JP6891775B2 - A decorative film and a method for manufacturing a decorative molded product using the decorative film. - Google Patents

Description

The present invention relates to a decorative film for attaching to a resin molded body by thermoforming, and a method for producing a decorative molded body using the decorative film. Specifically, the resin has excellent scratch resistance, weather resistance, and designability, can exhibit sufficient adhesive strength to the resin molded product, and has less grain return after heat molding and less damage to the film during molding. The present invention relates to a decorative film for sticking on a molded body by thermal molding and a method for manufacturing a decorative molded body using the decorative film.

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

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

Compared to other decorative moldings such as insert molding, vacuum forming by vacuum forming and vacuum forming has a greater degree of freedom in shape, and the end face of the decorative film is caught up to the back side of the object to be decorated, resulting in a seam. It is excellent in appearance because it does not occur, and it can be thermoformed at a relatively low temperature and low pressure. Therefore, by imparting grain or the like to the surface of the decorative film, the reproducibility of the grain or the like on the surface of the decorative molded body is reproducible. It has the advantage of being excellent in vacuum forming.

In such vacuum pressure forming and decorative molding by vacuum forming, acrylic which has excellent properties such as transparency, scratch resistance, weather resistance, and ease of printing, and is a thermoplastic resin and is easy to thermoform. A film made of a based resin is widely used as a decorative film. However, since a film made of an acrylic resin softens in a relatively short time when heated, it is not possible to give a heating time sufficient to be attached to a decorative object in three-dimensional decorative thermoforming, and the film. There was a problem that the adhesive strength with the object to be decorated was inferior. In response to this problem, the use of acrylic adhesives, urethane adhesives, tack fires, etc. has been proposed as a layer for improving the adhesive strength, but non-polar resins typified by polypropylene resins have been proposed. On the other hand, there is a problem that sufficient adhesive strength cannot be obtained.

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

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

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

With conventional techniques, the development of a decorative film containing an acrylic resin having good adhesion to a substrate made of a polypropylene resin has not yet been achieved. In view of the above problems, the subject of the present invention is a decorative film containing a polypropylene-based resin substrate and an acrylic resin capable of achieving high adhesive strength, and scratch resistance, weather resistance, designability, and recycling using the decorative film. An object of the present invention is to provide a decorative molded product having excellent properties.

In three-dimensional decorative thermoforming, it is necessary that the surface of the molded body and the film are sufficiently softened or melted in order to attach the decorative film in the solid state to the resin molded body in the solid state. It is important to apply the amount of heat required to soften or melt the surface of the molded product and the film, but since the acrylic resin film softens in a relatively short time, if the heating time is too long, the viscosity of the film will decrease, and the film will become tertiary. We focused on the fact that the film breaks or rampages due to the push-up of the molded product in the original decorative thermoforming process and the inflow of air when the vacuum chamber is returned to atmospheric pressure, leading to poor appearance. As a result, the seal layer (I) made of the propylene-ethylene block copolymer (A) capable of exhibiting good adhesive strength, the layer (II) made of the acrylic resin (B), and the seal layer (I) It has been found that a decorative film containing an adhesive layer (III) made of an adhesive resin (C) between the layer (II) and the layer (II) can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention includes the following.
[1] A decorative film for being adhered onto a resin molded body by thermal molding, wherein the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A) and an acrylic resin. A layer (II) composed of (B) and an adhesive layer (III) composed of an adhesive resin (C) between the seal layer (I) and the layer (II) are included.
The propylene-ethylene block copolymer (A) is a decorative film characterized by satisfying the following requirements (a1) to (a3).
Requirements for propylene-ethylene block copolymer (A) (a1) The component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer is 5 to 97% by weight, and the ethylene content is higher than that of the component (A1). It contains 3 to 95% by weight of a component (A2) composed of a large amount of propylene-ethylene random copolymer.
(A2) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(A3) The melting peak temperature (Tm (A)) is 110 to 170 ° C.
[2] The decorative film according to the above [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 decorative film according to the above [1] or [2], wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a5).
(A5) The ethylene content of the component (A1) is in the range of 0 to 6% by weight.
[4] The decorative film according to any one of the above [1] to [3], wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a6).
(A6) The ethylene content of the component (A2) is in the range of 5 to 90% by weight.
[5] The adhesive resin (C) is a polyolefin resin having a polar functional group containing at least one heteroatom, and its melt flow rate (230 ° C., 2.16 kg load) is 100 g / 10 minutes or less. The decorative film according to any one of the above [1] to [4], which is a polyolefin resin.
[6] The step of preparing the decorative film according to any one of [1] to [5], the step of preparing a resin molded body, and the resin molded body and the decorative film in a decompressable chamber box. The step of setting, the step of depressurizing the inside of the chamber box, the step of heating and softening the decorative film, the step of pressing the decorative film against the resin molded body, returning the inside of the depressurized chamber box to atmospheric pressure, or A method for producing a decorative molded product, which comprises a step of pressurizing.
[7] The method for producing a decorative molded product according to the above [6], wherein the resin molded product is made of a propylene-based resin composition.

According to the decorative film of the present invention, the decorative film containing an acrylic resin exhibits good adhesion strength even with a short heating time that does not cause appearance defects such as breakage or violence. Therefore, it is possible to obtain a decorative molded body having a good molded appearance and adhesive strength.

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

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

The decorative film in the present invention is a decorative film for being adhered onto a resin molded body by thermal molding, and the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A). ), The layer (II) made of the acrylic resin (B), and the adhesive layer (III) made of the adhesive resin (C) between the seal layer (I) and the layer (II).
The propylene-ethylene block copolymer (A) is a decorative film characterized by satisfying the following requirements (a1) to (a3).
(A1) A component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer containing 5 to 97% by weight, and a component consisting of a propylene-ethylene random copolymer having a higher ethylene content than the component (A1) (a1). A2) is contained in an amount of 3 to 95% by weight.
(A2) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(A3) The melting peak temperature (Tm (A)) is 110 to 170 ° C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Layer (II)
The decorative film of the present invention contains a layer (II) made of an acrylic resin (B). By including the layer (II) made of the acrylic resin (B), it has excellent designability utilizing the excellent properties of the acrylic resin such as transparency, scratch resistance, weather resistance, and ease of printing. A decorative molded body can be obtained.

Acrylic resin (B)
Examples of the acrylic resin (B) in the present invention include acrylic resins such as polymethylmethacrylate, polyethylmethacrylate, polybutylmethacrylate, methylmethacrylate-butylmethacrylate copolymer, and methylmethacrylate-styrene copolymer. Further, the above-mentioned mixed resin of the acrylic resin and the thermoplastic polyurethane resin, the mixed resin of the above-mentioned acrylic resin and the acrylic rubber, and the like can be used.

The acrylic resin (B) contains general additives such as stabilizers, lubricants, processing aids, impact resistant aids, fillers, colorants, matting agents, ultraviolet absorbers and the like, if necessary. be able to.
As the above-mentioned acrylic resin, commercially available products such as Mitsubishi Rayon's product name "Acrypet" and Sumitomo Chemical's product name "Sumipex" can be preferably used.

Adhesive layer (III)
The decorative film of the present invention contains an adhesive layer (III) made of an adhesive resin between the seal layer (I) and the layer (II). By providing the adhesive layer made of the adhesive resin (C), the layer (II) made of the acrylic resin and the seal layer (I) made of the propylene-ethylene block copolymer (A) can be separated from each other without using an organic solvent. Can be glued to.

Adhesive resin (C)
The adhesive resin (C) is not particularly limited as long as it is a resin that exhibits adhesiveness to both the propylene-ethylene block copolymer (A) and the acrylic resin (B), but has a polarity containing a hetero atom. A polyolefin resin having a functional group is preferable.

Examples of the polar functional group containing a hetero atom include an epoxy group, a carbonyl group, an ester group, an ether group, a hydroxy group, a carboxy group or a metal salt thereof, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, and an acid anhydride group. Examples thereof include an amino group, an imide group, an amide group, a nitrile group, a thiol group, a sulfo group, an isocyanate group and a halogen group.

Specific examples of the polyolefin resin having such a polar functional group include acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; both ethylene / vinyl chloride copolymer and ethylene / vinylidene chloride. Polymers, ethylene / acrylonitrile copolymers, ethylene / methacrylonitrile copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylamide copolymers, ethylene / methacrylic acid copolymers, ethylene / acrylic acid copolymers, Ethylene / methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer Combined, ethylene / isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / Butyl methacrylate copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethyl ethylene / maleic anhydride copolymer, Ethylene / metal acrylate copolymer, ethylene / metal methacrylate copolymer, ethylene / vinyl acetate copolymer or sacrifice thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer Ethylene or α-olefin / vinyl monomer copolymers such as ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer; chlorine such as chlorinated polypropylene chlorinated polyethylene Examples include copolymerized polyolefins. Further, these resins may be used alone or may be mixed in two or more kinds. Further, if necessary, other resins or rubbers, tackifiers, various additives and the like may be mixed.

Examples of the other resin or rubber include polyα-olefins such as polypentene-1 and polymethylpentene-1, ethylene or α-olefin / α-olefin copolymers such as propylene / butene-1 copolymers. Ethylene or α-olefin / α-olefin / diene monomer copolymer such as ethylene / propylene / 5-ethylidene-2-norbornene copolymer, polydiene copolymer such as polybutadiene, polyisoprene, styrene / butadiene random co Single amount of vinyl such as polymer, vinyl monomer / diene monomer random copolymer such as styrene / isoprene random copolymer, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer Hydrogenation (vinyl monomer / diene) such as body / diene monomer / vinyl monomer block copolymer, hydrogenation (styrene / butadiene random copolymer), hydrogenation (styrene / isoprene random copolymer) Hydrogenation (vinyl monomer / diene monomer) such as monomer random copolymer), hydrogenation (styrene / butadiene / styrene block copolymer), hydrogenation (styrene / isoprene / styrene block copolymer) / Vinyl monomer block copolymer), acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer and other vinyl monomers / diene monomer / vinyl monomer grafts Polymers, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, ethyl polyacrylate, butyl polyacrylate, methyl polymethacrylate, vinyl polymers such as polystyrene, vinyl chloride / acrylonitrile copolymer, vinyl chloride / Vinyl acetate copolymer, acrylonitrile / styrene copolymer, vinyl copolymer such as methyl methacrylate / styrene copolymer and the like can be mentioned.

Examples of the tackifier include rosin-based resins (gam rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resin, and terpene resin ( Polymers of α-pinene, β-pinene, limonene, etc.), aromatic hydrocarbon-modified terpene resin, petroleum resin (aliphatic, alicyclic, aromatic, etc.), kumaron inden resin, styrene resin, Examples thereof include phenol resins (alkylphenols, phenolxylene formaldehyde, rosin-modified phenolic resins, etc.), xylene resins, and the like, and these can be used alone or in combination of two or more. Of these, rosin-based resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferable from the viewpoint of thermal stability, and are compatible with the modified polyolefin-based resin of the present invention. However, rosin-based resins and terpene phenol resins are particularly preferable because they can contribute to adhesion to polar resins.

Examples of the additive include antioxidants, metal deactivators, phosphorus-based processing stabilizers, ultraviolet absorbers, ultraviolet stabilizers, fluorescent whitening agents, metal soaps, stabilizers such as antioxidative adsorbents, and cross-linking agents. , Chain transfer agent, nucleating agent, lubricant, plasticizer, filler, reinforcing material, pigment, dye, flame retardant, antistatic agent and the like, and may be added within a range that does not impair the effects of the present invention.

As a commercially available product of a polyolefin resin having a polar functional group, a product name "Admer" manufactured by Mitsui Chemicals, a product name "Modic" manufactured by Mitsubishi Chemical Corporation, "Youmex" manufactured by Sanyo Chemical Industries, etc. can be preferably used.

The melt flow rate (230 ° C., 2.16 kg load) (hereinafter referred to as “MFR”) of the adhesive resin (C) is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less, still more preferably 20 g. / 10 minutes or less. By setting the MFR of the adhesive resin (C) to the above value or less, the adhesive layer (III) made of the adhesive resin (C) can be laminated on the seal layer (I) by the extrusion molding method. The MFR of the adhesive resin (C) is preferably 0.1 g / 10 minutes or more, more preferably 0.3 g / 10 minutes or more. By setting the MFR of the adhesive resin (C) to the above value or more, roughening of the interface at the laminated interface occurs in the coextrusion molding of the propylene-ethylene block copolymer (A) and the adhesive resin (C). It is possible to prevent problems such as the adhesive resin (C) not being laminated to the edge of the film.

Decorative film The decorative film in the present invention comprises a seal layer (I) made of a propylene-ethylene block copolymer (A), a layer (II) made of an acrylic resin (B), and an adhesive resin (C). The adhesive layer (III) is included in the order of the seal layer (I) / adhesive layer (III) / layer (II). The decorative film can have various configurations in addition to the sealing layer (I), the adhesive layer (III), and the layer (II). That is, even if the decorative film is a three-layer film composed of the seal layer (I), the adhesive layer (III) and the layer (II), the decorative film includes the seal layer (I), the adhesive layer (III) and the layer (II). It may be a multilayer film having four or more layers composed of other layers. The seal layer (I) is attached along the resin molded body (base). Further, the surface of the decorative film may be textured, embossed, printed, sandplasted, scratched or the like.

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

In addition to the seal layer (I), the adhesive layer (III) and the layer (II), the multilayer film includes a surface layer, a surface decoration layer, a printing layer, a light-shielding layer, a colored layer, a base material layer, a barrier layer, and the like. A tie layer layer or the like that can be provided between the layers can be included.

In the multilayer film, the layers other than the seal layer (I), the adhesive layer (III) and the layer (II) are preferably a layer made of a thermoplastic resin, and more preferably a layer made of a polypropylene resin. The polypropylene-based resin constituting the layers other than the seal layer (I), the adhesive layer (III) and the layer (II) is composed as long as it can be distinguished from the seal layer (I), the adhesive layer (III) and the layer (II). Is not particularly limited. Each layer is preferably a layer that does not contain a thermosetting resin. By using the thermoplastic resin, the recyclability is improved, and by using the polypropylene-based resin, the complexity of the layer structure can be suppressed, and the recyclability is further improved.

When the decorative film is a multilayer film having four or more layers, the seal layer (I) / adhesive layer (III) / layer (II) / other layers (including a plurality of layers) from the sticking surface side of the resin molded product. Further, a configuration of a seal layer (I) / other layer (including a plurality of layers) / an adhesive layer (III) / a layer (II) / another layer (including a plurality of layers) can be mentioned.

1 (a) and 1 (b) are explanatory views schematically illustrating a cross section of an embodiment of a decorative film, and FIGS. 8 (a) and 8 (b) show a decorative film attached to a resin molded body. It is explanatory drawing which schematically exemplifies the cross section of the embodiment of the dressed decorative molded body. In FIGS. 1 (a) and 1 (b), and FIGS. 8 (a) and 8 (b), the arrangement of the seal layer (I), the adhesive layer (III), and the layer (II) is specified for ease of understanding. However, the layer structure of the decorative film is not limited to these examples. In the present specification, reference numeral 1 in the drawing is a decorative film, reference numeral 2 is a layer (II), reference numeral 3 is a seal layer (I), reference numeral 4 is a printing layer (IV), reference numeral 5 is a resin molded body, and reference numeral 7 is a resin molded body. The adhesive layer (III) is shown. The decorative film of FIG. 1 (a) is composed of a seal layer (I), an adhesive layer (III), and a layer (II), and as shown in FIG. 8 (a), a seal layer (I) is formed on the surface of the resin molded body 5. ) Is attached, and the adhesive layer (III) is laminated on the seal layer (I), and the layer (II) is laminated on the adhesive layer (III) in this order. The decorative film of FIG. 1 (b) is composed of a seal layer (I), an adhesive layer (III), a layer (II) and a print layer (IV), and as shown in FIG. 8 (b), the resin molded body 5 A seal layer (I) is attached to the surface, an adhesive layer (III) is placed on the seal layer (I), a layer (II) is placed on the adhesive layer (III), and a printed layer (II) is placed on the layer (II). IV) is laminated in this order. The printing layer (IV) is preferably a layer made of a polypropylene resin.

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

In the decorative film of the present invention, the ratio of the thickness of the seal layer (I) to the total thickness of the decorative film is preferably 1 to 69%, and the ratio of the thickness of the adhesive layer (III) is preferably 1. It is ~ 69%, and the ratio of the thickness of the layer (II) is preferably 30 to 98%. When the ratio of the thickness of the seal layer (I) to the entire decorative film is within the above value range, sufficient adhesive strength can be exhibited. Further, if the ratio of the thickness of the adhesive layer (III) to the entire decorative film is within the above value range, delamination of the layer (I) and the layer (III) can be suppressed. Further, if the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, it is possible to avoid insufficient thermoformability of the decorative film.

Production of Decorative Film The decorative film of the present invention can be produced by various known molding methods.
For example, a seal layer (I) containing a propylene-ethylene block copolymer (A), an adhesive layer (III) made of an adhesive resin (C), and a layer (II) made of an acrylic resin (B) (optionally). A method of co-extruding (with another layer), a layer (II) composed of an acrylic resin (B) extruded in advance by co-extruding the seal layer (I) and the adhesive layer (III) with another layer. ), A thermal lamination method in which the layer (II) and the adhesive layer (III) are bonded together by applying heat and pressure so that the layer (II) and the adhesive layer (III) are in contact with each other. And a dry lamination method and a wet lamination method in which a seal layer (I) containing a propylene-ethylene block copolymer (A) extruded in advance is bonded via an adhesive layer (III), and an acrylic system extruded in advance. Extrusion lamination method or pre-extrusion by melt extrusion of the adhesive layer (III) and the seal layer (I) containing the propylene-ethylene block copolymer (A) on the surface of the layer (II) made of the resin (B). The layer (II) made of the molded acrylic resin (B) and the seal layer (I) containing the propylene-ethylene block copolymer (A) extruded in advance are melt-extruded by the adhesive layer (III). Examples include a sand lamination method for bonding. As an apparatus for forming the decorative film, a known coextrusion T-die molding machine or a known laminating molding machine can be used.

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

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

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

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

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

Since polypropylene-based resin is non-polar, it is a poorly adhesive polymer. However, the decorative film in the present invention contains a seal layer (I) made of propylene-ethylene block copolymer (A). By sticking the decorative object made of polypropylene resin to the decorative film, it is possible to exhibit extremely high adhesive strength and make the scratches on the surface of the decorative object inconspicuous.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

At this time, a film made of a general polypropylene resin may be significantly deformed and ruptured by a slight pressure fluctuation due to a decrease in viscosity during heating.

The decorative film 1 of the present invention is not only difficult to draw down, but also resistant to film deformation due to pressure fluctuations.

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

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

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

The higher the heater temperature, the shorter the time required for heating, but the heater side is sufficiently heated until the inside of the decorative film 1 (or the surface opposite to the heater when the heater is installed on only one side) is sufficiently heated. The heater temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, and most preferably 400 ° C., because not only the moldability is deteriorated but also the resin is thermally deteriorated when the temperature is too high. It is as follows.

The appropriate heating time depends on the heater temperature, but at the shortest, it is preferable that the polypropylene-based decorative film is heated for a time until the re-tensioning called springback starts or longer.
That is, the decorative film heated by the heater expands thermally when heated from the solid state and sags once as the crystal melts, and when the crystal melt progresses, the molecules relax and the springback temporarily rebounds. Is observed, and then it hangs down due to its own weight. However, after springback, the crystals of the film are completely melted and the molecules are sufficiently relaxed, so that sufficient adhesive strength can be obtained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

3. 3. Other Materials Used As the resin for the seal layer (I) of the decorative film, the following polypropylene-based resins were used in addition to the above-mentioned propylene-ethylene block copolymers (A-1) to (A-4).
(A-5): Propylene homopolymer (MFR = 10 g / 10 minutes, Tm = 161 ° C., ethylene content E (A) 0% by weight, polymerized only in the first polymerization step, so component (A2) is not included), Product name "Novatec (registered trademark) FA3KM" manufactured by Japan Polypropylene Corporation
(A-6): Propylene-α-olefin copolymer (MFR = 7 g / 10 minutes, Tm = 146 ° C., ethylene content E (A) 2.5% by weight, component polymerized only in the first polymerization step (A-6) A propylene-α-olefin copolymer consisting only of A1) and does not contain the component (A2)), manufactured by Nippon Polypro Co., Ltd., trade name "Novatec (registered trademark) FW3GT"

As the decorative film layer (II), a film made of the following acrylic resin was used.
Film (B-1) made of acrylic resin (B): Polymethylmethacrylate resin film, manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acriprene (registered trademark) HBS010P, film thickness 75 μm"

The following adhesive resin was used as the resin for the adhesive layer (III) of the decorative film.
Adhesive resin (C)
(C-1): Maleic anhydride-modified polyolefin (MFR = 7 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F534A"
(C-2): Maleic anhydride-modified polyolefin (MFR = 1.6 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F532"

4. Production of Resin Molded Body (Base) An injection molded product was obtained by the following method using the following polypropylene-based resins (X-1) to (X-3).
(X-1): Propylene homopolymer (MFR = 40 g / 10 minutes, Tm = 165 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) MA04H"
(X-2): Propylene ethylene block copolymer (MFR = 30 g / 10 minutes, Tm = 164 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) NBC03HR"
(X-3): 60% by weight of polypropylene resin (X-2), 20% by weight of EBR (Toughmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Tarku) Talk P-6 manufactured by TARC Co., Ltd., average particle size 4.0 μm) 20% by weight blended polypropylene resin composition Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 100 tons Cylinder temperature: 200 ° C.
Mold temperature: 40 ° C
Injection mold: Width x Height x Thickness = 120 mm x 120 mm x 3 mm Flat plate Condition adjustment: Hold for 5 days in a constant temperature and humidity chamber with a temperature of 23 ° C and a humidity of 50% RH

Example 1
-Manufacture of decorative film Lip opening 0.8 mm to which an extruder for a seal layer (I) having a diameter of 30 mm (diameter) and an extruder for an adhesive layer (III) having a diameter of 40 mm (diameter) -2 are connected. , A two-kind two-layer T-die having a die width of 400 mm was used. The propylene-ethylene block copolymer (A-1) was charged into the extruder-1 for the seal (I) layer, and the adhesive resin (C-1) was charged into the extruder-2 for the adhesive layer (III). Melt extrusion was performed under the conditions of a resin temperature of 240 ° C., a discharge rate of the seal layer (I) extruder-1 of 4 kg / h, and a discharge rate of the adhesive layer (III) extruder-2 of 8 kg / h. The melt-extruded film was cooled and solidified while being pressed against the first roll rotating at 3 m / min at 80 ° C. with an air knife so that the seal layer (I) was in contact with the first roll. A two-layer unstretched film on which a 100 μm adhesive layer (III) was laminated was obtained.

The obtained unstretched film and the film (B-1) made of the acrylic resin (B) were cut out in a width of 250 mm and a length of 1000 mm so that the longitudinal direction was the MD direction of the film. The cut out acrylic resin (B) film and the cut out unstretched film adhesive layer (III) were laminated so as to be in contact with each other, and integrated using a thermal laminating machine under the following conditions to obtain a decorative film. .. The thermal laminating conditions are as follows.
Thermal laminating machine: "Small desktop laminator" manufactured by Tester Sangyo Co., Ltd.
Heating conditions: Acrylic film contact surface, 130 ° C
Seal layer contact surface, 23 ° C
Pressurization condition: 1.5 kgf / m
Line speed: 0.5m / min

-As the three-dimensional decorative thermoformed resin molded body (base) 5, an injection molded body made of the polypropylene-based resin (X-1) obtained above was used.
As a three-dimensional decorative thermoforming apparatus, "NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 was set on a film fixing jig 13 having an opening size of 210 mm × 300 mm so that the seal layer (I) faces the substrate. The resin molded body (base) 5 is placed on a sample setting table having a height of 20 mm, which is installed on a table 14 located below the film fixing jig 13, and is manufactured by Nichiban Co., Ltd. “Nystack NW-K15”. I pasted it through. The film fixing jig 13 and the table 14 were installed in the chamber boxes 11 and 12, and the chamber boxes were closed to close the inside of the chamber boxes 11 and 12. The chamber box is divided into upper and lower parts via the decorative film 1. With the upper and lower boxes vacuum sucked and the pressure reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80% to form the decorative film 1. It was heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated and temporarily sags, and then 25 seconds after the springback phenomenon of tensioning back is completed (that is, the heating time after the springback phenomenon is 25 seconds), it is installed in the lower chamber box 12. The table 14 is moved upward, the resin molded body (base) 5 is pressed against the decorative film 1, and immediately after that, compressed air is sent so that the pressure in the upper chamber box 11 becomes 270 kPa to make the resin molded body (base). ) 5 and the decorative film 1 were brought into close contact with each other. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was attached to the upper surface and the side surface of the resin molded body (base) 5 was obtained.

・ Evaluation of physical properties (1) Evaluation of thermoformability (appearance of decorative molded product)
Visually observe the draw-down state of the decorative film at the time of three-dimensional decorative thermoforming and the attached state of the decorative film of the decorative molded body in which the decorative film is attached to the substrate, and the criteria shown below are used. Evaluated in.
◯: During three-dimensional decorative thermoforming, the decorative film did not draw down and the substrate and the decorative film were in contact with each other at the same time on the entire contact surface, so that contact unevenness did not occur and the film was evenly attached. ing.
X: During three-dimensional decorative thermoforming, the decorative film was drawn down, causing uneven contact on the entire surface of the substrate.

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

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

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

Table 4 shows the results of evaluation of the physical properties of the obtained decorative molded product and the like. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 2
In the production of the decorative film of Example 1, except that the propylene-ethylene block copolymer (A-1) used for the seal layer (I) was changed to the propylene-ethylene block copolymer (A-2). Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 3
In the production of the decorative film of Example 1, except that the propylene-ethylene block copolymer (A-1) used for the seal layer (I) was changed to the propylene-ethylene block copolymer (A-3). Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 4
In the production of the decorative film of Example 1, except that the propylene-ethylene block copolymer (A-1) used for the seal layer (I) was changed to the propylene-ethylene block copolymer (A-4). Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 5
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the adhesive resin (C-1) used for the adhesive layer (III) was changed to the adhesive resin (C-2). went. The evaluation results are shown in Table 4. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 6
In the three-dimensional decorative thermoforming of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the substrate was changed to an injection molded product using a resin (X-2). The results obtained are shown in Table 4.
The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 7
In the three-dimensional decorative thermoforming of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the substrate was changed to an injection molded product using a resin (X-3). The results obtained are shown in Table 4.
The obtained decorative molded product was excellent in appearance and adhesive strength.

Comparative Example 1
Example 1 except that the propylene-ethylene block copolymer (A-1) used for the seal layer (I) was changed to a propylene homopolymer (A-5) in the production of the decorative film of Example 1. The evaluation was performed in the same manner as above. The evaluation results are shown in Table 5.
Since the propylene homopolymer (A-5) used for the seal layer did not contain the component (A2), it was inferior in adhesive strength.

Comparative Example 2
In the production of the decorative film of Example 1, except that the propylene-ethylene block copolymer (A-1) used for the seal layer (I) was changed to the propylene-α-olefin copolymer (A-6). , The evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 5.
The propylene-α-olefin copolymer (A-6) used for the seal layer did not contain the component (A2), and therefore had poor adhesive strength.

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 (I) was changed to a propylene homopolymer (A-5), and further three-dimensional decoration was performed. In the thermoforming, the evaluation was carried out in the same manner as in Example 1 except that heating was continued for 40 seconds after the springback phenomenon was completed and then decorative thermoforming was performed. The evaluation results are shown in Table 5.
Since the heating time was long, the decorative film came into contact with the substrate in a state of hanging down due to its own weight, so that contact unevenness occurred in the entire decorative molded body, which was inferior in appearance, and the adhesive strength and gloss were not evaluated. ..

Comparative Example 4
The evaluation was carried out in the same manner as in Example 1 except that only the film (B-1) made of the acrylic resin (B) was used instead of the decorative film of Example 1. The evaluation results are shown in Table 5.
Since the decorative film did not have the sealing layer (I) and the adhesive layer (III), it did not adhere to the substrate. No gross evaluation was performed.

According to the present invention, it is possible to achieve both sufficient adhesive strength and product appearance, reduce product defects by making scratches on the substrate inconspicuous, and use it for three-dimensional decorative thermoforming that facilitates recycling. A decorative film and a method for producing a decorative molded product using the decorative film are provided.

1 Decorative film 2 layers (II)
3 Seal layer (I)
4 Print layer (IV)
5 Resin molded body (decoration target, substrate)
6 Decorative molded product 7 Adhesive layer (III)
11 Upper chamber box 12 Lower chamber box 13 Jig 14 Table 15 Heater

Claims (7)

A decorative film for being adhered onto a resin molded body by thermal molding, wherein the decorative film is a seal layer (I) made of a propylene-ethylene block copolymer (A) and an acrylic resin (B). A layer (II) composed of, and an adhesive layer (III) composed of an adhesive resin (C) between the seal layer (I) and the layer (II) are included.
The propylene-ethylene block copolymer (A) is a decorative film characterized by satisfying the following requirements (a1) to (a3).
Requirements for propylene-ethylene block copolymer (A) (a1) The component (A1) composed of a propylene homopolymer or a propylene-ethylene random copolymer is 5 to 97% by weight, and the ethylene content is higher than that of the component (A1). It contains 3 to 95% by weight of a component (A2) composed of a large amount of propylene-ethylene random copolymer.
(A2) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(A3) The melting peak temperature (Tm (A)) is 110 to 170 ° C. The decorative film according to claim 1, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a4).
(A4) The ethylene content in the propylene-ethylene block copolymer (A) is 0.15 to 85% by weight. The decorative film according to claim 1 or 2, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a5).
(A5) The ethylene content of the component (A1) is in the range of 0 to 6% by weight. The decorative film according to any one of claims 1 to 3, wherein the propylene-ethylene block copolymer (A) satisfies the following requirement (a6).
(A6) The ethylene content of the component (A2) is in the range of 5 to 90% by weight. The adhesive resin (C) is a polyolefin resin having a polar functional group containing at least one heteroatom, and the melt flow rate (230 ° C., 2.16 kg load) is 100 g / 10 minutes or less. The decorative film according to any one of claims 1 to 4, wherein the decorative film is a resin. The step of preparing the decorative film according to any one of claims 1 to 5, the step of preparing a resin molded body, the step of setting the resin molded body and the decorative film in a decompressable chamber box, the step of setting the decorative film and the decorative film. Includes a step of depressurizing the inside of the chamber box, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the inside of the depressurized chamber box to atmospheric pressure. A method for manufacturing a decorative molded product. The method for producing a decorative molded product according to claim 6, wherein the resin molded product is made of a propylene-based resin composition.

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