JP7110951B2 - DECORATION FILM AND METHOD FOR MANUFACTURING DECORATION MOLDED PRODUCT USING IT - Google Patents

Description

The present invention relates to a decorative film to be adhered onto a resin molded article by thermoforming, and a method for producing a decorated molded article using the decorative film. More specifically, the present invention relates to a decorative film which is excellent in weather resistance before and after decorative molding and which is to be adhered to a resin molded article by thermoforming, and a method for producing a decorated molded article using the decorative film.

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

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

Decoration molding by vacuum pressure molding and vacuum molding has a greater degree of freedom in shape than other decoration molding represented by insert molding. In addition, since the film can be thermoformed at a relatively low temperature and a low pressure, it has the advantage of excellent reproducibility of texture such as embossed on the surface of the decorative film.

JP-A-2002-67137

Hindered amine light stabilizers and UV absorbers are sometimes added to impart weather resistance to the decorative film. However, a decorative film containing such a hindered amine light stabilizer or ultraviolet absorber has a problem that weather resistance is significantly impaired after decorative molding.

Conventional techniques have not yet achieved a decorative film in which deterioration of weather resistance is suppressed even after decorative molding by vacuum pressure forming and vacuum forming. An object of the present invention is to provide a decorative film that can be used for three-dimensional decorative thermoforming in which deterioration in weather resistance after decorative molding is suppressed, and a method for producing a decorative molded article using the same. be.

The present inventors have made intensive studies to solve the above problems, and found that hindered amine added to resin to impart weather resistance in the process of heating the decorative film under the decorative molding conditions, that is, in a vacuum. It was determined that the system light stabilizer and/or UV absorber volatilized significantly. On the other hand, in a decorative film containing a specific hindered amine light stabilizer and/or ultraviolet absorber, the hindered amine light stabilizer and/or ultraviolet absorber is difficult to volatilize even when heated in a vacuum, and after decorative molding It has been found that deterioration of weather resistance can be suppressed even if there is

That is, the present invention includes the following.

(1) A decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber to be adhered to a three-dimensional resin molding by thermoforming, wherein the hindered amine light stabilizer and/or ultraviolet light The absorbent is a decorative film that meets the following requirements.
Requirement: The amount of change in the haze value of the glass plate measured by the method based on JIS-K7136 after the following fogging test is performed by the method based on ISO6452 is 40 or less.
<Fogging test> 1 g (±0.01 g) of a hindered amine light stabilizer or ultraviolet absorber was placed in a glass sample bottle, and the sample bottle was covered with a glass plate and heated at 150° C. for 1 hour. Fogging is generated on the glass plate.

(2) The decorative film according to (1), wherein the hindered amine light stabilizer and/or ultraviolet absorber has a molecular weight of 490 g/mol or more.

(3) The decorative film includes at least one layer containing the hindered amine light stabilizer and/or ultraviolet absorber, and the layer contains 50% by weight or more of a polyolefin resin, (1) or (2) ).

(4) The decorative film according to (3), wherein the polyolefin resin is a polypropylene resin.

(5) Any one of (1) to (4), wherein the outermost layer of the decorative film opposite to the surface of the decorative film attached to the resin molding contains the hindered amine light stabilizer and/or ultraviolet absorber. or the decorative film according to one.

(6) preparing the decorative film according to any one of (1) to (5); preparing a resin molded body; a step of setting a film, a step of reducing the pressure in the chamber box, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molding, and bringing the pressure-reduced chamber box to atmospheric pressure. A method for manufacturing a decorative molded article, including the step of returning or pressing.

(7) The method for producing a decorative molded article according to (6), wherein the resin molded article is made of a polypropylene-based resin composition.

According to the decorative film of the present invention, a decorative film that can be used for three-dimensional decorative thermoforming in which deterioration of weather resistance after decorative molding is suppressed, and a method for producing a decorative molded article using the same. can provide.

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

As used herein, a decorative film refers to a film for decorating a molded article. Decorative molding refers to molding in which a decorative film and a molded body are adhered together. Three-dimensional decorative thermoforming is a process of adhering a decorative film to a molded body, and includes a step of thermoforming the decorative film along the adhering surface of the molded body and simultaneously adhering it, In this step, thermoforming is performed under reduced pressure (vacuum) in order to prevent air from being entrained between the decorative film and the molded article, the heated decorative film is adhered to the molded article, and pressure is applied. It refers to molding, which is the process of bringing into close contact by releasing (pressurizing). BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments for carrying out the present invention will be described in detail.

The decorative film of the present invention is a decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber to be adhered to a three-dimensional resin molding by thermoforming, wherein the hindered amine light stabilizer The agent and/or UV absorber are characterized by satisfying the following requirements.
Requirement: The amount of change in the haze value of the glass plate measured by the method based on JIS-K7136 after the following fogging test is performed by the method based on ISO6452 is 40 or less. The amount of change in haze value after the fogging test is calculated from the following formula.
Amount of change in haze value after fogging test = haze value of glass plate after fogging test - haze value of glass plate before fogging test It is placed in a glass sample bottle, and the sample bottle is covered with a glass plate and heated at 150° C. for 1 hour to generate fogging on the glass plate.

[Hindered amine light stabilizer and UV absorber]
The hindered amine light stabilizer and/or UV absorber in the present invention has a haze value change measured by a method conforming to JIS-K7136 of a glass plate after performing the following fogging test by a method conforming to ISO6452. It must be 40 or less, preferably 35 or less, more preferably 25 or less, and even more preferably 10 or less.
<Fogging test> 1 g (±0.01 g) of a hindered amine light stabilizer or ultraviolet absorber was placed in a glass sample bottle, and the sample bottle was covered with a glass plate and heated at 150° C. for 1 hour. Fogging is generated on the glass plate.
A normal fogging test is performed using a resin composition sample containing the additive of interest. cannot be grasped. In other words, it means that it is different from the bleeding phenomenon of ordinary additives. The volatility of the hindered amine light stabilizer and/or the ultraviolet absorber in the decorative film of the present invention can be ascertained by a fogging test in which the hindered amine light stabilizer or the ultraviolet absorber is directly heated.
When the haze value of the glass plate after performing the fogging test is within the above range, the hindered amine light stabilizer and/or the ultraviolet absorber are difficult to volatilize even during the decorative molding, so that the decorated molded product has excellent weather resistance. can be obtained. In addition, it is possible to prevent the hindered amine light stabilizer and/or the ultraviolet absorber from migrating to the surface (adhesive surface) of the decorative film, thereby reducing the adhesion to the object to be decorated. Furthermore, it is possible to prevent the interior of the chamber box of the thermoforming machine from being soiled by the hindered amine light stabilizer and/or the ultraviolet absorber.

In the present invention, the hindered amine light stabilizer or UV absorber (although they are additives, in order to distinguish them from other additives, in the following description, both of them may be particularly referred to as "weather resistance agents"), the above conditions Although not particularly limited as long as it satisfies the above, the molecular weight of the hindered amine light stabilizer or ultraviolet absorber is preferably 490 g/mol or more, more preferably 510 g/mol or more, and still more preferably 550 g/mol or more. . By setting the molecular weight within the above range, the hindered amine light stabilizer and/or the ultraviolet absorber are less likely to volatilize even under decorative molding conditions. Although the upper limit of the molecular weight is not particularly limited, it is practically preferable to be 10,000 g/mol or less.

Specific examples of hindered amine light stabilizers used in the present invention include poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2, 4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]}, bis(1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-ditert-butyl- 4-hydroxybenzyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)・di(tridecyl)butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4- piperidyl)・di(tridecyl)butane tetracarboxylate, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy }ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl -4-piperidyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,5,8,12-tetrakis[4,6-bis{N -(2,2,6,6-tetramethyl-4-piperidyl)butylamino}-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, 1-(2 -hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine/N,N'-bis( 2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine condensate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine/dibromoethane condensation bis(2,2,6,6-tetramethyl-4-oxylpiperidine) sebacate, tetrakis(2,2,6,6-tetramethyl-4-oxylpiperidyl)butane-1,2,3,4- Tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-penta methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis(1,1-dimethyl-2-(tris(2,2,6,6-tetramethyl-N-oxyl) piperidyl-4-oxycarbonyl)butylcarbonyloxy)ethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane and the like. Among these, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4diyl][(2,2,6 ,6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]}, 3,9-bis[1,1-dimethyl-2-{ tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis(2,2 ,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate.

Examples of commercially available products include LA-68 (registered trademark) and LA-57 (registered trademark) manufactured by ADEKA Corporation, Chimassorb 944 (registered trademark) and Tinuvin 622 (registered trademark) manufactured by BASF Corporation.

The hindered amine light stabilizers may be used alone or in appropriate combination of two or more.

The amount of the hindered amine light stabilizer added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.00 parts by weight, per 100 parts by weight of the resin constituting the layer containing the light stabilizer. .50 parts by weight. When the addition amount is within the above range, it is possible to obtain a decorative film and a decorative molded article with good weather resistance.

Specific examples of UV absorbers used in the present invention include 2,2′-methylenebis(4-t-octyl-6-benzotriazolyl)phenol, 2-(4,6-diphenyl-1,3 ,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)- 1,3,5-triazine and the like.

Examples of commercially available products include LA-31G (registered trademark), LA-46 (registered trademark) and LA-F70 (registered trademark) manufactured by ADEKA Corporation.

The ultraviolet absorbers can be used alone or in an appropriate combination of two or more.

The amount of the ultraviolet absorber to be added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50, per 100 parts by weight of the resin constituting the layer containing the ultraviolet absorber. weight part. When the addition amount is within the above range, it is possible to obtain a decorative film and a decorative molded article with good weather resistance.

Both the hindered amine light stabilizer and the ultraviolet absorber may be contained, in which case the total amount of both weathering agents is 0 per 100 parts by weight of the resin constituting the layer containing the weathering agent. A range of 0.002 to 2.00 parts by weight is preferred, more preferably 0.01 to 1.00 parts by weight.

A higher effect can be exhibited by setting the content ratio of the hindered amine light stabilizer and the ultraviolet absorber within a specific range. The mixing ratio of both weathering agents is preferably 1/5 to 5/1, more preferably 1/4 to 4/1, of hindered amine light stabilizer/ultraviolet absorber. By including both weathering agents, the synergistic effect of the weathering agents makes it possible to obtain a decorative film and a decorated molded article with better weather resistance.

[Layer containing hindered amine light stabilizer and/or UV absorber]
The decorative film of the present invention comprises at least one layer containing a hindered amine light stabilizer and/or an ultraviolet absorber. The decorative film may be composed of only the layer containing the hindered amine light stabilizer and/or ultraviolet absorber, or may have a multilayer structure containing other layers. By including the layer containing the weather resistant agent, it is possible to obtain a decorative film and a decorative molded article with good weather resistance. In particular, since deterioration due to light progresses from the surface of the molded article, it is more preferable that the outermost layer of the decorative film opposite to the adhered surface of the resin molded article contains the weather resistant agent.

[Polyolefin resin]
The layer containing the hindered amine light stabilizer and/or the ultraviolet absorber in the present invention preferably contains 50% by weight or more of the polyolefin resin from the viewpoint of moldability, recyclability, solvent resistance, and the like. The layer preferably contains 60% by weight or more of the polyolefin resin, particularly preferably 70% by weight or more. In the present invention, the polyolefin resin refers to a resin containing 50 mol % or more of polymerized units derived from olefin monomers. In the present invention, the modified polyolefin is a concept that includes polyolefin resins, and refers to resins containing polymerized units derived from olefin monomers and polymerized units derived from other monomers in an arbitrary ratio. Polyolefin-based resins are preferably homopolymers of α-olefins such as ethylene, propylene and butene, and copolymers of ethylene, propylene and the like with other α-olefins. Specifically, high-density polyethylene, low-density polyethylene, ethylene-α-olefin copolymer, propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer ( block polypropylene) and the like. Examples of monomer components other than olefin monomers that constitute polyolefin resins include aromatic monomers such as styrene; polar group-containing monomers such as maleic anhydride and acrylic acid; It preferably contains no polymerized units.
Among these, polypropylene resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene) are particularly preferred, and combinations thereof are selected. can also The polypropylene-based resin preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance, heat resistance, and the like. From the viewpoint of gloss and transparency (color development), a propylene-α-olefin copolymer is preferred.

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

The resin constituting the layer containing the hindered amine light stabilizer and/or the ultraviolet absorber may contain other additives, fillers, other resin components, etc. in addition to the above weather resistance agents, as long as the effects of the present invention are not impaired. may be However, the total amount of other additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition.

As other additives, various known additives such as antioxidants, neutralizers, antiblocking agents, lubricants, antistatic agents, metal deactivators, and nucleating agents can be blended.

Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, thio-based antioxidants, and the like. Examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate.

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

A nucleating agent is a component added to impart transparency, surface gloss, and the like to the decorative film. Nucleating agents include metal salts of aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives, nonitol derivatives, amide compounds, metal salts of rosin, and the like. Among these nucleating agents are aluminum pt-butylbenzoate, 2,2′-methylenebis(4,6-di-t-butylphenyl)sodium phosphate, 2,2′-methylenebis(4 ,6-di-t-butylphenyl)aluminum, bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphospho syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[ (4-Propylphenyl)methylene]-nonitol, rosin sodium salt and the like can be exemplified.

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

Examples of other resin components include styrene elastomers, modified polyolefin resins having less than 50 mol % polymerized units derived from olefin monomers, petroleum resins, and other thermoplastic resins.

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

When the decorative molded article according to the present invention is molded as a colored molded article, it is sufficient to use the coloring agent only in the decorative film. It is possible to suppress the use. In addition, it is possible to suppress changes in physical properties that accompany the addition of a colorant.

In the present invention, a resin composition containing a hindered amine light stabilizer and/or an ultraviolet absorber includes a resin, a hindered amine light stabilizer and/or an ultraviolet absorber, other additives, fillers, other resin components, and the like. A method of melt kneading, a method of dry blending a hindered amine light stabilizer and / or an ultraviolet absorber with a melt-kneaded resin and other additives, fillers, other resin components, etc., a resin with a hindered amine light stabilizer It can be produced by a method such as dry blending a masterbatch in which an agent and/or an ultraviolet absorber, other additives, fillers, other resin compositions, etc. are dispersed in a carrier resin at a high concentration.

[Decorative film]
The decorative film of the present invention comprises at least one layer containing a hindered amine light stabilizer and/or a UV absorber. That is, even if the decorative film is a single-layer film consisting only of a layer containing the hindered amine light stabilizer and/or ultraviolet absorber, it may be combined with a layer containing the hindered amine light stabilizer and/or ultraviolet absorber. A multilayer film composed of other layers may also be used. The surface of the decorative film of the present invention may be textured, embossed, printed, sandblasted, scratched, or the like.

Three-dimensional decorative thermoforming has a high degree of freedom in the shape of the object to be decorated. Various textures can be expressed by applying textures to the surface. For example, in the case of imparting texture such as embossing to a resin molding, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems when molding with a molded body mold that imparts embossing, that is, a molded body mold is required for each embossing pattern, and it is very difficult and expensive to apply complicated embossing to a curved surface mold. It is possible to solve the problem of being , and to obtain a decorative molded article to which various patterns of embossing are easily applied.

As a preferred embodiment of the decorative film, when it is a single-layer film, it preferably contains a resin having excellent thermoformability. For example, when the resin constituting the film is a polypropylene-based resin, (i) a resin composition (X) containing a polypropylene-based resin having a long-chain branched structure, wherein the resin composition (X) is a melt Flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.1 to 40 g / 10 minutes, and strain hardening degree λ is 1.1 or more, and / or (ii) linear polypropylene It is preferable that the resin composition (Y) contains a base resin, and the MFR of the resin composition (Y) is 0.1 to 2.0 g/10 minutes. By using the resin composition (X) and/or (Y), it is possible to obtain a decorative molded article with a good appearance.

Resin composition (X) containing a polypropylene-based resin having a long-chain branched structure
A resin composition (X) containing a polypropylene-based resin having a long-chain branched structure, which is preferable as a resin having excellent thermoformability, will be described.

(X1) Melt flow rate (MFR (X))
If the viscosity of the resin composition (X) is too low, sufficient molding stability cannot be obtained, so the resin composition (X) must have a certain viscosity. Define the MFR (230 ° C., 2.16 kg load) as.

In this specification, the MFR (230° C., 2.16 kg load) of the resin composition (X) is defined as MFR(X). MFR (X) preferably satisfies the following requirement (x1), more preferably satisfies requirement (x1′), and even more preferably satisfies requirement (x1″). MFR of resin composition (X) (X ) is set to the following value or less, it is possible to obtain a decorative molded article having a good appearance.
(x1) MFR(X) is 40 g/10 minutes or less.
(x1') MFR(X) is 20 g/10 minutes or less.
(x1″) MFR(X) is 12 g/10 minutes or less.

The lower limit of MFR (X) of resin composition (X) is not particularly limited, but is preferably 0.1 g/10 minutes or more, more preferably 0.3 g/10 minutes or more. By setting the MFR(X) to the above value or more, the moldability during production of the decorative film is improved, and it is possible to suppress the occurrence of appearance defects called sharkskin and interface roughness on the film surface.

In the present invention, the MFR of the polypropylene-based resin and the polypropylene-based resin composition was measured according to ISO 1133:1997 Conditions M under the conditions of 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

(X2) strain hardening degree λ
The strain hardening degree λ of the resin composition (X) preferably satisfies the following requirement (x2), more preferably satisfies the requirement (x2′), and further preferably satisfies the requirement (x2″). Resin composition By setting the strain hardening degree λ of (X) to a value within the following range, it is possible to obtain a decorated molded article having good moldability during decorative thermoforming and excellent appearance.
(x2) The strain hardening degree λ is 1.1 or more.
(x2') The strain hardening degree λ is 1.8 or more.
(x2″) The strain hardening degree λ is 2.3 or more.

Although the upper limit of the strain hardening degree λ of the resin composition (X) is not particularly limited, it is preferably 50 or less, more preferably 20 or less. By setting the strain hardening degree λ within the above range, the appearance of the decorative film can be improved.

The strain hardening degree λ of the polypropylene-based resin and the resin composition (X) is obtained based on strain hardening measurement in extensional viscosity measurement. Regarding the strain hardening property (nonlinearity) of elongational viscosity, refer to "Lecture/Rheology" edited by Japan Rheology Society, Kobunshi Publishing Association, 1992, pp. ^221-222 , and in this specification, the strain hardening degree λ shall be calculated by a method according to the method of determination illustrated in FIGS. .01), ηe (3.5) is adopted as the extensional viscosity value, and the strain hardening degree λ is defined by the following formula (b-1).
λ=ηe(3.5)/{3×η ^* (0.01)} Formula (b-1)
In the above formula (b-1), η ^* (0.01) is the complex viscosity at a measurement temperature of 180 ° C. and an angular frequency of ω = 0.01 rad / s [unit: Pa ·s], and the complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and the angular frequency ω by η ^* =G ^* /ω. ηe(3.5) is the elongational viscosity measured by elongational viscosity measurement at a measurement temperature of 180° C., a strain rate of 1.0 s ⁻¹ and a strain amount of 3.5.

Usually, the data obtained by these viscoelasticity measurements are collections of numerical values such as elastic modulus and viscosity at discrete frequencies or measurement time intervals. Therefore, when the measurement is performed with an apparatus and conditions different from those used in the present invention, the complex viscosity η ^* (0.01) at the angular frequency ω = 0.01 rad/s and the strain amount 3.5 There may be cases where there is no data for the elongational viscosity ηe (3.5) at , but in that case, the data before and after that is used to perform interpolation such as linear interpolation, spline interpolation, etc. to estimate the corresponding value It is permissible to When performing interpolation, it is common practice to use logarithmic scales for stress and time.

At this time, if the sample does not have strain hardening (nonlinearity) in extensional viscosity, the strain hardening degree λ is about 1 (for example, 0.9 or more and less than 1.1) or a smaller value, strain hardening The value of the strain hardening degree λ increases as the property (nonlinearity) increases.

Ordinary crystalline polypropylene is a linear polymer and usually does not have strain hardening properties. On the other hand, the polypropylene-based resin preferably used in the present invention is preferably a polypropylene-based resin (XL) having a long chain branched structure, whereby the resin composition (X) has good strain hardening You can express your sexuality.

The term "long-chain branched structure" as used in the present invention refers to a branched structure formed by a molecular chain having a carbon skeleton (branched main chain) with a carbon number of tens or more and a molecular weight of several hundred or more. This long-chain branched structure is distinguished from short-chain branches formed by copolymerization with α-olefins such as 1-butene.

Methods for introducing a long-chain branched structure into a polypropylene resin include a method of irradiating a polypropylene having no long-chain branched structure with high-energy ionizing radiation (JP-A-62-121704), and a method of introducing a long-chain branched structure. A method of reacting an organic peroxide with polypropylene that does not have (Japanese Patent Publication No. 2001-524565), or a method of producing a macromonomer having a terminal unsaturated bond and copolymerizing it with propylene (Japanese Patent Publication No. 2001-525460 JP-A-2003-110002), etc., and the strain hardening degree λ of the polypropylene-based resin can be increased regardless of which method is used for production.

The polypropylene-based resin (XL) having a long-chain branched structure is not particularly limited as long as it has a long-chain branched structure, but it must be a polypropylene-based resin produced by a method other than a cross-linking method. are preferred, and those obtained by a method using a macromer copolymerization method in which a long-chain branched structure is formed during polymerization are preferred. Examples of such methods include, for example, Japanese Patent Publication No. 2001-525460, Japanese Patent Application Laid-Open No. 10-338717, Japanese Patent Application Publication No. 2002-523575, Japanese Patent Application Publication No. 2009-57542, Japanese Patent No. 5027353, A method disclosed in JP-A-10-338717 can be mentioned. In particular, the macromer copolymerization method disclosed in Japanese Patent Laid-Open No. 2009-57542 is suitable for the present invention because it does not generate gels and allows obtaining a long chain branched polypropylene resin (XL).

Having a long-chain branched structure in polypropylene is defined by a method based on the rheological properties of the resin, a method of calculating the branching index g' using the relationship between molecular weight and viscosity, a method using ¹³ C-NMR, and the like. In the present invention, the long-chain branched structure is defined by the branching index g' and/or ¹³ C-NMR as shown below.

{branching index g'}
The branching index g' is known as a direct index for long-chain branched structures. A detailed description is given in "Developments in Polymer Characterization-4" (J.V. Dawkins ed. Applied Science Publishers, 1983), but the definition of the branching index g' is as follows.
Branching index g′=[η]br/[η]lin
[η]br: Intrinsic viscosity of polymer (br) having a long-chain branched structure [η]lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br) As is clear from the above definition, the branching index g′ is If it takes a value smaller than 1, it is determined that a long-chain branched structure exists, and the value of the branching index g' decreases as the number of long-chain branched structures increases.

The branching index g' can be obtained as a function of the absolute molecular weight Mabs by using GPC with a light scatterometer and a viscometer in the detector. Details of the method for measuring the branching index g' in the present invention are described in JP-A-2015-40213, and are as follows.
{Measuring method}
GPC: Alliance GPCV2000 (manufactured by Waters)
Detector: Listed in order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (manufactured by Wyatt Technology)
Differential refractometer (RI): GPC attached Viscometer: GPC attached Mobile phase solvent: 1,2,4-trichlorobenzene (Irganox 1076 added at a concentration of 0.5 mg/mL)
Mobile phase flow rate: 1 mL/min Column: Two GMHHR-H(S) HT manufactured by Tosoh Corporation Sample injection part temperature: 140 ° C.
Column temperature: 140°C
Detector temperature: all 140°C
Sample concentration: 1 mg/mL
Injection volume (sample loop volume): 0.2175 mL

{analysis method}
In determining the absolute molecular weight (Mabs), the root mean square radius of gyration (Rg) obtained from the multi-angle laser light scattering detector (MALLS), and the intrinsic viscosity ([η]) obtained from the Viscometer, the data processing provided with MALLS was used. Using the software ASTRA (version 4.73.04), calculation is performed with reference to the following literature.
References:
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

In the decorative film of the present invention, if the polypropylene-based resin or resin composition (X) having a long-chain branched structure contains a gel, the appearance of the film deteriorates. Alternatively, it is preferable to use the resin composition (X). In particular, as the polypropylene resin (XL) having a long-chain branched structure, a macromonomer having a terminal unsaturated bond is produced using a metallocene catalyst having a specific structure, and copolymerized with propylene. Those produced using a method of forming a long-chain branched structure are preferred. In particular, those satisfying the following branching index g′ at an absolute molecular weight Mabs of 1,000,000 of 0.3 or more and less than 1.0 are preferable, more preferably 0.55 or more and 0.98 or less, and still more preferably 0.55 or more and 0.98 or less. 75 or more and 0.96 or less, most preferably 0.78 or more and 0.95 or less. In the present invention, "low gel content" means that the branching index g' of the polypropylene-based resin at an absolute molecular weight Mabs of 1,000,000 is within the above range. When the branching index g' is within this range, highly crosslinked components are not formed, and no or very little gel is formed. It does not deteriorate the appearance when composing the surface.

{ ¹³ C-NMR}
¹³ C-NMR can distinguish between short and long chain branched structures. Macromol. Chem. Phys. 2003, vol. 204, 1738, a summary of which is as follows.

A polypropylene-based resin having a long-chain branched structure has a specific branched structure as represented by the following structural formula (1). In Structural Formula (1), C _a , C _b and C _c represent the methylene carbons adjacent to the branch carbon, C _br represents the methine carbon at the base of the branched chain, and P ¹ , P ² and P ³ , indicates a propylene-based polymer residue.

The propylene-based polymer residues P ¹ , P ² and P ³ may themselves contain a branched carbon (C _br ) different from the C _br described in Structural Formula (1). obtain.

Such branched structures are identified by ¹³ C-NMR analysis. The assignment of each peak is according to Macromolecules, Vol. 35, No. 10. 2002, pp. 3839-3842 can be referred to. That is, a total of three methylene carbons (C _a , C _b and C _c ) were observed, one each at 43.9 to 44.1 ppm, 44.5 to 44.7 ppm and 44.7 to 44.9 ppm, A methine carbon (C _br ) is observed at 31.5-31.7 ppm. The methine carbon observed at 31.5 to 31.7 ppm may hereinafter be abbreviated as branched methine carbon (C _br ).

The ¹³ C-NMR spectrum of a polypropylene-based resin having a long-chain branched structure is characterized by the observation that the three methylene carbons close to the branched methine carbon _Cbr are diastereotopically non-equivalently divided into three. is.

Such a branched chain assigned by ¹³ C-NMR indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the polypropylene-based resin, and the branch having 4 or less carbon atoms is a branched carbon Therefore, in the present invention, the presence or absence of a long-chain branched structure can be determined by confirming the peak of this branched methine carbon.
The method for measuring ¹³ C-NMR in the present invention is as follows.

{ ¹³ C-NMR measurement method}
200 mg of a sample was combined with 2.4 ml of o-dichlorobenzene/deuterobrominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane as a reference substance for chemical shift, and an NMR sample with an inner diameter of 10 mmφ. It was placed in a tube, dissolved, and subjected to ¹³ C-NMR measurement.
The ¹³ C-NMR measurement was performed using an AV400M type NMR apparatus (Bruker Biospin Co., Ltd.) equipped with a 10 mmφ cryoprobe.
The measurement was performed at a sample temperature of 120° C. by the proton complete decoupling method. Other conditions are as follows.
Pulse angle: 90°
Pulse interval: 4 seconds Accumulation times: 20,000 The chemical shift was set at 1.98 ppm for the methyl carbon peak of hexamethyldisiloxane, and the chemical shift for peaks due to other carbons was based on this.
The peak around 44 ppm can be used to calculate the amount of long chain branching.

In the ¹³ C-NMR spectrum of the polypropylene-based resin (XL) having a long-chain branched structure, the amount of long-chain branches quantified from the peak near 44 ppm is preferably 0.01/1000 total propylene or more, It is more preferably 0.03/1000 total propylene or more, still more preferably 0.05/1000 total propylene or more. If this value is too large, it may cause appearance defects such as gels and fish eyes. .30 pieces/1000 total propylene or less.

The polypropylene-based resin (XL) having such a long-chain branched structure may be contained in the resin composition (X) in an amount sufficient to impart strain hardening properties. The polypropylene resin (XL) having a long-chain branched structure is contained in an amount of preferably 1 to 100% by weight, more preferably 5% by weight or more, based on 100% by weight of the resin composition (X).

The polypropylene resin (XL) having a long-chain branched structure in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), or a propylene block copolymer (block polypropylene). Various types of propylene-based polymers such as, or combinations thereof can be selected. The polypropylene-based resin preferably contains 50 mol % or more of polymerized units derived from propylene monomers.

Resin composition (Y) containing linear polypropylene resin
A resin composition (Y) containing a linear polypropylene-based resin, which is preferable as a resin having excellent thermoformability, will be described.

The resin composition (Y) containing a linear polypropylene resin suitable for the present invention has an MFR (230° C., 2.16 kg load) of preferably 2.0 g/10 min or less, more preferably 1.5 g/10 min. minutes or less, more preferably 1.0 g/10 minutes or less. By setting the MFR of the resin composition (Y) to the above value or less, it is possible to obtain a decorative molded article having a good appearance.

Although the lower limit of the MFR of the resin composition (Y) is not particularly limited, it is preferably 0.1 g/10 minutes or more, more preferably 0.3 g/10 minutes or more. By setting the MFR to the above value or more, the formability of the decorative film during production is improved, and it is possible to suppress the appearance defects called sharkskin and interface roughness on the film surface.

As another preferred embodiment of the decorative film, in the case of a multilayer film, a surface layer, a surface decorative layer, a printed layer, a light-shielding layer, a colored layer, a substrate layer, a seal layer, a barrier layer, and between these layers may be provided. Can include tie layer layers, etc. The layer containing the hindered amine light stabilizer and/or ultraviolet absorber of the present invention may be any layer constituting a multilayer film. Also, a plurality of layers may contain the weather resistant agent, or all layers may contain the weather resistant agent. Above all, since deterioration due to light progresses from the surface of the molded article, it is more preferable that the outermost surface layer of the decorative film, which is opposite to the surface of the decorative film attached to the resin molded article, contains the weather resistant agent.

In the multilayer film, the layer other than the layer containing the hindered amine light stabilizer and/or ultraviolet absorber is preferably a layer made of a thermoplastic resin, more preferably a layer made of a polypropylene resin. In the case of polypropylene-based resins, various types of propylene-based polymers such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), or their You can choose a combination of Each layer is preferably a layer containing no thermosetting resin. Recyclability is improved by using a thermoplastic resin. Furthermore, by using a polypropylene-based resin, it is possible to suppress the complication of the layer structure, and further improve the co-extrusion property and recyclability.

For example, when the decorative film is a multilayer film having a two-layer structure, two layers, a surface layer serving as the surface of the decorated molded article and a substrate layer attached to the molded article, or the surface of the decorated molded article and It can consist of two layers of a base material layer and a sealing layer to be adhered to the molded body. Furthermore, in the case of a multilayer film having a three-layer structure, from three layers: a surface layer that is the surface of the decorative molded article, a seal layer that adheres to the molded article, and a base material layer interposed between the surface layer and the seal layer can become A multilayer film having a more complicated layer structure may be used, and at least one layer constituting the multilayer film contains a hindered amine light stabilizer and/or an ultraviolet absorber.

The decorative film preferably contains a hindered amine light stabilizer and/or an ultraviolet absorber in the outermost layer opposite to the surface to be adhered to the resin molding. For example, when the decorative film consists of two layers of a surface layer and a base layer, the surface layer, when it consists of two layers of a base layer and a seal layer, the base layer, and the surface layer and the base layer and a seal layer, it is preferred that each of the surface layers contains a hindered amine light stabilizer and/or an ultraviolet absorber.

[Base material layer]
In the present invention, the base layer refers to the thickest layer in the decorative film. When the decorative film is a single-layer film, that layer becomes the substrate layer. When the resin constituting the base layer of the decorative film of the present invention is a polypropylene-based resin, the base layer contains the resin composition (X) and/or (Y) as in the case of the single-layer film. is preferred. As a result, the thermoformability is improved, and a decorative molded article with a good appearance can be obtained.

[Surface layer and surface decorative layer]
In the present invention, the surface layer and the surface decoration layer refer to a layer different from the base material layer, which constitutes the outermost layer opposite to the adhered surface to the resin molding. The surface layer and the surface decoration layer may be provided directly on the base material layer, or may be provided after interposing one or more layers on the base material layer. Here, the surface decorative layer means a surface layer to which a nucleating agent, a coloring agent and the like are added in order to improve the transparency, surface glossiness, designability and the like of the decorative film.
When the resin constituting the surface layer or the surface decorative layer of the decorative film of the present invention is a polypropylene resin, the MFR (230° C., 2.16 kg load) preferably exceeds 2.0 g/10 min, more preferably. is 5.0 g/10 minutes or more, more preferably 9.0 g/10 minutes or more. By setting the MFR of the polypropylene resin within the above range, effects such as improving the surface smoothness and gloss of the decorative film and improving the grain transferability can be obtained, and the required surface shape of the molded product ( (glossy, non-glossy, embossed, etc.) can be obtained. In addition, the transferability of the surface during production and thermoforming of the decorative film is improved, and a decorative film having higher gloss can be obtained by using a mirror surface roll during thermoforming. Although the upper limit of MFR is not particularly limited, it is preferably 100 g/10 minutes or less, more preferably 50 g/10 minutes or less. By setting the MFR within the above range, good oil resistance, solvent resistance, scratch resistance, etc. can be exhibited.

[Seal layer]
In the present invention, the sealing layer refers to a layer different from the base layer, which constitutes the outermost layer on the sticking surface side of the decorative film for improving the adhesion to the resin molding. The resin constituting the sealing layer of the decorative film of the present invention can be selected from general thermoplastic resins, for example, polyethylene resins, polypropylene resins, polyolefins such as ethylene elastomers, modified polyolefins, styrene resins, etc. Elastomers, petroleum resins, etc. can be used, and combinations thereof can also be used. Examples of modified polyolefins include resins containing polymerized units derived from a polar group-containing monomer such as maleic anhydride and polymerized units derived from an olefin monomer in an arbitrary ratio. For example, when the seal layer according to the present invention is a polypropylene-based resin, the MFR (230° C., 2.16 kg load) of the resin is preferably 0.1 g/10 min or more in terms of adhesiveness, and more It is preferably 0.4 g/10 minutes or more, more preferably 2.0 g/10 minutes or more. Although the upper limit of MFR is not particularly limited, it is preferably 100 g/10 minutes or less, more preferably 50 g/10 minutes or less. Good adhesiveness can be obtained by setting the MFR within the above range.

FIGS. 8(a) to 8(c) are explanatory diagrams schematically illustrating cross sections of embodiments of the decorative film adhered to the resin molding. In FIGS. 8(a) to 8(c), the arrangement of the seal layer (I) and the base layer (II) will be specified and explained for ease of understanding, but the layer structure of the decorative film is shown in these examples. It should not be construed as being limited. In this specification, reference numeral 1 in the drawings denotes a decorative film, reference numeral 2 denotes a base layer (II), reference numeral 3 denotes a seal layer (I), reference numeral 4 denotes a surface decoration layer (III), and reference numeral 5 denotes a resin molding. indicates FIG. 8(a) shows an example in which the decorative film 1 is made of a two-layer film, the seal layer (I) 3 is adhered to the resin molding 5, and the base layer (I) 3 is placed on the seal layer (I) 3. II) 2 is laminated. The decorative film 1 of FIG. 8(b) is composed of a seal layer (I) 3, a substrate layer (II) 2 and a surface layer, and the seal layer (I) 3 is adhered to the surface of the resin molded body 5 to form a seal. The substrate layer (II) 2 and the surface layer are laminated in this order on the layer (I) 3 . The decorative film 1 of FIG. 8(c) comprises a seal layer (I) 3, a substrate layer (II) 2 and a surface decorative layer (III) 4. , and the base layer (II) 2 and the surface decorative layer (III) 4 are laminated in this order on the seal layer (I) 3 .

Each layer may contain additives other than the hindered amine light stabilizer and/or ultraviolet absorber, fillers, colorants, other resin components, and the like. The total amount of other additives, fillers, colorants, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition. As other additives, the additives described above and the like can be used.

The resin composition constituting each layer can be obtained by melt-kneading the resin and weathering agent, other additives, filler, colorant, other resin components, etc., resin and weathering agent, other additives, filler, colorant, etc. A method of dry-blending other resin components into a melt-kneaded product, a masterbatch in which weather resistance agents, other additives, fillers, colorants, etc. are dispersed in a carrier resin at a high concentration in addition to resin and other resin components. can be produced by a method such as dry blending.

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 even more preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting designability is improved, the stability during molding is also improved, and it becomes possible to obtain a better decorated molded product. . On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, even more preferably about 0.8 mm or less. By reducing the thickness of the decorative film to such a value or less, the time required for heating during thermoforming is shortened, thereby improving productivity and facilitating trimming of unnecessary portions.

[Manufacturing of decorative film]
The decorative film of the present invention can be produced by various known molding methods.
For example, in the case of a multilayer film, a method of coextrusion molding, a thermal lamination method of applying heat and pressure to laminate another layer on one side of one of the layers that have been extruded in advance, and an adhesive. Examples include a dry lamination method and a wet lamination method for lamination, and an extrusion lamination method and a sand lamination method for melt extruding a resin onto one side of one layer that has been extruded in advance. As a device for forming the decorative film, a known co-extrusion T-die molding machine or a known lamination molding machine can be used. Among these, a co-extrusion T-die molding machine is preferably used from the viewpoint of productivity.

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

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

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

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

[Decorative molding]
As the resin molded article (to be decorated) to be decorated in the present invention, preferably a thermoplastic resin, more preferably a polyolefin resin, more preferably a polypropylene resin or various molded articles made of a polypropylene resin composition (hereinafter referred to as It may be referred to as a "substrate".) can be used. The molding method of the molded article is not particularly limited, and examples thereof include injection molding, blow molding, press molding, extrusion molding and the like.

The base resin of the polypropylene-based resin and the polypropylene-based resin composition of the resin molding to be decorated may be a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, or a propylene block copolymer. Various types based on various known propylene monomers can be selected. In addition, it may contain a filler such as talc for imparting rigidity and an elastomer or the like for imparting impact resistance, as long as the effects of the present invention are not impaired. Further, like the polypropylene-based resin composition that can constitute the above-described decorative film, it may contain additive components including a weather resistant agent and other resin components.

The decorative molded article obtained by attaching the decorative film of the present invention to various molded articles formed in a three-dimensional shape has a large reduction in VOC contained in coatings and adhesives. (railroads, etc.), building materials, daily necessities, and the like.

[Manufacturing of decorative molding]
The method for manufacturing the decorated molded article of the present invention comprises the steps of preparing the above-described decorative film, preparing the resin molded article, and setting the resin molded article and the decorative film in a chamber box capable of reducing pressure. reducing the pressure in the chamber box; heating and softening the decorative film; pressing the decorative film against the resin molding; A step is included.

According to the method for producing a decorated molded article of the present invention, it is possible to obtain a beautiful decorated molded article with good texture reproducibility such as embossing without entrainment of air between the decorative film and the resin molded article. can.

In three-dimensional decorative thermoforming, a resin molded body and a decorative film are set in a chamber box that can be evacuated, the film is heated and softened while the pressure inside the chamber box is reduced, and the film is pressed against the resin molded body. It has a basic process of attaching the decorative film to the surface of the resin molding by returning the inside of the chamber box to the atmospheric pressure or pressurizing it, and the film is attached under reduced pressure. As a result, it is possible to obtain a clean decorative molded article free from air pockets. In the manufacturing method of the present invention, any known technique can be used as long as the device and conditions are suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the resin molding, the decorative film, the mechanism for pressing them, the device for heating the decorative film, etc., or the decorative film may A plurality of divided objects may be used.

Further, the mechanism for pressing the resin molded body and the decorative film against each other may be of any type, such as a mechanism for moving the resin molded body, a mechanism for moving the decorative film, or a mechanism for moving both.
More specifically, representative molding methods are exemplified below.

A method of adhering a decorative film to a resin molding using a three-dimensional decorative thermoforming machine will be exemplified below with reference to the drawings.

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

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

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

As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 opened, the resin molding 5 is placed on the table 14 in the lower chamber box 12, and the table 14 is lowered. Subsequently, the decorative film 1 is set on the film fixing jig 13 between the upper and lower chamber boxes 11 and 12 so that the adhering surface faces the resin molding 5 .

As shown in FIG. 4, after lowering the upper chamber box 11 and joining the upper and lower chamber boxes 11 and 12 to close the inside of the box, the inside of each of the chamber boxes 11 and 12 is brought into a vacuum suction state, and the heater 15 is heated. The decorative film 1 is heated by.

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

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

[Molding condition]
The pressure in the chamber boxes 11 and 12 may be reduced as long as air pockets are not generated, and the pressure in the chamber boxes is 10 kPa or less, preferably 3 kPa or less, and more preferably 1 kPa or less.

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

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

In the present invention, in order to adhere the decorative film 1 to the resin molded body 5, the surface of the resin molded body 5 and the decorative film 1 must be sufficiently softened or melted.

Therefore, the heater temperature must be higher than the melting temperature of the resin forming the resin molding 5 and the resin forming the decorative film 1 . In the case of a polypropylene-based decorative film, the heater temperature is preferably 160° C. or higher, more preferably 180° C. or higher, and most preferably 200° C. or higher.

The higher the heater temperature, the shorter the time required for heating. If the temperature of the heater becomes too high, not only the moldability deteriorates but also the resin thermally deteriorates. It is below.

Appropriate heating time varies depending on the heater temperature, but it is necessary that the decorative film is sufficiently softened or melted. In the case of a polypropylene-based decorative film, it is preferable that the decorative film is heated at least until it begins to stretch back, which is called springback. That is, the polypropylene-based decorative film heated by the heater expands thermally when heated from a solid state, and once sagged as the crystals melt, and when the crystals melt progresses throughout, the molecules relax and temporarily stretch back. After springback was observed, the film exhibited a behavior of sagging due to its own weight. After the springback, the crystals of the film were completely melted and the molecules were sufficiently relaxed, resulting in good thermoformability. Moreover, sufficient adhesive strength can be obtained.

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

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

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

1. Measurement method of various physical properties (i) Fogging test The haze value (HAZE) of the glass plate covering the mouth of the sample bottle after the following fogging test was performed by a method based on ISO6452 was measured using a haze meter (NDH5000 type, Nippon Denshi Kogyo Co., Ltd.). Co., Ltd.), and the amount of change in haze value before and after the fogging test was calculated from the following formula.
Amount of change in haze value after fogging test = haze value of glass plate after fogging test - haze value of glass plate before fogging test The haze value of the glass plate before the fogging test was 0.23. .
<Fogging test>
1 g (±0.01 g) of a hindered amine light stabilizer or ultraviolet absorber is placed in a glass sample bottle (inner diameter 83 mm, height 190 mm), and the sample bottle is covered with a glass plate (thickness 3.0 mm). The glass plate was heated at 150° C. for 1 hour to generate fogging. A windscreen fogging tester WF-2 (manufactured by Suga Test Instruments Co., Ltd.) was used as a fogging tester. Glass sample bottles and glass plates provided by Suga Test Instruments Co., Ltd. were used.

(ii) melt flow rate (MFR)
Measured according to ISO 1133:1997 Conditions M at 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

(iii) strain hardening degree λ
The method for obtaining the strain hardening degree λ was performed by the method described above. At this time, η* (0.01) used as the shear viscosity value and ηe (3.5) used as the elongational viscosity value were measured by the following methods. In addition, the sample used for the measurement at this time was formed into a flat plate with a thickness of 0.7 mm and 2 mm by pressing for 1 hour at a temperature of 180 ° C. and a pressure of 10 MPa. was used for extensional viscosity measurements and 2 mm samples for dynamic frequency sweep experiments.

(iii-1) shear viscosity η* (0.01)
Dynamic frequency sweep experiments were performed using a Rheometric Scientific ARES. Parallel discs with a diameter of 25 mm were used for the measurement geometry. The measurement was performed in the measurement mode Dynamic Frequency Sweep Test using the device control software TA Orchestrator. The sample used was a 2 mm-thick press-formed body produced by the above method. The measurement temperature was 180°C. The angular frequency ω was measured at 5 points per digit at equal intervals on a logarithmic scale between 0.01 and 100 rad/s.
The complex viscosity η*(0.01) [unit: Pa·s] at ω=0.01 rad/s is used as an index indicating the viscosity of the sample at a low shear rate. The complex viscosity η* is calculated by η*=G*/ω from the complex elastic modulus G* [unit: Pa] and ω.

(iii-2) elongational viscosity ηe (3.5)
The extensional viscosity was measured using an ARES measuring jig manufactured by Rheometric Scientific and an Extensional Viscosity Fixture manufactured by TA Instruments. The measurement was performed in the measurement mode Extensional Viscosity Test using the instrument control software TA Orchestrator. A test piece having a thickness of 0.7 mm molded by the above method was used as a sample. The test piece had a width of 10 mm and a length of 18 mm. The strain rate is 1.0 s-1 and the measurement temperature is 180°C. Other measurement parameters were set as follows.
Sampling Mode: log
Points Per Zone: 200
Solid Density: 0.9
Melt Density: 0.8
Prestretch Rate: 0.05s ^-1
Relaxation after Prestretch: 30sec
Under these conditions, data is collected for at least 3.7 seconds from the start of measurement. The software provides time dependent data of extensional viscosity. The elongational viscosity value of the obtained elongational viscosity curve at a time of 3.5 sec (that is, the amount of strain of 3.5) was defined as ηe (3.5) [unit: Pa·s].

(iv) Determination of the branching index g' at an absolute molecular weight Mabs of 1 million:
According to the method described above, measurement was performed using GPC equipped with a light scatterometer and a viscometer as detectors, and the branching index g' was obtained based on the analysis method described above.

(v) Detection of long-chain branched structures using ¹³ C-NMR:
According to the method described above, measurement using ¹³ C-NMR was performed to determine the presence or absence of long-chain branched structures.

2. Materials used (1) Hindered amine light stabilizer and UV absorber (A-1): Hindered amine light stabilizer (change in haze value after fogging test = 3.78, molecular weight = about 3000), manufactured by BASF Corporation , trade name "Chimassorb 944"
(A-2): Hindered amine light stabilizer (change in haze value after fogging test = 5.13, molecular weight = about 791), manufactured by ADEKA Co., Ltd., trade name "LA-57"
(A-3): Hindered amine light stabilizer (haze value change after fogging test = 3.98, molecular weight = about 1900), manufactured by ADEKA Co., Ltd., trade name "LA-68"
(A-4): Hindered amine light stabilizer (change in haze value after fogging test = 49.59, molecular weight = 480), manufactured by BASF Corporation, trade name "Tinuvin770"
(A-5): UV absorber (change in haze value after fogging test = 22.12, molecular weight = 659), manufactured by ADEKA Co., Ltd., trade name "ADEKA STAB LA-31G"

(2) Polypropylene resin The following polypropylene resin was used.
(B-1): Propylene homopolymer having no long chain branch (MFR = 0.4 g/10 min, strain hardening degree λ = 1.0), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark)" ) EA9”, branching index g′=1.0 at an absolute molecular weight Mabs of 1,000,000, and no long-chain branched structure was confirmed by ¹³ C-NMR measurement.
(B-1-1): A polypropylene resin composition (MFR = 0.4 g /10 minutes)
(B-1-2): A polypropylene resin composition (MFR = 0.4 g /10 minutes)
(B-1-3): polypropylene resin composition (MFR = 0.4 g /10 minutes)
(B-1-4): A polypropylene resin composition (MFR = 0.4 g /10 minutes)
(B-1-5): 100 parts by weight of polypropylene resin (B-1), 0.1 part by weight of hindered amine light stabilizer (A-1), and 0.1 part by weight of ultraviolet absorber (A-5). 2 parts by weight blended polypropylene resin composition (MFR = 0.4 g/10 minutes)
(B-2): A propylene homopolymer having long chain branches produced by a macromer copolymerization method, manufactured by Japan Polypropylene Corporation, trade name "WAYMAX (registered trademark) MFX8", MFR = 1.0 g/10 min. , strain hardening degree λ=9.7, branching index g′=0.89 at an absolute molecular weight ^Mabs of 1,000,000.
(B-2-1) A polypropylene resin composition (MFR = 1.0 g/ 10 minutes)
(B-3): Propylene homopolymer having no long chain branch (MFR = 10 g/10 min, strain hardening degree λ = 1.0), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FA3KM" ”, branching index g′=1.0 at an absolute molecular weight Mabs of 1,000,000, and no long-chain branched structure was confirmed by ¹³ C-NMR measurement.
(B-3-1) A polypropylene resin composition (MFR = 10 g/10 min )
(B-4): Propylene-α-olefin copolymer having no long chain branch (MFR = 7.0 g/10 min, strain hardening degree λ = 1.0), manufactured by Japan Polypropylene Corporation, trade name “ Wintech (registered trademark) WFX4M”, branching index g′=1.0 at absolute molecular weight Mabs of 1,000,000, and no long-chain branched structure was confirmed by ¹³ C-NMR measurement.

(3) Other thermoplastic resins The following thermoplastic resins were used.
(C-1): Maleic anhydride-modified polyolefin (MFR = 7.0 g/10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F534A"

3. Manufacture of resin molding (substrate) Propylene homopolymer (D-1) (MFR = 40 g/10 min, Tm = 165°C, manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) MA04H") was used. , an injection molded article was obtained by the following method.
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 200°C
Mold temperature: 40°C
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate Condition adjustment: Maintained 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 base layer extruder-1 with a diameter of 40 mm (diameter) and a seal layer extruder-2 with a diameter of 30 mm (diameter) are connected. A 2-kind 2-layer T-die was used. The polypropylene resin (B-1-1) was introduced into the extruder-1 for the base material layer, and the polypropylene resin (B-1) was introduced into the extruder-2 for the seal layer. Melt extrusion was carried out under the conditions of a discharge rate of 12 kg/h from the extruder-1 for the sealing layer and a discharge rate of 4 kg/h from the extruder-2 for the seal layer. The melt-extruded film is cooled and solidified while being pressed with an air knife so that the seal layer is in contact with the first roll rotating at 30° C. and 3 m/min. A laminated two-layer unstretched film was obtained.

-Three-dimensional decoration thermoforming As a three-dimensional decoration thermoforming device, "NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 is cut into a width of 250 mm and a length of 350 mm so that the seal layer faces the substrate and the longitudinal direction is in the MD direction of the film, and the size of the opening is 210 mm. It was set on a film fixing jig 13 of ×300 mm. The resin molded body (substrate) 5 was placed on a sample installation table with a height of 20 mm, which was installed on a table 14 located below the film fixing jig 13, and placed on a sample installation table manufactured by Nichiban Co., Ltd. “Nice Tac NW-K15. ” pasted through. The film fixing jig 13 and the table 14 were installed in the chamber boxes 11 and 12, and the chamber boxes were closed to make the insides of the chamber boxes 11 and 12 airtight. The chamber box is vertically divided through the decorative film 1. - 特許庁The upper and lower chamber boxes 11 and 12 were evacuated and the pressure was reduced from the atmospheric pressure (101.3 kPa) to 1.0 kPa. Decorative film 1 was heated. Vacuum suction was continued even during heating, and finally the pressure was reduced to 0.1 kPa. After the decorative film 1 is heated and temporarily loosened and then stretched back after the springback phenomenon is completed, it is further heated for 30 seconds, and the table 14 installed in the lower chamber box 12 is moved upward to perform resin molding. The body (substrate) 5 was pressed against the decorative film 1, and immediately after that, compressed air was supplied so that the pressure in the upper chamber box 11 was 270 kPa, and the resin molding (substrate) 5 and the decorative film 1 were brought into close contact with each other. Thus, a three-dimensional decorated thermoformed product 6 was obtained in which the decorative film 1 was adhered to the top and side surfaces of the resin molded body (substrate) 5 .

Example 2
Three-dimensionally decorated thermoformed product in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-1-2). got

Example 3
Three-dimensionally decorated thermoformed product in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-1-3). got

Example 4
Three-dimensionally decorated thermoformed product in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-1-5). got

Example 5
Three-dimensionally decorated thermoformed product in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-2-1). got

Example 6
In the production of the decorative film, a surface layer extruder-3 with a diameter of 30 mmφ, a base layer extruder-1 with a diameter of 40 mmφ, and a seal layer extruder-2 with a diameter of 30 mmφ are connected, and the lip opening degree is 0. A three-kind, three-layer T die with a die width of 400 mm and a die width of 400 mm was used. Polypropylene resin (B-3-1) for surface layer extruder -3, polypropylene resin (B-1-1) for base layer extruder -1, and polypropylene for seal layer extruder -2 The system resin (B-1) is charged respectively, the resin temperature is 240 ° C., the discharge rate of the surface layer extruder -3 is 4 kg / h, the discharge rate of the base layer extruder -1 is 8 kg / h, the seal layer Melt extrusion was carried out under the conditions of extruder-2 for a discharge rate of 4 kg/h.
The melt-extruded film is cooled and solidified while being pressed with an air knife so that the seal layer is in contact with the first roll rotating at 30° C. and 3 m/min, to form a surface layer with a thickness of 50 μm and a base layer with a thickness of 100 μm. , to obtain a three-layer unstretched film laminated with a seal layer having a thickness of 50 μm.

A three-dimensional decorated thermoformed product was obtained in the same manner as in Example 1, except that the unstretched film obtained in the production of the above decorated film was used.

Example 7
A three-dimensionally decorated thermoformed product was obtained in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the sealing layer was changed to polypropylene-based resin (B-4). .

Example 8
A three-dimensionally decorated thermoformed article was produced in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene resin used in the seal layer was changed to maleic anhydride-modified polyolefin (C-1). Obtained.

Comparative example 1
A three-dimensionally decorated thermoformed product was obtained in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-1). rice field.

Comparative example 2
Three-dimensionally decorated thermoformed product in the same manner as in Example 1, except that in the production of the decorative film of Example 1, the polypropylene-based resin used in the base material layer was changed to polypropylene-based resin (B-1-4). got

[Weather resistance evaluation]
For the three-dimensionally decorated thermoformed articles obtained in Examples 1 to 8 and Comparative Examples 1 and 2, the flat plate samples after three-dimensionally decorated thermoforming were held at 23° C. and 50% RH for 48 hours, and then the flat plate A test piece of 30 mm in length and 70 mm in width was cut out from the test piece, and was exposed to 504 MJ of xenon arc lamp light under the conditions of a black panel temperature of 89°C, humidity of 50%, and irradiance of 100 W/ ^m2 using an Atlas tester Ci65AW manufactured by Toyo Seiki Seisakusho Co., Ltd. The decorative film side of the decorative molding was irradiated. The decorative film before three-dimensional decorative molding was also irradiated with light under the same conditions. The surface of the test piece was observed with a microscope at 20 times magnification every 24 hours, and the time until fine cracks were generated on the surface was defined as "weather resistance time". The rate of decrease in weather resistance was evaluated according to the following criteria.
Good: The rate of decrease in the weather resistance time of the flat plate sample after the three-dimensional decoration thermoforming is less than 20% relative to the weather resistance time of the decorative film before the three-dimensional decoration molding.
x: The reduction rate of the weather resistance time of the flat plate sample after the three-dimensional decoration thermoforming is 20% or more with respect to the weather resistance time of the decorative film before the three-dimensional decoration molding.

Table 1 shows the layer structure and weather resistance evaluation results of the decorative films of Examples 1 to 8 and Comparative Examples 1 and 2.

The decorative molded articles obtained from the decorative films of Examples 1 to 8 were obtained by subjecting the hindered amine light stabilizer and/or UV absorber used to a fogging test according to ISO 6452 to the glass plate. Since the amount of change in the haze value measured by a method conforming to JIS-K7136 is 40 or less, the hindered amine light stabilizer and/or the ultraviolet absorber do not volatilize from the decorative film during decorative molding. The decorative molding maintained weather resistance.

On the other hand, the decorative film of Comparative Example 1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, was inferior in weather resistance of the decorative film and the decorative molding. For the hindered amine light stabilizer used, the amount of change in the haze value of the glass plate measured by the method conforming to JIS-K7136 after performing the fogging test according to the method conforming to ISO6452 is more than 40. In the decorative film, the hindered amine light stabilizer was volatilized during the decorative molding, and the obtained decorative molding had a marked decrease in weather resistance.

The decorative film of the present invention and the method for producing a decorated molded article using the same can be used for a three-dimensional decorated molded article and its production.

1 Decorative film 2 Base layer (II)
3 sealing layer (I)
4 Surface decoration layer (III)
5 Resin molding (decorative object, substrate)
6 decorative molding 11 upper chamber box 12 lower chamber box 13 jig 14 table 15 heater

Claims (6)

A decorative film containing a hindered amine light stabilizer for adhering to a three-dimensional shaped resin molding by thermoforming, wherein the decorative film comprises at least one layer containing the hindered amine light stabilizer. The layer contains 50% by weight or more of polyolefin resin,
The hindered amine light stabilizer satisfies the following requirements and poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4diyl ] [(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]} , or the above compound 3,9 - bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4, A decorative film containing 8,10-tetraoxaspiro[5,5]undecane.
Requirement: The amount of change in the haze value of the glass plate measured by the method based on JIS-K7136 after the following fogging test is performed by the method based on ISO6452 is 40 or less.
<Fogging test> 1 g (±0.01 g) of a hindered amine light stabilizer was placed in a glass sample bottle, and the sample bottle was covered with a glass plate and heated at 150° C. for 1 hour. produce fogging. 2. The decorative film according to claim 1, wherein the hindered amine light stabilizer has a molecular weight of 490 g/mol or more. The decorative film according to claim 1 or 2, wherein the polyolefin resin is a polypropylene resin. 4. The decorative film according to any one of claims 1 to 3, wherein the outermost layer of the decorative film opposite to the surface to be adhered to the resin molding contains the hindered amine light stabilizer. A step of preparing the decorative film according to any one of claims 1 to 4, a step of preparing a resin molded body, and a step of setting the resin molded body and the decorative film in a decompressible chamber box. , the step of reducing the pressure in the chamber box, the step of heating and softening the decorative film, the step of pressing the decorative film against the resin molding, and the step of returning or pressurizing the pressure-reduced chamber box to atmospheric pressure. A method for manufacturing a decorative molded body. 6. The method for producing a decorative molded article according to claim 5, wherein the resin molded article is made of a polypropylene-based resin composition.

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