JP2019111666A - Decorative molding and method for producing the same - Google Patents

Abstract

To provide a molding which is lightweight, is excellent in thermal recyclability, and is excellent in molded body surface appearance such as color tone and surface glossiness and touch feeling while having dimensional stability and rigidity.SOLUTION: There is provided a decorative molding in which a polypropylene decorative film is stuck onto a resin molding by thermal molding. The resin molding is a molding formed of a fiber-reinforced polypropylene resin composition containing 40-99 wt.% of (A) a polypropylene resin satisfying (A-i) and (A-ii) and 1-60 wt.% of a cellulose fiber (B) satisfying (B-i). (A-i) a melt peak temperature of 110°C or higher. (A-ii) MFR of 0.5-200 g/10 min. (B-i) a fiber diameter of the cellulose fiber (B) of 10 nm to 500 μm. The polypropylene decorative film contains a layer (I) formed of a polypropylene resin (A) having an MFR of 2 g/10 min or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorated molded body and a method of manufacturing the same. Specifically, a decorative molded body excellent in the surface shape obtained by sticking a polypropylene decorative film by thermoforming on the surface of a resin molded body made of a fiber-reinforced polypropylene resin composition and a decorative molded body thereof It relates to the manufacturing method.

Polypropylene is widely used as a household material or an industrial material because it is excellent in physical properties, moldability, recyclability, economy and the like. In particular, there is a strong demand for weight reduction and design improvement in automotive parts, electrical equipment parts such as televisions and vacuum cleaners, and polypropylene is widely used to satisfy these demands.
Polypropylene used as the material of the above parts is required to have properties such as rigidity, impact resistance, dimensional stability and the like in a highly balanced manner, and conventionally, talc, mica, calcium carbonate, glass fiber, etc. It has been devised to blend the inorganic filler of

  However, since the specific gravity of the resin composition containing the inorganic filler increases, there is a limit to the weight reduction of the molded product. In addition, since the filler is an inorganic substance, when incinerated, the ash content of the inorganic substance remains as industrial waste, which is not suitable for thermal recyclability.

In order to solve such problems, attempts have been made to replace inorganic fillers with organic fillers, and in recent years, from the viewpoint of reduction of petroleum materials, polypropylene incorporating cellulose fibers produced from plant raw materials Based resin compositions have been proposed (Patent Documents 1 and 2).
However, since cellulose fibers contain lignin and hemicellulose that decomposes at 200 ° C. or higher, when a polypropylene-based resin composition containing cellulose fibers is molded at 230 ° C. or higher, which is a general polypropylene molding temperature, There is a problem that the molded body becomes yellowish or an odor is generated.

  For such a problem, for example, Patent Document 3 discloses a method of suppressing the generation of coloring and odor by blending powdered cellulose which has been subjected to a specific treatment to a thermoplastic resin. Even in the strand molding in the above, the generation of coloring and odor still occurs, and it can not be said that the improvement is sufficiently made.

JP-A-9-302240 JP, 2005-187524, A JP, 2013-60544, A

  In view of the above-mentioned prior art, the object of the present invention is a molded article which is lightweight, excellent in thermal recyclability, has dimensional stability and rigidity, and is excellent in molded article surface appearance such as tint and surface gloss and touch. It is to provide.

  As a result of earnest research, the present inventors found that a polypropylene-based decorative film comprising a specific layer made of a polypropylene-based resin satisfying a specific requirement is a resin molded article made of a polypropylene-based resin composition containing a specific fiber. As it is made to be bonded, it is possible to provide a molded body which is lightweight, excellent in thermal recyclability, has dimensional stability and rigidity, and is excellent in surface appearance and touch of molded bodies such as color and surface gloss. It was possible.

The present invention has the following configuration. That is, the present invention is a decorative molded body in which a polypropylene-based decorative film is stuck on a resin molded body by thermoforming, and the polypropylene-based decorative film is a layer made of a polypropylene-based resin (A) I), the polypropylene resin (A) has a MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the resin molded product has the following requirements (Ai) to (A) Polypropylene-based resin (A) satisfying 40) to 99% by weight, and cellulose fiber (A) meeting 1% to 60% by weight satisfying the following requirements (A-i) (however, (A) and (A) And a total of 100% by weight of the fiber-reinforced polypropylene-based resin composition (C).
(Ai): The melting peak temperature Tm (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) is not less than 0.5 g / 10 minutes and not more than 200 g / 10 minutes.
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm.

Further, the present invention is a decorative molded body in which a polypropylene-based decorative film is stuck on a resin molded body by thermoforming, and the polypropylene-based decorative film is a layer comprising a polypropylene-based resin (A) (I ) And a polypropylene-based resin (B), and the polypropylene-based resin (A) has a MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, the polypropylene-based resin (B) MFR (230 ° C., 2.16 kg load) exceeds 2 g / 10 min, and the resin molded product is a polypropylene resin (A) 40 weight satisfying the following requirements (A-i) to (A-ii) % To 99% by weight, and 1% to 60% by weight of cellulose fibers (i) satisfying the following requirements (ii) (provided that the total amount of (i) and (i) is 100 wt.%) Containing fibers And a multi-layer decorative film and the resin molded article which are pasted through a seal layer (II). is there.
(Ai): The melting peak temperature Tm (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) is not less than 0.5 g / 10 minutes and not more than 200 g / 10 minutes.
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm.

In the present invention, when MFR of the polypropylene resin (A) is MFR (A) and MFR of the polypropylene resin (B) is MFR (B), the following relational expression (1) is satisfied. It is said decoration molded object which is said.
MFR (B) / MFR (A)> 1.5 (1)

Further, the present invention is characterized in that the polypropylene-based decorative film has a surface decoration layer (III) made of a surface decoration layer resin on the surface opposite to the bonding surface with the resin molded body. The above-mentioned decorated molding.
In the present invention, the surface decorative layer resin is made of a polypropylene resin (D), and MFR (230 ° C., 2.16 kg load) of the polypropylene resin (D) exceeds 2 g / 10 min. It is the said decorated molded object made into the characteristics.

  Further, the present invention is a method for producing the above-mentioned decorated molded body, which comprises the steps of preparing a polypropylene-based decorated film, preparing a resin molded body, and reducing the pressure of the resin molded body in a depressurizable chamber box. The step of setting the decorative film, the step of depressurizing the inside of the chamber, the step of heating and softening the decorative film, the step of pressing the decorative film against the resin molded body, the chamber is returned to atmospheric pressure or pressurized. It is a manufacturing method of the decorating molded object characterized by including a step.

According to the decorative molding of the present invention, a polypropylene-based decorative film comprising a resin molding comprising a polypropylene-based resin composition containing a specific fiber, and a specific layer comprising a polypropylene-based resin satisfying specific requirements To provide a molded article excellent in surface appearance and touch of molded articles such as tint and surface gloss while being lightweight, excellent in thermal recyclability, and having dimensional stability and rigidity. Made possible.
Furthermore, according to the method for producing a decorative molded article of the present invention, there are no holes or wrinkles on the surface, no air entrapment between the decorative film and the resin molded article, and a beautiful decorative mold in which a scratch is not noticeable You can get the body. In addition, the decorative film can be beautifully attached to a resin molded body having a complicated shape which has been difficult to be bonded conventionally. Furthermore, the decorative molded body obtained in this manner does not contain a thermosetting resin layer, so that the appearance and performance thereof are not significantly reduced at the time of recycling, and the recycling suitability is high.

It is a figure which shows the example of the laminated constitution of the decorating molded body of this invention. It is a schematic cross section explaining the outline | summary of the apparatus used for the manufacturing method of the decorating molded object of this invention. It is a schematic cross section explaining the mode that the resin molding and the decoration film were set in the apparatus of FIG. It is a schematic cross section explaining the mode of heating and pressure-reducing the inside of the apparatus of FIG. It is a schematic cross section explaining the mode that a decoration film is pressed on a resin molding in the apparatus of FIG. FIG. 3 is a schematic cross-sectional view for explaining how the inside of the apparatus of FIG. 2 is returned to atmospheric pressure or pressurized. In the obtained decorative molded object, it is a schematic cross section explaining the mode that the edge of the unnecessary decorative film was trimmed.

  In the present specification, a decorative film refers to a film for decorating a formed body. Decorative molding refers to molding in which a decorative film and a molded body are attached. Three-dimensional decorative thermoforming is a process of adhering a decorative film and a molded body, and has a step of thermoforming the decorative film along the adhering surface of the molded body and simultaneously attaching it. In this process, in order to suppress air being trapped between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), and the heated decorative film is attached to the molded body, and pressure is applied. It refers to molding, which is a process of bringing into close contact by releasing (pressurizing). Hereinafter, modes for carrying out the present invention will be described in detail.

The basic configuration of the decorated molded body of the present invention is a decorated molded body in which a polypropylene-based decorative film is stuck on a resin molded body by thermoforming, and the resin molded body has the following requirements (Ar ) 40% by weight to 99% by weight of a polypropylene-based resin (a) satisfying (a)-(ii) and 1% by weight to 60% by weight of cellulose fibers (i) satisfying (i) It is a molded object which consists of a fiber reinforced polypropylene resin composition (C) containing the total amount of (A) and (B) at 100% by weight).
(Ai): The melting peak temperature Tm (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) is not less than 0.5 g / 10 minutes and not more than 200 g / 10 minutes.
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm.

In the first aspect of the decorated molded body according to the present invention, in the basic configuration of the decorated molded body, the polypropylene-based decorative film includes a layer (I) made of a polypropylene-based resin (A), and the polypropylene-based resin (A) is a molded object whose MFR (230 degreeC, 2.16 kg load) is 2 g / 10 minutes or less.
In the second aspect of the decorated molded body according to the present invention, in the basic configuration of the decorated molded body, the polypropylene-based decorative film comprises a layer (I) comprising a polypropylene-based resin (A) and a polypropylene-based resin (B) The polypropylene-based resin (A) has a MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene-based resin (B) has an MFR (230 ° C., 2.16 kg load) exceeds 2 g / 10 min, and the polypropylene-based decorative film and the resin molded product are molded products attached via the seal layer (II).

Polypropylene resin (A)
In one aspect of the present invention, the decorative film includes the layer (I) made of a polypropylene resin (A), thereby suppressing the occurrence of appearance defects due to the film being broken or violent during thermoforming. I can do it. Since the thermoforming property of a decoration film is improved by this, it is not necessary to include the thermosetting resin layer which is excellent in thermoforming property.

  The polypropylene-based resin (A) in the present invention is a propylene-based resin of various types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof, can be selected. The propylene-based polymer preferably contains 50 mol% or more of a propylene monomer.

  The polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, preferably 1.5 g / 10 min or less, more preferably 1 g / 10 min or less. By making MFR of a polypropylene resin (A) below into the said value, a decorative molded object with a favorable external appearance can be obtained.

  The lower limit of the MFR of the polypropylene resin (A) is not particularly limited, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.3 g / 10 minutes or more. By making MFR more than said value, the moldability at the time of manufacture of a decorating film improves, and it can suppress that the appearance defect called a shark skin or interface roughening generate | occur | produces on the film surface.

  In this specification, the measurement of MFR of a polypropylene resin and a polypropylene resin composition to be described later was measured at 230 ° C. under a load of 2.16 kg in accordance with ISO 1133: 1997 Conditions M. The unit is g / 10 minutes.

  The polypropylene resin (A) in the present invention preferably has high crystallinity from the viewpoint of heat resistance, scratch resistance and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene resin (A) is preferably 155 ° C. or higher, more preferably 158 to 170 ° C., and further preferably 160 to 168 ° C. The polypropylene resin (A) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, since the scratch resistance and solvent resistance are reduced if the low melting point component is included even if the melting point is high, the polypropylene resin (A) is an ethylene-α-olefin having an ethylene content of 50 to 70% by weight It is preferred not to contain a copolymer.

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

  When a polypropylene resin (A) is a polypropylene resin composition, it is preferable that a polypropylene resin composition has the characteristic of said polypropylene resin (A). That is, the MFR (230 ° C., 2.16 kg load) of the polypropylene resin composition is 2 g / 10 min or less.

  When the decorated molded body of the present invention is molded as a colored molded body, it is sufficient to use a coloring agent only for the decorating film, so use of an expensive coloring agent as compared to the case of coloring the entire resin molded body It is possible to suppress In addition, it is possible to suppress the change in physical properties associated with the blending of the colorant.

  Additives can be used for polypropylene resins such as antioxidants, neutralizing agents, light stabilizers, ultraviolet light absorbers, crystal nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc. Various known additives can be blended.

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

  Examples of crystal nucleating agents include metal amides of aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Among these crystal nucleating agents, aluminum p-t-butylbenzoate, phosphoric acid 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium, phosphoric acid 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 A complex of aluminum (6-hydroxyl) hydroxide and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples include (4-propylphenyl) methylene] -nonitol, sodium salts of rosin and the like.

  As the lubricant, higher fatty acid amides such as stearic acid amide can be exemplified. As an antistatic agent, fatty acid partial esters, such as glycerol fatty acid monoester, etc. can be illustrated. Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

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

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

  Moreover, it is also possible to color in order to provide design property, and various coloring agents, such as an inorganic pigment, an organic pigment, dye, can be used for coloring. In addition, bright materials such as aluminum flakes, titanium oxide flakes and (synthetic) mica can also be used.

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

Decorative Film The decorative film of the first aspect in the present invention comprises a layer (I) comprising a polypropylene resin (A). That is, the decorative film may be a single layer film comprising layer (I) or a multilayer film comprising layer (I) and another layer. The decorative film of the present invention can have various configurations in addition to the layer (I). The decorative film of the present invention may have emboss, emboss, print, sandplast, scratch, etc. on its surface.

  The decorative film has a high degree of freedom in shape, and since the end face of the decorative film is wound up to the back side of the object to be decorated, no seam is generated, and the appearance is excellent, and furthermore, the surface of the decorative film is embossed. Can express various textures. For example, in the case of applying a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using the embossed decorative film. For this reason, the problem in the case of molding with a molded body mold to which embossing is applied, that is, the molded body mold is required for each embossing pattern, it is very difficult and expensive to complexly emboss a curved mold. It is possible to solve the problem of being, and to obtain a decorated molded body to which embossing of various patterns is easily imparted.

  The multilayer film can include a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a colored layer, a base layer, a sealing layer, a barrier layer, a tie layer layer that can be provided between these layers, and the like. The layer (I) made of a polypropylene resin (A) may be any layer constituting a multilayer film.

  When it is a single layer film as a preferable aspect of a decoration film, it is a film which consists of a polypropylene resin (A) of MFR2g / 10 minutes or less.

  As another preferable embodiment of the decorative film, in the case of a multilayer film having a two-layer structure, a polypropylene having an MFR of 2 g / 10 min or less is an inner layer to be adhered to a surface layer and / or a molded body to be a surface of the decorated molded body. It is a layer which consists of system resin (A). More preferably, the inner layer to be attached to the molded product is a layer comprising a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less.

  As still another preferred embodiment of the decorative film, in the case of a multilayer film having a three-layer structure, the surface layer which is the surface of the decorated molded article, the inner layer to be stuck to the molded article and / or the intermediate layer between the surface layer and the inner layer The intermediate layer interposed between the layers is a layer made of a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less. More preferably, the inner layer to be attached to the molded product is a layer comprising a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less.

  Even in the case of a multilayer film having a more complicated layer structure, at least one layer constituting the multilayer film is also made of a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less.

  In the multilayer film, layers other than the layer (I) consisting of a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less are preferably layers consisting of a thermoplastic resin, more preferably polypropylene other than the polypropylene resin (A) It is a layer made of a resin. Each layer is preferably a layer not containing a thermosetting resin. By using a thermoplastic resin, the recyclability is improved. Further, by using a polypropylene-based resin other than the polypropylene-based resin (A), complication of the layer structure can be suppressed, and the recyclability is further improved.

  As a further preferable aspect of a decoration film, it is provided in the surface on the opposite side to the sticking surface of the layer (I) which consists of a polypropylene resin (A) of MFR2g / 10 minutes or less, and the resin molding of this layer. And a multilayer film including a surface decoration layer (III) made of a surface decoration layer resin.

  The surface decoration layer resin is preferably made of a thermoplastic resin, more preferably made of a polypropylene resin (D). By using a polypropylene resin (D), it is possible to suppress the complication of the layer structure and the decrease in the recyclability. In addition, by using the polypropylene resin (D) for the surface decoration layer of the decoration film, it is possible to make the solvent resistance and the like excellent. In addition, by using a polypropylene resin (D) for the surface decoration layer, the transferability of the surface at the time of production and thermoforming of the decoration film is improved, and higher glossiness is obtained by using a mirror roll at the time of thermoforming. It can be a decorative film.

  The polypropylene-based resin (D) in the present invention is a propylene-based resin of various types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof, can be selected. The propylene-based polymer preferably contains 50 mol% or more of a propylene monomer. The propylene-based polymer is preferably one that does not contain a polar group-containing monomer unit. The polypropylene resin (D) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance and the like. Also, from the viewpoint of gloss and transparency (coloring), a propylene-α-olefin copolymer is preferred.

  The MFR (230 ° C., 2.16 kg load) of the polypropylene resin (D) is preferably more than 2 g / 10 min, more preferably 5 g / 10 min or more, still more preferably 9 g / 10 min or more. By setting the MFR of the polypropylene resin (D) within the above range, the effect of improving the gloss of the decorative film, improving the emboss transferability, etc. is obtained, and the required surface shape of the molded body ( With respect to gloss, non-gloss, emboss etc.), it is possible to obtain a decorated molding having a good appearance.

  The upper limit of the MFR of the polypropylene resin (D) is not particularly limited, but it is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less. By setting MFR in the above-mentioned range, good oil resistance, solvent resistance, scratch resistance and the like can be exhibited.

  The polypropylene resin (D) may contain additives, fillers, colorants, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) comprising a propylene-based polymer and an additive, a filler, a colorant, another resin component, and the like. The total amount of additives, fillers, colorants and other resin components is preferably 50% by weight or less based on the polypropylene resin composition.

  As an additive, the additive etc. which may be contained in said polypropylene resin (A) can be used.

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

  The decorative film of the present invention preferably has a thickness of about 20 μm or more, more preferably about 50 μm or more, and still more preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of providing the designability is improved, the stability at the time of molding is also improved, and it becomes possible to obtain a better decorated molded body. 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, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film equal to or less than this value, the time required for heating at the time of thermoforming is shortened, the productivity is improved, and it becomes easy to trim unnecessary portions.

  When the decorative film is a single layer film, the ratio of the thickness of the layer (I) to the total thickness of the decorative film is 100%. When the decorative film is a multilayer film, the ratio of the thickness of the layer (I) to the total thickness of the decorative film is preferably 30% or more, more preferably 50% or more. The upper limit is not particularly limited but is preferably less than 100%. If the ratio of the thickness of the layer (I) to the entire decorative film is in the above range, it can be avoided that the thermoformability of the decorative film becomes insufficient.

  In one aspect (second aspect) of the present invention, the decorative film includes a layer (I) comprising a polypropylene resin (A) and a seal layer (II) comprising a polypropylene resin (B), wherein The resin (A) has a MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene resin (B) has a multilayer of MFR (230 ° C., 2.16 kg load) exceeding 2 g / 10 min A film is mentioned.

Polypropylene resin (A)
As a polypropylene resin (A), the description of said polypropylene resin (A) and layer (I) can be read as it is, or it can be read suitably, and can be applied.

Polypropylene resin (B)
The decorative film of the present invention may make a scratch attached to the surface of a substrate less noticeable by including a seal layer (II) made of a polypropylene resin (B) on the affixing surface with a resin molded product (substrate). To reduce product defects.

  This is because the flowability of the polypropylene resin (B) constituting the sealing layer (II) is higher than that of the polypropylene resin (A) constituting the layer (I) imparting thermoforming properties. Layer (II) is easier to deform than when it is deformed, and the seal layer (II) deforms in accordance with the shape of the scratch when the seal layer (II) is scratched against the scratch of the substrate. Suppress the relief.

In order for the decorative film to exhibit such an effect, the MFR (230 ° C., 2.16 kg load) of the polypropylene resin (B) needs to exceed 2 g / 10 min, preferably 4 g / min. 10 minutes or more. When MFR of the polypropylene resin (A) is MFR (A) and MFR of the polypropylene resin (B) is MFR (B), the following general formula (1) is preferably satisfied.
MFR (B) / MFR (A)> 1.5 (1)

  The ratio MFR (B) / MFR (A) of the MFRs of the polypropylene resin (B) and the polypropylene resin (A) is preferably 2 or more, and more preferably 10 or more. The higher the MFR (B) and the larger the MFR (B) / MFR (A), the greater the effect of suppressing the relief of scratches, but if the MFR (B) / MFR (A) becomes too large, lamination at the time of film formation MFR (B) / MFR (A) is preferably 1000 or less, more preferably 100 or less.

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

  The melting point (DSC melting peak temperature) of the polypropylene resin (B) is preferably 100 to 170 ° C., more preferably 115 to 165 ° C.

  The polypropylene-based resin (B) is preferably a propylene-α-olefin copolymer from the viewpoint of sealability, and the propylene-α-olefin copolymer usually has a melting point lower than that of a propylene homopolymer. Since the crystallization temperature is also lowered, the effect of making the damage easy to be deformed by thermoforming and making the scratches less noticeable is high.

  Moreover, an additive, a filler, the other resin component etc. may be contained in the polypropylene resin (B). That is, it may be a resin composition (polypropylene resin composition) comprising a propylene polymer, an additive, a filler, and other resin components. The total amount of additives, fillers, other resin components and the like is preferably 95% by weight or less based on the polypropylene resin composition.

Additives can be used for polypropylene resins such as antioxidants, neutralizing agents, light stabilizers, ultraviolet light absorbers, crystal nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc. Various known additives can be blended.
Examples of the antioxidant include phenol-based antioxidants, phosphite-based antioxidants, and thio-based antioxidants. As a neutralizing agent, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. Examples of light stabilizers and ultraviolet light absorbers include hindered amines, benzotriazoles, benzophenones and the like.

  Examples of crystal nucleating agents include metal amides of aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Among these crystal nucleating agents, aluminum p-t-butylbenzoate, phosphoric acid 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium, phosphoric acid 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 A complex of aluminum (6-hydroxyl) hydroxide and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples include (4-propylphenyl) methylene] -nonitol, sodium salts of rosin and the like.

  As the lubricant, higher fatty acid amides such as stearic acid amide can be exemplified. As an antistatic agent, fatty acid partial esters, such as glycerol fatty acid monoester, etc. can be illustrated. Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

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

  Other resin components include ethylene-α-olefin random copolymer, thermoplastic elastomer mainly composed of propylene and / or butene, styrenic elastomer, aromatic hydrocarbon resin, polar functional group having a hetero atom The polyolefin resin etc. which it has can be illustrated.

The ethylene-α-olefin random copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specifically as said C3-C20 alpha-olefin, a propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, 1-heptene, 1-octene, 1- Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like can be mentioned. Among these, in particular, propylene, 1-butene, 1-hexene and 1-octene are preferably used.
As commercially available products of such ethylene-α-olefin random copolymer, Kernel series made by Nippon Polyethylene Co., Ltd., Toughmer P series made by Mitsui Chemical Co., Ltd., Tafmer A series, Engage EG series made by DuPont Dow Etc.

As a thermoplastic elastomer containing propylene and / or butene as a main component, thermoplastic elastomer containing propylene as a main component, thermoplastic elastomer containing butene as a main component, thermoplasticity containing a component obtained by combining propylene and butene as a main component Elastomers are included. Such thermoplastic elastomer is preferably a copolymer of propylene and / or butene, and propylene and an α-olefin other than butene. Specific examples of α-olefins include ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-eikosen etc. are mentioned. These α-olefins can be used alone or in combination.
As such thermoplastic elastomers, as commercially available products, Tafmer XM series, Tafmer BL series, Tafmer PN series manufactured by Mitsui Chemicals, Inc., VISTAMAXX series manufactured by ExxonMobil Chemical, etc. may be mentioned.

As styrene-based elastomers, styrene-butadiene-styrene triblock copolymer elastomer (SBS), styrene-isoprene-styrene triblock copolymer elastomer (SIS), styrene-ethylene-butylene copolymer elastomer (SEB), styrene -Ethylene-propylene copolymer elastomer (SEP), styrene-ethylene-butylene-styrene copolymer elastomer (SEBS), styrene-ethylene-butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene-butadiene elastomer (HSBR) Styrene-ethylene-propylene-styrene copolymer elastomer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer elastomer (SEEPS), styrene Tajien butylene - styrene copolymer elastomer (SBBS) or the like can be exemplified, those hydrogenated can be particularly preferably used.
Examples of commercially available products include Dynaron series manufactured by JSR Corporation, Kraton G series manufactured by Kraton Polymer Japan KK, Tuftec series manufactured by Asahi Kasei Corporation, and the like.

  As an aromatic hydrocarbon resin, a hydrocarbon resin obtained by polymerizing a mixture of one or two or more kinds of dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene or the like as a main raw material, Hydrogenated coumarone / indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, etc., and commercial products Specifically, Alcon series manufactured by Arakawa Chemical Co., Ltd., T-REZ series manufactured by Tonen Chemical Co., Ltd., Quintone series manufactured by Nippon Zeon Co., Ltd., manufactured by Idemitsu Kosan Co., Ltd. Imarb series etc. can be mentioned.

  As the polar functional group having a hetero atom, epoxy group, carbonyl group, ester group, ether group, hydroxy group, carboxy group or metal salt thereof, alkoxy group, aryloxy group, acyl group, acyloxy group, acid anhydride group, Examples thereof include amino group, imide group, amido group, nitrile group, thiol group, sulfo group, isocyanate group, halogen group and the like. Specific examples of such polar functional group-containing polyolefins include acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer Combined, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide 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 , Echire / Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / methacrylic acid Butyl 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 / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer, or a saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / Ethyl acrylate / glycidyl methacrylate Copolymers, ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer; and chlorinated polyolefins such as chlorinated polypropylene chlorinated polyethylene. As a commercial item, Mitsui Chemical Co., Ltd. trade name "Admer", Mitsubishi Chemical Corp. trade name "Modic", Sanyo Chemical Industries "Yumex" etc. can be mentioned.

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

Decorative Film The decorative film of the second aspect includes a layer (I) comprising a polypropylene resin (A) and a seal layer (II) comprising a polypropylene resin (B). A decoration film can take various composition other than layer (I) and seal layer (II). That is, the decorative film may be a two-layer film consisting of the layer (I) and the seal layer (II) or a multilayer film consisting of the layer (I) and the seal layer (II) and other layers . In addition, sealing layer (II) adheres along a resin molding (base | substrate). In addition, the decorative film may be embossed, embossed, printed, sandblasted, scratched or the like on its surface.

  The decorative film has a high degree of freedom in shape, and since the end face of the decorative film is wound up to the back side of the object to be decorated, no seam is generated, and the appearance is excellent, and furthermore, the surface of the decorative film is embossed. Can express various textures. For example, in the case of applying a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using the embossed decorative film. For this reason, the problem in the case of molding with a molded body mold to which embossing is applied, that is, the molded body mold is required for each embossing pattern, it is very difficult and expensive to complexly emboss a curved mold. It is possible to solve the problem of being, and to obtain a decorated molded body to which embossing of various patterns is easily imparted.

  The multilayer film can include a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a colored layer, a base layer, a barrier layer, a tie layer layer that can be provided between these layers, and the like. Layer (I) which consists of polypropylene resin (A) may be any layer except a sealing layer among the layers which constitute a multilayer film.

  In the multilayer film, layers other than the layer (I) and the seal layer (II) are preferably layers made of a thermoplastic resin, and more preferably layers made of a polypropylene resin. As far as the layers (I) and the seal layer (II) can be distinguished from the layer (I) and the seal layer (II), the MFR (230 ° C., 2.16 kg load) of the constituting polypropylene resin is It is not particularly limited. Each layer is preferably a layer not containing a thermosetting resin. By using a thermoplastic resin, the recyclability is improved, and by using a polypropylene resin, it is possible to suppress the complication of the layer structure, and the recyclability is further improved.

  When the decorative film is a two-layer film, the layer (I) composed of a polypropylene resin (A) constitutes a surface layer opposite to the surface to which the resin molded article is attached, and from the polypropylene resin (B) The seal layer (II) as described above constitutes a seal layer of the bonding surface to the resin molded body.

  When the decorative film is a multilayer film having three or more layers, another layer intervenes between the layer (I) comprising the polypropylene resin (A) and the seal layer (II) comprising the polypropylene resin (B) Then, the effect which suppresses the relief | lifting of the flaw of the base | substrate surface may fall. For this reason, a multilayer film is a layer (I) which consists of a resin composition (A) containing seal layer (II) / polypropylene resin (A) which consists of polypropylene resin (B) from the sticking surface side of a resin molding. A configuration of other layers (including a plurality of layers) is preferable.

As another preferable aspect of a decoration film, the multilayer film containing surface decoration layer (III) which consists of surface decoration layer resin in the outermost surface on the opposite side to the adhesion surface to a resin molding is mentioned. The surface modification layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (D) having an MFR (230 ° C., 2.16 kg load) exceeding 2 g / 10 min. That is, the layer (I) comprising a polypropylene resin (A) having a MFR of 2 g / 10 minutes or less which improves the thermoformability may generally be inferior in gloss and emboss transferability due to the low MFR. By further providing a layer (III) made of a polypropylene resin (D) on the surface layer, it is possible to improve the gloss and the emboss transferability without significantly reducing the thermoforming property.
Further, by using the polypropylene resin (D), it is possible to suppress the complication of the layer structure and the decrease in the recyclability. In addition, by using the polypropylene resin (D) for the surface decoration layer of the decoration film, it is possible to make the solvent resistance and the like excellent. In addition, by using a polypropylene resin (D) for the surface decoration layer, the transferability of the surface at the time of production of the decoration film and at the time of thermoforming is improved, and when a mirror surface roll is used at the time of thermoforming It can be a decorative film.

Polypropylene resin (D)
As a polypropylene resin (D), the description of said polypropylene resin (D) and surface decoration layer (III) can be read as it is, or it can be read suitably, and can be applied.

  In the second aspect, the polypropylene resin (D) constituting the surface decorative layer (III) may be the same as or different from the polypropylene resin (B) constituting the sealing layer (II).

  In the second aspect, when the polypropylene-based resin (D) constituting the surface decorative layer (III) is a polypropylene-based resin composition, this polypropylene-based resin composition is a polypropylene-based resin constituting the sealing layer (II) It may be the same as or different from the polypropylene resin composition that constitutes the resin (B). When both polypropylene resin compositions are the same, it is possible to form the seal layer (II) and the surface decoration layer (III) using a feed block or the like in one extruder. Have an advantage.

  The decorative film of the present invention preferably has a thickness of about 20 μm or more, more preferably about 50 μm or more, and still more preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of providing the designability is improved, the stability at the time of molding is also improved, and it is possible to obtain a better decorated molded body. 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, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film equal to or less than this value, the time required for heating at the time of thermoforming is shortened, the productivity is improved, and it becomes easy to trim unnecessary portions.

  In the decorative film of the second aspect, the ratio of the thickness of the layer (I) to the thickness of the entire decorative film is preferably 30 to 99%, and the ratio of the seal layer (II) is preferably 1 to 70%. If the ratio of the thickness of the layer (I) to the entire decorative film is in the above range, it can be avoided that the thermoformability of the decorative film becomes insufficient. Moreover, if the ratio of the thickness of the seal layer (II) occupied in the entire decorative film is in the range of the above value, it is possible to suppress the damage of the resin molded body (substrate) from floating on the surface.

  Moreover, in the multilayer film which provided surface decoration layer (III) which consists of polypropylene resin (D) in the outermost surface of a decoration film, thickness of the whole decoration film of the thickness of layer (III) in a decoration film Preferably, the ratio of at least 30%.

Production of Decorative Film The decorative film of the present invention can be produced by various known molding methods.
For example, a method of extruding layer (I), a method of coextrusion of layer (I) and layer (II), a method of coextrusion of layer (I) and layer (II) and further layers, Thermal lamination method in which the other layer is bonded by heat and pressure on one surface of one layer extruded in advance, dry lamination method in which bonding is performed via an adhesive and wet lamination method, previously extruded The extrusion lamination method which melt-extrudes polypropylene resin on one side of one layer, the sand lamination method, etc. are mentioned. As an apparatus for forming a decoration film, a well-known co-extrusion T-die molding machine and a well-known lamination molding machine can be used. Among these, from the viewpoint of productivity, a co-extrusion T-die molding machine is preferably used.

  As a method of cooling a molten decorative film extruded from a die, a method of bringing a molten decorative film into contact with one cooling roll via air discharged from an air knife unit or an air chamber unit, The method of pressure-bonding and cooling by several cooling rolls is mentioned.

  In the case of imparting gloss to the decorative film of the present invention, a method is used in which a mirror-like cooling roll is surface-transferred onto a design surface of a product of the decorative film to perform mirror processing.

  Furthermore, the surface of the decorative film of the present invention may have an embossed shape. Such a decorative film is a method of directly pressing the molten resin extruded from a die with a roll having a concavo-convex shape and a smooth roll to transfer the concavo-convex shape, a smooth film having a concavo-convex shape It can manufacture by the method etc. of pressure-contacting with the heating roll and the smooth cooling roll which were given. Examples of the emboss shape include satin, animal skin tone, hairline tone, carbon tone and the like.

  The decorative film of the present invention may be heat-treated after film formation. As a method of heat treatment, 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, etc. may be mentioned.

Resin Molded Article The resin molded article (target to be decorated) to be decorated in the present invention comprises 40% by weight to 99% by weight of a polypropylene resin (A) and 1% to 60% by weight of a cellulose fiber (A). It is a molded object obtained by shape | molding a fiber reinforced polypropylene resin composition (C).

Polypropylene resin (A)
The polypropylene resin (a) to be used in the present invention is selected from various known types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer, or propylene block copolymer. The following requirements (A-i) to (A-ii) are satisfied.
(Ai): The melting peak temperature Tm (A) of the polypropylene resin (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) of the polypropylene resin (A) is 0.5 g / 10 minutes or more and 200 g / 10 minutes or less.

  The melting peak temperature Tm (A) of the polypropylene resin (A) causes a problem in practical use due to a decrease in heat resistance and a decrease in rigidity, so 110 ° C. or more is necessary, preferably 125 ° C. or more, more preferably It is 130 ° C. or higher. The melting peak temperature Tm (a) can be controlled by adjusting the catalyst used and the content of ethylene copolymerized with propylene.

  The MFR (a) (230 ° C., 2.16 kg load) of the polypropylene resin (A) is 0.5 to 200 g / 10 min, preferably 1 to 150 g / 10 min, more preferably 5 to 100 g / 10 It is a minute. Within the above range, it is possible to suppress the deterioration of the molded appearance that occurs during the production of the molded body, such as the reduction of the weld appearance.

  The polypropylene resin (a) is a variety of types based on various known propylene monomers such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, or a propylene block copolymer. You can choose one.

Cellulose fiber (a)
The cellulose fiber (i) used in the present invention satisfies the following characteristics (ii).
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm.
The cellulose fiber (i) used in the present invention has high tensile modulus and tensile strength, so physical properties such as rigidity and heat resistance of the resin composition and its molded body, dimensional stability (reduction of coefficient of linear expansion, etc.) It has a feature that contributes to each improvement in environmental adaptability.

  The cellulose fiber (a) can also be used in the form of a so-called master batch which is previously contained in a polypropylene resin or the like in a relatively high concentration.

The cellulose fiber (a) can be used alone or in combination of two or more.
In addition, various inorganic or organic fillers such as talc, mica, glass beads, glass balloons, whiskers, glass fibers and organic fibers other than cellulose fibers can be used in combination as long as the effects of the present invention are not significantly impaired.

  Hereinafter, the cellulose fiber in the present invention will be described in detail.

Cellulose Fiber As raw material cellulose of cellulose fiber used in the present invention, plants (eg, wood, bamboo, hemp, jude, kenaf, farmland waste, cloth, pulp, regenerated pulp, used paper), animals (eg, sea squirts) Although algae, microorganisms (for example, acetic acid bacteria), microbial products and the like are known to be sources, any of them can be used in the present invention. It is preferably cellulose of plant or microorganism origin, more preferably cellulose of plant origin.
As a cellulose fiber used for this invention, what was manufactured by various well-known methods can be used. For example, it is manufactured by mechanically opening with a refiner, a twin screw kneader, a high pressure homogenizer, a medium stirring mill, a vibration mill, a grinder, a ball mill, high pressure jet water or the like. In the present invention, as long as cellulose is in a fiber state, there is no limitation on its production method. As a cellulose fiber used for this invention, a commercially available thing can be used.

Examples of commercially available products include BiNFi-s series manufactured by Sugino Machine Co., Ltd., Celish series manufactured by Daicel Finechem Co., Ltd., cellenpia series manufactured by Nippon Paper Industries Co., Ltd., KC floc series, and the like.
The fiber diameter of the cellulose fiber is preferably 10 nm to 500 μm, more preferably 20 nm to 400 μm. If the fiber diameter is in this range, each improvement effect such as the rigidity of the resin composition and the molded article thereof can be sufficiently obtained.

  The fiber length of the cellulose fiber is not particularly limited, but from the viewpoint of moldability (flowability) and dispersibility, the aspect ratio (fiber length / fiber diameter) is 10 to 10,000. Is preferred.

The fiber length is determined by measuring with a microscope and calculating the average of the lengths of 20 or more fibers. Specifically, for example, cellulose fiber is mixed with surfactant-containing water, and the mixed aqueous solution is dropped and diffused onto a thin glass plate, and then a digital microscope (for example, VHX-900 manufactured by KEYENCE Corporation) is used. According to the method of measuring the fiber length of 20 or more and calculating the average value.
The fiber diameter is determined by observing the diameter by observing with a scanning electron microscope (SEM) and calculating the average value of the diameters of 20 or more fibers.

Fiber-reinforced polypropylene resin composition (c)
The content ratio of the cellulose fiber (i) used in the present invention is 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, more preferably 10 wt% to the polypropylene resin (a). It is 50% by weight. When the content ratio of the cellulose fiber (b) is within the above range, excellent physical properties such as low shrinkage and high rigidity can be expressed.
Here, the content ratio of the cellulose fiber (i) is an actual amount, and for example, when using a cellulose fiber-containing pellet, the content is calculated based on the actual content of the cellulose fiber (i) contained in the pellet.

The fiber-reinforced polypropylene resin composition (c) of the present invention, as an optional additive component, to the extent that the effects of the present invention are not significantly impaired, such as thermoplastic elastomers, modified polyolefins, molecular weight depressants, lubricants, antioxidants, etc. Various optional additives can be included.
The optional additive components may be used in combination of two or more. In the invention, the total amount of optional additive components is preferably 50% by weight or less based on the fiber-reinforced polypropylene resin composition, and is appropriately selected according to the purpose.

The above-mentioned thermoplastic elastomer refers to a thermoplastic elastomer selected from an olefin elastomer, a styrenic elastomer and the like.
As an olefin elastomer, for example, ethylene-propylene copolymer elastomer (EPR), ethylene-butene copolymer elastomer (EBR), ethylene-hexene copolymer elastomer (EHR), ethylene-octene copolymer elastomer (EOR) Etc.); ethylene • propylene • ethylidene norbornene copolymer, ethylene • propylene • butadiene copolymer, ethylene • propylene • isoprene copolymer, etc. For example, a former copolymer elastomer can be mentioned.
Also, as the styrene-based elastomer, for example, styrene-butadiene-styrene triblock copolymer elastomer (SBS), styrene-isoprene-styrene triblock copolymer elastomer (SIS), styrene-ethylene-butylene copolymer elastomer ( SEB), styrene-ethylene-propylene copolymer elastomer (SEP), styrene-ethylene-butylene-styrene copolymer elastomer (SEBS), styrene-ethylene-butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene Butadiene elastomer (HSBR), styrene-ethylene-propylene-styrene copolymer elastomer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer elastomer (SEEPS , Styrene - butadiene butylene - styrene copolymer elastomer (SBBS) can be exemplified.
Furthermore, hydrogenated polymer-based elastomers such as ethylene-ethylene-butylene-ethylene copolymer elastomer (CEBC) can also be mentioned.
Among them, when at least one selected from the group consisting of ethylene / octene copolymer elastomer (EOR), ethylene / butene copolymer elastomer (EBR) and ethylene / propylene copolymer elastomer is used, a resin composition and a molded article thereof In the above, it is preferable from the viewpoint that the performances such as low shrinkage, touch and impact strength tend to be more excellent and the economy is also excellent.
In addition, 2 or more types of thermoplastic elastomers can also be used together.

The modified polyolefin is an acid-modified polyolefin and / or a hydroxy-modified polyolefin, and by improving the interfacial strength between the polypropylene resin (a) and the cellulose fiber (i), rigidity and impact of the resin composition and its molded body can be improved. It is effective to improve physical properties such as strength.
There is no restriction | limiting in particular as an acid modified polyolefin, A conventionally well-known thing can be used. The acid-modified polyolefin is, for example, polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-non-conjugated diene compound copolymer (EPDM etc.), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber And polyolefins are graft-copolymerized and modified with an unsaturated carboxylic acid such as, for example, maleic acid or maleic anhydride. This graft copolymerization is carried out, for example, by reacting the above-mentioned polyolefin with an unsaturated carboxylic acid using a radical generator such as benzoyl peroxide in a suitable solvent. The components of the unsaturated carboxylic acid or its derivative can also be introduced into the polymer chain by random or block copolymerization with a monomer for polyolefin.
The hydroxy-modified polyolefin is a modified polyolefin containing a hydroxyl group. The modified polyolefin may have a hydroxyl group at an appropriate site, for example, at the end or side chain of the main chain. The olefin resin constituting the hydroxy-modified polyolefin is, for example, a homopolymer or copolymer of an α-olefin such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene and dodecene, the above α -A copolymer of an olefin and a copolymerizable monomer can be exemplified. As hydroxy-modified polyolefin, hydroxy-modified polyethylene (for example, low density, medium density or high density polyethylene, linear low density polyethylene, ultra-high molecular weight polyethylene, ethylene- (meth) acrylate copolymer, ethylene-vinyl acetate copolymer Polymers, etc.), Hydroxy-modified polypropylene (eg, polypropylene homopolymer such as isotactic polypropylene, etc., random copolymer of propylene and α-olefin (eg, ethylene, butene, hexane etc.), propylene-α-olefin block co-polymer Polymers, etc.), hydroxy-modified poly (4-methylpentene-1), etc. can be mentioned.

Molecular weight depressants are effective in imparting and improving moldability (flowability) and the like.
As the molecular weight depressant, for example, various kinds of organic peroxides, and so-called decomposition (oxidation) accelerators can be used, and organic peroxides are preferable.
As the organic peroxide, for example, benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (benzoyl peroxy) Oxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexa Noate, methyl-ethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-b Ruperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) Cyclohexane, 2,2-bis-t-butylperoxybutane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1 Or one or more selected from the group consisting of 1,1,3,3-tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane It can be mentioned.

The lubricant is effective for imparting and improving the releasability and the like at the time of molding of the resin composition and the molded article thereof.
Examples of the lubricant include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide and behenic acid amide, butyl stearate, silicone oil and the like.

Antioxidants are effective in preventing quality deterioration of the resin composition and the molded article thereof.
Examples of the antioxidant include phenol-based, phosphorus-based and sulfur-based antioxidants.

Further, the resin composition of the present invention can contain a polyolefin resin other than the polypropylene resin (A), a thermoplastic resin such as a polyamide resin and a polyester resin, and the like within the range not significantly impairing the effects of the present invention. .
Various components of these optional components are commercially available from many companies, and depending on the purpose, desired products can be obtained and used.

Production of Fiber-Reinforced Polypropylene Resin Composition (C) The fiber-reinforced polypropylene resin composition (C) of the present invention is a polypropylene resin (A) (hereinafter also referred to as component (A)) and cellulose fiber (A). These components can be produced by passing through a kneading step of adding optionally added components as necessary, blending them in the content ratio by a conventionally known method, and melt kneading.

  The mixing is usually carried out using a mixing apparatus such as tumbler, V blender, ribbon blender, and the melt-kneading is usually carried out by a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, stirring The mixture is (semi) melted and granulated using a kneading machine such as a granulator and granulated. (Semi) Melt-kneading / granulation may be carried out simultaneously by mixing the components of the above-described components, and in order to improve performance, the components are divided and kneaded, ie, for example, first It is also possible to employ a method of kneading a part or all of the component (a) and a part of the cellulose fiber (i) and thereafter kneading and granulating the remaining components.

  In addition, as a preferred method for producing the fiber-reinforced polypropylene resin composition (c), for example, after melt-kneading the component (a) sufficiently in melt-kneading with a twin-screw extruder, for example, the fiber (i) is side-fed And the like, and methods such as dispersing the focused fibers while minimizing breakage of the fibers are included.

Also, for example, a so-called agitation granulation method in which the cellulose fibers (i) in the mixture are kneaded while the component (a) is stirred at high speed in a Henschel mixer to bring them into a semi-molten state also minimizes fiber breakage. However, it is one of the preferred production methods because it is easy to disperse the fibers.
Furthermore, the components other than cellulose fiber (i) are melt-kneaded in advance with an extruder or the like to form pellets, and the pellets and the above-mentioned cellulose fiber-containing pellets are mixed to obtain a fiber reinforced composition. It is one of the preferable manufacturing methods for the same reason and the like.

  As described above, as a preferred method of producing the fiber-reinforced polypropylene resin composition (c) of the present invention, a method of adding the cellulose fiber (i) after kneading the components other than the cellulose fiber (i) in the kneading step The fiber-reinforced polypropylene-based resin composition (c) of the present invention can be produced by the easy production method.

Production of Molded Article The molded article of the present invention is produced by, for example, injection molding (gas injection molding, two-color injection molding, core back injection molding, sandwich injection molding) of the fiber-reinforced polypropylene resin composition (c) produced by the above method. It can be obtained by molding by a known molding method such as injection molding (press injection), extrusion molding, sheet molding and hollow molding. Among these, it is preferable to obtain by injection molding or injection compression molding.

Decorative Molding The molding to be decorated in the present invention (the object to be decorated) is a molding comprising a fiber-reinforced polypropylene resin composition (C), and because it is a nonpolar resin, it has poor adhesion. The decorative film in the present invention includes a layer (I) made of a polypropylene resin (A) or a sealing layer (II) made of a polypropylene resin (B) to be a target for decoration made of a polypropylene resin The decorative film exhibits very high adhesive strength by sticking and because the decorative film covers the fiber shape and the aggregate of the cellulose fibers which have appeared on the surface of the object to be decorated, The appearance is smooth. In addition, since the molded product is covered with the decorative film, the appearance of the decorated molded product is also improved because the molded product is covered with the decorative film due to the coloring of the cellulose fibers generated in the production of the molded product (object to be decorated).

  A decorative molded article obtained by sticking the decorative film of the present invention to various molded articles formed in a three-dimensional shape of a fiber reinforced polypropylene resin composition is lightweight, excellent in thermal recyclability, dimensional stability and rigidity Because it has excellent appearance and touch on the surface of molded products such as color and surface gloss, and VOCs contained in painting and adhesives are greatly reduced, automobile parts, home appliances, vehicles (such as railways), building materials, etc. It can be suitably used as daily necessities and the like.

Fig.1 (a)-(c) is explanatory drawing which illustrates typically the cross section of embodiment of the decorating molded object by which the decorating film was stuck on the resin molding. In FIGS. 1 (a) to 1 (c), the arrangement of the layer (I) is specified and described for ease of understanding, but the layer configuration of the decorated molded body is interpreted as being limited to these examples. is not. In the present specification, reference numeral 1 in the drawings denotes a decorative film, reference numeral 2 denotes a layer (I), reference numeral 3 denotes a seal layer (II), reference numeral 4 denotes a surface decoration layer (III), and reference numeral 5 denotes a resin molding. . FIG. 1A is an example in which the decorative film is a single layer film, and a layer (I) made of a resin composition (A) is attached to the resin molded body 5. FIG.1 (b) and (c) are examples in which a decoration film consists of multilayer films. The decorative film of FIG. 1 (b) is composed of a layer (I) and a seal layer (II), and the seal layer (II) is adhered to the surface of the resin molded body 5, and the surface is decorated on the layer (I). Layer (III) is laminated. The decorative film of FIG. 1 (c) comprises a layer (I), a seal layer (II) and a surface decoration layer (III), and the seal layer (II) is adhered to the surface of the resin molded body 5 to form a seal layer. Layer (I) and surface decoration layer (III) are laminated in this order on (II).

The method for producing a decorated molded body according to the present invention comprises the steps of preparing the above-mentioned decorated film, preparing a resin molded body, and reducing the pressure of the resin molded body in a depressurizable chamber box. Step of setting the decorative film (step of setting the resin molded body and the seal layer of the decorative film to face each other when there is a seal layer), decompressing the inside of the chamber box, The method further comprises the steps of heat softening the decorative film, pressing the decorative film against the resin molded body, and returning or pressurizing the interior of the reduced pressure chamber box to atmospheric pressure.

  In three-dimensional decoration thermoforming, the decoration target and the decoration film are set in a depressurizable chamber box, the film is heated and softened in a state where the pressure in the chamber box is reduced, and the film is pressed against the decoration target It has a basic process of sticking a decoration film on the surface of decoration object by returning the inside of a chamber box to atmospheric pressure, or pressurizing, and pastes a film under pressure reduction. This makes it possible to obtain a beautifully decorated molded body free of air stagnation. In the manufacturing method of the present invention, any known device can be used as long as it is an apparatus and conditions suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the object to be decorated, the decoration film, the mechanism for pressing it, the device for heating the decoration film, etc. It may be a plurality of divided ones.
The mechanism for pressing the decoration target and the decoration film may be any type that moves the decoration target, moves the decoration film, or moves both.

More specific representative forming methods will be exemplified below.
Hereinafter, the method of sticking a decoration film on a decoration object using a three-dimensional decoration thermoforming machine is demonstrated illustratively, referring a figure.

  As shown in FIG. 2, the three-dimensional decorative thermoforming machine of this embodiment comprises chamber boxes 11 and 12 at the top and bottom, and performs thermoforming of the decorative film 1 in the two chamber boxes 11 and 12. It is like that. A vacuum circuit (not shown) and an air circuit (not shown) are connected 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 being raised and lowered is installed in the lower chamber box 12, and the resin molded body (target for decoration) 5 is set on this table 14 (via a jig or the like or directly). Ru. A heater 15 is incorporated in the upper chamber box 11, and the decorative film 1 is heated by the heater 15. The object to be decorated 5 can have a fiber-reinforced polypropylene resin composition as a base.

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

  As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 opened, the object to be decorated 5 is placed on the table 14 in the lower chamber box 12 and the table 14 is lowered. Subsequently, when the decorative film 1 is provided on the film fixing jig 13 between the upper and lower chamber boxes 11 and 12 and the seal layer (II) is present, the seal layer (II) is set to face 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, and the inside of the box is closed, and then the insides of the respective chamber boxes 11 and 12 are vacuum suctioned. Heating of the decorative film 1 is performed.

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 with the interior of the upper and lower chamber boxes 11 and 12 kept in the vacuum suction state. The decorative film 1 is pressed against the object to be decorated 5 to cover the object to be decorated 5. Further, as shown in FIG. 6, the upper chamber box 11 is opened at atmospheric pressure or compressed air is supplied from a pressurized air tank, thereby bringing the decorative film 1 into close contact with the object 5 to be decorated with a greater force.
Subsequently, the insides of the upper and lower chamber boxes 11 and 12 are opened to atmospheric pressure, and the decorated formed 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 formed body 6 are trimmed.

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

Moreover, in the two chamber boxes 11 and 12 divided up and down by the decoration film 1, the pressure in the chamber box on the side to which the decoration object 5 and the decoration film 1 are attached may be in this range, The drawdown of the decorative film 1 can also be suppressed by changing the pressure of the chamber boxes 11, 12.
At this time, a film made of a general polypropylene-based resin may be largely deformed and ruptured by a slight pressure fluctuation due to a decrease in viscosity at the time of 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 fluctuation.

  The heating of the decorative film 1 is controlled by the heater temperature (output) and the heating time. In addition, 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 standard of appropriate conditions.

In the present invention, in order to attach the polypropylene-based decorative film 1 to the decorative object 5 made of a polypropylene-based resin, it is necessary that the surface of the resin molded body 5 and the decorative film 1 be sufficiently softened or melted.
Therefore, it is necessary that the heater temperature is higher than the melting temperature of the polypropylene-based resin constituting the object to be decorated 5 and the polypropylene-based resin constituting the decorative film 1. The heater temperature is preferably 160 ° C. or more, more preferably 180 ° C. or more, and most preferably 200 ° C. or more.

  The higher the heater temperature, the shorter the time required for heating, but the heater side is sufficient to heat the interior of the decorative film 1 (or the surface opposite to the heater if the heater is installed on only one side). Since the resin is thermally deteriorated as well as the moldability is deteriorated due to the temperature of the resin becoming too high, the heater temperature is preferably 500.degree. C. or less, more preferably 450.degree. C. or less, most preferably 400.degree. It is below.

Although the appropriate heating time varies depending on the heater temperature, it is preferable to heat at least the polypropylene-based decorative film until heating starts and retension called springback starts.
That is, the decorative film heated by the heater is thermally expanded by being heated from the solid state, and once stretched along with crystal melting, the spring back temporarily recoils by relaxation of the molecules as the crystal melting progresses to the whole. Is observed and then hangs down under its own weight, but after springback, the film is completely melted in crystals, and sufficient adhesion strength is obtained because molecular relaxation is sufficient.
On the other hand, if the heating time is too long, the film sags due to its own weight or deforms 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 spring back.

  It is preferable to supply compressed air when the decorative film is brought into close contact with the substrate, in the case of decorating a molded article having a complicated shape having asperities or when achieving higher adhesion. 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, there is a risk of damaging the device, so 450 kPa or less, preferably 400 kPa or less is good.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

1. Measurement method of various physical properties (i) MFR
In accordance with ISO 1133: 1997 Conditions M, it was measured at 230 ° C. under a 2.16 kg load. The unit is g / 10 minutes.

(Ii) melting peak temperature Tm:
Using a differential scanning calorimeter (DSC), raise the temperature to 200 ° C and hold for 10 minutes, and then drop the temperature to 40 ° C at a temperature drop rate of 10 ° C / min, and again at a temperature rise rate of 10 ° C / min The temperature of the endothermic peak top at the time of measurement was taken as the melting peak temperature Tm. The unit is ° C.

(Iii) GPC measurement GPC measurement was performed under the following apparatus and conditions to calculate Mw / Mn.
Equipment: GPC (ALC / GPC 150C) manufactured by Waters
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
・ Column: Showa Denko AD 806 M / S (3)
Mobile phase solvent: ortho-dichlorobenzene (ODCB)
・ Measurement temperature: 140 ° C
・ Flow rate: 1.0 ml / min
Injection volume: 0.2 ml
Preparation of sample: The sample is prepared by dissolving 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) at 140 ° C. for about 1 hour.
The conversion from the retention volume to the molecular weight obtained by the GPC measurement is performed using a calibration curve with standard polystyrene (PS) prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is generated by injecting 0.2 mL of a solution of ODCB (containing 0.5 mg / mL BHT) to 0.5 mg / mL each. The calibration curve uses a cubic equation obtained by approximation using the least squares method.
In addition, the following numerical values are used for the viscosity formula [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

2. Materials Used (1) Polypropylene Based Resin The following polypropylene based resin was used.
(A-1): Nippon Polypro Co., Ltd., Novatec (registered trademark) EA 9 (a propylene homopolymer with a Ziegler-Natta catalyst, MFR = 0.4 g / 10 min, Tm = 161 ° C.) 96 wt%, Polypropylene resin composition obtained by blending 4% by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.), MFR = 0.4 g / 10 min, Tm = 161 ° C.
(A-2): Nippon Polypro Co., Ltd., Novatec (registered trademark) EA 6 A (a propylene homopolymer (MFR = 1.9 g / 10 min, Tm = 161 ° C.) with a Ziegler-Natta catalyst) to 96 wt% Polypropylene resin composition obtained by blending 4% by weight of black pigment MB (EPP-K-120601, manufactured by Polycol Kogyo Co., Ltd.), MFR = 1.9 g / 10 min, Tm = 161 ° C.
(A-3): Nippon Polypro Co., Ltd., Novatec (registered trademark) FY6 (a propylene homopolymer with a Ziegler-Natta catalyst, MFR = 2.4 g / 10 min, Tm = 161 ° C) 96 wt%, Polypropylene resin composition obtained by blending 4% by weight of black pigment MB (EPP-K-120601 manufactured by Polycole Kogyo Co., Ltd.), MFR = 2.4 g / 10 min, Tm = 161 ° C.

(B-1): Propylene homopolymer with a Ziegler-Natta catalyst (MFR = 5 g / 10 min, Tm = 160 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name "Novatec (registered trademark) FY4"
(B-2): Propylene homopolymer with a Ziegler-Natta catalyst (MFR = 25 g / 10 min, Tm = 159 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “Novatec (registered trademark) SA1”
(B-3): Propylene-ethylene-random copolymer (MFR = 7 g / 10 min, Tm = 146 ° C.) by Ziegler-Natta catalyst, manufactured by Nippon Polypropylene Corporation, trade name “Novatec® FW3 GT” "
(B-4): Propylene-ethylene-random copolymer (MFR = 7 g / 10 min, Tm = 138 ° C.) by Ziegler-Natta catalyst, manufactured by Nippon Polypropylene Corporation, trade name “Novatec (registered trademark) FW 4 B "
(B-5): Propylene-ethylene-random copolymer (MFR = 6 g / 10 min, Tm = 131 ° C.) catalyzed by Ziegler-Natta catalyst, manufactured by Nippon Polypropylene Corporation, trade name “Novatec® FX4E” "
(B-6): Propylene-ethylene-random copolymer (MFR = 5 g / 10 min, Tm = 127 ° C.) with Ziegler-Natta catalyst, Japan Polypropylene Corp., trade name “Novatec® FX4G” "

(D-1): Propylene homopolymer with a Ziegler-Natta catalyst (MFR = 10 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name "Novatec (registered trademark) FA3KM"
(D-2): Polypropylene resin obtained by blending 0.4 parts by weight of nucleating agent (Milliken Japan Ltd., trade name “Millad NX 8000 J”) with 100 parts by weight of polypropylene resin (D-1) Composition (MFR = 10 g / 10 min, Tm = 164 ° C.)
(D-3): Propylene-α-olefin copolymer catalyzed by metallocene catalyst (MFR = 7 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Nippon Polypro Co., Ltd., trade name “ Wintech (registered trademark) WFX4M "
(D-4): A polypropylene resin composition in which 0.4 parts by weight of a nucleating agent (Milliken Japan Co., Ltd., trade name "Millad NX 8000 J") is blended with 100 parts by weight of a polypropylene resin (D-3). (MFR = 7 g / 10 min, Tm = 127 ° C.)
(D-5): Polypropylene resin composition (MFR = 10 g / 10) obtained by blending 4% by weight of a silver pigment MB (manufactured by Toyo Color Co., Ltd. PPCM 913Y-42 SILVER 21X) with 96% by weight of a polypropylene resin (D-1) Min, Tm = 161 ° C)

(A-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 158 ° C.) with a Ziegler-Natta catalyst, manufactured by Nippon Polypro Co., Ltd., trade name "Novatec (registered trademark) MA04A"
(A-2): The grade of the following composition of Nippon Polypro Co., Ltd. make, brand name "Novatec (registered trademark)" was used.
Propylene-ethylene block copolymer polymerized with Ziegler-Natta catalyst, melting peak temperature Tm of the whole propylene-ethylene block copolymer is 161 ° C, MFR (230 ° C, 2.16 kg load) is 28 g / 10 minutes, the content of the propylene homopolymer portion with respect to the whole propylene / ethylene copolymer is 73% by weight, the content of the propylene / ethylene copolymer portion is 27% by weight, and the ethylene content of the propylene / ethylene copolymer portion Is 37% by weight.

(2) Cellulose fiber (a)
(A-1): Nippon Paper Industries Co., Ltd. cellulose fiber, KC floc (registered trademark) W-100 GK, fiber diameter 15 μm, fiber length 300 μm

(3) Fiber-reinforced polypropylene-based resin composition (c)
(U-1) to (U-5): The components (A) and (I) were compounded in the proportions shown in Table 1, and kneaded and granulated under the following conditions to obtain resin composition pellets.
Kneading apparatus: "KZW-15-MG" type twin screw extruder manufactured by TechNovel Kneading conditions: extrusion temperature = 190 ° C, screw rotation speed = 400 rpm, discharge amount = 3 kg / h
The cellulose fiber (i) was compounded and kneaded by a method of side feeding from a position two barrels before the tip of the extruder using a side feeder so as to obtain a predetermined concentration.

3. Production of Resin Molded Body (Substrate) The fiber-reinforced polypropylene resin compositions (C-1) to (C-5) were subjected to injection molding by the following method to obtain a resin molded body (substrate).
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., clamping pressure 100 tons cylinder temperature: 190 ° C.
Mold temperature: 40 ° C
Injection mold: Width × height × thickness = 120 mm × 120 mm × 3 mm flat plate adjustment: Hold for 5 days in a constant temperature and humidity room with a temperature of 23 ° C and a humidity of 50% RH

Example 1
Production of Decorative Film A T-die with a lip opening of 0.8 mm and a die width of 400 mm, to which an extruder 1 with a diameter of 40 mm (diameter) was connected, was used. The polypropylene resin (A-1) was put into the extruder 1, and melt extrusion was performed under the conditions of a resin temperature of 240 ° C. and a discharge amount of 12 kg / h. The melt-extruded film was cooled and solidified while pressed against a first roll rotating at 80 ° C. at 3 m / min with an air knife to obtain a 150 μm-thick single-layer unstretched film.

Three-Dimensional Decorative Thermoforming As the resin molded body (base) 5, an injection molded body made of the fiber-reinforced polypropylene resin composition (C-1) obtained as described above was used. As a three-dimensional decorative thermoforming apparatus, "NGF-0406-SW" manufactured by NUSHIYAKU Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 is cut out with a width of 250 mm and a length of 350 mm so that the cooling roll contact surface faces the substrate and the longitudinal direction is the MD direction of the film, and the size of the opening Were set in a 210 mm × 300 mm film fixing jig 13. The resin molded body (base) 5 is mounted on a table 20 mm high mounted on a table 14 located below the film fixing jig 13 and is manufactured by Nichiban Co., Ltd. “Nystack NW-K15”. "Pasted through". The film fixing jig 13 and the table 14 were placed in the chambers 11 and 12, and the chambers were closed to seal the inside of the chamber boxes 11 and 12. The chamber box is divided up and down via the decorative film 1. Under the condition that the upper and lower boxes are vacuum suctioned and the pressure is 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 with an output of 80% and the decorative film 1 is Heated. During heating, vacuum suction was continued, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated and temporarily slackened, and then, 20 seconds after the tension-back phenomenon is finished, the table 14 installed in the lower chamber box 12 is moved upward, and the resin molded body (Substrate) 5 was pressed against the decorative film 1 and compressed air was sent immediately so that the pressure in the upper chamber box 11 became 270 kPa, to bring the resin molded body (substrate) 5 and the decorative film 1 into close contact. Thus, a three-dimensional decorative thermoformed article 6 having the decorative film 1 attached to the upper surface and the side surface of the resin molded body (base) 5 was obtained.

· Physical property evaluation (1) Evaluation of thermoforming property (appearance of decorated molded body)
The criteria for visual observation of the drawdown state of the decorative film at the time of three-dimensional decorative thermoforming and the adhesion state of the decorative film of the decorative molded body having the decorative film adhered to the substrate are shown below It evaluated by.
Good: At the time of three-dimensional decorative thermoforming, since the contact between the base and the decorative film was simultaneously made on the entire contact surface without drawdown of the decorative film, contact unevenness does not occur, and adhesion is uniformly performed. ing.
×: At the time of three-dimensional decorative thermoforming, since the decorative film was drawn down largely, contact unevenness occurs on the entire surface of the substrate.

(2) Adhesive force between resin molded body (substrate) and decorative film "Kraft adhesive tape No. 712 N" manufactured by NITOMS CORPORATION is cut out to 75 mm in width and 120 mm in length, and from the end of the resin molded body (substrate) It was stuck to a resin molding (substrate) in the range of 75 mm × 120 mm and subjected to masking treatment (substrate surface exposed portion is 45 mm wide and 120 mm long). It installed in three-dimensional decoration thermoforming apparatus NGF-0406-SW so that the masking surface of a resin molding (substrate) might contact with a decoration film, and performed three-dimensional decoration thermoforming.

  The decorative film surface of the resulting decorative molded body was cut to a substrate surface with a width of 10 mm in a direction perpendicular to the longitudinal direction of the pressure-sensitive adhesive tape, using a cutter, to prepare a test piece. In the obtained test piece, the adhesion surface of the base and the decoration film is 10 mm wide × 45 mm long. Attach to a tensile tester so that the base part of the test piece and the decorative film part become 180 °, measure the 180 ° peel strength of the adhesive surface at a tensile speed of 200 mm / min, and measure the maximum strength at peeling or breaking. The (N / 10 mm) was measured five times, and the average strength was taken as the adhesive strength.

(3) Appearance of the decorated molded body The appearance of the decorated film of the decorated molded body in which the decorative film was attached to the substrate was visually observed and evaluated according to the criteria shown below.
Good: The yellowing due to the discoloration of the cellulose fiber is not confirmed by the coating of the film, and the unevenness of the aggregated part of the cellulose is not felt, so the appearance is excellent.
X: A yellowing due to the discoloration of the cellulose fiber is confirmed, and unevenness of the aggregated part of cellulose is felt.

(4) Gloss The gloss (gloss) around 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 VG 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. . The measuring method conformed to JIS K7105-1981.

Table 2 shows the evaluation results of the physical properties of the obtained decorative molded product and the like.
As all the requirements of the present invention are satisfied, the resulting decorated molded article is excellent in thermoforming and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed and the touch is excellent. Met.

(Examples 2 to 5)
The three-dimensional decorative thermoforming described in Example 1 is the same as Example 1 except that the resin molding (base) 5 is changed to fiber-reinforced polypropylene resin compositions (W-2) to (W-5). It was evaluated. The evaluation results are shown in Table 2, respectively.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent.

(Example 6)
In the production of the decorative film of Example 1, an extruder 1 with a diameter of 40 mm (diameter) and an extruder 2 with a diameter of 30 mm (diameter) were connected, lip opening 0.8 mm, die width A 400 mm two-kind two-layer T-die was used. The polypropylene resin (A-1) is put into the extruder 1, and the polypropylene resin (D-1) is put into the surface layer extruder 2, and the discharge temperature of the extruder 1 is 12 kg and the resin temperature is 240 ° C. Melt-extrusion was carried out under the conditions of 4 kg / h for the discharge amount of 1 / h and the extruder for surface layer-2.
The melt-extruded film is cooled and solidified so that a layer composed of a polypropylene resin (A-1) is in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a 150 μm thick layer and 50 μm thick An unstretched film of two layers in which a surface decoration layer was laminated was obtained.
Except using the unstretched film obtained in the above-mentioned decorative film production and changing the resin molded body (base) 5 to a fiber-reinforced polypropylene resin composition (C-3) in three-dimensional decorative thermoforming, The molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. Moreover, it was a result which is excellent in glossiness by having laminated | stacked polypropylene resin (D-1) on the outermost surface side as surface decoration layer (III) [layer (III)].

(Example 7)
In the production of the decorative film of Example 1, a lip opening 0.8 mm, die width connected with an extruder 1 with a diameter of 40 mm (diameter) and an extruder 3 with a diameter of 30 mm (diameter) A 400 mm two-kind two-layer T-die was used. The polypropylene-based resin (A-1) is put into the extruder 1, and the polypropylene-based resin (B-1) is put into the seal layer extruder 3, and the discharge temperature of the extruder 1 is 12 kg. Melt-extrusion was carried out under the conditions of 4 kg / h for the discharge amount of / h and the extruder for sealing layer-3.
The melt-extruded film was cooled and solidified so that the seal layer was in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a 150 μm thick layer and a 50 μm thick surface decoration layer were laminated. An unstretched film of 2 layers was obtained.
Except using the unstretched film obtained in the above-mentioned decorative film production and changing the resin molded body (base) 5 to a fiber-reinforced polypropylene resin composition (C-3) in three-dimensional decorative thermoforming, The molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent.

(Examples 8 to 12)
In the production of the decorative film of Example 7, molding was performed in the same manner as in Example 9, except that the polypropylene resin (B-1) was changed to polypropylene resins (B-2) to (B-6), I made an evaluation. The evaluation results are shown in Table 3.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent.

(Example 13)
In the production of the decorative film of Example 12, molding and evaluation were performed in the same manner as in Example 13 except that the polypropylene resin (A-1) was changed to the polypropylene resin (A-2). The evaluation results are shown in Table 3.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent.

(Example 14)
In the production of the decorative film of Example 1, an extruder with a diameter of 40 mm (diameter), an extruder with a diameter of 30 mm (diameter) for a surface layer, and an extruder with a diameter of 30 mm (diameter)-3 A three-kind three-layer T-die with a lip opening of 0.8 mm and a die width of 400 mm was used. The polypropylene-based resin (A-1) is used for the extruder 1, the polypropylene-based resin (D-1) for the surface layer extruder 2, and the polypropylene-based resin (B-6) for the seal layer extruder 3. Each is charged, resin temperature is 240 ° C., discharge amount of extruder 1 is 12 kg / h, discharge amount of surface layer extruder 2 is 4 kg / h, discharge amount of seal layer extruder 3 is 4 kg / h The melt extrusion was performed under the following conditions.
The melt-extruded film is cooled and solidified so that the seal layer is in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a 150 μm thick layer, a 50 μm thick surface decoration layer, and 50 μm thick A three-layer unstretched film in which the seal layer of the above was laminated was obtained.
Except using the unstretched film obtained in the above-mentioned decorative film production and changing the resin molded body (base) 5 to a fiber-reinforced polypropylene resin composition (C-3) in three-dimensional decorative thermoforming, The molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 4.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. Moreover, it was a result which is excellent in glossiness by having laminated | stacked polypropylene resin (D-1) on the outermost surface side as surface decoration layer (III) [layer (III)].

(Example 15)
In the production of the decorative film of Example 14, molding and evaluation were performed in the same manner as in Example 14 except that the polypropylene resin (D-1) was changed to the polypropylene resin (D-2). The evaluation results are shown in Table 4.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. Moreover, it was a result excellent in glossiness by having laminated | stacked the polypropylene resin (D-2) to which the nucleating agent was added on the outermost surface side as surface decoration layer (III) [layer (III)].

(Example 16)
In the production of the decorative film of Example 14, molding and evaluation were performed in the same manner as in Example 14 except that the polypropylene resin (D-1) was changed to the polypropylene resin (D-3). The evaluation results are shown in Table 4.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. Moreover, it was a result which is excellent in glossiness by having laminated | stacked polypropylene resin (D-3) on the outermost surface side as surface decoration layer (III) [layer (III)].

(Example 17)
In the production of the decorative film of Example 14, molding and evaluation were performed in the same manner as in Example 14 except that the polypropylene resin (D-1) was changed to a polypropylene resin (D-4). The evaluation results are shown in Table 4.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. Moreover, it was a result which is excellent in glossiness by having laminated | stacked the polypropylene resin (D-4) to which the nucleating agent was added on the outermost surface side as surface decoration layer (III) [layer (III)].

(Example 18)
In the production of the decorative film of Example 14, molding and evaluation were performed in the same manner as in Example 14 except that the polypropylene resin (D-1) was changed to the polypropylene resin (D-5). The evaluation results are shown in Table 4.
All of the above satisfy all the requirements of the present invention, so the resulting decorated molded article is excellent in thermoforming property and adhesion, and the surface of the molded article is covered with a film so that no yellowing is observed, and the touch is good It was excellent. In addition, since the layer (I) was colored in black and the surface decoration layer (III) [layer (III)] was colored in silver, it became a metal-like film, and the appearance was excellent.

(Comparative example 1)
Evaluation was performed using only the injection-molded object which consists of a fiber reinforced polypropylene-type resin composition (c-1). The results are shown in Table 5.
Since the decorative film was not stuck, yellow discoloration was noticeable and it was not a practical surface shape.

(Comparative examples 2 to 5)
The evaluation was performed in the same manner as Comparative Example 1 except that the injection-molded article was changed from the fiber-reinforced polypropylene resin composition (C-1) to an injection-molded article consisting of (C-2) to (C-5). . The results are shown in Table 5.
Since no decorative film was attached to any of the injection molded articles, yellowing was noticeable, and irregularities due to aggregates of cellulose fibers were observed, and the texture was rough and was not a practicable surface shape. .

(Comparative example 6)
An unstretched film was obtained in the same manner as in Example 1 except that in the production of the decorative film of Example 1, the polypropylene resin (A-1) was changed to the polypropylene resin (A-3).
Except using the unstretched film obtained in the above-mentioned decorative film production and changing the resin molded body (base) 5 to a fiber-reinforced polypropylene resin composition (C-3) in three-dimensional decorative thermoforming, The molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 5.
Since the polypropylene resin (A-3) has a high MFR of 2.4 g / 10 min, it is inferior to the stability of thermoforming, and the decoration film is largely drawn down at the time of three-dimensional decoration thermoforming. It was generated and the result of the appearance of the decorated molding was extremely poor.

1 Decorative film 2 layers (I)
3 Seal layer (II)
4 surface decoration layer (III)
5 Resin moldings (deterioration target, substrate)
6 Decoration molding 11 upper chamber box 12 lower chamber box 13 jig 14 table 15 heater

Claims (6)

It is a decorative molded body in which a polypropylene-based decorative film is stuck on a resin molded body by thermoforming, and the polypropylene-based decorative film includes a layer (I) made of a polypropylene-based resin (A), The polypropylene resin (A) has a MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the resin molded product is a polypropylene resin satisfying the following requirements (ai) to (ai) Resin (A) 40% by weight to 99% by weight and cellulose fiber (a) 1% by weight to 60% by weight satisfying the following requirements (i) (however, the total amount of (a) and (i) is 100 What is claimed is: 1. A decorated molded body, which is a molded body comprising a fiber-reinforced polypropylene-based resin composition (C) comprising (% by weight).
(Ai): The melting peak temperature Tm (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) is not less than 0.5 g / 10 minutes and not more than 200 g / 10 minutes.
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm. It is a decorative molded body in which a polypropylene-based decorative film is stuck on a resin molded body by thermoforming, and the polypropylene-based decorative film is a layer (I) comprising a polypropylene-based resin (A) and a polypropylene-based resin (B) includes a sealing layer (II), and the polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene resin (B) has an MFR (MFR) 230 ° C., 2.16 kg load) exceeds 2 g / 10 min, and the resin molded product is 40 wt% to 99 wt% of polypropylene resin (A) satisfying the following requirements (Ai) to (A-ii) Fiber reinforced polypropylene containing 1% by weight to 60% by weight of cellulose fibers (i) satisfying the following requirements (ii) (provided that the total amount of (i) and (i) is 100% by weight): Made emissions based resin composition (c), decorative moldings, characterized in that said polypropylene based decorative film and the resin molded body is a molded body which is bonded via seal layer (II).
(Ai): The melting peak temperature Tm (A) is 110 ° C. or more.
(A-ii): MFR (A) (230 ° C., 2.16 kg load) is not less than 0.5 g / 10 minutes and not more than 200 g / 10 minutes.
(Ii): The fiber diameter of the cellulose fiber (i) is 10 nm to 500 μm. When the MFR of the polypropylene resin (A) is MFR (A) and the MFR of the polypropylene resin (B) is MFR (B), the following relational expression (1) is satisfied: The decorated molding as described in.
MFR (B) / MFR (A)> 1.5 (1)   The surface modification layer (III) which consists of surface decoration layer resin on the surface on the opposite side to the affixing surface with the said resin-molding body has the said polypropylene-type decoration film, It is characterized by the above-mentioned. The decorated molded object in any one of 3.   The said surface decoration layer resin consists of polypropylene resin (D), MFR (230 degreeC, 2.16 kg load) of this polypropylene resin (D) is characterized by exceeding 2 g / 10 minutes. The decorated molding as described in 4.   It is a method of manufacturing the decoration molding according to any one of claims 1 to 5, and is provided with a step of preparing a polypropylene-based decoration film, a step of preparing a resin molding, the pressure reduction chamber box. The step of setting the resin molding and the decoration film, the step of depressurizing the inside of the chamber, the step of heating and softening the decoration film, the step of pressing the decoration film against the resin molding, and the atmosphere inside the chamber A method for producing a decorated formed body, comprising the steps of returning or pressing.

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