JP6958281B2 - 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 body, and has less wrinkle return after thermoforming and less damage to the film during molding. The present invention relates to a decorative film for being attached onto a molded body by thermoforming, and a method for producing a decorative molded body using the decorative film.

In recent years, there has been an increasing demand for decoration technology that replaces painting due to VOC (volatile organic compound) reduction demands 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 typified by insert molding, vacuum pressure air forming and decorative molding by vacuum forming have a greater degree of freedom in shape, and the end face of the decorative film is caught up to the back side of the object to be decorated, resulting in a seam. It is excellent in appearance because it does not occur, and it can be thermoformed at a relatively low temperature and low pressure. 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. To solve this problem, it has been proposed to use acrylic adhesives, urethane adhesives, tack fires, etc. as layers 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, the decorative film and the molded body are heat-sealed by applying a decorative film containing an adhesive layer containing the polypropylene resin to a substrate (molded body) made of a polypropylene resin. (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, making it impossible to obtain a decorative molded product having an excellent appearance. In particular, when polyurethane resin is contained as a dissimilar raw material, polyurethane resin, which is a thermosetting resin, does not melt when heated, so that it is easy to maintain the form of the film and the thermoformability is greatly improved, but there is a problem that recyclability is extremely low. rice field.
Further, vacuum pressure air molding and decorative thermoforming by vacuum molding have an advantage that a molded product having a high degree of integration between the base molded in a process such as injection molding and the decorative film can be obtained, while the decorative film is the base. There is a problem that the scratches on the surface of the decorative molded product are picked up, and the appearance of the decorative molded product is likely to be poor due to the influence of the scratches on the surface of the substrate.

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

With conventional techniques, 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 be 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, a seal layer (I) made of a resin composition capable of exhibiting good adhesive strength containing polypropylene resin (A) and thermoplastic elastomer (B) as main components, and a layer made of acrylic resin (II). ), And a decorative film containing an adhesive layer (III) made of an adhesive resin (D) between the seal layer (I) and the layer (II) can solve the above-mentioned problems. It came to be completed.

That is, the present invention includes the following.
[1] A decorative film for attaching to a resin molded body by thermoforming.
The decorative film contains a polypropylene-based resin (A) and a thermoplastic elastomer (B) as main components, and the weight ratio of the polypropylene-based resin (A) to the thermoplastic elastomer (B) is 97: 3 to 5:95. The seal layer (I) made of the resin composition, the layer (II) made of the acrylic resin (C), and the adhesive resin (D) between the seal layer (I) and the layer (II). Includes layer (III)
The polypropylene-based resin (A) satisfies the following requirement (a1).
A decorative film characterized in that the thermoplastic elastomer (B) satisfies the following requirements (b1) to (b3).
(A1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(B1) A thermoplastic elastomer containing propylene and / or butene as a main component.
(B2) The density is 0.850 to 0.950 g / cm ³ .
(B3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 minutes.
[2] The thermoplastic elastomer (B) is a propylene-ethylene copolymer having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of 50% by weight. The decorative film according to [1], wherein the decorative film is less than a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer.
[3] The decorative film according to [1] or [2], wherein the thermoplastic elastomer (B) satisfies the following requirement (b4).
(B4) The melting peak temperature (Tm (B)) is 30 to 170 ° C.
[4] The adhesive resin (D) is a polyolefin resin having a polar functional group containing at least one heteroatom, and its MFR (230 ° C., 2.16 kg load) (MFR (D)) is 100 g. The decorative film according to any one of [1] to [3], which is a polyolefin resin having a time of 10 minutes or less.
[5] The step of preparing the decorative film according to any one of [1] to [4], the step of preparing a resin molded body, and the resin molded body and the decorative film in a decompressable chamber box. A step of setting, 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, a step of returning or applying the pressure inside the decompressed chamber box to atmospheric pressure. A method for producing a decorative molded product, which comprises a step of pressing.
[6] The method for producing a decorative molded product according to [5], wherein the resin molded product is made of a propylene-based resin composition.

Since the decorative film of the present invention exhibits good adhesive strength to the molded product even when heated for a short time, it does not break or run wild during processing, and a decorative molded product having a good appearance can be obtained. Can be done. According to the decorative film of the present invention, it is possible to impart excellent designability to a molded product while taking advantage of excellent properties such as transparency, scratch resistance, weather resistance, and ease of printing of an acrylic resin. ..

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

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 bonded to each other, and has a step of thermoforming the decorative film along the bonding surface of the molded body and simultaneously bonding the decorative film. In this step, in order to prevent air from being entrained between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is attached to the molded body, and pressure is applied. Molding is a process of bringing the product into close contact 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 attached to a resin molded body by thermoforming.
The decorative film contains a polypropylene-based resin (A) and a thermoplastic elastomer (B) as main components, and the weight ratio of the polypropylene-based resin (A) to the thermoplastic elastomer (B) is 97: 3 to 5:95. The seal layer (I) made of the resin composition, the layer (II) made of the acrylic resin (C), and the adhesive resin (D) between the seal layer (I) and the layer (II). Includes layer (III)
The polypropylene-based resin (A) satisfies the following requirement (a1).
The thermoplastic elastomer (B) is a decorative film characterized by satisfying the following requirements (b1) to (b3).
(A1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 minutes.
(B1) A thermoplastic elastomer containing propylene and / or butene as a main component.
(B2) The density is 0.850 to 0.950 g / cm ³ .
(B3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 minutes.

[Seal layer (I)]
The decorative film of the present invention contains a seal layer (I) composed of a resin composition containing a polypropylene resin (A) and a thermoplastic elastomer (B) as main components. 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 decorative thermoforming is short, and scratches on the surface of the substrate can be made inconspicuous.

[Polypropylene resin (A)]
The polypropylene-based resin (A) in the present invention is various types of propylene-based resins such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), and a propylene block copolymer (block polypropylene). Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of polymerization units derived from the propylene monomer. The propylene-based polymer preferably does not contain a polymerization unit derived from a polar group-containing monomer.

(A1) Melt flow rate (MFR (A))
The melt flow rate (230 ° C., 2.16 kg load) MFR (A) of the polypropylene-based resin (A) contained in the seal layer (I) needs to exceed 0.5 g / 10 minutes, preferably 1 g. / 10 minutes or more, more preferably 2 g / 10 minutes or more. Within the above range, relaxation during three-dimensional decorative thermoforming proceeds sufficiently, sufficient adhesive strength can be exhibited, and scratches on the substrate become 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 MFR of the polypropylene-based resin and the polypropylene-based resin composition described later was measured in accordance with ISO 1133: 1997 Connections M under the conditions of 230 ° C. and a 2.16 kg load. The unit is g / 10 minutes.

(A2) Melting peak temperature (Tm (A))
The melting peak temperature (DSC melting peak temperature, sometimes referred to as “melting point” in the present specification) (Tm (A)) of the polypropylene-based resin (A) is preferably 110 ° C. or higher, preferably 115 ° C. or higher. It is more preferable that the temperature is 120 ° C. or higher. Within the above range, the moldability at the time of three-dimensional decorative thermoforming is good. There is no limit to the upper limit of the melting peak temperature, but it is preferably 170 ° C. or lower, and if it is in the above range, sufficient adhesive strength can be exhibited.

The polypropylene-based resin (A) in the present invention can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene-based resin (A) can be a Ziegler-catalyzed propylene polymer or a metallocene-catalyzed propylene polymer.

[Thermoplastic Elastomer (B)]
The thermoplastic elastomer (B) used as an essential component in the seal layer (I) of the present invention has the following properties (b1) to (b3), preferably further (b4) and / or (b5). ..

(B1) Composition The thermoplastic elastomer (B) of the present invention is a thermoplastic elastomer containing propylene and / or butene as a main component. Here, the "thermoplastic elastomer containing propylene and / or butene as a main component" includes (i) a thermoplastic elastomer containing propylene as a main component, (ii) a thermoplastic elastomer containing butene as a main component, and (iii) propylene. Includes a thermoplastic elastomer whose main component is the sum of and butene. In addition, in this specification, the unit "wt%" means the weight%.

The content of propylene or butene in the thermoplastic elastomer (B) is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more. For example, the thermoplastic elastomer (B) can contain more than 35% by weight of propylene or butene.
Further, the thermoplastic elastomer (B) may contain both propylene and butene. In that case, the total component of propylene and butene becomes the main component of the thermoplastic elastomer (B), and the total content of propylene and butene is It is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. When both propylene and butene are included, for example, the thermoplastic elastomer (B) can contain more than 35% by weight of propylene and butene in total. Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the effect of making scratches on the substrate inconspicuous is high. It is considered that the thermoplastic elastomer containing propylene or butene as a main component has high uniform dispersibility in the polypropylene-based resin (A), which further enhances the effect of making scratches on the substrate less noticeable. The thermoplastic elastomer (B) can also be a single component of propylene or butene.

(B2) the density of the density thermoplastic elastomer (B) is required to be 0.850~0.950g / cm ^3, preferably 0.855~0.940g / cm ^3, more preferably 0.86 ~ 0.93 g / cm ³ . Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, and film formability is also improved.

(B3) Melt flow rate (MFR (B))
The melt flow rate (230 ° C., 2.16 kg load) MFR (B) of the thermoplastic elastomer (B) needs to be 0.1 to 100 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes. Minutes, more preferably 1 to 30 g / 10 minutes. Within the above range, the effect of making scratches on the substrate inconspicuous is high.

(B4) Melting peak temperature (Tm (B))
The melting temperature peak (DSC melting peak temperature) Tm (B) of the thermoplastic elastomer (B) is preferably 30 to 170 ° C., more preferably 35 to 168 ° C., and even more preferably 40 to 165 ° C. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

(B5) Ethylene content [E (B)]
The thermoplastic elastomer (B) of the present invention can be appropriately selected and used as long as it satisfies the above-mentioned properties (b1) to (b3), but the propylene-ethylene copolymer having an ethylene content of less than 50% by weight is used. Combined, butene-ethylene copolymer having an ethylene content of less than 50% by weight, a propylene-ethylene-butene copolymer having an ethylene content of less than 50% by weight, a propylene-butene copolymer, or a butene homopolymer. Is preferable.

The ethylene content [E (B)] of the propylene-ethylene copolymer, butene-ethylene copolymer or propylene-ethylene-butene copolymer is more preferably 45% by weight or less, still more preferably 40% by weight or less. If it is within the above range, sufficient adhesive strength can be exhibited at the time of three-dimensional decorative heat molding.

[Calculation method of ethylene content [E (B)]]
When the thermoplastic elastomer (B) is an elastomer containing ethylene, the ethylene content [E (B)] of the thermoplastic elastomer (B) can be determined from the integrated strength obtained by ^{13 C-NMR measurement.}

[Calculation method 1 (binary system)]
The ethylene content [E (B)] in a binary elastomer (propylene-ethylene copolymer, butene-ethylene copolymer, etc.) composed of two types of repeating units will be described. The ethylene content of the ethylene-α-olefin binary elastomer can be determined by (Equation-1-1) and (Equation 1-1-2).
Ethylene content (mol%) = IE x 100 / (IE + IX) ... (Equation-1-1)
Ethylene content (% by weight) = [ethylene content (mol%) x molecular weight of ethylene] x 100 / [ethylene content (mol%) x molecular weight of ethylene + α-olefin content (mol%) x molecular weight of α-olefin] ...・ (Equation-1-2)

Here, IE and IX are integrated intensities for ethylene and α-olefin, respectively, and can be obtained by the following formulas (Equation-2) and (Equation-3).
_{IE = (I ββ + I γγ} + I βδ + I γδ + I δδ) / 2 + (I αγ + I αδ) / 4 ··· ( Formula -2)
_{IX = I αα + (I αγ} + I αδ) / 2 ··· ( wherein -3)
Here, the subscript symbol of I on the right side indicates the carbon described in the following structural formulas (a) to (d). For example, αα represents methylene carbon based on the α-olefin chain, and I _αα represents the integrated intensity of the signal of methylene carbon based on the α-olefin chain.

構造式（ｄ）中、ｎは１以上の奇数を表す。
以下に、（式―２）、（式―３）に用いる積分強度について記載する。
プロピレン−エチレン共重合体であれば、（式―２）、（式―３）に以下の積分強度を代入し、エチレン含量を求める。
Ｉ_ββ＝Ｉ_{２５．０−２４．２}
Ｉ_γγ＝Ｉ_{３０．８−３０．６}
Ｉ_βδ＝Ｉ_{２７．８−２６．８}
Ｉ_γδ＝Ｉ_{３０．６−３０．２}
Ｉ_δδ＝Ｉ_{３０．２−２８．０}
Ｉ_αα＝Ｉ_{４８．０−４３．９}
Ｉ_αγ＋Ｉ_αδ＝Ｉ_{３９．０−３６．２}

In the structural formula (d), n represents an odd number of 1 or more.
The integrated intensities used in (Equation-2) and (Equation-3) will be described below.
In the case of a propylene-ethylene copolymer, the following integrated intensities are substituted into (Equation-2) and (Equation-3) to determine the ethylene content.
I _ββ = I _25.0-24.2
I γγ = I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _48.0-43.9
I _αγ + I _αδ = I _39.0-36.2

Here, I indicates the integrated intensity, and the value of the subscript of I on the right side indicates the range of the chemical shift. For example, I _39.0-36.2 indicates the integrated intensity of ^{the 13} C signal detected between 39.0 ppm and 36.2 ppm.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shift of the signal due ^{to the other 13 C was based on this.}
In the case of a butene-ethylene copolymer, the following integrated intensity values are substituted into (Equation-2) and (Equation-3) to obtain the ethylene content [E (B)].
I _ββ = I _24.6-24.4
I γγ = I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ = I _30.5-30.2
I _δδ = I _30.2-28.0
I αα = I _39.3-38.1
I _αγ + I _αδ = I _34.5-33.8

[Calculation method 2 (ternary system)]
Next, the ethylene content [E (B)] in the ternary elastomer composed of three types of repeating units will be described. The ethylene content of the propylene-ethylene-butene ternary elastomer can be determined by the following formulas (formula-4-1) and (formula-4-2).
Ethylene content (mol%) = IE x 100 / (IE + IP + IB) ... (Formula-4-1)
Ethylene content [E (B)] (% by weight) = [ethylene content (mol%) x ethylene molecular weight] x 100 / [ethylene content (mol%) x ethylene molecular weight + propylene content (mol%) x propylene molecular weight + Butene content (mol%) x molecular weight of butene] ... (Formula-4-2)
Here, IE, IP, and IB are integrated intensities for ethylene, propylene, and butene, respectively, and can be obtained by (Equation-5), (Equation-6), and (Equation-7), respectively.
_{IE = (I ββ + I γγ} + I βδ + I γδ + I δδ) / 2 + (I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B)) / 4 ··· ( wherein -5)
IP = 1/3 × [I _{CH3 (P)} + I _{CH (P)} + I _{αα (PP)} + 1/2 × ( _{I αα (PB)} + I _{αγ (P)} + I _{αδ (P)} )] ・ ・ ・ (Equation- 6)
IB = 1/4 × [(I _{CH3 (B)} + I _{CH (B)} + I _2B2 + I _{αα (BB)} ) + 1/2 × ( _{I αα (PB)} + I _{αγ (B)} + I _{αδ (B)} )] ・ ・・ (Equation-7)
Here, the subscript (P) means a signal based on a methyl group branch derived from propylene, and similarly (B) means a signal based on an ethyl group branch derived from butene.
Further, αα (PP) means a signal of methylene carbon based on a propylene chain, similarly, αα (BB) means a signal of methylene carbon based on a butene chain, and αα (PB) means a signal of methylene carbon based on a propylene-butene chain. Means the signal of.

Here, since the γγ signal overlaps the tail of the signal of the methine carbon CH (PPE) of propylene in the center along with propylene-propylene-ethylene, it is difficult to separate the γγ signal.
In the γγ signal, the ethylene chain appears in the two structural formulas (c), and (Equation-8) holds for the integral strength of γγ derived from ethylene and the integral strength of βδ in the structural formula (c).
I _βδ (Structural formula (c)) = 2 × I _γγ ... (Formula-8)
Further, βδ appears in the structural formula (d) having three or more ethylene chains, and the integral strength of βδ in the structural formula (d) is equal to the integral strength of γδ (Equation -9).
I _βδ (Structural formula (d)) = I _γδ・ ・ ・ (Equation-9)
Therefore, βδ based on the structural formula (c) and the structural formula (d) can be obtained by (Equation −10).
I _βδ = I _βδ (structural formula (c)) + I _βδ (structural formula (d)) = 2 × I _γγ + I _γδ ... (Equation -10)
_{That, I γγ = (I βδ -I} γδ) / 2 ··· ( wherein -10 ')
Therefore, by substituting (Equation -10') for (Equation -5), IE can be replaced with (Equation -11).
IE = (I _ββ + I _δδ ) / 2 + (I _{αγ (P)} + I _{αδ (P)} + I _{αγ (B)} + I _{αδ (B)} +3 × I _βδ + I _γδ ) / 4 ... (Equation -11)
Here, the βδ signal corrects the overlap of ethyl branches based on 1-butene and becomes (Equation -12).
I _βδ = I _{αγ (P)} + I _{αδ (P)} + I _{αγ (B)} + I _{αδ (B)} -2 × I _ββ ... (Equation -12)
From (Equation -11) and (Equation -12), IE becomes (Equation -13).
IE = I _δδ / 2 + I _γδ / 4-I _ββ + I _{αγ (P)} + I _{αδ (P)} + I _{αγ (B)} + I _{αδ (B)} ... (Equation -13)
Substitute the following into (Equation-13), (Equation-6), and (Equation-7) to determine the ethylene content.
I _ββ = I _25.2-23.8
I _γδ = I _30.4-30.2
I _δδ = I _30.2-29.8
I _{αγ (P)} + I _{αδ (P)} = I _39.5-37.3
I _{αγ (B)} + I _{αδ (B)} = I _34.6-33.9
I _{CH3 (P)} = I _22.6-19.0
I _{CH (P)} = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I _{αα (PP)} = I 48.0-45.0
I _{CH3 (B)} = I _11.4-10.0
I _{CH (B)} = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
I _{αα (BB)} = I 40.3-40.0
I _{αα (PB)} = I 44.2-42.0
I _2B2 = I _26.7-26.4

For the attribution of each signal, the following five documents were referred to.
Macromolecules, Vol. 10, No. 4,1977,
Macromolecules, Vol. 36, No. 11,2003,
Analytical Chemistry, Vol. 76, No. 19, 2004,
Macromolecules, 2001, 34, 4757-4767,
Macromolecules, Vol. 25, No. 1,1992

Further, the thermoplastic elastomer (B) may be a copolymer of propylene and an α-olefin other than butene as long as the effects of the present invention are not impaired. Specific examples of the α-olefin include ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-. Hexadecene, 1-eikosen and the like can be mentioned. These α-olefins can be used alone or in combination. Among these, 1-hexene and 1-octene are particularly preferably used.

Such a thermoplastic elastomer is produced by copolymerizing each monomer in the presence of a catalyst. Specifically, the thermoplastic elastomer uses a catalyst such as a Cheegler catalyst, a Phillips catalyst, or a metallocene catalyst as an olefin polymerization catalyst, and is propylene in a process such as a vapor phase method, a solution method, a high pressure method, or a slurry method. , 1-butene, ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene and other α-olefins can be copolymerized for production.

Further, the thermoplastic elastomer (B) used for the seal layer (I) of the present invention can be used alone or in combination of two or more as long as the effects of the present invention are not impaired.
Examples of such thermoplastic elastomers include Toughmer XM series, Toughmer BL series, Toughmer PN series manufactured by Mitsui Chemicals, Inc., VISTAMAXX series manufactured by ExxonMobil Chemicals, and the like.

[Resin composition]
The resin composition constituting the seal layer (I) contains a polypropylene-based resin (A) and a thermoplastic elastomer (B). The resin composition may be a mixture of a polypropylene-based resin (A) and a thermoplastic elastomer (B) or a melt-kneaded product, or a sequential polymerization of a polypropylene-based resin (A) and a thermoplastic elastomer (B). It may be a thing.

In the resin composition constituting the seal layer (I), the weight ratio ((A) :( B)) of the polypropylene-based resin (A) and the thermoplastic elastomer (B) is composed of 97: 3 to 5:95. It is necessary, preferably 95: 5 to 10:90, and more preferably 93: 7 to 20:80. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the adhesiveness between the seal layer (I) and the layer (II) is good. Become.

Further, the resin composition may contain additives, fillers, other resin components and the like. The total amount of additives, fillers, other resin components and the like is preferably 50% by weight or less based on the resin composition.

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

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

Examples of the crystal nucleating agent include amide-based nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol-based derivatives, and rosin metal salts. Among these crystal nucleating agents, pt-butyl benzoate aluminum, phosphate 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium, phosphate 2,2′-methylenebis (4) , 6-di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-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 modified polyolefins, petroleum resins, and other thermoplastic resins.

The method for producing the resin composition is a method of melt-kneading a polypropylene-based resin (A), a thermoplastic elastomer (B), an additive, a filler, other resin components, and the like, and a polypropylene-based resin (A) and an additive. , Filler and other resin components are melt-kneaded, and the thermoplastic elastomer (B) is dry-blended. Polypropylene resin (A) is added to the thermoplastic elastomer (B), and additives, fillers, and other resins are added. It can be produced by a method of dry blending a master batch in which a composition or the like is dispersed in a carrier resin at a high concentration.

[Layer (II)]
The decorative film of the present invention contains a layer (II) made of an acrylic resin (C). By including the layer (II) made of the acrylic resin (C), the excellent designability of the acrylic resin, such as transparency, scratch resistance, weather resistance, and ease of printing, can be obtained. It is possible to obtain a decorative molded product having the product.

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

The acrylic resin (C) 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.

[Layer (III)]
The decorative film of the present invention contains an adhesive layer (III) made of an adhesive resin. By providing the adhesive layer made of the adhesive resin (D), the layer (II) made of the acrylic resin and the seal layer (I) made of the polypropylene resin (A) and the thermoplastic elastomer (B) are made into an organic solvent. Can be bonded without using.

Adhesive resin (D)
The adhesive resin (D) is not particularly limited as long as it is a resin composition composed of the polypropylene resin (A) and the thermoplastic elastomer (B) and a resin exhibiting adhesiveness to both the acrylic resin (C). However, it is preferably a polyolefin resin having a polar functional group containing a hetero atom.

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 polyolefins having such polar functional groups include acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer and ethylene / vinylidene chloride copolymer. Combined, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer , Ethethylene / 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, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / Acrylic acid metal salt copolymer, ethylene / methacrylate metal salt copolymer, ethylene / vinyl acetate copolymer or its sacrifice, 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; chlorinated polypropylene Chlorinated polyethylene such as chlorinated polyethylene Examples include 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 (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpenephenol 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, Phenol resins (alkylphenols, phenolxylene formaldehydes, rosin-modified phenol resins, etc.), xylene resins and the like can be mentioned, 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, "Umex" manufactured by Sanyo Chemical Industries, etc. can be preferably used.

Melt flow rate (MFR (D))
The MFR (230 ° C., 2.16 kg load) (MFR (D)) of the adhesive resin (D) 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. Is. By setting the MFR (D) of the adhesive resin (D) to the above value or less, it is possible to laminate the adhesive layer (III) made of the adhesive resin (D) on the seal layer (I) by the extrusion molding method. It becomes. The MFR (D) of the adhesive resin (D) is preferably 0.1 g / 10 minutes or more, and more preferably 0.3 g / 10 minutes or more. By setting the MFR (D) of the adhesive resin (D) to the above value or more, the resin composition composed of the polypropylene resin (A) and the thermoplastic elastomer (B) and the adhesive resin (D) are co-extruded. In molding, it is possible to suppress problems such as roughing of the interface at the laminated interface and the adhesive resin (D) not being laminated to the edge of the film.

Decorative film The decorative film in the present invention includes a seal layer (I) containing a resin composition composed of a polypropylene resin (A) and a thermoplastic elastomer (B), a layer (II) composed of an acrylic resin (C), and a layer (II). The adhesive layer (III) made of the adhesive resin is contained 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 giving a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems in molding with a molded body mold to be embossed, that is, a molded body mold is required for each embossing pattern, and it is very difficult and expensive to apply complicated embossing to a curved mold. It is possible to solve the problem of being, and to obtain a decorative molded body easily embossed with various patterns.

In addition to the seal layer (I), 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. Tie layer layers and the like that can be provided between the layers can be laminated and included in any order.

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 body. 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.

1A and 1B are explanatory views schematically illustrating a cross section of an embodiment of a decorative film. In FIGS. 1 (a) and 1 (b), in order to facilitate understanding, the arrangement of the seal layer (I), the adhesive layer (III), and the layer (II) will be specified and described, but the layer structure of the decorative film will be described. Is not construed as being 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. 1A is composed of a seal layer (I), an adhesive layer (III), and a layer (II), and as shown in FIG. 8, the seal layer (I) is attached to the surface of the resin molded body 5. 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 printing layer (IV) composed of a polypropylene-based resin, and as shown in FIG. 8, a resin molded body. The seal layer (I) is attached to the surface of 5, and is printed on the adhesive layer (III) on the seal layer (I), the layer (II) on the adhesive layer (III), and the layer (II). Layers (IV) are laminated in this order.

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, it is composed of a seal layer (I) containing a resin composition composed of a polypropylene-based resin (A) and a thermoplastic elastomer (B), an adhesive layer (III) composed of an adhesive resin (D), and an acrylic resin (C). A method of co-extruding the layer (II) (with a further layer), a pre-extruded acrylic resin (C) by co-extruding the seal layer (I) and the adhesive layer (III) with the other layer. ) On the surface of the layer (II), the heat and pressure are applied so that the layer (II) and the adhesive layer (III) are in contact with each other. The layer (II) made of the material and the seal layer (I) containing the resin composition made of the polypropylene-based resin (A) extruded in advance and the thermoplastic elastomer (B) are bonded together via the adhesive layer (III). From the adhesive layer (III), polypropylene resin (A) and thermoplastic elastomer (B) on the surface of the layer (II) made of the acrylic resin (C) extruded in advance by the dry lamination method and the wet lamination method. The extruded lamination method in which the seal layer (I) containing the resin composition is melt-extruded, the layer (II) made of the acrylic resin (C) extruded in advance, the polypropylene resin (A) extruded in advance, and heat. Examples thereof include a sand lamination method in which a seal layer (I) containing a resin composition made of a plastic elastomer (B) is bonded by a melt-extruded adhesive layer (III). 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 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, but the decorative film in the present invention is a seal containing a resin composition composed of polypropylene-based resin (A) and thermoplastic elastomer (B). By including the layer (I), the decorative object made of polypropylene resin and the decorative film are adhered to each other to exhibit extremely high adhesive strength, and the scratches on the surface of the decorative object are made inconspicuous. Can be done.

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

In the decorative molded body in which the decorative film of the present invention is attached to various molded bodies formed of polypropylene-based resin in a three-dimensional shape, 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 body of the present invention, the resin molded body and the decorative film are set in a step of preparing the above-mentioned decorative film, a step of preparing a resin molded body, and a chamber box capable of reducing pressure. A step, a step of depressurizing the inside of the chamber box, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the inside of the depressurized chamber box to atmospheric pressure. It is characterized by including.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The appropriate heating time depends on the heater temperature, but at the shortest, it is preferable that the polypropylene-based decorative film is heated for a time until the re-tensioning called springback starts or longer.
That is, the decorative film heated by the heater expands thermally when heated from the solid state and sags once as the crystal melts, and when the crystal melt progresses, the molecules relax and the springback temporarily rebounds. Is observed, and then it hangs down due to its own weight, but 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 defined as the melting peak temperature (melting point). The unit is ° C.

(Iii) Density The density of the thermoplastic elastomer (B) was measured according to JIS K7112: 1999 Density Gradient Tube Method.

(Iv) Ethylene content (E (B))
The ethylene content (E (B)) of the thermoplastic elastomer (B) was determined from the integrated strength obtained by ^{13 C-NMR measurement based on the method as described above.} The sample preparation and measurement conditions are as follows.
The thermoplastic elastomer (B) 200 mg as a sample, o- dichlorobenzene / deuterated benzene bromide _{(C 6} D 5 Br) = mixed solution 2.4ml and chemical shifts of the reference material 4/1 (volume ratio) Hexamethyldisiloxane was placed in an NMR sample tube having an inner diameter of 10 mmφ and dissolved.
The NMR measurement was performed using an AV400 type NMR apparatus manufactured by Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe.
^{13 The} C-NMR measurement conditions were a sample temperature of 120 ° C., a pulse angle of 90 °, a pulse interval of 20 seconds, and an integration number of 512 times, and were carried out by a broadband decoupling method.

2. Materials used (1) Polypropylene resin The following polypropylene resin was used.
(A-1): Propylene-α-olefin copolymer (MFR (A) = 7 g / 10 minutes, Tm (A) = 146 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FW3GT""
(A-2): Propylene homopolymer (MFR (A) = 10 g / 10 minutes, Tm (A) = 161 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FA3KM"

(2) Thermoplastic elastomer (B)
The following thermoplastic elastomers were used.
(B-1): Propylene-butene random copolymer containing propylene as a main component (MFR (B) = 7.0 g / 10 minutes, Tm (B) = 75 ° C., density = 0.885 g / cm ³ , propylene Content = 69% by weight, butene content = 31% by weight, ethylene content ([E (B)]) = 0% by weight): Mitsui Kagaku Co., Ltd., trade name "Toughmer XM7070"
(B-2): Butene homopolymer (MFR (B) = 5.0 g / 10 minutes, Tm (B) = 125 ° C., density = 0.915 g / cm ³ , ethylene content [E (B)] = 0 Weight%): Made by Mitsui Chemicals, Inc., trade name "Toughmer BL4000"
(B-3): Propylene-ethylene-butene random copolymer containing propylene as a main component (MFR (B) = 6.0 g / 10 minutes, Tm (B) = 160 ° C., density = 0.868 g / cm ³⁾ , Propylene content = 84% by weight, ethylene content [E (B)] = 9% by weight, butene content = 7% by weight): Mitsui Kagaku Co., Ltd., trade name "Toughmer PN2060"
(B-4): Propylene-ethylene random copolymer containing propylene as a main component (MFR (B) = 8.0 g / 10 minutes, Tm (B) = 61 ° C., density = 0.871 g / cm ³ , propylene Content = 89% by weight, ethylene content [E (B)] = 11% by weight): Made by ExxonMobil Chemical Co., Ltd., trade name "VISTAMAXX3000"

(3) Acrylic resin (C)
(C-1): Polymethylmethacrylate resin film, manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acriprene (registered trademark) HBS010P, film thickness 75 μm"

(4) Adhesive resin (D)
(D-1): Maleic anhydride-modified polyolefin (MFR (D) = 7 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F534A"
(D-2): Maleic anhydride-modified polyolefin (MFR (D) = 1.6 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F532"

3. 3. 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 2 with a lip opening of 0.8 mm and a die width of 400 mm, to which an extruder for a seal layer with a diameter of 30 mm (diameter) and an extruder for an adhesive layer with a diameter of 40 mm (diameter) -2 are connected. A seed two-layer T-die was used. A blend of a polypropylene resin (A-1) and a thermoplastic elastomer (B-1) in a seal layer extruder-1 so as to have a weight ratio of 85:15 is used in an adhesive layer extruder-2. The adhesive resin (D-1) is charged, the resin temperature is 240 ° C., the discharge amount of the seal layer extruder-1 is 4 kg / h, and the discharge amount of the adhesive layer extruder-2 is 8 kg / h. The melt extrusion was performed in. 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 was in contact with the first roll, and a seal layer having a thickness of 50 μm and an adhesive layer having a thickness of 100 μm were laminated. A two-layer unstretched film was obtained.
The obtained unstretched film and the film (C-1) made of an acrylic resin (C) 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 film and the adhesive layer of the cut out unstretched film were laminated so as to be in contact with each other, and integrated under the following conditions using a thermal laminating machine 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 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 a decorative film 1. With the upper and lower boxes vacuum sucked and the pressure reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80% to form the decorative film 1. It was heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. Twenty-five seconds after the decorative film 1 is heated and temporarily sags, and then the springback phenomenon of tensioning back is completed, the table 14 installed in the lower chamber box 12 is moved upward to form a resin molded body ( The base) 5 was pressed against the decorative film 1, and immediately after that, compressed air was sent so that the pressure in the upper chamber box 11 became 270 kPa to bring the resin molded body (base) 5 and the decorative film 1 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 Nitoms Co., Ltd. "Craft Adhesive Tape No. 712N" was cut out to a width of 75 mm and a length of 120 mm, and from the end of the resin molded body (base). It was attached to a resin molded body (base) in a range of 75 mm × 120 mm and subjected to masking treatment (the exposed portion of the surface of the base has a width of 45 mm and a length of 120 mm). It was installed in the three-dimensional decorative thermoforming apparatus NGF-0406-SW so that the masking surface of the resin molded body (base) was in 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 (60 °)
The gloss near the center of the decorative molded product to which the decorative film was attached was measured at an incident angle of 60 ° using a GLOSS meter Gloss Meter VG2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The measuring method was based on JIS K7105-1981.

Table 1 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, the evaluation was carried out in the same manner as in Example 1 except that the thermoplastic elastomer used for the seal layer was changed to (B-2). The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 3
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 thermoplastic elastomer used for the seal layer was changed to (B-3). The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 4
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 thermoplastic elastomer used for the seal layer was changed to (B-4). The evaluation results are shown in Table 1. 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 compounding ratio of the polypropylene resin (A-1) and the thermoplastic elastomer (B-1) was 70:30. went. The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 6
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 blending ratio of the polypropylene resin (A-1) and the thermoplastic elastomer (B-1) was 30:70. went. The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 7
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 used for the adhesive layer was changed to (D-2). The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 8
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the polypropylene-based resin used for the seal layer was changed to (A-2). The evaluation results are shown in Table 1. The obtained decorative molded product was excellent in appearance and adhesive strength.

Comparative Example 1
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 seal layer was not blended with the thermoplastic elastomer and only the polypropylene resin (A-1) was used. The evaluation results are shown in Table 1.
Since the seal layer did not contain a thermoplastic elastomer, the adhesive strength was inferior.

Comparative Example 2
In the three-dimensional decorative thermoforming of Comparative Example 1, the evaluation was carried out in the same manner as in Example 1 except that the heating time after springback was changed from 25 seconds to 40 seconds. The evaluation results are shown in Table 1.
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 3
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 seal layer (I) and the adhesive layer (III) were not provided and only the acrylic film (C-1) was used. The evaluation results are shown in Table 1.
Since the adhesive layer was not laminated on the decorative film, it did not adhere to the substrate. No gross evaluation was performed.

Example 9
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 1.
The obtained decorative molded product was excellent in appearance and adhesive strength.

Example 10
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 1.
The obtained decorative molded product was excellent in appearance and adhesive strength.

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 (6)

A decorative film for attaching to a resin molded body by thermoforming.
The decorative film is a seal layer (I) containing a polypropylene-based resin (A) (excluding the thermoplastic elastomer (B)) and a resin composition containing the thermoplastic elastomer (B), and has a resin composition. The total content ratio of the polypropylene resin (A) and the thermoplastic elastomer (B) to the product is 50% by weight or more, and the weight ratio of the polypropylene resin (A) to the thermoplastic elastomer (B) is 97: 3 to The seal layer (I) containing the resin composition of 5:95, the layer (II) containing the acrylic resin (C), and the adhesive resin (D) between the seal layer (I) and the layer (II). Includes an adhesive layer (III) containing
The polypropylene-based resin (A) satisfies the following requirement (a1).
A decorative film characterized in that the thermoplastic elastomer (B) satisfies the following requirements (b1) to (b3).
(A1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) is 1 g / 10 minutes or more.
(B1) a thermoplastic elastomer (B) comprises propylene and / or polymerized units derived from butene, the total content of the thermoplastic elastomer (B) propylene and blanking Ten derived polymerized units in the 30 weight % Or more and 100% by weight or less .
(B2) When the thermoplastic elastomer (B) contains a polymerization unit derived from propylene, the density is 0.850 to 0.885 g / cm ³ , and the thermoplastic elastomer (B) does not contain a polymerization unit derived from propylene. In the case, the density is 0.850 to 0.950 g / cm ³ .
(B3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 minutes. The thermoplastic elastomer (B) is a propylene-ethylene copolymer having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of less than 50% by weight. The decorative film according to claim 1, wherein the decorative film is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer. The decorative film according to claim 1 or 2, wherein the thermoplastic elastomer (B) satisfies the following requirement (b4).
(B4) The melting peak temperature (Tm (B)) is 30 to 170 ° C. The adhesive resin (D) is a polyolefin resin having a polar functional group containing at least one heteroatom, and its MFR (230 ° C., 2.16 kg load) (MFR (D)) is 100 g / 10 min. The decorative film according to any one of claims 1 to 3, wherein the decorative film is the following polyolefin resin. The step of preparing the decorative film according to any one of claims 1 to 4, 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. 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 5, wherein the resin molded product contains a propylene-based resin composition.

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