JP2013039724A - Vehicle paint alternative film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vehicle paint alternative film which is capable of providing a predetermined car body color, exhibits excellent shape following property to a three-dimensional shape and is produced at a low cost.SOLUTION: The vehicle paint alternative film includes a transparent material layer and a colored adhesive layer. The colored adhesive layer contains (i) a colorant premix including (a) acrylic polyol and (b) colorants which are dispersed in the acrylic polyol and selected from a group comprising a combination of an organic pigment with an inorganic pigment, that of the organic pigment with an aluminum bright material, that of the organic pigment with a mica bright material, that of the inorganic pigment with the aluminum bright material, that of the inorganic pigment with the mica bright material, that of the aluminum bright material with the mica bright material, and any combination of these combinations and (ii) an adhesive polymer. The solid content mass ratio shown by (the adhesive polymer)/((the adhesive polymer)+(the acrylic polyol)) is ≥25%.

Description

  The present disclosure relates to a vehicle painting substitute film (vehicle color film) and a method for manufacturing the same. More specifically, the present disclosure relates to a vehicle painting substitute film that can provide a predetermined vehicle body color and is excellent in shape followability with respect to a three-dimensional shape, and a manufacturing method thereof.

  The vehicle body color of a vehicle such as an automobile is created by blending two or more organic pigments, inorganic pigments, aluminum glitter materials, and mica glitter materials according to design requirements. In general, organic pigments and inorganic pigments provide a chromatic color or become a white or black base, an aluminum glitter material giving a metallic color, and a mica glitter material giving a pearl color. For example, even when the vehicle body color is black, in order to express a subtle difference in color tone, a small amount of organic pigment, aluminum glitter material, and / or mica glitter material is added to an inorganic pigment such as carbon black. It is common to add.

  A vehicle paint substitute film (sometimes called a car body color film) is a colored film that can be used in place of a conventional paint for car paint applied by a spray method, and is desired to have high formability. ing. For example, it is desirable that the vehicle coating substitute film can be bonded to a deeply drawn three-dimensional shaped part and panel by vacuum forming or vacuum / pressure forming. Alternatively, it is desirable that it can be used for in-mold molding that is preformed by vacuum molding, heating press, etc., and then set in a cavity of an injection mold and injected to inject the resin. In either method, the film is stretched at a high temperature such as 120 ° C. Depending on the shape of the adherend, it is necessary to stretch 50% or more, usually 100% (stretched 2 times) or more, and 200% (stretched 3 times) or more for deep-drawn shapes. It is said.

  Conventional vehicle paint replacement that is used by manual crimping or thermo-rolling with a roller at room temperature, such as roof molding to hide the welded part of the car body, belt molding of the door frame or directly to the vehicle outer plate The film has a three-layer laminated structure composed of a transparent material layer (top layer), a colored layer (color layer), and an adhesive layer. The colored layer is formed using a two-component polyurethane coating composition used as a resin bumper coating. The transparent material layer is formed by coating a transparent material such as a reactive polyurethane composition on the colored layer.

  Customers such as automobile manufacturers continue to demand further reduction of the product cost of alternative film for vehicle coating, and the target cost of alternative film for vehicle coating is low enough to compete with general spray coating. In addition, a colored layer formed using a two-component polyurethane coating composition contained in a conventional vehicle paint substitute film is relatively tough and extends only about 30% particularly at high temperatures. Therefore, the vehicle paint substitute film having such a three-layer laminated structure does not have characteristics such as elongation and bending sufficient to be applied to a complicated three-dimensional shape.

  Japanese Patent No. 3500240 (Patent Document 1) states that “in a colored film in which at least one colored adhesive layer is provided on one surface of a transparent film, the adhesive layer is composed of a pigment and a dispersant. The dispersant is colored by a colorant, and the dispersant has, as a monomer component, an aromatic vinyl monomer, a primary to tertiary amino group-containing (meth) acrylic acid ester monomer, and an ammonium group quaternized with an aromatic compound (meta )) A colored film comprising a (meth) acrylic acid ester polymer having an acrylic acid ester monomer as an essential component.

  Japanese Patent Laid-Open No. 2004-051753 (Patent Document 2) states that “a white toner is prepared by uniformly dispersing a white pigment and a polyester plasticizer having a glass transition temperature of −10 ° C. or less, and this white toner is adhered to the polyester. 3 to 150 parts by weight of white pigment with respect to 100 parts by weight of the pressure-sensitive adhesive is contained on one side of the colored film having a total light transmittance of 3 to 80% by the white pressure-sensitive adhesive composition obtained by mixing the adhesive. A method for producing a decorative pressure-sensitive adhesive sheet characterized by forming a white pressure-sensitive adhesive layer ”and“ white toner ”used in the method are described.

  Japanese Patent Application Laid-Open No. 2008-308646 (Patent Document 3) states that “acrylic containing a carboxyl group-containing (meth) acrylic polymer, a pigment or dye, and an amino group-containing (meth) acrylic polymer that does not contain an aromatic vinyl monomer. System coloring adhesive ".

  None of these conventional technologies provide a vehicle paint substitute film having a vehicle body color composed of a blend of two or more of organic pigments, inorganic pigments, aluminum glitter materials and mica glitter materials. Nor is an adhesive other than a pressure adhesive used.

Japanese Patent No. 3500240 JP 2004-051753 A JP 2008-308646 A

  The present disclosure provides a low-cost vehicle coating substitute film that can provide a predetermined vehicle body color and is excellent in shape followability with respect to a three-dimensional shape.

  According to the present disclosure, there is provided a vehicle coating substitute film including a transparent material layer and a colored adhesive layer, wherein the colored adhesive layer is dispersed in (i) (a) an acrylic polyol and (b) the acrylic polyol. A combination of an organic pigment and an inorganic pigment, a combination of an organic pigment and an aluminum glitter material, a combination of an organic pigment and a mica glitter material, a combination of an inorganic pigment and an aluminum glitter material, and an inorganic pigment and a mica glitter material. A colorant premix comprising a combination and a combination of an aluminum glitter material and a mica glitter material, and a colorant selected from the group consisting of these combinations; and (ii) an adhesive polymer, A vehicle paint substitute film having a solid mass ratio represented by (adhesive polymer + acrylic polyol) of about 25% or more is provided.

  In addition, according to the present disclosure, (a) acrylic polyol, (b) combination of organic pigment and inorganic pigment, combination of organic pigment and aluminum glitter material, combination of organic pigment and mica glitter material, inorganic pigment and aluminum glitter A colorant premix is prepared by dispersing a colorant selected from the group consisting of a combination of materials, a combination of an inorganic pigment and a mica glitter material, a combination of an aluminum glitter material and a mica glitter material, and a combination thereof. Forming a colored adhesive layer using the colored adhesive composition obtained by mixing the colorant premix and the adhesive polymer, laminating a transparent material on the formed colored adhesive layer, or There is provided a method for producing a vehicle paint substitute film comprising forming a transparent material layer by coating.

  The vehicle paint substitute film of the present disclosure can accurately and easily provide various types of predetermined vehicle body colors by using a colored adhesive layer including a colorant premix and an adhesive polymer that have been color-matched in advance. In addition, the number of layers composing the vehicle painting substitute film can also be reduced compared to conventional vehicle painting substitute films such as roof molding tape, excellent tensile elongation, high shape followability to three-dimensional shapes, and low cost vehicles. A paint replacement film can be provided.

  A colored adhesive composition for forming a colored adhesive layer can be obtained by selecting various types of adhesive polymers according to the adherend and mixing the adhesive polymer with a colorant premix. In the manufacturing process, it is easy to change the product according to the adherend. Moreover, since the colored layer has adhesiveness, the transparent material layer can be formed by either lamination or coating, and the degree of freedom in the manufacturing process can be increased. These manufacturing advantages also contribute to the cost reduction of the vehicle paint substitute film of the present disclosure.

  The above description should not be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.

The cross section of the vehicle painting substitute film of one embodiment of this indication is shown typically. 3 schematically illustrates a cross section of a vehicle paint substitute film of another embodiment of the present disclosure. 3 schematically illustrates a cross section of a vehicle paint substitute film of another embodiment of the present disclosure.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  “Vehicle” means a moving body such as a truck, a bus, a motor vehicle such as a passenger car, a motorcycle such as a motorcycle or a scooter, a boat such as a bicycle, a train, a pleasure boat, a yacht or a motor boat. The vehicle paint substitute film of the present disclosure is applied to the main body (including a roof, a door, a bonnet, etc.) or a part thereof, or a component of the mobile body (for example, a bumper, a roof molding, a side guard molding, a pillar, etc.). Can be applied.

  “(Meth) acryl” means “acryl” or “methacryl”, and “(meth) acrylate” means “acrylate” or “methacrylate”.

  FIG. 1 schematically shows a cross section of a vehicle paint substitute film according to an embodiment of the present disclosure. The vehicle coating substitute film 10 includes a transparent material layer 20 and a colored adhesive layer 30, and the colored adhesive layer 30 includes (i) (a) an acrylic polyol and (b) a colorant dispersed in the acrylic polyol. A colorant premix and (ii) an adhesive polymer. Here, the solid content mass ratio represented by adhesive polymer / (adhesive polymer + acryl polyol) is about 25% or more. The vehicle painting substitute film 10 can be applied to an adherend (not shown) such as an automobile roof, a door, or a bumper through the colored adhesive layer 30. The transparent material layer 20 can protect the adherend and the colored adhesive layer 30 from external impacts, dust, rain, ultraviolet rays, and the like.

  The transparent material layer can be formed from various transparent materials. In the present disclosure, “transparent” means that the transmittance of light having a wavelength in the visible light region is about 50% or more, and the transmittance is about 70% or more, or about 90% or more. It is advantageous. The transparent material layer is coated with a transparent material such as a reactive polyurethane composition on the colored adhesive layer by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, etc., and heated as necessary. It can be formed by curing. Since the reactive polyurethane composition is excellent in weather resistance and scratch resistance, it can be advantageously used to form a transparent material layer of the vehicle paint substitute film of the present disclosure.

  The reactive polyurethane composition generally comprises a polyol and a crosslinker. Examples of the polyol include polyester polyols such as acrylic polyol and polycaprolactone diol, polyether polyols such as polycarbonate polyol, polyethylene glycol, and polypropylene glycol. As the crosslinking agent, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene bis (4-phenylisocyanate), polyisocyanates such as burette, isocyanurate or adduct, polycarbodiimide and the like can be used. The reactive polyurethane composition may be aqueous or non-aqueous.

  When the transparent material layer is formed by coating, its thickness is generally about 5 μm or more, about 10 μm or more, or about 25 μm or more, about 500 μm or less, about 200 μm or less, or about 100 μm or less. When high shape followability is required, it is advantageous that the transparent material layer is thin. For example, it is preferably about 200 μm or less, or about 100 μm or less. On the other hand, in order to improve the light resistance and / or weather resistance of the vehicle coating substitute film, it is advantageous that the transparent material layer is thicker, for example, about 10 μm or more, or about 25 μm or more.

  According to the present disclosure, since the colored adhesive layer has adhesiveness, a vehicle paint substitute film can be produced by laminating a transparent material layer formed in advance as a film on the colored adhesive layer. Normally, about 5 to 10 car body colors are set for each car model, and these substitute paint films of those colors are required in various amounts while the car model is manufactured, and the usage ratios between colors are constantly changing. However, according to this embodiment, the transparent material layer film, which is a common material, is manufactured in a large lot in advance, and only the amount necessary for the manufacturing process of the colored adhesive layer of each color is obtained. Since lamination may be performed, the manufacturing process can be further simplified and cost reduction can be achieved. Moreover, by using a film having high flatness as the transparent material layer, a vehicle paint substitute film having higher surface flatness can be obtained. Further, the vehicle paint substitute film obtained by laminating the transparent material layer on the colored adhesive layer has a higher elongation at break and / or better than the vehicle paint substitute film having a transparent material layer formed by coating. The appearance after stretching may be shown.

  The film used for the transparent material layer is not limited to the following, but includes acrylic resin including polymethyl methacrylate (PMMA), ethylene / tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), methyl methacrylate / Fluororesin such as vinylidene fluoride copolymer (PMMA / PVDF), Polycarbonate such as polycarbonate (PC), Vinyl chloride (PVC), Polyethylene, Polypropylene, Polyester such as polyethylene terephthalate, Polyethylene naphthalate, Polyurethane, Ethylene / acrylic acid Examples thereof include a film prepared from a copolymer, an ethylene / ethyl acrylate copolymer, a copolymer such as an ethylene / vinyl acetate copolymer, and the like. Acrylic resin, fluororesin, PVC, and polyurethane, which are excellent in weather resistance for use as an automobile exterior, are preferable, and acrylic and polyurethane are particularly preferable in consideration of environmental load when incinerated or landfilled as waste. These films can be used in various thicknesses, but are generally about 5 μm or more, about 10 μm or more, or about 25 μm or more, about 500 μm or less, about 200 μm or less, or about 100 μm or less. When high shape followability is required, it is advantageous that the transparent material layer is thin. For example, it is preferably about 200 μm or less, or about 100 μm or less. On the other hand, in order to improve the light resistance and / or weather resistance of the vehicle coating substitute film, it is advantageous that the transparent material layer is thicker, for example, about 10 μm or more, or about 25 μm or more.

  The transparent material layer may contain an ultraviolet absorber such as benzotriazole, a hindered amine light stabilizer (HALS) such as Tinuvin (registered trademark) 292, and the like as necessary. By using ultraviolet absorbers, hindered amine light stabilizers, etc., the colorant contained in the colored adhesive layer under the transparent material layer, particularly the organic pigments having a relatively high sensitivity to light such as ultraviolet rays, Fading, deterioration and the like can be effectively prevented, and as a result, the light resistance and / or weather resistance of the vehicle coating substitute film can be further enhanced. You may form a hard-coat layer in the surface of the transparent material layer used as an outer side when it is set as a vehicle coating substitute film.

  The colored adhesive layer can be formed using a colored adhesive composition obtained by mixing (i) a colorant premix and (ii) an adhesive polymer. The colorant premix includes (a) an acrylic polyol and (b) a colorant, and the colorant is dispersed in the acrylic polyol.

  As an acrylic polyol contained in the colorant premix, for example, an acrylic copolymer containing a hydroxyl group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or hydroxybutyl (meth) acrylate is used. can do. As a monomer that can be copolymerized with a hydroxyl group-containing (meth) acrylate, a monomer having an ethylenically unsaturated group can be used. For example, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, Alkyl (meth) acrylates such as isobornyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, styrene sulfonic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N, N- Methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acrylonitrile, styrene and the like. The acrylic polyol uses a azo-based initiator such as 2,2-azobisisobutyronitrile as a polymerization initiator, or a peroxide-based initiator such as benzoyl peroxide. It can be obtained by polymerizing a monomer having a polymerizable unsaturated group. During the polymerization, a chain transfer agent having a hydroxyl group such as 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, and p-mercaptophenol may be used.

  The hydroxyl value of the acrylic polyol is generally about 10 mg / g or more, about 20 mg / g or more, or about 40 mg / g or more, about 1000 mg / g or less, about 500 mg / g or less, or about 200 mg / g or less. The acid value of the acrylic polyol is generally about 0.1 mg / g or more, about 0.5 mg / g or more, or 2 mg / g or more. By setting the hydroxyl value and / or acid value of the acrylic polyol to the above values, the colorant can be well dispersed in the acrylic polyol, and the miscibility with the adhesive polymer described later can be improved. The average molecular weight of the acrylic polyol is generally about 2,000 or more, about 5,000 or more, or about 10,000 or more, and is about 300,000 or less, about 200,000 or less, or about 100,000 or less. By setting the average molecular weight of the acrylic polyol to the above value, the colorant can be favorably dispersed in the acrylic polyol, and the miscibility with the adhesive polymer described later can be improved.

  The colorant in the vehicle paint substitute film of the present disclosure is a blend of two or more of an organic pigment, an inorganic pigment, an aluminum glitter material, and a mica glitter material in order to provide a predetermined vehicle body color to a vehicle such as an automobile. In other words, the colorant is a combination of an organic pigment and an inorganic pigment, a combination of an organic pigment and an aluminum glitter material, a combination of an organic pigment and an mica glitter material, a combination of an inorganic pigment and an aluminum glitter material, and a combination of an inorganic pigment and an mica glitter material. And a combination of an aluminum glitter material and a mica glitter material, and a group consisting of these combinations. The vehicle coating substitute film of the present disclosure exhibits various types of color tone by using the colorant, and can meet high design requirements.

  As the organic pigment, known organic pigments that have been conventionally blended in paints can be used. Examples of organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo lake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, and quinacridone pigments such as quinacridone red. Can be mentioned.

  As the inorganic pigment, known inorganic pigments that have been conventionally blended in paints can be used. Examples of the inorganic pigment include inorganic pigments such as titanium dioxide, yellow lead, yellow iron oxide, bengara, red iron oxide, and carbon black.

  As the aluminum glitter material, a known aluminum glitter material that has been conventionally blended in paints can be used. Examples of the aluminum glitter material include aluminum flakes, vapor-deposited aluminum flakes, metal oxide-coated aluminum flakes, and colored aluminum flakes.

  As the mica glitter material, a known mica glitter material conventionally blended in a paint can be used. Examples of the mica glitter material include flake-like mica covered with a metal oxide such as titanium dioxide and iron oxide, and synthetic mica.

  Colorant premixes include, for example, UV absorbers such as benzotriazole, antioxidants such as phenolic antioxidants, leveling agents such as silicone, viscosity control agents such as wax and organic bentonite, cellulose acetate butyrate, and the like. Thickeners such as rate, sedimentary barium sulfate, clay, silica, talc, kaolin, bentonite and other extender pigments, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol, propylene glycol, ethylene glycol An organic solvent such as dimethyl ether or propylene glycol monomethyl ether acetate may further be included.

  The colorant content of the colorant premix is considerably higher than the colorant content of the coating composition used to form the colored layer of a conventional three-layer laminated vehicle paint replacement film. The present inventors have found that even with such a high colorant content, the colorant is dispersed in the acrylic polyol, contrary to the expectations of those skilled in the art. The amount of (b) colorant in the colorant premix is about 20% by weight or more, or about 30% by weight or more, based on the total weight of (a) acrylic polyol and (b) colorant, It can be less than or equal to about 70% by weight. The entire amount of the acrylic polyol may be used for dispersing the colorant, or a part of the acrylic polyol may be used for dispersing the colorant and then the remainder may be added. Necessary to obtain sufficient adhesive strength for the adhesive polymer to be described later in the colored adhesive layer while providing a predetermined body color by setting the amount of the colorant in the colorant premix within the above range. Can be blended in any amount. According to the present disclosure, the above-described coloring can be applied to various adhesive polymer solutions described later, in which it is difficult to disperse the pigment even when using special means for dispersing the pigment such as a sand mill, a ball mill, and a three-roll. A simple dispersion can be made by simply mixing the agent premix.

  The adhesive polymer imparts adhesion to the adherend to the colored adhesive layer. Various types of adhesive polymers such as acrylic, polyolefin, polyurethane, polyester, and rubber can be used as the adhesive polymer, and commercially available adhesive compositions can be used as they are. As the adhesive polymer, acrylic, polyolefin, and polyurethane adhesive polymers can be advantageously used. If necessary, the adhesive polymer can be crosslinked using a crosslinking agent. From the viewpoints of workability and adhesive strength of an alternative film for vehicle coating, it is advantageous to use a heat-sensitive (heat-activated) adhesive polymer, a pressure-sensitive adhesive polymer, or a thermosetting adhesive polymer as the adhesive polymer. is there.

  The solid content mass ratio represented by adhesive polymer / (adhesive polymer + acrylic polyol) is about 25% or more, preferably about 50% or more, more preferably about 75% or more. The solid content mass ratio here relates to the dry mass of the adhesive polymer and the acrylic polyol, and does not include the mass of the added crosslinking agent. By setting the solid content mass ratio represented by adhesive polymer / (adhesive polymer + acrylic polyol) to the above value, the stretchability of the colored adhesive layer is enhanced, and as a result, the stretchability of the vehicle coating substitute film is enhanced. In addition, excellent appearance (for example, sharpness, gloss retention, etc.) can be maintained even after stretching.

  Colored adhesive compositions include, for example, UV absorbers such as benzotriazole, antioxidants such as phenolic antioxidants, leveling agents such as silicone, viscosity control agents such as wax and organic bentonite, cellulose acetate, and the like. Thickeners such as butyrate, extender pigments such as precipitated barium sulfate, clay, silica, talc, kaolin, bentonite, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol, propylene glycol, ethylene An organic solvent such as glycol dimethyl ether or propylene glycol monomethyl ether acetate may be further included.

  The thickness of the colored adhesive layer can vary, but is generally about 5 μm or more, about 10 μm or more, or about 20 μm or more, about 300 μm or less, about 200 μm or less, or about 100 μm or less. A sufficient adhesive force can be provided by setting the thickness of the colored adhesive layer to about 5 μm or more. When high shape followability is required, it is advantageous that the colored adhesive layer is thin. For example, it is preferably about 200 μm or less, or about 100 μm or less.

  In applications where a film is pasted by vacuum forming or vacuum / pressure forming, if the vehicle coating substitute film is a two-layer laminate comprising a transparent material layer and a colored adhesive layer, less material is required than a conventional laminate of three or more layers. Since production is possible and the number of processes is small and the structure is simple, the probability of occurrence of defects such as dust adhesion, blisters, streaks, and dents during film production is desirable.

  The vehicle paint substitute film according to another embodiment of the present disclosure further includes a second adhesive layer disposed adjacent to the colored adhesive layer as an additional layer in order to enhance adhesion to the adherend. May be. FIG. 2 schematically shows a cross section of a vehicle paint substitute film according to such an embodiment. In the vehicle coating substitute film 10 shown in FIG. 2, the second adhesive layer 40 is disposed adjacent to the surface of the colored adhesive layer 30 on the side opposite to the transparent material layer 20. The second adhesive layer can be formed using the above-described adhesive polymer. In addition, for example, a vehicle painting substitute film is used as an in-mold injection molding film, and an adherend composed of ABS resin, AES resin, or the like is molded on the film while the surface of the adherend is substituted for vehicle painting. When adhering the film, a second adhesive layer composed of an ABS extruded film having chemical properties close to those of the adherend can be used. In this case, the second adhesive layer can be formed by attaching such a film to the colored adhesive layer, or by applying a colored adhesive composition on the film. The thickness of the second adhesive layer may vary, but when the film is applied by vacuum forming or vacuum / pressure forming, generally it is about 5 μm or more, about 10 μm or more, or about 20 μm or more, about 500 μm or less, It is about 200 μm or less, or about 100 μm or less. A sufficient adhesive force can be obtained by setting the thickness of the second adhesive layer to about 5 μm or more. When high shape followability is required, it is advantageous that the second adhesive layer is thin. For example, it is preferably about 200 μm or less, or about 100 μm or less. In the case of in-mold molding that is integrated with the adherend resin by injection molding after pre-molding by vacuum molding, heating press, etc., the second adhesive layer is made hard and thick in order to maintain the shaped shape. It is desirable. In this case, the thickness of the second adhesive layer is advantageously about 150 μm or more and about 3000 μm or less, preferably about 200 μm or more and about 1000 μm or less, more preferably about 300 μm or more and about 700 μm or less.

  The thickness of the vehicle coating substitute film including the transparent material layer, the colored adhesive layer, and the second adhesive layer as required may vary, but when the film is applied by vacuum forming or vacuum / pressure forming Generally, it is about 10 μm or more, about 20 μm or more, or about 50 μm or more, about 1 mm or less, about 500 μm or less, or about 200 μm or less. When high shape followability is required, it is advantageous that the vehicle coating substitute film is thin. For example, it is preferably about 500 μm or less, or about 200 μm or less. In the case of in-mold molding, which is preformed by vacuum molding, heating press, etc., and then integrated with the adherend resin by injection molding, the vehicle coating substitute film should be made thick and thick to maintain the shape. desirable. In this case, the thickness of the vehicle paint substitute film is advantageously about 200 μm or more and about 4000 μm or less, preferably about 250 μm or more and about 1500 μm or less, more preferably about 350 μm or more and about 1000 μm or less.

  In the vehicle coating substitute film according to the present disclosure, a color layer includes an adhesive component that has a long linear portion as compared with a conventional highly crosslinked hard paint and exhibits thermoplastic properties. Therefore, the vehicle paint substitute film according to an embodiment of the present disclosure has a higher tensile elongation than the conventional vehicle paint substitute film and is excellent in shape followability with respect to a complicated three-dimensional shape. According to JIS K7127: 1999, the breaking elongation of such a vehicle paint substitute film is about 50% or more when stretched at a film width of 30 mm, a gripping interval of 50 mm, an ambient temperature of 120 ° C., and a tensile speed of 200 mm / min. About 100% or more, or about 300% or more. Here, the elongation at break is defined as the elongation of the film at the time when any one of the layers constituting the film is broken or cracked when the film is stretched from the initial length. The value (percentage) of elongation at break is defined as the distance traveled from the initial length / the initial length. For example, the elongation at break of 50% means that the initial length of 50 mm is 75 mm ((50-25) mm. / 50 mm × 100 (%)). The breaking elongation can be achieved by appropriately selecting the material type and thickness of the transparent material layer, the colored adhesive layer, and, if present, the second adhesive layer.

  The vehicle paint substitute film according to yet another embodiment of the present disclosure may further include a liner disposed adjacent to the colored adhesive layer as an additional layer. The liner may have a release treatment such as a silicone coating. FIG. 3 schematically shows a cross section of a vehicle paint substitute film according to such an embodiment. In the vehicle coating substitute film 10 shown in FIG. 3, the liner 50 is disposed adjacent to the surface of the colored adhesive layer 30 on the side opposite to the transparent material layer 20.

  In addition, the carrier film can be arranged on the surface of the transparent material layer of the vehicle paint substitute film to improve the handleability of the vehicle paint substitute film. The carrier film may have a release treatment such as a silicone coating. The carrier film protects the surface of the transparent material layer until the vehicle paint substitute film is attached to the adherend, and is removed by peeling from the transparent material layer before the vehicle paint substitute film is attached to the adherend. Is done. When the transparent material layer is formed by coating, the glossiness of the transparent material layer can be controlled using a carrier film. For example, the transparency of the carrier film can be made transparent by laminating the surface of the coated transparent material with a carrier film with adjusted surface gloss before applying the transparent material on the colored adhesive layer and before curing. It can be reflected in the glossiness of the material layer.

  The vehicle paint substitute film of the present disclosure can be manufactured as follows, for example. First, an organic pigment and / or an inorganic pigment is dispersed in an acrylic polyol using a sand grind mill, a ball mill, a three-roll mill or the like to form a pigment dispersion. The entire amount of the acrylic polyol may be used for dispersing the pigment, or a part of the acrylic polyol may be used for dispersing the pigment and then the remainder may be added. In consideration of adjusting the composition for reproducing the vehicle body color, it is preferable to prepare a dispersion for each pigment. The aluminum glitter material and / or the pearl glitter material are wetted with an organic solvent, mixed with the pigment dispersion, and stirred with a paint shaker, a propeller mixer or the like until uniform. In this way, a colorant premix can be prepared. If necessary, the above-mentioned additives may be added to the pigment dispersion and / or the colorant premix during the dispersion step, and a part or all of the organic solvent may be distilled off after the dispersion step.

  Next, the prepared colorant premix and the adhesive polymer are mixed to prepare a colored adhesive composition. The colored adhesive composition can be easily prepared by, for example, stirring for several minutes using a propeller mixer, a centrifugal stirrer, or the like, or, if a small amount, using a glass rod by hand. This colored adhesive composition is applied on the above-mentioned liner or the previously formed second adhesive layer, and heated and dried as necessary to form a colored adhesive layer. Thereafter, a vehicle paint substitute film can be produced by laminating or coating the transparent material described above on the formed colored adhesive layer. After production, the liner may be peeled off and removed if necessary.

  The color matching for the vehicle body color can be performed by the following method, for example. Prepare a colored adhesive composition with a formulation that estimates the target body color, create a film using the above procedure, and visually compare the sample with the body color sample or measure the color difference value to reproduce the target body color Judgment is made. If this is not possible, add a pigment dispersion or a wet luster of a color that appears to be insufficient for the colored adhesive composition, or add an adhesive polymer solution to adjust the concentration, and follow the same procedure. Repeat the process of creating the film and checking the color until the body color is reproduced. Calculate the blending amount of the colorant in the colorant premix and the blending amount of the colorant premix and adhesive polymer from the blending when the body color is finally reproduced, and prepare the colorant premix in advance. If so, it is always possible to produce a film that reproduces the desired color by mixing the colorant premix and the adhesive polymer solution.

  When the colorant premix includes an aluminum glitter material, a mica glitter material, or a combination thereof, the colored adhesive composition can be applied by applying a colored adhesive composition on an additional layer such as a liner or a second adhesive layer. It is desirable to form an agent layer. The reason is as follows. The flaky particles contained in the aluminum glitter material and the mica glitter material are dispersed in the colored adhesive layer in various orientations to provide a metallic color and a pearl color visual effect, respectively. The aluminum glitter material and mica glitter material are distributed in a deeper part of the colored adhesive layer, that is, a part farther from the transparent material layer. It is advantageous to further increase. On the other hand, the aluminum glitter material and the mica glitter material are more likely to settle in the colored adhesive composition as compared with other components. Therefore, when the colored adhesive composition is applied on an additional layer such as a liner or a second adhesive layer as in the above-described production method, the aluminum glitter material and the colored adhesive layer are formed before the formation of the colored adhesive layer is completed. Since a part of the mica glitter material settles, the aluminum glitter material and / or the mica glitter material can be distributed more on the side closer to the additional layer, that is, on the deeper portion of the colored adhesive layer.

  The vehicle paint substitute film of the present disclosure can be manually attached to the surface of the adherend using a squeegee or the like, but is applied to the adherend by a mechanical method such as a vacuum forming method or a vacuum / pressure forming method. You can also. Since the vehicle coating substitute film of one embodiment of the present disclosure is excellent in shape followability to an adherend having a curved surface or a complicated partial shape, such a three-dimensional shape is obtained by a vacuum forming method or a vacuum / pressure forming method. It is particularly suitable for adhering to an adherend having an adhesive, or being integrated with an adherend resin that has been preformed by a vacuum forming method or a vacuum / pressure forming method and then injected into a mold and injected by an injection molding method. .

  The vehicle paint substitute film of the present disclosure will be further described with reference to the following examples. In the examples, “part” relating to the quantity means “part by mass”.

<Transparent material>
MT: Weatherable polyurethane having moldability (polycaprolactone diol / isophorone diisocyanate trimer, see JP-A No. 05-155976)
R985: Weatherable polyurethane having moldability (polycarbonate aqueous polyurethane dispersion / polycarbodiimide, see JP 2010-260942 A)
S001: Weather-resistant acrylic film mainly made of polymethyl methacrylate (PMMA) having moldability (manufactured by Sumitomo Chemical Co., Ltd.)

<Paint (reference)>
The following paints are used in the colored layer of conventional vehicle paint substitute film (roof molding film) after adjusting the spray paint for vehicle exterior parts for bar coating and matching the color to a predetermined car body color. The color of the paint number of Toyota Motor Corporation listed in parentheses is reproduced. The vehicle paint substitute film colorant premix of the present disclosure contains the same colorants as these paints.
Blue mica paint (8M6)
Dark green mica paint (6Q7)
Sparkling gold metallic paint (4P2)

<Colorant premix>
The following colorant premix was prepared as a composition in which about 80 wt% acrylic polyol and about 60 wt% organic solvent were removed from the paint. These colorant premixes contain a high concentration of colorant.
Blue mica colorant premix (8M6)
Dark green mica colorant premix (6Q7)
Sparkling Gold Metallic Colorant Premix (4P2)

  The composition of the paint and colorant premix is shown in Table 1 below.

<Adhesive polymer>
In this example, the following adhesive polymers were used.
PUR-HAA (heat-activated adhesive): polyurethane heat-sensitive adhesive (base polymer: Desmocoll 530 (manufactured by Sumika Bayer Urethane Co., Ltd.)), cross-linking agent: Coronate HL (Nippon Polyurethane) Manufactured by Kogyo Co., Ltd.))
PO-HAA: polyolefin thermosensitive (thermal activation) adhesive (base polymer: UNISTOLE P801 (made by Mitsui Chemicals), crosslinker: Coronate HL (made by Nippon Polyurethane Industry Co., Ltd.))
AC-HAA: acrylic thermosensitive (thermally activated) adhesive (base polymer: carboxyl group-containing acrylic polymer and amino group-containing acrylic polymer (both manufactured by Sumitomo 3M Limited)), epoxy-based cross-linking agent: E-5XM (Soken Chemical Co., Ltd.) (Refer to JP 2009-035588)
AC-PSA (pressure-sensitive adhesive): acrylic pressure-sensitive adhesive (base polymer: copolymer of isooctyl acrylate and acrylic acid, cross-linking agent: aziridine (both manufactured by Sumitomo 3M Limited))
PUR-TSA (thermo-setting adhesive): polyurethane two-component curable adhesive (base polymer: NIPPOLAN 3124, cross-linking agent: Coronate HL (all manufactured by Nippon Polyurethane Industry Co., Ltd.))
<For comparison>
AC-Paint-2: TAKELAC UA-702 (base polymer: acrylic polyol (made by Mitsui Takeda Chemical Co., Ltd.), cross-linking agent: Coronate HL (made by Nippon Polyurethane Industry Co., Ltd.))

<Additional layer>
ABS: Extruded ABS film with a thickness of 0.4 mm (manufactured by Shin-Etsu Polymer Co., Ltd., second adhesive layer, can be used as an adhesive layer for in-mold injection molding films with ABS resin or AES resin)
PP: biaxially stretched polypropylene film with a thickness of 0.06 mm (manufactured by Mitsui Chemicals Tosero Co., Ltd., liner)

<Film sample preparation>
A color solution (colored adhesive composition and comparative coating solution) for forming a color layer (colored adhesive layer or comparative colored layer) is prepared by cupping raw materials in the blending amounts shown in Table 2 below. And prepared by mixing for 1.5 minutes with a centrifugal rotary mixer.

  The color layer was formed with a thickness of 30 μm when dried by bar coating the color solution on the additional layer (ABS and PP) and volatilizing the solvent in an air oven at a temperature of 80 ° C. for 3 to 5 minutes.

  Top layer by coating transparent material on color layer, or by laminating purchased transparent material film (S001) or film formed by coating transparent material on another liner on color layer (Transparent material layer) was formed. The composition of the film samples of Examples 1-31 and Comparative Example 1-9 produced in this manner are shown in Table 3 (Example 1-28 and Comparative Example 1-8) and Table 4 (Examples 29-31 and Comparative Example) below. 9 and Example 24). For Examples 24, 29, 30 and 31, and Comparative Example 9, the solids mass ratio expressed as Adhesive Polymer / (Adhesive Polymer + Acrylic Polyol) listed in Table 4 is determined by drying the adhesive polymer and acrylic polyol. It is based on mass only and does not include the amount of crosslinker added.

<Evaluation of mass production and appearance>
It was confirmed whether the color layer and the top layer were laminated (mass productivity) for each of the prepared film samples. All the films in which the color layer was derived from the colored adhesive composition formed a clean multilayer film regardless of the type of the top layer and the lamination method. On the other hand, the film derived from the coating solution formed a multilayer film only when MT was coated. However, the laminate could not be laminated because the top layer did not adhere. Next, it was confirmed that the desired vehicle body color could be reproduced by comparing each of the laminated films with the coating (appearance). The results are shown in Table 5 for reference.

<Evaluation of adhesive strength>
The samples shown in Table 6 below were heated and laminated on an ABS panel at 70 ° C., held at 80 ° C. for 0.5 hours, and the adhesive strength after 168 hours was measured. For the same sample, as test items for confirming the durability when used as an automobile exterior, the adhesive strength after being immersed in water at 40 ° C. for 168 hours and the adhesive strength after heating at 80 ° C. for 168 hours were also measured. It was. Comparative Example 7 is a conventional vehicle having a three-layer laminated structure including a top layer (transparent material layer), a color layer (derived from a coating solution), and a non-colored polyurethane heat-sensitive adhesive layer (PUR-HAA). It is a paint substitute film (MT7000 roof molding tape, manufactured by Sumitomo 3M Limited). The adhesion was measured at 25 ° C., 180 ° peel, 300 mm / min, and the unit was N / 25 mm. Comparative Example 1 composed of two layers, a color layer derived from a coating solution and a top layer, shows no adhesion, but the color layer contains the same components as the adhesive layer of the roof molding tape (Comparative Example 7). And Example 2 had adhesiveness equal to or higher than that of Comparative Example 7 although it was a two-layered product. Example 7 and Example 8 which changed the adhesive layer component into the acrylic heat-sensitive adhesive also showed high adhesiveness comparable to them. Example 10 and Example 11 using an acrylic pressure-sensitive adhesive showed practically sufficient adhesion, although at a slightly lower level. The results are shown in Table 6.

<Evaluation of weather resistance>
The sample shown in Table 7 below is at least 1 year in two ways: a horizontal state (0 °) and a 35 ° angle from the horizontal (35 °) toward the south at about 1 km from the coast of Fuji City, Japan. Placed outdoors, the color shift was measured, and the appearance was visually observed. For color shift, Spectraflash SF-600 (manufactured by Data Color) was used to measure the color difference ΔE * of the post-test sample with respect to the pre-test sample.

  Despite the fact that the blue mica colorant premix contains organic pigments that are relatively UV sensitive, the example sample using the color layer derived from the colorant premix is a color layer with a conventional paint using acrylic polyol. Excellent weather resistance equivalent to that of Comparative Example 4 having The results are shown in Table 7.

<Evaluation of elongation at break>
Each sample in Table 8 was stretched by a tensile tester with a thermostatic bath under the conditions of a film width of 30 mm, a gripping interval of 50 mm, an atmospheric temperature of 120 ° C., and a tensile speed of 200 mm / min. The elongation at break was determined as the elongation of the film at the time when a break or crack occurred in any one of all the layers constituting the film. Specifically, during stretching, the color layer is cracked, the entire layer is broken, the layers other than the ABS layer are broken, and the breaking behavior differs depending on the type of film. When the break or crack occurred, it was considered that the film had lost practicality, and the elongation at that time was defined as the break elongation (%) (= movement distance (mm) / 50 mm × 100). The results are shown in Table 8.

＜延伸後の表面性（鮮映度・光沢保持率）の評価＞
破断伸度の評価手順における延伸操作を同様に行い、移動距離１０ｍｍ（２０％延伸）、２０ｍｍ（４０％延伸）、５０ｍｍ（１００％延伸）の時点で装置を止めて延伸した状態のフィルムを取り出して、延伸前フィルムと共に平滑な板に貼り付けて以下の方法で表面性を測定した。

<Evaluation of surface properties after stretching (sharpness / gloss retention)>
The stretching operation in the evaluation procedure for breaking elongation was performed in the same manner, and the stretched film was taken out by stopping the apparatus at a moving distance of 10 mm (20% stretching), 20 mm (40% stretching), and 50 mm (100% stretching). Then, it was attached to a smooth plate together with the film before stretching, and the surface property was measured by the following method.

  The sharpness measurement was performed using PGD-IV (manufactured by Tokyo Kogyo Co., Ltd.) to measure the sharpness value (brightness value) of the film having each stretching ratio and the film before stretching. The higher the number, the better the smoothness of the surface and the better the reflection of the scenery. A horizontal spray-painted surface such as an automobile bonnet is considered to be very beautiful with no paint dripping, and the sharpness is about 0.4 or more. Since the sprayed paint drips down and the surface becomes rough, the vertical surface often shows a sharpness of about 0.2. The results are shown in Table 9.

  Gloss retention is measured using GMX-203 (manufactured by Murakami Color Research Laboratories Co., Ltd.) to measure the 60 ° gloss value, and the gloss retention (%) (= glossiness of the film at each stretching ratio / film stretching before stretching) (Glossiness × 100) was determined. If the gloss of the paint substitute film is greatly reduced by stretching by molding, it is judged as abnormal compared with the original glossy part. If the gloss retention is about 90% or more, the difference in appearance is not found when viewed with the naked eye, which is very preferable. If the gloss retention is about 80% or more, there is no practical problem. The results are shown in Table 9.

  From the results of Table 8 and Table 9, Comparative Example 1, Comparative Example 4 and Comparative Example 8 using a conventional coating solution for the color layer stretched about 60% as a film, but the color was about 30% stretched. Cracks occur in the layer. The deterioration of the appearance due to cracks in the color layer can also be seen from the fact that the gloss retention is greatly reduced at 40% stretching (Comparative Examples 4 and 8). Furthermore, the sharpness representing the smoothness of the surface is very low at the time of 20% stretching that does not lead to cracks in the color layer.

  On the other hand, the color layer containing the colorant premix and the adhesive polymer according to the present disclosure can be stretched greatly, and a film having a high elongation limit can be produced by combining with a top layer having high stretchability. In addition, the film of the present disclosure that contains an adhesive polymer in the color layer is superior in appearance (strength and gloss retention) after stretching compared to a film having a conventional color layer, and is suitable for high stretch molding. It is. The series of results of Examples 24, 29, 30 and 31 and Comparative Example 9 show the relationship between the amount of adhesive polymer used in the color layer and the appearance enhancement effect. Furthermore, the film obtained by laminating the top layer and the color layer realized according to the present disclosure has a high elongation at break and excellent stretch after the film obtained by coating the top layer on the conventional color layer. Since it shows an appearance, it can be suitably used for deep drawing.

10 vehicle coating substitute film 20 transparent material layer 30 colored adhesive layer 40 second adhesive layer 50 liner

Claims (9)

A vehicle paint substitute film comprising a transparent material layer and a colored adhesive layer, wherein the colored adhesive layer comprises:
(I) (a) an acrylic polyol;
(B) A colorant dispersed in the acrylic polyol, comprising a combination of an organic pigment and an inorganic pigment, a combination of an organic pigment and an aluminum glitter material, a combination of an organic pigment and a mica glitter material, and an inorganic pigment and an aluminum glitter material. A colorant premix comprising: a combination; a combination of an inorganic pigment and a mica glitter; and a combination of an aluminum glitter and a mica glitter; and a colorant selected from the group consisting of these combinations;
(Ii) A vehicle coating substitute film comprising an adhesive polymer and having a solid content mass ratio represented by adhesive polymer / (adhesive polymer + acrylic polyol) of 25% or more.   The vehicle coating substitute film according to claim 1, wherein the film has a breaking elongation of 50% or more when stretched at a film width of 30 mm, a gripping interval of 50 mm, an atmospheric temperature of 120 ° C, and a tensile speed of 200 mm / min.   The vehicle coating according to claim 1, wherein the amount of the colorant in the colorant premix is 20% by mass to 80% by mass based on the total mass of the acrylic polyol and the colorant. Alternative film.   The vehicle coating substitute film according to any one of claims 1 to 3, wherein the adhesive polymer is a heat-sensitive adhesive polymer, a pressure-sensitive adhesive polymer, or a thermosetting adhesive polymer.   The vehicle coating substitute film according to any one of claims 1 to 4, which is a two-layer laminate comprising the transparent material layer and the colored adhesive layer.   The vehicle coating substitute according to any one of claims 1 to 5, wherein the colored adhesive layer is formed from a colored adhesive composition obtained by mixing the colorant premix and the adhesive polymer. the film.   The vehicle coating substitute film according to any one of claims 1 to 6, further comprising an additional layer selected from a liner or a second adhesive layer disposed adjacent to the colored adhesive layer. The colorant premix includes the aluminum glitter material, the mica glitter material, or a combination thereof, and the colored adhesive layer applies the colored adhesive composition on the additional layer. A vehicle paint substitute film, wherein the transparent material layer is formed by laminating a transparent material on the formed colored adhesive layer.   It is adapted to be able to adhere to the adherend by vacuum forming method or vacuum / pressure forming method, or after being pre-formed by vacuum forming method or vacuum / pressure forming method, it is put into the mold and injected by injection molding method. The vehicle coating substitute film according to any one of claims 1 to 7, which is adapted to be integrated with an adherend resin. (A) In acrylic polyol, (b) Combination of organic pigment and inorganic pigment, Combination of organic pigment and aluminum glitter material, Combination of organic pigment and mica glitter material, Combination of inorganic pigment and aluminum glitter material, Inorganic pigment and mica A colorant premix is prepared by dispersing a combination of glitter materials, a combination of aluminum glitter materials and mica glitter materials, and a colorant selected from the group consisting of these combinations,
Forming a colored adhesive layer using a colored adhesive composition obtained by mixing the colorant premix and the adhesive polymer;
A method for producing a vehicle paint substitute film, comprising: forming a transparent material layer by laminating or coating a transparent material on the formed colored adhesive layer.

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