JP2019089243A - Film for three-dimensional decoration, method for manufacturing film for three-dimensional decoration, and method for manufacturing molded product using film for three-dimensional decoration - Google Patents

Abstract

To provide a film for a three-dimensional decoration possible to be plastically deformed along a component surface of a complex three-dimensional structure, with high surface hardness and excellent appearance.SOLUTION: There is provided a film 100b for a three-dimensional decoration, including: a base layer 200; uncured or semi-cured resin layer 300 composed of a resin composition laminated on the base layer 200; and a shielding layer 600 laminated on the resin layer 300, wherein the resin composition contains radically polymerizable resin and thermal radical polymerizable initiator. When a content of the thermal radical polymerizable initiator is less than 0.5 to 1.5 wt.%, a thickness of the resin layer 300 is 5 to 65 μm, and when the content of the thermal radical polymerizable initiator is less than 1.5 to 2.5 wt.%, the thickness of the resin layer 300 is 5 to 20 μm, and when the content of the thermal radical polymerizable initiator is 2.5 to 4.0 wt.%, the thickness of the resin layer 300 is 5 to 10 μm.SELECTED DRAWING: Figure 3

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a technique for decorating a curved surface portion to be decorated having a curved surface portion. More specifically, the present invention relates to a film for three-dimensional decoration used to decorate the curved surface part to be decorated having a curved surface part, a method for producing a film for three-dimensional decoration, and three-dimensional decoration TECHNICAL FIELD The present invention relates to a method for producing a molded article using a film.

  Conventionally, decorative films used for home appliances, communication devices, interior and exterior parts of automobiles, OA devices, building materials and the like are known.

  For example, JP-A-2016-141706 (Patent Document 1) is a single-layer adhesive resin layer formed of an acrylic adhesive resin composition having transparency, and the adhesive resin composition is A) an acrylic polymer, (B) an acrylic monomer, and (C) a thermal polymerization initiator, the adhesive resin layer has adhesiveness on both sides at normal temperature, and a temperature of 100 to 250 ° C. An adhesive resin layer is disclosed, which can be thermally cured by heating for 30 seconds to 10 minutes.

  Moreover, in JP-A-2015-91936 (Patent Document 2), a cellulose ester comprising one or two or more layers and containing 2 to 20% by mass of a thermal polymerization initiator based on cellulose ester and cellulose ester A roll-like film comprising a thermal polymerization initiator is disclosed, in which a film having a layer at least at the air interface is rolled up.

  In addition, according to International Publication No. WO 2014/021283 (Patent Document 3), after semi-curing a film or sheet of a resin composition, the semi-cured film or sheet is formed into a desired three-dimensional shape, and the above-mentioned shape is There is disclosed a method of producing a cured resin molded article characterized by secondary curing in a held state.

  Further, in JP-A-2015-66778 (Patent Document 4), a curable resin composition is semi-cured on a transparent substrate, and has a thickness of 10 μm to 1 mm, and an elongation of 5% or more at room temperature The semi-cured film laminate in which the semi-cured resin layer having the above is laminated is disposed in the injection mold so that the semi-cured resin layer side adheres to the mold, and the injection molding resin is injected into the mold from the transparent substrate side. The resin for injection molding is molded simultaneously, and at the same time the resin for injection molding and the semi-cured film laminate are integrated, and then the semi-cured resin layer is completely cured to inject the hard coat layer, the transparent layer and the injection. There is disclosed a method of producing a molded body characterized in that a laminate is integrally formed with a molding resin.

JP, 2016-141706, A JP, 2015-91936, A International Publication Number WO2014 / 021283 JP, 2015-66778, A

In Patent Document 1, since the adhesive resin layer has adhesiveness at normal temperature and heat press is performed to cure the resin, generation of air bubbles can be prevented even if it is bonded to a substrate having a step. is there. In this case, air bubbles associated with the step can be suppressed, but a gas may be generated from the polymerization initiator at the time of heat curing. Further, the invention of Patent Document 1 relates to the adhesive resin layer between the substrates, so there is a problem that the surface hardness of the resin layer is not sufficient.
Moreover, although patent document 2 is a thing with high surface hardness because it has a hard coat film, since it is a sheet member used for optical instruments, such as a liquid crystal display, it can not use for the surface of a three-dimensional complicated shape. There is a problem of
Moreover, although patent document 3 carries out secondary hardening of the resin of a semi-hardened state, gas may be emitted from a polymerization initiator at the time of thermosetting, and the external appearance of a resin molded product may worsen. In addition, if UV irradiation is not performed before heat curing, there is a problem that moldability is deteriorated.
Moreover, in patent document 4, a gas may be emitted from a polymerization initiator at the time of thermosetting, and the external appearance of a resin molded product may worsen.

In the field of films for decorative use, a precure type in which curing is performed by a photopolymerization initiator before molding and an aftercure type in which curing is performed by a photopolymerization initiator after completion of molding processing are used. In order to sufficiently increase the hardness, a pre-cure type is generally used, and after curing is generally used when the amount of deformation of the molding is large. Thus, as the film for decoration, a photopolymerization type material system has mainly been used.
And application examination of a film for decoration is spreading to a product which needs three-dimensional processing, such as interior and exterior parts of parts for vehicles, by expansion of a use of a film for decoration. Along with this, it is required to cope with upsizing of facilities and complication of the shape, but since a conventional film for decoration is to be cured by photopolymerization, it requires a complicated and large-sized UV irradiation device, That is an impediment to introduction. Therefore, there is a need for a method of producing a decorated molded article in an existing process using an existing production apparatus without introducing a complicated and expensive UV irradiation apparatus.
Further, from the viewpoint of improving the abrasion resistance and the abrasion resistance of the molded article, it is required to increase the surface hardness of the surface of the molded article. For that purpose, when the thickness of the resin layer formed on the surface of the molded product is increased, the pencil hardness tends to be increased. However, in the case of a decorative film that is cured by photopolymerization, ultraviolet rays can be absorbed near the surface, so that the ultraviolet rays can not be irradiated to the inside of the thick resin layer, so there is a problem that the resin layer is not sufficiently cured.

Therefore, an object of the present invention is to produce a film for three-dimensional decoration and a film for three-dimensional decoration having high surface hardness and appearance that can be plastically deformed along a component surface of a complicated three-dimensional structure. A method and a method for producing a molded article using a three-dimensional decorative film.
Another object of the present invention is to utilize the heat of a mold used at the time of molding of a molded article for the polymerization reaction of a film for decoration, to provide on-vehicle interior and exterior parts, and other complex three-dimensional resin molded article surfaces. A three-dimensional decorative film that can be plastically deformed along the surface, has a very high surface hardness as a hard coat, is excellent in appearance, and is excellent in adhesion to a three-dimensionally curved resin molded product and followability. A method of manufacturing a film for three-dimensional decoration and a method of manufacturing a molded article using the film for three-dimensional decoration.

  In order to achieve the above object, the present invention includes the following inventions.

(1)
A three-dimensional decorative film according to one aspect includes a base material layer, an uncured or semi-cured resin layer composed of a resin composition laminated on the substrate layer, and a shielding layer laminated on the resin layer. A film for three-dimensional decoration comprising the resin composition containing at least a resin having a radically polymerizable functional group and a thermal radical polymerization initiator of 0.5% by weight or more and 4.0% by weight or less. When the thickness of the resin layer is 5 μm or more and 65 μm or less and the content of the thermal radical polymerization initiator is 0.5% by weight or more and less than 1.5% by weight, the thickness of the resin layer is 5 μm or more and 65 μm or less When the content of the thermal radical polymerization initiator is 1.5% by weight or more and less than 2.5% by weight, the thickness of the resin layer is 5 μm or more and 20 μm or less, and the content of the thermal radical polymerization initiator is 2.5 Thickness of resin layer in case of weight% or more and 4.0 weight% or less There is 5μm or more 10μm or less.

When a surface of a molded article having a complicated three-dimensional structure is decorated using a film for three-dimensional decoration using a photocurable resin, the amount of light irradiation to the film disposed on the surface of the molded article is uneven. It is easy (that is, the amount of light irradiation is small in the depressions of the molded article), and the light absorption of the photocurable resin itself may result in insufficient curability.
However, even in the case of producing a resin molded product having a complicated three-dimensional structure by thermally curing a resin layer comprising a resin composition containing a thermal radical polymerization initiator as in the present invention, three-dimensional addition is The decorative film can be sufficiently cured uniformly. Thus, it can be used for producing a molded article having a complicated three-dimensional structure, and the thickness of the resin layer can be increased, so that a molded article with high surface hardness can be produced.
In addition, since the resin layer is disposed between the base material layer and the shielding layer, the resin layer is not in direct contact with the air, so that the inhibition of the reaction by oxygen during the thermal radical polymerization reaction is reduced. Can. Thereby, the polymerization degree of the resin layer can be improved, and the hardness of the surface of the molded article can be further increased.

The content of the thermal radical polymerization initiator contained in the resin composition constituting the resin layer is 0.5% by weight or more, and preferably 0.8% by weight or more. Thereby, the curing reaction of the resin layer can be sufficiently performed, and the effect of improving the surface curing degree can be sufficiently obtained when the film for three-dimensional decoration is cured.
Further, the content of the thermal radical polymerization initiator contained in the resin composition is 4.0% by weight or less, preferably 1.5% by weight or less, and 1.2% by weight or less More preferable. As a result, it is possible to minimize the deterioration in appearance due to the nitrogen gas generated when the thermal radical polymerization initiator is decomposed.
Therefore, a molded article having a high surface hardness and an excellent appearance can be obtained.

The thickness of the resin layer is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
The thickness of the resin layer is 65 μm or less, preferably 40 μm or less, and more preferably 30 μm or less. Thereby, the influence of the cure shrinkage of the resin layer can be minimized. Moreover, since the influence of the gas generated at the time of resin hardening can be suppressed, the appearance of a molded article can be improved. And it is preferable from a viewpoint of thickness accuracy, a curl characteristic, and crack generation | occurrence | production prevention.
However, in order to obtain a molded article excellent in both surface hardness and appearance, the content of the thermal radical polymerization initiator and the thickness of the resin layer are adjusted within the setting range as described above. When the content of the thermal radical polymerization initiator is out of the above range and / or the thickness of the resin layer is out of the above range, either one of the surface hardness and the appearance is lowered, and a satisfactory molded article can not be obtained. .

  By using an uncured or semi-cured three-dimensional decorative film, it is formed into a three-dimensional shape together with the molded product, and secondarily cured while maintaining a desired shape even with a complex three-dimensional structure Can. In addition, by curing the film for three-dimensional decoration in a plurality of stages, it is possible to prevent rapid curing shrinkage of the resin and to allow the reaction to proceed slowly as a whole. Thereby, since the gas generated during the reaction can be released out of the system, the influence of the gas generated during the curing can be suppressed. Therefore, the molded product can be provided with excellent appearance and decoration.

(2)
The film for three-dimensional decoration according to the second invention is a film for three-dimensional decoration according to one aspect of the invention, wherein the thermal radical polymerization initiator has a 10-hour half-life temperature of 60 ° C to 90 ° C. It may have characteristics.

When the half-life temperature of the thermal radical polymerization initiator is in the above range, the storage stability is good, and furthermore, the film for three-dimensional decoration is not cured in a plurality of processing steps such as printing at low temperature and drying. It is possible to provide a three-dimensional decorative film in which the resin layer is thermally cured at the time of three-dimensional molding. Therefore, the molded product can be provided with excellent appearance and decoration.
Moreover, the hardness of a resin layer can be made high by making the 10-hour half-life temperature of a thermal radical polymerization initiator into 90 degrees C or less. And by making the 10-hour half-life temperature of the thermal radical polymerization initiator 60.degree. C. or higher, the surface condition can be improved and an excellent appearance can be obtained.

(3)
The film for three-dimensional decoration according to the third invention is a film for three-dimensional decoration according to the one aspect or the second invention, which is a tensile test based on JIS K7127 in a 60.degree. The breaking elongation at 20 mm / min) may be 50% or more. In addition, with a fracture | rupture said here, not only when a base material fracture | ruptures but the case where a coating film fracture | ruptures is included.
When the breaking elongation in a tensile test based on JIS K7127 in a 60 ° C. environment of the resin layer is 50% or more, a suitable semi-hardened three-dimensional decorative film can be molded into a three-dimensional shape with a molded product it can. Therefore, even a complicated three-dimensional structure can be secondarily cured while maintaining a desired shape. In addition to preventing rapid curing shrinkage of the resin, it is possible to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with an excellent appearance and decoration.

(4)
The film for three-dimensional decoration according to the fourth invention is a film for three-dimensional decoration according to any one of the first to third inventions, and the thermal radical polymerization initiator may contain an azo compound.

  By using the thermal radical polymerization initiator comprising an azo compound, the polymerization of the resin layer can be initiated at a relatively high temperature, so that the polymerization does not easily proceed in the steps of coating and lamination of the resin layer, while three-dimensional The polymerization of the resin layer can be effectively advanced by being placed in a high temperature environment at the time of molding.

(5)
The film for three-dimensional decoration according to the fifth invention is a film for three-dimensional decoration according to any one of the first to fourth inventions, wherein the resin having a radically polymerizable functional group is an acrylate resin, It may also include at least one resin selected from the group consisting of methacrylate resins and urethane acrylate resins.

  Thereby, a film for three-dimensional decoration having high surface hardness and excellent appearance can be obtained.

(6)
A film for three-dimensional decoration according to a sixth aspect of the present invention is the film for three-dimensional decoration according to any one of the first to fifth aspects, wherein at least one of the base layer and the shielding layer is provided. Printing may be applied, or a design layer may be laminated on the surface of the base material layer.

  Thereby, high designability can be provided to the film for three-dimensional decoration. The lamination of the printing and / or design layer may be on the resin layer side of the base layer or the shielding layer, or may be on the opposite side.

(7)
The film for three-dimensional decoration according to the seventh invention is a film for three-dimensional decoration according to any one of the aspects from the one aspect to the sixth aspect, wherein the surface of the shielding layer or the substrate layer on the resin layer side is uneven. A shape may be formed, and the concavo-convex shape of the shielding layer or the base material layer may be transferred to the resin layer.

  By this, by curing the resin layer using the shielding layer or the base material layer having the concavo-convex shape, the concavo-convex structure is transferred to the surface of the resin layer, and the concavo-convex structure such as improvement of scattering rate or reduction of reflectance. Can be imparted to the resin layer.

(A) In the film for three-dimensional decoration of the present invention, the concavo-convex pitch in the concavo-convex shape may be 400 nm or less.
As a result, it is possible to provide a three-dimensional molded body in which the reflectance of the visible light region on the surface is reduced by the uneven shape.

(B) The uneven | corrugated pitch in uneven | corrugated shape may be 3 micrometers or more in the film for three-dimensional decoration of this invention.
As a result, by scattering light on the surface due to the uneven shape, it is possible to give a molded article in which the surface is perceived as whitish.

(C) In the film for three-dimensional decoration of the present invention, the asperity shape includes the main unevenness and the sub unevenness forming the surface of the main unevenness, and the unevenness pitch in the main unevenness is 3 μm or more and 1 mm or less, the sub unevenness The uneven | corrugated pitch in these may be 100 nm-400 nm.
As a result, it is possible to give a molded article having a high degree of blackness by further scattering the reflected light which is suppressed while suppressing the reflectance on the surface by the sub-relief shape.

(8)
According to another aspect of the present invention, there is provided a method of producing a three-dimensional decorative film comprising: a base material layer; a semi-cured or uncured resin layer composed of a resin composition laminated on the base material layer; A method of producing a film for three-dimensional decoration comprising a layer, wherein a resin composition having at least a resin having a radically polymerizable functional group and a thermal radical polymerization initiator is prepared. Applying a resin composition to the base material layer to form a film of the resin composition, laminating a shielding layer on the film of the resin composition, uncuring or semi-curing the film of the resin composition And forming a resin layer, wherein the resin composition comprises a resin having a radically polymerizable functional group, and 0.5% by weight or more and 4.0% by weight or less of a thermal radical polymerization initiator At least, and the thickness of the resin layer is 5 μm or more The thickness of the resin layer is 5 μm or more and 65 μm or less when the content of the heat radical polymerization initiator is 5 μm or less and the content of the heat radical polymerization initiator is 0.5% by weight or more and less than 1.5% by weight in the preparation step When the content of is 1.5% by weight or more and less than 2.5% by weight, the thickness of the resin layer is 5 .mu.m or more and 20 .mu.m or less, and the content of the thermal radical polymerization initiator is 2.5% by weight or more and 4.0% In the case of% or less, the resin composition is prepared such that the thickness of the resin layer is 5 μm or more and 10 μm or less.

  By thermally curing the resin layer using a thermal radical polymerization initiator, the film for three-dimensional decoration can be sufficiently cured. Thereby, while being able to use for a complicated three-dimensional structure, since the thickness of a resin layer can be thickened, the film for three-dimensional decoration with high surface hardness can be obtained.

  In addition, since the resin layer is not in direct contact with air because the resin layer is between the base material layer and the shielding layer, oxygen inhibition in the thermal radical polymerization reaction can be reduced. Thereby, the polymerization degree of a resin layer can be improved and the surface hardness of the film for three-dimensional decoration can be made higher.

The content of the thermal radical polymerization initiator in the resin layer is 0.5% by weight or more, and preferably 0.8% by weight or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
Further, the content of the thermal radical polymerization initiator with respect to the resin layer is 4.0% by weight or less, and preferably 1.5% by weight or less. This makes it possible to minimize the deterioration of the appearance associated with the nitrogen gas generated from the thermal initiator. Therefore, a film for three-dimensional decoration having high surface hardness and excellent appearance can be obtained.

The thickness of the resin layer is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. Thereby, even when an external force is applied to the film, it is hard to be influenced by the flexible base layer, and the effect of improving the surface hardening degree of the film for three-dimensional decoration can be sufficiently obtained.
The thickness of the resin layer is preferably 65 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. This can minimize the effects of curing shrinkage of the resin layer, such as curling and cracking. Moreover, since the influence of nitrogen gas generated at the time of resin curing can be suppressed, the appearance of the film for three-dimensional decoration can be improved. And generation | occurrence | production of a crack etc. can be prevented preferably. Further, by setting the resin thickness to a certain range or less, it is possible to smoothly release the gas generated by the curing reaction to the outside of the resin, and the appearance of the film for three-dimensional decoration can be improved.
However, in order to obtain a molded article excellent in both surface hardness and appearance, the content of the thermal radical polymerization initiator and the thickness of the resin layer are adjusted within the setting range as described above. When the content of the thermal radical polymerization initiator is out of the above range and / or the thickness of the resin layer is out of the above range, either one of the surface hardness and the appearance is lowered, and a satisfactory molded article can not be obtained. .

  By using a semi-cured three-dimensional decorative film, it is possible to perform secondary curing while maintaining a desired shape even with a complex three-dimensional structure by forming it into a three-dimensional shape with a molded product it can. In addition, by curing the three-dimensional decorative film in two steps, it is possible to prevent rapid curing shrinkage of the resin and to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with excellent appearance and decoration.

(9)
According to another aspect of the present invention, there is provided a method of producing a molded article using a three-dimensional decorative film, comprising placing the three-dimensional decorative film according to any one of the first to seventh inventions in a mold and A method for producing a molded article in which an injection-molded product and a three-dimensional decorative film are integrated by injection molding a resin for injection molding, comprising: a curing step of thermally curing a resin layer during injection molding. .

Since the resin layer can be hardened using the heat of the mold at the time of injection molding by this, the molded article by which the film for three-dimensional decoration was bonded simultaneously with injection molding can be obtained.
Moreover, the film for three-dimensional decoration can fully be hardened by thermosetting the resin layer using a thermal radical polymerization initiator. Thereby, while being able to use for a complicated three-dimensional structure, since the thickness of a resin layer can be thickened, the film for three-dimensional decoration with high surface hardness can be obtained.

  In addition, since the resin layer is not in direct contact with air because the resin layer is between the base material layer and the shielding layer, oxygen inhibition in the thermal radical polymerization reaction can be reduced. Thereby, the polymerization degree of a resin layer can be improved and the surface hardness of the film for three-dimensional decoration can be made higher.

The content of the thermal radical polymerization initiator in the resin layer is 0.5% by weight or more, and preferably 0.8% by weight or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
Further, the content of the thermal radical polymerization initiator with respect to the resin layer is 4.0% by weight or less, preferably 1.5% by weight or less, and more preferably 1.2% by weight or less. This makes it possible to minimize the deterioration of the appearance associated with the nitrogen gas generated from the thermal initiator. Therefore, a film for three-dimensional decoration having high surface hardness and excellent appearance can be obtained.

The thickness of the resin layer is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
The thickness of the resin layer is 65 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. Thereby, the influence of the cure shrinkage of the resin layer can be minimized. Moreover, since the influence of nitrogen gas generated at the time of resin curing can be suppressed, the appearance of the film for three-dimensional decoration can be improved. And generation | occurrence | production of a crack etc. can be prevented preferably.
However, in order to obtain a molded article excellent in both surface hardness and appearance, the content of the thermal radical polymerization initiator and the thickness of the resin layer are adjusted within the setting range as described above. When the content of the thermal radical polymerization initiator is out of the above range and / or the thickness of the resin layer is out of the above range, either one of the surface hardness and the appearance is lowered, and a satisfactory molded article can not be obtained. .

  By using a semi-cured three-dimensional decorative film, it is possible to perform secondary curing while maintaining a desired shape even with a complex three-dimensional structure by forming it into a three-dimensional shape with a molded product it can. In addition, by curing the three-dimensional decorative film in two steps, it is possible to prevent rapid curing shrinkage of the resin and to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with excellent appearance and decoration.

(10)
The manufacturing method of the molded article using the film for three-dimensional decoration according to another aspect vacuum-molds or pressure-molds the film for three-dimensional decoration and the object to be molded according to any one of the first to seventh inventions. Thus, a method for producing a molded article in which the object to be molded and the three-dimensional decorative film are integrated, and including a curing step of thermally curing the resin layer during vacuum molding or pressure forming.

By this, the resin layer can be cured using the heat of the object to be molded (mold) at the time of vacuum forming or pressure forming, so that the film for three-dimensional decoration is bonded simultaneously with vacuum forming or pressure forming. Can be obtained.
Moreover, the film for three-dimensional decoration can fully be hardened by thermosetting the resin layer using a thermal radical polymerization initiator. Thereby, while being able to use for a complicated three-dimensional structure, since the thickness of a resin layer can be thickened, the film for three-dimensional decoration with high surface hardness can be obtained.
In addition, since the resin layer is not in direct contact with air because the resin layer is between the base material layer and the shielding layer, oxygen inhibition in the thermal radical polymerization reaction can be reduced. Thereby, the polymerization degree of a resin layer can be improved and the surface hardness of the film for three-dimensional decoration can be made higher.

The content of the thermal radical polymerization initiator in the resin layer is 0.5% by weight or more, and more preferably 0.8% by weight or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
Further, the content of the thermal radical polymerization initiator with respect to the resin layer is 4.0% by weight or less, preferably 1.5% by weight or less, and more preferably 1.2% by weight or less. This makes it possible to minimize the deterioration of the appearance associated with the nitrogen gas generated from the thermal initiator. Therefore, a film for three-dimensional decoration having high surface hardness and excellent appearance can be obtained.

The thickness of the resin layer is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. Thereby, the effect of surface hardening degree improvement of the film for three-dimensional decoration can fully be acquired.
The thickness of the resin layer is 65 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. Thereby, the influence of the cure shrinkage of the resin layer can be minimized. Moreover, since the influence of nitrogen gas generated at the time of resin curing can be suppressed, the appearance of the film for three-dimensional decoration can be improved. And generation | occurrence | production of a crack etc. can be prevented preferably.
However, in order to obtain a molded article excellent in both surface hardness and appearance, the content of the thermal radical polymerization initiator and the thickness of the resin layer are adjusted within the setting range as described above. When the content of the thermal radical polymerization initiator is out of the above range and / or the thickness of the resin layer is out of the above range, either one of the surface hardness and the appearance is lowered, and a satisfactory molded article can not be obtained. .

  By using a semi-cured three-dimensional decorative film, it is possible to perform secondary curing while maintaining a desired shape even with a complex three-dimensional structure by forming it into a three-dimensional shape with a molded product it can. In addition, by curing the three-dimensional decorative film in two steps, it is possible to prevent rapid curing shrinkage of the resin and to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with excellent appearance and decoration.

(11)
A method of producing a molded article using a film for three-dimensional decoration according to an eleventh invention is a method of producing a molded article according to the ninth or tenth invention, wherein a resin having a concavo-convex shape formed in a shielding layer is used. The uneven configuration of the shielding layer may be transferred to the surface of the resin layer by the composition coming in intimate contact and entering and the resin composition being cured.

  By curing the resin layer using the shielding layer having the concavo-convex shape, the concavo-convex structure is transferred to the surface of the resin layer, and optical characteristics according to the concavo-convex structure such as improvement of scattering rate and reduction of reflectance It can be applied to

(12)
A method of producing a molded article using a film for three-dimensional decoration according to a twelfth invention is a method of producing a molded article according to any of the ninth to eleventh inventions, wherein at least at least a substrate layer and a shielding layer The method may further include a printing step of printing on one of the surfaces or a design layer lamination step of laminating a design layer on the surface of the base material layer.

  Thereby, high designability can be provided to the film for three-dimensional decoration. The printing step or the design layer lamination step may be performed on the resin layer side of the base layer or the shielding layer, or may be performed on the opposite side.

It is a typical sectional view showing an example of a film for three-dimensional decoration. It is a typical sectional view showing other examples of a film for three-dimensional decoration. It is a schematic cross section which shows the further another example of the film for three-dimensional decoration. It is a schematic diagram which shows the example of the temperature profile which the film for three-dimensional decoration receives. It is a typical sectional view showing the process of injection molding using the film for three-dimensional decoration. It is a typical sectional view showing the process of carrying out vacuum forming using a film for three-dimensional decoration. It is a schematic cross section of the molded article vacuum-formed using the film for three-dimensional decoration.

Hereinafter, the present invention will be described in detail.
As shown in FIG. 1, the film 100 for three-dimensional decoration of the present invention comprises a base layer 200, a semi-cured resin layer 300 made of a resin composition laminated on the base layer 200, and a resin layer 300. And the shielding layer 600 laminated | stacked on this, and the base material layer 200, the resin layer 300 of a semi-hardened state, and the shielding layer 600 were laminated | stacked in this order.
Thus, the film 100 for three-dimensional decoration of the present invention has at least a three-layer structure as described above, and is a laminate of a four-layer structure in which a design layer 400 is further laminated, as described below. It may be a laminate of five or more layers.
For example, as shown in FIG. 3, the three-dimensional decorative film 100 b includes a base layer 200, a semi-cured resin layer 300 made of a resin composition laminated on the lower surface of the base layer 200, and a resin layer. And a shielding layer 600 laminated on the lower surface of the substrate 300.

In the present invention, the "semi-cured state" of the resin layer means a state in which the resin layer is between the uncured state and the cured state. That is, by cross-linking reaction of a part of the monomer, oligomer or polymer base material contained in the resin layer, a three-dimensional network structure is formed, unreacted components are held in the network structure, and plastic deformation is possible. State.
Specifically, the degree of the semi-cured state of the resin layer can be measured by the following method (1) and / or (2).
(1) Elongation at break of resin layer The elongation at break in a tensile test (sample width 10 mm, observation distance between chucks 50 mm, tensile speed 20 mm / min) in a 60 ° C. environment is 50% or more. In addition, with a fracture | rupture said here, not only when a base material fracture | ruptures but the case where a coating film fracture | ruptures is included.
When the resin layer is allowed to stand in an environment at 60 ° C. and the breaking elongation in a tensile test based on JIS K7127 is 50% or more, the resin layer is in a semi-cured state.

When the breaking elongation in a tensile test in accordance with JIS K7127 in a 60 ° C. environment is 50% or more, an appropriately semi-cured three-dimensional decorative film can be molded into a three-dimensional shape together with a molded product. Therefore, even a complicated three-dimensional structure can be secondarily cured while maintaining a desired shape. In addition to preventing rapid curing shrinkage of the resin, it is possible to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with an excellent appearance and decoration.
(2) Estimation of degree of polymerization by infrared absorption spectrum measurement of resin layer Infrared absorption spectra of the resin layer and the uncured coating material (resin composition) are measured by Fourier type infrared spectroscopy measurement, and polymerization of the resin is performed from here The indicator related to the degree was calculated.
In the infrared absorption spectrum measurement, when the peak intensity PA near wavenumber 810 cm ⁻¹ and the polymerization index R (%) calculated from the peak intensity PB near wavenumber 1700 cm ⁻¹ are 30% or less, the resin layer is It is semi-cured or uncured.

  As a result, since an appropriate uncured or semi-cured three-dimensional decorative film can be formed into a three-dimensional shape together with the molded product, it is possible to maintain the desired shape even with a complex three-dimensional structure. It can be cured next. In addition to preventing rapid curing shrinkage of the resin, it is possible to suppress the influence of nitrogen gas generated at the time of curing. Therefore, the molded product can be provided with an excellent appearance and decoration.

In the infrared absorption spectrum measurement, the peak of the absorbance at around the wave number 1700 cm ⁻¹ of the resin layer in the uncured state is Aao, the peak of the absorbance at around the wave number 810 cm ⁻¹ is Abo, and the absorbances in the desired state When the peak of is designated as Aam and Abm, the degree of polymerization index R (%) calculated from the infrared absorption spectrum is represented as the following (formula 1).

Abo and Abm are absorptions due to out-of-plane vibration such as acrylate, and the absorbance decreases as the curing reaction of the resin proceeds. On the other hand, Aao and Aam are absorptions due to the C = O vibration of acrylate, and do not change before and after the curing reaction of the resin.
From the viewpoint of obtaining an appropriate uncured or semi-cured resin layer, the value of R is preferably 30% or less. Thereby, even if it is a complicated three-dimensional structure, it can be secondarily hardened in the state where a desired shape is held.

(Base material layer 200)
The base layer 200 is a base for forming a resin layer.
The base material layer 200 is made of polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, polyvinyl chloride resin, polycarbonate resin, polyurethane resin, polystyrene resin, acetate resin, polyamide resin. A resin sheet made of a resin or the like, a sheet in which these are combined, or the like can be used.
The base layer 200 is flexible and preferably made of a transparent resin. Specifically, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethacrylic acid Thermoplastic resins such as methyl (PMMA), polycarbonate (PC), cycloolefin polymer (COP), polystyrene (PS) or polyurethane can be mentioned.
Among these resins, transparent non-crystalline resins which do not impair the decorative property, and a polymer film having a glass transition point Tg of room temperature (25.degree. C.) or more, preferably 50.degree. C. or more, more preferably 90.degree. preferable. Specifically, PMMA, PC, COP, and PS are more preferably mentioned.

Although the film thickness of the base material layer 200 is not limited, it can be 25 micrometers or more and 200 micrometers or less. If the thickness of the base layer is less than 25 μm, the base layer may not be rigid and may not support the resin layer. If the thickness is more than 200 μm, the base layer may be too rigid to handle.
There are roughly two types of films for decoration, and there are two types: a type in which a base material is simultaneously incorporated into a 3D molded product, and a transfer foil system that is removed from the molded product after molding.
In the latter case, a step of peeling the base material from the base material after work-hardening of the base material is involved, so a release layer is required on the base material. Specifically, polyethylene terephthalate (PET) films having a thickness of 50 μm, 38 μm, etc. can be suitably used.
In addition, in the base material layer, an adhesive layer or an adhesive layer for adhering or adhering to the molded body may be provided in advance.

(Resin layer 300)
Any resin material having a radically polymerizable functional group can be used as the resin layer. For example, acrylates and methacrylates, acrylamide, styrene derivatives and the like.
The resin layer 300 is disposed between the base layer 200 and the shielding layer 600. Thereby, since resin layer 300 does not touch air directly, inhibition of the reaction by oxygen at the time of thermal radical polymerization reaction can be reduced. Therefore, the polymerization degree of the resin layer can be improved, and the surface hardness of the film for three-dimensional decoration can be increased.

The thickness of the resin layer 300 is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. Thereby, even if the base material layer 200 to be the base is a flexible film, the effect of improving the surface hardening degree of the film for three-dimensional decoration can be sufficiently obtained.
The thickness of the resin layer 300 is 65 μm or less, preferably 40 μm or less, and more preferably 30 μm or less. Thereby, the influence of the cure shrinkage of the resin layer can be minimized. Moreover, since the influence of the gas generated at the time of resin hardening can be suppressed, the appearance of the film for three-dimensional decoration can be improved. And it is preferable from a viewpoint of thickness accuracy, a curl characteristic, and crack generation | occurrence | production prevention.
However, in order to obtain a molded article excellent in both surface hardness and appearance, the content of the thermal radical polymerization initiator and the thickness of the resin layer are prepared within the setting range as described above.

  The resin layer can also be formed by laminating a plurality of layers. For example, two layers of a coating material coated and formed with a thickness of 30 μm on a substrate are prepared, and a thick hard coat layer formed by combining respective resin surfaces is formed by thermal polymerization radical reaction. It can also be done.

The resin layer 300 is made of a resin composition in an uncured or semi-cured state laminated on a base material layer. By using a film for three-dimensional decoration having a resin layer in an uncured or semi-cured state, it can be easily formed into a three-dimensional shape along the surface shape of a formed product, and a complex three-dimensional structure is desirable The secondary curing can be performed while maintaining the shape of
Moreover, the function of a hard coat can be provided to the film 100 for three-dimensional decoration by making hardness after hardening of the resin layer 300 high.

  The monomer, the oligomer, and the polymer base material contained in the resin composition which comprises the resin layer 300 should just be a material which can be radically polymerized. It is necessary for causing a crosslinking reaction to have two or more functional groups having a double bond, such as acrylate and methacrylate, and it is preferable to have a large number of functional groups. Thereby, the hardness after hardening of a resin layer can be made high.

  The curable resin composition constituting the resin layer 300 preferably contains an oligomer having a relatively large molecular weight as an uncured component. The uncured component may have a polymerizable functional group. The polymerizable functional group may be any group as long as it generates a radical, cation, anion or the like to cause polymerization, and examples thereof include a polymerizable unsaturated group and an epoxy group. Examples of the polymerizable unsaturated group include a (meth) acrylate group and an acrylamide group. These polymerizable functional groups can be polymerized by post curing. By this, the hardness of the surface layer after post-curing can be increased, and deterioration of the characteristics can be prevented.

  Specific oligomers include, for example, urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, ether (meth) acrylate oligomers, ester (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, polyol (Meth) acrylate oligomers, fluorine-based (meth) acrylate oligomers, silicone-based (meth) acrylate oligomers, oligomers of unsaturated polyesters (condensates of unsaturated dicarboxylic acid and polyhydric alcohol, etc.), cationically polymerizable epoxy compounds, The homopolymer or copolymer of the below-mentioned monomer which has a radically polymerizable bond in a side chain etc. are mentioned.

  Furthermore, although the said oligomer may be any of a monofunctional oligomer and a bifunctional or more polyfunctional oligomer, it is preferable that it is a bifunctional or more polyfunctional oligomer from a viewpoint of obtaining a suitable crosslinking density after hardening.

The curable resin composition constituting the resin layer 300 may contain a monomer as a further uncured component from the viewpoint of exhibiting the function as a reactive diluent (solvent) and the like. The monomer may be either a monofunctional monomer or a bifunctional or higher polyfunctional monomer.
Specifically, as monofunctional monomers, for example, (meth) acrylates (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) Acrylate, s-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate etc.); (meth) acrylic acid; ) Acrylonitrile; Styrenes (styrene, α-methylstyrene etc.); (Meth) Acrylamides ((Meth) Acrylamide, N-Dimethyl (meth) Acrylamide, N-Diethyl (meth) Acrylamide, Dimethylaminopropyl (meth) Acrylamide etc And the like.

  As polyfunctional monomers, ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene oxide modified with isocyanurate ethylene oxide di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (meth) ) Acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3) -(Meta Acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) butane , Dimethylol tricyclodecane di (meth) acrylate, ethylene oxide adduct of bisphenol A di (meth) acrylate, propylene oxide adduct of bisphenol A di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, divinyl Difunctional monomers such as benzene and methylene bis acrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri ( Data) acrylate, trimethylolpropane propylene oxide-modified triacrylate, trimethylolpropane ethylene oxide-modified triacrylate, include trifunctional monomers such as isocyanuric acid ethylene oxide-modified tri (meth) acrylate. Furthermore, a condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tetra (meth) acrylate And polyfunctional ethylene oxide adducts of these polyfunctional monomers, propylene oxide adducts, and the like; difunctional or higher urethane acrylates, and difunctional or higher polyester acrylates.

(Thermal radical polymerization initiator)
When a photocurable resin is used as the film 100 for three-dimensional decoration to decorate the surface of a resin molded product, a complex three-dimensional structure tends to cause unevenness in the amount of light irradiation, and the photocurable resin itself The light absorption of the resin may result in insufficient curing.
However, the film for three-dimensional decoration can be sufficiently cured uniformly by heating and thermally curing the resin layer made of the resin composition containing the thermal radical polymerization initiator as in the present invention. Thereby, while being able to be used for a complicated three-dimensional structure, since the thickness of a resin layer can be thickened, the film 100 for three-dimensional decoration with high surface hardness can be obtained.

As described above, as the thermal radical polymerization initiator, one having a characteristic of 60 ° C. to 90 ° C. as a preferable 10-hour half-life temperature is preferable. More preferably, it has a characteristic of 65 ° C. to 88 ° C. as a 10 hour half-life temperature. When one having a half-life temperature of less than 60 ° C. is used as the 10 hour half-life temperature of the thermal radical polymerization initiator, the cleavage reaction proceeds due to the thermal history such as drying to the three-dimensional molding, solvent removal and preheating, three-dimensional May affect molding. On the other hand, if the 10 hour half-life temperature of the thermal radical polymerization initiator is higher than 90 ° C., the amount of radicals generated may be small, so the polymerization may not proceed sufficiently.
Specific examples of thermal radical polymerization initiators include V40 (88 ° C.), V59 (67 ° C.), AIBN (65 ° C.), V601 (66 ° C.), VE-073 (73 ° C.) and the like manufactured by Wako Pure Chemical Industries, Ltd. In the parenthesis of the thermal radical polymerization initiator, the temperature at which the half life of each initiator is 10 hours is shown.
Thermal radical polymerization initiators include an azo compound and an organic peroxide as described below.

The thermal radical polymerization initiator containing an azo compound generates two radicals and one nitrogen molecule as gas in one molecule reaction as shown in Formula 2.
R-N = N-R → 2R · + N ₂ (Equation 2)
On the other hand, in the thermal radical polymerization initiator containing an organic peroxide, carbon dioxide is generated as a bimolecular gas as shown in Formula 3.
RCO-OO-COR → 2R · + 2CO ₂ (Equation 3)
Comparing the two, the amount of gas generated from the initiator unit molecule is about half of that of the thermal radical polymerization initiator containing an azo compound, and from the viewpoint of bubble generation, the thermal radical polymerization initiator containing an azo compound is It is preferred to use

The content of the thermal radical polymerization initiator contained in the resin composition constituting the resin layer is 0.5% by weight or more, and preferably 0.8% by weight or more. Thereby, the curing reaction of the resin layer can be sufficiently performed, and the effect of improving the surface curing degree of the film for three-dimensional decoration can be sufficiently obtained.
Further, the content of the thermal radical polymerization initiator contained in the resin composition is 4.0% by weight or less, preferably 1.5% by weight or less, and 1.2% by weight or less More preferable. As a result, it is possible to minimize the deterioration of the appearance due to the nitrogen gas generated at the time of decomposition of the thermal radical polymerization initiator.
Therefore, it is possible to obtain a three-dimensional decorating film 100 having a high surface hardness and an excellent appearance.

The schematic diagram which shows the example of the temperature profile which the film for three-dimensional decoration receives is shown in FIG.
The radical generation rate vR of the thermal polymerization initiator can be expressed by a half life T because the cleavage rate follows a first-order reaction rate equation. The half life T can be described at a temperature of 10 hours from a practical point of view. The radical polymerization initiator does not cause much thermal polymerization when passing through each step such as drying after application step, printing step for decoration, etc., and a thermal polymerization initiator in a curing step in three-dimensional molding Select those which generate radicals and allow the curing reaction to proceed sufficiently.

As a 10-hour half-life temperature, 60 to 90 degreeC is preferable. When the half-life temperature of the thermal radical polymerization initiator is in the above range, the reaction does not proceed during storage, so storage stability is good, and furthermore, for three-dimensional decoration in a plurality of processing steps such as printing and drying at low temperatures The film is not completely cured, and a three-dimensional decorative film can be provided in which the resin layer is thermally cured during three-dimensional molding.
As a result, during three-dimensional molding in the curing step, deformation is not insufficient or cracking does not occur, and further, the hardness of the resin surface is not sufficiently increased, and there is no occurrence of mold distortion. Therefore, the molded product can be provided with excellent appearance and decoration.

  Examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2) -Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) ) 2-Methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) etc. are mentioned.

  As the organic peroxides, known ones such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides and peroxy esters can be used. Specific examples thereof include benzoyl peroxide, 1, and 1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl 2,5- Di (t-butylperoxy) hexane, 2,5-dimethyl 2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumyl peroxide, p-methyl hydroperoxide, t- Butyl hydroperoxide, cumene hydroperoxide, di Mill peroxide, such as di -t- butyl peroxide and 2,5-dimethyl-2,5-dibutyl peroxy f relaxin-3 and the like.

  The curable resin composition constituting the resin layer 300 may contain optional additives in addition to the above-described oligomer, monomer, polymer matrix, and polymerization initiator. Additives include release agents, lubricants, UV absorbers, light stabilizers, plasticizers, antistatic agents, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents, colorants, reinforcements Agents, impact modifiers and the like.

(Shield layer 600)
In the thermal radical polymerization reaction, the radical generation rate by the cleavage reaction of the thermal radical polymerization initiator is slower than the radical generation of the photoinitiator. Therefore, if the penetration speed of oxygen entering the resin layer 300 from the air is high, the polymerization reaction may not proceed sufficiently. Therefore, in order to prevent the entry of oxygen, it is effective to provide the shielding layer 600 particularly when the thickness of the resin layer 300 exceeds a certain value. Thereby, since inhibition of the reaction by oxygen in the thermal radical polymerization reaction can be reduced, the polymerization degree of the resin layer 300 can be improved, and the surface hardness of the film 100 for three-dimensional decoration can be further increased. .

As the shielding layer 600, a polymer film with low oxygen permeability can be used. Specifically, Eval, stretched polyethylene terephthalate (PET), stretched polyamide, stretched polypropylene and the like can be used.
The thickness of the shielding layer 600 may be 30 μm or more from the viewpoint of oxygen permeability, and is preferably 100 μm or less from the viewpoint of handleability and cost.

(Uneven structure)
It is preferable that a concavo-convex shape is formed in advance on the surface of the shielding layer 600 on the resin layer side. When the asperity shape is formed in the shielding layer 600, the resin composition of the resin layer 300 adheres and enters into the asperity shape of the shielding layer 600 in the laminating step, and the resin composition is cured in the curing step. The uneven shape of the shielding layer 600 can be transferred to the surface of the resin layer 300. Thereafter, by peeling the shielding layer 600 from the three-dimensional decoration film 100, it is possible to expose the uneven shape on the surface of the three-dimensional decoration film 100.

FIG. 2 is a schematic cross-sectional view showing another example of the three-dimensional decorating film 100 having the concavo-convex shape.
The shape of the unevenness formed on the three-dimensional decoration film 100a is not particularly limited. For example, a structure (for example, a moth-eye structure) in which the convex portions are interspersed with a conical shape (which may be a rounded conical shape) as a convex portion, and a plurality of convex stripes extending along the surface of the resin layer 300 Structure (for example, parallel wave structure, more specifically, retardation plate structure, etc.), wire grid structure, and structure in which a number of columnar structures with a thickness of 100 nm to 300 nm found in a cell culture sheet are arranged innumerably Be

  The asperities may be formed such that the asperity pitch p of the asperity shape (that is, the distance between the apexes of the two closest projections 310) is on the nanometer order (specifically, 1 nm or more and less than 1000 nm).

  When the concavo-convex pitch p is in the order of nanometers and particularly when the concavo-convex pitch p is 400 nm or less, preferably 150 nm or less, when forming a three-dimensional article by post curing, reflection of the surface of the molded article It can be decorated to reduce the rate. In addition, it is possible to predict in advance the deformation at the time of use of the film for three-dimensional decoration, and make adjustments such that appropriate performance is exhibited after deformation (lamination process) by making the pitch at the time of creation small. The lower limit in the range of the concavo-convex pitch p in this case is not particularly limited. However, for example, from the viewpoint of ensuring an appropriate pitch which is not too small after deformation (lamination stroke) from a pitch created in advance, The lower limit of p may be, for example, 100 nm.

  When the concavo-convex pitch p of the concavo-convex shape is nanometer order, the height t of the convex portion 310 may be, for example, 100 nm or more and 250 nm or less. It is preferable that the height t is equal to or more than the lower limit because a wavelength part where low reflectivity can not be secured appears, so that the reflected color appears to be colored, and is preferably equal to or less than the above upper limit facilitates the embossing process. It is preferable from the viewpoint of From the viewpoint of obtaining these effects better, the height t is more preferably 100 nm or more and 250 nm or less.

  As a modification of the above-mentioned concavo-convex structure, concavities and convexities may be formed so that the concavo-convex pitch p of concavo-convex shape may become micrometer order (1 micrometer or more and less than 10 micrometers). In this case, an anti-glare effect or the like that scatters light can be obtained.

  When the concavo-convex pitch p of the concavo-convex shape is on the order of micrometers, when the concavo-convex pitch p is particularly 3 μm or more, preferably 5 μm or more, light is scattered on the surface of the molded product, thereby reflecting an external reflected image on the surface. It can be decorated so as not to be reflected. The upper limit value in the range of the concavo-convex pitch p in this case is not particularly limited, but may be, for example, 20 μm, preferably 10 μm, from the viewpoint of suppression of glaring (feeling of glitter particles).

  When the concavo-convex pitch p of the concavo-convex shape is on the order of micrometers, the height t of the convex portion may be, for example, 0.1 μm to 2 μm. That the height t is equal to or more than the above lower limit value is preferable from the viewpoint of effectively causing light scattering, and being equal to or less than the above upper limit value is preferable from the viewpoint of suppression of glaring feeling (bright particle feeling). From the viewpoint of obtaining these effects better, the height t is more preferably 0.4 μm or more and 1 μm or less.

(Design layer)
The design layer 400 may be laminated on the surface of the base layer 200 or the shielding layer 600. Thereby, high designability can be provided to the film 100 for three-dimensional decoration.
The lamination of the design layer 400 may be between the base material layer 200 and the resin layer 300, or may be on the opposite side of the base material layer 200 from the resin layer 300 side. The lamination of the base material layer 400 may be between the shielding layer 600 and the resin layer 300 or may be on the opposite side of the shielding layer 600 from the resin layer 300 side.

As the design layer 400, a polymer film can be used. Specifically, a film can be used as the substrate layer. The film thickness is not limited, but can be 0.5 μm or more and 200 μm or less, preferably 5 μm or more and 50 μm or less.
The design to be formed on the design layer 400 is to decorate the surface of a molded article with a decoration such as a pattern or other single color decoration. Examples of the design include grain, stone, grain, grain, geometric pattern, unevenness and the like.

(Manufacturing method of film for three-dimensional decoration)
The film 100 for three-dimensional decoration of the present invention can be manufactured as follows.
First, a liquid curable resin composition is prepared. The curable resin composition can be prepared such that the viscosity at 25 ° C. is 10 Pa · s or more and 500 Pa · s or less (preparation step). The viscosity was measured according to JIS Z 8803 using a B-type viscometer as a single cylindrical viscometer. 7 rotor, measured at 23 ° C.
Next, the curable resin composition obtained in the above preparation step is applied onto the base film to be the base layer 200 to form a film of the resin composition (coating step). It does not specifically limit as a coating method of a curable resin composition, For example, die coating, gravure printing, a dip method etc. are mentioned.

Next, the shielding layer 600 is laminated on the film of the resin composition formed in the application step (lamination step).
After the laminating step, the resin composition is semi-cured to form a resin layer (resin layer forming step). In the resin layer forming step, it is preferable to set a semi-cured state in which the resin layer is not completely cured.
Thus, as shown in FIG. 1, the base layer 200, the resin layer 300 laminated on the base layer 200 and composed of the curable resin composition, and the shielding layer laminated on the resin layer 300. And a three-dimensional decorative film 100 including

  As described above, by forming a film for three-dimensional decoration having a resin layer in an uncured or semi-cured state, the film has sufficient plastic deformability, so that it can be formed into a three-dimensional shape with a molded product, which is complicated. Even with a three-dimensional structure, secondary curing (full curing) can be performed while maintaining a desired shape. In addition, by curing the film for three-dimensional decoration in a plurality of stages, it is possible to prevent rapid curing shrinkage of the resin and to allow the reaction to proceed slowly as a whole. Thereby, the nitrogen gas generated during the reaction can be released out of the system, so the influence of the nitrogen gas generated at the time of curing can be suppressed. Therefore, the molded product can be provided with excellent appearance and decoration.

(Manufacturing method of molded article-injection molding)
Based on FIG. 5, a method of manufacturing a molded article using injection molding will be described.
As shown in FIG. 5A, a resin layer 300 is laminated on a base material layer 200, and a three-dimensional decorative film 100 is prepared in which a design layer 400 is laminated on the resin layer 300. A release layer (not shown) is formed on the surface of the base layer 200 on the resin layer 300 side. This three-dimensional decorative film 100 is placed in a mold for injection molding. The mold has a core 20 and a cavity 10, and after clamping, the injection molding resin 30 is injected from a spool formed on the core 20 into a cavity formed between the core 20 and the cavity 10 To mold.

The resin for injection molding is not particularly limited as long as it is a thermoplastic resin that can be integrated with the film for three-dimensional decoration, but polycarbonate resin, acrylic resin, PET resin, styrene resin, ABS resin, etc. are desirable. It may be mixed.
The polymerization does not proceed so much with the heat of the mold before injection molding (relatively low temperature of about 80 ° C.), and the resin layer 300 of the film 100 for three-dimensional decoration by the heat (high temperature) of the injected resin simultaneously with the injection molding. The curing of the resin composition proceeds to obtain a molded product in which the injection molded product and the three-dimensional decorative film 100 are integrated.

Next, as shown in FIG. 5 (B), after the molded article is removed, as shown in FIG. 5 (C), the base material layer 200 is peeled off from the resin layer 300.
By designing the resin layer 300 to be completely cured by the heat of the mold, the productivity of the molded article can be enhanced. If curing of the resin layer 300 is not sufficient by only heating at the time of injection molding, additional heating may be performed after the injection molding to completely cure the resin layer 300.
According to this manufacturing method, since the design layer 400 covers the resin layer 300, the design layer 400 functions as a mask film of the resin layer 300 to prevent oxygen from intruding into the resin layer 300 from the outside. It is possible to prevent the reaction of the resin layer from being inhibited. Furthermore, in this manufacturing method, the resin injected into the mold also functions as a mask film.

(Manufacturing method of molded article-vacuum molding)
Next, based on FIG. 6, a method of manufacturing a molded article using vacuum molding will be described.
As shown in FIG. 6A, the resin layer 300 is laminated on the base material layer 200, the shielding layer 600 is laminated on the resin layer 300, and the design layer 400 is laminated on the lower surface of the base material layer 200. A film 100 for three-dimensional decoration is prepared. At the time of bonding of these layers, the layers are bonded under the condition that the resin layer 300 is not completely cured.

Next, as shown to FIG. 6 (B)-FIG.6 (C), the obtained film 100 for three-dimensional decorations is arrange | positioned on the resin molding (mold | type) 50. As shown in FIG. Vacuum holes can be formed at appropriate positions of the resin molded body 50. The three-dimensional decorative film 100 is pressed against the resin molded body (mold) 50 and vacuumed from vacuum holes to form the resin molded body (object to be molded) 50 and the three-dimensional decorative film 100 integrally. The resulting molded article is obtained (FIG. 6 (C)). Thereafter, as shown in FIG. 6D, the shielding layer 600 is removed from the surface of the resin layer 300.
Here, the resin of the resin layer 300 of the three-dimensional decorative film 100 can be cured by heating the resin molded body (mold) 50 at the time of vacuum forming. If the curing of the resin layer 300 is not sufficient by only heating at the time of vacuum forming, additional heating may be performed after vacuum forming. In that case, the surface of the resin layer 300 is covered with the shielding layer 600 at the time of heating.
In addition, although the said embodiment demonstrated the manufacturing method of the molded article which used vacuum molding, a molded article can be manufactured similarly by pressure forming.

[Creation of film for three-dimensional decoration]
A polyethylene terephthalate (easy moldable PET) film (made by Toray Industries, thickness 50 μm) is prepared as a base material layer, VE-073 (10 hours half life temperature 77 ° C.), AIBN (10 hours half life temperature 65 ° C. Vam-110 (10-hour half-life temperature is 110 ° C.) and V65 (10-hour half-life temperature 51 ° C.) are prepared.
As resin contained in the resin composition which comprises a resin layer, radically polymerizable resin (SC-1601 by Gokyo Co., Ltd.) which contains acrylate resin was prepared. As a thermal radical polymerization initiator, an azo compound thermal radical polymerization initiator (V-40 manufactured by Wako Pure Chemical Industries, Ltd .: temperature at which the half life becomes 10 hours is 88 ° C.) was prepared.
As a shielding layer, a PET film with silicon release 4030: 50 μm thickness (manufactured by Toyo Cross Co., Ltd.) was prepared.
As a resin molded body, 700-X10 (Toytec manufactured by Toray Industries, Inc.) of ABS-based resin was molded into a rectangular shape (width 20 mm, height 5 mm, depth 30 mm) as a test pattern by injection molding. The injection molding conditions were that the temperature of the mold was 80 ° C., and the resin temperature at the outlet of the cylinder was 210 ° C.

[1. Addition process]
A thermal radical polymerization initiator is mixed with resin SC1601 (manufactured by Gokyo Co., Ltd.) contained in the resin layer so that the addition amount (% by weight) described in the examples and comparative examples becomes to prepare a resin composition. did.

[2. Coating process]
The resin composition obtained in the above addition step was applied onto the base layer. The application of the resin composition was made to have the thickness described in Examples and Comparative Examples using a bar coater. The thickness is adjusted by changing the number of the bar coater (the diameter of the wire wound on the bar coater), diluting with MIBK as a solvent, and changing the solid content ratio of the coating material (resin composition) I did it. The coating material was dried by heating at 80 ° C. for 10 minutes using a hot plate.

[3. Lamination process]
On the resin layer formed in the application step, the PET film with silicon release of the shielding layer was bonded by a heat laminator. The lamination temperature was 80.degree.

[4. Design print]
Design printing was performed on the substrate layer side. Design printing was performed by the inkjet method. As a heat drying of printing, it carried out for 5 minutes at a drying temperature of 80.degree. A pressure-sensitive adhesive was used on the printed surface in order to improve the adhesion with the resin molded body.
A semi-cured resin layer was formed by these heating, and a film for three-dimensional decoration was obtained.

[5. Thermal polymerization process]
Thereafter, the three-dimensional decorative film subjected to designability printing and the resin molding are fixed to a vacuum molding machine, vacuum molded at a molding temperature of 80 ° C. for 3 minutes, and then set in a jig in a thermostatic bath. As it was, heat treatment was performed at 160 ° C. for 3 minutes. As a result, as shown in FIG. 7, a three-dimensional decorative film 100a was integrally formed on the surface of the resin molded body 500, and a molded object decorated with the three-dimensional decorative film 100a was obtained.

[6. Evaluation]
(1) Pencil hardness was evaluated in accordance with JIS K5600-5-4.
That is, five tests were conducted using a pencil hardness of 1 H or more and 4 H or less or a pencil hardness of 1 H or more and 8 H or less, and the number of times of scratching at each pencil hardness was described. The evaluation results are shown in the table.
(2) The steel wool test was evaluated in accordance with JIS K5400.
The evaluation results are described in the table. The evaluation criteria in the table are as follows.
:: no scar is visible, △: scar is thin, x: scar is clearly visible (3) bubble generation confirmation: visual observation of the film top after molding heat history (160 ° C., 3 minutes).

[7. result]
The conditions of the film for three-dimensional decoration of an Example and a comparative example, and an evaluation result are shown to the following Tables 1-3.

In Table 1, the steel wool test is a test based on JIS K5400 (20 times), "〇" if no scar is visible at all, "△" if scar is visible thin, if a scar is clearly visible " It evaluated as x ".
In addition, in the appearance test (confirmation of generation of air bubbles during polymerization), the case where no air bubbles were observed on the surface of the molded article was regarded as "o", and the case where air bubbles were observed on the surface of the molded article was evaluated as "x" did.
As a result, in Examples 1 to 5, both the pencil hardness test, the steel wool test and the appearance test were good.

On the other hand, in Comparative Example 1, the results of the pencil hardness test and the steel wool test were not good. Since there is no mask film, oxygen penetrates the resin layer 300 from the outside to inhibit curing, and it is considered that the hardness of the resin layer 300 is not sufficient.
Further, in Comparative Example 2, it is considered that the hardness of the resin layer 300 was not sufficient because the amount of the polymerization initiator was not sufficient. It is considered that in Comparative Example 3, the appearance was bad because the amount of the polymerization initiator was large. In Comparative Example 4, since the thickness of the resin layer is not sufficient, it is considered that the hardness of the resin layer 300 is not sufficient.

Moreover, in Comparative Example 5, the results of the pencil hardness test and the steel wool test were not good. It is considered that the hardness of the resin layer 300 was not sufficient because the 10-hour half-life temperature of the thermal initiator was 110 ° C.
Further, in Comparative Example 6, air bubbles were generated during polymerization, and the surface condition became worse. It is considered that the 10-hour half-life temperature of the thermal initiator was as low as 51 ° C.

In Examples 6 to 10, the pencil hardness test, the steel wool test, and the appearance after polymerization were all good. In Examples 6 to 10, the thickness of the resin layer 300 is 10 μm to 65 μm, and the resin composition contains 0.5% by weight to 1.5% by weight of a thermal radical polymerization initiator.
On the other hand, in Comparative Examples 7 to 11, the result of the steel wool test was bad, and in Comparative Examples 8 to 11, the result of appearance after polymerization was bad. It is considered that the content of the thermal radical polymerization initiator contained in the resin composition was 3%.
In Comparative Example 10, the thickness of the resin layer was as thick as 75 μm with respect to 0.7% of the thermal radical polymerization initiator, so the results of pencil hardness, steel wool test and appearance were poor. In Comparative Example 11, the thickness of the resin layer was 30 μm but the thermal radical polymerization initiator was 2.0%, so the results of pencil hardness, steel wool test and appearance were poor.
In addition, Comparative Example 12 shows the result of curing the resin composition using a photoinitiator (Irugacure 184 1%) instead of using a thermal initiator. As a result, the result of the steel wool test was bad.

In Example 11, the mask film was a mask film with antiglare (Haze 10%), and the other conditions were the same as in Example 7, and the pencil hardness test, the steel wool test, the appearance test and the reflection test were performed.
The reflection test is as follows. The three-dimensional decorative film was pasted on the display of the mobile phone so that the unevenness was on the surface side, and it was placed by a bright window exposed to direct sunlight. Then, it was judged whether or not the display of the mobile phone was visible in the state where the external light was totally reflected so that the scenery was reflected. As a result, in Examples 1, 3 and 7, the display of the mobile phone was almost invisible, but in Example 11, the display of the mobile phone could be seen.

  Table 4 below shows that the elongation at break of the resin layer and the infrared absorption spectrum measurement of the resin layer are correlated, which is a method of measuring the degree of the semi-cured state of the resin layer.

As shown in Table 4, in order to investigate the influence of thermal polymerization (cure) before molding, a breaking elongation test was performed. In this breaking elongation test, in order to minimize the influence of the substrate, a 50 μm thick PMMA film was used as a substrate without using PET. In the test, the conditions of Example 3 (3% of initiator V40, 6 μm of resin thickness) were used.
As a result, those heated at 80 ° C. for 60 minutes had a degree of polymerization index R of 25 and those heated at 80 ° C. for 3 minutes to 30 minutes had a degree of polymerization index R of 5 or less. In this case, the three-dimensional decorative film was in a state of appropriate semi-curing (pre-cure), and passed the tensile test.
On the other hand, those heated at 160 ° C. for 3 minutes or more had a degree of polymerization index R of 80 or more. In this case, since the curing of the resin layer proceeds too much, when it was pulled, coating film breakage occurred and it did not pass the tensile test.

[Correspondence between each part in the embodiment and each component of the claims]
The film 100 for three-dimensional decoration in this specification corresponds to a "film for three-dimensional decoration", the base material layer 200 corresponds to a "base material layer", and the resin layer 300 corresponds to a "resin layer". The design layer 400 corresponds to a "design layer", the molded body 500 corresponds to a "molded body", and the shielding layer 600 corresponds to a "shielding layer".

100 Three-dimensional decoration film 200 Base layer 300 Resin layer 400 Design layer 500 Molded body 600 Shielding layer

Claims (12)

A substrate layer,
An uncured or semi-cured resin layer composed of the resin composition laminated on the substrate layer;
It is a film for three-dimensional decoration including the shielding layer laminated | stacked on the said resin layer, Comprising:
The resin composition contains at least a resin having a radically polymerizable functional group and a thermal radical polymerization initiator of 0.5% by weight or more and 4.0% by weight or less, and the thickness of the resin layer is 5 μm. Not less than 65 μm,
When the content of the thermal radical polymerization initiator is 0.5% by weight or more and less than 1.5% by weight, the thickness of the resin layer is 5 μm or more and 65 μm or less,
When the content of the thermal radical polymerization initiator is 1.5% by weight or more and less than 2.5% by weight, the thickness of the resin layer is 5 μm or more and 20 μm or less,
The film for three-dimensional decoration whose thickness of the said resin layer is 5 micrometers or more and 10 micrometers or less, when content of the said thermal radical polymerization initiator is 2.5 weight% or more and 4.0 weight% or less. The film for three-dimensional decoration according to claim 1, wherein the thermal radical polymerization initiator has a 10 hour half-life temperature of 60 ° C to 90 ° C. The film for three-dimensional decoration according to claim 1 or 2 whose breaking extension in the tension test based on JIS K7127 in 60 ° C environment of said resin layer is 50% or more.   The film for three-dimensional decoration according to any one of claims 1 to 3, wherein the thermal radical polymerization initiator comprises an azo compound.   The tertiary resin according to any one of claims 1 to 4, wherein the resin having a radically polymerizable functional group comprises at least one resin selected from the group consisting of acrylate resin, methacrylate resin, and urethane acrylate resin. Original decorative film.   The printing according to any one of claims 1 to 5, wherein printing is applied to at least one of the base layer and the shielding layer, or a design layer is laminated on the side of the base layer. Film for three-dimensional decoration.   The uneven | corrugated shape is formed in the surface by the side of the resin layer of the said shielding layer or the said base material layer, The said uneven | corrugated shape of the said shielding layer or the said base material layer is transcribe | transferred by the said resin layer. The film for three-dimensional decoration described in or 1 above. Production of a film for three-dimensional decoration comprising a base material layer, a semi-cured or uncured resin layer composed of a resin composition laminated on the base material layer, and a shielding layer laminated on the resin layer Method,
Preparing the resin composition containing at least a resin having a radically polymerizable functional group and a thermal radical polymerization initiator;
Applying the resin composition to the base material layer to form a film of the resin composition;
Laminating the shielding layer on a film of the resin composition;
A resin layer forming step of forming the resin layer by unhardening or semi-curing a film of the resin composition;
The resin composition contains at least a resin having a radically polymerizable functional group and a thermal radical polymerization initiator of 0.5% by weight or more and 4.0% by weight or less, and the thickness of the resin layer is 5 μm. Not less than 65 μm,
In the preparation step, when the content of the thermal radical polymerization initiator is 0.5% by weight or more and less than 1.5% by weight, the thickness of the resin layer is 5 μm or more and 65 μm or less,
When the content of the thermal radical polymerization initiator is 1.5% by weight or more and less than 2.5% by weight, the thickness of the resin layer is 5 μm or more and 20 μm or less,
When the content of the thermal radical polymerization initiator is 2.5% by weight or more and 4.0% by weight or less, the resin composition is prepared such that the thickness of the resin layer is 5 μm or more and 10 μm or less The manufacturing method of the film for decoration. The film for three-dimensional decoration according to any one of claims 1 to 7 is disposed in a mold, and an injection-molded resin is injected into the mold to form an injection-molded product and the three-dimensional additive. A method for producing a molded article in which a film for decoration is integrated,
A curing step of thermally curing the resin layer during the injection molding;
The manufacturing method of the molded article using the film for three-dimensional decoration which contains. The film forming object and the film for three-dimensional decoration are integrated by vacuum forming or pressure forming the film for three-dimensional decoration according to any one of claims 1 to 7 and the object to be formed. A method of producing a molded article,
A curing step of thermally curing the resin layer during the vacuum forming or pressure forming;
The manufacturing method of the molded article using the film for three-dimensional decoration which contains. The resin composition is intimately intruded into the concavo-convex shape formed in the shielding layer, and the resin composition is cured to transfer the concavo-convex shape of the shielding layer to the surface of the resin layer.
The manufacturing method of the molded article using the film for three-dimensional decoration of Claim 9 or 10.   The printing process which prints on the surface of at least any one of the said base material layer and the said shielding layer, or the design layer lamination process of laminating a design layer on the surface of the said base material layer further any of Claim 9 to 11 The manufacturing method of the molded article using the film for three-dimensional decoration as described in any one of-.