JP2021120227A - Method for producing decorative molded body using decorative film - Google Patents

Abstract

To provide a method for producing a decorative molded body, in which a polypropylene-based decorative film is used, and a three-dimensional decorative thermoforming that achieves both sufficient adhesive strength and product appearance, has less emboss return, reduces product defects and facilitates recycling is used.SOLUTION: There is provided a method for producing a decorative molded body, the method comprises: a step of preparing a decorative film 1 including a seal layer (I) made of a propylene-ethylene block copolymer (A) that meets specific requirements (a1) to (a3), and a layer (II) composed of a polypropylene resin (B) that meets a specific requirement (b1); a step of preparing a resin molding body 5; a step of setting the resin molded body 5 and the decorative film 1 in chamber boxes 11 and 12 which can be decompressed; a step of decompressing an inside of chamber boxes 11 and 12; a step of heating and softening the decorative film 1; a step of pressing the decorative film 1 against the resin molded body 5; and a step of returning or pressurizing the inside of the decompressed chamber boxes 11 and 12 to or from atmospheric pressure.SELECTED DRAWING: Figure 3

Description

The present invention relates to a method for producing a decorative molded product using a decorative film for attaching to the resin molded product by thermoforming. Specifically, it is possible to suppress wrinkles and rupture of the film during thermoforming, to develop sufficient adhesive strength to the resin molded body, to return the grain after thermoforming, and to be contained in the film during thermoforming. The present invention relates to a method for producing a decorative molded product using a decorative film for attaching to a resin molded product by thermoforming, which causes less damage to the film such as the additive migrating to the outside of the film.

In recent years, there has been an increasing demand for decoration technology instead of painting due to demands for VOC (volatile organic compound) reduction and the like, and various decoration technologies have been proposed.

Among them, a technique has been proposed in which a decorative film instead of a coating film is applied to a molded product by vacuum pressure molding or vacuum molding to form a decorative molded product in which the decorative film and the molded product are integrated (for example, Patent Document 1). (See), in recent years, it has received particular attention.

Compared to other decorative moldings typified by insert molding, vacuum compacted air forming and decorative molding by vacuum forming have a greater degree of freedom in shape, and the end face of the decorative film is caught up to the back side of the object to be decorated, resulting in a seam. The appearance is excellent because no ..

In such vacuum pressure molding and decorative molding by vacuum molding, when the decorative film and the molded body are attached to each other, wrinkles or rupture occur in the decorative film, or the decorative film and the molded body adhere to each other. There was a problem that sufficient strength could not be obtained. In addition, the use of adhesives, tack fires, etc. has been proposed as a layer for improving the adhesive strength, but it is expensive, the layer structure becomes extremely complicated, and solvent resistance and heat resistance are insufficient. , Etc.

To solve such a problem, by applying a decorative film containing an adhesive layer containing a polypropylene resin to a substrate (molded body) made of polypropylene resin, the decorative film and the molded body are heat-sealed. (See, for example, Patent Documents 2 and 3). The inventions disclosed in Patent Documents 2 and 3 use a polypropylene-based resin as an adhesive layer of a decorative film, but substantially further, an acrylic is used as a surface layer, a bonding layer and a bulk layer on the adhesive layer. It is necessary to provide a layer of resin, polyurethane resin, polycarbonate or the like. By combining different kinds of raw materials in this way, thermoformability such as draw-down property is exhibited, and it is possible to ensure thermoformability in a decorative film made of polypropylene resin that does not contain these different kinds of raw materials. This was not possible, and holes, wrinkles, and air entrainment were likely to occur on the surface of the molded product to which the molded product was attached, and further, film rupture occurred, and it was not possible to obtain a decorative molded product having an excellent appearance. In particular, when polyurethane resin is contained as a dissimilar raw material, polyurethane resin, which is a thermosetting resin, does not melt when heated, so that it is easy to maintain the form of the film and the thermoformability is greatly improved, but there is a problem that recyclability is extremely low. rice field.

That is, the decorative films described in Patent Documents 2 and 3 contain different raw materials in order to ensure thermoformability such as adhesiveness and appearance, have a complicated layer structure, and require many steps for their production. In addition, there is a problem that it is difficult to recycle a decorative film in which different kinds of raw materials are combined.

Further, there is a problem that a phenomenon of wrinkle return occurs in which wrinkles and the like on the film surface disappear due to heating and melting of the film during thermoforming.

Further, vacuum pressure air molding and decorative thermoforming by vacuum molding have an advantage that a molded product having a high degree of integration between the base molded in a process such as injection molding and the decorative film can be obtained, while the decorative film is the base. There is a problem that the scratches on the surface of the decorative molded product are picked up, and the appearance of the decorative molded product is likely to be poor due to the influence of the scratches on the surface of the substrate.

JP-A-2002-67137 Japanese Unexamined Patent Publication No. 2013-14027 Japanese Unexamined Patent Publication No. 2014-124940

With conventional techniques, a decorative film made of a propylene-based resin that is easy to recycle and has both adhesiveness and appearance has not yet been achieved. In view of the above problems, the subject of the present invention is that sufficient adhesive strength and product appearance can be achieved at the same time, there is little wrinkle return, and by making the scratches on the substrate inconspicuous, it is possible to reduce product defects, and further to recycle. It is an object of the present invention to provide a method for manufacturing a decorative molded product using a decorative film used for three-dimensional decorative thermoforming, which facilitates the process.

In three-dimensional decorative thermoforming, it is necessary that the surface of the molded body and the film are sufficiently softened or melted in order to attach the decorative film in the solid state to the resin molded body in the solid state. Therefore, it is important to apply the amount of heat required for softening or melting the surface of the molded product and the film, or to use the molded product and film that are easily softened or melted. On the other hand, if the film is heated too much, the viscosity of the film decreases, and the film breaks due to the thrust of the molded body in the three-dimensional decorative thermoforming process and the inflow of air when the vacuum chamber is returned to atmospheric pressure. Rampaging or rampaging leads to poor appearance. Further, if the film is heated too much, the additive contained in the film is transferred to the outside of the film, which causes a problem that the addition function derived from the additive such as heat resistance, weather resistance, and nucleation performance is deteriorated. Further, there arises a problem that grain return is likely to occur. Therefore, the present inventors have focused on and examined the composition of the decorative film in order not only to solve these problems but also to make the scratches on the surface of the substrate inconspicuous. As a result, the seal layer (I) made of the propylene-ethylene block copolymer (A) capable of exhibiting good adhesive strength, the decrease in the viscosity of the entire film is suppressed, the thermoformability is maintained, and the texture return is suppressed. It has been found that the above-mentioned problems can be solved by the combination of the layer (II) made of the polypropylene-based resin (B) to be carried out.
Furthermore, surprisingly, such a decorative film has a high effect of making scratches inconspicuous, and it has been found that the above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention comprises any of the following configurations (i) to (v).
(I) A step of preparing a decorative film, a step of preparing a resin molded body, a step of setting the resin molded body and the decorative film in a decompressable chamber box, a step of depressurizing the inside of the chamber box, A method for producing a decorative molded article, which comprises a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded article, and a step of returning or pressurizing the inside of the depressurized chamber box to atmospheric pressure. hand,
The decorative film is a decorative film for being attached onto a resin molded body by thermal molding, and the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A) and polypropylene. The propylene-ethylene block copolymer (A) contains the layer (II) composed of the based resin (B), satisfies the following requirements (a1) to (a3), and the polypropylene-based resin (B) meets the following requirements (b1). ) Satisfying the above. A method for manufacturing a decorative molded product using a decorative film.
Requirements for propylene-ethylene block copolymer (A) (a1) The component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer is 5 to 97% by weight, and the ethylene content is higher than that of the component (A1). It contains 3 to 95% by weight of a component (A2) composed of a propylene-ethylene random copolymer.
(A2) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(A3) The melting peak temperature (Tm (A)) is 110 to 170 ° C.
The requirement (b1) melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) of the polypropylene-based resin (B) satisfies the following relational expression (b-1) with respect to the MFR (A).
MFR (B) <MFR (A) ... Equation (b-1)
(Ii) The method for producing a decorative molded product using the decorative film according to (i) above, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a4).
(A4) The ethylene content in the propylene-ethylene block copolymer (A) is 0.15 to 85% by weight.
(Iii) The propylene-ethylene block copolymer (A) is a decorative molded product using the decorative film according to the above (i) or (ii), which satisfies the following requirement (a5). Production method.
(A5) The ethylene content of the component (A1) is in the range of 0 to 6% by weight.
(Iv) The propylene-ethylene block copolymer (A) is decorated with the decorative film according to any one of (i) to (iii), wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a6). A method for manufacturing a molded product.
(A6) The ethylene content of the component (A2) is in the range of 5 to 90% by weight.
(V) The method for producing a decorative molded product using the decorative film according to any one of (i) to (iv) above, wherein the resin molded product is made of a propylene-based resin composition.

According to the decorative film used in the method for producing a decorative molded article of the present invention, the three-dimensional decorative thermoformability is good, the adhesive force with the molded article is high, and the article can be attached to the molded article in a short heating time. Since the texture can be suppressed and scratches on the surface of the molded product can be made inconspicuous, the appearance of the three-dimensional decorative molded product can be improved, and a decorative film having good recyclability can be obtained.

According to the method for producing a decorative molded product of the present invention, there are no holes or wrinkles on the surface, there is no air entrainment between the decorative film and the resin molded product, and the reproducibility of textures such as wrinkles is good. It is possible to obtain a beautiful decorative molded product in which scratches are inconspicuous. In addition, the decorative film can be neatly attached to the resin molded body, which has been difficult to adhere in the past. Further, in the decorative molded product thus obtained, the constituent materials of the decorative film are propylene-ethylene block copolymer (A) and polypropylene-based resin (B), and do not contain a thermosetting resin layer. Because it does not have to be included or included, there is little deterioration in appearance and performance during recycling, and it is highly suitable for recycling.

It is a figure which shows an example of the layer structure of the decorative film used in this invention. It is a schematic cross-sectional view explaining the outline of the apparatus used in the manufacturing method of the decorative molded article of this invention. FIG. 5 is a schematic cross-sectional view illustrating a state in which a resin molded body and a decorative film are set in the apparatus of FIG. It is a schematic cross-sectional view explaining the state of heating and depressurizing the inside of the apparatus of FIG. FIG. 5 is a schematic cross-sectional view illustrating a state in which a decorative film is pressed against a resin molded body in the apparatus of FIG. It is a schematic cross-sectional view explaining how the inside of the apparatus of FIG. 2 returns to atmospheric pressure or pressurizes. It is a schematic cross-sectional view explaining how the edge of an unnecessary decorative film was trimmed in the obtained decorative molded body. It is a figure which shows an example of the layer structure of the decorative molded article of this invention.

In the present specification, the decorative film means a film for decorating a molded product. Decorative molding refers to molding in which a decorative film and a molded body are attached to each other. The three-dimensional decorative thermoforming is a molding in which a decorative film and a molded body are attached to each other, and has a step of thermoforming the decorative film along the attachment surface of the molded body and at the same time attaching the decorative film. In this step, in order to prevent air from being entrained between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is attached to the molded body, and pressure is applied. Molding is a process of bringing the product into close contact with each other by releasing (pressurizing) it. Hereinafter, embodiments for carrying out the present invention will be described in detail.

The decorative film used in the present invention is a decorative film for being attached onto a resin molded body by thermal molding, and the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A). ) And the polypropylene-based resin (B) (II), the propylene-ethylene block copolymer (A) satisfies the following requirements (a1) to (a3), and the polypropylene-based resin (B) is described below. It is characterized by satisfying the requirement (b1).
Requirements for propylene-ethylene block copolymer (A) (a1) 5 to 97% by weight of the component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer component, and an ethylene content higher than that of the component (A1). It contains 3 to 95% by weight of a component (A2) composed of a propylene-ethylene random copolymer having a large amount.
(A2) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes (a3) Melting peak temperature (Tm (A)) is 110-170 ° C. be.
The requirement (b1) melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) of the polypropylene-based resin (B) satisfies the following relational expression (b-1) with respect to the MFR (A).
MFR (B) <MFR (A) ... Equation (b-1)

Seal layer (I)
The decorative film contains a seal layer (I) made of a propylene-ethylene block copolymer (A). The seal layer (I) is a layer that comes into contact with a resin molded body (base) during three-dimensional decorative thermoforming. By providing the seal layer (I), sufficient adhesive strength can be exhibited even if the film heating time during three-dimensional thermoforming is short, and scratches on the surface of the substrate can be made inconspicuous.

Propylene-ethylene block copolymer (A)
The propylene-ethylene block copolymer (A) of the present invention contains a component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and propylene-ethylene containing more ethylene than the component (A1). It contains a component (A2) composed of a random copolymer. The component (A2), which is a rubber component in the propylene-ethylene block copolymer (A), improves the adhesive force with the resin molded product (base). In addition, the component (A2) has a high uniformity of dispersion form with respect to propylene, and accordingly, the effect of making scratches inconspicuous is high. The propylene-ethylene block copolymer (A) is obtained by (co) copolymerizing a component (A1) composed of propylene alone or a propylene-ethylene random copolymer in the first polymerization step, and from the component (A1) in the second polymerization step. It is also obtained by sequentially copolymerizing a component (A2) composed of a propylene-ethylene random copolymer containing a large amount of ethylene.

(A1) Ratio of component (A1) and component (A2) The content ratio of the component (A1) and the ratio of the component (A2) constituting the propylene-ethylene block copolymer (A) of the present invention is the component. It is necessary that the ratio of (A1) is 5 to 97% by weight and the ratio of the component (A2) is 3 to 95% by weight. The proportion of the component (A1) is preferably 30 to 95% by weight and the proportion of the component (A2) is 5 to 70% by weight, and more preferably the proportion of the component (A1) is 52 to 92% by weight and the component (A2). The ratio of is 8 to 48% by weight. When the ratio of the component (A1) and the ratio of the component (A2) are within the above ranges, sufficient adhesive strength can be exhibited, and the effect of making scratches inconspicuous is high. Further, within the above range, the film is not sticky and the film formability is good.

(A2) Melt flow rate The melt flow rate (230 ° C., 2.16 kg load) of the propylene-ethylene block copolymer (A) (hereinafter referred to as "MFR (A)") is 0.5 g / 10 minutes. It is necessary to exceed, preferably 1 g / 10 minutes or more, and more preferably 2 g / 10 minutes or more. When the MFR (A) is in the above range, the propylene-ethylene block copolymer (A) can be sufficiently relaxed during the three-dimensional decorative thermoforming, and sufficient adhesive strength can be exhibited and the substrate is attached to the substrate. The scratches are less noticeable. The upper limit of MFR (A) is not limited, but is preferably 100 g / 10 minutes or less. Within the above range, deterioration of adhesive strength due to deterioration of physical properties does not occur.

In the present specification, the measurement of MFR of the propylene-ethylene block copolymer (A), the polypropylene-based resin (B) and the polypropylene-based resin composition described later is based on ISO 1133: 1997 Conditions M, and is measured at 230 ° C., 2 ° C. Measured under the condition of .16 kg load. The unit is g / 10 minutes.

(A3) Melting Peak Temperature The melting point (melting peak temperature) of the propylene-ethylene block copolymer (A) (hereinafter referred to as "Tm (A)") needs to be 110 to 170 ° C. It is preferably 113 to 169 ° C, more preferably 115 to 168 ° C. When Tm (A) is in the above range, the moldability at the time of three-dimensional decorative thermoforming is good. The melting peak temperature is mainly derived from a component having a low ethylene content (A1), that is, a component having a high crystallinity (A1), and the melting peak temperature can be changed depending on the content of ethylene to be copolymerized.

(A4) Ethylene content in propylene-ethylene block copolymer (A) (E (A))
The ethylene content (hereinafter referred to as "E (A)") in the propylene-ethylene block copolymer (A) of the present invention is preferably 0.15 to 85% by weight. It is more preferably 0.5 to 75% by weight, still more preferably 2 to 50% by weight. When E (A) is in the above range, sufficient adhesive strength can be exhibited, and the adhesiveness to the decorative film layer (II) is good, and the film formability is also excellent.

(A5) Ethylene content of component (A1) (E (A1))
The component (A1) is a propylene homopolymer or a propylene-ethylene random copolymer having a relatively high melting point and an ethylene content (hereinafter referred to as “E (A1)”) in the range of 0 to 6% by weight. Is preferable. More preferably, it is 0 to 5% by weight. When E (A1) is in the above range, the moldability at the time of three-dimensional decorative thermoforming is good, the stickiness of the film is small, and the film moldability is also excellent.

(A6) Ethylene content of component (A2) (E (A2))
The ethylene content of the component (A2) (hereinafter referred to as "E (A2)") is higher than that of the ethylene content E (A1) of the component (A1). Further, it is preferable that E (A2) is a propylene-ethylene random copolymer in the range of 5 to 90% by weight. E (A2) is more preferably 7 to 80% by weight, still more preferably 9 to 50% by weight. When E (A2) is in the above range, sufficient adhesive strength can be exhibited, and the effect of making scratches inconspicuous is high.

[Method for producing propylene-ethylene block copolymer (A)]
A component (A1) composed of the propylene-ethylene block copolymer (A) used in the present invention, a propylene homopolymer or a propylene-ethylene random copolymer constituting the same, and a component (A2) composed of a propylene-ethylene random copolymer. ) Can be preferably produced by the following raw materials and polymerization method. The method for producing the propylene-ethylene block copolymer (A) used in the present invention will be described below.

-Materials used The catalysts used in producing the propylene-ethylene block copolymer (A) used in the present invention include magnesium, halogen, titanium, a magnesium-supported catalyst containing an electron donor as a catalyst component, and trichloride. A catalyst composed of a solid catalyst component using titanium as a catalyst and organic aluminum, or a metallocene catalyst can be used. The specific method for producing the catalyst is not particularly limited, and examples thereof include the Ziegler catalyst disclosed in JP-A-2007-254671 and the metallocene catalyst disclosed in JP-A-2010-105197. Can be done.

Further, the raw material olefins to be polymerized are propylene and ethylene, and if necessary, other olefins to the extent that the object of the present invention is not impaired, such as butene-1,1-hexene, 1-octene and 4-methyl-pentene. -1 and the like can also be used.

-Polymerization step The polymerization step performed in the presence of the catalyst comprises a multi-step of a first polymerization step for producing the component (A1) and a second polymerization step for producing the component (A2).

First Polymerization Step In the first polymerization step, propylene alone or a mixture of propylene / ethylene is supplied to a polymerization system to which the catalyst is added to produce a propylene homopolymer or a propylene-ethylene random copolymer, and the total weight is increased. This is a step of forming the component (A1) so as to be an amount corresponding to 5 to 97% by weight of the combined amount.

The MFR of the component (A1) (hereinafter referred to as "MFR (A1)") can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen, which is a chain transfer agent, is increased, the MFR (A1) of the component (A1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, the amount of hydrogen supplied to the polymerization tank may be increased, which is extremely easy for those skilled in the art. When the component (A1) is a propylene-ethylene random copolymer, it is convenient to use a method of controlling the amount of ethylene supplied to the polymerization tank as a means for controlling the ethylene content. Specifically, if the amount ratio of ethylene supplied to the polymerization tank to propylene (ethylene supply amount ÷ propylene supply amount) is increased, the ethylene content of the component (A1) increases. The reverse is also true. The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the component (A1) differs depending on the type of catalyst used, but the component having the desired ethylene content by adjusting the supply amount ratio as appropriate. Obtaining (A1) is extremely easy for those skilled in the art.

Second Polymerization Step In the second polymerization step, a propylene / ethylene mixture is further introduced following the first polymerization step to produce a propylene-ethylene random copolymer, which is 3 to 95% by weight of the total amount of the polymer. This is a step of forming the component (A2) so as to have a corresponding amount.

The MFR of the component (A2) (hereinafter referred to as "MFR (A2)") can be adjusted by using hydrogen as a chain transfer agent. The specific control method is the same as the control method of the MFR of the component (A1). As a means for controlling the ethylene content of the component (A2), it is convenient to use a method of controlling the amount of ethylene supplied to the polymerization tank. The specific control method is the same as when the component (A1) is a propylene-ethylene random copolymer.

Next, a method of controlling the index of the propylene-ethylene block copolymer (A) will be described.
First, a method of controlling the weight ratio of the component (A1) and the component (A2) will be described. The weight ratio of the component (A1) to the component (A2) is controlled by the production amount in the first polymerization step for producing the component (A1) and the production amount in the second polymerization step for producing the component (A2). For example, in order to increase the amount of the component (A1) and decrease the amount of the component (A2), the production amount of the second polymerization step may be reduced while maintaining the production amount of the first polymerization step, which is the second. The residence time in the polymerization step may be shortened, or the polymerization temperature may be lowered. It can also be controlled by adding a polymerization inhibitor such as ethanol or oxygen, or by increasing the amount of the originally added polymer. The reverse is also true.

Usually, the weight ratio of the component (A1) to the component (A2) is defined by the production amount in the first polymerization step for producing the component (A1) and the production amount in the second polymerization step for producing the component (A2). The formula is shown below.
Weight of component (A1): Weight of component (A2) = W (A1): W (A2)
W (A1) = production amount of the first polymerization step ÷ (production amount of the first polymerization step + production amount of the second polymerization step)
W (A2) = production amount of the second polymerization step ÷ (production amount of the first polymerization step + production amount of the second polymerization step)
W (A1) + W (A2) = 1
(Here, W (A1) and W (A2) are the weight ratios of the component (A1) and the component (A2) in the propylene-ethylene block copolymer (A), respectively.)

In industrial manufacturing equipment, the production amount is usually obtained from the heat balance and material balance of each polymerization tank. When the crystallinity of the component (A1) and the component (A2) are sufficiently different, the two may be separated and identified by an analytical method such as TREF (temperature temperature rise elution separation method) to obtain the quantity ratio. Methods for evaluating the crystallinity distribution of polypropylene by TREF measurement are well known to those skilled in the art, and G.I. Glokner, J. et al. Apple. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L. et al. Wild, Adv. Polym. Sci. 98, 1-47 (1990), J. Mol. B. P. Soares, A. E. Detailed measurement methods are shown in the literature such as Hamielek, Polymer; 36, 8, 1639-1654 (1995).

Next, a method for controlling the ethylene content will be described. Since the propylene-ethylene block copolymer (A) is a mixture of a component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and a component (A2) composed of a propylene-ethylene random copolymer, respectively. The following relational expression holds between the ethylene contents of.
E (A) = E (A1) x W (A1) + E (A2) x W (A2)
(Here, E (A), E (A1), and E (A2) are components (A1) composed of a propylene-ethylene block copolymer (A), a propylene homopolymer, or a propylene-ethylene random copolymer, respectively. , Ethylene content of component (A2) composed of propylene-ethylene random copolymer.)

This formula shows the material balance with respect to the ethylene content.
Therefore, if the weight ratio of the component (A1) to the component (A2) is determined, that is, if W (A1) and W (A2) are determined, E (A) is unique by E (A1) and E (A2). It is decided to. That is, E (A) can be controlled by controlling three factors, the weight ratio of the component (A1) and the component (A2), E (A1), and E (A2). For example, in order to increase E (A), E (A1) may be increased or E (A2) may be increased. Also, if it is noted that E (A2) is higher than E (A1), it can be easily understood that W (A1) may be made smaller and W (A2) may be made larger. The same applies to the control method in the reverse direction.

It should be noted that it is E (A) and E (A1) that can actually obtain the measured values directly, and E (A2) is calculated using the measured values of both. Therefore, if the operation of increasing E (A2) is performed and the operation of increasing E (A2), that is, the operation of increasing the amount of ethylene supplied to the second polymerization step is selected as a means, the measured value is directly applied. It is E (A) that can be confirmed, not E (A2), but it is obvious that the cause of the increase in E (A) is the increase in E (A2).

Finally, the control method of MFR (A) will be described. In the present application, MFR (A2) will be defined by the following equation.
MFR (A2) = exp {(loge [MFR (A)]-W (A1) x loge [MFR (A1)]) ÷ W (A2)}
(Here, loge is a logarithm with e as the base. MFR (A), MFR (A1), and MFR (A2) are propylene-ethylene block copolymer (A), propylene homopolymer, or propylene-, respectively. It is an MFR of a component (A1) composed of an ethylene random copolymer and a component (A2) composed of a propylene-ethylene random copolymer.)

This formula is an empirical formula generally called the logarithmic addition law of viscosity loge [MFR (A)] = W (A1) x loge [MFR (A1)] + W (A2) x loge [MFR (A2)]
It is a variant of, and is used on a daily basis in the industry.

In order to define by this formula, the weight ratio of the component (A1) to the component (A2), MFR (A), MFR (A1), and MFR (A2) are not independent. Therefore, in order to control the MFR (A), three factors of the weight ratio of the component (A1) and the component (A2), the MFR (A1), and the MFR (A2) may be controlled. For example, in order to increase the MFR (A), the MFR (A1) may be increased or the MFR (A2) may be increased. It is also easy to understand that when MFR (A2) is lower than MFR (A1), MFR (A) can be increased even if W (A1) is increased and W (A2) is decreased. NS. The same applies to the control method in the reverse direction.

It is MFR (A) and MFR (A1) that can actually obtain the measured values directly, and MFR (A2) is calculated using both measured values. Therefore, if the operation of increasing the MFR (A) is performed and the operation of increasing the MFR (A2), that is, the operation of increasing the amount of hydrogen supplied to the second polymerization step is selected as a means, the measured value is directly applied. It is MFR (A) that can be confirmed, not MFR (A2), but it is obvious that the cause of the increase in MFR (A) is the increase in MFR (A2).

The polymerization process of the propylene-ethylene block copolymer can be carried out by either a batch method or a continuous method. At this time, a method of polymerizing in an inert hydrocarbon solvent such as hexane or heptane, a method of using propylene as a solvent without substantially using an inert solvent, or a method of using a gaseous substance substantially without using a liquid solvent. A method of polymerizing in a monomer and a method of combining these can be adopted. Further, the first polymerization step and the second polymerization step may use the same polymerization tank or separate polymerization tanks.

(1) Measurement of Ethylene Content in Copolymer Using the propylene-ethylene block copolymer (A), the content of each ethylene in the copolymer was measured. That is, the component (A1) composed of the propylene homopolymer or the propylene-ethylene random copolymer obtained at the end of the first polymerization step, and the propylene-ethylene block copolymer (A) obtained through the second polymerization step. ^{The ethylene content of each of them was determined by analyzing the 13} C-NMR spectrum measured according to the following conditions by the proton complete decoupling method.
Model: JEOL Ltd. GSX-400 or equivalent device (carbon nuclear resonance frequency 100 MHz or higher)
Solvent: o-dichlorobenzene + heavy benzene (4: 1 (volume ratio))
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Number of integrations: 5,000 or more Spectrum attribution may be performed with reference to, for example, Macromolecules, 17, 1950 (1984). The attribution of the spectrum measured under the above conditions is as shown in the table below. In Table 1, symbols such as Sαα represent methyl carbon, S represents methylene carbon, and T represents methine carbon, respectively, according to the notation of Carman et al. (Macropolymers, 10, 536 (1977)).

Hereinafter, assuming that "P" is a propylene unit in the copolymer chain and "E" is an ethylene unit, there may be six types of triads in the chain: PPP, PPE, EPE, PEP, PEE, and EEE. As described in Macromolecules, 15, 1150 (1982), etc., the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (Tββ) (1)
[PPE] = k × I (Tβδ) (2)
[EPE] = k × I (Tδδ) (3)
[PEP] = k × I (Sββ) (4)
[PEE] = k × I (Sβδ) (5)
[EEE] = k × {I (Sδδ) / 2 + I (Sγδ) / 4} (6)
Here, the parentheses [] indicate the fraction of the triad, for example, [PPP] is the fraction of the PPP triad in all the triads. therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
Is. Further, k is a constant, I indicates the spectral intensity, and for example, I (Tββ) means the intensity of the peak of 28.7 ppm attributed to Tββ. By using the relational expressions (1) to (7) above, the fraction of each triad can be obtained, and further, the ethylene content can be obtained by the following formula.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) x 100
The ethylene content is converted from mol% to weight% using the following formula.
Ethylene content (% by weight) = (28 x X / 100) / {28 x X / 100 + 42 x (1-X / 100)} x 100
Here, X is the ethylene content in molar%.

The propylene-ethylene block copolymer (A) of the present invention may contain additives, fillers, other resin components and the like. That is, it may be a resin composition (polypropylene resin composition) of the propylene-ethylene block copolymer (A) and additives, fillers, other resin components and the like. The total amount of additives, fillers, other resin components and the like is preferably 50% by weight or less based on the resin composition.

As the additive, it can be used for polypropylene-based resins such as antioxidants, neutralizers, light stabilizers, ultraviolet absorbers, crystal nucleating agents, blocking inhibitors, lubricants, antistatic agents, and metal deactivators. Various known additives can be blended.

Examples of the antioxidant include a phenol-based antioxidant, a phosphite-based antioxidant, and a thio-based antioxidant. Examples of the neutralizing agent include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, benzotriazoles, benzophenones and the like.

Examples of the crystal nucleating agent include amide-based nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol-based derivatives, and rosin metal salts. Among these crystal nucleating agents, aluminum pt-butyl benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebis phosphate (4) , 6-di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-benzylene sorbitol, p-ethyl-benzylene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples include (4-propylphenyl) methylene] -nonitol, a sodium salt of rosin, and the like.

Examples of the lubricant include higher fatty acid amides such as stearic acid amide. Examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester. Examples of the metal deactivator include triazines, phosphons, epoxies, triazoles, hydrazides, oxamides and the like.

As the filler, various known fillers that can be used for polypropylene-based resins, such as inorganic fillers and organic fillers, can be blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber and carbon fiber. Examples of the organic filler include crosslinked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles.

Examples of other resin components include polyethylene-based resins, polyolefins such as ethylene-based elastomers, modified polyolefins, petroleum resins, and other thermoplastic resins.

The resin composition is a method of melt-kneading a propylene-ethylene block copolymer (A) with an additive, a filler, other resin components, etc., and melting the propylene-ethylene block copolymer (A) with an additive, a filler, etc. A method of dry-blending other resin components into the kneaded product, a master batch in which additives, fillers, etc. are dispersed in a carrier resin in addition to the propylene-ethylene block copolymer (A) and other resin components is dried. It can be produced by a blending method or the like.

Polypropylene resin (B)
The decorative film used in the present invention contains a layer (II) made of a polypropylene-based resin (B). The polypropylene-based resin (B) is preferably a resin that is harder to melt and relax than the polypropylene-ethylene block copolymer (A) described above. By providing the layer (II), it is possible to suppress the occurrence of poor appearance due to the film breaking or violent during thermoforming. As a result, the decorative film does not need to contain a thermosetting resin layer having excellent thermoformability in order to improve thermoformability.

The melt flow rate (230 ° C., 2.16 kg load) (hereinafter referred to as “MFR (B)”) of the polypropylene-based resin (B) needs to be lower than that of the MFR (A). The ratio of each MFR, MFR (B) / MFR (A), is less than 1, preferably 0.7 or less, and more preferably 0.5 or less. When MFR (B) / MFR (A) is in the above range, the thermoformability is good. The lower limit of MFR (B) / MFR (A) is not limited, but is preferably 0.01 or more.

The MFR (B) is not particularly limited as long as it is within the above range, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.2 g / 10 minutes or more. Within the above range, the ductility of the decorative film is good during thermoforming. The MFR (B) is preferably 20 g / 10 minutes or less, more preferably 15 g / 10 minutes or less.

The melting peak temperature (hereinafter referred to as “Tm (B)”) in the DSC measurement of the polypropylene-based resin (B) is not particularly limited, but is preferably 150 ° C. or higher, more preferably 155 ° C. or higher. When Tm (B) is in the above range, heat resistance, scratch resistance, and solvent resistance are good.

The polypropylene-based resin (B) can be selected from a metallocene-catalyzed propylene-based polymer, a Ziegler-Natta-catalyzed propylene-based polymer, and the like. Ziegler-Natta catalytic propylene-based polymers are preferred.

The polypropylene-based resin (B) in the present invention includes various propylene homopolymers (homopolypropylene), propylene-α-olefin copolymers (random polypropylene), propylene-α-olefin block copolymers (block polypropylene), and the like. A type of propylene-based polymer or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of the polymerization unit derived from the propylene monomer.

The polypropylene-based resin (B) may contain additives, fillers, colorants, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) containing the polypropylene resin (B) and additives, fillers, colorants, other resin components and the like. The total amount of additives, fillers, colorants, other resin components and the like is preferably 50% by weight or less based on the polypropylene resin composition.

As the additive, an additive or the like that may be contained in the propylene-ethylene block copolymer (A) can be used.

The polypropylene-based resin composition is prepared by a method of melt-kneading a propylene-based polymer with an additive, a filler, and other resin components, and by melt-kneading a propylene-based polymer with an additive, a filler, and the like, and drying the other resin components. It can be produced by a method of blending, a method of dry blending a masterbatch in which additives, fillers and the like are dispersed in a carrier resin in addition to a propylene polymer and other resin components at a high concentration.

When the polypropylene-based resin (B) is a polypropylene-based resin composition, it is preferable that the polypropylene-based resin composition has the characteristics of the polypropylene-based resin (B).

It is also possible to color the product in order to impart designability, and various colorants such as inorganic pigments, organic pigments, and dyes can be used for coloring. It is also possible to use bright materials such as aluminum flakes, titanium oxide flakes, and (synthetic) mica.

When the decorative molded product of the present invention is molded as a colored molded product, a colorant needs to be used only for the decorative film, so that an expensive colorant is used as compared with the case where the entire resin molded product is colored. It is possible to suppress. In addition, changes in physical properties associated with the addition of a colorant can be suppressed.

Decorative film The decorative film in the present invention includes a seal layer (I) made of a propylene-ethylene block copolymer (A) and a layer (II) made of a polypropylene-based resin (B). The decorative film can have various configurations in addition to the seal layer (I) and the layer (II). That is, even if the decorative film is a two-layer film composed of the seal layer (I) and the layer (II), it is a multilayer film having three or more layers composed of the seal layer (I) and the layer (II) and another layer. There may be. The seal layer (I) is attached along the resin molded body (base). Further, the surface of the decorative film may be textured, embossed, printed, sandplasted, scratched or the like.

The decorative film has a large degree of freedom in shape, and the end face of the decorative film is caught up to the back side of the object to be decorated, so that no seam is formed, so that the appearance is excellent. You can express various textures with. For example, when giving a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems in molding with a molded body mold to be embossed, that is, a molded body mold is required for each embossing pattern, and it is very difficult and expensive to apply complicated embossing to a curved mold. It is possible to solve the problem of being, and to obtain a decorative molded body easily embossed with various patterns.

In addition to the seal layer (I) and the layer (II), the multilayer film can be provided with a surface layer, a surface decoration layer, a printing layer, a light-shielding layer, a coloring layer, a base material layer, a barrier layer, and layers thereof. A tie layer layer and the like can be included. The layer (II) made of the polypropylene-based resin (B) may be any layer other than the seal layer among the layers constituting the multilayer film.

In the multilayer film, the layers other than the seal layer (I) and the layer (II) are preferably a layer made of a thermoplastic resin, and more preferably a layer made of a polypropylene-based resin. As long as the layers other than the seal layer (I) and the layer (II) can be distinguished from the seal layer (I) and the layer (II), the constituent polypropylene resin MFR (230 ° C., 2.16 kg load) is There are no particular restrictions. Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, the complexity of the layer structure can be suppressed, and the recyclability is further improved.

When the decorative film is a two-layer film, the seal layer (I) made of the propylene-ethylene block copolymer (A) constitutes the seal layer on the surface to be attached to the resin molded product, and the polypropylene-based resin (B). ) Consists of a surface layer opposite to the surface to be attached to the resin molded product.

When the decorative film is a multilayer film having three or more layers, between the seal layer (I) made of the propylene-ethylene block copolymer (A) and the layer (II) made of the polypropylene-based resin (B), etc. If a layer of ethylene is present, the effect of suppressing the emergence of scratches on the surface of the substrate may be reduced. Therefore, the multilayer film is a seal layer (I) made of a propylene-ethylene block copolymer (A) / a layer (II) made of a polypropylene-based resin (B) / another layer from the sticking surface side of the resin molded product. The configuration (including a plurality of layers) is preferable.

1 (a) to 1 (c) are explanatory views schematically illustrating a cross section of an embodiment of a decorative film attached to a resin molded body. In FIGS. 1 (a) to 1 (c), the arrangement of the seal layer (I) and the layer (II) will be specified and described for ease of understanding, but the layer structure of the decorative film is limited to these examples. It is not interpreted as. In the present specification, reference numeral 1 in the drawing indicates a decorative film, reference numeral 2 indicates a layer (II), reference numeral 3 indicates a seal layer (I), and reference numeral 4 indicates a surface decorative layer (III). FIG. 1A shows an example in which the decorative film 1 is made of a two-layer film, and is a layer made of a polypropylene-based resin (B) on a seal layer (I) made of a propylene-ethylene block copolymer (A). (II) is laminated. The decorative film 1 of FIG. 1B is composed of a seal layer (I), a layer (II) and a surface layer, and the layer (II) and the surface layer are laminated in this order on the seal layer (I). The decorative film 1 of FIG. 1 (c) is composed of a surface decorative layer (III) composed of a sealing layer (I), a layer (II) and a polypropylene-based resin (C), and is layered on the sealing layer (I). II) and the surface decorative layer (III) are laminated in this order.

8 (a) to 8 (c) are explanatory views schematically illustrating a cross section of an embodiment of a decorative molded body 6 in which a decorative film 1 is attached to a resin molded body 5. In FIGS. 8 (a) to 8 (c), the arrangement of the seal layer (I) and the layer (II) will be specified and described for ease of understanding, but the layer structure of the decorative film 1 is limited to these examples. It is not interpreted as. FIG. 8A shows an example in which the decorative film 1 is made of a two-layer film, and a seal layer (I) made of a propylene-ethylene block copolymer (A) is attached to the resin molded body 5 to form a seal layer. A layer (II) made of a polypropylene-based resin (B) is laminated on the (I). The decorative film 1 of FIG. 8B is composed of a seal layer (I), a layer (II) and a surface layer, and the seal layer (I) is attached to the surface of the resin molded body 5 to form a seal layer (I). The layer (II) and the surface layer are laminated on top in this order. The decorative film 1 of FIG. 8C is composed of a surface decorative layer (III) composed of a sealing layer (I), a layer (II) and a polypropylene-based resin (C), and a sealing layer (3) is formed on the surface of the resin molded body 5. I) is attached, and the layer (II) and the surface decoration layer (III) are laminated in this order on the seal layer (I).

Another preferred embodiment of the decorative film is a multilayer film containing a surface decorative layer (III) made of a surface decorative layer resin on the outermost surface on the side opposite to the surface to be attached to the resin molded product. Be done. The surface decorative layer resin is preferably a thermoplastic resin, more preferably a polypropylene-based resin (C).

The melt flow rate (230 ° C., 2.16 kg load) of the polypropylene-based resin (C) in the present invention (hereinafter, referred to as “(MFR (C)”)) preferably satisfies MFR (C)> MFR (B). By setting the value in the above range, a more beautiful surface texture can be expressed.

The polypropylene-based resin (C) in the present invention has various types such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), and a propylene α-olefin block copolymer (block polypropylene). The propylene-based polymer of the above, or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of the polymerization unit derived from the propylene monomer. The propylene-based polymer preferably does not contain a polymerization unit derived from a polar group-containing monomer. The polypropylene-based resin (C) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance and the like. Further, from the viewpoint of gloss and transparency (color development), a propylene-α-olefin copolymer is preferable. In the present invention, the polypropylene-based resin (C) constituting the surface decorative layer (III) may be the same as or different from the propylene-ethylene block copolymer (A) constituting the seal layer (I). good.

The polypropylene-based resin (C) may contain additives, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) of the polypropylene resin (C) and additives, fillers, other resin components and the like. The total amount of additives, fillers, other resin components and the like is preferably 50% by weight or less based on the polypropylene resin composition.

As the additive, an additive or the like that may be contained in the propylene-ethylene block copolymer (A) can be used.

The polypropylene-based resin composition is prepared by a method of melt-kneading a propylene-based polymer with an additive, a filler, and other resin components, and by melt-kneading a propylene-based polymer with an additive, a filler, and the like, and drying the other resin components. It can be produced by a method of blending, a method of dry blending a masterbatch in which additives, fillers and the like are dispersed in a carrier resin in addition to a propylene polymer and other resin components at a high concentration.

When the propylene-based resin (C) constituting the surface decorative layer (III) is a polypropylene-based resin composition, this polypropylene-based resin composition is a propylene-ethylene block copolymer constituting the seal layer (I). It may be the same as or different from the polypropylene-based resin composition constituting A).

The decorative film used in the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, still more preferably about 80 μm or more. By increasing the thickness of the decorative film to such a value or more, the effect of imparting designability is improved, the stability during molding is also improved, and a better decorative molded body can be obtained. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, still more preferably about 0.8 mm or less. By reducing the thickness of the decorative film to such a value or less, the time required for heating during thermoforming is shortened, the productivity is improved, and it becomes easy to trim unnecessary parts.

In the decorative film, the ratio of the thickness of the seal layer (I) to the total thickness of the decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. be. If the ratio of the thickness of the seal layer (I) to the entire decorative film is within the above value range, sufficient adhesive strength can be exhibited and scratches on the resin molded body (base) are exposed on the surface. Can be suppressed. Further, if the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, it is possible to avoid insufficient thermoformability of the decorative film.

Further, in the multilayer film in which the surface decorative layer (III) made of polypropylene resin (C) is provided on the outermost surface of the decorative film, the thickness of the entire decorative film having the thickness of the layer (III) in the decorative film. The ratio to the above is preferably 30% or less.

Production of Decorative Film The Decorative Film can be produced by various known molding methods.
For example, a method of coextruding a seal layer (I) made of a propylene-ethylene block copolymer (A) and a layer (II) made of a polypropylene-based resin (B), the seal layer (I) and the layer (II). Further, a method of coextruding with another layer, a thermal lamination method of laminating the other layer on one surface of one pre-extruded layer by applying heat and pressure, and laminating via an adhesive. Examples thereof include a dry lamination method and a wet lamination method, and an extrusion lamination method and a sand lamination method in which a polypropylene-based resin is melt-extruded onto one surface of one layer extruded in advance. As an apparatus for forming the decorative film, a known coextrusion T-die molding machine or a known laminating molding machine can be used. Among these, a coextrusion T-die molding machine is preferably used from the viewpoint of productivity.

As a method of cooling the molten decorative film extruded from the die, a method of bringing the molten decorative film into contact with one cooling roll through the air discharged from the air knife unit or the air chamber unit, or Examples thereof include a method of crimping with a plurality of cooling rolls to cool the film.

In order to impart gloss to the decorative film, a method is used in which a mirror-shaped cooling roll is surface-transferred to the design surface of the product to perform mirror surface processing.

Further, the surface of the decorative film may have a textured shape. Such a decorative film is a method in which a molten resin extruded from a die is directly pressure-bonded between a roll having an uneven shape and a smooth roll to transfer the uneven shape to a surface. It can be produced by a method of surface transfer by pressure contacting a heated roll and a smooth cooling roll. Examples of the grain shape include satin finish, animal skin tone, hairline tone, carbon tone and the like.

The decorative film may be heat-treated after the film is formed. Examples of the heat treatment method include a method of heating with a heat roll, a method of heating with a heating furnace or a far-infrared heater, a method of blowing hot air, and the like.

Decorative molded article As the molded article (object to be decorated) to be decorated in the present invention, various molded articles (hereinafter, may be referred to as "base") preferably made of polypropylene-based resin or polypropylene-based resin composition. Can be used. The molding method of the molded body is not particularly limited, and examples thereof include injection molding, blow molding, press molding, extrusion molding and the like.

Since the polypropylene-based resin is non-polar, it is a poorly adhesive polymer. However, the decorative film in the present invention has a seal layer (I) made of a propylene-ethylene block copolymer (A) and a polypropylene-based resin. By including the layer (II) made of (B), the decorative object made of polypropylene-based resin and the decorative film are adhered to each other to exhibit extremely high adhesive strength, and are attached to the surface of the decorative object. The scratches can be made inconspicuous.

As the base resin of the polypropylene-based resin and the polypropylene-based resin composition, various known propylene monomers such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, or a propylene block copolymer are mainly used. Various types of raw materials can be selected. Further, as long as the effect of the present invention is not impaired, a filler such as talc may be contained for imparting rigidity, and an elastomer or the like may be contained for imparting impact resistance. Further, the additive component and other resin components may be contained in the same manner as the polypropylene-based resin composition that can form the decorative film described above.

In the decorative molded body in which the decorative film of the present invention is attached to various molded bodies formed of polypropylene-based resin in a three-dimensional shape, VOCs contained in coatings and adhesives are greatly reduced. It can be suitably used as home appliances, vehicles (railroads, etc.), building materials, daily necessities, etc.

In the method for producing a decorative molded article of the present invention, the resin molded article and the decorative film are set in a step of preparing the above-mentioned decorative film, a step of preparing a resin molded article, and a chamber box capable of reducing pressure. A step, a step of depressurizing the inside of the chamber box, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded product, and a step of returning or pressurizing the inside of the depressurized chamber box to atmospheric pressure. It is characterized by including.

In three-dimensional decorative thermoforming, a decorative object and a decorative film are set in a chamber box that can be depressurized, the film is heated and softened while the inside of the chamber box is depressurized, and the film is pressed against the decorative object. It has a basic process of attaching the decorative film to the surface of the object to be decorated by returning the inside of the chamber box to atmospheric pressure or pressurizing the inside of the chamber box, and the film is attached under reduced pressure. As a result, it is possible to obtain a clean decorative molded product that does not generate air pools. In the production method of the present invention, any known technique can be used as long as the apparatus and conditions are suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the decoration object, the decoration film, the mechanism for pressing the decoration film, the device for heating the decoration film, and the like, or depending on the decoration film. It may be a plurality of divided ones.

Further, the mechanism for pressing the decoration target and the decoration film may be any type of a mechanism for moving the decoration target, a mechanism for moving the decoration film, and a mechanism for moving both of them.
More specifically, a typical molding method is illustrated below.

Hereinafter, a method of attaching a decorative film to a decorative object by using a three-dimensional decorative thermoforming machine will be exemplified with reference to the drawings.

As shown in FIG. 2, the three-dimensional decorative thermoforming machine of this embodiment includes chamber boxes 11 and 12 at the top and bottom, and thermoforms the decorative film 1 in the two chamber boxes 11 and 12. I am trying to do it. A vacuum circuit (not shown) and an air circuit (not shown) are piped to the upper and lower chamber boxes 11 and 12, respectively.

Further, a jig 13 for fixing the decorative film 1 is provided between the upper and lower chamber boxes 11 and 12. Further, a table 14 capable of ascending / descending is installed in the lower chamber box 12, and the resin molded body (decoration target) 5 is set on the table 14 (via a jig or the like or directly). NS. A heater 15 is incorporated in the upper chamber box 11, and the decorative film 1 is heated by the heater 15. The decoration target 5 can use a propylene-based resin composition as a substrate.

As such a three-dimensional decorative thermoforming machine, a commercially available molding machine (for example, NGF series manufactured by Fuse Vacuum Co., Ltd.) can be used.

As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 open, the decoration target 5 is placed on the table 14 in the lower chamber box 12, and the table 14 is lowered. Subsequently, the decorative film 1 is set on the film fixing jig 13 between the upper and lower chamber boxes 11 and 12 so that the seal layer (I) faces the substrate.

As shown in FIG. 4, the upper chamber box 11 is lowered, the upper and lower chamber boxes 11 and 12 are joined to close the inside of the box, and then the insides of the respective chamber boxes 11 and 12 are put into a vacuum suction state, and the heater 15 is used. The decorative film 1 is heated by the above method.

After the decorative film 1 is heated and softened, as shown in FIG. 5, the table 14 in the lower chamber box 12 is raised while the upper and lower chamber boxes 11 and 12 are in a vacuum suction state. The decorative film 1 is pressed against the decorative object 5 to cover the decorative object 5. Further, as shown in FIG. 6, by opening the upper chamber box 11 under atmospheric pressure or supplying compressed air from the air pressure tank, the decorative film 1 is brought into close contact with the decorative object 5 with a larger force.

Subsequently, the insides of the upper and lower chamber boxes 11 and 12 are opened under atmospheric pressure, and the decorative molded body 6 is taken out from the lower chamber box 12. Finally, as illustrated in FIG. 7, the edges of the unnecessary decorative film 1 around the decorative molded body 6 are trimmed.

Molding conditions The depressurization in the chamber boxes 11 and 12 may be such that no air pool is generated, and the pressure in the chamber box is 10 KPa or less, preferably 3 KPa, more preferably 1 KPa or less.

Further, in the two chamber boxes 11 and 12 divided into upper and lower parts by the decorative film 1, the pressure inside the chamber box on the side where the decorative object 5 and the decorative film 1 are attached may be within this range, and the upper and lower chamber boxes may be up and down. The drawdown of the decorative film 1 can be suppressed by changing the pressures of the chamber boxes 11 and 12 of the above.

The heating of the decorative film 1 is controlled by the heater temperature (output) and the heating time. It is also possible to measure the surface temperature of the film with a thermometer such as a radiation thermometer and use it as a guideline for appropriate conditions.

In the present invention, in order to attach the polypropylene-based decorative film 1 to the decorative object 5 made of polypropylene-based resin, it is necessary that the surface of the resin molded body 5 and the decorative film 1 are sufficiently softened or melted.

Therefore, the heater temperature needs to be higher than the melting temperature of the polypropylene-based resin constituting the decoration target 5 and the polypropylene-based resin constituting the decoration film 1. The heater temperature is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher.

The higher the heater temperature, the shorter the time required for heating, but the heater side is sufficiently heated until the inside of the decorative film 1 (or the surface opposite to the heater when the heater is installed on only one side) is sufficiently heated. The heater temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, and most preferably 400 ° C. It is as follows.

The appropriate heating time depends on the heater temperature, but at the shortest, it is preferable that the polypropylene-based decorative film is heated for a time until the re-tensioning called springback starts or longer.

That is, the decorative film heated by the heater expands thermally when heated from the solid state and sags once as the crystal melts, and when the crystal melt progresses, the molecules relax and the springback temporarily rebounds. Is observed, and then it hangs down due to its own weight. However, after springback, the crystals of the film are completely melted and the molecules are sufficiently relaxed, so that sufficient adhesive strength can be obtained.

Further, the decorative film used in the present invention can be surprisingly strongly adhered to the substrate even if it is subjected to decorative thermoforming before the tensioning is completed, which is very effective in suppressing the texture return.

On the other hand, if the heating time is too long, the film may hang down due to its own weight or may be deformed due to the pressure difference between the upper and lower chamber boxes. Therefore, the heating time is preferably less than 120 seconds after the end of springback.

When decorating a molded product having an uneven shape or achieving higher adhesive strength, it is preferable to supply compressed air when the decorative film is brought into close contact with the substrate. The pressure in the upper chamber box when compressed air is introduced is 150 kPa or more, preferably 200 kPa or more, and more preferably 250 kPa or more. The upper limit is not particularly limited, but if the pressure is too high, the equipment may be damaged. Therefore, 450 kPa or less, preferably 400 kPa or less is preferable.

Hereinafter, the present invention will be described in more detail as examples, but the present invention is not limited to this example.

1. 1. Measurement method of various physical properties (i) MFR
Measured at 230 ° C. with a 2.16 kg load according to ISO 1133: 1997 Connections M. The unit is g / 10 minutes.

(Ii) Melting point:
Using a differential scanning calorimeter (DSC), once the temperature was raised to 200 ° C. and held for 10 minutes, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and then again at a heating rate of 10 ° C./min. The temperature at the top of the endothermic peak at the time of measurement was taken as the melting point. The unit is ° C.

(Iii): Calculation of ethylene content of propylene-ethylene block copolymer (A), component (A1) and component (A2) Of propylene-ethylene block copolymer (A), component (A1) and component (A2). The ethylene content of the above was measured using the above-mentioned method for measuring the ethylene content by ^{13 C-NMR.}

2. Materials used Production of propylene-ethylene block copolymer (A) As the propylene-ethylene block copolymer (A) used for the seal layer (I) of the decorative film, both the propylene-ethylene blocks obtained in the production examples described below are used. Polymers (A-1) to (A-4) were used. The polymerization conditions and polymerization results are shown in Table 2, and the results of polymer analysis are shown in Table 3.

[Production Example A-1: Production of Propylene-Ethylene Block Copolymer (A-1)]
Analysis of catalyst composition Ti content: The sample was accurately weighed, hydrolyzed, and then measured using the colorimetric method. For the sample after prepolymerization, the content was calculated using the weight excluding the prepolymerized polymer.
Silicon compound content: The sample was accurately weighed and decomposed with methanol. The concentration of the silicon compound in the obtained methanol solution was determined by comparing with the standard sample using gas chromatography. The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in methanol and the weight of the sample. For the sample after prepolymerization, the content was calculated using the weight excluding the prepolymerized polymer.

Preparation of Prepolymerization Catalyst (1) Preparation of Solid Catalyst A 10 L capacity autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. At room temperature, 200 g of magnesium diethoxydo [Mg (OEt) ₂ ] was added, and 1 L of titanium tetrachloride (TiCl _{4) was slowly added.} The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Then, the temperature was raised to 110 ° C. and the reaction was carried out for 3 hours. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Further, using purified n-heptane, toluene was replaced with n-heptane to obtain a slurry of solid components. A part of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component was 2.7% by weight.

Next, an autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component was introduced as a solid component. Purified n-heptane was introduced to adjust the concentration of the solid component to 25 g / L. 50 ml of silicon tetrachloride (SiCl ₄ ) was added, and the reaction was carried out at 90 ° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane.

Then, purified n-heptane was introduced to adjust the liquid level to 4 L. To this, 30 ml of dimethyldivinylsilane, 30 ml of diisopropyldimethoxysilane [i-Pr ₂ Si (OMe) ₂ ], and 80 g of an n-heptane diluted solution of _{triethylaluminum (Et 3 Al) were added as Et 3} Al, and the temperature was 40 ° C. The reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A part of the obtained solid catalyst slurry was sampled, dried, and analyzed. The solid catalyst contained 1.2% by weight of Ti and 8.9% by weight of _{i-Pr 2} Si (OMe) _2.

(2) Prepolymerization Using the solid catalyst obtained above, prepolymerization was carried out by the following procedure. Purified n-heptane was introduced into the above slurry to adjust the concentration of the solid catalyst to 20 g / L. After cooling the slurry to 10 ° C., and 10g added n- heptane dilution of Et ₃ Al as Et ₃ Al, were added over 4 hours propylene 280 g. After the supply of propylene was completed, the reaction was continued for another 30 minutes. The gas phase was then thoroughly replaced with nitrogen and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a prepolymerization catalyst. This prepolymerization catalyst contained 2.5 g of polypropylene per 1 g of solid catalyst. As a result of analysis, 1.0% by weight of Ti and 8.3% by weight of _{i-Pr 2} Si (OMe) _{2 were contained in the portion of the prepolymerization catalyst excluding polypropylene.}
Using this prepolymerization catalyst, the propylene-ethylene block copolymer (A) was produced according to the following procedure.

(3) Production of propylene-ethylene block copolymer (A) Production of propylene-ethylene block copolymer using a two-tank continuous polymerization facility in which two fluidized bed-type polymerization tanks with an ^{internal volume of 2 m 3 are connected in series.} went. The propylene, ethylene, hydrogen, and nitrogen used were purified using a general purification catalyst. The production amount of the component (A1) in the first polymerization tank and the production amount of the component (A2) in the second polymerization tank were obtained from the values of the cooling water temperature of the heat exchanger used for temperature control of the polymerization tank.

First polymerization step: Production of component (A1) composed of propylene homopolymer, propylene homopolymerization was carried out using the first polymerization tank. The polymerization temperature was 65 ° C., the total pressure was 3.0 MPaG (gauge pressure, the same applies hereinafter), and the powder hold amount was 40 kg. Propylene, hydrogen, and nitrogen were continuously supplied to the polymerization tank, and the concentrations of propylene and hydrogen were adjusted to 70.83 mol% and 0.92 mol%, respectively. As a co-catalyst, Et ₃ Al was continuously supplied at a rate of 5.0 g / hour. The prepolymerization catalyst obtained above was continuously supplied to the polymerization tank so that the production amount of the component (A1) in the first polymerization tank was 20.0 kg / hour. The produced component (A1) was continuously extracted and adjusted so that the powder hold amount was constant at 40 kg. The component (A1) extracted from the first polymerization tank was continuously supplied to the second polymerization tank, and the production of the component (A2) composed of a propylene-ethylene random copolymer was continued.

Second Polymerization Step: Production of Propylene-Ethylene Random Copolymer Component (A2) Random copolymerization of propylene and ethylene was carried out using a second polymerization tank. The polymerization temperature was 65 ° C., the total pressure was 2.0 MPaG, and the powder hold amount was 40 kg. Propylene, ethylene, hydrogen, and nitrogen were continuously supplied to the polymerization tank, and the concentrations of propylene, ethylene, and hydrogen were adjusted to 54.29 mol%, 17.14 mol%, and 0.41 mol%, respectively. .. By continuously supplying ethanol as a polymerization inhibitor, the production amount of the propylene-ethylene random copolymer component (A2) in the second polymerization tank was adjusted to 6.7 kg / h. The propylene-ethylene block copolymer (A) thus produced was continuously extracted and adjusted so that the powder hold amount was constant at 40 kg. The propylene-ethylene block copolymer (A) extracted from the second polymerization tank was further transferred to a dryer and sufficiently dried.

When a part of the produced propylene-ethylene block copolymer (A) was analyzed, the MFR (A) was 7.0 g / 10 min and the ethylene content E (A) was 9.5% by weight. The weight ratio W (A1) of the component (A1) and the weight ratio W (A2) of the component (A2) were obtained from the production amount of the first polymerization step and the production amount of the second polymerization step. , 0.25.

From the W (A1), W (A2), and E (A) thus obtained, the ethylene content E (A2) of the propylene-ethylene random copolymer component (A2) was calculated.
The following formula was used for the calculation.
E (A2) = {E (A) -E (A1) x W (A1)} ÷ W (A2)
(Here, since the component (A1) is a propylene homopolymer, E (A1) is 0% by weight. Further, in the above formula, what is described for the above-mentioned E (A) is rearranged for E (A2). It was done.)
The ethylene content E (A2) was 38.0% by weight.

[Production Examples A-2 and A-3: Production of Propylene-Ethylene Block Copolymers (A-2) and (A-3)]
The propylene-ethylene block copolymers (A-2) and (A-3) were prepared in the same manner as in the production example of the propylene-ethylene block copolymer (A-1) except that the conditions shown in Table 2 were used. Manufactured.

[Production Example A-4: Production of Propylene-Ethylene Block Copolymer (A-4)]
Preparation of prepolymerization catalyst (1) Chemical treatment of silicate 3.75 liters of distilled water followed by 2.5 kg of concentrated sulfuric acid (96%) was slowly added to a glass separable flask equipped with a 10 liter stirring blade. bottom. At 50 ° C., 1 kg of montmorillonite (Benclay SL manufactured by Mizusawa Industrial Chemicals Co., Ltd .; average particle size = 25 μm, particle size distribution = 10 to 60 μm) was further dispersed, the temperature was raised to 90 ° C., and the temperature was maintained for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to collect the cake. 7 liters of distilled water was added to this cake to reslurry it, and then the cake was filtered. This washing operation was carried out until the pH of the washing liquid (filtrate) exceeded 3.5. The recovered cake was dried overnight at 110 ° C. in a nitrogen atmosphere. The weight after drying was 707 g.

(2) Drying of silicate The previously chemically treated silicate was dried by a kiln dryer. The specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (electric furnace)
Rotation speed with raised wings: 2 rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C (powder temperature)

(3) Preparation of catalyst An autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently replaced with nitrogen. To this, 200 g of dry silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry to 2,000 ml. Next, 9.6 ml of a heptane solution (0.71 M) of triisobutylaluminum was added to the silicate slurry prepared above, and the mixture was reacted at 25 ° C. for 1 hour. In parallel, to 870 ml of mixed heptane with (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium 2,180 mg (0.3 mM) , 33.1 ml of triisobutylaluminum heptane solution (0.71M) was added, and the mixture was reacted at room temperature for 1 hour. The mixture was added to the silicate slurry, stirred for 1 hour, and then mixed heptane was added to add 5,000 ml. Prepared in.

(4) Prepolymerization / Washing Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature became stable, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the residual monomer was purged, stirring was stopped, and the mixture was allowed to stand for about 10 minutes, and then 2,400 ml of the supernatant was decanted. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M) and 5600 ml of mixed heptane were added, the mixture was stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. Further, this operation was repeated three times. When the component analysis of the final supernatant was carried out, the concentration of the organoaluminum component was 1.23 mM / liter, and the concentration of zirconium (Zr) was 8.6 × 10 ^-6 g / L. The abundance of was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71M) was added, and then drying under reduced pressure was carried out at 45 ° C. A prepolymerization catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.

(5) Production of propylene-ethylene block copolymer (A) First polymerization step: Production of component (A1) composed of propylene-ethylene random copolymer (L / D = 6, contents) The product (100 liters of product) was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. In the presence of a polypropylene powder bed, while stirring at a rotation speed of 30 rpm, a prepolymerized catalyst adjusted to the upstream part of the reactor was added to the prepolymerized catalyst (as the amount of solid catalyst excluding the prepolymerized powder) at 0.444 g / hour, and triisobutylaluminum was added. It was continuously supplied at 15.0 mmol / hour. The monomer mixed gas is continuously reacted so that the temperature of the reactor is maintained at 65 ° C., the pressure is maintained at 2.00 MPaG, the ethylene / propylene molar ratio in the gas phase inside the reactor is 0.058, and the hydrogen concentration is 150 ppm. It was circulated in the reactor and vapor phase polymerization was performed. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the amount of powder bed in the reactor was constant. At this time, the amount of polymer extracted when the steady state was reached was 10.0 kg / hour.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, the ethylene content was 1.7% by weight.

Second polymerization step: Production of a component (A2) composed of a propylene-ethylene random copolymer A propylene-ethylene extracted from the first step in a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. The copolymer was continuously supplied. While stirring at a rotation speed of 25 rpm, keep the temperature of the reactor at 70 ° C. and the pressure at 1.88 MPaG, and make the ethylene / propylene molar ratio of the gas phase part in the reactor 0.450 and the hydrogen concentration 300 ppm. The monomer mixed gas was continuously circulated in the reactor to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the amount of powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 18.0 kg / hour, and the amount of polymerization reaction in the second step was controlled.
When the propylene-ethylene block copolymer (A-4) thus obtained was analyzed, the MFR was 7.0 g / 10 minutes and the ethylene content was 6.3% by weight.

Table 3 shows the results of polymer analysis of the propylene-ethylene block copolymers (A-1) to (A-4).

Pelletization of Propylene-Ethylene Block Copolymer (A) With respect to 100 parts by weight of each of the propylene-ethylene block copolymers (A) obtained in Production Examples A-1 to A-4, tetrakis [methylene-3-3]. (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate] 0.05 parts by weight of methane, 0.10 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, calcium stearate 0.05 parts by weight were mixed with a tumbler to homogenize them, and the obtained mixture was melt-kneaded at 230 ° C. using a twin-screw extruder having a diameter of 35 mm to obtain propylene-ethylene block copolymers (A-1) to (A). Each pellet of -4) was obtained.

3. 3. Other Materials Used As the resin for the seal layer (I) of the decorative film, the following polypropylene-based resins were used in addition to the above-mentioned propylene-ethylene block copolymers (A-1) to (A-4).
(A-5): Propylene homopolymer (MFR = 10 g / 10 minutes, Tm = 161 ° C., ethylene content E (A) 0% by weight, polymerized only in the first polymerization step, so component (A2) is not included), Product name "Novatec (registered trademark) FA3KM" manufactured by Japan Polypropylene Corporation
(A-6): Propylene-α-olefin copolymer (MFR = 7 g / 10 minutes, Tm = 146 ° C., ethylene content E (A) 2.5% by weight, polymerization only in the first polymerization step, so component (A2) ) Is not included), manufactured by Japan Polypropylene Corporation, product name "Novatec (registered trademark) FW3GT"

The following polypropylene-based resin was used as the resin for the decorative film layer (II).
(B-1): Propylene homopolymer (MFR = 2.4 g / 10 minutes, Tm = 161 ° C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FY6"
(B-2): Propylene homopolymer (MFR = 0.4 g / 10 minutes, Tm = 161 ° C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) EA9"
(B-3): Polypropylene resin composition (MFR = 2.) in which 96% by weight of polypropylene resin (B-1) is blended with 4% by weight of black pigment MB (EPP-K-12601 manufactured by Polycol Kogyo Co., Ltd.). 4 g / 10 minutes, Tm = 161 ° C)

The following polypropylene-based resin was used as the resin for the surface decorative layer (III) of the decorative film.
(C-1): Polypropylene resin composition blended with 100 parts by weight of polypropylene resin (A-5) by 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Milllad NX8000J"). (MFR = 10 g / 10 minutes, Tm = 164 ° C)
(C-2): Metallocene-catalyzed propylene-α-olefin copolymer (MFR = 7 g / 10 minutes, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Japan Polypropylene Corporation, trade name " Wintech (registered trademark) WFX4M "
(C-3): Polypropylene resin composition blended with 100 parts by weight of polypropylene resin (C-2) by 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Milllad NX8000J"). (MFR = 7 g / 10 minutes, Tm = 127 ° C)
(C-4): Polypropylene resin (A-5) 96% by weight with MFR = 11 g / 10 minutes white pigment MB (EPP-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80% by weight) Polypropylene resin composition blended by 4% by weight (MFR = 10 g / 10 minutes, Tm = 161 ° C.)
(C-5): Polypropylene resin composition (MFR = 10 g / 10) in which 96% by weight of polypropylene resin (A-5) is blended with 4% by weight of silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyo Color Co., Ltd.). Minutes, Tm = 161 ° C)

The following polypropylene-based resin was used as the resin for the resin molded product.
(X-1): Propylene homopolymer (MFR = 40 g / 10 minutes, Tm = 165 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) MA04H"
(X-2): Propylene-ethylene block copolymer (MFR = 30 g / 10 minutes, Tm = 164 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) NBC03HR"
(X-3): 60% by weight of polypropylene resin (X-2), 20% by weight of EBR (Toughmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Talc) Talc P-6 manufactured by Co., Ltd., average particle size 4.0 μm) 20% by weight blended polypropylene resin composition

3. 3. Production of Resin Molded Body (Base) Using polypropylene-based resins (X-1) to (X-3), an injection molded product was obtained by the following method. Further, the obtained injection molded product was scratched by the following method to obtain a resin molded product (base).
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 100 tons Cylinder temperature: 200 ° C
Mold temperature: 40 ° C
Injection mold: Width x Height x Thickness = 120 mm x 120 mm x 3 mm Flat plate Condition adjustment: Hold for 5 days in a constant temperature and humidity chamber with a temperature of 23 ° C and a humidity of 50% RH Processing for scratch evaluation: Temperature 23 ° C, humidity Scratch tester (ROCKWOOD SYSTEMS AND EQUIPMENT "SCRATCH & MAR TESTER") in a constant temperature and humidity chamber with 50% RH, and a pull with a shape (radius of curvature 0.5 mm, ball shape) processed under a load of 25 N. The injection molded body was scratched by scratching at the scratching tip at a scratching speed of 100 mm / min.

When the scratches on the surface of the resin molded body (base) were measured with a shape measuring instrument laser microscope (“VX-X200” manufactured by KEYENCE), the depth of the scratches was 16 μm. In addition, the scratch was a whitening scratch.

Example 1
-Manufacture of decorative film Two types of two layers with a lip opening of 0.8 mm and a die width of 400 mm, to which an extruder-1 for a seal layer with a diameter of 30 mm (diameter) and an extruder-2 with a diameter of 40 mm (diameter) are connected. A T-die was used. A propylene-ethylene block copolymer (A-1) is charged into the seal layer extruder-1, and a polypropylene-based resin (B-1) is charged into the extruder-2. The resin temperature is 240 ° C., and the seal layer extruder is used. Melt extrusion was performed under the conditions that the discharge amount of -1 was 4 kg / h and the discharge amount of the extruder-2 was 12 kg / h. The melt-extruded film was cooled and solidified while being pressed with an air knife against a first roll rotated at 3 m / min at 80 ° C. so that the seal layer was on the outside, and a seal layer having a thickness of 50 μm and a layer having a thickness of 150 μm were formed. A laminated two-layer unstretched film was obtained.

-As the three-dimensional decorative thermoformed resin molded body (base) 5, an injection molded body made of the polypropylene-based resin (X-1) obtained above was used.
As a three-dimensional decorative thermoforming apparatus, "NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 is cut out with a width of 250 mm and a length of 350 mm so that the seal layer faces the substrate and the longitudinal direction is the MD direction of the film, and the size of the opening is 210 mm. It was set on a film fixing jig 13 of × 300 mm. The resin molded body (base) 5 is placed on a sample setting table having a height of 20 mm, which is installed on a table 14 located below the film fixing jig 13, and is manufactured by Nichiban Co., Ltd. “Nystack NW-K15”. I pasted it through. The film fixing jig 13 and the table 14 were installed in the chamber boxes 11 and 12, and the chamber boxes were closed to close the inside of the chamber boxes 11 and 12. The chamber box is divided into upper and lower parts via a decorative film 1. With the upper and lower boxes vacuum sucked and the pressure reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80% to form the decorative film 1. It was heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. Immediately after the decorative film 1 is heated and temporarily sags, and then the springback phenomenon of tensioning back is completed (that is, the heating time after the springback phenomenon is 0 seconds), the table 14 installed in the lower chamber box 12 Is moved upward, the resin molded body (base) 5 is pressed against the decorative film 1, and immediately after that, compressed air is sent so that the pressure in the upper chamber box 11 becomes 270 kPa to form the resin molded body (base) 5 and the resin molded body (base) 5. The decorative film 1 was brought into close contact. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was attached to the upper surface and the side surface of the resin molded body (base) 5 was obtained.

-Evaluation of physical properties (1) Evaluation of thermoformability The draw-down state of the decorative film during three-dimensional decorative thermoforming, and the attached state of the decorative film of the decorative molded body with the decorative film attached to the substrate. It was visually observed and evaluated according to the criteria shown below.
◯: During three-dimensional decorative thermoforming, the decorative film did not draw down and the substrate and the decorative film were in contact with each other at the same time on the entire contact surface, so that contact unevenness did not occur and the film was evenly attached. ing.
X: During three-dimensional decorative thermoforming, the decorative film drew down significantly, causing uneven contact on the entire surface of the substrate.

(2) Adhesive strength between the resin molded body (base) and the decorative film "Craft Adhesive Tape No. 712N" manufactured by Nitoms Co., Ltd. was cut out to a width of 75 mm and a length of 120 mm, and from the end of the resin molded body (base). It was attached to a resin molded body (base) in a range of 75 mm × 120 mm and subjected to masking treatment (the exposed portion of the surface of the base has a width of 45 mm and a length of 120 mm). The masking surface of the resin molded body (base) was installed in the three-dimensional decorative thermoforming apparatus NGF-0406-SW so as to come into contact with the decorative film, and three-dimensional decorative thermoforming was performed.

The decorative film surface of the obtained decorative molded product was cut to the surface of the substrate with a width of 10 mm using a cutter in the direction perpendicular to the longitudinal direction of the adhesive tape to prepare a test piece. In the obtained test piece, the adhesive surface between the substrate and the decorative film has a width of 10 mm and a length of 45 mm. Attached to a tensile tester so that the base part of the test piece and the decorative film part are 180 °, 180 ° peel strength of the adhesive surface is measured at a tensile speed of 200 mm / min, and the maximum strength at the time of peeling or breaking is measured. (N / 10 mm) was measured 5 times, and the average strength was taken as the adhesive strength.

(3) Evaluation of the effect of making scratches inconspicuous Shape measurement of the scratch depth of the scratched part of the three-dimensional decorative thermoformed product of the molded body (base) damaged by a load of 25 N Laser microscope (Measured by KEYENCE "VX-X200"). The number of measurements was n = 5, and the average value was defined as the scratch depth (μm).
Further, as the whitening appearance, it was visually determined and evaluated based on the following criteria whether or not the whitening scratches on the molded body (base) damaged by the load of 25 N were not conspicuous by the decorative film.
◯: Traces of whitening scratches are inconspicuous, and the appearance is excellent.
X: Whitening scratches remain as a whole, and the appearance is poor.

(4) Gloss The gloss near the center of the decorative molded product to which the decorative film was attached was measured at an incident angle of 60 ° using a GLOSS meter Gloss Meter VG2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The measuring method was based on JIS K7105-1981.

(5) Evaluation of Recyclability The obtained decorative molded product was crushed to obtain a recycled molded product by injection molding in the same manner as in the production of the resin molded product (base), and the appearance was visually evaluated. Those with excellent appearance are marked with "○".

Table 4 shows the results of evaluation of the physical properties of the obtained decorative molded product and the like.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 2
Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to the propylene-ethylene block copolymer (A-2) in the production of the decorative film of Example 1. The evaluation was performed in the same manner as above. The evaluation results are shown in Table 4.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 3
Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to the propylene-ethylene block copolymer (A-3) in the production of the decorative film of Example 1. The evaluation was performed in the same manner as above. The evaluation results are shown in Table 4.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 4
Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to the propylene-ethylene block copolymer (A-4) in the production of the decorative film of Example 1. The evaluation was performed in the same manner as above. The evaluation results are shown in Table 4.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 5
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the polypropylene-based resin (B-1) used for the layer (II) was changed to the polypropylene-based resin (B-2). rice field. The evaluation results are shown in Table 4.
Since the polypropylene resin (A) and the polypropylene resin (B) all satisfy the requirements of the present invention, the obtained decorative molded product was excellent in appearance and adhesive strength, and scratches were inconspicuous. In addition, the recycled molded product had an excellent appearance.

Comparative Example 1
In the production of the decorative film of Example 1, the same as in Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to the propylene homopolymer (A-5). Evaluation was performed. The evaluation results are shown in Table 4.
Since the propylene homopolymer (A-5) used for the seal layer does not contain the component (A2), the adhesive strength is small, and the appearance of scratches cannot be sufficiently suppressed, resulting in inferior appearance. there were.

Comparative Example 2
Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to a propylene-ethylene random copolymer (A-6) in the production of the decorative film of Example 1. The evaluation was performed in the same manner as above. The evaluation results are shown in Table 4.
Since the propylene-ethylene random copolymer (A-6) used for the seal layer does not contain the component (A2), the adhesive strength is low, and the appearance of scratches cannot be sufficiently suppressed, resulting in an appearance. It was inferior.

Comparative Example 3
In the production of the decorative film of Example 1, the propylene-ethylene block copolymer (A-1) used for the seal layer was changed to a propylene-ethylene random copolymer (A-5), and further three-dimensional decoration was performed. In the thermoforming, the evaluation was carried out in the same manner as in Example 4 except that heating was continued for 20 seconds after the springback phenomenon was completed and then decorative thermoforming was performed. The evaluation results are shown in Table 1.
Although the adhesive strength was improved by lengthening the film heating time, the drawdown of the film was severe and the appearance of the decorative molded product was inferior, and scratches were not evaluated.

Example 6
In the three-dimensional decorative thermoforming of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the substrate was changed to an injection molded product using a resin (X-2). The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 7
In the three-dimensional decorative thermoforming of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the substrate was changed to an injection molded product using a resin (X-3). The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the recycled molded product had an excellent appearance.

Example 8
In the production of the decorative film of Example 1, a seal layer extruder-1 having a diameter of 30 mm (diameter), an extruder-2 having a diameter of 40 mm (diameter), and a surface layer extruder having a diameter of 30 mm (diameter)- A three-kind three-layer T-die having a lip opening of 0.8 mm and a die width of 400 mm to which 3 was connected was used. Polypropylene resin (A-1) is used for the seal layer extruder-1, polypropylene resin (B-1) is used for the extruder-2, and polypropylene resin (A-5) is used for the surface layer extruder-3. The resin temperature is 240 ° C., the discharge amount of the seal layer extruder-1 is 4 kg / h, the discharge amount of the extruder-2 is 8 kg / h, and the discharge amount of the surface layer extruder-3 is 4 kg / h. The melt extrusion was performed under the conditions of.

The melt-extruded film was cooled and solidified on a cooling roll rotating at 80 ° C. and 3 m / min so that the surface decorative layer was in contact with the surface decorative layer, and the surface decorative layer having a thickness of 50 μm and the layer having a thickness of 100 μm were formed. A three-layer unstretched film having a 50 μm seal layer laminated on it was obtained.

The evaluation was carried out in the same manner as in Example 1 except that the unstretched film obtained in the above-mentioned production of the decorative film was used. The evaluation results are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. Further, the polypropylene-based resin (A-5) was laminated on the outermost surface side as the surface decorative layer (III), resulting in excellent gloss. In addition, the recycled molded product had an excellent appearance.

Example 9
In the production of the decorative film of Example 8, the evaluation was carried out in the same manner as in Example 8 except that the polypropylene-based resin (A-5) used for the surface decorative layer was changed to the polypropylene-based resin (C-1). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. Further, the polypropylene-based resin (C-1) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorative layer (III), resulting in excellent gloss. In addition, the recycled molded product had an excellent appearance.

Example 10
In the production of the decorative film of Example 8, the evaluation was carried out in the same manner as in Example 8 except that the polypropylene-based resin (A-5) used for the surface decorative layer was changed to the polypropylene-based resin (C-2). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. Further, the polypropylene-based resin (C-2) was laminated on the outermost surface side as the surface decorative layer (III), resulting in excellent gloss. In addition, the recycled molded product had an excellent appearance.

Example 11
In the production of the decorative film of Example 8, the evaluation was carried out in the same manner as in Example 8 except that the polypropylene-based resin (A-5) used for the surface decorative layer was changed to the polypropylene-based resin (C-3). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. Further, the polypropylene-based resin (C-3) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorative layer (III), resulting in excellent gloss. In addition, the recycled molded product had an excellent appearance.

Example 12
In the production of the decorative film of Example 8, the evaluation was carried out in the same manner as in Example 8 except that the polypropylene-based resin (A-5) used for the surface decorative layer was changed to the polypropylene-based resin (C-4). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the white-colored decorative film was attached, and the scratches were sufficiently concealed so that the scratched part could not be identified. Therefore, the wound depth was not measured. Further, since the surface decorative layer (III) having excellent gloss was colored white, the appearance was excellent. In addition, the recycled molded product had an excellent appearance.

Example 13
In the production of the decorative film of Example 8, the evaluation was carried out in the same manner as in Example 8 except that the polypropylene-based resin (B-1) used for the layer (II) was changed to the polypropylene-based resin (B-3). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the black-colored decorative film was attached, and the scratches were sufficiently concealed so that the scratched part could not be identified. Therefore, the wound depth was not measured. Further, since the layer (II) was colored black, the appearance was excellent. Further, since the polypropylene-based resin (A-5) is laminated on the outermost surface side as the surface decorative layer (III), the result is excellent in gloss. In addition, the recycled molded product had an excellent appearance.

Example 14
In the production of the decorative film of Example 13, the evaluation was carried out in the same manner as in Example 13 except that the polypropylene-based resin (A-5) used for the surface decorative layer was changed to the polypropylene-based resin (C-5). rice field. The results obtained are shown in Table 5.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded product has excellent appearance and adhesive strength, and scratches are not noticeable. It was a thing. In addition, the colored decorative film was attached, and the scratches were sufficiently concealed so that the damaged part could not be identified. Therefore, the wound depth was not measured. Further, since the polypropylene-based resin (C-5) was laminated on the outermost surface side as the surface decorative layer (III), the result was excellent in gloss. Further, since the layer (II) is colored black and the surface layer decorative layer (III) is colored silver, the film is metallic and has an excellent appearance. In addition, the recycled molded product had an excellent appearance.

Example 15
-Manufacture of Decorative Film In the production of the decorative film of Example 14, the discharge amount of the seal layer extruder-1 is 4 kg / h, the discharge amount of the extruder-2 is 12 kg / h, and the surface layer extruder-. Melt extrusion was performed under the condition that the discharge rate of 3 was 4 kg / h, and the obtained three layers of unstretched film were slit to a width of 200 mm to form a surface decorative layer having a thickness of 50 μm and a layer having a thickness of 150 μm. , A three-layer unstretched film in which a seal layer having a thickness of 50 μm was laminated was obtained.

-Manufacturing of embossed film An electric heating type test embossing machine manufactured by Yuri Roll Co., Ltd. was used as an embossing molding device. The electric heating type test embossing machine heat-presses the film with a roll (embossed roll) that has a heatable uneven shape installed in the upper stage and a smooth roll installed in the lower stage, so that the uneven shape of the upper stage is formed. Has a mechanism to transfer to the film surface. For the embossing roll, a hairline pattern having a depth of 0.030 mm was used.
The three layers of unstretched film obtained by producing the decorative film were fed out to two rolls of the embossing machine so that the surface decorative layer was in contact with the embossing roll. By performing embossing transfer under the conditions of an embossing roll temperature of 145 ° C., a contact pressure of 3 MPa, and a roll speed of 3 m / min, a decorative film having a hairline pattern transferred to the surface of the surface decorative layer was obtained.

-Three-dimensional decorative thermoforming A three-dimensional decorative thermoforming product was obtained in the same manner as in Example 1.

-Evaluation of physical properties (1) Evaluation of embossed transfer The depth of the hairline pattern part applied to the surface decorative layer of the obtained decorative film was measured with a shape measurement laser microscope ("VX-X200" manufactured by KEYENCE). .. The number of measurements was n = 5, and the average value was taken as the embossing depth (μm).

(2) Evaluation of embossed pattern after thermoforming The remaining embossed pattern after three-dimensional decorative thermoforming was visually observed and evaluated according to the following criteria.
◯: The embossed pattern remains on the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design is excellent.
X: The embossed pattern disappears on most of the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design is inferior.

Table 6 shows the results of evaluation of the physical properties of the obtained decorative molded product and the like.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the embossing depth of the film obtained by producing the embossed film was excellent at 24 μm. Further, the hairline pattern remained strongly on the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design was excellent.

According to the present invention, sufficient adhesive strength and product appearance can be achieved at the same time, there is little wrinkle return, product defects can be reduced by making scratches on the substrate inconspicuous, and three-dimensional addition that facilitates recycling. A decorative film used for decorative thermoforming and a method for producing a decorative molded product using the same are provided.

1 Decorative film 2 layers (II)
3 Seal layer (I)
5 Resin molded body (decoration target, substrate)
6 Decorative molding 11 Upper chamber box 12 Lower chamber box 13 Jig 14 Table 15 Heater

Claims (5)

A step of preparing a decorative film, a step of preparing a resin molded body, a step of setting the resin molded body and the decorative film in a decompressable chamber box, a step of depressurizing the inside of the chamber box, the decoration A method for producing a decorative molded product, which comprises a step of heating and softening the film, a step of pressing the decorative film against the resin molded product, and a step of returning or pressurizing the inside of the depressurized chamber box to atmospheric pressure.
The decorative film is a decorative film for being attached onto a resin molded body by thermal molding, and the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A) and polypropylene. The propylene-ethylene block copolymer (A) contains the layer (II) composed of the based resin (B), satisfies the following requirements (a1) to (a3), and the polypropylene-based resin (B) meets the following requirements (b1). ) Satisfying the above. A method for manufacturing a decorative molded product using a decorative film.
Requirements for propylene-ethylene block copolymer (A) (a1) The component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer is 5 to 97% by weight, and the ethylene content is higher than that of the component (A1). It contains 3 to 95% by weight of a component (A2) composed of a large amount of propylene-ethylene random copolymer.
(A2) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(A3) The melting peak temperature (Tm (A)) is 110 to 170 ° C.
The requirement (b1) melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) of the polypropylene-based resin (B) satisfies the following relational expression (b-1) with respect to the MFR (A).
MFR (B) <MFR (A) ... Equation (b-1) The method for producing a decorative molded product using the decorative film according to claim 1, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a4).
(A4) The ethylene content in the propylene-ethylene block copolymer (A) is 0.15 to 85% by weight. The method for producing a decorative molded product using the decorative film according to claim 1 or 2, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a5).
(A5) The ethylene content of the component (A1) is in the range of 0 to 6% by weight. The method for producing a decorative molded product using the decorative film according to any one of claims 1 to 3, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a6).
(A6) The ethylene content of the component (A2) is in the range of 5 to 90% by weight. The method for producing a decorative molded product using the decorative film according to any one of claims 1 to 4, wherein the resin molded product is made of a propylene-based resin composition.

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