JP2013193343A - Method of manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminate provided with no adhesive layer and having excellent planarity.SOLUTION: A method of manufacturing a laminate includes a step (a) and (b). (a) A thermoplastic resin layer (I) is formed on one surface of a stretched film by melt extrusion molding having a first cooling roll, a second cooling roll and a third cooling roll, where the second cooling roll is arranged between the first cooling roll and the third cooling roll and an interposition point is present between the first cooling roll and the second cooling roll and after that, (b) a thermoplastic resin layer (II) is formed on the other surface of the stretched film under a condition of T2≥130°C and T2+T3≥ 270°C when the temperature of the second cooling roll and the temperature of the third cooling roll are expressed by T2 and T3, respectively.

Description

  The present invention relates to a method for manufacturing a laminate.

  Examples of the resin film having various functions include a multilayer film having a laminated structure, and a stretched film obtained by stretching a film that is a raw fabric. Examples of the stretched film include those obtained by stretching a single layer film, and those obtained by stretching a multilayer film obtained in advance by multilayer melt coextrusion, etc. The resin constituting the film is usually a glass transition. The resin film is stretched in a state of being softened to some extent at a stretching temperature under a temperature condition such that the temperature is higher than the temperature.

  Since the stretched film undergoes dimensional change and warpage deformation accompanying the dimensional change in a high-temperature environment or a high-temperature and high-humidity environment from around the glass transition temperature to near the stretching temperature, the environmental resistance is not good.

  In order to improve environmental resistance, it has been studied to laminate a protective film on one side or both sides of a stretched film to form a laminate. Usually, stretching of a stretched film and a protective film is a stretched film. Between the protective film and the protective film. The protective film is usually made of a thermoplastic resin, is not a stretched film, and has heat resistance (high glass transition temperature) and rigidity that can satisfy the required environmental resistance. .

  For the adhesive layer, a pressure-sensitive adhesive or a curable resin that is cured by an active energy ray such as ultraviolet rays is usually used. Therefore, since the laminated body provided with the adhesive layer also uses a pressure-sensitive adhesive and a curable resin in addition to the stretched film and the protective film, the cost may increase and the cost may become high. Furthermore, when the stretched film and the protective film are bonded using an adhesive or a curable resin, the planarity of the resulting laminate may be inferior. Moreover, in order to obtain a laminated body, since the process of bonding a stretched film and a protective film through an contact bonding layer is needed, a manufacturing process becomes complicated.

  Then, the subject of this invention is providing the method of manufacturing the laminated body which is excellent in planarity, without providing an adhesive layer.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the present invention relates to the following inventions.
(1) A method for producing a laminate including steps (a) and (b).
(A) The first cooling roll is disposed between the first cooling roll and the third cooling roll, and has a clamping point between the first cooling roll and the second cooling roll, Forming a thermoplastic resin layer on one side of the stretched film by melt extrusion with two cooling rolls and a third cooling roll;
(B) A thermoplastic resin layer is formed on the other surface of the stretched film when the second cooling roll temperature (T2) and the third cooling roll temperature (T3) are T2 ≧ 130 ° C. and T2 + T3 ≧ 270 ° C.
(2) The production method according to (1), wherein the stretched film is a uniaxially stretched film.
(3) The manufacturing method of the laminated body as described in said (2) whose extending | stretching direction of a stretched film is a direction which is not parallel with the extrusion direction of the melt extrusion molding of a thermoplastic resin layer.
(4) The manufacturing method as described in said (1)-(3) whose thermoplastic resin has a glass transition temperature of 80 degreeC or more.
(5) The production method according to (4), wherein the thermoplastic resin is a polycarbonate resin.
(6) In the step (b), the second cooling roll temperature (T2) and the third cooling roll temperature (T3) are T2 ≧ 130 ° C. and T2 + T3 ≧ 275 ° C. 6. Production method.
(7) The manufacturing method as described in (1) to (6) above, wherein the surface form of the second cooling roll is mat-like.
(8) A manufacturing method given in the above (1)-(7), wherein the 1st cooling roll is a rubber roll.
(9) A laminate obtained by the production method according to (1) to (8).

  According to the manufacturing method of the laminated body of this invention, the laminated body which is excellent in planarity without providing an adhesive layer is obtained. Since the thermoplastic resin layer is formed on both sides of the stretched film via the adhesive layer, it is not necessary to use a pressure-sensitive adhesive or a curable resin, and the bonding process can be further reduced.

It is a schematic explanatory drawing which shows one Embodiment of the process (a) in the manufacturing method of this invention. It is a schematic explanatory drawing which shows one Embodiment of the process (b) in the manufacturing method of this invention.

Hereinafter, the present invention will be described in detail.
In the method for manufacturing a laminated body of the present invention (hereinafter sometimes referred to as the manufacturing method of the present invention), first, the second cooling roll is disposed between the first cooling roll and the third cooling roll, and the first cooling roll A thermoplastic resin layer is formed on one surface of the stretched film by melt extrusion molding having a first cooling roll, a second cooling roll, and a third cooling roll having a clamping point between the roll and the second cooling roll. (Step (a)), then the second cooling roll temperature (T2) and the third cooling roll temperature (T3) are T2 ≧ 130 ° C. and T2 + T3 ≧ 270 ° C. This is a method for producing a laminate by forming a layer (step (b)).

[Stretched film]
The stretched film of the present invention is not particularly limited, but is preferably a stretched thermoplastic resin film.

  Examples of the thermoplastic resin constituting the thermoplastic resin film include polyester resins such as polyethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene and polypropylene, polycarbonate resins, acrylic resins, cyclic olefin resins, styrene resins, and methacrylic resins. Acid methyl-styrene resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, AS (acrylonitrile-styrene copolymer) resin, vinyl chloride resin, polyamide resin, polyacetal resin, polymethylpentene resin, polyphenylene ether resin, poly Phenyl sulfide resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyarylate resin, Riete ether ketone resins, and cellulose resins. Above all, since a thermoplastic resin layer is formed on both sides of the stretched film by melt extrusion molding, thermoplasticity that is more easily heat-sealed in consideration of the melted resin temperature of the thermoplastic resin used for melt extrusion molding. Resins are preferred. Generally, the temperature of the molten resin at the time of melt extrusion is about 200 ° C. to 350 ° C., and it is preferable to select a stretched film that is easily heat-sealed with a thermoplastic resin at the resin temperature. Therefore, it is preferable that the glass transition temperature and softening temperature of the thermoplastic resin forming the stretched film are equal to or lower than the resin temperature of the melt-extruded thermoplastic resin.

  The thermoplastic resin film can be molded from the above-mentioned thermoplastic resin as a raw material by a melt extrusion molding method, a solution casting method, a calendering method, etc., but is not limited to this molding method. What is necessary is just to select a suitable shaping | molding method suitably according to dimensions, such as a kind and the thickness and width | variety of a laminated body.

The stretched film is obtained by stretching a thermoplastic resin film, and may be a uniaxially stretched film formed by stretching a thermoplastic resin film in one direction, or two formed by stretching a thermoplastic resin film in two directions. An axially stretched film may be used.
In a uniaxially stretched film, the stretched direction of the stretched film is perpendicular to and parallel to the extrusion flow direction in melt extrusion when one side of the stretched film and the thermoplastic resin layer are formed on the other side. The direction (oblique direction) which is neither an orthogonal direction nor a parallel direction is mentioned. On the other hand, in a biaxially stretched film, usually, the two stretching directions are orthogonal to each other, and when the two stretching directions respectively match the orthogonal direction and the parallel direction with respect to the extrusion flow direction, they are parallel to the orthogonal direction. The case where it is inconsistent with a direction (when it becomes a diagonal direction) is mentioned.

The stretched film tends to shrink in the direction of the stretching axis under a high temperature environment. In the production method of the present invention, the thermoplastic resin layer is formed on one side and the other side of the stretched film by melt extrusion. Therefore, the stretched film is exposed to a high temperature environment when forming the thermoplastic resin layer, and is particularly likely to shrink in the stretch axis direction on the surface side in contact with the thermoplastic resin layer. Therefore, as the laminate is contracted in the stretch axis direction of the stretched film, the surface in contact with the thermoplastic resin layer is concave, warping deformation warps in the stretch axis direction of the stretched film, and flatness tends to be inferior. .
Since the warped direction is the direction in which the stretched film shrinks, that is, the stretched axis direction, if the stretched film constituting the laminate is a uniaxially stretched film, the laminate is warped only in one direction and is a biaxially stretched film The laminate is warped in two directions. From the viewpoint of suppressing the warp deformation of the laminate and improving the flatness, the stretched film is preferably a uniaxially stretched film that warps only in one direction.

  As described above, the stretching direction of the uniaxially stretched film may be any of the orthogonal direction, the parallel direction, and the oblique direction with respect to the extrusion flow direction in the melt extrusion molding, but among them, the orthogonal direction is preferable. If the stretching direction is parallel or oblique to the extrusion flow direction in melt extrusion molding, the warping of the film in the extrusion direction increases, so that the extrusion process can be performed on a cooling roll, a guide roll, a take-up roll, etc. There is a possibility that winding of the laminated body of this becomes easy to occur. From the standpoint that the state of warping of the laminate can be easily made constant, the stretched direction of the stretched film is preferably closer to the direction orthogonal to the extrusion flow direction in melt extrusion molding.

  Although the thickness of the stretched film is not particularly limited, it is usually about 5 to 500 μm from the viewpoint of supplying the stretched film between the first cooling roll and the second cooling roll while continuously unwinding the stretched film during melt extrusion molding. Preferably, it is 10-300 micrometers, More preferably, it is 15-150 micrometers. When it is thicker than 500 μm, it is difficult to roll the stretched film, so that it may be difficult to continuously supply the stretched film between the cooling rolls. On the other hand, when the thickness is less than 5 μm, the strength of the stretched film itself is weakened, so that the stretched film may be easily cut.

[Thermoplastic resin layer]
Each of the thermoplastic resin layers formed by melt extrusion molding on one side and the other side of the stretched film is made of a thermoplastic resin. The thermoplastic resins constituting these thermoplastic resin layers may be the same or different from each other, but the resulting laminate may have a dimensional change that occurs in a high temperature environment, a high temperature / high humidity environment, or the like. From the viewpoint of suppressing warpage deformation accompanying the dimensional change, it is preferable that they are the same.

  As the thermoplastic resin constituting the thermoplastic resin layer, the same thermoplastic resin as exemplified as the thermoplastic resin constituting the thermoplastic resin film can be used. However, the resulting laminate has a high temperature environment. It is preferable to use a resin having excellent heat resistance, rigidity, and the like from the viewpoint of suppressing dimensional changes that occur under high-temperature and high-humidity environments and warping deformation accompanying the dimensional changes. As a high temperature environment or a high temperature / high humidity environment, for example, it may be an environment such as 60 ° C. dry, 80 ° C. dry, 60 ° C. 90% RH, and the like. As, since it is preferable that the dimensional change under these circumstances and warp deformation accompanying the dimensional change are suppressed, the glass transition temperature of the thermoplastic resin is preferably 60 ° C. or higher, and 80 ° C. More preferably, it is more preferably 100 ° C. or higher.

  From the viewpoints of heat resistance, rigidity, and economical (cost) of the resulting laminate, the thermoplastic resin constituting the thermoplastic resin layer includes polycarbonate resin, acrylic resin, cyclic olefin resin, and styrene. It is preferably at least one selected from the group consisting of a resin, methyl methacrylate-styrene resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, and AS (acrylonitrile-styrene copolymer) resin. Is preferred.

  As the polycarbonate resin, for example, an aromatic polycarbonate resin excellent in heat resistance, mechanical strength, transparency and the like is preferably used. The aromatic polycarbonate resin is usually obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or by polymerizing a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5- Dibromo) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis { 4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxy) Phenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydro Cis-3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α ′ -Bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, and 4,4′-dihydroxydiphenyl ester. These may be used alone or in combination of two or more. Can be used.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl)- 3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) ) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used alone or in combination of two or more. Bisphenol A alone, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, At least one selected from the group consisting of enol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene. The combined use with a monohydric phenol is preferred.

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  The thermoplastic resin layer may have a single-layer configuration composed of the above-described thermoplastic resins, or may have a multilayer configuration composed of two or more kinds of thermoplastic resins. When the thermoplastic resin layer has a multilayer structure (2 types, 2 layers, 2 types, 3 layers, etc.), a plurality of melt extruders are used in the melt extrusion molding to be described later, and a multilayer die (feed block die, multi manifold) is used. A die or the like) may be used.

Although it does not specifically limit as thickness of a thermoplastic resin layer, Usually, it is 10-500 micrometers, Preferably it is 20-400 micrometers. The thermoplastic resin layer formed on one surface of the stretched film and the thermoplastic resin layer formed on the other surface may be the same as or different from each other.
What is the preferred thickness of the thermoplastic resin layer?
In order to adjust the thickness of the thermoplastic resin layer, in the melt extrusion molding of the thermoplastic resin layer, the screw rotation speed of the extruder, the take-up speed of the extruded material, and the like may be adjusted.

  The thermoplastic resin layer may be, for example, a light diffusing agent, a matting agent, an ultraviolet absorber, a surfactant, an impact resistance agent, a polymer antistatic agent, an antioxidant, a flame retardant, a lubricant, a dye, It may contain pigments and the like.

[Manufacturing method of laminate]
Hereinafter, the production method of the present invention will be described in detail with reference to the drawings.
The production method of the present invention comprises a step (a) forming a thermoplastic resin layer on one side of a stretched film by melt extrusion, and a step (b) thermoplasticity on the other side of the stretched film by melt extrusion. Forming a resin layer.

(Process (a))
FIG. 1 is a schematic explanatory view showing one embodiment of step (a) in the production method of the present invention.
As shown in FIG. 1, this embodiment includes first to third cooling rolls 3 to 5, and the second cooling roll 4 is disposed between the first cooling roll 3 and the third cooling roll 5, There is a clamping point between the first cooling roll 3 and the second cooling roll 4. Here, the nipping point refers to a gap between the two cooling rolls where the first cooling roll 3 and the second cooling roll 4 are closest to each other.
First, a thermoplastic resin constituting a thermoplastic resin layer is supplied to the extruder 1, and the thermoplastic resin is melt-kneaded in the extruder 1 and then supplied to the die 2, and the thermoplastic resin layer is supplied from the tip of the die 2. (I) is extruded as a film and supplied between the first cooling roll 3 and the second cooling roll 4.
On the other hand, the stretched film 8 unwound from the unwinding machine 6 disposed on the side opposite to the side on which the second cooling roll 4 of the first cooling roll 3 is disposed has the stretched film 8 first cooled. It is inserted between the first cooling roll 3 and the second cooling roll 4 so that the thermoplastic resin layer contacts the roll 3 and the thermoplastic resin layer contacts the second cooling roll 4.
The film-like thermoplastic resin layer and the stretched film 8 supplied between the first cooling roll 3 and the second cooling roll 4 are laminated and integrated at a holding point between the first cooling roll 3 and the second cooling roll 4. Is formed into a laminated film 9, and the laminated film 9 is sequentially wound around the second cooling roll 4 and the third cooling roll 5. The laminated film 9 wound around the third cooling roll further passes over several guide rolls (not shown), and further passes through a take-up roll (not shown), and is then wound by a winder (not shown). The laminated film 9 in which the thermoplastic resin layer is formed on one surface of the stretched film 8 is obtained.

  Here, the clamping point is preferably adjusted to an interval corresponding to the thickness of the laminated film 9 to be obtained. Moreover, what is necessary is just to set suitably the screw speed of an extruder, and the taking-up speed of the laminated | multilayer film 9 in order to adjust the thickness of a thermoplastic resin layer.

  The set temperatures of the first to third cooling rolls 3 to 5 in the step (a) are such that the thermoplastic resin layer and the stretched film 8 are not too close to the cooling roll and are not wound, and are cooled. The temperature is not particularly limited as long as the thermoplastic resin layer and the stretched film 8 are not sufficiently adhered to the roll, and may be set as appropriate.

(Process (b))
FIG. 2 is a schematic explanatory view showing an embodiment of the step (b) in the production method of the present invention.
As shown in FIG. 2, this embodiment includes first to third cooling rolls 3 to 5 as in the embodiment of the step (a) shown in FIG. 1, and the second cooling roll 4 is a first cooling roll. 3 and the third cooling roll 5, and there is a clamping point between the first cooling roll 3 and the second cooling roll 4.
First, a thermoplastic resin constituting a thermoplastic resin layer is supplied to the extruder 1, and the thermoplastic resin is melt-kneaded in the extruder 1 and then supplied to the die 2, and the thermoplastic resin layer is supplied from the tip of the die 2. Is extruded as a film and supplied between the first cooling roll 3 and the second cooling roll 4.
On the other hand, the laminated film 9 obtained in the step (a) is unwound from the unwinder 6, and the laminated film 9 is first cooled so that a thermoplastic resin layer is formed on the stretched film surface of the laminated film 9. It is inserted between the roll 3 and the second cooling roll.
The film-like thermoplastic resin layer and the laminated film 9 supplied between the first cooling roll 3 and the second cooling roll are laminated and integrated at the holding point between the first cooling roll 3 and the second cooling roll 4. Then, the film is wound around the second cooling roll 4 and the third cooling roll 5 in sequence, a thermoplastic resin layer is formed on one side of the stretched film, and a thermoplastic resin layer is formed on the other side. The laminated body 10 is obtained. The obtained laminate 10 may be further passed through a take-up roll and then cut into a desired size, or may be taken up by a winder.

  Here, the clamping point is preferably adjusted to an interval corresponding to the thickness of the laminate 10 to be obtained. Moreover, what is necessary is just to set suitably the screw speed of an extruder, and the taking-up speed of the laminated body 10 in order to adjust the thickness of a thermoplastic resin layer.

The set temperatures of the first to third cooling rolls 3 to 5 in the step (b) are such that the thermoplastic resin layer and the laminated film 9 are not too close to the cooling roll and are not wound, and are cooled. The temperature is not particularly limited as long as the thermoplastic resin layer and the laminated film 9 are not sufficiently adhered to the roll, and the temperature may be set as appropriate. In order to obtain the second cooling roll temperature (T2), which is the set temperature of the second cooling roll, and the third cooling roll temperature (T3), which is the set temperature of the third cooling roll, T2 ≧ 130 ° C. and It is necessary that T2 + T3 ≧ 270 ° C. Moreover, it is more preferable that T2 ≧ 130 ° C. and T2 + T3 ≧ 275 ° C. from the viewpoint of suppressing warpage deformation of the laminated body. When T2 is less than 130 ° C. or T2 + T3 is less than 270 ° C., the warped deformation of the laminate is increased and the planarity is lowered. T2 is preferably 200 ° C. or lower, and more preferably 180 ° C. or lower. T2 + T3 is preferably 400 ° C. or lower, and more preferably 360 ° C. or lower. When T2 exceeds 200 ° C. or T2 + T3 exceeds 400 ° C., the thermoplastic resin layer may be taken too close to the cooling roll and may be easily wound. T3 is not particularly limited as long as T2 satisfies the relationship of T2 ≧ 130 ° C. and T2 + T3 satisfies the relationship of T2 + T3 ≧ 270 ° C., but is preferably 200 ° C. or less, and more preferably 180 ° C. or less.
T1 is preferably 10 to 200 ° C, more preferably 20 to 180 ° C. When the temperature is lower than 10 ° C., the thermoplastic resin layer is excessively cooled, so that the appearance of the film may be deteriorated or a large amount of distortion may remain in the film. Moreover, when it exceeds 200 degreeC, there exists a possibility that a thermoplastic resin layer may stick too much to a cooling roll, and it may become easy to generate | occur | produce and a winding.

  As described above, in the step (a) and the step (b), after the laminated film is first wound up by the winder in the step (a), the wound laminated film is unwound again in the step (b). A laminate may be obtained by using a machine, and the step (a) and the step (b) may be performed continuously. For example, the melt extruder and the first to third cooling rolls are set as one set. The two sets are arranged in series, and a laminated film is obtained as the step (a) in the first set, and the obtained laminated film is conveyed as it is without being wound, and the step (b) is carried out in the second set. A laminate may be obtained.

  As for the cooling roll, in the above description, the first cooling roll, the second cooling roll, and the third cooling roll are shown. However, the cooling roll further includes one or a plurality of cooling rolls after the third cooling roll. It does not matter.

  As a cooling roll, a metal rigid roll, a rubber roll, a metal elastic roll, etc. can be used. The surface of the rubber roll may be finished with excellent smoothness, or may be a roll having a relatively rough surface roughness. The metal roll and metal elastic roll may be mirror-finished with chrome plating on the roll surface, or may have a concavo-convex shape such as a mat shape on the surface.

  As the 1st cooling roll 3, it is preferable to use the cooling roll which has a diameter of about 25-100 cm and consists of a rubber roll or a metal elastic roll, and uses a rubber roll especially. When the stretched film is inserted and laminated with the thermoplastic resin melt-extruded between the first cooling roll 3 and the second cooling roll 4, the stretched film is inserted so as to be in contact with the first cooling roll side. Therefore, when the stretched film and the thermoplastic resin are sandwiched between the first cooling roll 3 and the second cooling roll 4, the stretched film is sandwiched on the first cooling roll side. The first cooling roll is preferably a flexible rubber roll or a metal elastic roll, and more preferably a flexible rubber roll.

  Examples of the rubber roll include a silicon rubber roll and a fluororubber roll, and a mixture of sand in order to improve releasability can also be employed. The hardness of the rubber roll is preferably in the range of A60 ° to A90 ° measured according to JIS K6253. In order to make the hardness of the rubber roll within the above range, for example, it can be arbitrarily performed by adjusting the degree of crosslinking and composition of the rubber constituting the rubber roll.

  The metal elastic roll is one in which the inside of the roll is made of rubber or one in which a fluid is injected, and the outer peripheral part is made of a metal thin film having flexibility. . Specifically, the inside of the roll is composed of a silicon rubber roll, and a cylindrical stainless steel thin film having a thickness of about 0.2 to 1 mm is coated on the outer periphery of the roll, In the case of injecting a fluid such as oil, a cylindrical thin film made of stainless steel having a thickness of about 2 to 5 mm is fixed at the end of the roll and the fluid is sealed inside.

  As such a 1st cooling roll 3, what was comprised with the metal material and the elastic body, and finished in the mirror surface shape with the plating etc. can be used. Further, as described above, the surface of the metal thin film of the metal elastic roll or the rubber roll is not necessarily smooth, and there is no problem even if the surface is provided with an uneven shape such as a mat.

  The second cooling roll 4 has a diameter of about 25 to 100 cm, and it is preferable to use a metal roll. Specifically, a drilled roll from which a metal lump has been cut out, a metal roll that can control the temperature of the roll surface through a fluid, steam, or the like inside a roll such as a spiral roll having a hollow structure. The metal roll surface may be mirror-finished with plating or the like, or a metal roll having a desired mat shape (uneven shape) formed by sandblasting or engraving on the outer peripheral surface. When a metal roll with a mat shape formed on the outer peripheral surface is used, even when the roll temperature is considerably high, the thermoplastic resin on the surface of the laminated film or laminate may be taken up or wound around the roll. Since it becomes difficult, as the 2nd cooling roll 4, it is preferable to use the metal roll whose mat | matte shape is formed in an outer peripheral surface and whose surface form is a mat | matte shape.

The laminated film 9 obtained in the step (a) in which the thermoplastic resin layer is laminated on one surface of the stretched film 8 or the stretched film 8 is the side on which the second cooling roll 4 of the first cooling roll 3 is disposed. It is unwound from the unwinding machine 6 arranged on the opposite side to and inserted between the first cooling roll 3 and the second cooling roll 4. As the unwinding machine 6, for example, with a powder brake It is preferable to use an unwinder that can adjust the unwinding tension, such as an unwinder.
When inserting a stretched film or laminated film 9 from the unwinder 6 between the first cooling roll 3 and the second cooling roll 4, it is preferable to provide a guide roll 7, and the stretched film 8 or laminated film 9 to be inserted is provided. In order to prevent wrinkles from entering, an expander roll or the like is preferably used as the guide roll 7.
The position where the unwinding machine 6 is arranged is not limited to the side of the first cooling roll 3 opposite to the side where the second cooling roll 4 is arranged, and the stretched film 8 or the laminated film 9 is used as the first cooling roll. 3 and the 2nd cooling roll 4 should just be a position which can be inserted, for example, may be the upper side or lower side of the 1st cooling roll. When the stretched film 8 or the laminated film 9 is inserted between the first cooling roll 3 and the second cooling roll 4, one or more guide rolls may be provided.
Moreover, in order to make the lamination integration with the thermoplastic resin layer melt-extruded into a film shape stronger and more reliable, the stretched film 8 or the laminated film 9 is made up of the first cooling roll 3 and the second cooling roll 4. Before inserting between them, a heater or the like may be arranged on one side or both sides of the stretched film 8 or the laminated film 9, and the stretched film 8 or the laminated film 9 before insertion may be heated appropriately.

  The production method of the present invention does not require a bonding step between the stretched film and the thermoplastic resin layer, can obtain a laminate more easily than the conventional production method, and further includes an adhesive layer. Therefore, it is possible to obtain a laminated body having a more simplified configuration. The obtained laminate is suppressed in warpage deformation and excellent in flatness. Furthermore, since dimensional change under high temperature environment or high temperature and high humidity environment and warping deformation accompanying the dimensional change are suppressed, it can be suitably used in various fields.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

The extrusion apparatuses used in the following examples and comparative examples are as follows.
Extruder 1: Single screw extruder with vented screw diameter 65 mm (manufactured by Hitachi Zosen Corporation)
Dice 2: T die

  As shown in FIG. 1 in the step (a), the extruder 1, the die 2, the first to third cooling rolls 3 to 5, the unwinder 6 and the guide roll 7 are shown in FIG. 2 in the step (a). It arrange | positioned and each cooling roll 3-5 was comprised as follows.

<Roll configuration>
The 1st-3rd cooling rolls 3-5 were comprised as follows.
-1st cooling roll 3: Silicon rubber roll with an outer diameter of 250 mmφ and hardness A70 °-Second cooling roll 4: Stainless steel with an irregular shape of arithmetic average roughness (Ra) 3.5 μm formed by blasting with an outer diameter of 250 mmφ Metal roll (drilled roll)
(Arithmetic mean roughness (Ra) is measured with a surface roughness meter ("Surf Test SJ-201" manufactured by Mitutoyo Corporation) in accordance with JIS B0601-2001)
Third cooling roll 5: mirror-finished stainless steel metal roll (drilled roll) with an outer diameter of 250 mmφ

  In Examples and Comparative Examples, a polycarbonate resin (“Caliver 300-15” manufactured by Sumika Stylon Polycarbonate Co., Ltd., glass transition temperature 145 ° C.) is used as a thermoplastic resin to be melt extruded, and a polyester resin is used as a stretched film. And a uniaxially stretched film having a thickness of 28 μm (a film uniaxially stretched in a direction substantially perpendicular to the melt extrusion direction of the thermoplastic resin) was used. The glass transition temperature of the thermoplastic resin was determined by the midpoint method of DSC.

<Examples 1 to 23, Comparative Examples 1 and 2>
(Process (a))
As the thermoplastic resin layer, when the thermoplastic resin layer is formed on one surface of the stretched film 8, the polycarbonate resin is melted so that the thickness of the thermoplastic resin layer becomes the thickness shown in Table 1. The film-like thermoplastic resin layer fed from the extruder 1 (cylinder temperature: 230 to 260 ° C.) to the die 2 (die temperature: 260 ° C.) and then extruded from the die 2 is fed to the first cooling roll 3 and the second cooling roller. On the other hand, the stretched film 8 set on the unwinder 6 is externally attached to the guide roll 7, and then the first cooling roll 3 and the second cooling roll 3 are arranged along the first cooling roll 3. Inserted between the cooling rolls 4, a thermoplastic resin layer was laminated and integrated on one surface of the stretched film 8. Furthermore, a laminated film 9 having a thermoplastic resin layer on one surface of the stretched film 8 was obtained via the second cooling roll 4 and the third cooling roll 5. In addition, the preset temperature of the 1st-3rd cooling rolls 3-5 was the 1st cooling roll 3 / the 2nd cooling roll 4 / the 3rd cooling roll 5 = 35 degreeC / 120 degreeC / 125 degreeC.

(Process (b))
As the thermoplastic resin layer, when the thermoplastic resin layer is formed on the stretched film surface of the laminated film 9, the polycarbonate resin is melted and extruded so that the thickness of the thermoplastic resin layer becomes the thickness shown in Table 1. The film-like thermoplastic resin layer fed from the machine 1 (cylinder temperature: 230 to 260 ° C.) to the die 2 (die temperature: 260 ° C.) and then extruded from the die 2 is used as the first cooling roll 3 and the second cooling roll. On the other hand, the laminated film 9 obtained in the step (a) is set on the unwinder 6 so that the stretched film surface is in contact with the melt-extruded polycarbonate resin, and is externally attached to the guide roll 7. After that, it is inserted between the first cooling roll 3 and the second cooling roll 4 so as to be along the first cooling roll 3, and the thermoplastic resin layer is laminated and integrated on the stretched film surface of the laminated film 9. It was. Furthermore, the laminated body 10 provided with a thermoplastic resin layer on one surface of the stretched film 8 and a thermoplastic resin layer on the other surface via the second cooling roll 4 and the third cooling roll 5 was obtained. The obtained laminated body 10 was a laminated body warped in a direction orthogonal to the melt extrusion direction. Here, the first cooling roll temperature (T1), the second cooling roll temperature (T2), and the third cooling roll temperature (T3), which are set temperatures of the first to third cooling rolls 3 to 5, are shown in Table 1, respectively. Adjusted to the indicated temperature.

  The obtained laminate 10 was evaluated as follows. The results are shown in Table 1.

<Flatness>
First, a test piece was cut out from the obtained laminate 10. The shape of each test piece was 10 mm in the melt extrusion direction and 100 mm in the direction orthogonal to the melt extrusion direction.

  Next, each test piece was placed on the surface plate so that the convex surface of each test piece was in contact with the surface plate, and the amount of lifting of the four corners of each test piece was measured using a gap gauge. And about each test piece, the average value of the amount of lifting of four corners was computed, and this was made into curvature amount.

  Furthermore, the curvature radius was calculated from the obtained amount of warpage and the test piece length (100 mm) in the direction in which the test piece is warped (direction orthogonal to the melt extrusion direction).

  Then, the reciprocal of the radius of curvature was calculated, and the calculated value was taken as the curvature. Note that the smaller the curvature, the smaller the warp deformation and the better the flatness.

DESCRIPTION OF SYMBOLS 1 Extruder 2 Dies 3 1st cooling roll 4 2nd cooling roll 5 3rd cooling roll 6 Unwinding machine 7 Guide roll 8 Stretched film 9 Laminated film 10 Laminate

Claims (9)

The manufacturing method of the laminated body containing process (a) and (b).
(A) The first cooling roll is disposed between the first cooling roll and the third cooling roll, and has a clamping point between the first cooling roll and the second cooling roll, Forming a thermoplastic resin layer on one side of the stretched film by melt extrusion with two cooling rolls and a third cooling roll;
(B) A thermoplastic resin layer is formed on the other surface of the stretched film when the second cooling roll temperature (T2) and the third cooling roll temperature (T3) are T2 ≧ 130 ° C. and T2 + T3 ≧ 270 ° C.   The manufacturing method according to claim 1, wherein the stretched film is a uniaxially stretched film.   The production method according to claim 2, wherein the stretched direction of the stretched film is a direction that is not parallel to the extrusion direction of the melt extrusion molding of the thermoplastic resin layer.   The manufacturing method according to claim 1, wherein the thermoplastic resin has a glass transition temperature of 80 ° C. or higher.   The manufacturing method according to claim 4, wherein the thermoplastic resin is a polycarbonate resin.   The method according to any one of claims 1 to 5, wherein in the step (b), the second cooling roll temperature (T2) and the third cooling roll temperature (T3) satisfy T2 ≧ 130 ° C and T2 + T3 ≧ 275 ° C.   The manufacturing method according to claim 1, wherein the surface form of the second cooling roll is a mat shape.   The manufacturing method according to claim 1, wherein the first cooling roll is a rubber roll.   The laminated body obtained with the manufacturing method of Claims 1-8.

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