JP2008238529A - Shaped film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shaped film with high emboss transfer rate and further, high emboss heat resistance in the heating process of fabrication. <P>SOLUTION: This shaped film has at least, a face layer formed of a resin, with 100 to 150°C glass transition temperature, composed mainly of a polycarbonate resin. This face layer is subjected to a shaping process and satisfies formula (1) Ra (f2)/Ra (f)= not less than 80%. In this formula (1), Ra (f) is the surface roughness of the shaped film and Ra (f2) is the surface roughness of the shaped film after being retained at 100°C for 60 s. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a shaped film capable of imparting high designability to a film surface by heat molding and a method for producing the same.

  Design steel plates used mainly for interior and exterior of buildings are roughly classified into two types: painted steel plates and resin-laminated steel plates. Painted steel plates are useful because of their high surface hardness. Are limited, and it is particularly difficult to express a three-dimensional sense of depth. On the other hand, a resin-laminated steel sheet can impart a three-dimensional depth feeling by laminating a heat-molded shaping film on a steel sheet or the like.

  Conventionally, as a shaping film used for a resin-laminated steel sheet, a film made of a soft vinyl chloride resin has been used from the viewpoint of formability, but in recent years, there has been a trend toward non-vinyl chloride from the environmental viewpoint, and the vinyl chloride resin Development of moldable films using resins that change to For example, a shaping film using EVOH, polyester resin, polycarbonate resin or the like has been developed (see Patent Documents 1 to 3 below).

Japanese Patent Laid-Open No. 7-258889 JP 2003-291260 A JP-A-2005-231257

As a shaping film, a film having good processing suitability and simultaneously satisfying design characteristics such as a three-dimensional depth feeling and practical characteristics such as surface hardness is desired.
The conventional moldable film has a wide rubber-like elastic region in the temperature dependence of the elastic modulus, which is important in the process of heating and embossing (including wrinkles, the same applies hereinafter). Since the emboss transfer rate is low and the emboss heat resistance in the thermal process of the secondary processing is low, the emboss pattern is not sufficient to put a clear, deep and fine emboss pattern.

  Then, the objective of this invention is providing the shaping | molding film with high emboss transfer rate, and also high emboss heat resistance in the heat process of secondary processing, and its manufacturing method.

The shaped film of the present invention has a glass transition temperature of 100 ° C. to 150 ° C. and has at least a surface layer formed of a resin mainly composed of a polycarbonate resin, and is subjected to a shaping process on the surface layer. The following expression (1) is satisfied.
Ra (f2) / Ra (f) = 80% or more (1)
Here, Ra (f) represents the surface roughness of the shaped film, and Ra (f2) represents the surface roughness after holding the shaped film at 100 ° C. for 60 seconds.

  As a result, the surface hardness and processability are excellent, and the embossing transfer rate is high, and the embossing heat resistance is high, and when the secondary processing is performed, the temperature of the drying furnace can be increased. The cost can be reduced by increasing the line speed.

The surface layer preferably has a storage elastic modulus (E ′) in the range of 120 ° C. to 200 ° C. of 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa.

  Those satisfying the above storage elastic modulus (E ′) are less likely to be embossed during the cooling process, and therefore can be given high designability.

The shaped film preferably has a surface hardness at 23 ° C. of 1.0 × 10 ⁹ Pa or more, and this can prevent the surface from being damaged.

  The shaped film preferably has an ultraviolet absorbing layer, which can effectively absorb ultraviolet rays and prevent yellowing of the surface layer and the like.

  The shaped film preferably has either or both of a printed layer or a colored layer that has been subjected to a printing process, whereby the shaped film can be provided with a pattern, color, etc. Can be increased.

  The above-mentioned shaping film preferably has at least one layer filled with a filler, and further includes at least one flat particle size filler having a major axis of 30 μm to 80 μm and an aspect ratio of 1.1 or more. It is preferable to include, thereby increasing the light reflectance and improving the design.

  Using the above-mentioned shaping film, it is possible to form a laminate such as wallpaper laminated on a paper material, a decorative metal plate laminated on a metal plate, and a building wall material such as an interior material or an exterior material.

Moreover, this invention is a manufacturing method of the shaping | molding film formed by giving a shaping | molding process to the film which has a surface layer at least, Comprising: This surface layer makes glass transition temperature 100 to 150 degreeC, 120 to 200 degreeC. The storage elastic modulus (E ′) in the range is 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa, and is made of a resin mainly composed of a polycarbonate resin. The manufacturing method of the shaping | molding film including the process cooled after heat-molding in the temperature range used as 10 < ⁷ > Pa or less is also provided.

  Thereby, if it heat-molds in the said temperature range and it cools, the emboss transcription | transfer rate is high and it can manufacture the shaping | molding film of a clear and deep fine embossed pattern.

The cooling is preferably rapid cooling so that the elastic modulus is 1.0 × 10 ⁹ Pa or more, whereby a shaped film with less embossing return and high design property can be produced.

In general, a “film” is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited as defined by JIS. “Sheet” means a product that is thin and generally flat with a small thickness instead of length and width (Japanese Industrial Standard JISK6900). However, the boundary between the film and the sheet is not clear, and in the present invention, it is not necessary to distinguish the two from the viewpoint of the wording. Therefore, in the present invention, even when the term “film” is used, “sheet” is included.
In the present invention, the “main component” is not particularly limited, but is 50% by weight or more, particularly 70% by weight or more, and further 90% by weight or more (including 100%) in the composition. preferable.

Hereinafter, the present invention will be described based on embodiments.
However, the embodiment described below is an example of the embodiment of the present invention, and the scope of the present invention is not limited to the following embodiment.

The shaped film of the present invention has at least a surface layer, for example, a single layer shaped film comprising only this surface layer, or other layers such as an ultraviolet absorbing layer, a printed layer, a colored layer, etc. Can be made into a multilayer shaped film, which satisfies the following formula (1).
Ra (f2) / Ra (f) = 80% or more (1)
Here, Ra (f) represents the surface roughness of the shaped film, and Ra (f2) represents the surface roughness after holding the shaped film at 100 ° C. for 60 seconds.

(Surface)
The surface layer is made of a resin having a glass transition temperature of 100 ° C. to 150 ° C. and a polycarbonate resin as a main component, and the surface of this layer is subjected to a shaping process. The resin forming the surface layer preferably has a storage elastic modulus (E ′) in the range of 120 ° C. to 200 ° C. of 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa.

The polycarbonate resin used for the surface layer is a linear polymer having a carbonate bond —O—R—OCO— in the main chain, and is generally produced by a condensation reaction of a divalent hydroxy compound and a carbonate ester. High molecular organic compounds that can be produced by the phosgene method, transesterification method, and the like. From the viewpoint of durability, those having a high molecular weight are preferred, and those having an average molecular weight of about 20000 to 30000 are preferred.
As the polycarbonate resin, a commercially available product can be used. For example, trade name Novarex manufactured by Mitsubishi Engineering Plastics, trade name Caliber manufactured by Sumitomo Dow, etc. can be used.

  In addition to the polycarbonate resin, for example, a copolymer polyester resin or acrylic rubber having a structure in which a part of ethylene glycol, which is a diol component of polyethylene terephthalate (PET) resin, is substituted with 1,4-cyclohexanedimethanol is added to the surface layer. It can be added as a material. Specifically, "PCTG 5445" (about 65% of the diol component is 1,4-cyclohexanedimethanol), Eastman Chemical Co., Ltd., which is completely compatible with polycarbonate resin, impact resistance, weather resistance, etc. For example, “Metablene W450” manufactured by Mitsubishi Rayon Co., Ltd. can be used as an additive material. By including such an additive material, it becomes possible to alloy and adjust to a glass transition temperature suitable for processing. Further, the rubber-like flat part can be shifted to the low temperature side, and the processing temperature at the time of molding can be adjusted.

  The surface layer may be formed of 100% by weight of the polycarbonate resin, but is preferably formed at a blending ratio of 90 to 50% by weight of the polycarbonate resin and 50 to 5% by weight of the additive material, particularly 95 to 75% by weight of the polycarbonate resin. The additive material is preferably formed at a blending ratio of 25 to 5% by weight. By setting it as such a mixture ratio, the glass transition temperature of the resin which forms a surface layer, and the storage elastic modulus (E ') in the range of 120 to 200 degreeC can be made into the said range.

  The thickness of the surface layer is not particularly limited, but is preferably 5 μm to 100 μm, and particularly preferably 5 μm to 50 μm.

(UV absorbing layer)
The ultraviolet absorbing layer can be laminated on the surface layer, and in this case, it is preferably formed on the surface side of the surface layer, whereby yellowing of the film can be prevented.
As an ultraviolet absorption layer, what added the ultraviolet absorber to resin, such as a polycarbonate-type resin, can be used, for example. A conventionally well-known thing can be used as a ultraviolet absorber, For example, various commercially available things can be used, "Chibinu 1577FF" etc. of Ciba Specialty Chemicals can be mentioned.

(Print layer)
The printing layer can be laminated on the surface layer, and in this case, it is preferably formed on the back side of the surface layer, whereby a pattern such as a wood grain tone or a stone tone tone can be imparted to the film.
The printed layer can be printed by a known printing method such as gravure printing, offset printing, or screen printing.

(Colored layer)
The colored layer can be laminated on the surface layer, and in this case, it is preferable to form the colored layer on the back side of the surface layer, thereby imparting a color tone or the like to the film.
As the colored layer, a resin such as a polycarbonate resin, a polyester resin, or an acrylic resin mixed with a pigment or a dye can be used.

(Filler)
When formed as a single layer, a filler can be contained in the surface layer, and when formed as a multilayer, at least one layer can contain a filler, whereby a film with a sense of depth can be obtained. The filler preferably contains at least one flat particle size filler having a major axis of 30 μm to 80 μm and an aspect ratio of 1.1 or more.
As the filler, for example, a metal filler such as aluminum, an inorganic filler such as glass, and the like can be used. Specifically, an aluminum filler, a titanium vapor-deposited glass filler, mica, talc, and the like can be used. Two or more fillers may be mixed.

(Production method)
Other layers such as a surface layer, an ultraviolet absorbing layer, a printed layer, and a colored layer can be produced by a conventionally known method. For example, the material is put into a single-screw extruder and produced as a film with a heated roll or the like. can do.
When the other layer is laminated on the surface layer, it can be laminated by a conventionally known method. For example, it can be laminated by heat fusion to form a multilayer film, or it can be laminated by an adhesive to form a multilayer film. it can. Moreover, you may laminate | stack a surface layer and these other layers by coextrusion.

(Shaping process)
The forming process can be performed by a conventionally known method. For example, the film can be heated by a heating drum with an embossing machine and passed between the embossing roll and the nip roll.
In the forming process, the glass transition temperature is set to 100 ° C. to 150 ° C., the storage elastic modulus (E ′) in the range of 120 ° C. to 200 ° C. is set to 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa, and Using a film having at least a surface layer made of a resin mainly composed of a polycarbonate resin, this film was molded by heating in a temperature range where the elastic modulus is 5.0 × 10 ⁷ Pa or less, for example, 170 ° C. or more. Thereafter, it is preferable to produce a shaped film by cooling. Furthermore, in this cooling, it is preferable to perform rapid cooling so that the elastic modulus of the surface layer is 1.0 × 10 ⁹ Pa or more. Thereby, the embossing transcription | transfer rate is high and it can manufacture the shaping | molding film of a clear and deep fine embossing pattern.

(Shaping film)
The shaped film of the present invention produced as described above satisfies the following formula (1).
Ra (f2) / Ra (f) = 80% or more (1)
Here, Ra (f) represents the surface roughness of the shaped film, and Ra (f2) represents the surface roughness after holding the shaped film at 100 ° C. for 60 seconds.
The surface roughness can be measured based on JIS B0601-2001.

  In order to satisfy the above formula (1), for example, the mixing ratio of the polycarbonate resin of the surface layer and the additive material can be adjusted as appropriate, or the thickness of each layer can be adjusted as appropriate.

In consideration of surface scratchability, the moldable film preferably has a surface hardness at 23 ° C. of 1.0 × 10 ⁹ Pa or more. In order to set the surface hardness to 1.0 × 10 ⁹ Pa or more, for example, it is preferable to increase the compounding ratio of the polycarbonate resin, or to use the polycarbonate resin alone in at least the layer forming the surface. Moreover, you may give a hard coat to the front side of a shaping film, and may raise hardness.

(Laminate)
The shaped film of the present invention can be laminated on a metal plate, paper material, etc. with an adhesive or the like to create a laminate such as a wall material for construction such as wallpaper, decorative metal plate, interior material, exterior material, etc. . As this adhesive, acrylic adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and the like can be used.

  Use various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, etc. Can do.

Hereinafter, the present invention will be described based on examples.
However, the embodiment described below is an example of the embodiment of the present invention, and the scope of the present invention is not limited to the following embodiment.

  The following shaping | molding films of Examples 1-4 and Comparative Examples 1-3 were created, and the following moldability evaluation and heat resistance evaluation were performed.

Example 1
A cast roll in which a polycarbonate resin (trade name NOVAREX 7027A manufactured by Mitsubishi Engineering Plastics) is put into a single screw extruder (manufactured by Toshiba Machine) with a vent mechanism set at a resin temperature of 280 ° C. and heated to 140 ° C. A polycarbonate film having a thickness of 30 μm was formed.
This film was heated again and subjected to a shaping process with a sevo roll to obtain a shaping film.
In addition, Shivo roll is roughened by blast surface treatment with sand of count 100 and hard chrome plated, and the surface is heated with an infrared heater to a temperature at which the elastic modulus of the film becomes 5.0 × 10 ⁷ Pa or less. The mold was processed.

(Example 2)
Copolyester resin in which about 65% of the additive material diol component is 1,4-cyclohexanedimethanol (trade name PCTG, manufactured by Eastman Chemical Co., Ltd.) is 80% by weight of polycarbonate resin (Mitsubishi Engineering Plastics Novalex 7027A). 5445) 20% by weight is mixed, and this is put into a single screw extruder (manufactured by Toshiba Machine) with a vent mechanism set at a resin temperature of 280 ° C., and a polycarbonate having a thickness of 30 μm with a cast roll heated to 140 ° C. A film containing as a main component was formed.
This film was heated again, and was subjected to a shaping process with a textured roll shown in Example 1 to obtain a shaped film.

(Example 3)
Copolyester resin in which about 65% of the additive diol component is 1,4-cyclohexanedimethanol (trade name PCTG • made by Eastman Chemical Co., Ltd.) is 75% by weight of polycarbonate resin (Novarex 7027A manufactured by Mitsubishi Engineering Plastics). 5445) Mixing 25% by weight, this was put into a single screw extruder (manufactured by Toshiba Machine) with a vent mechanism set at a resin temperature of 280 ° C, and a polycarbonate having a thickness of 30 µm with a cast roll heated to 140 ° C A film containing as a main component was formed.
This film was heated again, and was subjected to a shaping process with a textured roll shown in Example 1 to obtain a shaped film.

Example 4
Polycarbonate resin (Mitsubishi Engineering Plastics Novalex 7027A) 85% by weight, additive material acrylic rubber (Mitsubishi Rayon brand name Metabrene W450) 15% by weight is mixed, this is 280 ℃ resin temperature A single screw extruder (manufactured by TOSHIBA MACHINE) with a set vent mechanism was put in, and a film composed mainly of polycarbonate having a thickness of 30 μm was formed by a cast roll heated to 140 ° C.
This film was heated again, and was subjected to a shaping process with a textured roll shown in Example 1 to obtain a shaped film.

(Comparative Example 1)
About 25% by weight of polycarbonate resin (Novalex 7027A manufactured by Mitsubishi Engineering Plastics), about 65% of the additive diol component is a copolymerized polyester resin of 1,4-cyclohexanedimethanol (trade name PCTG, manufactured by Eastman Chemical Co., Ltd.). 5445) A mixture of 75% by weight, put this into a single screw extruder (manufactured by Toshiba Machine) with a vent mechanism set at a resin temperature of 280 ° C, and a polycarbonate with a thickness of 30 µm using a cast roll heated to 140 ° C A film containing as a main component was formed.
This film was heated again, and was subjected to a shaping process with a textured roll shown in Example 1 to obtain a shaped film.

(Comparative Example 2)
Using an EVOH film having a thickness of 30 μm (trade name EVALFILM EF-HS, manufactured by Kuraray Co., Ltd.), this film was heated and subjected to shaping with the embossing roll shown in Example 1 to obtain a shaping film.

(Comparative Example 3)
A soft PVC film having a thickness of 80 μm was used, and this film was heated and subjected to a shaping process using a shivo roll shown in Example 1 to obtain a shaping film.

(Evaluation of moldability)
Ra (r) is the surface roughness of the above-mentioned shibo roll, Ra (f) is the surface roughness of the shaped films of Examples 1 to 4 and Comparative Examples 1 to 3, and the transfer rate Ra (f) / Ra (r). Was calculated and evaluated as follows, and a transfer rate of 50% or more was regarded as a practically acceptable level. The results are shown in Table 1 below.
Ra (f) / Ra (r) = 80% or more Evaluation A
Ra (f) / Ra (r) = 60% or more and less than 80% Evaluation B
Ra (f) / Ra (r) = 50% or more and less than 60% Evaluation C
Ra (f) / Ra (r) = less than 50% Evaluation D

(Heat resistance evaluation)
The surface roughness of the shaped films of Examples 1 to 4 and Comparative Examples 1 to 3 is Ra (f), and the shaped films of Examples 1 to 4 and Comparative Examples 1 to 3 are placed in an oven at 100 ° C. Heat treatment was performed for 60 seconds, and the surface roughness of the shaped film after the heat treatment was set to Ra (f2), and the wrinkle remaining rate Ra (f2) / Ra (f) was calculated and evaluated as follows. The above was set to a level with no practical problem. The results are shown in Table 1 below.
Ra (f2) / Ra (f) = 95% or more Evaluation A
Ra (f2) / Ra (f) = 90% or more and less than 95% Evaluation B
Ra (f2) / Ra (f) = 80% or more and less than 90% Evaluation C
Ra (f2) / Ra (f) = less than 80% Evaluation D

  The glass transition temperature (Tg) and elastic modulus (E) shown in Table 1 above are measured using a dynamic viscoelasticity measuring device (manufactured by IT Meter Measurement Law Control Co., Ltd.), deformation mode “tensile”, temperature “−50 ° C. to Measurement was performed at a “limitation temperature” and a heating rate of “3 ° C./min”.

(result)
The moldable films of Examples 1 to 4 maintained excellent characteristics in moldability and heat resistance, and became moldable films with high design properties. Such a moldable film can increase the temperature of the drying furnace, particularly when performing a printing process or the like by secondary processing, and can reduce the cost by increasing the line speed.
On the other hand, the shaped films of Comparative Examples 1 to 3 have no heat resistance, and such shaped films are unsuitable for raising the temperature of the drying furnace in the secondary processing.

Claims (13)

It has a glass transition temperature of 100 ° C. to 150 ° C. and has at least a surface layer formed of a resin mainly composed of a polycarbonate resin. The surface layer is subjected to a shaping process, and satisfies the following formula (1). A shaped film characterized by that.
Ra (f2) / Ra (f) = 80% or more (1)
Here, Ra (f) represents the surface roughness of the shaped film, and Ra (f2) represents the surface roughness after holding the shaped film at 100 ° C. for 60 seconds. The resin forming the surface layer has a storage elastic modulus (E ′) in a range of 120 ° C. to 200 ° C. of 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa. The shaped film as described. 3. The shaped film according to claim 1 or 2, wherein the surface hardness at 23 ° C. is 1.0 × 10 ⁹ Pa or more.   It has an ultraviolet absorption layer, The shaping film in any one of Claims 1-3 characterized by the above-mentioned.   The shaped film according to any one of claims 1 to 4, which has one or both of a printed layer and a colored layer that have been subjected to a printing process.   The shaped film according to claim 1, wherein at least one layer is filled with a filler.   The shaped film according to claim 6, wherein the filler contains at least one kind of flat particle size filler having a major axis of 30 μm to 80 μm and an aspect ratio of 1.1 or more.   The laminated body using the shaping film in any one of Claims 1-7.   The wallpaper using the shaping film in any one of Claims 1-7.   A decorative metal plate using the shaped film according to claim 1.   A building wall material using the shaping film according to claim 1. It is a manufacturing method of the shaping film formed by giving shaping processing to the film which has a surface layer at least, Comprising: This surface layer makes the glass transition temperature 100 to 150 degreeC, and the storage elastic modulus in the range of 120 to 200 degreeC ( E ′) is 1.0 × 10 ⁶ Pa to 1.0 × 10 ⁹ Pa and is made of a resin mainly composed of a polycarbonate resin, and the film has an elastic modulus of 5.0 × 10 ⁷ Pa or less. The manufacturing method of the shaping | molding film including the process cooled after heat-molding in a temperature range. The method for producing a shaped film according to claim 12, wherein the cooling is performed so that the elastic modulus of the film is 1.0 × 10 ⁹ Pa or more.