JP6434273B2 - Laminated body for decorative molding, method for producing decorative molded product, and decorative molded product - Google Patents

Description

  The present invention relates to a decorative molded laminate, a method for producing a decorative molded product using the decorative molded laminate, and a decorative molded product.

In various products such as electric appliances such as mobile phone covers, vehicle interior parts, and motorcycle cowlings, a design such as a pattern, a pattern, or a letter is applied to the surface of a molded product and decorated.
For example, a decorative molded product is manufactured by laminating a decorative film on the surface of a core material having a complicated surface shape such as a three-dimensional curved surface using vacuum forming, vacuum / pressure forming, etc. Yes. Here, as the decorative film, a decorative film in which a printed layer is formed on one surface of the base film and an adhesive layer is formed on the other surface is used.

In such a method using vacuum forming or vacuum / pressure forming, after the decorative film is introduced into the closed forming chamber of the forming apparatus, the decorative film is softened by heating, and the softened decorative film is used as the core material. It is decorated by sticking to the surface.
At this time, the decorative film softened by heating may hang down due to its own weight, and in that case, the moldability to the core material may be adversely affected.
For example, when an image is drawn on a base film as a printing layer, the image may be distorted in a decorative molded product after molding.

  In order to prevent such deterioration of the formability due to the hanging of the decorative film, for example, in Patent Document 1, after the decorative film softened by heating hangs down by its own weight, a pressure difference is provided above and below the decorative film. Thus, a method for returning the decorative film to a horizontal state has been proposed.

JP 2002-67137 A

  However, in the technique proposed in Patent Document 1, air is injected into the molding chamber in order to provide a pressure difference above and below the decorative film so that the hanging decorative film is returned to the horizontal state. The decorative film flutters and becomes wavy due to the injection of, and the image is distorted. For this reason, it is difficult to reliably avoid image distortion even when the hanging decorative film is returned to a horizontal state and then attached to the core.

  As a result of intensive studies to solve such problems, the present inventors have used a predetermined vinyl chloride resin film as a base film, and a decorative film having a printed layer formed on the surface thereof, The present inventors have found that a decorative molded product without image distortion can be produced by laminating an application film on a printed layer and performing vacuum forming or vacuum / pressure forming in that state, thereby completing the present invention.

JP-A-2011-83901 discloses a decoration method using a transfer film in which a carrier film made of an unstretched polyester resin or a urethane elastomer is laminated on a decoration film. However, this document makes no mention of image distortion.
In addition, when a polyester film is laminated on a decorative film using a vinyl chloride resin film as a base film, and a decorative molded product is produced by vacuum forming or vacuum / pressure forming using this laminate, polyester Since the film has a low elongation rate, the followability to the core material is poor depending on the shape of the core material, and the core material may not be decorated, and the degree of freedom in selecting the core material is extremely low.
Furthermore, a film made of urethane elastomer is laminated on a decorative film using a vinyl chloride resin film as a base film, and a decorative molded product is produced by vacuum forming or vacuum / pressure forming using this laminate. In this case, since the film made of urethane elastomer is soft and cannot prevent sagging due to its own weight, it is difficult to avoid image distortion.

The laminate for decorative molding of the present invention comprises a decorative film and an application film laminated on the decorative film,
In the decorative film, the adhesive layer, the first base film and the printing layer are laminated in this order,
The first base film contains a vinyl chloride resin having an average degree of polymerization of 700 to 1400 and a plasticizer having a number average molecular weight of 350 to 3000, and the blending amount of the plasticizer is 100 parts by mass of the vinyl chloride resin. On the other hand, the plasticizer comprises a first vinyl chloride resin composition that is 5 to 40 parts by mass,
The application film is laminated with an adhesive layer and a second base film in order from the decorative film side,
The second base film is composed of a second vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer,
The breaking elongation at 100 ° C. of the second base film is smaller than the breaking elongation at 100 ° C. of the first base film,
It is characterized by that.

  In the decorative molding laminate, the second vinyl chloride resin composition contains a vinyl chloride resin having an average degree of polymerization of 700 to 1500 and a plasticizer having an average molecular weight of 350 to 3000, and the plasticizer Is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  In the decorative molding laminate, the elongation at break of the second base film at 100 ° C. is preferably 100 to 150%.

  In the decorative molding laminate, the second base film preferably has a thickness of 50 to 300 μm.

The method for producing a decorative molded product of the present invention is characterized in that the application film is peeled off after the decorative molded laminate of the present invention is attached to the surface of the core material by vacuum molding or vacuum / pressure forming. And
The decorative molded product of the present invention is produced using the above-described method for producing a decorative molded product.

According to the laminate for decorative molding of the present invention, when decorating the surface of the core material by vacuum forming or vacuum / pressure forming, the surface of the core material does not cause distortion in the image drawn on the printed layer. Can be decorated. Moreover, it can decorate to the edge part of a core material reliably.
According to the method for producing a decorative molded product of the present invention, it is possible to produce a decorative molded product with no distortion in the image of the decorative surface.
The decorative molded product of the present invention has a good decorative surface without distortion in the image.

It is sectional drawing which shows typically an example of the laminated body for decorating shaping | molding of this invention. It is sectional drawing which shows typically another example of the laminated body for decorating shaping | molding of this invention. (A)-(c) is a schematic diagram for demonstrating the manufacturing method of the decorative molded product of this invention. (D)-(f) is a schematic diagram for demonstrating the manufacturing method of the decorative molded product of this invention. It is a schematic diagram for demonstrating the manufacturing method of the conventional decorative molded product. It is a perspective view for demonstrating the decorative molded product produced in the Example and the comparative example. 2 is a color photograph of a decorative molded product produced in Example 1. FIG. 2 is a color photograph of a decorative molded product produced in Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail.
First, the decorative molded laminate of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing an example of a decorative molding laminate of the present invention.

As shown in FIG. 1, the decorative molded laminate 100 of the present invention includes a decorative film 10 and an application film 20 laminated on the decorative film 10.
In the decorative film 10, an adhesive layer 12, a first base film 11, and a printing layer 13 are laminated in this order on a separator 14.
As for the application film 20, the adhesive layer 22 and the 2nd base film 21 are laminated | stacked in order from the decorating film 10 side.

The 1st base film 11 which comprises the decorating film 10 consists of a 1st vinyl chloride-type resin composition.
The first vinyl chloride resin composition contains a vinyl chloride resin and a plasticizer.
Examples of the vinyl chloride resin include vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers copolymerizable therewith.
Examples of the other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and styrene, methyl acrylate, ethyl acrylate, and methyl methacrylate. ) Acrylic acid esters, maleic acid diesters such as dibutyl maleate and diethyl maleate, fumaric acid diesters such as dibutyl fumarate and diethyl fumarate, vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene chloride and vinyl bromide Examples thereof include vinyl ethers such as vinyl halide, methyl vinyl ether, and ethyl vinyl ether. These may be used alone or in combination of two or more.

The content of the other copolymerizable monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. When it exceeds 50% by weight, the bending resistance of the decorative film is lowered, and for example, it may not be suitable for being attached to a core material.
Among the vinyl chloride resins, a vinyl chloride homopolymer is preferable from the viewpoints of excellent printability and visibility, and excellent dimensional stability.

The vinyl chloride resin has an average degree of polymerization of 700 to 1400.
In this case, it is excellent in printability (for example, coloring property at the time of printing, ink fixing property, etc.) when a printing layer is formed using a solvent-based ink. On the other hand, if the average degree of polymerization is less than 700, the solvent-based ink is absorbed too much, and the ink oozes out in a swollen state in the film, so that the color developability and sharpness during printing are insufficient. Become. On the other hand, when the average degree of polymerization exceeds 1400, the solvent-based ink has low absorbability, the ink hardly penetrates into the film, and adheres to the surface of the film. The nature will be impaired.
In the present invention, the average degree of polymerization of the vinyl chloride resin means the average degree of polymerization measured according to JIS K-6721 “Testing method for vinyl chloride resin”.

The plasticizer has a molecular weight of 350 to 3000.
When the molecular weight is less than 350, it is easy to bleed from the first base film, and when the plasticizer bleeds, it moves to the adhesive layer and decreases the adhesive force of the adhesive layer, or moves to the surface of the base film. When printing layers are formed, printing unevenness may occur.
On the other hand, when the molecular weight exceeds 3000, the plasticizer absorbs ink too much, blurring occurs in the image formed on the printing layer, and the sharpness of the printing layer may be deteriorated.

In addition, when the said plasticizer consists of a high molecular compound, the molecular weight is a number average molecular weight.
The number average molecular weight is a measured value in terms of polystyrene by GPC (gel permeation chromatograph) measurement.
The GPC measurement is performed according to a standard method. For example, a dilute tetrahydrofuran solution of a plasticizer to be measured is prepared and measured using a GPC measuring device “HLC-8220GPC” manufactured by Tosoh Corporation under a flow rate condition of 0.6 ml / min. As the column, “KF606M” and “KF603” manufactured by Showa Denko KK are used.

Specific examples of the plasticizer include phthalic acid diesters such as octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate and dinonyl phthalate, cyclohexane dicarboxylic acid ester, dioctyl adipate, and sebacic acid. Examples include aliphatic dibasic acid diesters such as dioctyl, phosphoric acid triesters such as tricresyl phosphate and trioctyl phosphate, epoxy plasticizers such as epoxidized soybean oil and epoxy resins, and polymer polyester plasticizers. .
Examples of the polymer polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester of phthalic acid, and polyethylene glycols of aliphatic dibasic acids such as adipic acid and sebacic acid. Examples include polyalkylene glycol diesters such as diesters, polypropylene glycol diesters, and polyethylene glycol polypropylene glycol diesters.
These may be used alone or in combination of two or more.

The amount of the plasticizer is 5 to 40 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
When the blending amount of the plasticizer is less than 5 parts by weight, the absorbability of the solvent-based ink of the base film becomes insufficient, so that bleeding occurs and the solvent-based ink may have poor printability. On the other hand, if it exceeds 40 parts by weight, the base film is too soft, and when heated in a vacuum forming or vacuum / pressure forming process, it tends to sag due to its own weight, and even if there is an application film, the image may be distorted. There is.

  The first vinyl chloride resin composition is a stabilizer, a colorant, a foaming agent, a lubricant, a modifier, inorganic particles or inorganic fibers that are generally used in vinyl chloride resin compositions as necessary. Various additives such as fillers and diluents may be contained.

The thickness of the first base film 11 is preferably 50 to 500 μm.
If the thickness of the 1st base film 11 is less than 50 micrometers, the intensity | strength of a film is inadequate and it may be inferior to decorative moldability. On the other hand, if it exceeds 500 μm, it may be impossible to follow the surface shape of the core material. More preferably, it is 80-200 micrometers.

The print layer 13 is composed of an image such as an arbitrary pattern, character, or design.
The print layer 13 is preferably formed on the surface of the first base film 11 using a solvent-based ink.
The printing layer 13 formed using the solvent-based ink is fixed on the surface of the base film in a state where it has soaked into the first base film 11. Therefore, the image is excellent in sharpness and fastness.

As the solvent-based ink, a conventionally known solvent-based ink mainly composed of a solvent, a pigment, a vehicle, and an auxiliary agent blended as necessary can be used.
In particular, as a vehicle, a vinyl resin such as vinyl chloride-vinyl acetate copolymer resin, an acrylic-vinyl acetate copolymer resin, or a solvent-based ink containing an acrylic resin is used for adhesion to the base film. It is preferable in that it is excellent. Two or more of the above vehicles may be used in combination.

Examples of the solvent include glycol ether solvents such as diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol monobutyl ether, lactone solvents such as γ-butyrolactone, low boiling aromatic naphtha, and propylene glycol monomethyl ether acetate. Can be mentioned.
Examples of the pigment include carbon black (black), copper phthalocyanine (cyan), dimethylquinacridone (magenta), pigment yellow (yellow), titanium oxide, aluminum oxide, zirconium oxide, nickel compound, and the like. Various other pigments are already known as the pigment, and are not limited to those described above.

  Specific examples of such solvent-based inks include, for example, SS21 ink, ES3 ink (both manufactured by Mimaki), Eco-Sol MAX (manufactured by Roland).

The method for forming the printing layer 13 is not particularly limited, and a conventionally known printing method such as direct gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing can be used. Of these, inkjet printing is preferred. This is because it is easy to deal with multi-product and small-lot production.
Although the inkjet apparatus used by the said inkjet printing is not specifically limited, For example, CJV-30, TPC-1000 (both made by Mimaki), XC-540, SP-300 (both made by Rolland) etc. are mentioned.

The adhesive layer 12 is preferably a layer made of a hot melt adhesive (hot melt adhesive layer).
Examples of the hot melt adhesive include polyester hot melt adhesives, acrylic hot melt adhesives, rubber hot melt adhesives, and silicone hot melt adhesives.
Since the hot melt adhesive layer does not contain a solvent, it is suitable for performing decoration using a decorative film by vacuum forming or vacuum / pressure forming.

The thickness of the adhesive layer 12 is preferably 25 to 50 μm.
If the thickness of the adhesive layer 12 is less than 25 μm, it may not be possible to secure a sufficient adhesive force with the core material. On the other hand, if it exceeds 50 μm, cohesive failure tends to occur in the adhesive layer, and it may be difficult to apply the adhesive layer so that the surface thereof is smooth.

As shown in FIG. 1, the separator 14 is laminated | stacked on the opposite side to the 1st base film 11 side of the adhesive bond layer 13. As shown in FIG. The separator is an arbitrary layer provided as necessary in the present invention.
It does not specifically limit as the separator 14, A conventionally well-known thing can be used, For example, resin films, such as PET film and polypropylene film surface-treated with the silicone resin, can be used conveniently.

  Moreover, in the decorating film 10, surface treatments, such as embossing, may be given to the surface of the 1st base film 11 or the printing layer 13 as needed.

The second base film 21 constituting the application film 20 is made of the second vinyl chloride resin composition.
The second vinyl chloride resin composition contains a vinyl chloride resin and a plasticizer.
Here, specific examples of the vinyl chloride resin and the plasticizer include the same vinyl chloride resins and plasticizers as those contained in the first vinyl chloride resin composition.

The second vinyl chloride resin composition preferably contains a vinyl chloride resin having an average degree of polymerization of 700 to 1500 and a plasticizer having a molecular weight (or number average molecular weight) of 350 to 3000.
This is because the second base film made of the second vinyl chloride resin composition having such a composition starts to soften at the same temperature as the first base film when heated.
On the other hand, when a film having a significantly different softening temperature is used for the second base film, when heated in the vacuum forming or vacuum / pressure forming process, a difference occurs in the melt state with the first base film, A float may generate | occur | produce between a 1st base film and a 2nd base film, and a moldability may be impaired.

In the second vinyl chloride resin composition, the amount of the plasticizer is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
When the blending amount of the plasticizer is less than 5 parts by weight, the application film may be damaged during vacuum molding or vacuum / pressure forming, and the moldability (decorative property) may be impaired. The application film is too soft, and it may not be possible to prevent the decorative film from sagging when heated in a vacuum forming or vacuum / pressure forming process.

  The second vinyl chloride resin composition is a stabilizer, a colorant, a foaming agent, a lubricant, a modifier, inorganic particles or inorganic fibers that are generally used in vinyl chloride resin compositions as required. Various additives such as fillers and diluents may be contained.

As for the thickness of the said 2nd base film, 50-300 micrometers is preferable.
If the thickness of the second base film is less than 50 μm, the heat resistance of the application film is insufficient, and the decorative film cannot be prevented from hanging down when heated in the vacuum forming or vacuum / pressure forming process. There is a fear. On the other hand, if it exceeds 300 μm, the followability to the shape of the surface to be decorated of the core material is lowered. Moreover, since heat becomes difficult to be transmitted to the decorative film, it takes time to soften the decorative film, which may lead to a decrease in productivity.

The pressure-sensitive adhesive layer 22 is formed by using, for example, an acrylic pressure-sensitive adhesive containing an acrylic polymer.
Examples of the acrylic polymer include homopolymers of (meth) acrylic acid alkyl esters or copolymers thereof, (meth) acrylic acid alkyl esters and copolymerizable monomers, and the like. Among these, a copolymer of (meth) acrylic acid alkyl ester is preferable.

  Specific examples of the acrylic polymer include a copolymer composed of 2-ethylhexyl acrylate and acrylic acid, a copolymer composed of 2-ethylhexyl acrylate and hydroxyethyl acrylate, and composed of 2-ethylhexyl acrylate and methyl methacrylate. Copolymer, copolymer composed of 2-ethylhexyl acrylate, 2-methoxyethyl acrylate and vinyl acetate, copolymer composed of 2-ethylhexyl acrylate and vinyl pyrrolidone, 2-ethylhexyl acrylate, methyl methacrylate and 2-methoxyethyl Examples thereof include a copolymer composed of acrylate, a copolymer composed of 2-ethylhexyl acrylate, vinyl pyrrolidone and acrylic acid. These may be used alone or in combination of two or more.

The pressure-sensitive adhesive layer may further contain a curing agent, a tackifier, a known additive, and the like.
Examples of the curing agent include an isocyanate curing agent and an epoxy curing agent.

In the decorative molded laminate 100, it is important that the breaking elongation at 100 ° C. of the second base film 21 is smaller than the breaking elongation at 100 ° C. of the first base film 11.
By satisfying such a requirement, it is possible to prevent the decorative film (decorative molding laminate) from sagging when heated in a vacuum forming or vacuum / pressure forming process.
The elongation at break at 100 ° C. is measured by the following method.
That is, using a tensile tester, a test is performed in accordance with JIS K 7162, and the film elongation at break is calculated. In addition, the atmospheric temperature at the time of tension shall be 100 degreeC.
In addition, the measurement temperature (100 degreeC) set here is one of the typical temperatures employ | adopted when heating the laminated body for decorative shaping | molding of this invention by vacuum forming or vacuum / pressure forming.

  The breaking elongation at 100 ° C. of the second base film 21 constituting the application film 20 is preferably 100 to 150%. It is because it is excellent in followability with respect to a decorative film. On the other hand, if the breaking elongation is less than 100%, it may not be possible to mold depending on the shape of the core material. On the other hand, if the elongation at break exceeds 150%, it may not be possible to prevent the decorative film from sagging during heating.

  On the other hand, the breaking elongation at 100 ° C. of the first base film 11 constituting the decorative film 10 is preferably 130 to 180%. If the breaking elongation is less than 130%, it may be impossible to mold depending on the shape of the core material. On the other hand, if the elongation at break exceeds 180%, the moldability can be sufficiently secured, but it is too soft as a base film, so even if the application film is laminated, the decorative film hangs down during heating ( It becomes difficult to avoid distortion of the printed image due to (drawdown).

In the decorative molded laminate 100, the adhesive strength of the application film 20 to the decorative film 10 is preferably 0.5 to 10 (N / 25 mm).
If the adhesive strength is less than 0.5 N / 25 mm, the decorative film may not be held in a series of steps of attaching the decorative molding laminate to the core material, whereas if it exceeds 10 N / 25 mm, the core material may not be retained. When the application film is peeled off from the decorative film, it cannot be peeled off smoothly, resulting in damage to the printed layer, or after the application film is peeled off, there is adhesive residue on the surface of the decorative film. May occur.
As for the said adhesive force, 0.9-7 (N / 25mm) are more preferable.

The adhesive strength of the application film to the decorative film is measured by a method based on JIS Z 0237.
Here, what laminated | stacked the decoration film on the aluminum plate is used as a test board (adhered body). At this time, the width of the application film is 25 mm, the peeling distance is 50 mm, and the peeling speed is 300 mm / min.

The configuration of the decorative molding laminate of the present invention is not limited to the decorative molding laminate 100 shown in FIG. 1, and may include, for example, the configuration shown in FIG. 2.
FIG. 2 is a cross-sectional view schematically showing another example of the decorative molding laminate of the present invention.

The decorative molding laminate 110 shown in FIG. 2 includes a decorative film 10 ′ and an application film 20 ′ laminated on the decorative film 10 ′.
In the decorative film 10 ′, an adhesive layer 12, a first base film 11, a printing layer 13, an adhesive layer 16 and a surface protective layer 15 are laminated in this order on a separator 14.
As for application film 20 ', the adhesive layer 22 and the 2nd base film 21 are laminated | stacked in order from the decorating film 10' side.

That is, it differs from the decorative molded laminate 100 in that the surface protective layer 15 is laminated on the printed layer 13 of the decorative film 10 ′ via the adhesive layer 16.
In the decorative molded product produced using such a decorative molded laminate 110, the surface of the decorative surface is protected by the surface protective layer 15.

The surface protective layer 15 is a layer formed using, for example, a vinyl chloride resin composition or an acrylic resin composition, and is transparent.
The surface protective layer 15 may be one using a commercially available vinyl chloride resin film or acrylic resin film.

As a surface protective layer formed using the said vinyl chloride resin composition, the layer which consists of a vinyl chloride resin composition which mix | blended the plasticizer and the stabilizer with the vinyl chloride resin is mentioned, for example.
Here, the average degree of polymerization of the vinyl chloride resin is preferably 700 to 1500. As the plasticizer, a plasticizer having an average molecular weight of 350 to 3000 such as diethylhexyl phthalate (DOP) is preferable.
Furthermore, the blending amount of the plasticizer is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Examples of the surface protective layer formed using the acrylic resin composition include acrylite, acrylene (both manufactured by Mitsubishi Rayon Co., Ltd.), sand durene (manufactured by Kaneka Corp.), and the like.
The surface protective layer 15 is preferably a layer formed using an acrylic resin composition from the viewpoint of excellent transparency.

The adhesive layer 16 is a layer formed using, for example, an acrylic adhesive, a rubber adhesive, or a polyester adhesive, and is transparent.
Examples of the acrylic adhesive include those containing a C1 / C4 acrylic ester copolymer, a C4 acrylic ester copolymer, a C8 acrylic ester copolymer, etc. as the composition of the acrylic component, What is necessary is just to select suitably the combination of a composition of an acrylic component, and a hardening | curing agent according to uses, such as adhesiveness and heat resistance.
Specific examples of the acrylic adhesive include SK Dyne 1506 (manufactured by Soken Chemical Co., Ltd.).

  When the decorative film includes a surface protective layer, the surface protective layer does not necessarily have to be laminated via an adhesive layer, and is directly laminated on the first base film on which the printed layer is formed. Also good.

  Moreover, like a decorative film 10 'shown in FIG. 2, when a decorative film is provided with a surface protective layer, the laminated body which consists of the 1st base film 11, the printing layer 13, the adhesive bond layer 16, and the surface protective layer 15 It is preferable that the breaking elongation of the entire laminate is larger than the breaking elongation of the application film. This is because the application film can reliably achieve its purpose.

Next, a method for producing the decorative molding laminate will be described.
The said laminated body for decorating shaping | molding should just bond both, for example, after producing a decorating film and an application film separately.
(1) Production of a decorative film.
(1-1) First, a first vinyl chloride resin composition is prepared, and then the obtained first vinyl chloride resin composition is formed to produce a first base film.
The first vinyl chloride resin composition can be prepared by melt-kneading a predetermined amount of each compounding component using a continuous kneader, a Banbury mixer, a kneader, an extruder, or the like.
The film formation can be performed by calendar molding, extrusion molding, injection molding, or the like.
The film formation is preferably performed by calendering. Calendar molding makes it easy to make the thickness of the base film uniform, can be formed regardless of the composition of the vinyl chloride resin composition, and can be used to form bases of various sizes such as larger sizes. This is because it is suitable and it is easy to handle small lots.
Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.
Moreover, the roll temperature at the time of calendering may be appropriately selected according to the composition of the first vinyl chloride resin composition, but is usually 140 to 190 ° C, preferably 160 to 180 ° C.

(1-2) Next, an adhesive layer is formed on one side of the first base film.
When the adhesive layer is made of a hot-melt adhesive, the adhesive layer may be formed by a conventionally known method, which is formed by directly applying to the first base film using a hot-melt applicator or the like. Alternatively, it may be formed by once coating on a separately prepared support and then transferring. If a separator is used as the support, the separator can be laminated simultaneously with the formation of the hot melt adhesive layer.

(1-3) Next, a printing layer is formed on the surface opposite to the side on which the adhesive layer of the first base film is formed. The print layer is formed using solvent-based ink or the like as described above.
The method for forming the print layer is as described above.
The order of forming the adhesive layer and forming the print layer may be reversed.

(1-4) Then, a surface protective layer is laminated | stacked on the said printing layer as needed.
For example, after producing a transparent film to be a surface protective layer by calendering, etc., an adhesive is applied to one side of this transparent film, and this is attached to the surface on which the printed layer is formed on the first base film, and bonded. A surface protective layer is laminated via the agent layer.
For example, after producing the said transparent film, this transparent film may be directly affixed on the said printing layer by the heat laminating method, and a surface protective layer may be laminated | stacked.
Any of these methods can be suitably used when the design of the printed layer is a pattern or a solid print, but when the design is a logo or a photographic image, A method of laminating a surface protective layer via an adhesive layer is preferred. This is because in the case of laminating by the thermal laminating method, the first base film is stretched during the thermal laminating, and the printed layer design may be distorted.
A decorative film can be manufactured by passing through such a process.

(2) Production of application film.
(2-1) First, a second base film is produced.
The second substrate film can be produced by the same method as the production of the first substrate film. After the second vinyl chloride resin composition is prepared, it may be formed by calendering or the like. .

(2-2) Next, an adhesive layer is formed on one side of the second base film.
The pressure-sensitive adhesive layer is formed, for example, by previously forming a pressure-sensitive adhesive layer made of a solvent-type or emulsion-type pressure-sensitive adhesive on one side of the support, and bonding the second substrate film on the pressure-sensitive adhesive layer, It can carry out by what is called a transfer method which transfers an adhesive layer to the 2nd substrate film.
An application film can be manufactured through such a process.

(3) Production of decorative molded laminate The application film produced through the above-described steps is pasted to the surface on which the printed layer (or surface protective layer) of the decorative film is formed using a conventionally known method. The laminate for decorative molding is used.
The laminated body for decorative molding of this invention can be manufactured by passing through such a process.

Next, the manufacturing method of the decorative molded product of this invention is demonstrated, referring drawings.
(A)-(f) shown to FIG. 3A and 3B is a schematic diagram for demonstrating the manufacturing method of the decorative molded product of this invention. FIG. 4 is a schematic diagram for explaining a part of a conventional method for producing a decorative molded product.

The method for producing a decorative molded product of the present invention is characterized in that the application film is peeled off after the decorative molded laminate of the present invention is attached to the surface of the core material by vacuum molding or vacuum / pressure forming. And
The core material is not particularly limited as long as it is generally used for decorative molded products, and for example, a core material made of resin, metal, or ceramic can be used.
Further, the shape of the core material is not particularly limited.

  The material of the core material (resin core material) made of the above resin is not particularly limited. For example, polyethylene resin, polypropylene resin, polystyrene resin, polyethylene terephthalate resin, polyvinyl alcohol resin, vinyl chloride resin, polyamide Resin, polyacetal resin, polycarbonate resin, acrylonitrile / butadiene / styrene (ABS) resin, ionomer resin, and resin compositions obtained by adding various additives such as inorganic fibers to these resins.

  It does not specifically limit as a material of the said metal core material (metal core material), For example, iron, aluminum, copper, SUS, etc. are mentioned.

Here, the manufacturing method of the decorative molded product of the present invention will be described in the order of steps, taking as an example the case of decorating the surface of the core material by vacuum / pressure forming.
3A and 3B includes a molding chamber (an upper molding chamber 32 and a lower molding chamber 33) on the upper and lower sides, and the surface of the core material 31 is formed in the molding chamber by vacuum and pressure molding. The laminate 100 for decorative molding is affixed to.

(1) First, in a state where the upper molding chamber 32 is raised (not shown), the core material 31 is set on the table 35 in the lower molding chamber 33 and the decorative molding laminate 100 to be attached to the core material 31 is provided. Set on the upper surface of the lower molding chamber 33. Thereafter, the upper molding chamber 32 is lowered by the driving device 34, and the upper and lower molding chambers are respectively airtight (see FIG. 3A (a)).

(2) Next, each of the upper and lower molding chambers is evacuated from the vacuum tank 37 through the pipe 38 to be in a vacuum state (extremely low pressure state) (see FIG. 3A (b)).
Thereafter, the heater 36 is turned on to heat the decorative molded laminate 100 (see FIG. 3A (c)). As a result, the decorative molded laminate 100 is softened and can be attached to the core material 31 along the surface shape.

At this time, in the conventional vacuum / pressure forming, as shown in FIG. 4, the decorative molded laminate 100 'softened by heating hangs down by its own weight, and as a result, in the finished decorative molded product, an image of the printed layer Cause distortion.
On the other hand, since the decorative molded laminate 100 of the present invention includes the application film, the sagging due to its own weight hardly occurs in this step.

  In the present invention, when the decorative molded laminate is heated, drooping due to its own weight that does not cause distortion of the image may occur. In this case, a valve (not shown) in the pipe 38 is used. The degree of vacuum in the upper and lower molding chambers 32 and 33 may be adjusted so that the decorative molding laminate is horizontal. However, if this adjustment is performed, the number of processes increases, which is disadvantageous in terms of productivity.

(3) Next, the table 35 in the lower molding chamber 33 is raised by the drive device 34, and the core material 31 is brought into contact with the softened decorative molding laminate 100 (see FIG. 3B (d)).

(4) Next, the vacuum on the upper molding chamber 32 side is released to an atmospheric pressure state (the lower molding chamber 33 is in a vacuum state), and further, compressed air is introduced into the upper molding chamber 32 from the pressurized air tank 39. The decorative molding laminate 100 is pressed against the core material 31 and attached along its shape (see FIG. 3B (e)).

(5) Thereafter, the inside of the upper molding chamber 32 and the lower molding chamber 33 are returned to the atmospheric pressure state, the upper molding chamber 32 is raised, and the core material 31 covered with the decorative molding laminate 100 is taken out (see FIG. 3B (f)).
Finally, a decorative molded product can be manufactured by peeling the application film from the decorative molding laminate 100.

  In addition, although the method demonstrated here is a method using vacuum and pressure forming, when sticking the laminated body for decorative shaping | molding to a core material using vacuum forming, the upper shaping | molding chamber in said (4) The process of putting compressed air from the pressurized air tank 39 into the inside 32 may be omitted.

The decorative molded product manufactured by such a method is also one aspect of the present invention.
Specific examples of the above-mentioned decorative molded product are not particularly limited. Designs such as patterns, designs, letters, etc. on the surface of electrical appliances for mobile phones, smartphones, tablets, etc., vehicle interiors, motorcycle cowlings, etc. Various decorative molded products decorated with can be mentioned.

  EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

<Production of decorative film>
(Production Example 1: Production of decorative film A)
(1) 23 parts by weight of a plasticizer (Jplus Co., DOP) is blended with 100 parts by weight of a vinyl chloride resin (Kaneka, Kanevinyl S1008: average polymerization degree 800), and melt kneaded with a Banbury mixer. The first vinyl chloride resin composition was prepared. Thereafter, a vinyl chloride resin film (first base film) having a thickness of 80 μm was formed through each roll (roll temperature, 160 to 180 ° C.) of an inverted L-type calendar apparatus.

About the produced 1st base film, when the elongation at break in 100 degreeC was measured, it was 165%.
The measurement of the elongation at break was performed in accordance with JIS K 7162 using a tensile tester (manufactured by Shimadzu Corporation, AG-100NXplus). In addition, the atmospheric temperature at the time of tension | pulling was 100 degreeC.

(2) Next, a hot melt adhesive (manufactured by Hitachi Chemical Co., Ltd., Hibon 7663) is applied on the separator so that the thickness as an adhesive layer is 40 μm, and this is applied to the first base film. It transferred, and it was set as the laminated body by which the 1st base film, the adhesive bond layer, and the separator were laminated | stacked in this order.

(3) Next, a printing layer was formed on the surface of the first base film (the surface opposite to the side on which the adhesive layer was formed) using the following method.
Mimaki Engineering's inkjet printer CJV-30 is used as the printing device, Mimaki Engineering's ES3 ink is used as the solvent-based ink, and ink jet printing is performed on the surface of the vinyl chloride resin film, and a lattice pattern (line width of the lattice pattern: A printing layer of 0.5 pt (about 0.175 mm, lattice spacing: 2 mm) was formed.
The decorative film A was produced through the steps (1) to (3).

(Production Example 2: Production of decorative film B)
On the printed layer of the decorative film A produced in Production Example 1, an 80 μm-thick vinyl chloride resin film produced by the following method was used to form an adhesive layer having a thickness of 20 μm after drying (manufactured by Soken Chemical Co., Ltd., The decorative film B in which the surface protective layer was formed was produced by laminating via SK1506).
The vinyl chloride-based resin film is blended with 15 parts by weight of a plasticizer (JPLUS, manufactured by Kanevinyl S1008) and 100 parts by weight of a vinyl chloride-based resin (Kaneka S1008), and melt kneaded with a Banbury mixer. Then, after preparing the vinyl chloride resin composition, the obtained vinyl chloride resin composition was produced through each roll (roll temperature, 160 to 180 ° C.) of an inverted L-type calendar apparatus.

(Production Example 3: Production of decorative film C)
A 50 μm thick acrylic resin film (manufactured by Mitsubishi Rayon Co., Ltd., acrylate) is applied on the printed layer of the decorative film A produced in Production Example 1, and an adhesive layer having a thickness of 20 μm after drying (manufactured by Soken Chemical Co., Ltd. , SK1506) to produce a decorative film C on which a surface protective layer was formed.

<Production of application film>
(Production Example 4: Production of Application Film A)
(1) 15 parts by weight of a plasticizer (Jplus Co., DOP) is blended with 100 parts by weight of a vinyl chloride resin (Kaneka, Kanevinyl S1008: average polymerization degree 800), and melt kneaded with a Banbury mixer. A second vinyl chloride resin composition was prepared. Thereafter, a vinyl chloride resin film (second base film) having a thickness of 100 μm was formed through each roll (roll temperature, 160 to 180 ° C.) of an inverted L-type calendar apparatus.

  About the produced 2nd base film, when the elongation at break in 100 degreeC was measured, it was 130%. The method for measuring the elongation at break is the same as the method for measuring the first base film.

(2) Next, 1.5 parts by weight of a curing agent (manufactured by Soken Chemical Co., Ltd., L-45) is mixed with 100 parts by weight of an acrylic adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 1495). After adjusting and coating on the separator so as to have a thickness of 20 μm after drying, it is transferred to the second base film, and the second base film, the adhesive layer and the separator are stacked in this order. The body.
The application film A was produced through the steps (1) and (2).

(Production Example 5: Production of application film B)
Application film B was produced in the same manner as in Production Example 4 except that the blending amount of the plasticizer in the second vinyl chloride resin composition for producing the second base film was changed to 20 parts by weight.
The breaking elongation at 100 ° C. of the second base film constituting the application film B was 140%.

(Production Example 6: Production of application film C)
5 parts by weight of a plasticizer (manufactured by Kaneka Corporation, DOP) and 3 parts by weight of an acrylic compound (manufactured by Kaneka Corporation, P530) were blended with 100 parts by weight of a vinyl chloride resin (manufactured by Kaneka Corporation, Kane Vinyl S1008). An application film C was produced in the same manner as in Production Example 4 except that the second vinyl chloride resin composition was used.
The breaking elongation at 100 ° C. of the second base film constituting the application film C was 130%.

(Production Example 7: Production of application film D)
An application film D was produced in the same manner as in Production Example 4 except that the thickness of the second base film was changed to 50 μm.
The breaking elongation at 100 ° C. of the second base film constituting the application film D was 105%.

(Production Example 8: Production of application film E)
An application film E was produced in the same manner as in Production Example 4 except that the thickness of the second base film was changed to 300 μm.
The breaking elongation at 100 ° C. of the second base film constituting the application film E was 150%.

(Production Example 9: Production of application film F)
Except for using a second vinyl chloride resin composition in which 30 parts by weight of a plasticizer (manufactured by Jplus Co., DOP) is used with respect to 100 parts by weight of a vinyl chloride resin (manufactured by Kaneka, Kanevinyl S1008), Application film F was produced in the same manner as in Production Example 4.
The breaking elongation at 100 ° C. of the second base film constituting the application film F was 180%.

(Production Example 10: Production of application film G)
Application film in the same manner as in Production Example 4 except that a film having a thickness of 100 μm made of PMMA (copolymer of methyl methacrylate and acrylic ester: Mitsubishi Rayon Co., Ltd., HBS series) was used as the second base film. G was produced.
The breaking elongation at 100 ° C. of the second base film constituting the application film G was 190%.

(Production Example 11: Production of application film H)
As the pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition obtained by mixing 2.0 parts by weight of a curing agent (manufactured by Soken Chemical Co., Ltd., E-50C) with 100 parts by weight of an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK1439U) was used. Produced an application film H in the same manner as in Production Example 4.

(Production Example 12: Production of application film I)
As the pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition obtained by mixing 100 parts by weight of an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK1473) with 1.0 part by weight of a curing agent (manufactured by Soken Chemical Co., Ltd., L-45) was used. Produced Application Film I in the same manner as in Production Example 4.

(Production Example 13: Production of application film J)
As an adhesive composition, an adhesive composition prepared by mixing 100 parts by weight of an acrylic adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 1473H) with 0.5 part by weight of a curing agent (manufactured by Soken Chemical Co., Ltd., L-45) is used. An application film J was produced in the same manner as in Production Example 4 except that.

(Examples 1-10 and Comparative Examples 1-5)
(1) Production of decorative molded laminate A decorative molded laminate was produced by bonding one of the application films A to J to one of the decorative films A to C produced by the method described above. In this process, of course, the separator of the application film was peeled off.
The combinations of the decorative film and the application film are shown in Table 1. In Comparative Examples 1 to 3, the application films were not laminated, and the decorative films A to C themselves were used as decorative molded laminates.

(Measurement of adhesive strength of application film)
The adhesive force of the application film to the decorative film was measured. The results are shown in Table 1. The method for measuring the adhesive strength is as described above.

(2) Manufacture of a decorative molded product Next, as shown in FIG. 5, using the laminate for decorative molding, a part of the back surface 131a and the side surface 131b of the smartphone cover 131 (hatching in FIG. 5). Part) was decorated to produce a decorative molded product.
Specifically, first, a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd., model number: NGF-0406) is used as a vacuum / compressed air molding machine, and the heating temperature of the heater is 80 to 120 ° C. The laminated body for decorative molding was affixed on the back surface and side surface of (base material). In this process, of course, the separator of the decorative molding laminate (decorative film separator) was peeled off.
Thereafter, the core material to which the decorative molding laminate was attached was taken out from the vacuum / pressure forming machine, and the application film was peeled off and unnecessary portions were trimmed to obtain a decorative molded product.

(Evaluation)
The following evaluation was performed about the decorative molded product produced in the Example and the comparative example. The results are shown in Table 1. In addition, evaluation of the following (2) is performed before peeling the application film, evaluation of the following (3) is performed when peeling the application film, and evaluation of the following (1) and (4) is peeling of the application film. I went later.

(1) Image distortion The image of the printed layer of the decorative film before vacuum / pressure forming was compared with the image of the printed layer in the finished decorative molded product, and evaluated according to the following criteria.
A: The distortion of the image dimension of the image after molding is less than 0.50 mm with respect to the image before vacuum / pressure forming.
(Triangle | delta): The distortion of the image dimension of the image after shaping | molding is 0.50 mm or more and less than 0.75 mm with respect to the image before vacuum and pressure forming.
X: The distortion of the image dimension of the image after shaping | molding is 0.75 mm or more with respect to the image before vacuum and pressure forming.
In this evaluation, “distortion of image size” was calculated by the following method.
That is, for the image after molding, the vertical and horizontal lengths of each lattice of the lattice pattern are measured, the difference between the maximum value and the lattice interval (2 mm) of the lattice pattern before molding is calculated, and the value is calculated. The image dimensions were distorted.

For reference, color photographs of the decorative molded products produced are shown in FIGS.
6 is a color photograph of the decorative molded product produced in Example 1, and FIG. 7 is a color photograph of the decorative molded product produced in Comparative Example 1.
From comparison of these photographs, it can be understood that distortion can be suppressed in an image by producing a decorative molded product using the laminate for decorative molding of the present invention. For example, it can be confirmed that a large distortion has occurred in the image in the area A in FIG.

(2) Formability to core material The molded product before peeling the application film taken out from the vacuum / pressure forming machine was observed and evaluated according to the following criteria.
○: The application film follows the decorative film to the end with respect to the core material.
(Triangle | delta): Although the application film has tracked to the edge part of the core material with the decorating film, the tear has occurred in the application film at the edge part of the core material.
X: Although the upper surface of the core material could be decorated, the decorative film did not follow a part (for example, end part) of the side surface of the core material, and there was a portion that could not be decorated.

(3) Peelability of application film After taking out from a vacuum / pressure forming machine, the peelability when peeling the application film was evaluated according to the following criteria.
○: It can be peeled smoothly and without adhesive residue on the decorative film side.
(Triangle | delta): Although it is heavy peeling, it can peel without the adhesive residue on the decorative film side.
* 1: It cannot peel without damaging an application film.
X2: Although it can peel, the adhesive residue generate | occur | produces on the decorative film side.

(4) Appearance of the decorated surface The appearance (wrinkle and presence of occurrence of mold) of the manufactured decorative molded product was visually observed and evaluated according to the following criteria. In this evaluation, “wrinkle” refers to what occurred in the decorative film when the laminate for decorative molding is attached to the core material, and “mold” refers to the decorative film by peeling the application film. This refers to the trace of peeling that occurred.
○: Wrinkles and molds are not observed.
Δ: Wrinkles are observed.
X: A type | mold is observed.

  From the results of the above Examples and Comparative Examples, it was revealed that the decorative molded laminate of the present invention can suppress the occurrence of image distortion while ensuring the moldability to the core material. Moreover, it became clear that the laminated body for decorating shaping | molding of this invention has a characteristic with practicality also in the peelability of an application film and the external appearance of a decorating surface.

DESCRIPTION OF SYMBOLS 10 Decorating film 11 1st base film 12 Adhesive layer 13 Print layer 14 Separator 15 Surface protection layer 16 Adhesive layer 20 Application film 21 2nd base film 30 Molding apparatus 31 Core material 32 Upper molding chamber 33 Lower molding chamber 34 Drive device 35 Table 36 Heater 37 Vacuum tank 38 Piping 39 Pressurized air tank 100 Laminate for decorative molding

Claims (4)

A laminate for decorative molding for attaching to a core material by vacuum forming or vacuum / pressure forming,
A decorative film and an application film laminated on the decorative film;
In the decorative film, the adhesive layer, the first base film and the printing layer are laminated in this order,
The first base film contains a vinyl chloride resin having an average degree of polymerization of 700 to 1400 and a plasticizer having a molecular weight of 350 to 3000, and the blending amount of the plasticizer is 100 parts by mass of the vinyl chloride resin. The plasticizer comprises a first vinyl chloride resin composition that is 5 to 40 parts by mass,
The application film is laminated with an adhesive layer and a second base film in order from the decorative film side,
The second base film is composed of a second vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer,
The breaking elongation at 100 ° C. of the second base film is smaller than the breaking elongation at 100 ° C. of the first base film,
A laminate for decorative molding characterized by the above.   The second vinyl chloride resin composition contains a vinyl chloride resin having an average degree of polymerization of 700 to 1500 and a plasticizer having a molecular weight of 350 to 3000, and the blending amount of the plasticizer is 100 weight of vinyl chloride resin. The laminated body for decorative molding of Claim 1 which is 5-30 weight part with respect to a part. The laminate for decorative molding according to claim 1 or 2, wherein the second base film has a thickness of 50 to 300 µm. Decorating characterized in that the application film is peeled off after applying the decorative molding laminate according to any one of claims 1 to 3 to the surface of the core material by vacuum forming or vacuum / pressure forming. Manufacturing method of molded products.