JP2018065333A - Method for producing forming decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a forming decorative sheet which can prevent or reduce an ink flow phenomenon, the forming decorative sheet, and a method for producing a molded article.SOLUTION: A method for producing a forming decorative sheet has a step of heating a decorative sheet including a base layer and a printed layer by heating means disposed so as to face a surface of the decorative sheet on the printed layer side, and a step of forming the decorative sheet after heating.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a shaped decorative sheet, a shaped decorative sheet, a method for producing a molded body, and a molded body.

An insert molding method or an in-mold molding method is used as a technique for decorating a molded body such as a vehicle interior material or a home appliance housing. In these methods, a decorative molded body can be manufactured by integrally molding a decorative sheet including a printed layer and a casing (injection resin).
Patent Document 1 discloses a mold for in-mold molding provided with a specific heating device, a method for manufacturing a molded product using the mold, and the like.

JP 2008-94038 A

In order to prevent the decorative surface of the decorative sheet from being damaged or peeled off, the decorative surface of the decorative sheet is generally arranged on the side in contact with the housing (molding resin) instead of the outermost surface of the molded body. However, when the molded body is manufactured, the design surface of the decorative sheet is arranged on the side on which the molding resin is injected, so that the molten resin for molding and the printed layer of the decorative sheet come into contact with each other and the design properties are impaired. (Hereinafter referred to as “ink flow phenomenon”).
An object of the present invention is to provide a method for producing a shaped decorative sheet, a method for producing a shaped decorative sheet, and a method for producing a molded body, which can cause or reduce an ink flow phenomenon.

As a result of examining the cause of the ink flow phenomenon, the present inventors have found that the decorative sheet itself is melted by the heat of the molten molding resin.
As a result of intensive studies based on the above findings, the present inventors have prevented the decorative sheet from melting by improving the heat resistance of the decorative sheet, particularly the heat resistance of the surface of the base layer on the printed layer side. The present inventors have found that the ink flow phenomenon can be suppressed and completed the present invention.
According to the present invention, the following method for producing a decorative sheet is provided.
1. A step of heating a decorative sheet including a base material layer and a printed layer, the step of heating the decorative sheet by a heating means disposed so as to face the printed layer side surface of the decorative sheet; and A method for producing a shaped decorative sheet, comprising a step of shaping the decorated sheet after heating.
2. The manufacturing method of the shaping decoration sheet of 1 which heats the said decoration sheet on the conditions from which the surface temperature of the surface at the side of the printing layer of the base material layer in the said decoration sheet becomes 130 to 170 degreeC.
3. In the process of heating the decorating sheet, in addition to the heating means, the decorating sheet is heated by a heating means installed so as to face the surface on the base material layer side of the decorating sheet. Manufacturing method for shaped decorative sheets.
4). The manufacturing method of the shaping decoration sheet of 3 which heats the said decoration sheet on the conditions from which the surface temperature of the surface on the opposite side to the printing layer of the base material layer in the said decoration sheet becomes 130 to 170 degreeC. .
5). The method for producing a shaped decorative sheet according to any one of 1 to 4, wherein the shaping is performed by one or more methods selected from vacuum forming, pressure forming, vacuum pressure forming, press forming and plug assist forming.
6). The manufacturing method of the shaped decorating sheet in any one of 1-5 in which the said base material layer contains a polypropylene.
7). The manufacturing method of the shaped decorating sheet of 6 whose crystallization rate in 130 degreeC of the polypropylene of the said base material layer before the said heating is 2.5 min < ^-1 > or less.
8). The manufacturing method of the shaped decoration sheet of 6 or 7 whose isotactic pentat fraction of the polypropylene of the said base material layer before the said heating is 85 mol%-99 mol%.
9. The manufacturing method of the shaped decorating sheet in any one of 6-8 in which the polypropylene of the said base material layer before the said heating contains a smectic crystal.
10. The shaped additive according to any one of 6 to 9, wherein the polypropylene of the base material layer before the heating has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak in a curve obtained by differential scanning calorimetry. A method for producing a decorative sheet.
11. A decorative decorative sheet comprising a base material layer and a printed layer,
A shaped decorative sheet having a crystallinity of 55% or more on the surface of the substrate layer on the printed layer side.
12 A decorative decorative sheet comprising a base material layer and a printed layer,
A shaped decorative sheet, wherein a difference between a crystallinity of the surface of the base material layer on the printed layer side and a crystallinity of the surface of the base material layer opposite to the printed layer is within 10%.
13. The shaped decorative sheet according to 11 or 12, wherein the haze value of the base material layer is 15% or less.
14 The shaped decorative sheet according to any one of 11 to 13, which does not contain a nucleating agent.
15. The shaped decorative sheet according to any one of 11 to 14, wherein the base material layer contains polypropylene.
16. 16. The shaped decorative sheet according to 15, wherein the polypropylene of the base material layer has a crystallization rate at 130 ° C. of 2.5 min ⁻¹ or less.
The process of manufacturing a shaped decorative sheet by the method for producing a shaped decorative sheet according to any one of 17.1 to 9,
Mounting the shaped decorative sheet in the first mold;
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, The manufacturing method of the molded object including the process of integrating the said shaping decorative sheet and the said resin for shaping | molding.
18. A step of mounting the shaped decorative sheet according to any one of 11 to 16 in the first mold,
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, The manufacturing method of the molded object including the process of integrating the said shaping decorative sheet and the said resin for shaping | molding.
19. A step of heating a decorative sheet including a base material layer and a printed layer, the step of heating the decorative sheet by a heating means installed so as to face the printed layer side surface of the decorative sheet,
Cooling the decorated sheet to room temperature and placing it on the first mold,
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, Integrating the decorative sheet and the molding resin;
The manufacturing method of the molded object containing this.
20. The manufacturing method of the molded object of 19 which heats the said decoration sheet on the conditions from which the surface temperature of the surface at the side of the printing layer of the base material layer in the said decoration sheet becomes 130 to 170 degreeC.
21. In the step of heating the decorative sheet, in addition to the heating means, the decorative sheet is heated by a heating means installed so as to face the surface on the base material layer side of the decorative sheet. A method for producing a molded article.
22. The manufacturing method of the molded object of 21 which heats the said decoration sheet on the conditions from which the surface temperature of the surface on the opposite side to the printing layer of the base material layer in the said decoration sheet becomes 130 to 170 degreeC.
The molded object manufactured using the shaping decorative sheet in any one of 23.11-16.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the shaping decorative sheet which can raise | generate or reduce an ink flow phenomenon, the shaping decorative sheet, and the manufacturing method of a molded object can be provided.

It is the schematic of the decorating sheet used for the manufacturing method of the shaped decorating sheet of this invention. It is a figure which shows one Embodiment of the manufacturing method of the shaped decorating sheet of this invention. It is a figure which shows one Embodiment of the manufacturing method of the shaped decorating sheet of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is a figure which shows one Embodiment of the manufacturing method of the molded object of this invention. It is the schematic of the apparatus used for manufacture of the polypropylene sheet (base material layer) in Example 1. FIG.

[Method for manufacturing shaped decorative sheet]
The method for producing a shaped decorative sheet according to the present invention is a step of heating a decorative sheet including a base material layer and a printed layer, and the heating is installed so as to face the surface on the printed layer side of the decorative sheet. The process of heating a decorating sheet by a means and the process of shaping the decorating sheet after a heating are included.
In the present specification, the “surface on the printed layer side of the decorative sheet (or shaped decorative sheet)” is the surface formed by the printed layer of the upper and lower surfaces of the decorative sheet (or shaped decorative sheet). Or the surface closer to the printed layer than the base material layer, and the “surface on the base material layer side of the decorative sheet (or shaped decorative sheet)” is a decorative sheet (or shaped decorative sheet) Of the upper and lower surfaces, the surface formed by the base material layer or the surface closer to the base material layer than the printed layer.
Further, the drawings are schematic, and the ratio of each dimension is different from the actual one.
Hereinafter, each member and each process used for this invention are demonstrated.

(Decorative sheet)
A decorating sheet is a sheet | seat for giving decoration to the molded object used as a vehicle interior material or a housing | casing of household appliances, for example, and providing designability.
The decorative sheet usually includes a base material layer and a print layer, and a desired pattern, characters, colors, and the like are applied to the print layer. By integrating the decorative sheet and the molding resin, it is possible to produce a molded body to which the design of the printing layer is applied.
One embodiment of the decorative sheet is shown in FIG. The decorative sheet 1 has a laminated structure of a base material layer 10 and a printing layer 20.

Although there is no restriction | limiting in particular as a material used for a base material layer, Usually, it is a crystalline resin, For example, polyolefin can be used.
Examples of the polyolefin include polyethylene, polypropylene, and cyclic polyolefin resin. In particular, polypropylene is preferable from the viewpoint of heat resistance and hardness.

Polypropylene is a polymer containing at least a structural unit derived from propylene. Specific examples include homopolypropylene and copolymers of propylene and other olefins (such as ethylene). It is good also as a mixture with which polyolefin and copolymers, such as polyethylene, and polypropylene were mixed.
The polypropylene copolymer may be random polypropylene, block polypropylene, or a mixture thereof.
These may be used alone or in combination of two or more.

You may mix | blend an additive, such as a pigment, antioxidant, a stabilizer, a ultraviolet absorber, with a polypropylene as needed.
Further, polyolefins such as polypropylene and polyethylene are modified with a modifying compound such as maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, etc. You may mix | blend the modified polyolefin resin obtained by doing.

In the case of using polypropylene for the base material layer, it is preferable that the polypropylene contains smectic crystals before the heat treatment described later.
Polypropylene is a crystalline resin, and can take crystal forms such as α crystal, β crystal, γ crystal, and smectic crystal. Among these crystal forms, smectic crystals can be produced as an intermediate between amorphous and crystalline by cooling polypropylene from a molten state at a rate of 80 ° C. or more per second. The smectic crystal is not a stable structure having a regular structure like a crystal but a metastable structure in which fine structures are gathered together. For this reason, the interaction between the molecular chains is weak, and it has the property of being easily softened when heated as compared with α crystals having a stable structure.
The crystal structure of polypropylene is measured by the method described in the examples.

Moreover, it is preferable that a base material layer does not contain a nucleating agent. Even if it is included, the content of the nucleating agent in the base material layer is 1.0% by mass or less, preferably 0.5% by mass or less.
Examples of the nucleating agent include sorbitol-based crystal nucleating agents, and examples of commercially available products include Gelol MD (Shin Nihon Riken Co., Ltd.) and Riquemaster FC-1 (RIKEN Vitamin Co., Ltd.).

To make polypropylene, which is a crystalline resin, transparent, for example, a method of forming a smectic crystal by cooling at 80 ° C./second or more during the production of a base material layer, and forcibly producing fine crystals by adding a nucleating agent There is a way to make it. The nucleating agent improves the crystallization rate of polypropylene to a rate exceeding 2.5 min ⁻¹ , generates a large number of crystals and fills them, thereby eliminating the physical growth space and reducing the size of the crystals. Yes. However, since the nucleating agent has a core substance, it is slightly white even if it becomes transparent, and there is a possibility that the design property may be lowered.

Therefore, a crystallization rate of polypropylene is set to 2.5 min ⁻¹ or less without adding a nucleating agent, and cooling is performed at 80 ° C./second or more to form a smectic crystal, thereby obtaining a laminate having excellent design properties. Can do. Furthermore, if it shapes after heating mentioned later, a base material layer will change to (alpha) crystal, maintaining the fine structure derived from a smectic crystal. This transition can further improve the surface hardness and transparency.

The polypropylene of the substrate layer is preferably a polypropylene having an isotactic pendant fraction of 85 mol% to 99 mol% from the viewpoint of scratch resistance.
The isotactic pentad fraction is an isotactic fraction in a pentad unit in a molecular chain (in which five propylene monomers are continuously isotactic bonded).
The isotactic pentat fraction of polypropylene is preferably 85 mol% to 99 mol%, more preferably 90 mol% or more. When the isotactic pentat fraction is less than 85 mol%, the surface hardness is inferior, and the laminate surface may be damaged and the appearance may be impaired.
On the other hand, polypropylene with a high isopentat fraction has a high degree of crystallinity, and therefore, a method such as adding a nucleating agent or cooling at a rate of 80 ° C./second or more must be used when manufacturing a sheet described later. , It may become an opaque sheet.
The isotactic pendant fraction is measured by the method described in the examples.

Preferably the crystallization rate of the polypropylene used in the base layer (130 ° C.) is at 2.5 min ^-1 or less, more preferably 2.0Min ^-1 or less. The crystallization rate is measured by the method described in the examples.
In addition, the crystallization speed of polypropylene does not change before and after the heat treatment described later.

  In addition, before the heat treatment described below, the polypropylene of the base material layer has an exothermic peak of 1.0 J / g or more, preferably 1.5 J / g or more on the low temperature side of the maximum endothermic peak in the differential scanning calorimetry curve. .

The thickness of the base material layer is usually 50 to 500 μm.
A base material layer can be manufactured by the method as described in an Example.

  A printing layer is a layer for expressing a pattern, a character, a color, etc., and may be formed in a part on base material layer, and may be formed in the whole surface. The form of the pattern or the like is not particularly limited, and various forms such as a solid shape, a carbon tone, and a woodgrain tone can be used.

The print layer can be formed by printing a desired pattern or the like on the base material layer.
As a printing method, a general printing method such as a screen printing method, an offset printing method, a gravure printing method, a roll coating method, a spray coating method, or an ink jet method can be used. In particular, the screen printing method is preferable because the ink film thickness can be increased, and therefore, ink cracking hardly occurs when the ink is formed into a complicated shape.
For example, in the case of screen printing, an ink excellent in elongation at the time of molding is preferable, and examples thereof include “FM3107 high density white” and “SIM3207 high density white” manufactured by Jujo Chemical Co., Ltd., but are not limited thereto.

  The thickness of the printing layer is usually 1 to 50 μm.

You may include a binder layer on the surface on the opposite side to the base material layer of a printing layer. The binder layer can improve the adhesion between the decorative sheet and the molding resin described later.
Although there is no restriction | limiting in particular as a material used for a binder layer, For example, polyolefin can be used. The polyolefin is as described above.
The thickness of the binder layer is usually 5 to 50 μm.
A binder layer can be laminated | stacked by printing on the surface on the opposite side to the base material layer of a printing layer.

(Other layers)
In addition to the above layers, the decorative sheet can include a hard coat layer to increase the hardness. The hard coat layer is usually formed by applying to the surface of the base material layer opposite to the printed layer.

(Heating process)
In the production of the shaped decorative sheet, first, the heat treatment of the decorative sheet is performed. The heat treatment is performed by using a heating means (hereinafter sometimes referred to as “first heating means”) installed so as to face at least the surface of the decorative sheet on the printed layer side.
One embodiment of this process is shown in FIG. A first heating unit 100 is installed at a position (upward in FIG. 2) facing the surface on the printed layer 20 side of the decorative sheet 1, and the decorative sheet 1 is heated by the first heating unit 100.

  By heating intensively from the printed layer side surface of the decorative sheet by the above heat treatment, the crystallinity of the printed layer side surface of the base material layer can be increased and the heat resistance can be improved. As a result, the ink flow phenomenon can be suppressed during integration with the molding resin described later.

The heating method by the first heating means may be direct heating or indirect heating. In the case of direct heating, for example, hot plate heating can be performed, and in the case of indirect heating, an infrared heater or the like can be used.
The heating by the first heating means is preferably performed under the condition that the surface temperature of the surface on the printed layer side of the base material layer is 130 ° C to 170 ° C, preferably 150 to 170 ° C.

In addition to the first heating means, the decorative sheet using a heating means (hereinafter sometimes referred to as “second heating means”) installed so as to face the surface of the decorative sheet on the base material layer side. May be heated.
This embodiment is shown in FIG. The second heating means 110 is installed at a position (downward in FIG. 3) facing the surface of the decorating sheet 1 on the base material layer 10 side, and the decorating sheet 1 is heated by the second heating means 110.

By using a 2nd heating means in addition to a 1st heating means, it can be set as the shaping decoration sheet which is excellent in surface hardness and chemical resistance in addition to heat resistance.
Specific examples of the second heating means and the heating time are the same as those of the first heating means. The heating by the second heating means is preferably performed under the condition that the sheet surface temperature of the surface of the base material layer opposite to the printed layer is 130 ° C to 170 ° C, preferably 150 to 170 ° C.

  The method for heating the decorative sheet is not particularly limited as long as the above conditions are satisfied. For example, heating may be performed once for each decorative sheet to be shaped, or a continuous vertically long decorative sheet is moved so as to pass in the vicinity of the first heating means, or the first heating is performed. Heating may be performed continuously by moving between the means and the second heating means.

(Shaping process)
After performing said heat processing, a decorative sheet is shaped. Forming means processing the decorative sheet into a desired shape, for example, it can be shaped into a shape that matches the uneven shape in the first mold described later.
The shaping method is not particularly limited, but can be performed by one or more methods selected from vacuum forming, pressure forming, vacuum pressure forming, press forming and plug assist forming.

[Shaped decorative sheet]
The 1st shaping decorative sheet of this invention contains a base material layer and a printing layer, and the crystallinity degree of the surface at the side of the printing layer of a base material layer is 55% or more. The crystallinity of the surface on the printed layer side of the base material layer is preferably 60% or more. The crystallinity is measured by the method described in the examples.

In the first shaped decorative sheet, the degree of crystallinity of the surface of the base layer opposite to the printed layer is not particularly limited, but is usually 30% or more, preferably 40% or more, more preferably 50% or more.
A high degree of crystallinity on the surface opposite to the printed layer side of the base material layer is preferable from the viewpoint of surface hardness and chemical resistance.

  In the second decorative sheet of the present invention, the difference between the crystallinity of the surface of the base material layer on the printed layer side and the crystallinity of the surface of the base material layer opposite to the printed layer is 10% or less. is there. The difference in crystallinity is preferably 5% or less.

  In the second shaped decorative sheet of the present invention, the crystallinity of the surface on the printed layer side of the base material layer is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. It is. Moreover, the crystallinity degree of the surface on the opposite side to the printing layer of a base material layer becomes like this. Preferably it is 40% or more, More preferably, it is 50% or more, More preferably, it is 60% or more.

  In the first and second shaped decorative sheets of the present invention, the haze value of the base material layer is preferably 15% or less, more preferably 10% or less. The haze value is measured by the method described in the examples.

The first and second shaped decorative sheets of the present invention preferably do not contain a nucleator. Even if it is included, the content of the nucleating agent in the base material layer is 1.0% by mass or less, preferably 0.5% by mass or less.
The nucleating agent is as described above.

First and second shaping decorative sheet of the present invention, when using a polypropylene substrate layer, the crystallization rate (130 ° C.) is preferable to be 2.5 min ^-1 or less, 2.0Min ^-1 or less Is more preferable. The crystallization rate is measured by the method described in the examples.

Further, by calculating the scattering intensity distribution and the long period by the small-angle X-ray scattering analysis method, it is possible to determine whether or not the substrate layer is obtained by cooling at 80 ° C./second or more. That is, it is possible to determine whether or not the base material layer has a fine structure derived from smectic crystals by the above analysis. The measurement is performed under the following conditions.
-An X-ray generator uses ultraX 18HF (made by Rigaku Corporation), and an imaging plate is used for detection of scattering.
・ Light source wavelength: 0.154 nm
・ Voltage / current: 50 kV / 250 mA
・ Irradiation time: 60 min
・ Camera length: 1.085mm
Sample thickness: The sheets are stacked so that the thickness is 1.5 to 2.0 mm. The sheets are stacked so that the film forming (MD) directions are aligned.

  The shaped decorative sheet of the present invention can be produced by the method for producing a shaped decorative sheet described above. The configuration of each layer of the shaped decorative sheet is the same as that described in the method for producing the shaped decorative sheet.

[Method for producing first molded body]
The manufacturing method of the 1st molded object of this invention is the process of manufacturing a shaped decorative sheet by the manufacturing method of said shaped decorative sheet, The process of mounting a shaped decorative sheet in a 1st metal mold | die. A step of clamping the first mold and the second mold facing the first mold, and a molding resin is supplied from an injection port provided in the second mold, Including a step of integrating the decorative sheet and the molding resin.
The above-described shaped decorative sheet of the present invention may be used instead of the shaped decorative sheet obtained by the method for producing the shaped decorative sheet.
Hereinafter, an embodiment of each process will be described with reference to the drawings.

(Manufacturing process of shaped decorative sheet)
In this step, a shaped decorative sheet is produced by the method for producing a shaped decorative sheet of the present invention described above. As shown in FIG. 4, it is preferable that the shaped decorative sheet 201 is shaped so as to match the concave shape of the first mold 210.

(Clamping process)
In this step, the decorative decorative sheet 201 is mounted in the first mold 210, and the second mold 220 facing the first mold 210 is combined with the first mold 210 to perform mold clamping. Perform (FIG. 5).

(Molding resin supply process)
In this step, the molding resin 222 is supplied from the injection port provided in the second mold 220 to the cavity formed in the first mold 210 and the second mold 220, and is shaped. The decorative sheet 201 and the molding resin 222 are integrated.
Although there is no restriction | limiting in particular as resin for shaping | molding, For example, polyolefin can be used. The polyolefin is as described above.

  After supplying the molding resin 222, the molded body 230 is obtained by opening the first mold 210 and the second mold 220 after cooling for a certain period of time.

[Method for producing second molded body]
The manufacturing method of the 2nd molded object of this invention is a process of heating the decorating sheet containing a base material layer and a printing layer, Comprising: The heating installed so as to oppose the surface by the side of the printing layer of a decorating sheet The step of heating the decorative sheet by means, the step of placing the decorative sheet after heating on the first mold, and clamping the first mold and the second mold facing the first mold And a step of supplying a molding resin from an injection port provided in the second mold and integrating the decorative sheet and the molding resin.
Hereinafter, an embodiment of each process will be described with reference to the drawings.

(Decoration sheet heating process)
In the production of the molded body, first, the decorative sheet 1 is heat-treated (FIG. 8). The decorative sheet 1 is as described above.
The heat treatment of the decorative sheet 1 is performed using a heating unit 310 (hereinafter, also referred to as “first heating unit”) that is installed so as to face at least the surface of the decorative sheet 1 on the printed layer side. . The 1st heating means 310 and heating conditions are the same as the 1st heating means in the manufacturing method of the shaping decoration sheet of this invention mentioned above.

  By heating intensively from the printed layer side surface of the decorative sheet by the above heat treatment, the crystallinity of the printed layer side surface of the base material layer can be increased and the heat resistance can be improved. As a result, the ink flow phenomenon can be suppressed during integration with the molding resin described later.

  In addition to the first heating means 310, a heating means 312 (hereinafter, also referred to as “second heating means”) installed so as to face the surface on the base material layer side of the decorative sheet 1 is used. The decorative sheet 1 may be heated (FIG. 9).

By using the 2nd heating means 312 in addition to the 1st heating means 310, it can be set as the decorating sheet which is excellent in surface hardness and chemical resistance in addition to heat resistance.
The 2nd heating means 312 and a heating condition are the same as the 2nd heating means in the manufacturing method of the shaping decoration sheet of this invention mentioned above.

(Process of arranging the decorative sheet on the first mold, mold clamping process)
Next, the decorative sheet 1 subjected to the heat treatment is cooled to room temperature and placed on the first mold 320. Although there is no restriction | limiting in particular in the method of arrangement | positioning, Usually, the decorating sheet 1 is arrange | positioned so that a part or all of the cavity part of the 1st metal mold | die 320 may be covered (FIG. 10).
After arranging the decorative sheet 1, the second mold 330 facing the first mold 320 is combined with the first mold 320 to perform mold clamping.

(Molding resin supply process)
In this step, the molding resin 332 is supplied from the injection port provided in the second mold 330, and the decorative sheet 1 and the molding resin 332 are integrated (FIG. 11).
After supplying the molding resin 332, after cooling for a certain period of time, the molded body 340 is obtained by opening the first mold 320 and the second mold 330 (FIG. 12).

[Molded body]
The molded body of the present invention can be produced using the above-described shaped decorative sheet of the present invention. Moreover, the molded object of this invention can be manufactured with the manufacturing method of the 1st-2nd molded object of this invention mentioned above.
The molded body of the present invention can be used for vehicle interior materials, exterior materials, housings for home appliances, decorative steel plates, decorative plates, housing equipment, housings for information communication devices, and the like.

Example 1
[Manufacture of decorative decorative sheet]
A polypropylene sheet (base material layer) 51 was manufactured using the manufacturing apparatus shown in FIG.
The operation of the apparatus will be described. The molten resin (polypropylene) extruded from the T-die 52 of the extruder is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 on the first cooling roll 53. In this state, the molten resin is pressed by the first and fourth cooling rolls 53 and 56 and rapidly cooled. Subsequently, the polypropylene sheet is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 at a circular arc portion corresponding to the substantially lower half circumference of the fourth cooling roll 56, and is pressed in a planar form. After the sheet pressure contact and cooling by the fourth cooling roll 56, the polypropylene sheet that is in close contact with the metal endless belt 57 is moved onto the second cooling roll 54 as the metal endless belt 57 rotates. As described above, the polypropylene sheet is brought into pressure contact with the metal endless belt 57 at the arc portion corresponding to the substantially upper half circumference of the second cooling roll 54, and is cooled again. The polypropylene sheet cooled on the second cooling roll 54 is then peeled off from the metal endless belt 57. The surfaces of the first and second cooling rolls 53 and 54 are covered with an elastic material 62 made of nitrile-butadiene rubber (NBR).

The production conditions of the polypropylene sheet (base material layer) 51 are as follows.
・ Extruder diameter: 90 mm
・ Width of T-die 52: 800mm
Polypropylene (PP): trade name “Prime Polypro F-133A” (manufactured by Prime Polymer Co., Ltd. (melt flow index 2.8 g / 10 min, homopolypropylene))
-Take-up speed of the polypropylene sheet 51: 6 m / min
The surface temperature of the fourth cooling roll 56 and the metal endless belt 57: 14 ° C.
・ Sheet thickness: 220 μm
-Haze value of sheet: 9.7%

  The following evaluation was performed about the obtained polypropylene sheet.

[Measurement of isotactic pendant fraction]
By measuring the ¹³ C-NMR spectrum of the obtained polypropylene, the isotactic pendant fraction was measured. Specifically, the measurement of the isotactic pendart fraction is carried out according to the following equipment and conditions according to the attribution of the peak proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli et al. And the calculation formula.
[Equipment / Conditions]
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times [calculation formula]
Isotactic pendant fraction [mmmm] = m / S × 100
S: Signal intensity of side chain methyl carbon atoms of all propylene units m: Mesopentad chain: 21.7 to 22.5 ppm
The obtained polypropylene sheet had an isotactic pendant fraction of 98%.

[Measurement of crystallization rate]
The crystallization rate was measured using a differential scanning calorimeter (DSC) (product name “Diamond DSC”, manufactured by PerkinElmer). Specifically, the temperature of polypropylene is raised from 50 ° C. to 230 ° C. at 10 ° C./min, held at 230 ° C. for 5 minutes, cooled from 230 ° C. to 130 ° C. at 80 ° C./min, and then raised to 130 ° C. Crystallization was carried out by holding. From the time when the temperature reached 130 ° C., the measurement of the change in calorific value was started, and a DSC curve was obtained. From the obtained DSC curve, the crystallization speed was determined by the following procedures (i) to (iv).
(I) A baseline obtained by approximating a change in calorie from a time point 10 times from the start of measurement to the peak top to a time point 20 times by a straight line was used as a baseline.
(Ii) The intersection of the tangent line having the slope at the inflection point of the peak and the baseline was determined, and the crystallization start and end times were determined.
(Iii) The time from the obtained crystallization start time to the peak top was measured as the crystallization time.
(Iv) The crystallization speed was determined from the reciprocal of the obtained crystallization time.
The crystallization rate of the obtained polypropylene sheet was 0.1 min ⁻¹ .

[Confirmation of crystal structure]
The crystal structure of polypropylene is Referring to the method used by Konishi et al. (Macromolecules, 38, 8749, 2005), it was confirmed by wide-angle X-ray diffraction (WAXD: Wide-angle X-ray Diffraction).
In the analysis, the amorphous phase, the intermediate phase, and the crystalline phase were subjected to peak separation for the X-ray diffraction profile, and the abundance ratio was obtained from the peak area attributed to each phase.
It was confirmed that the obtained polypropylene sheet had a smectic crystal.

[Differential scanning calorimetry]
The obtained polypropylene sheet was subjected to differential scanning calorimetry. As the differential scanning calorimeter, the same apparatus as used in [Measurement of crystallization rate] was used. Specifically, the temperature of polypropylene was increased from 50 ° C. to 230 ° C. at 10 ° C./min, and endothermic and exothermic peaks were observed. Observation of the obtained endothermic exothermic peak confirmed that it had an exothermic peak of 1.8 J / g on the lower temperature side than the maximum endothermic peak.

Printing was performed on the polypropylene sheet (base material layer) to provide a printing layer. The outline of printing is as follows.
・ Printing method: Screen printing method ・ Printing layer: 6 layers (6-color printing)
・ Ink: General-purpose ink (Non-polypropylene ink: Teikoku Mfg. Co., Ltd.)
Moreover, the binder layer was provided on the printing layer using the 2 liquid curing type polypropylene binder (made by Teikoku Ink Manufacturing Co., Ltd.), and the decorating sheet was obtained.

About the obtained decorating sheet, as shown in FIG. 3, indirect heating was performed using the 1st heating means and the 2nd heating means (all are infrared heaters). The heating conditions were set so that the temperature of both surfaces of the decorative sheet was 160 ° C. FIG. 3 does not show the binder layer.
Next, the decorative sheet after heating was formed by a vacuum / pressure forming method to produce a shaped decorative sheet. The pressure of the vacuum / pressure forming method was 0.3 MPa.

[Measurement of crystallinity]
Since the density calculation is affected when trying to measure the crystallinity of the base material layer of the shaped decorative sheet, the base material layer without the print layer and the binder layer was used for the evaluation of the crystallinity. In addition, when the heat treatment of the same conditions is performed in the case where the printing layer and the binder layer are included, the crystallinity of the base material layer is the same.
Specifically, it is as follows.
The polypropylene sheet (base material layer) is subjected to the same heat treatment and molding as described above without providing a printing layer and a binder layer, and the first heating means side surface and the second heating means side surface are crystallized. Each degree was measured. The surface on the first heating means side corresponds to the surface on the printed layer side of the base material layer in the decorative sheet, and the surface on the second heating means side is the surface opposite to the printed layer on the base material layer in the decorative sheet. Corresponding to
The surface on the first heating means side and the surface on the second heating means side of the heat-treated and molded polypropylene sheet (base material layer) are respectively cut by 25 μm by the SAICAS (Daipura Wintes) method, The density of the cut piece was measured by a gradient tube method (manufactured by Shibayama Scientific Instruments: A type), and the crystallinity was calculated from the density of the cut piece. The results are shown in Table 1.

[Measurement of haze value]
The haze value of a polypropylene sheet (base material layer) obtained in the same manner as in [Measurement of crystallinity] was measured. The results are shown in Table 1. The haze value was measured by using a haze meter (NDH2000) manufactured by Nippon Denshoku Industries Co., Ltd.

Example 2
During the production of the polypropylene sheet used for the base material layer, 1.5 mass% of sorbitol nucleating agent “Rike Master FC-1” (manufactured by Riken Vitamin Co., Ltd.) is added as a nucleating agent, and the fourth cooling of the film forming apparatus is performed. The surface cooling temperature of the roll and the endless belt was set to 120 ° C. Further, a polypropylene sheet was produced in the same manner as in Example 1, except that the take-up speed of the propylene sheet was set to 10 m / min.
The crystallization speed of the obtained polypropylene sheet is 3.7 min ⁻¹ , has no smectic crystals, has α crystals, and is 1.0 J / g or more on the lower temperature side than the maximum endothermic peak by differential scanning calorimetry. It was confirmed that there was no exothermic peak. The isotactic pendant fraction was 98%.

  In addition, a shaped decorative sheet was produced and evaluated in the same manner as in Example 1 using the above polypropylene sheet. The results are shown in Table 1.

Comparative Example 1
A shaped decorative sheet was produced and evaluated in the same manner as in Example 1 except that the first heating means was not used. The results are shown in Table 1.

Example 3
[Manufacture of molded products]
The shaped decorative sheet obtained in Example 1 is mounted in a mold (flat plate mold: width 65 mm × length 150 mm × thickness 2 mm (one side gate: center of long side)), and the mold is clamped for injection. The molding resin “Prime Polypro J705UG” (Prime Polymer: Melt Flow Index 9.0 g / 10 min, block polypropylene) is supplied into the mold by a molding machine “IS80EPN” (Toshiba Machine Co., Ltd.), and decorated. The sheet and the molding resin were integrated to produce a molded body. The mold temperature was 45 ° C., the molding resin temperature was 240 ° C., and the molding resin injection speed was 18 mm / second.

[Evaluation of ink flow]
The surface of the obtained molded body on the printed layer side was visually observed and enlarged in cross section near the mold gate, and the ink flow phenomenon was evaluated based on the following criteria. The cross-sectional enlarged observation was performed with a microscope (VHX-600 (manufactured by Keyence), magnification 100 times) after adjusting the cross-section with HM340E (manufactured by Microme). The results are shown in Table 2.
◯: There was no change in the design properties of the printed layer.
(Triangle | delta): The designability of the printing layer fell.
X: A part or all of the printing layer was lost.

Example 4
A molded body was prepared and evaluated in the same manner as in Example 3 except that the decorative sheet obtained in Example 2 was used instead of the decorative sheet obtained in Example 1. The results are shown in Table 2.

Comparative Example 2
A molded body was produced and evaluated in the same manner as in Example 3 except that the decorative sheet obtained in Comparative Example 1 was used instead of the decorative sheet obtained in Example 1. The results are shown in Table 2.

Example 5
A molded article was produced and evaluated in the same manner as in Example 3 except that the mold temperature and the injection speed of the molding resin were changed as shown in Table 3. The results are shown in Table 3.

Example 6
A molded body was produced and evaluated in the same manner as in Example 5 except that the decorative sheet obtained in Example 2 was used instead of the decorative sheet obtained in Example 1. The results are shown in Table 3.

Comparative Example 3
A molded body was prepared and evaluated in the same manner as in Example 5 except that the decorative sheet obtained in Comparative Example 1 was used instead of the decorative sheet obtained in Example 1. The results are shown in Table 3.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 10 Base material layer 20 Print layer 51 Polypropylene sheet (base material layer)
52 T die 53 1st cooling roll 54 2nd cooling roll 55 3rd cooling roll 56 4th cooling roll 57 Metal endless belt 62 Elastic agent 100,310 1st heating means 110,312 2nd heating means 201 Shaping Decorative sheet 210, 320 First mold 220, 330 First mold 222, 332 Molding resin 230, 340 Molded body 320 First mold 330 Second mold

Claims (23)

A step of heating a decorative sheet including a base material layer and a printed layer, the step of heating the decorative sheet by a heating means disposed so as to face the printed layer side surface of the decorative sheet; and A method for producing a shaped decorative sheet, comprising a step of shaping the decorated sheet after heating.   The method for producing a shaped decorative sheet according to claim 1, wherein the heating of the decorative sheet is performed under a condition that the surface temperature of the printed layer side of the base material layer in the decorative sheet is 130 ° C to 170 ° C. .   In the process of heating the said decorating sheet, in addition to the said heating means, a decorating sheet is heated by the heating means installed so as to oppose the surface by the side of the base material layer of the said decorating sheet. The manufacturing method of the shaping decoration sheet as described in 2.   The shaped decorative sheet according to claim 3, wherein the decorative sheet is heated under the condition that the surface temperature of the surface of the decorative sheet opposite to the printed layer of the base material layer is 130 ° C. to 170 ° C. 5. Production method.   The method for producing a shaped decorative sheet according to any one of claims 1 to 4, wherein the shaping is performed by one or more methods selected from vacuum forming, pressure forming, vacuum pressure forming, press forming and plug assist forming. .   The method for producing a shaped decorative sheet according to any one of claims 1 to 5, wherein the base material layer contains polypropylene. The method for producing a shaped decorative sheet according to claim 6, wherein a crystallization rate at 130 ° C. of the polypropylene of the base material layer before the heating is 2.5 min ⁻¹ or less.   The method for producing a shaped decorative sheet according to claim 6 or 7, wherein an isotactic pentat fraction of polypropylene in the base material layer before the heating is 85 mol% to 99 mol%.   The manufacturing method of the shaping decoration sheet in any one of Claims 6-8 in which the polypropylene of the said base material layer before the said heating contains a smectic crystal.   The reinforcement according to any one of claims 6 to 9, wherein the polypropylene of the base material layer before the heating has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak in a curve obtained by differential scanning calorimetry. A method for manufacturing a shaped decorative sheet. A decorative decorative sheet comprising a base material layer and a printed layer,
A shaped decorative sheet having a crystallinity of 55% or more on the surface of the substrate layer on the printed layer side. A decorative decorative sheet comprising a base material layer and a printed layer,
A shaped decorative sheet, wherein a difference between a crystallinity of the surface of the base material layer on the printed layer side and a crystallinity of the surface of the base material layer opposite to the printed layer is within 10%.   The shaped decorative sheet according to claim 11 or 12, wherein the haze value of the base material layer is 15% or less.   The shaped decorative sheet according to any one of claims 11 to 13, which does not contain a nucleator.   The shaped decorative sheet according to any one of claims 11 to 14, wherein the base material layer contains polypropylene. The shaped decorative sheet according to claim 15, wherein the polypropylene of the base material layer has a crystallization rate at 130 ° C. of 2.5 min ⁻¹ or less. A step of producing a shaped decorative sheet by the method of producing a shaped decorative sheet according to claim 1,
Mounting the shaped decorative sheet in the first mold;
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, The manufacturing method of the molded object including the process of integrating the said shaping decorative sheet and the said resin for shaping | molding. The process of mounting the shaped decorative sheet according to any one of claims 11 to 16 in a first mold,
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, The manufacturing method of the molded object including the process of integrating the said shaping decorative sheet and the said resin for shaping | molding. A step of heating a decorative sheet including a base material layer and a printed layer, the step of heating the decorative sheet by a heating means installed so as to face the printed layer side surface of the decorative sheet,
Cooling the decorated sheet to room temperature and placing it on the first mold,
A step of clamping the first mold and a second mold facing the first mold, and supplying a molding resin from an injection port provided in the second mold, Integrating the decorative sheet and the molding resin;
The manufacturing method of the molded object containing this.   The manufacturing method of the molded object of Claim 19 which heats the said decorating sheet on the conditions from which the surface temperature of the surface at the side of the printing layer of the base material layer in the said decorating sheet becomes 130 to 170 degreeC.   In the step of heating the decorative sheet, in addition to the heating means, the decorative sheet is heated by a heating means installed so as to face the surface on the base material layer side of the decorative sheet. The manufacturing method of the molded object of description.   The manufacturing method of the molded object of Claim 21 which heats the said decorating sheet on the conditions from which the surface temperature of the surface on the opposite side to the printing layer of the base material layer in the said decorating sheet becomes 130 to 170 degreeC.   The molded object manufactured using the shaping decoration sheet in any one of Claims 11-16.

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