first cooling guide roller 23 1 , a second cooling guide roller 232 , and a pair of guide rollers 233 . For the first cooling guide roller 231, the second cooling guide roller 232, and the pair of guide rollers 233, for example, a material having excellent thermal conductivity such as metal can be used. The first cooling guide roller 231, the second cooling guide roller 232, and the pair of guiding rollers 233 are made of a transparent resin 158273.doc -15-201213127 laminated body 3 which has been heat-treated by the heat treatment apparatus body 220. The state of the erection is located on a substantially straight line. The first cooling guide roller 231 and the second cooling guide roller 232 are provided with a temperature adjustment mechanism (not shown) such as a vapor heating type that can adjust the temperature of the surface. Further, the temperature adjustment mechanism is not limited to being directly provided in each of the cooling guide rolls 231 and 232, and may be formed by separately providing a cooling-dedicated roller or cooling by a cooling device provided outside. Further, a pair of guide rollers 233 are disposed on the downstream side of the second cooling guide roller 232. In addition, the guide rolls 233 are arranged in a state in which the outer peripheral surface faces the outer peripheral surface and the cooled transparent resin laminated body 3 is interposed therebetween, and is arranged in a direction perpendicular to the moving direction of the transparent resin laminated body 3. Further, the cooling device 230 is not limited to the configuration of the first cooling guide roller 23 i, the second cooling guide roller 232, and the pair of guiding rollers 233, and may be configured with one or a plurality of rollers or The transparent resin laminated body 3 can be cooled by any configuration using an endless belt or the like. [Structure of the entire sheet] Next, the configuration of the entire sheet 2 in which the transparent resin laminate is produced by the above-described manufacturing apparatus 1 will be described. The entire sheet 2 is, for example, two kinds of three-layer structures in which the surface layer 2B is provided on both sides of the sheet-like intermediate layer 2A. The intermediate layer 2A is formed of a crystalline resin such as a polypropylene resin. It is particularly preferable that the intermediate layer 2A is formed of a polypropylene-based resin containing a propylene-based resin (a) and a metallocene-based ethylene_α-olefin copolymer (b) as a main component. The propylene-based resin (a) preferably has an isotactic pentad fraction of 85% or more and 99 〇/〇 158273.doc 16 - 201213127 or less, and a melt flow rate (Melt Flow Rate, hereinafter referred to as "^1? 0.5 g/U) min or more and 5. 〇g/10 min or less. Further preferably, the isotactic pentad fraction is 90% or more and 99% or less, and the MFR is 2.0 g/1 〇 min to 4 〇 g/10 min. Here, the isotactic pentad fraction refers to the isocratic ratio in the pentad unit (the propylene monomer is continuously and isotactically bonded) in the molecular chain of the resin composition. The measurement method of this fraction is described, for example, in Macromolecules, Vol. 8 (1975), page 687, and can be measured by 丨3C_NMR. Further, the measurement of MFR can be carried out according to ns_K721〇 at a measurement temperature of 230° (:, a load of 2.16 1 < ^. Moreover, if the ratio of the quaternary component of the propylene matrix resin (a) is less than 85%, On the other hand, if the isotactic pentad fraction is higher than 99%, the transparency is lowered. Therefore, the propylene resin (a) is preferably an isotactic five-element. The component ratio is set to be 85% or more and 99% or less. Further, if the MFR is less than 〇.5 g/l〇min, the propylene resin (a) has a strong shear stress at the lip of the mold during extrusion molding. On the other hand, when the MFR is more than 5.0 g/l〇min, the draw-down becomes large at the time of thermoforming, and the formability is lowered. Therefore, the propylene-based resin (a) is preferred. In order to set the MFR to 0.5 g/l〇min or more and 5_〇g/i〇min or less. On the other hand, the metallocene ethylene_α-olefin copolymer (b) is produced by using a metallocene catalyst, and has a density. It is 898 kg/m3 or more and 913 kg/m3 or less, MFR is 〇.5 g/i〇min or more and 6 〇g/1〇min or less. 158273.doc 17 201213127 Here, density It is measured at 23 ° C according to JIS-K7112 "Method for Measuring Density and Specific Gravity of Plastic-Non-Foamed Plastics". For the measurement of MFR, the temperature can be measured according to JIS-K7210 by 19 〇. (:, load 2.1 6 kg The measurement is carried out. Further, the metallocene-based ethylene-ot-olefin copolymer (b) is preferably a material having substantially the same refractive index as that of the propylene-based resin, and more preferably a linear low-density polyethylene. When the metallocene ethylene-(X-olefin copolymer (b) has a density of less than 898 kg/m3 or a density of more than 913 kg/m3, the refractive index of the propylene-based resin (4) with the matrix becomes inconsistent with the propylene system. The refraction of light at the interface between the resin (a) and the metallocene-based ethylene-heart olefin copolymer (b) becomes large and the transparency is impaired. That is, if the propylene resin (&) and the metallocene ethylene _α When the refractive index of the olefin copolymer (b) is substantially the same, the transparency of the produced transparent resin laminate 3 is improved. Fig. 3 is a graph showing the formation of a sheet by rapid cooling and crystallization by heat treatment. A graph of the relationship between refractive index and density of propylene sheets. See Figure 3 for When the rapidly cooled polypropylene sheet is heat-treated to be crystallized, the refractive index is 504 to 1.509, and the density is in the range of 900 to 907 kg/m3. Therefore, 'as long as the metallocene is added to ethylene_α_ The refractive index of the olefin copolymer (b) is in the range of 1504 to 1.509, and the transparency is not impaired. Here, the relationship between the refractive index and the density of the substance can be expressed by the following formula (1). (L〇rentz_L〇renz) expression. n is the refractive index of the target substance, Ρ is the density of the target substance, Μ is the molecular weight of the target substance, Ν is the Yafot number, and Ρ is the polarizability of the target substance. 158273.doc 201213127 n2~l Μ η2 + 2 p

=rNP (1), the refraction is expressed by the following formula (2) which has a density ρ as a parameter because the Yafot number N and the polarizability P' molecular weight M are constant. -(2) ll + 2Kp l-Kp where K = Απ

ΝΡ Ί α As shown in the above formula (2), since the density is related to the refractive index, the metallocene ethylene-α-olefin copolymer (b) can be selected by density. Therefore, the metallocene-based ethylene-α-olefin copolymer (b) preferably has a density of 898 kg/m3 or more and 913 kg/m3 or less. Further, the metallocene-based ethylene-α-olefin copolymer (b) gMFR is less than g5 g/i〇min ^, and the dispersion in the molecule of the propylene-based resin (4) of the matrix becomes difficult. The dispersion diameter of the substance (b) becomes large, and light scattering scatters and transparency is caused. On the other hand, if the face is larger than "g 〇min, the compatibility with the matrix propylene resin (a) is deteriorated, and the metallocene ethylene-α-ene fe copolymer (8) is not completely dispersed and is in the form of huge particles. The reason for this is that, in this state, light is scattered by the particles of the metallocene-based ethylene (8), which impairs the transparency. When the various polymer blends are kneaded to equilibrium, the dispersion of the admixture (4) D is expressed by the following formula (3), where d is the dispersion, Y is the interfacial tension, and % is the viscosity of the matrix. , G is the shear rate and is the viscosity of the dispersed phase. i5S273.doc •]9- (3) 201213127

D .4/ GVm U±vm \0.84 where, ····gt;1 nm Since the viscosity of the matrix is ~ and the shear rate G is fixed, the dispersion phase diameter D dispersion phase viscosity and interfacial tension γ become parameters. As described in the above formula (3), it is known that the closer the viscosity of the matrix to the dispersed phase is to 丨, the smaller the dispersed phase diameter D is, the less the scattering of light is, and the transparency is improved. In the present invention, when the viscosity ratio at a shear rate of 6 sec sec 1 is from 1 〇 to 3.0, good transparency is exhibited. The metallocene ethylene_α• olefin copolymer (b) tMFR in the above viscosity range is 0.5 g/l 〇 min or more and 6 〇 g/1 〇 min or less. Further, the intermediate layer 2A is preferably a copolymer of 80% by mass or more and 995 % by mass or less of the propylene-based resin (a) and 5% by mass or more and 2% by mass or less of the metallocene-based ethylene-α-olefin. The substance (b) is formulated. That is, the reason is that if the amount of the metallocene-thin-α-dilute hydrocarbon copolymer (8) is increased, the rigidity of the obtained whole sheet 2 is lowered. On the other hand, when the amount of the metallocene-based ethylene/α-olefin copolymer (b) is small, the metallocene-based ethylene-α·olefin copolymer (b) is not sufficiently dispersed in the acryl-based resin. The suppression of growth is insufficient, and it is difficult to obtain transparency. On the other hand, the surface layer 2B has a larger melt flow rate (Meft Flow Rate, hereinafter referred to as MFR) and relaxation by the intermediate layer 2B. The crystalline resin having a shorter time is formed, for example, a polypropylene resin. Specifically, the surface layer 2B preferably has an MFR which is 15 times or more larger than that of the intermediate layer 2, because the MFR is less than 1.5 times, and the transparency is The improvement effect is small. Further, 158273.doc •20· 201213127 is the relaxation time of 80% of the intermediate layer 2A to ττ -a- U/〇. The reason is that if the relaxation time is greater than 80%, the transparency is The improvement effect is small. The measurement of MFR is based on m_K721〇 measured at a temperature of 2 and a load of 2.16 kg. The other time is (1) the cone-shaped plate is set in a rotary rheometer manufactured by Rhe〇metrics. For 25 one, the cone angle is set from i radians (four)) and at the temperature When the frequency dispersion measurement is performed at a degree of 175t, 'the angular frequency is obtained. (4) When the time is determined, the time I is determined by the specific time and t' is as shown in the following formula (4), and the stress σ· and the strain γ are σ*/γ ♦ The composite elastic modulus G(i〇) measured for the resin particles is defined, and the relaxation time τ is obtained by the following formula (5). G (ico)=, /y=G'(to)+IG"((〇) ...(4) t(c〇)=G'((〇)/(g)G"(co)) ... (5) (where G' denotes the storage elastic modulus, and G" denotes the loss elastic modulus.) Here, the relaxation time (τ) is described in detail. The following phenomenon is called relaxation: the pair is in equilibrium When the material system of the state applies an external force to reach a new equilibrium state or a stable state, if the external force is removed, the system returns to the initial equilibrium state by the internal motion of the system; and it will become the time required for relaxation. The standard characteristic time constant is called the relaxation time. In the case of polymer forming (for example, extrusion molding), the molten polymer flows, but at this time, the molecular chain is stretched and pulled in the flow direction. (Orientation). When the flow is completed and the cold part is started, the stress applied to the molecules disappears, and the molecular chains start to move, and soon they go in an arbitrary direction (this is called the relaxation of the molecular chain). The relaxation time is Molecular chain oriented in the direction of extrusion during extrusion 158273.doc -21 · 201213127 In the case where the time is short, it means that it is easy to recover. Further, in the present embodiment, the entire sheet 2 is formed in three layers, but it is not limited thereto, and may be formed only in the middle layer 2 Two layers of the surface layer 2B are formed on one surface. Further, the entire sheet 2 may be formed such that an intermediate layer 2A is provided on at least the surface of the substrate layer, and a surface layer is provided on the surface of the intermediate layer 2A. In addition, the resin raw material is not limited to the polypropylene resin. [Manufacturing method of the transparent resin laminated body] Next, the operation of producing the sheet-like transparent resin laminated body 3 by the above-described manufacturing apparatus First, the temperature of the outer circumferential surface of the cooling endless belt 115 and the third cooling pro-113 of the cooling and pressing device 11 of the entire web forming apparatus 10 is maintained at a temperature equal to or higher than the dew point of the refining resin 2C. The temperature adjustment mechanism is used to control the temperature. Here, when the temperature exceeds 5 (in the case of rc, the transparency of the entire sheet 2 may not be obtained, and the α crystal is too large to be formed. Therefore, the control is performed. Below 5 (TC below, preferably It is 3 (rc or less. Further, when it is lower than the dew point, condensation may occur on the surface to cause water droplets on the sheet, and uniform film formation becomes difficult, so it is controlled above the dew point. Further, heat treatment in the heat treatment device 20 In the apparatus main body 22, the temperature of the outer circumferential surface of the heating endless belt 227 or the fourth heating roller 224 is maintained at a temperature higher than the crystallization temperature of the entire sheet 2 and below the melting point, and (4) temperature control mechanism performs temperature control. Furthermore, in the preheating device 210 of the heat treatment device 20, the temperature is cooled to 50 ° C or more and is crystallized by preheating to the cooling extrusion device 158273.doc • 22· 201213127 of the entire web forming device 1 . Temperature control can be performed in the following manner. In this state, the molten resin 2C of the inter-layer 2A and the surface layer 2B is extruded from the τ-die 102 of the τ-die extrusion apparatus 100 in a state in which the laminate is in the form of a sheet, and is introduced into the rotational movement of the cooling and pressing device 110. The cooling endless belt 115 and the outer peripheral surface of the rotating third cooling roll 113 are interposed. The intermediate layer 2A and the surface layer 2B thus introduced are rapidly cooled by surface-bonding of the molten resin 2C which is laminated in a sheet shape. At the time of rapid cooling at s, the elastic material Π 1A is elastically deformed into a compressed state due to the pressing force between the second cooling roll 1丨2 and the third cooling roll 1 i 3 , and the molten resin 2C is in the elastic material 111 a The angle Θ1 portion (refer to FIG. 2) which is elastically deformed from the center of the second cooling roller 112 and the third cooling roller 134, is clamped together with the cooling endless belt 115, and is restored by the elastic material u丨a. Force and squeeze through the surface. Further, the surface pressure at this time is preferably 〇1 MPa or more and 20.0 MPa or less. Here, when the surface pressure is lower than 〇.i MPa, air is trapped between the cooling endless belt j 15 and the third cooling roll 113 and the molten resin 2C, and the appearance of the sheet becomes poor. On the other hand, if the surface pressure is higher than 2 〇.〇 MPa, the life of the endless belt 115 for cooling is not good. Therefore, the surface pressure of the planar extrusion is set to be 0.1 MPa or more and 20.0 MPa or less. Then, the intermediate layer 2A and the surface layer 2B sandwiched between the second cooling roller 112 and the cooling endless belt ι 15 are in a circular arc portion corresponding to the substantially lower half of the second cooling roller 112, by the second cooling roller 112. It is crimped in a plane shape with the endless belt 115 for cooling. Further, the intermediate layer 2A and the surface layer 2B are further rapidly cooled by the cooling water spray 158273.doc -23-201213127 attached to the nozzle 116 to the cooling water n6A on the back side of the cooling endless belt 115. Further, the surface pressure at this time is preferably set to 〇 〇 1 MPa or more and 〇 5 MPa or less. Further, the temperature of the cooling water 1 i6A is preferably set to 〇. 〇 above and below 30 C. Furthermore, the 'cooled water U6A sprayed is recovered into the water tank 11 7' and the recovered water 117 a is discharged by the drain port η 7B. Here, if the surface pressure is lower than 〇.〇1 MPa, there is The control of the cooling ring belt π 5 becomes difficult, and the production cannot be stabilized. On the other hand, if the surface pressure is higher than 0.5 MPa', the tension acting on the cooling endless belt n5 becomes high, which is not preferable in terms of life. Therefore, it is preferable to set the surface pressure of the surface extrusion to 0.01 MPa or more and 0.5 MPa or less. In this manner, between the second cooling roll 112 and the cooling endless belt 115, the intermediate layer 2A and the surface layer 2B are pressure-contacted and cooled, and then adhered to the intermediate layer 2 A and the surface layer 2B of the cooling endless belt 115. The rotation of the endless belt 115 for cooling moves to the third cooling roller 113. Further, the intermediate layer 2A and the surface layer 2B guided by the peeling roller 119 are cooled by the third cooling roll 113 via the cooling endless belt 115. Further, the water adhered to the back surface of the cooling endless belt 115 is removed by the suction roll 118 provided in the middle of the movement from the second cooling roll 112 to the third cooling roll 113. The intermediate layer 2A and the surface layer 2B which have been cooled on the third cooling roll 113 are peeled off from the cooling endless belt 115 by the peeling roller 119 to form the entire sheet 2. The whole sheet 2 obtained has an internal haze of 20% or less, and at least one surface has a rough surface roughness of Rmax = 0.5 μm or less. That is, in the cooling extrusion 158273.doc -24 - 201213127, it is preferable to obtain the entire sheet 2 with an internal haze of 20% or less and at least one surface roughness of Rmax = 0.5 μm or less. The conditions are rapid cooling and surface crimping. Here, the turbidity (turbidity) is based on JIS-K-7105, and the total light transmittance (Tt) indicating the total amount of light irradiated to and transmitted through the entire sheet 2 is diffused and transmitted by the entire sheet 2. The ratio of the diffused light transmittance (D) is determined by the following formula (6). Further, the total light transmittance (Tt) is a parallel light transmittance (Tp) and a diffused light transmission which are transmitted coaxially with the incident light. The sum of the ratios (Td). Turbidity (H) = (Td/Tt) xl00 (6) Further, the term "internal turbidity" means that the transparency inside the sheet is measured in order not to be affected by the surface roughness of the sheet. The surface of the sheet is coated with polyfluorene oxide and the turbidity is measured. Here, when the value of the internal turbidity is more than 2%, even if the heating by the heat treatment apparatus body 220 in the subsequent stage is performed, the surface dusting treatment is performed. In addition, the internal turbidity becomes large, and the highly transparent transparent resin laminate 3 cannot be obtained. On the other hand, if the surface roughness is greater than Rmax = 〇.5, the heat treatment apparatus body 220 is thermally bonded to the subsequent stage. When the fourth heating roller 224 and the heating endless belt 227 are entrained with air, a so-called bubble is generated. Preferably, the entire sheet 2 is formed in such a manner that the internal haze is 20% or less and the surface roughness is Rmax = 〇5 μπι or less. Then, the entire sheet 2 formed by the cooling and pressing device 110 is erected in the preheating. The outer surfaces of the first preheating roller 211, the second preheating roller 212, and the third preheating roller i213 of the apparatus 210 are moved and preheated. Then, the whole web 2 preheated by the preheating device 210 is performed. It is introduced into the heat treatment device 158273.doc -25- 201213127 between the rubber roller 225 of the main body 220 and the outer circumferential surface of the heating endless belt 227. The introduced whole web 2 is pressed and heated by the rubber roller 225. The outer circumferential surface of the heating endless belt 227 is adhered to the outer surface of the heating endless belt 227. The heat-sealed whole web 2 is moved together with the rotationally-applied heating endless belt 227, and introduced into the outer circumference of the heating endless belt 227 and the fourth heating rod 224. Between the faces, the introduced entire sheet 2 is subjected to surface dusting by a fourth heating roller 224 sandwiching the entire sheet 2 and a heating endless belt 227 by which the tension is applied by the fourth heating roller 224. The heating temperature in the heat treatment of the whole sheet 2 is the crystallization temperature of the entire sheet 2 In the case where the entire sheet 2 is the one comprising the propylene-based resin (a) and the metallocene-based ethylene-α-olefin copolymer (b), the surface temperature of the entire sheet 2 is & Heating is carried out under conditions of 12 〇t or more and not reaching the melting point. Further, the surface pressure at the time of heat treatment is appropriately set depending on the shape of the molding. The reason is that, here, the temperature is lower than the crystallization temperature of the entire sheet 2, Then, the softening of the entire sheet 2 becomes insufficient, and the & method is formed into a desired shape. On the other hand, if it is a temperature higher than the melting point of the entire sheet 2, it is cooled by cooling (4). The obtained high-order structure is destroyed, and it is cloudy and cannot be obtained transparency. Thereafter, the entire sheet 2 is peeled off from the outer surface of the fourth heating report 224 to be dense.

It is heated while moving in the state of the ring belt 227, which can be heated in the state of A ^ A 27 . Then, the entire sheet 2 of 2' = heat is extracted by the guide ring 226, and the self-heating ring type ' is extracted as the sheet-like transparent resin laminate 3 . The deposited and affixed resin resin laminated body is erected on the outer peripheral surface of the first cooling guide roller 231 and the second cooling guide roller 232 by the cooling device 23 158273.doc -26 - 201213127, and moves in a meandering manner. And cooled, it is sent out between a pair of guide rolls 233. In addition, the transparent resin laminated body 3 which is a product to be delivered is wound up, for example, from a winding device (not shown). The total thickness of the transparent resin laminate 3 obtained by the above production method is preferably set to 160 μm or more and less than 500 μm. The reason for this is that, in the case where the total thickness dimension of the transparent resin laminate 3 is thinner than 160 μm, the rapid cooling effect of each of the cooling rolls 111 to 114 of the cooling press device is sufficiently obtained, so that the layer is not required to be laminated. Transparency. On the other hand, when the total thickness of the transparent resin laminate 3 is 500 μm or more, the rapid cooling effect by heat conduction cannot be expected, and as a result, the effect of lamination cannot be exhibited. [Effects and Effects of the Embodiments] In the above embodiment, the intermediate layer 2 of the crystalline resin is formed, and

It is an ethylene-α-olefin copolymer.

The formation and growth are suppressed, and the size is also changed to ‘ethylene-α-olefin copolymer. The amount of spherulites of spherulites is reduced and the size of spherulites is 158273.doc -27- 201213127 small. Therefore, the scattering of light by spherulites is reduced to improve transparency (lower turbidity). Further, the respective crystalline resin of the intermediate layer 2 and the surface layer 2 is extruded in a molten state and cooled in a state in which the laminate is in a sheet form to form the entire sheet 2. The temperature of the entire sheet 2 is not less than the crystallization temperature and not higher than the melting point. Heat treatment is performed. Therefore, the high-order structure in the entire sheet 2 which is obtained by cooling the obtained good crystallinity is broken and the transparency is impaired, and it can be favorably formed into a sheet shape, whereby a sheet having high transparency can be obtained. The transparent resin laminate 3 is formed. Further, as the intermediate layer 2, an isotactic pentad fraction of 8 〇 mass% or more and 99 5 mass% or less is 85% or more and 99% or less, and 1^11 is 〇5 g/H) min or more. 5. propylene resin (4) of less than /10g/10 min and 5% by mass of 〇5 mass and 20 mass% or less, manufactured using a metallocene catalyst, having a density of 898 kg/m3 or more and 913 kg/m3 or less, MFR It is formed by a metallocene-based ethylene olefin copolymer sand of g5 g/i〇 or more and 6.0 g/1 〇min or less. Therefore, the propylene-based resin (4) in the intermediate layer 2 A and the metallocene-based ethylene-α-glycol copolymer (b) which inhibits the growth of the spherulites are substantially the same degree, and the transparency can be improved. Further, since the viscosity ratio of the propylene-based resin (a) to the metallocene-based ethylene-α-olefin copolymer (b) is not more than 1 〇 and not more than 3.0, it can be uniformly dispersed uniformly, thereby preventing uniform dispersion. And the resulting decline in transparency. Further, the propylene resin (a) was 80% by mass. 〇 〇 且 9 9 9 9 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 两 两 两 两 两 两 两 两 两Therefore, it is possible to prevent a problem that the metallocene-based compound (8) which becomes a hetero 3 is oxidized due to the propylene-based resin (1). On the other hand, it is also possible to prevent the pentad metal-based ethylene olefin copolymer (8) which suppresses the growth of the ball from growing, and the propylene resin (4) is not sufficiently smeared, and the spherulite growth cannot be sufficiently suppressed. After that. Further, it is preferred to use an acrylic resin as the crystalline resin which forms the intermediate layer 2 and the surface layer 2Β. a can be widely used and can be easily formed into a sheet shape, heat treatment or the like by using an acrylic resin which does not affect the human body, and the transparent tree moon layer laminate 3 can be used for a long time. The transparent resin laminate 3 can be provided at low cost in various fields. Further, a linear low-density polyethylene is used as the metallocene ethylene-α-olefin copolymer. Therefore, the refractive index of the propylene-based resin (4) is substantially the same, and the mixture can be easily uniformly dispersed and mixed ('9), and the transparency can be easily improved. Therefore, the highly transparent transparent resin laminate 3 can be easily formed. Further, the entire web 2 is formed by two three-layer structures in which the surface layer (5) is provided on both sides of the sheet-like intermediate layer 2-8. Therefore, the stress applied to the extrusion of the intermediate layer 2Α can be further relaxed as compared with the case of being disposed on one side, and the residual stress can be further reduced, whereby the transparency can be further improved. Further, 'the intermediate layer 2A may be formed on both surfaces of the substrate layer 158273.doc -29-201213127 formed of a crystalline resin to be a substrate, and further provided on the surface of the intermediate layer 2A The five-layer structure of the surface layer 2B. When formed into such three five-layer structures, even if a low-viscosity propylene-based resin (a) is deposited on the surface layer, the growth of residual spherulites can be suppressed, thereby suppressing the decrease in transparency due to scattering of light. That is, the production of giant spherulites. Further, by reducing the layer thickness of the metallocene-based ethylene·α-olefin copolymer (b), it is possible to prevent the metallocene-based ethylene_α_dilute hydrocarbon copolymer (b) from being different. The refraction of light 'thus can further improve transparency. In particular, since a propylene-based resin is used as the crystalline resin of the base layer, the refractive index of the base layer and the intermediate layer 2A and the surface layer 2B are substantially the same, so that high transparency can be obtained even for three five-layer structures. A transparent resin laminate 3 is used. Further, in the manufacturing apparatus 1 of the present embodiment, the entire sheet 2' is produced by the cooling and pressing device 110, and the heat treatment device 20 is directly used for heat treatment to continuously manufacture the transparent resin laminate 3. Therefore, the desired transparent resin laminate 3 having high transparency can be efficiently produced. [Modifications] Further, the aspect described above shows an aspect of the present invention, and the present invention is not limited to the above embodiment. Variations or improvements within the scope of the objects and effects of the invention are included in the scope of the present invention. For example, it is also possible to take up the entire sheet 2 and wind it up, and supply the entire sheet 2 produced by heat treatment to the heat treatment strip 20 and heat-treat it, and the manufacturing of the transparent resin laminated body 3' is not limited to the above embodiment. . 158273.doc •30· 201213127 Further, as the entire sheet 2, a surface layer 2B is formed on both sides of the intermediate layer 2, but it may be formed only on one side of the intermediate layer 2 The two layers of the surface layer 2B are formed. Further, an intermediate layer 2A may be formed on one surface of the base material layer, and three three-layer structures of the surface layer 2B may be provided on the surface of the intermediate layer 2A. Further, it is also possible to form three kinds of four-layer structures or the like in which the surface layer 2B is provided on the surface of only one intermediate layer 2A in the intermediate layer 2A provided on both surfaces of the base material layer. In addition, the physical properties, the blending amount, and the like of the propylene-based resin (a) and the metallocene-based ethylene_α-olefin copolymer (b) are larger than the MFR of the surface layer 2B with respect to the intermediate layer 2A of the crystalline resin. The condition that the relaxation time is shorter can be appropriately set according to the desired transparent resin laminate 3 . Further, it is not limited to the propylene resin (a) and the metallocene ethylene/α-olefin copolymer (b). [Examples] [Examples 1 to 8 and Comparative Examples 1 to 5] In the above embodiment, the specific conditions of the manufacturing apparatus and the manufacturing method are as follows. Further, the raw material resins in the respective examples and the comparative examples are shown in Table 1. The layer constitutions are shown in Tables 2 to 4. Determination of melt flow rate of raw material resin I58273.doc -31 · 201213127 [Table i] Trade name (manufacturer) Flow rate of smelting fg/10 min] Relaxation time W pentad fraction r%i Density [kg/ M3] Polypropylene resin Y-2005GP (Prime Polymer Co., Ltd.) 20 0.26 93.5 - E-103WA (Prime Polymer Co., Ltd.) 3 12.2 92 - F-704NP (Prime Polymer Co., Ltd.) 6.4 0.41 90 - F- 300SV (Prime Polymer Co., Ltd.) 2.8 8.28 98 .- Metallocene Ethylene-α-Dilute Hydrocarbon Copolymer KF270 (Sakamoto Polyethylene Co., Ltd.) 2 - - 907 KF271 (Sakamoto Polyethylene Co., Ltd.) 2.4 - - 913 KF370 (Sakamoto Polyethylene Co., Ltd.) 3.5 - - 905 KS240T (Sakamoto Polyethylene Co., Ltd.) 2 - - 880 KF283 (Sakamoto Polyethylene Co., Ltd.) 2.5 - - 921 KC570S (Sakamoto Polyethylene Co., Ltd.) 10.5 - - 906 Using the raw material resin shown in Table 1, the container was manufactured from the entire sheet 2 by the heat treatment apparatus 20 of the above-described manufacturing apparatus 1. The manufacturing conditions are as follows. Extruder: • For the first substrate layer: 90 mm in diameter • For the second substrate layer: 50 mm diameter. Width of the hanger-type die: 900 mm (layer of molten resin 2C in the feed block mode) Surface roughness: Rmax=0.1 μηι Cooling ring: • Material: Precipitated hardened stainless steel • Surface roughness: Rmax=0.1 μηι 158273.doc -32- 201213127 • Width: 900 mm • Length: 7700 mm • Thickness: 0.8 mm The temperature of the cooling ring 115 and the third cooling roll n3 of the cooling resin 2C is introduced into the cooling extrusion device 11: 16 < t The extraction speed of the entire sheet 2: 1 〇 m / min Width of sheet 2: 780 mm Temperature at the time of heat forming of the container: surface temperature of the entire sheet 2 (Γ(: and 'The inner turbidity of the entire sheet 2 obtained and the turbidity of the container. The internal turbidity was measured using a turbidity measuring machine (NE) H-3〇〇A, manufactured by Nippon Denshoku Industries Co., Ltd. The internal turbidity was applied to the both sides of the sheet, and the glass slab was used. Clamp both sides of the sheet to eliminate the effects of the outside of the sheet and utilize turbidity The turbidity of the container is determined by the ratio of the total light transmittance (Tt) indicating the total amount of light irradiated to the sheet and transmitted, and the ratio of the diffused light transmittance (Td) diffused by the sheet and transmitted. The average thickness of the container was measured using a micrometer (ID_C112C, manufactured by Mitutoyo Co., Ltd.). The top surface of the container was cut out by $cmx5 cm, and the center was cut. The average of the three points of the two endpoints is taken as i samples. The average of the five samples is taken as the average thickness of the container. Linear low density polyethylene as a metallocene ethylene-α-olefin copolymer (linear The MFR and density of low density polyethylene (LLDPE) are as described in the above embodiments. The measurement results are shown in Tables 2 to 4. I58273.doc •33·201213127 Example 5 Y-2005GP*1 〇H _ S f N Φ Φ4 均ο ·— ο ro Pu E-103WA*2 " I 4.91 1 1.82 s as <ri 1.44 Example 4 Y-2005GP*1 ♦1 g CN^ _ s ώ 1〇271*410% by mass | E -103WA*2 ! 6.45 | 2.85 Γ^ϊ CS mm inch oi m 00 Example 3 S Y-2005GP*1 | _ η 00 cj ί s ώ KF270*3 15% by mass E-103WA*2 | 6.32 2.03 m cn Os o CN 2.08 Example 2 1 Y-2005GP*1 E-103WA*2 99% by mass 1 η * & | E -103WA*2 | 7.71 2.83 1 312 1 907 〇cs | 2.08 | Example 1 i Y-2005GP*1 CN 0 S ώ _ Ο § s | E-103WA*2 5.99 2.14 g cn 〇\ o (N 2.08 surface Layer CL, CU mm -ti LLDPE substrate layer turbidity [%] 1 container turbidity [%] average thickness [μτη] I Yang ω CU Q hJ LLDPE melt flow rate [g/10 min] viscosity ratio ( ? Ρίιπ<<^杷 umbrella^3slxqp>*OJ-4B)荽龄沭敦载-a-发ο%' eating 呦粑: (3T05. pants) 0Αε& :5P (啭铋t?<<BaiJ杷 umbrella ^3δ>;ψ3/ςοα--4Β)荽铋沭敦袈-?费洛夫璎如粑:(eos.Box)UCNJS: inch* (制铋^々嗟杷甶驾3sl/cql3/{od4B )荽铋咪3⁄4众έ-装to shouting®^ target: (5TOS. Box) 0/, 3⁄43⁄4 : e* (澍铕t§<<ul Potassium umbrella^ss>, ocu3UI-cCI} Love: ( 3r^'box) νΜεοιώ :CN* (锄铋nF<<u^^^su^oOH3UI-dPH)^«^: (W05.柩)dosooCN-A :Γ 158273.doc -34- 201213127

[S 158273.doc Example 8 Y-2005GP*1 1 £-103% 八*2 85质量% φ| o CN Ph 1 ! 6.77 I 2.95 | 304 907 o CN 2.08 Example 7 Y-2005GP*1 as σ \ > C/D 〇ώ i KF270*3 1% by mass E-103WA*2 8.12 3.66 CN Os <N i 907 o CN 1 Example 6 F-704NP*4 φΊ ί s ώ φ>1 ο O ( N Mh E-103WA*2 | 6.25 3.19 309 On o <N 2.08 Surface layer Oh LLDPE Substrate layer Whole web turbidity [%] Vessel turbidity [%] Average thickness [μιη] r^1 1 s Throw a Q LLDPE melt flow rate [g/10 min] viscosity than the middle layer "^Boiw<s07w"(fF^nF^^-^-^Ris/ioPHiHd)#^ 铋:(3T05. cabinet) dosoz-Λ :肊 Purple age: 005. Pivot) Asooro-d: s* Love: (WOS. Box) - οΓ~ώ: inch* (Help 铕阳<<some 杷 umbrella^3SIXqp/io&H-4B #龄沭敦«-? Install S3 shouting target: (3TDS box οζζδ: Γ -35- 201213127 158273.doc [inch] Comparative example 5 Y-2005GP*1 ♦1 ON SO k ο m ώ i KC570S *5 10% by mass 1 26.55 1 9.91 sm 00 ON o 0.49 inch 锑Y-2005GP*1 φ4 %3ζ fS^ $ s τ-Ή ώ face io V» o E-103WA*2 20.16 6.23 00 (N m Ο § 10.5 | 0.49 Compare 3 Y-2005GP*1 | φ4 % CN^ ί s ώ 容! οο CO oo <N E-103WA*2 6.01 4.05 m (Ν ON to oi 00 Comparative Example 2 Y-2005GP*1_j 〇Η tK γν ^ _ S ώ KS240T*3 10% by mass j E-103WA*2 (N vd 6.71 ro Oi ms 00 o (N | 2.09 Comparative Example 1 Y-2005GP*1 | E-103WA*2 100 Quality 0/〇1 E -103WA*2 14.06 5.54 (N 1 1 1 surface layer cx τέ or QL -Ϊ T, BJ/W niDpFI | substrate layer turbidity [%] container turbidity [%] average thickness [μτη] riT1 锑ω Pl QJ LLDPE melt flow rate [g/10 mini viscosity ratio (锄铋c§<^^fe^^SOI/coeL, 3UI£) Mounting: (3TOS. Box) is.3 : CN* (He 铋 可 <<咝杯伞祝10^|!£) Installed 铋:(^DgsOHos0<NA:Γ (Mocking tf<<ul·^Umbrella^3J /clp3xoCL,4B) 铋沭 铋沭 - -? 爱 (0 shouting Φ target: (wa' box) 08 inch S: Bu * (^nt? <4^·^牟^ss/coaam-c,! }装¢-3⁄4 : (5TOS.Box) aose-w: 9* (Jiyu w^^-fe^^s long f>.od4B)荽岁咪ΐί爱-?爱to shout _φ^: (STOS柩)esis : inch* ^ mi .. ^one^wHOS^ - -36- 201213127 [Results] According to the results shown in Tables 2 to 4, a density of 898 kg/m3 or more and 913 kg/ is added to the intermediate layer. A sheet having a metallocene-based ethylene_α-olefin copolymer (b) having an MFR of 〇·5 g/1 〇min or more and 6.〇g/l〇min or less can obtain good transparency. The addition of the metal-based ethylene olefin copolymer sand) has a large effect of improving the transparency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a transparent resin laminate body of the embodiment of the present invention. The outline of the manufacturing apparatus in the manufacturing method is a schematic view of the extraction unit in the above-described manufacturing apparatus: the illustration shows the polyacryl film of the present invention. Graph of relationship between refractive index and density, and the horizontal axis is density, and the vertical axis is refractive index. I main component symbol description] 1 2 manufacturing device whole film 2Α 2Β 2C 3 10 20 100 1〇1 intermediate layer surface layer molten resin Transparent resin laminated body whole web forming apparatus heat treatment apparatus τ die extrusion apparatus extruder 158273.doc • 37· 201213127 102 T die 110 cooling extrusion apparatus 111 first cooling roll 111A elastic material 112 second cooling roll 113 Third cooling roller 114 Fourth cooling roller 115 Cooling annular belt 116 Cooling water spray nozzle 116A Cooling water 117 Water tank 117A Water 117B recovered Water outlet 118 Water absorption 119 Stripping roller 210 Preheating device 211 First preheating Kuikun 212 Second preheating roller 213 Third preheating roller 220 Heat treatment apparatus body 221 First heating pro 222 Second heating roller 223 Third heating roller 224 Fourth heating report 158273.doc -38- 201213127 225 Rubber roller 226 Guide roller 227 Heating With the endless belt 230 cooling device 231 first cooling guide roller 232 second cooling guide roller 233 guiding roller Θ 1 angle 158273.doc -39-

Claims (1)

201213127 VII. Patent Application Range: 1. A method for producing a transparent resin laminate, characterized in that it comprises an intermediate layer formed of a crystalline resin and is provided on at least the surface of the intermediate layer and A method for producing a transparent resin laminate of a surface layer formed of a crystalline resin, wherein the crystalline resin of the surface layer has a larger melt flow rate and a shorter relaxation time than a crystalline resin forming the intermediate layer. At least one of the crystalline resin forming the intermediate layer and the crystalline resin forming the surface layer contains a pentylene-based ethylene-(X-futosan copolymer) produced by using a metallocene catalyst, which will form the middle The crystalline resin of the layer and the crystalline resin forming the surface layer are respectively melted, extruded, and cooled in a state in which the laminate is in a sheet form to form a resin laminate, and the resin laminate is heated at a temperature equal to or higher than the melting temperature and not higher than the melting point. 2. The method for producing a transparent resin laminate according to claim 1, wherein the intermediate layer is 80% by mass or more and 99.5% by mass or less of the isotactic pentad fraction is 85% or more and 99% or less, and the melt flow rate is 0.5 g/10 min or more and 5 · 0 g/10 min or less of the acrylic resin, and 0.5% by mass More than 20% by mass of a metallocene system manufactured using a metallocene catalyst, having a density of 898 kg/m3 or more and 913 kg/m3 or less, and a melt flow rate of 0.5 g/10 min or more and 6.0 g/10 min or less 3. The method for producing a transparent resin laminate according to claim 1 wherein 158273.doc 201213127 The crystalline resin of the intermediate layer and the surface layer is a propylene resin. 4. The method for producing a transparent resin laminate according to claim 3, wherein the metallocene-based ethylene-α-olefin copolymer is a linear low-density polyethylene. 5. The transparent resin laminate according to claim 2 In the manufacturing method, the crystalline resin forming the ten-layer and the surface layer is a propylene-based resin. The method for producing a transparent resin laminate according to claim 5, wherein the metallocene is _α_ Olefin copolymer is linear low density The method for producing a transparent resin laminate according to any one of claims 1 to 6, wherein the intermediate layer is provided on both sides of the substrate layer formed of the crystalline resin, and in the middle The surface layer is provided on the surface of the layer. The method for producing a transparent resin laminate according to claim 7, wherein the crystalline resin forming the base layer is a propylene resin. 9. A molded body characterized by: It is provided with ten layers formed of a crystalline resin, and a surface layer formed of at least one surface of the intermediate layer and formed of a crystalline resin, and the crystalline resin of the surface layer and the intermediate layer are formed. Compared with the crystalline resin, the melt flow rate is larger and the relaxation time is shorter, and at least one of the crystalline resin forming the intermediate layer and the junction resin forming the surface layer includes the use of the metallocene catalyst. The metallocene-based ethylene-a-dilute hydrocarbon copolymer is produced, and the surface layer of the above-mentioned surface layer is formed into a crystalline resin of the above intermediate layer and formed into a crystalline resin of 158273.doc 201213127 Molten state into a sheet and laminated rapid cooling of the resulting laminate to obtain the resin and the crystallization temperature or a temperature below the melting point of the intake line thermal molding. 10. The formed body according to claim 9, wherein the intermediate layer is provided on both surfaces of the base material layer formed of the crystalline resin, and the surface layer is provided on both surfaces of the intermediate layer. A resin laminate which is formed by heat treatment to form a transparent resin laminate, and includes an intermediate layer formed of a crystalline resin and provided on at least one side of the intermediate layer and crystallized The surface layer formed of the resin, the crystalline resin of the intermediate layer contains 8 〇 mass% or more and 99.5% by mass or less, and the isotactic pentad fraction is 85% or more and 99% or less, and the melt flow rate is 0.5 g. / 〇 〇 min and 5 〇 g / 1 〇 _ or less of the propylene resin and 0 to 5 mass % or more and 2 〇 mass % or less using a metallocene catalyst, and the degree of twist is 898 kg / m 3 or more and 913 kg / a metallocene-based ethylene-a-olefin copolymer having a melt flow rate of 0.5 g/l/min or more and 6 〇g/1 〇min or less, a crystalline resin of the surface layer, and crystallinity of the intermediate layer formed thereon Compared with the resin, the melt flow rate is larger and the relaxation time is shorter. 12. The resin laminate according to claim 11, wherein the intermediate layer is provided on both surfaces of the base material layer formed of the crystalline resin, and the surface layer is provided on both surfaces of the intermediate layer. 158273.doc