JP2014012366A - Method of manufacturing highly elastic transparent resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a highly elastic transparent resin laminate excellent in transparency, excoriation resistance, weatherability, and the like.SOLUTION: The method of manufacturing a resin laminate comprises the steps of: overlapping a biaxially-drawn polyester film with a sheet-like resin while pouring an adhesive onto one surface or both surfaces of the sheet-like resin, extruded from a T-die; pressure-bonding them; and thereafter curing the adhesive.

Description

  The present invention relates to a method for producing a transparent resin sheet exhibiting a high flexural modulus that can be used for a front panel of a capacitive touch panel type display surface of a mobile phone, a personal computer, a tablet PC, or a car navigation system.

Polycarbonate resin has excellent transparency, impact resistance, and high heat distortion temperature, and also has excellent dimensional stability, workability, and self-extinguishing properties. Used in.
However, the polycarbonate resin has low scratch resistance and inferior weather resistance, and therefore has a problem that when used outdoors exposed to direct sunlight, the impact strength is reduced and the yellow color is changed.

  In order to improve these problems economically with a simple process, after applying a solvent-free UV-curable coating composition on a polycarbonate resin molded article, and appropriately passing between the rolls by overlapping a polyester film, A method of peeling a polyester film after curing the ultraviolet curable coating composition is known (Patent Document 1).

  In addition, for the purpose of improving the weather resistance, which is an insufficient point in this method, by preparing a specific component as a coating composition, a composition showing good adhesion to the polymethyl methacrylate surface was prepared, and this A layer formed on one side of a polyester film is superimposed on the polymethyl methacrylate surface of a coextruded sheet composed of an aromatic polycarbonate resin and polymethyl methacrylate, passed between rolls, and then the coating composition is cured to obtain a polyester. A method for peeling a film is known (Patent Document 2).

Japanese Patent No. 2798261 JP-A-2005-305698

  By the conventional method, a sheet having improved scratch resistance and weather resistance can be obtained. However, when used for a portable touch panel type display surface front plate, depending on the size of the front plate, the flexural modulus of a polycarbonate sheet or a laminated sheet in which a polymethacrylate resin layer and a polycarbonate resin layer are laminated If the face plate is pressed strongly when touched, there is a problem that the sheet is bent and the liquid crystal or organic EL display surface glass is excessively pressed, and the display screen is distorted or the glass is broken. Therefore, a highly elastic transparent sheet (front plate) has been demanded. Therefore, as a result of intensive studies on a method for laminating a highly elastic transparent sheet, a method for laminating a biaxially stretched polyester film on a surface layer was found, and the present invention was completed based on the method.

That is, the present invention
<1> The biaxially stretched polyester film and the sheet-shaped resin are overlapped and pressed while injecting the adhesive onto one or both sides of the sheet-shaped resin extruded from the T-die, and then the adhesive is cured. It is a manufacturing method of the resin laminated body characterized by the above-mentioned.
<2> The method for producing a resin laminate according to <1>, wherein the sheet-like resin extruded from the T die is an aromatic polycarbonate resin.
<3> The method for producing a resin laminate according to <1> or <2>, wherein the sheet extruded from the T die has a thickness of 0.25 to 1 mm.
<4> The method for producing a resin laminate according to any one of <1> to <3>, wherein the biaxially stretched polyester film is laminated on both surfaces of the sheet-like resin.
<5> In any one of the above items <1> to <4>, the biaxially stretched polyester film comprises a laminate comprising a hard coat layer and / or a weather-resistant hard resin on one side, and is bonded to the sheet-like resin. It is the manufacturing method of the resin laminated body which is what was integrated with the agent.
<6> The method for producing a resin laminate according to any one of <1> to <5>, wherein the biaxially stretched polyester film has a thickness of 0.02 to 0.25 mm.
<7> The method for producing a resin laminate according to any one of <1> to <6>, wherein a solvent-free curable or hot-melt resin composition is used for the adhesive layer.
<8> The method for producing a resin laminate according to any one of <1> to <7>, wherein the adhesive layer has a thickness of 20 μm or less.

  The resin laminate according to the production method of the present invention is produced by an in-line method, and has an advantage that an existing production process can be effectively used as it is. In addition, it exhibits a high flexural modulus, and can appropriately impart high scratch resistance and weather resistance without substantially impairing this high flexural modulus. It can be used for members, optical members, LCD and EL display protective sheets, and others.

1 is a cross-sectional view of the resin laminate of Example 1. FIG. 2 is a cross-sectional view of the resin laminates of Example 2, Example 4, and Example 5. FIG. FIG. 3 is a cross-sectional view of the resin laminate of Example 3. FIG. 4 is a cross-sectional view of the resin laminate of Example 6. FIG. 5 is a cross-sectional view of the resin laminate of Example 7.

  Hereinafter, the present invention will be described. In the present invention, the biaxially stretched polyester film and the sheet-like resin are overlapped and pressure-bonded while injecting the adhesive onto one or both sides of the sheet-like resin extruded from the T-die, and then the adhesive is cured. The manufacturing method of the resin laminated body characterized by becoming is provided. A preferred embodiment of the present invention provides a method for producing a highly elastic transparent resin laminate excellent in transparency, scratch resistance, weather resistance and the like.

(Biaxially stretched polyester film (PES) used in the present invention)
The highly elastic resin for lamination used in the present invention is a biaxially stretched polyester film having a high tensile elastic modulus. The tensile elastic modulus of the biaxially stretched polyester film varies depending on the type, the stretch rate, etc., but shows a high value of about 4 GPa, for example. In addition, regarding the bending elastic modulus of commercially available biaxially stretched polyester film, there is no description in the catalog etc., and since it is a thin film, it is usually difficult to measure, but there are no structural factors, and general plastics Assuming that the film is equivalent to a molded product, the flexural modulus of these films is presumed to exhibit a value similar to the tensile modulus.

Examples of the raw material polyester include polyethylene terephthalate and polyethylene naphthalate, and copolymers thereof. The thickness of the biaxially stretched polyester film may be appropriately selected from the commercially available thickness range of 0.02 to 0.25 mm, preferably 0.08 mm to 0.2 mm, and more preferably 0.1 mm to 0.00 mm. 188 mm is particularly preferable.
A biaxially stretched polyester film is usually difficult to produce a biaxially stretched biaxially identical film having no anisotropy in the plane direction (xy direction). It is a thing with. For this reason, it is used in applications or usage methods in which large retardation with unspecified direction is not a problem. When the thickness of the biaxially stretched polyester film exceeds the above range, warpage after pasting due to a change in the stretch ratio of TD / MD increases.

  If the biaxially stretched polyester film is thicker or the ratio of the stretch ratio is higher, a laminate having a slightly higher elastic modulus can be produced. Furthermore, as also shown in the examples described later, it is shown that the arrangement of the biaxially stretched polyester film in the laminated structure greatly affects the increase in the elastic modulus.

  Biaxially stretched polyester film is commercially available with one surface or both surfaces treated for adhesion, and as a commercial product with surface treatment for adhesion, Cosmo Shine (registered) Trademark) A4100 (manufactured by Toyobo Co., Ltd.), Cosmo Shine (registered trademark) A4300 (manufactured by Toyobo Co., Ltd.), which has been treated for double-sided bonding, and the like. Furthermore, what carried out surface treatments, such as a hard-coat layer, on one side is also marketed, and can also be suitably selected according to a usage method. The biaxially stretched polyester film is preferably a surface-treated film so that it can be easily adhered, but depending on conditions and composition, it can be easily and firmly adhered to the adhesive without surface treatment. .

Adhesive or hard coat agent The adhesive may be in a substantially solvent-free state at the time of use, and either a curable resin or a hot-melt resin can be used. When using a curable resin, the same resin as that used in the hard coat layer described below can be used. A hot-melt adhesive such as a copolyester can also be used. A general-purpose apparatus can be used for the injection of the adhesive, and the adhesive can be injected between the biaxially stretched polyester film and the extruded sheet by a known method.

  The thickness of the adhesive layer after curing is required to be sufficiently thin, and one adhesive layer is preferably 1 μm to 20 μm, more preferably 3 μm to 10 μm. In addition, if the adhesive layer is sufficiently thin, for example, about 10 μm or less per layer, in the case of adhesion of the extruded resin layer, a laminate having a sufficiently high elastic modulus can be obtained even if the elastic modulus is small, It is not necessary to select one having a high elastic modulus. On the other hand, in the case where films having a high elastic modulus are bonded to each other, it is preferable to use an adhesive layer that exhibits an elastic modulus equal to or higher than that of the film.

Sheet-like resin extruded from a T-die For the production of an extruded sheet extruded from a T-die, a general-purpose device used for manufacturing a resin sheet can be used.
Examples of the resin used for the extruded sheet (core layer or base material layer) on which the biaxially stretched polyester film is laminated and pressure-bonded include aromatic polycarbonate, amorphous polyolefin resin (alicyclic polyolefin resin), and polyacrylate resin. And transparent resins such as polysulfone resin, acetyl cellulose resin, polystyrene resin, polyester resin, and transparent polyamide resin. Among these, resins used for optical purposes are preferable, and aromatic polycarbonate resins, acrylic resins, styrene-acrylic copolymer resins, hydrogenated styrene-acrylic copolymer resins (benzene of the styrene component of styrene-acrylic copolymer resins). Those in which the ring is hydrogenated to partially alicyclic) are preferred, transparent polyamide resins are preferred, and aromatic polycarbonate resins are particularly preferred.

  As an aromatic polycarbonate (hereinafter abbreviated as “PC”) used as an extrusion resin for pressure bonding, 2,2-bis (4-hydroxyphenyl) alkane or 2,2 from the viewpoint of film strength, heat resistance, durability, or bending workability. A polymer produced by a known method from a bisphenol compound typified by 2- (4-hydroxy-3,5-dihalogenophenyl) alkane is preferable, and a structural unit or ester bond derived from a fatty acid diol is present in the polymer skeleton. In particular, an aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane is preferable. Examples of commercially available aromatic polycarbonate resins include Iupilon (registered trademark) E2000, Iupilon (registered trademark) S1000, and Iupilon (registered trademark) S2000.

  The extruded resin layer (resin used as a core layer or a base layer) is produced by single layer extrusion or coextrusion of two or more layers, and has a thickness in the range of 0.25 to 1.2 mm, preferably 0. It is selected from the range of 25 to 1.0 mm, more preferably from the range of 0.3 to 0.8 mm.

The resin is melt-extruded so as to have a predetermined thickness, and when it reaches a predetermined temperature, it is overlapped while injecting an adhesive between the biaxially stretched polyester film, and after pressure bonding, the adhesive is appropriately cured, Cut into predetermined dimensions to produce a highly elastic transparent resin laminate.
Usually, the temperature at which the biaxially stretched polyester film is superimposed on the extruded sheet-like resin on the adhesive layer side is selected according to the adhesive. For example, in the case of an ultraviolet curable adhesive layer, it is usually laminated at a temperature of 40 to 100 ° C., and the adhesive is discharged while removing bubbles in a molten state by roll pressurization while making the layer thinner and uniform. Then, UV curing is performed.

Instead of a normal curable or hot melt adhesive, a biaxially stretched polyester film on which a heat-resistant primer layer for adhesion is formed is used to melt the resin from the extrusion die into the first mirror roll. It is also possible to integrate by overlapping at the time of introduction.
Further, depending on the selection of conditions for pressure bonding, curing and cooling, distortion occurs due to the difference in behavior between the base material layer and the biaxially stretched polyester film. This can usually be solved by selecting the cooling process conditions, for example, cooling while applying strain in the direction opposite to the strain direction.

Other Resin Layers Other resin layers that are pasted with an adhesive before being integrated by extrusion or adhesive can be used.
In addition to having a high elastic modulus, the resin laminate of the present invention preferably has at least one surface of the resin laminate having excellent scratch resistance and weather resistance. From the viewpoint of imparting scratch resistance, it is essential that at least the surface (front surface) of the resin laminate has a hard coat layer (HC).
Furthermore, the surface of the resin laminate may have excellent weather resistance. Although there is a method of imparting weather resistance to the hard coat layer, since it is usually insufficient, a hard resin layer having excellent weather resistance is formed on the surface of the resin laminate, and further from the viewpoint of scratch resistance. It is more preferable to form a hard coat layer on the hard resin layer surface. From these, it is preferable that the surface has a hard coat layer, a weather-resistant hard resin layer, or both a hard coat layer and a weather-resistant hard resin layer.
The thickness of these layers is sufficient if the scratch resistance and weather resistance are expressed, and thinner ones are preferable, and the total thickness of the hard coat layer and the weather resistant hard resin layer is within a wide range of 180 μm or less. Select in consideration of performance.

(Hard coat layer (HC))
When forming the hard coat layer, a compound that forms a known crosslinked film can be used from acrylic resin, silicon resin, melamine resin, urethane resin, epoxy resin, and the like. As the curing method, a known method such as ultraviolet curing, thermal curing, electron beam curing or the like can be used. Among these, those that can have a pencil hardness of 3H or more are particularly preferable for the surface to be the surface side, and acrylic resins and silicon resins are exemplified as preferable ones, and acrylic resins are particularly preferable from the balance between workability and hardness. Is preferred. The hard coat layer may be applied by an ordinary method, and can be formed by a coating method such as a roll coating method, a dipping method, or a transfer method.

An acrylic resin is a cross-linkable polymerizable compound having at least two (meth) acryloyloxy groups (meaning acryloyloxy group and / or methacryloyloxy group, the same shall apply hereinafter) in the molecule, and each (meth) acryloyl A residue containing an oxy group can be a hydrocarbon or a derivative thereof, and a compound containing an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like in the molecule can be used.
In the case of using a silicon-based resin, a thermosetting polyorganosiloxane composition containing an ultraviolet absorber or the like can be used as appropriate. The polyorganosiloxane is formed as a hydrolyzate and / or a partial condensate obtained by hydrolyzing and condensing a normal organosilane represented by the general formula R ₁ nSi (OR ₂ ) 4 -n.
When used in the present invention, the hard coat layer is preferably 1 μm to 20 μm.

(Weather-resistant hard resin layer)
Moreover, as a hard resin layer excellent in weather resistance, an acrylic resin, a copolymer obtained by copolymerizing a (meth) acrylic acid ester monomer and an aromatic vinyl monomer (hereinafter referred to as MS resin), MS A resin obtained by hydrogenating a part or most of the aromatic ring of the resin (hereinafter referred to as “nuclear hydrogenated MS resin”) or 2,2- (4-hydroxy-3-methylphenyl) alkane is polymerized or co-polymerized. Examples include polymerized aromatic polycarbonate resins, compositions of acrylic resins copolymerized with acrylic monomers having an aromatic ring that is compatible with aromatic polycarbonate resins, and aromatic polycarbonate resins. To a composition containing an ultraviolet absorber. Examples of UV absorbers added to these acrylic resin layers include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based UV absorbers in order to maintain the transparency of the acrylic resin layer.

  Examples of the benzotriazole ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo Triazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H-benzotriazole -2-yl) phenol] and the like.

  Examples of benzophenone ultraviolet absorbers include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone. 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and the like.

  Examples of the salicylic acid phenyl ester ultraviolet absorber include pt-butylphenyl salicylic acid ester.

  Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine (trade name: Tinuvin 1577), 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphe) ) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- And hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine, and the like.

  Among these ultraviolet absorbers, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine (trade name: Tinuvin 1577) is particularly preferable.

  When this weather-resistant hard resin layer is difficult to handle by itself, for example, a hard-coated one having a high molecular weight using a softening component as a copolymer component, a multilayer sheet having a base material layer, For example, it is used as a film having a structure of hard coat layer / weather-resistant hard resin layer / aromatic polycarbonate resin layer and having a thickness of less than 180 μm.

  When the layer of the extruded resin to be pressure-bonded is a multilayer sheet, the thickness of the hard resin layer formed on one side or both sides is preferably selected from 0.01 mm to 0.1 mm. This hard resin layer is usually used as a composition containing an ultraviolet absorber in order to improve weather resistance.

  The biaxially stretched polyester film in which these hard coat layer and / or hard resin layer are formed is, for example, (1) unwinding a roll-like film and sticking it through an adhesive, curing the adhesive, (2) In a coextrusion process of a weather resistant hard resin layer / aromatic polycarbonate resin layer, at a predetermined temperature during the extrusion process, a single-sided mirror biaxially stretched polyester (PES) film is coated with an ultraviolet curable hard Double-sided surface-treated biaxially stretched with a coating layer formed on the surface of a weather-resistant hard resin layer, and an ultraviolet-curing hard coat layer for adhesion is formed on one side on the opposite side of the polycarbonate resin (PC) surface Polyester (PES) can be produced by a method in which polyester (PES) is stacked and irradiated with ultraviolet rays from both sides and cured.

  As described above, according to the present invention, by applying the conventional in-line process as it is, a desired highly elastic transparent resin laminate can be produced, and the method for producing a resin laminate of the present invention is extremely useful. is there.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Raw materials and abbreviations used in Examples and Comparative Examples are as follows.
-Biaxially stretched polyester film (PES);
PET film (trade name: Cosmo Shine (registered trademark) A4100 (processed for single-sided adhesive), Cosmo Shine (registered trademark) A4300 (processed for double-sided adhesive), (manufactured by Toyobo Co., Ltd.))
PEN film (trade name: Teonex (registered trademark) Q65F (processed for single-sided bonding), (manufactured by Teijin DuPont Films))
・ Extruded sheet resin (PC)
An aromatic polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon E-2000) was used for the extruded sheet extruded from the T-die.
-Adhesive or hard coat agent;
55 parts by weight of tris (acryloxyethyl) isocyanurate (product name: GX-8430, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 15 parts by weight of dipropylene glycol diacrylate (product name: Actilane 422, manufactured by Acros Chemicals) and trimethylolpropane tri 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BFS Japan Co., Ltd.) in 30 parts by weight of acrylate (product name: TMP-3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 3 parts by weight, 1 part by weight of 1-hydroxy-cyclohexyl phenyl ketone (product name; Irgacure 184: manufactured by Ciba Specialty Chemicals), and UV absorber: 2- (hydroxy-5-tert-butylphenyl) benzotriazole (product name) ; Tinuvin-PS, Ciba Bae rice-party Chemicals Co.) 3 parts by weight blended, to prepare a UV-curable composition and uniformly mixed.
-Polymethyl methacrylate (PMMA);
Copolymer of methyl methacrylate / methyl acrylate = 95.6 / 4.4
Weight average molecular weight (Mw) by styrene column GPC 85,000 UV absorber (2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine (trade name: Tinuvin 1577 Ciba Specialty Chemicals Co., Ltd.)) 0.5wt%
・ Hard coat paint;
1. An adhesive between the sheet-like resin and the polyester film and a hard coat agent, 1, a hard coat agent 1 (and an adhesive); an ultraviolet curable composition having the same composition as the above adhesive.
As the hard coat agent for gravure coater, 2, hard coat agent 2; (trade name: XR39-5095 Momentive Performance Materials Japan GK) was used.

<Hardcoat layer and / or hard resin layer formation on surface-treated biaxially stretched polyester film>
Using the above-mentioned biaxially stretched polyester film (PES), a hard coat and / or a weather resistant hard resin layer was applied and bonded to one side by the following procedure.

  Among single-sided surface-treated PET films (Cosmo Shine (registered trademark) A4100), those having thicknesses of 100 μm and 188 μm are used, and these films are referred to as PES1 and PES2, respectively.

  Next, among the double-sided surface-treated PET film (Cosmo Shine (registered trademark) A4300) having a thickness of 100 μm and 188 μm, a hard coat layer 2 (XR39-5095) was prepared on one side. These are referred to as PES3 and PES4, respectively.

  Next, for a PEN film (Teonex (registered trademark) Q65F) having a thickness of 125 μm, a hard coat layer 2 was prepared on the untreated surface using hard coat agent 2 (XR39-5095). The biaxially stretched polyester film after the treatment is referred to as PES5.

  Also, a hard coat layer (HC) is formed on the PMMA surface of a 125 μm (PMMA layer thickness 40 μm) film of PMMA and PC containing UV absorber by gravure coating method using hard coat agent 2 (XR39-5095). did. The biaxially stretched polyester film (Cosmo Shine (registered trademark) A4300, thickness 100 μm) having been subjected to double-sided surface treatment was layered and roll-bonded while injecting an adhesive therebetween, and then cured by ultraviolet irradiation from the PES film side. Hereinafter referred to as PES6.

PES1 to PES6 produced by the above process have a biaxially stretched polyester film (PES) and a structure having the following thickness.
PES1: Thickness 100 μm PET
PES2: PET having a thickness of 188 μm
PES3: Thickness 100 μm PET: Single-sided HC
PES4: thickness 188 μm PET: single-sided HC
PES5: Thickness 125 μm PEN: Single-sided HC
PES6: HC-PMMA-PC / bonded 100 μm thick PET

Examples 1-5 and Comparative Examples 1-2
As an aromatic polycarbonate resin extruder, a cylinder diameter of 65 mm and a screw L / D = 35 TEM manufactured by Toshiba Machine Co., Ltd.) was used, and the cylinder temperature was set to 270 ° C. Further, as an extruder for an acrylic resin (PMMA) blended with an ultraviolet absorber, a cylinder having a barrel diameter of 32 mm and screw L / D = 32 (TEM manufactured by Toshiba Machine Co., Ltd.) was used, and the cylinder temperature was 250 ° C.

  Two types of resin are melt-extruded at the same time in a multi-layer sheet manufacturing device, and when laminated, a feed block is used, and one side of an aromatic polycarbonate resin (trade name: Iupilon E-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) The above-mentioned PMMA was laminated. The temperature inside the die head is 260 ° C., and the resin laminated and integrated in the die is guided to three mirror-finished polishing rolls, the first roll temperature is 110 ° C., the second roll temperature is 140 ° C., and the third roll temperature. Set to 180 ° C. A bank was formed at the first inflow roll interval, and then a coextruded sheet was produced by passing the second and third rolls.

Example 1
A co-extruded sheet (PMMA layer thickness 0.06 mm) with a thickness of 0.8 mm was extruded, and a hard coating agent was applied to the polymethacrylate resin surface of the co-extruded sheet with a surface temperature of 80 ° C. at 4 m from the final end of the three rolls. A PET film (Cosmo Shine (registered trademark) A4100) having a thickness of 100 μm is layered while injecting 1 onto the untreated surface, and an adhesive is pumped between the PES 1 and the PC surface on the opposite side. After injecting an appropriate amount from the nozzle, it is stacked between rolls, and after pressure bonding, a high-pressure mercury lamp with an output density of 80 W / cm is used, and UV light is irradiated from both sides at a conveyor speed of 1.5 m / min at a position 12 cm below the light source. After curing, the PMMA side PET film was peeled off to obtain a polycarbonate resin laminate of Example 1. A cross-sectional view of the resin laminate of Example 1 is shown in FIG. 1, and from the top, hard coat layer (HC) / polymethyl methacrylate (PMMA) / polycarbonate resin (PC) / adhesive layer / PES1 (PET). It is. The thickness of the main layer is HC (6 μm), PC (0.8 mm), and PET (100 μm).

Example 2
Extrude an extruded sheet (PC) with a thickness of 0.5 mm, 4 m from the final end of the three rolls, on both sides of the extruded sheet with a surface temperature of 80 ° C, and an appropriate amount of adhesive between them from the nozzle of the injection device with a pump PES3 and PES1 are piled up while being injected, and after pressure bonding, using a high-pressure mercury lamp with an output density of 80 W / cm, curing and bonding by irradiating ultraviolet rays from both sides at a conveyor speed of 1.5 m / min. Thus, a polycarbonate resin laminate of Example 2 was obtained. A cross-sectional view of the resin laminate of Example 2 is shown in FIG. 2, from the top, PES3 (HC, PET) / adhesive layer / PC / adhesive layer / PES1 (PET). The thicknesses of the main layers are PET (upper) (100 μm), PC (0.5 mm), and PET (lower) (100 μm).

Example 3
While extruding an extruded sheet (PC) with a thickness of 0.5 mm, and injecting an appropriate amount of adhesive from both nozzles of the extruded sheet having a surface temperature of 80 ° C. from the nozzle of an injection device with a pump at 4 m from the final end of the three rolls. After PES3 is stacked and pressure-bonded so that each hard coat layer is on the surface, UV light is applied from both sides at a conveyor speed of 1.5 m / min at a position of 12 cm under the light source using a high-pressure mercury lamp with an output density of 80 W / cm. Irradiated to cure and bond to obtain a polycarbonate resin laminate of Example 3. A sectional view of the resin laminate of Example 3 is shown in FIG. In the figure, from the top, PES3 (HC, PET) / adhesive layer / PC / adhesive layer / PES3 / (PET, HC). The thickness of the main layer is HC (6 μm), PET (upper part) (100 μm), PC (0.5 mm), PET (lower part) (100 μm).

Example 4
Extruded 1mm thick extruded sheet (PC), 4m from the end of 3 rolls, PES3 on the surface of extruded sheet with surface temperature of 80 ° C, PES1 on the opposite side, and contact with PC After injecting an appropriate amount of the agent from the nozzle of the injection device with a pump, after overlapping and press-bonding, using a high-pressure mercury lamp with an output density of 80 W / cm, UV light from both sides at a position of 12 cm below the light source at a conveyor speed of 1.5 m / min. Was cured and bonded to obtain a polycarbonate resin laminate of Example 4. A sectional view of the resin laminate of Example 4 is shown in FIG. From the top in the figure, PES3 (HC, PET) / adhesive layer / PC / adhesive layer / PES1 (PET). The thicknesses of the main layers are HC (6 μm), PET (upper) (100 μm), PC (1 mm), and PET (lower) (100 μm).

Example 5
Extruded extruded sheet (PC) with a thickness of 0.5mm, 4m from the end of 3 rolls, PES4 on the surface of the extruded sheet with a surface temperature of 80 ° C, PES2 on the opposite side, and the side in contact with the PC Adhesive adhesive is poured onto the nozzle of an injection device with a pump, and after pressure bonding, a high-pressure mercury lamp with a power density of 80 W / cm is used, and the conveyor speed is 1.5 m / min. Curing and bonding were performed by irradiating with ultraviolet rays to obtain a polycarbonate resin laminate of Example 2. A cross-sectional view of the resin laminate of Example 5 is shown in FIG. 2, and from the top, PES4 (HC, PET) / adhesive layer / PC / adhesive layer / PES2 (PET). The thicknesses of the main layers are PET (upper) (188 μm), PC (0.5 mm), and PET (lower) (188 μm).

Example 6
Extrude 0.5mm thick extruded sheet (PC), 4m from the final end of 3 rolls, PES5 on one side of extruded sheet with surface temperature of 80 ° C and PES1 on the opposite side to contact with PC Adhesive agent is poured from the nozzle of an injection device with a pump, and after pressure bonding, using a high-pressure mercury lamp with an output density of 80 W / cm, PES5 is placed at a position of 12 cm below the light source at a conveyor speed of 0.7 m / min. The polycarbonate resin laminate of Example 6 was obtained by irradiating with ultraviolet rays from the opposite surface of the stacked surface and curing and bonding. A cross-sectional view of the resin laminate of Example 6 is shown in FIG. 4, and from the top, PES5 (HC, PEN) / adhesive layer / PC / adhesive layer / PES1 (PET). The thicknesses of the main layers are PEN (upper part) (125 μm), PC (0.5 mm), and PET (lower part) (100 μm).

Example 7
Extruded extruded sheet (PC) with a thickness of 0.5mm, 4m from the end of 3 rolls, PES6 on the surface of the extruded sheet with surface temperature of 80 ° C, PES1 on the opposite side, and the side in contact with PC Adhesive agent was poured onto the nozzle of an injection device with a pump while being piled up and pressure-bonded. After that, using a high-pressure mercury lamp with an output density of 80 W / cm, under the condition of a conveyor speed of 0.7 m / min at a position of 12 cm below the light source, PES4 The polycarbonate resin laminate of Example 7 was obtained by irradiating with ultraviolet rays from the surface opposite to the surface where the two layers were cured and bonded. A cross-sectional view of the resin laminate of Example 7 is shown in FIG. From the top in the figure, PES6 (HC, PMMA / PC, laminated PET) / adhesive layer / PC / adhesive layer / PES1 (PET). The thicknesses of the main layers are HC (6 μm), PMMA / PC (0.125 mm), PET (upper) (100 μm), PC (lower) (0.5 mm), and PET (lower) (100 μm).

<Measurement of elastic modulus>
Using an autograph device (AGS-X, manufactured by Shimadzu Corporation), a test piece of the laminate of Examples 1 to 5 having a width of 10 mm was subjected to a three-point bending test at a distance between lower fulcrums of 30 mm and a test speed of 2 mm / min. The bending elastic modulus was obtained from the inclination of the test force from 5N to 10N.
As Comparative Example 1, a 1 mm thick polycarbonate resin sheet was used (Iupilon (registered trademark) NF2000). Further, as Comparative Example 2, a PMMA-laminated HC-treated polycarbonate resin sheet having a thickness of 1 mm was prepared in the same manner as described above (Iupilon (registered trademark) MR58), and the elastic modulus was measured. In the samples of Examples 1 to 7, the layers were firmly adhered so that they were not peeled off from the adhesive layers during the measurement.
Table 1 shows the evaluation results of the samples of Examples 1-7 and Comparative Examples 1-2.

  From the above experimental example, when the thickness is 0.8, 0.5 mm as an aromatic polycarbonate, in the case of one sheet and a plurality of sheets on one side, in the case of different thicknesses, in the case of one side and both sides It is also shown that the difference in the thickness ratio of the biaxially stretched polyester film to be used and the arrangement are the largest factors contributing to the increase in the elastic modulus.

Claims (8)

  The biaxially stretched polyester film and the sheet-like resin are overlapped and pressure-bonded while injecting the adhesive onto one or both sides of the sheet-like resin extruded from the T-die, and then the adhesive is cured. A method for producing a resin laminate.   The method for producing a resin laminate according to claim 1, wherein the sheet-like resin extruded from the T die is an aromatic polycarbonate resin.   The method for producing a resin laminate according to claim 1 or 2, wherein a thickness of the sheet extruded from the T die is 0.25 to 1 mm.   The manufacturing method of the resin laminated body in any one of Claim 1 to 3 which piles up the said biaxially stretched polyester film on both surfaces of the said sheet-like resin.   The biaxially stretched polyester film comprises a laminate comprising a hard coat layer and / or a weather-resistant hard resin on one side, and is integrated with the sheet-like resin and an adhesive. The manufacturing method of the resin laminated body of crab.   The method for producing a resin laminate according to any one of claims 1 to 5, wherein the biaxially stretched polyester film has a thickness of 0.02 to 0.25 mm.   The method for producing a resin laminate according to any one of claims 1 to 6, wherein a solvent-free curable or hot-melt resin composition is used for the adhesive layer.   The method for producing a resin laminate according to claim 1, wherein the adhesive layer has a thickness of 20 μm or less.