JP7120384B2 - Method for manufacturing decorative molding using decorative film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a decorative molded article using a decorative film to be adhered onto a resin molded article by thermoforming. Specifically, it can suppress wrinkles and film breakage of the film during thermoforming, can exhibit sufficient adhesive strength to the resin molded body, and can be contained in the film during thermoforming. The present invention relates to a method for producing a decorative molded article using a decorative film to be adhered onto a resin molded article by thermoforming, which causes less damage to the film such as additives migrating out of the film.

In recent years, demand for decoration techniques to replace painting has increased due to demands for reduction of VOCs (volatile organic compounds), etc., and various decoration techniques have been proposed.

Among them, a technique has been proposed for forming a decorative molded article in which a decorative film and a molded body are integrated by applying a decorative film instead of a coating film to a molded body by vacuum pressure forming or vacuum forming (for example, Patent Document 1 ), which has received particular attention in recent years.

Decoration molding by vacuum pressure molding and vacuum molding has a greater degree of freedom in shape than other decoration molding represented by insert molding. The appearance is excellent because it does not occur, and it can be thermoformed at a relatively low temperature and low pressure, so it has the advantage of excellent reproducibility of texture when using a decorative film with texture on the surface. .

In such decorative molding by vacuum pressure forming and vacuum forming, when the decorative film and the molded article are adhered, wrinkles or film breakage may occur in the decorative film, or adhesion between the decorative film and the molded article may occur. There was a problem that sufficient strength could not be obtained. Also, the use of adhesives, tackifiers, etc. has been proposed as a layer for improving the adhesive strength, but they are expensive, the layer structure is extremely complicated, and the solvent resistance and heat resistance are insufficient. , etc.

In order to solve such problems, a decorative film including an adhesive layer containing a polypropylene-based resin is applied to a substrate (molded article) made of a polypropylene-based resin, so that the decorative film and the molded article are heat-sealed. has been proposed (see Patent Documents 2 and 3, for example). The inventions disclosed in Patent Documents 2 and 3 use a polypropylene-based resin as the adhesive layer of the decorative film. 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 drawdown property is expressed, and it is possible to ensure thermoformability in a decorative film made of polypropylene-based resin that does not contain these different kinds of raw materials. The surface of the molded product to which this was adhered was likely to have holes, wrinkles, and entrainment of air, and the membrane was broken, making it impossible to obtain a decorative molded product with excellent appearance. In particular, when polyurethane resin is included as a different raw material, polyurethane resin, which is a thermosetting resin, does not melt when heated, so it is easy to maintain the shape of the film and greatly improves thermoformability, 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, and the layer structure is complicated and many steps are required for its production. Another problem is that it is difficult to recycle decorative films in which different kinds of raw materials are combined.

Furthermore, there is a problem that the film is heated and melted during thermoforming, causing a phenomenon called grain return, in which the grain on the surface of the film disappears.

In addition, the decorative thermoforming by vacuum pressure forming and vacuum forming has the advantage that a molded product having a high degree of integration between the base formed by the process such as injection molding and the decorative film can be obtained. There is a problem that scratches on the surface of the decorative molded product tend to cause poor appearance due to scratches on the surface of the base.

JP-A-2002-67137 JP 2013-14027 A JP 2014-124940 A

Conventional techniques have not yet achieved a decorative film made of a propylene-based resin that is easy to recycle and has both adhesiveness and appearance. In view of the above problems, the problem of the present invention is to achieve both sufficient adhesive strength and product appearance, reduce grain return, make scratches on the substrate inconspicuous, and reduce product defects. An object of the present invention is to provide a method for producing a decorated molding using a decorative film used for three-dimensional decorative thermoforming, which facilitates manufacturing.

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 adhere the solid decorative film to the solid resin molded body. Therefore, it is important to apply heat necessary for softening or melting the surface of the molded article and the film, or to use a molded article and film that are easily softened or melted. On the other hand, if the film is heated sufficiently too much, the viscosity of the film will decrease, and the film will break due to the push-up of the molded product in the three-dimensional decoration thermoforming process or the inflow of air when returning the vacuum chamber to atmospheric pressure. or violent behavior leads to poor appearance. In addition, if the film is heated too much, the additives contained in the film migrate out of the film, resulting in a problem of lowering the functions derived from the additives such as heat resistance, weather resistance, and nucleation performance. Furthermore, there arises a problem that grain return tends to occur. Therefore, the inventors of the present invention not only solved these problems, but also focused on and studied the configuration of the decorative film in order to make the scratches on the substrate surface less noticeable. As a result, the seal layer (I) made of the propylene-ethylene block copolymer (A) capable of exhibiting good adhesive strength and the decrease in the viscosity of the entire film are suppressed to maintain the thermoformability and suppress the return of the grain. It was found that the above problems can be solved by combining the layer (II) made of the polypropylene-based resin (B).
Furthermore, the present inventors have surprisingly found that such a decorative film has a high effect of making scratches less noticeable and can solve the above problems, and have completed the present invention.

That is, the present invention comprises any one 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 decompressible chamber box, and a step of reducing the pressure in the chamber box; A method for producing a decorated molded product, comprising the steps of: heating and softening the decorative film; pressing the decorative film against the resin molded product; hand,
The decorative film is a decorative film to be adhered onto the resin molding by thermoforming, and the decorative film comprises a seal layer (I) made of a propylene-ethylene block copolymer (A) and a polypropylene The layer (II) made of the resin (B) is included, the propylene-ethylene block copolymer (A) satisfies the following requirements (a1) to (a3), and the polypropylene resin (B) satisfies the following requirements (b1 ) is satisfied.
Requirements for the propylene-ethylene block copolymer (A) (a1) 5 to 97% by weight of the component (A1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and having a higher ethylene content than the component (A1) It contains 3 to 95% by weight of component (A2) consisting of a propylene-ethylene random copolymer.
(a2) 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.
Requirement (b1) melt flow rate (230° C., 2.16 kg load) (MFR (B)) of polypropylene resin (B) satisfies the following relational expression (b-1) with respect to MFR (A).
MFR(B)<MFR(A) Formula (b-1)
(ii) The method for producing a decorated molded article using a 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 decorated molded article using the decorative film according to (i) or (ii), wherein the following requirement (a5) is satisfied: Production method.
(a5) The ethylene content of component (A1) is in the range of 0 to 6% by weight.
(iv) Decoration using 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 producing a molded article.
(a6) The ethylene content of component (A2) is in the range of 5 to 90% by weight.
(v) A method for producing a decorated molded article using a decorative film according to any one of (i) to (iv) above, wherein the resin molded article is made of a propylene-based resin composition.

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

According to the method for producing the decorated molded article of the present invention, the surface has no holes or wrinkles, air is not entrained between the decorative film and the resin molded article, texture such as embossing can be reproduced with good reproducibility, It is possible to obtain a beautiful decorative molding with inconspicuous scratches. In addition, the decorative film can be adhered neatly to resin moldings that have conventionally been difficult to adhere to. Furthermore, in the thus-obtained decorative molded article, the constituent materials of the decorative film are the propylene-ethylene block copolymer (A) and the polypropylene-based resin (B), and the thermosetting resin layer is not included. Since it does not need to be contained or contained, there is little deterioration in appearance and performance during recycling, and it is highly recyclable.

1 is a diagram showing an example of the layer structure of a decorative film used in the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view for explaining the outline of an apparatus used in the method for manufacturing a decorative molded article of the present invention; FIG. 3 is a schematic cross-sectional view for explaining how a resin molding and a decorative film are set in the apparatus of FIG. 2; FIG. 3 is a schematic cross-sectional view for explaining how the inside of the apparatus of FIG. 2 is heated and depressurized; FIG. 3 is a schematic cross-sectional view for explaining how a decorative film is pressed against a resin molding in the apparatus of FIG. 2; FIG. 3 is a schematic cross-sectional view illustrating how the inside of the apparatus of FIG. 2 is returned to atmospheric pressure or pressurized. FIG. 4 is a schematic cross-sectional view for explaining how the edge of the unnecessary decorative film is trimmed in the obtained decorative molded article. It is a figure which shows an example of the layer structure of the decorative molding of this invention.

As used herein, a decorative film refers to a film for decorating a molded article. Decorative molding refers to molding in which a decorative film and a molded body are adhered together. Three-dimensional decorative thermoforming is a process of adhering a decorative film to a molded body, and includes a step of thermoforming the decorative film along the adhering surface of the molded body and simultaneously adhering it, In this step, thermoforming is performed under reduced pressure (vacuum) in order to prevent air from being entrained between the decorative film and the molded article, the heated decorative film is adhered to the molded article, and pressure is applied. It refers to molding, which is the process of bringing into close contact by releasing (pressurizing). BEST MODE FOR CARRYING OUT THE INVENTION 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 to be adhered onto a resin molding by thermoforming, and the decorative film is a seal layer (I ) and a layer (II) made of a polypropylene resin (B), the propylene-ethylene block copolymer (A) satisfies the following requirements (a1) to (a3), and the polypropylene resin (B) is the following It is characterized by satisfying the requirement (b1).
Requirements for the propylene-ethylene block copolymer (A) (a1) 5 to 97% by weight of the component (A1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer component, and an ethylene content higher than that of the component (A1) 3 to 95% by weight of the component (A2) consisting of a propylene-ethylene random copolymer having a large amount of
(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 to 170 ° C. be.
Requirement (b1) melt flow rate (230° C., 2.16 kg load) (MFR (B)) of polypropylene resin (B) satisfies the following relational expression (b-1) with respect to MFR (A).
MFR(B)<MFR(A) Formula (b-1)

Seal layer (I)
The decorative film contains a sealing layer (I) made of a propylene-ethylene block copolymer (A). The seal layer (I) is a layer that comes into contact with the resin molding (substrate) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength can be exhibited even if the film is heated for a short time during three-dimensional thermoforming, 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 comprises a component (A1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and a propylene-ethylene containing more ethylene than the component (A1). It contains a component (A2) consisting of a random copolymer. The component (A2), which is a rubber component in the propylene-ethylene block copolymer (A), improves the adhesive strength to the resin molding (substrate). In addition, the component (A2) has a highly uniform dispersion form in propylene, and is highly effective in making scratches inconspicuous. The propylene-ethylene block copolymer (A) is prepared by (co)polymerizing the component (A1) consisting of propylene alone or a propylene-ethylene random copolymer in the first polymerization step, and then the component (A1) in the second polymerization step. obtained by successive copolymerization of the component (A2) comprising a propylene-ethylene random copolymer containing a large amount of ethylene.

(a1) Ratio of component (A1) and component (A2) It is necessary that the proportion of (A1) is 5 to 97% by weight and the proportion of component (A2) is 3 to 95% by weight. Preferably, the proportion of component (A1) is 30 to 95% by weight and the proportion of component (A2) is 5 to 70% by weight, and more preferably the proportion of component (A1) is 52 to 92% by weight and component (A2) is 8 to 48% by weight. When the ratio of the component (A1) and the ratio of the component (A2) are within the above range, sufficient adhesive strength can be exhibited, and the effect of making scratches less noticeable is high. Moreover, when it is 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 must be exceeded, preferably 1 g/10 min or more, more preferably 2 g/10 min or more. When the MFR (A) is within the above range, the relaxation of the propylene-ethylene block copolymer (A) can be sufficiently progressed during three-dimensional decorative thermoforming, and sufficient adhesive strength can be exhibited, and at the same time, it can be adhered to the substrate. Scratches become less noticeable. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

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

(a3) Melting peak temperature The melting point (melting peak temperature) (hereinafter referred to as "Tm(A)") of the propylene-ethylene block copolymer (A) must be 110 to 170°C. It is preferably 113 to 169°C, more preferably 115 to 168°C. When Tm(A) is within the above range, moldability during three-dimensional decorative thermoforming is good. The peak melting temperature is mainly derived from the component (A1) with a low ethylene content, that is, the component (A1) with high crystallinity, and the peak melting temperature can be changed depending on the content of ethylene to be copolymerized.

(a4) Ethylene content (E(A)) in propylene-ethylene block copolymer (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. More preferably 0.5 to 75% by weight, still more preferably 2 to 50% by weight. When E(A) is within the above range, sufficient adhesive strength can be exhibited, and adhesiveness to layer (II) of the decorative film is good, and film formability is also excellent.

(a5) Ethylene content of component (A1) (E (A1))
Component (A1) is a propylene homopolymer or 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 preferred. More preferably 0 to 5% by weight. When E(A1) is within the above range, the moldability during three-dimensional decoration thermoforming is good, and the film is less sticky and excellent in film moldability.

(a6) Ethylene content of component (A2) (E (A2))
The ethylene content of component (A2) (hereinafter referred to as "E(A2)") is higher than the ethylene content E(A1) of component (A1). Further, it is preferably a propylene-ethylene random copolymer in which E(A2) is in the range of 5 to 90% by weight. E(A2) is more preferably 7 to 80% by weight, more preferably 9 to 50% by weight. When E(A2) is within the above range, sufficient adhesive strength can be exhibited, and the effect of making scratches less noticeable is high.

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

・Materials used The catalysts used in the production of 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 consisting of a titanium-catalyzed solid catalyst component and an organoaluminum, or a metallocene catalyst can be used. A specific catalyst manufacturing method is not particularly limited, but examples include the Ziegler catalyst disclosed in JP-A-2007-254671 and the metallocene catalyst disclosed in JP-A-2010-105197. can be done.

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

-Polymerization step The polymerization step performed in the presence of the catalyst consists of multiple steps 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 propylene/ethylene mixture is supplied to the polymerization system to which the catalyst is added to produce a propylene homopolymer or a propylene-ethylene random copolymer. In this step, component (A1) is formed in an amount corresponding to 5 to 97% by weight of the combined amount.

The MFR of 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 as a chain transfer agent is increased, the MFR (A1) of 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 can be increased, and adjustment is extremely easy for those skilled in the art. Further, 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 reactor as means for controlling the ethylene content. Specifically, the ethylene content of the component (A1) is increased by increasing the ratio of ethylene to propylene supplied to the polymerization reactor (ethylene supply amount/propylene supply amount). The same is true vice versa. The relationship between the ratio of propylene and ethylene supplied to the polymerization reactor and the ethylene content of component (A1) varies depending on the type of catalyst used, but the component having the desired ethylene content can be obtained by appropriately adjusting the supply ratio. Obtaining (A1) is extremely easy for those skilled in the art.

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

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

Next, a method for controlling the index of the propylene-ethylene block copolymer (A) will be explained.
First, a method for controlling the weight ratio of component (A1) and component (A2) will be described. The weight ratio of component (A1) to component (A2) is controlled by the production amount in the first polymerization step for producing component (A1) and the production amount in the second polymerization step for producing component (A2). For example, in order to increase the amount of component (A1) and decrease the amount of component (A2), the production amount in the second polymerization step may be reduced while maintaining the production amount in the first polymerization step. 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 addition if it is already added. And vice versa.

Usually, the weight ratio of component (A1) to component (A2) is defined by the production amount in the first polymerization step for producing component (A1) and the production amount in the second polymerization step for producing component (A2). The formula is shown below.
Weight of component (A1): weight of component (A2) = W(A1):W(A2)
W (A1) = Production amount in the first polymerization step ÷ (Production amount in the first polymerization step + Production amount in the second polymerization step)
W (A2) = production amount in the second polymerization step / (production amount in the first polymerization step + production amount in 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 facilities, it is common to obtain the production amount from the heat balance and material balance of each polymerization tank. Further, when the crystallinity of the component (A1) and the component (A2) are sufficiently different, the two may be separated and identified using an analysis method such as TREF (temperature rising elution fractionation method) to determine the quantitative ratio. Techniques for evaluating the crystallinity distribution of polypropylene by TREF measurement are well known to those skilled in the art. Glokner, J.; Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990); Wild, Adv. Polym. Sci. 98, 1-47 (1990), J. Am. B. P. Soares, A.; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995) and other literatures show detailed measurement methods.

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

This formula shows the material balance with respect to ethylene content.
Therefore, if the weight ratio of component (A1) and component (A2) is determined, that is, if W(A1) and W(A2) are determined, E(A) is uniquely defined by E(A1) and E(A2). Determined by In other words, E(A) can be controlled by controlling the weight ratio of component (A1) to 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 decreased and W(A2) may be increased. The control method in the reverse direction is also the same.

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 an operation to increase E (A) is performed, and an operation to increase E (A2), that is, an operation to increase the amount of ethylene supplied to the second polymerization step is selected as a means, the measured value is directly What can be confirmed is E(A), not E(A2), but it is obvious that the cause of the increase in E(A) is the increase in E(A2).

Finally, a method for controlling MFR(A) will be described. In the present application, MFR(A2) is defined by the following formula.
MFR(A2)=exp{(loge[MFR(A)]−W(A1)×loge[MFR(A1)])÷W(A2)}
(Here, log 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- MFR of component (A1) composed of ethylene random copolymer and component (A2) composed of propylene-ethylene random copolymer.)

This formula is an empirical formula generally called logarithmic addition rule of viscosity log [MFR (A)] = W (A1) × log [MFR (A1)] + W (A2) × log [MFR (A2)]
and is routinely used in the industry.

Due to the definition by this formula, the weight ratios of component (A1) and component (A2), MFR(A), MFR(A1) and MFR(A2) are not independent. Therefore, in order to control MFR(A), it is sufficient to control three factors: the weight ratio of component (A1) and component (A2), MFR(A1), and MFR(A2). For example, in order to increase MFR(A), MFR(A1) may be increased, or 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 by increasing W(A1) and decreasing W(A2). Yo. The control method in the reverse direction is also the same.

It should be noted that MFR(A) and MFR(A1) can actually be directly measured, and MFR(A2) is calculated using the measured values of both. Therefore, if an operation to increase the MFR (A) is performed, if an operation to increase the MFR (A2), that is, an operation to increase the amount of hydrogen supplied to the second polymerization step is selected as a means, the measured value is directly What can be confirmed is MFR(A), not MFR(A2), but it is self-evident that the reason why MFR(A) increases is that MFR(A2) increases.

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

(1) Measurement of Ethylene Content in Copolymer Using the propylene-ethylene block copolymer (A), each ethylene content in this copolymer was measured. Namely, 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 in each was obtained by analyzing the ¹³ C-NMR spectrum measured under the following conditions by the proton complete decoupling method.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or higher)
Solvent: o-dichlorobenzene + deuterated benzene (4:1 (volume ratio))
Concentration: 100 mg/mL
Temperature: 130°C
Pulse angle: 90°
Pulse interval: 15 seconds Accumulation times: 5,000 times or more Spectral 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. Symbols such as Sαα in Table 1 follow the notation of Carman et al. (Macromolecules, 10, 536 (1977)), P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.

Hereinafter, if "P" is the propylene unit in the copolymer chain and "E" is the ethylene unit, there can 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 related 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)
where brackets [ ] indicate the fraction of triads, eg [PPP] is the fraction of PPP triads in all triads. therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
is. Also, k is a constant and I indicates spectral intensity, for example, I(Tββ) means the intensity of the peak at 28.7 ppm attributed to Tββ. By using the relational expressions (1) to (7) above, the fraction of each triad can be obtained, and the ethylene content can be obtained by the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) x 100
The ethylene content is converted from mol% to wt% 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 mol%.

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-based resin composition) of the propylene-ethylene block copolymer (A), an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition.

As additives, antioxidants, neutralizers, light stabilizers, ultraviolet absorbers, crystal nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc., can be used in polypropylene resins. Various known additives can be blended.

Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, and thio-based antioxidants. Examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate. Hindered amines, benzotriazoles, benzophenones and the like can be exemplified as light stabilizers and ultraviolet absorbers.

Examples of crystal nucleating agents include amide-based nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, and rosin metal salts. Among these crystal nucleating agents, pt-butyl benzoate aluminum, 2,2′-methylenebis(4,6-di-t-butylphenyl)sodium phosphate, 2,2′-methylenebis(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-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[ (4-Propylphenyl)methylene]-nonitol, rosin sodium salt and the like can be exemplified.

Examples of lubricants include higher fatty acid amides such as stearamide. Examples of antistatic agents include fatty acid partial esters such as glycerin fatty acid monoester. Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, and oxamides.

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

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 can be prepared by melt-kneading the propylene-ethylene block copolymer (A), additives, fillers, other resin components, etc., or by melting the propylene-ethylene block copolymer (A), additives, fillers, etc. A method of dry blending the kneaded material with other resin components, a method of drying a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-ethylene block copolymer (A) and other resin components. It can be produced by a method such as blending.

Polypropylene resin (B)
The decorative film used in the present invention contains a layer (II) made of a polypropylene resin (B). The polypropylene-based resin (B) is preferably a resin that is more difficult to melt and relax than the polypropylene-ethylene block copolymer (A). By providing the layer (II), it is possible to suppress the occurrence of poor appearance due to breakage or roughening of the film during thermoforming. As a result, the decorative film improves the thermoformability, so that the thermosetting resin layer having excellent thermoformability does not have to be included.

The melt flow rate (230° C., 2.16 kg load) of polypropylene resin (B) (hereinafter referred to as “MFR (B)”) must be lower than MFR (A). The ratio of each MFR, MFR(B)/MFR(A), is less than 1, preferably 0.7 or less, more preferably 0.5 or less. When MFR(B)/MFR(A) is within the above range, good thermoformability is achieved. Although there is no lower limit for MFR(B)/MFR(A), it is preferably 0.01 or more.

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, more preferably 0.2 g/10 minutes or more. Within the above range, the spreadability of the decorative film is good during thermoforming. Also, 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 DSC measurement of the polypropylene resin (B) is not particularly limited, but is preferably 150° C. or higher, more preferably 155° C. or higher. When Tm(B) is within the above range, good heat resistance, scratch resistance, and solvent resistance are obtained.

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

The polypropylene-based resin (B) in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene-α-olefin block copolymer (block polypropylene), and various other type of propylene-based polymer, or combinations thereof. The propylene-based polymer preferably contains 50 mol % or more of polymerized units derived from a 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-based resin composition) containing a polypropylene-based resin (B), an additive, a filler, a colorant, other resin components, and the like. The total amount of additives, fillers, colorants, other resin components, etc. is preferably 50% by weight or less with respect to the polypropylene-based resin composition.

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

Polypropylene-based resin compositions are produced by melt-kneading a propylene-based polymer, additives, filler, other resin components, etc., or by melt-kneading a propylene-based polymer, additives, filler, etc., and drying other resin components. It can be produced by a method of blending, a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-based polymer and other resin components.

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

In addition, it can be colored to impart a design property, and various coloring agents such as inorganic pigments, organic pigments, and dyes can be used for coloring. In addition, it is also possible to use luster materials such as aluminum flakes, titanium oxide flakes, and (synthetic) mica.

When the decorated molded article of the present invention is molded as a colored molded article, it is sufficient to use the coloring agent only in the decorative film, so the use of an expensive coloring agent compared to the case of coloring the entire resin molded article. can be suppressed. In addition, it is possible to suppress changes in physical properties that accompany the addition of a colorant.

Decorative Film The decorative film in the present invention comprises a seal layer (I) made of a propylene-ethylene block copolymer (A) and a layer (II) made of a polypropylene resin (B). The decorative film can have various configurations other than the sealing layer (I) and layer (II). That is, the decorative film may be a two-layer film consisting of the sealing layer (I) and the layer (II), or may be a multilayer film consisting of three or more layers consisting of the sealing layer (I) and the layer (II) and another layer. There may be. The seal layer (I) is adhered along the resin molding (substrate). The surface of the decorative film may be textured, embossed, printed, sandblasted, scratched, or the like.

The decorative film has a large degree of freedom in shape, and the edge face of the decorative film is rolled up to the back side of the object to be decorated, so that no seam is formed, so that the appearance is excellent, and further, the surface of the decorative film is given a grain or the like. can express various textures. For example, in the case of imparting texture such as embossing to a resin molding, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems when molding with a molded body mold that imparts embossing, 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 surface mold. It is possible to solve the problem of being , and to obtain a decorative molded article to which various patterns of embossing are easily applied.

In addition to the sealing layer (I) and layer (II), the multilayer film can have a surface layer, a surface decorative layer, a printed layer, a light shielding layer, a colored layer, a substrate layer, a barrier layer, and between these layers. Tie layer layers and the like can be included. The layer (II) made of the polypropylene-based resin (B) may be any layer, excluding the seal layer, among the layers constituting the multilayer film.

In the multilayer film, the layers other than the seal layer (I) and layer (II) are preferably thermoplastic resin layers, more preferably polypropylene resin layers. As long as the layers other than the sealing layer (I) and the layer (II) can be distinguished from the sealing layer (I) and the layer (II), the MFR (230 ° C., 2.16 kg load) of the polypropylene resin constituting It is not particularly limited. Each layer is preferably a layer containing no thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication of the layer structure can be suppressed, and 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 adhered to the resin molding, and the polypropylene-based resin (B ) constitutes the surface layer opposite to the surface to be adhered to the resin molding.

When the decorative film is a multilayer film having three or more layers, other intervening layer may reduce the effect of suppressing the emergence of scratches on the surface of the substrate. For this reason, the multilayer film consists of a seal layer (I) made of the propylene-ethylene block copolymer (A), a layer (II) made of the polypropylene-based resin (B), and other layers from the adhesion surface side of the resin molding. (comprising multiple layers) is preferred.

FIGS. 1(a) to 1(c) are explanatory diagrams schematically illustrating cross sections of embodiments of a decorative film adhered to a resin molding. In FIGS. 1(a) to 1(c), the arrangement of the sealing layer (I) and the layer (II) will be specified and explained for ease of understanding, but the layer structure of the decorative film is limited to these examples. not be construed as In this specification, reference numeral 1 in the drawing indicates the decorative film, reference numeral 2 indicates the layer (II), reference numeral 3 indicates the sealing layer (I), and reference numeral 4 indicates the surface decoration layer (III). FIG. 1(a) shows an example in which the decorative film 1 is composed of a two-layer film, and a layer composed of a polypropylene resin (B) on a seal layer (I) composed of a propylene-ethylene block copolymer (A). (II) is laminated. The decorative film 1 in FIG. 1(b) consists of a sealing layer (I), a layer (II) and a surface layer, and the layer (II) and the surface layer are laminated in this order on the sealing layer (I). The decorative film 1 in FIG. 1(c) consists of a sealing layer (I), a layer (II) and a surface decorative layer (III) made of a polypropylene resin (C). II) and the surface decorative layer (III) are laminated in this order.

FIGS. 8A to 8C are explanatory diagrams schematically illustrating cross sections of embodiments of a decorative molded body 6 in which a decorative film 1 is adhered to a resin molded body 5. FIG. In FIGS. 8(a) to 8(c), the arrangement of the seal layer (I) and the layer (II) will be specified to facilitate understanding, but the layer structure of the decorative film 1 is limited to these examples. not to be construed as FIG. 8(a) shows an example in which the decorative film 1 is made of a two-layer film, and a sealing layer (I) made of a propylene-ethylene block copolymer (A) is adhered to the resin molding 5. A layer (II) made of a polypropylene-based resin (B) is laminated on (I). The decorative film 1 in FIG. 8(b) is composed of a seal layer (I), a layer (II) and a surface layer. Layer (II) and surface layer are laminated in this order on top. The decorative film 1 shown in FIG. 8(c) is composed of a seal layer (I), a layer (II), and a surface decorative layer (III) made of a polypropylene resin (C). I) is attached, and the layer (II) and the surface decorative layer (III) are laminated in this order on the sealing layer (I).

Another preferred embodiment of the decorative film is a multilayer film comprising a surface decorative layer (III) made of a surface decorative layer resin on the outermost surface opposite to the surface to be adhered to the resin molding. 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 resin (C) in the present invention (hereinafter referred to as “(MFR(C)”) preferably satisfies MFR(C)>MFR(B). A more beautiful surface texture can be expressed by setting the value within the above range.

The polypropylene-based resin (C) in the present invention includes various types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene α-olefin block copolymer (block polypropylene). propylene-based polymers, or combinations thereof. The propylene-based polymer preferably contains 50 mol % or more of polymerized units derived from a propylene monomer. The propylene-based polymer preferably does not contain polymerized units 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. Propylene-α-olefin copolymers are preferred from the viewpoint of gloss and transparency (color development). In the present invention, the polypropylene 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-based resin composition) of a polypropylene-based resin (C), an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the polypropylene-based resin composition.

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

Polypropylene-based resin compositions are produced by melt-kneading a propylene-based polymer, additives, filler, other resin components, etc., or by melt-kneading a propylene-based polymer, additives, filler, etc., and drying other resin components. It can be produced by a method of blending, a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-based polymer and other resin components.

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

The decorative film used in the present invention preferably has a thickness of about 20 μm or more, more preferably about 50 μm or more, and even more preferably about 80 μm or more. By setting 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 it becomes possible to obtain a better decorated molded product. 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, thereby improving productivity and facilitating trimming of unnecessary portions.

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 range, sufficient adhesive strength can be exhibited, and scratches on the resin molded body (substrate) will not stand out on the surface. can be suppressed. Further, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above range, it is possible to avoid insufficient thermoformability of the decorative film.

In addition, in a multilayer film in which a surface decorative layer (III) made of a polypropylene resin (C) is provided on the outermost surface of the decorative film, the thickness of the entire decorative film equal to the thickness of the layer (III) in the decorative film 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 co-extrusion molding a seal layer (I) made of a propylene-ethylene block copolymer (A) and a layer (II) made of a polypropylene-based resin (B); Furthermore, a method of co-extrusion molding with another layer, a heat lamination method of applying heat and pressure to laminate another layer on one side of one extruded layer in advance, and bonding via an adhesive A dry lamination method, a wet lamination method, an extrusion lamination method and a sand lamination method in which a polypropylene-based resin is melt-extruded onto one surface of one layer that has been extruded in advance can be used. As a device for forming the decorative film, a known co-extrusion T-die molding machine or a known lamination molding machine can be used. Among these, a co-extrusion T-die molding machine is preferably used from the viewpoint of productivity.

Methods for cooling the molten decorative film extruded from the die include a method of bringing the molten decorative film into contact with one cooling roll via air discharged from an air knife unit or an air chamber unit, A method of pressing and cooling with a plurality of cooling rolls can be used.

In the case of imparting gloss to the decorative film, a mirror-finishing method is used in which a mirror-finished cooling roll is surface-transferred onto the design surface of the decorative film.

Furthermore, the surface of the decorative film may have a crimped shape. Such a decorative film is produced by a method in which a melted resin extruded from a die is directly pressed between a roll having an uneven shape and a smooth roll to transfer the uneven shape. It can be manufactured by a surface transfer method or the like in which a heated roll and a smooth cooled roll are brought into pressure contact with each other. The embossed shape is exemplified by pear-skin tone, animal skin tone, hairline tone, carbon tone, and the like.

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

Decorated Molded Article As a molded article (to be decorated) to be decorated in the present invention, various molded articles (hereinafter sometimes referred to as "substrate") preferably made of a polypropylene resin or a polypropylene resin composition are used. can be used. The molding method of the molded article is not particularly limited, and examples thereof include injection molding, blow molding, press molding, extrusion molding and the like.

Since the polypropylene resin is non-polar, it is a difficult-to-adhere polymer. By including the layer (II) made of (B), the decorative film made of polypropylene resin is adhered to the decorative object, thereby exhibiting extremely high adhesive strength and adhering to the surface of the decorative object. It can make scars less noticeable.

As base resins for polypropylene-based resins and polypropylene-based resin compositions, various known propylene monomers such as propylene homopolymers (homopolypropylene), propylene-α-olefin copolymers, or propylene block copolymers are mainly used. Various types of raw materials can be selected. In addition, it may contain a filler such as talc for imparting rigidity and an elastomer or the like for imparting impact resistance, as long as the effects of the present invention are not impaired. In addition, it may contain additive components and other resin components in the same manner as the polypropylene-based resin composition that can constitute the decorative film described above.

The decorative molded article obtained by attaching the decorative film of the present invention to various molded articles formed in a three-dimensional shape made of polypropylene resin has a greatly reduced amount of VOC contained in coatings and adhesives. It can be suitably used as home electric appliances, vehicles (railways, etc.), building materials, daily necessities, and the like.

The method for manufacturing the decorated molded article of the present invention comprises the steps of preparing the above-described decorative film, preparing the resin molded article, and setting the resin molded article and the decorative film in a chamber box capable of reducing pressure. reducing the pressure in the chamber box; heating and softening the decorative film; pressing the decorative film against the resin molded body; characterized by comprising

In three-dimensional decorative thermoforming, the object to be decorated and the decorative film are set in a decompressible chamber box, the film is heated and softened while the chamber box is decompressed, and the film is pressed against the object to be decorated. 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 the atmospheric pressure or pressurizing it, and the film is attached under reduced pressure. As a result, it is possible to obtain a clean decorative molded article free from air pockets. In the manufacturing 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 object to be decorated, the decorative film, the mechanism for pressing them, the device for heating the decorative film, etc., or the decorative film may A plurality of divided objects may be used.

The mechanism for pressing the decorative film against the decorative object may be of any type, such as one that moves the decorative object, one that moves the decorative film, or one that moves both.
More specifically, representative molding methods are exemplified below.

A method of adhering a decorative film to an object to be decorated using a three-dimensional decorating thermoforming machine will be exemplified below with reference to the drawings.

As shown in FIG. 2, the three-dimensional decorating thermoforming machine of this embodiment comprises upper and lower chamber boxes 11 and 12, and the decorating film 1 is thermoformed in the two chamber boxes 11 and 12. I'm trying A vacuum circuit (not shown) and an air circuit (not shown) are piped to the upper and lower chamber boxes 11 and 12, respectively.

A jig 13 for fixing the decorative film 1 is provided between the upper and lower chamber boxes 11 and 12 . A table 14 that can be raised and lowered is installed in the lower chamber box 12, and the resin molding (to be decorated) 5 is set on this table 14 (via a jig or the like or directly). be. A heater 15 is incorporated in the upper chamber box 11 and the decorative film 1 is heated by the heater 15 . The object to be decorated 5 can use a propylene-based resin composition as a base.

As such a three-dimensional decoration 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 opened, the object to be decorated 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, after lowering the upper chamber box 11 and joining the upper and lower chamber boxes 11 and 12 to close the inside of the box, the inside of each of the chamber boxes 11 and 12 is brought into a vacuum suction state, and the heater 15 is heated. The decorative film 1 is heated by.

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

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

Molding Conditions The pressure reduction in the chamber boxes 11 and 12 is sufficient as long as air pockets are not generated, and the pressure in the chamber boxes is 10 KPa or less, preferably 3 KPa, and more preferably 1 KPa or less.

In addition, in the two chamber boxes 11 and 12 divided into upper and lower parts by the decorative film 1, the internal pressure of the chamber box on the side where the decorative film 1 is attached to the object to be decorated 5 should be within this range. The drawdown of the decorative film 1 can also be suppressed by changing the pressures of the chamber boxes 11 and 12 .

The heating of the decorative film 1 is controlled by the heater temperature (output) and 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 adhere the polypropylene-based decorative film 1 to the decoration target 5 made of polypropylene-based resin, the surface of the resin molding 5 and the decorative film 1 must be sufficiently softened or melted.

Therefore, it is necessary that the heater temperature is higher than the melting temperature of the polypropylene-based resin that constitutes the object to be decorated 5 and the polypropylene-based resin that constitutes the decorative 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. If the temperature of the heater becomes too high, not only the moldability deteriorates but also the resin thermally deteriorates. It is below.

An appropriate heating time varies depending on the heater temperature, but it is preferable that the polypropylene-based decorative film is heated and heated for a period of time longer than the time until the polypropylene-based decorative film starts to stretch back, which is called springback, although it varies depending on the heater temperature.

In other words, the decorative film heated by the heater thermally expands when heated from a solid state and sags once as the crystals melt. After that, the film shows the behavior of sagging under its own weight. However, after springback, the crystals of the film are completely melted, and the molecules relax sufficiently, so sufficient adhesive strength can be obtained.

Furthermore, surprisingly, the decorative film used in the present invention can be strongly adhered to the substrate even if the decorative thermoforming is performed before the unrolling is completed, and it is highly effective in suppressing the wrinkling.

On the other hand, if the heating time is too long, the film may sag under its own weight or be deformed due to the pressure difference between the upper and lower chamber boxes.

In the case of decorating a molded article having a complicated shape having unevenness or in the case of achieving higher adhesive strength, it is preferable to supply compressed air when adhering the decorative film to the substrate. The pressure in the upper chamber box when the compressed air is introduced is 150 kPa or higher, preferably 200 kPa or higher, more preferably 250 kPa or higher. Although there is no particular upper limit, the pressure is 450 kPa or less, preferably 400 kPa or less, since there is a risk of damaging the equipment if the pressure is too high.

EXAMPLES Hereinafter, the present invention will be described more specifically as examples, but the present invention is not limited to these examples.

1. Measurement method of various physical properties (i) MFR
Measured according to ISO 1133:1997 Conditions M at 230° C. and a load of 2.16 kg. 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 cooling rate of 10° C./min, and again at a heating rate of 10° C./min. The temperature at the endothermic peak top 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) The ethylene content of was determined using the method for measuring ethylene content by ¹³ C-NMR described above.

2. Materials used Production of propylene-ethylene block copolymer (A) As the propylene-ethylene block copolymer (A) used for the sealing layer (I) of the decorative film, the propylene-ethylene block copolymer obtained in the production example described later was used. Polymers (A-1) to (A-4) were used. Polymerization conditions and polymerization results are shown in Table 2, and polymer analysis results are shown in Table 3.

[Production Example A-1: Production of propylene-ethylene block copolymer (A-1)]
Analysis of catalyst composition Ti content: A sample was weighed accurately, hydrolyzed and measured using a colorimetric method. For the prepolymerized sample, the content was calculated using the weight excluding the prepolymerized polymer.
Silicon compound content: Samples were accurately weighed and digested with methanol. The silicon compound concentration in the resulting methanol solution was determined by comparison with a standard sample using gas chromatography. The silicon compound content in the sample was calculated from the silicon compound concentration in methanol and the weight of the sample. For the prepolymerized sample, the content was calculated using the weight excluding the prepolymerized polymer.

Preparation of Prepolymerized Catalyst (1) Preparation of Solid Catalyst A 10 L capacity autoclave equipped with a stirring device was sufficiently purged with nitrogen, and 2 L of purified toluene was introduced. At room temperature, 200 g of magnesium diethoxide [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 were introduced. After that, 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. Next, refined 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. Next, refined 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, purified n-heptane was used to replace toluene with n-heptane to obtain a slurry of solid components. A portion of this slurry was sampled and dried. An analysis revealed that the Ti content of the solid component was 2.7% by weight.

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

Thereafter, purified n-heptane was introduced to adjust the liquid level to 4L. 30 ml of dimethyldivinylsilane, 30 ml of diisopropyldimethoxysilane [i-Pr ₂ Si(OMe) ₂ ], and 80 g of Et ₃ Al diluted with triethylaluminum (Et ₃ Al) in n-heptane were added. for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A part of the resulting 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 performed according to the following procedure. Refined n-heptane was introduced into the above slurry to adjust the solid catalyst concentration to 20 g/L. After cooling the slurry to 10° C., 10 g of Et ₃ Al diluted in n-heptane was added as Et ₃ Al and 280 g of propylene was fed over 4 hours. After the supply of propylene was finished, the reaction was continued for another 30 minutes. Then, the gas phase was sufficiently purged with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was extracted from the autoclave and dried in a vacuum to obtain a prepolymerized catalyst. This prepolymerized catalyst contained 2.5 grams of polypropylene per gram of solid catalyst. Analysis revealed that the portion of the prepolymerized catalyst excluding polypropylene contained 1.0% by weight of Ti and 8.3% by weight of i-Pr ₂ Si(OMe) ₂ .
Using this prepolymerization catalyst, a propylene-ethylene block copolymer (A) was produced according to the following procedure.

(3) Production of propylene-ethylene block copolymer (A) A propylene-ethylene block copolymer is produced using a two-tank continuous polymerization facility in which two fluidized-bed polymerization tanks with an internal volume of 2 m ³ are connected in series. gone. The propylene, ethylene, hydrogen and nitrogen used were purified using a common 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 cooling water temperature of the heat exchanger used for temperature control of the polymerization tank.

First Polymerization Step: Production of Component (A1) Consisting of Propylene Homopolymer Propylene was homopolymerized using the first polymerization tank. The polymerization temperature was 65° C., the total pressure was 3.0 MPaG (gauge pressure, hereinafter the same), 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 fed continuously at a rate of 5.0 g/hour. The prepolymerized 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) withdrawn from the first polymerization tank was continuously supplied to the second polymerization tank, and the production of the component (A2) consisting of the 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 the 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 dried sufficiently.

A portion of the produced propylene-ethylene block copolymer (A) was analyzed and found to have an MFR (A) of 7.0 g/10 min and an ethylene content E (A) of 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 in the first polymerization step and the production amount in the second polymerization step, and each was 0.75. , 0.25.

The ethylene content E (A2) of the propylene-ethylene random copolymer component (A2) was calculated from W (A1), W (A2) and E (A) thus obtained.
The following formula was used for the calculation.
E(A2)={E(A)−E(A1)×W(A1)}÷W(A2)
(Here, since component (A1) is a propylene homopolymer, E(A1) is 0% by weight. In the above formula, the above formula for E(A) is rearranged for E(A2). It is what 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)]
Propylene-ethylene block copolymers (A-2) and (A-3) were produced in the same manner as in the production example of 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 prepolymerized catalyst (1) Chemical treatment of silicate 3.75 liters of distilled water and then 2.5 kg of concentrated sulfuric acid (96%) were slowly added to a 10 liter separable glass flask equipped with a stirring blade. did. At 50° C., 1 kg of montmorillonite (Benclay SL manufactured by Mizusawa Chemical; average particle size=25 μm, particle size distribution=10 to 60 μm) was dispersed, heated to 90° C., and maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was filtered under reduced pressure to collect a cake. The cake was reslurried by adding 7 liters of distilled water and filtered. This washing operation was carried out until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried overnight at 110° C. under a nitrogen atmosphere. The weight after drying was 707 g.

(2) Drying of silicate The previously chemically treated silicate was dried using a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotation speed with scraping blade: 2 rpm
Tilt angle: 20/520
Feed rate of silicate: 2.5 g/min Gas flow rate: Nitrogen 96 l/h Countercurrent drying temperature: 200°C (powder temperature)

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

(4) Prepolymerization/Washing Subsequently, the temperature inside the tank was raised by 40° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g/hour to maintain the temperature. After 4 hours the propylene feed was stopped and maintained for an additional 2 hours.
After the prepolymerization was completed, the residual monomer was purged, the stirring was stopped, and the mixture was allowed to stand still for about 10 minutes, after which 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, stirred at 40° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. Furthermore, this operation was repeated 3 times. A component analysis of the final supernatant liquid revealed that the concentration of the organoaluminum component was 1.23 mmol/liter and the concentration of zirconium (Zr) was 8.6 × 10 ^-6 g/liter. The abundance of was 0.016%. Subsequently, after adding 170 ml of a heptane solution of triisobutylaluminum (0.71 M), drying was performed under reduced pressure at 45°C. A prepolymerized catalyst containing 2.0 g of polypropylene per g of catalyst was obtained.

(5) Production of propylene-ethylene block copolymer (A) First polymerization step: Production of component (A1) consisting of propylene-ethylene random copolymer Horizontal reactor with stirring blades (L/D = 6, content 100 liters) 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, 0.444 g / hour of prepolymerized catalyst (as a solid catalyst amount excluding prepolymerized powder) and triisobutyl aluminum prepared in the upstream part of the reactor. It was fed continuously at 15.0 mmol/hour. The temperature of the reactor is maintained at 65°C and the pressure at 2.00 MPaG, and the monomer mixed gas is continuously reacted so that the gas phase in the reactor has an ethylene/propylene molar ratio of 0.058 and a hydrogen concentration of 150 ppm. Gas phase polymerization was carried out by circulating in the vessel. The polymer powder produced by the reaction was continuously withdrawn from the downstream portion of the reactor so that the amount of powder bed in the reactor was constant. At this time, the amount of polymer withdrawn when the steady state was reached was 10.0 kg/hour.
Analysis of the propylene-ethylene random copolymer obtained in the first step revealed that the ethylene content was 1.7% by weight.

Second polymerization step: Production of component (A2) composed of propylene-ethylene random copolymer Propylene-ethylene extracted from the first step was placed in a horizontal reactor (L/D = 6, internal volume: 100 liters) having a stirring blade. The copolymer was fed continuously. While stirring at a rotation speed of 25 rpm, the temperature of the reactor was kept at 70 ° C., the pressure was kept at 1.88 MPaG, and the ethylene / propylene molar ratio in the gas phase part in the reactor was 0.450, and the hydrogen concentration was 300 ppm. Gas phase polymerization was performed by continuously circulating the monomer mixed gas in the reactor. The polymer powder produced by the reaction was continuously withdrawn from the downstream portion 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 withdrawn was 18.0 kg/hour, and the amount of polymerization reaction in the second step was controlled.
The propylene-ethylene block copolymer (A-4) thus obtained was analyzed and found to have an MFR of 7.0 g/10 min and an ethylene content of 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) Tetrakis[methylene-3- (3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methane 0.05 parts by weight, tris(2,4-di-t-butylphenyl)phosphite 0.10 parts by weight, calcium stearate 0.05 part by weight of each was mixed and homogenized in a tumbler, and the resulting mixture was melt-kneaded at 230°C by a twin-screw extruder with a diameter of 35 mm to obtain propylene-ethylene block copolymers (A-1) to (A -4) were obtained.

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

The following polypropylene-based resin was used as the resin for the layer (II) of the decorative film.
(B-1): Propylene homopolymer (MFR = 2.4 g/10 min, Tm = 161°C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FY6"
(B-2): Propylene homopolymer (MFR = 0.4 g/10 min, Tm = 161°C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) EA9"
(B-3): A polypropylene-based resin composition (MFR=2.00) obtained by blending 96% by weight of polypropylene-based resin (B-1) with 4% by weight of black pigment MB (EPP-K-120601 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): A polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (A-5) with 0.4 parts by weight of a nucleating agent (trade name "Millad NX8000J" manufactured by Milliken Japan Co., Ltd.). (MFR=10 g/10 min, Tm=164° C.)
(C-2): Propylene-α-olefin copolymer with a metallocene catalyst (MFR = 7 g/10 min, Tm = 125°C, Mw/Mn = 2.5), manufactured by Japan Polypropylene Corporation, trade name " Wintech (registered trademark) WFX4M”
(C-3): A polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (C-2) with 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Millad NX8000J"). (MFR=7 g/10 min, Tm=127° C.)
(C-4): White pigment MB (EPP-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80% by weight) is added to 96% by weight of polypropylene resin (A-5) with MFR = 11 g/10 minutes. 4 wt% blended polypropylene resin composition (MFR = 10 g/10 min, Tm = 161°C)
(C-5): A polypropylene resin composition (MFR = 10 g/10 minutes, Tm = 161°C)

The following polypropylene-based resins were used as resins for resin moldings.
(X-1): Propylene homopolymer (MFR = 40 g/10 min, Tm = 165°C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) MA04H"
(X-2): Propylene-ethylene block copolymer (MFR = 30 g/10 min, Tm = 164°C), trade name "Novatec (registered trademark) NBC03HR" manufactured by Japan Polypropylene Corporation
(X-3): 60% by weight of polypropylene resin (X-2), 20% by weight of EBR (Tafmer (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. Production of Resin Molded Article (Substrate) Using the polypropylene resins (X-1) to (X-3), an injection molded article was obtained by the following method. The obtained injection molded article was scratched by the following method to obtain a resin molded article (substrate).
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 Conditioning: Temperature 23°C, humidity 50% RH in a constant temperature and humidity room for 5 days Processing for scratch evaluation: temperature 23°C, humidity Using a scratch tester (“SCRATCH & MAR TESTER” manufactured by ROCKWOOD SYSTEMS AND EQUIPMENT) in a constant temperature and humidity chamber at 50% RH, a load of 25 N was applied to shape (curvature radius 0.5 mm, ball shape). The scraping tip was scratched at a scratch speed of 100 mm/min to scratch the injection molded body.

Scratches on the surface of the resin molding (substrate) were measured with a laser microscope ("VX-X200" manufactured by KEYENCE), and the depth of the scratches was 16 μm. In addition, the scratch was whitening.

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

• Three-dimensional decorative thermoforming As the resin molded body (substrate) 5, an injection molded body made of the polypropylene-based resin (X-1) obtained above was used.
"NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used as a three-dimensional decoration thermoforming apparatus. As shown in FIGS. 2 to 7, the decorative film 1 is cut into a width of 250 mm and a length of 350 mm so that the seal layer faces the substrate and the longitudinal direction is in 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 (substrate) 5 was placed on a sample installation table with a height of 20 mm, which was installed on a table 14 located below the film fixing jig 13, and placed on a sample installation table manufactured by Nichiban Co., Ltd. “Nice Tac NW-K15. ” pasted 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 make the insides of the chamber boxes 11 and 12 airtight. The chamber box is vertically divided through the decorative film 1. - 特許庁The upper and lower boxes are evacuated and the pressure is reduced from the atmospheric pressure (101.3 kPa) to 1.0 kPa. heated. Vacuum suction was continued even during heating, and finally the pressure was reduced to 0.1 kPa. A table 14 placed in a lower chamber box 12 immediately after the completion of the springback phenomenon in which the decorative film 1 is heated, temporarily slackened, and then stretched back (that is, the heating time after the springback phenomenon is 0 seconds). is moved upward to press the resin molded body (substrate) 5 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, and the resin molded body (substrate) 5 and The decorative film 1 was adhered. Thus, a three-dimensional decorated thermoformed product 6 was obtained in which the decorative film 1 was adhered to the top and side surfaces of the resin molded body (substrate) 5 .

・Evaluation of physical properties (1) Evaluation of thermoformability It was visually observed and evaluated according to the criteria shown below.
○: During the three-dimensional decorative thermoforming, the decorative film did not draw down and the base and the decorative film were in contact with each other over the entire contact surface at the same time. ing.
x: Contact unevenness occurred over the entire surface of the substrate due to a large drawdown of the decorative film during three-dimensional decorative thermoforming.

(2) Adhesive strength between the resin molded body (substrate) and the decorative film "Craft Adhesive Tape No. 712N" manufactured by Nitoms Co., Ltd. was cut into a width of 75 mm and a length of 120 mm, and the edge of the resin molded body (substrate) was cut. The area of 75 mm×120 mm was affixed to a resin molded body (substrate) and masked (the exposed portion of the substrate surface had a width of 45 mm and a length of 120 mm). The resin molding (substrate) was placed in a three-dimensional decorative thermoforming apparatus NGF-0406-SW so that the masking surface of the resin molded body (substrate) was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

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

(3) Evaluation of the effect of making scratches less noticeable Shape measurement of the depth of scratches at the part where the three-dimensional decorative thermoformed product of the molded body (substrate) with a load of 25 N was scratched Shape measurement laser microscope ("VX-X200" manufactured by KEYENCE). The number of measurements was set to n=5, and the average value was taken as the scratch depth (μm).
In addition, as the whitening appearance, whether or not the decorative film made the whitening scratches on the molding (substrate) scratched with a load of 25 N less noticeable was visually judged and evaluated according to the following criteria.
◯: The appearance is excellent with no traces of whitening scars.
x: Whitening flaws remained on the whole, and the appearance was poor.

(4) Gloss The gloss around the center of the decorative molding to which the decorative film was adhered was measured using a GLOSS meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. at an incident angle of 60°. The measuring method complies with JIS K7105-1981.

(5) Evaluation of recyclability The obtained decorative molded article was pulverized, a recycled molded article was obtained by injection molding in the same manner as in the production of the resin molded article (substrate), and the appearance was visually evaluated. Those with excellent appearance were evaluated as “○”.

Table 4 shows the physical property evaluation results of the obtained decorative moldings.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

Example 2
Example 1 except that the propylene-ethylene block copolymer (A-1) used in the seal layer in the production of the decorative film of Example 1 was changed to the propylene-ethylene block copolymer (A-2). was evaluated in the same way. Table 4 shows the evaluation results.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

Example 3
Example 1 except that the propylene-ethylene block copolymer (A-1) used in the sealing layer in the production of the decorative film of Example 1 was changed to the propylene-ethylene block copolymer (A-3). was evaluated in the same way. Table 4 shows the evaluation results.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

Example 4
Example 1 except that the propylene-ethylene block copolymer (A-1) used in the seal layer in the production of the decorative film of Example 1 was changed to the propylene-ethylene block copolymer (A-4). was evaluated in the same way. Table 4 shows the evaluation results.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

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

Comparative example 1
In the production of the decorative film of Example 1, the procedure was carried out in the same manner 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). made an evaluation. Table 4 shows the evaluation results.
The propylene homopolymer (A-5) used for the seal layer does not contain the component (A2), and therefore has a low adhesive strength, cannot sufficiently suppress the emergence of scratches, and is inferior in appearance. there were.

Comparative example 2
Example 1 except that the propylene-ethylene block copolymer (A-1) used in the seal layer in the production of the decorative film of Example 1 was changed to the propylene-ethylene random copolymer (A-6). was evaluated in the same way. Table 4 shows the evaluation results.
Since the propylene-ethylene random copolymer (A-6) used for the sealing layer does not contain the component (A2), it has a low adhesive strength and cannot sufficiently suppress the appearance of scratches, resulting in poor appearance. 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 the propylene-ethylene random copolymer (A-5), and three-dimensional decoration was performed. Evaluation was performed in the same manner as in Example 4, except that in thermoforming, heating was continued for 20 seconds after the springback phenomenon ended, and then decorative thermoforming was performed. Table 1 shows the evaluation results.
Adhesive strength was improved by increasing the film heating time, but the drawdown of the film was severe and the external appearance of the decorated molding was poor, so damage was not evaluated.

Example 6
Evaluation was carried out in the same manner as in Example 1, except that in the three-dimensional decorative thermoforming of Example 1, the substrate was changed to an injection molded body using resin (X-2). Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

Example 7
Evaluation was carried out in the same manner as in Example 1, except that in the three-dimensional decorative thermoforming of Example 1, the substrate was changed to an injection molded body using resin (X-3). Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the recycled molded article was excellent in appearance.

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

The melt-extruded film is cooled and solidified on a cooling roll rotating at 80 ° C. and 3 m / min so that the surface decoration layer is in contact, and a surface decoration layer with a thickness of 50 μm, a layer with a thickness of 100 μm, and a layer with a thickness of 100 μm are cooled and solidified. A three-layer unstretched film laminated with a 50 μm-thick sealing layer was obtained.

Evaluation was performed in the same manner as in Example 1, except that the unstretched film obtained in the production of the decorative film was used. Table 5 shows the evaluation results.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, since the polypropylene resin (A-5) was laminated as the surface decorative layer (III) on the outermost surface side, the gloss was excellent. In addition, the recycled molded article was excellent in appearance.

Example 9
Evaluation was carried out in the same manner as in Example 8, except that in the production of the decorative film of Example 8, the polypropylene resin (A-5) used in the surface decorative layer was changed to the polypropylene resin (C-1). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the polypropylene resin (C-1) to which the nucleating agent was added was laminated as the surface decorative layer (III) on the outermost surface side, resulting in excellent gloss. In addition, the recycled molded article was excellent in appearance.

Example 10
Evaluation was performed in the same manner as in Example 8, except that in the production of the decorative film of Example 8, the polypropylene resin (A-5) used in the surface decorative layer was changed to the polypropylene resin (C-2). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, since the polypropylene resin (C-2) was laminated as the surface decorative layer (III) on the outermost surface side, the gloss was excellent. In addition, the recycled molded article was excellent in appearance.

Example 11
Evaluation was carried out in the same manner as in Example 8, except that in the production of the decorative film of Example 8, the polypropylene resin (A-5) used in the surface decorative layer was changed to the polypropylene resin (C-3). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, the polypropylene resin (C-3) to which a nucleating agent was added was laminated as the surface decorative layer (III) on the outermost surface side, resulting in excellent gloss. In addition, the recycled molded article was excellent in appearance.

Example 12
Evaluation was carried out in the same manner as in Example 8, except that in the production of the decorative film of Example 8, the polypropylene resin (A-5) used in the surface decorative layer was changed to the polypropylene resin (C-4). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, together with the adhering of the white-colored decorative film, the scratch was sufficiently concealed so that the scratched portion could not be identified. Therefore, the wound depth was not measured. In addition, since the surface decorative layer (III) having excellent glossiness was colored white, the appearance was excellent. In addition, the recycled molded article was excellent in appearance.

Example 13
Evaluation was carried out in the same manner as in Example 8, except that in the production of the decorative film of Example 8, the polypropylene resin (B-1) used in the layer (II) was changed to the polypropylene resin (B-3). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, together with the adhering of the decorative film colored black, the scratch was sufficiently concealed so that the scratched portion could not be identified. Therefore, the wound depth was not measured. Moreover, since the layer (II) was colored black, the appearance was excellent. Furthermore, since the polypropylene-based resin (A-5) was laminated as the surface decorative layer (III) on the outermost surface side, the gloss was excellent. In addition, the recycled molded article was excellent in appearance.

Example 14
Evaluation was carried out in the same manner as in Example 13, except that in the production of the decorative film of Example 13, the polypropylene resin (A-5) used in the surface decorative layer was changed to the polypropylene resin (C-5). rice field. Table 5 shows the results obtained.
Since the propylene-ethylene block copolymer (A) and the polypropylene resin (B) satisfy all the requirements of the present invention, the obtained decorative molded article has excellent appearance and adhesive strength, and scratches are inconspicuous. It was something. In addition, combined with the fact that the colored decorative film was adhered, the damage was sufficiently concealed so that the damaged portion could not be identified. Therefore, the wound depth was not measured. Further, since the polypropylene-based resin (C-5) was laminated as the surface decorative layer (III) on the outermost surface side, the gloss was excellent. Furthermore, since the layer (II) was colored black and the surface layer decorative layer (III) was colored silver, the film had a metallic tone and was excellent in appearance. In addition, the recycled molded article was excellent in appearance.

Example 15
Production of decorative film In the production of the decorative film of Example 14, the discharge rate of seal layer extruder-1 was 4 kg / h, the discharge rate of extruder-2 was 12 kg / h, and the surface layer extruder - Melt extrusion is performed at a discharge rate of 3 of 4 kg/h, and the resulting three-layer unstretched film is slit to a width of 200 mm to form a surface decoration layer with a thickness of 50 μm and a layer with a thickness of 150 μm. , to obtain a three-layer unstretched film laminated with a seal layer having a thickness of 50 μm.

- Production of embossed film As an embossing device, an electric heating type test embossing machine manufactured by Yuri Roll Co., Ltd. was used. The electric heating type test embossing machine heats and presses the film between a heatable roll (embossing roll) installed in the upper stage and a smooth roll installed in the lower stage to create the uneven shape of the upper stage. has a mechanism to transfer to the film surface. A hairline pattern with a depth of 0.030 mm was used for the emboss roll.
The 3-layer unstretched film obtained by the production of the decorative film was let out to two rolls of an embossing machine so that the surface decorative layer was in contact with the embossing roll. Emboss transfer was performed under the conditions of an emboss roll temperature of 145° C., a contact pressure of 3 MPa, and a roll speed of 3 m/min to obtain a decorative film having a hairline pattern transferred to the surface of the surface decorative layer.

- Three-dimensionally decorated thermoforming A three-dimensionally decorated thermoformed product was obtained in the same manner as in Example 1.

・ Physical property evaluation (1) Evaluation of embossed transfer The depth of the hairline pattern portion 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.
◯: An embossed pattern remains on the surface of the three-dimensionally decorated thermoformed article after three-dimensionally decorated thermoforming, and the design is excellent.
x: The embossed pattern has disappeared on most of the surface of the three-dimensionally decorated thermoformed article after three-dimensionally decorated thermoforming, and the design is poor.

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

According to the present invention, it is possible to achieve both sufficient adhesive strength and product appearance. A decorative film used for decorative thermoforming and a method for producing a decorative molded article using the same are provided.

1 decorative film 2 layer (II)
3 sealing layer (I)
5 Resin molding (decorative object, substrate)
6 Decorative molding 11 Upper chamber box 12 Lower chamber box 13 Jig 14 Table 15 Heater

Claims (5)

preparing a decorative film; preparing a resin molded body; setting the resin molded body and the decorative film in a decompressible chamber box; reducing the pressure in the chamber box; A method for producing a decorated molded product, comprising: a step of heating and softening a film; a step of pressing the decorative film against the resin molded product;
The decorative film is a decorative film to be adhered onto a resin molded body by thermoforming, and the decorative film comprises a seal layer (I) made of a propylene-ethylene block copolymer (A) and a polypropylene The layer (II) made of the resin (B) is included, the propylene-ethylene block copolymer (A) satisfies the following requirements (a1) to (a3), and the polypropylene resin (B) satisfies the following requirements (b1 ) is satisfied.
Requirements for the propylene-ethylene block copolymer (A) (a1) 5 to 97% by weight of the component (A1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and having an ethylene content higher than that of the component (A1) It contains 3 to 95% by weight of component (A2) consisting of a large amount of propylene-ethylene random copolymer.
(a2) 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.
Requirement (b1) melt flow rate (230° C., 2.16 kg load) (MFR (B)) of polypropylene resin (B) satisfies the following relational expression (b-1) with respect to MFR (A).
MFR(B)<MFR(A) Formula (b-1) 2. The method for producing a decorated molded article using a 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. 3. The method for producing a decorated molded article using a 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 component (A1) is in the range of 0 to 6% by weight. 4. The method for producing a decorated molded article using a 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 component (A2) is in the range of 5 to 90% by weight. 5. The method for producing a decorative molded article using a decorative film according to any one of claims 1 to 4, wherein the resin molded article is made of a propylene-based resin composition.

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