WO2023013404A1 - メタクリル酸エステル系樹脂を主成分とするフィルム - Google Patents

メタクリル酸エステル系樹脂を主成分とするフィルム Download PDF

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Publication number
WO2023013404A1
WO2023013404A1 PCT/JP2022/028095 JP2022028095W WO2023013404A1 WO 2023013404 A1 WO2023013404 A1 WO 2023013404A1 JP 2022028095 W JP2022028095 W JP 2022028095W WO 2023013404 A1 WO2023013404 A1 WO 2023013404A1
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Prior art keywords
film
acid ester
resin
mass
parts
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Ceased
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PCT/JP2022/028095
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English (en)
French (fr)
Japanese (ja)
Inventor
憲朗 安本
康史 宮村
敬司 ▲高▼野
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Denka Co Ltd
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Denka Co Ltd
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Publication date
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to EP22852828.7A priority Critical patent/EP4382558A4/en
Priority to JP2023540234A priority patent/JPWO2023013404A1/ja
Priority to US18/293,470 priority patent/US20240343899A1/en
Priority to CN202280052866.XA priority patent/CN117794987A/zh
Publication of WO2023013404A1 publication Critical patent/WO2023013404A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present invention relates to a single-layer film or laminated film having a film containing a methacrylic acid ester-based resin as a main component.
  • the present invention relates to a single-layer film or laminated film that can be applied as the outermost layer of a metallic decorative film.
  • a decorative film is generally manufactured through a step of laminating a decorative layer to an outermost film. Lamination using an adhesive and thermal lamination are generally used as the method of bonding.
  • Patent Document 1 International Publication No. 2011/142453
  • a vinylidene fluoride resin (A) and an acrylic resin (B) A film having an arithmetic average roughness of 0.1 to 20 nm on at least one surface, a heat of crystal fusion of 18 to 40 J / g as measured by a differential scanning calorimeter, and a haze value of 3.5 or less is proposed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2012-187934 discloses that by using a fluorine-based (meth)acrylic resin containing a fluorine-containing alkyl (meth)acrylate component, it can be used for vehicle interior and exterior parts, and is transparent. It describes the successful production of a novel fluororesin film with excellent properties, surface hardness, chemical resistance, and stain resistance.
  • a fluororesin-laminated acrylic resin film in which a fluororesin film layer is laminated on at least one side of a film layer made of an acrylic resin (A), wherein the fluororesin film layer is A fluororesin-laminated acrylic resin film obtained by molding a fluororesin (C) containing a fluororesin (B) containing a fluorine-containing alkyl (meth)acrylate polymer component is specifically disclosed. ing.
  • the present invention was created in view of the above circumstances, and an object of one embodiment is to provide a resin film having both high transparency and excellent blocking resistance.
  • the present inventors have found that a film containing a methacrylic acid ester-based resin as a main component and not containing a vinylidene fluoride-based resin is coated with a crosslinked (meth)acrylic resin having a predetermined size.
  • the inventors have found that the addition of acid ester-based resin particles is effective, and have completed the present invention as exemplified below.
  • the crosslinked (meth)acrylic acid ester resin particles have an average particle diameter of 1% or more and 10% or less with respect to the average thickness of the film,
  • the film does not contain a vinylidene fluoride resin,
  • the haze of the film measured according to JIS K7136:2000 is 5% or less
  • Clarity (CLR) of the film calculated from the following formula is 97% or more, said film.
  • the film containing the vinylidene fluoride resin is one or two selected from a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride (A), and a methacrylate ester resin
  • the laminated film according to [3] which contains 50 parts by mass or more and 80 parts by mass or less of (A) and 20 parts by mass or more and 50 parts by mass or less of (B) with respect to a total of 100 parts by mass of (B). .
  • a metallic decorative film in which the film described in [1] or [2] is laminated as the outermost layer, or a film in which the laminated film described in [3] or [4] contains a vinylidene fluoride resin A metallic decorative film laminated as the outermost layer with the .
  • a single layer film or laminated film having both high transparency and excellent blocking resistance can be obtained.
  • the single-layer film or laminated film can be used by being attached to a substrate, and can be suitably used, for example, as the outermost layer of a decorative film, especially a metallic decorative film.
  • FIG. 4 is a schematic cross-sectional view showing a laminated structure of a film according to a second embodiment of the invention.
  • the film according to the first embodiment contains crosslinked (meth)acrylic acid ester resin particles and can be composed of a resin composition containing a methacrylic acid ester resin as a main component.
  • the methacrylic acid ester resin is a homopolymer of a methacrylic acid ester such as methyl methacrylate, a copolymer of a methacrylic acid ester and a monomer copolymerizable with the methacrylic acid ester, and is used in the film. with a particle size of less than 0.2 ⁇ m (including those with an unspecified particle size and those forming a matrix phase). Conversely, resin particles having a particle size of 0.2 ⁇ m or more in the film are not included in the methacrylic acid ester resin in the present specification.
  • the particle size of the resin particles was determined by fixing the film in a small metal vice, cutting the film with a single-edged knife so that the cross section of the film was smooth, and holding the film in the vice. It refers to the diameter of the smallest circle that can surround the resin particles when the cross section of the film is observed at a magnification of 2000 using a laser microscope (eg VK-X110 manufactured by Keyence Corporation).
  • Monomers copolymerizable with methacrylates include (meth)acrylates such as butyl acrylate, butyl methacrylate, ethyl acrylate, and ethyl methacrylate; styrene, ⁇ -methylstyrene, p-methylstyrene , o-methylstyrene, t-butylstyrene, divinylbenzene, and tristyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; glycidyl group-containing monomers such as glycidyl (meth)acrylate; monomers; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; diene monomers such as 1,3-butadiene and isoprene; maleic acid and anhydrous Unsaturated carboxylic acid-based monomers such as
  • the copolymers include random copolymers, graft copolymers, block copolymers (e.g., diblock copolymers, triblock copolymers, linear types such as gradient copolymers, star copolymers polymerized by the arm-first method or the core-first method). polymers, etc.), copolymers (macromonomer copolymers) obtained by polymerization using a macromonomer, which is a polymer compound having a polymerizable functional group, and mixtures thereof.
  • graft copolymers and block copolymers are preferable from the viewpoint of resin productivity.
  • Polymerization reactions for obtaining methacrylic acid ester resins include known polymerization reactions such as radical polymerization, living radical polymerization, living anion polymerization, and living cationic polymerization.
  • the polymerization method includes known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Polymerization reactions and polymerization methods change the mechanical properties of the resulting resin.
  • the film according to the first embodiment contains a methacrylic acid ester-based resin as a main component means that the methacrylic acid ester-based resin is the component with the highest mass ratio among the constituent components of the film.
  • the amount of the methacrylic acid ester resin in the film is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more. and can be, for example, 50 to 99% by mass.
  • the film according to the first embodiment contains crosslinked (meth)acrylic acid ester resin particles in addition to the methacrylic acid ester resin.
  • the crosslinked (meth)acrylate resin particles are present in a dispersed state in the matrix of the methacrylate ester resin. Since the crosslinked (meth)acrylic acid ester resin particles have a refractive index similar to that of the main component methacrylic acid ester resin, even if they are dispersed in the methacrylic acid ester resin, the transparency of the film is impaired. It is characterized by difficulty.
  • crosslinked (meth)acrylic acid ester resin particles refer to particles having a particle size of 0.2 ⁇ m or more in the film.
  • the particle size of the resin particles refers to the diameter of the smallest circle that can enclose the resin particles when the film is observed by the method described above. Therefore, even if it is a particulate crosslinked (meth)acrylic ester-based resin, if the particle size in the film is less than 0.2 ⁇ m, if it satisfies the definition of the methacrylic ester-based resin described above, the methacrylic ester-based It corresponds to resin.
  • the crosslinked (meth)acrylic acid ester-based resin particles in the film preferably have an average particle diameter of 1% or more and 10% or less with respect to the average thickness of the film.
  • the crosslinked (meth)acrylic acid ester-based resin particles preferably have an average particle diameter of 1% or more, more preferably 2% or more, and even more preferably 3% or more with respect to the average thickness of the film. Blocking resistance can be improved by imparting moderate unevenness to the surface.
  • the crosslinked (meth)acrylic acid ester resin particles are preferably 10% or less, more preferably 9% or less, still more preferably 8% or less, and still more preferably 7% or less with respect to the average thickness of the film. Still more preferably, having an average particle diameter of 6% or less makes it possible to improve the clarity of the film without excessively increasing the unevenness of the film surface.
  • the average particle size of the crosslinked (meth)acrylic acid ester resin particles is not so important, but considering the thickness of the normally assumed film, the average particle size of the crosslinked (meth)acrylic acid ester resin particles is preferably 0.5 to 5 ⁇ m, more preferably 0.5 to 2 ⁇ m.
  • the average particle size of the crosslinked (meth)acrylic acid ester resin particles refers to the D50 value (volume basis) of particle size distribution measured by a laser diffraction/scattering method.
  • the average thickness of the film according to the first embodiment is preferably 10 to 100 ⁇ m, more preferably 15 to 90 ⁇ m, even more preferably 20 to 85 ⁇ m, even more preferably 25 to 80 ⁇ m. Especially preferred.
  • the film formability is improved, and the protective function when used as the outermost layer of the laminated film can be improved. improvement in performance can be realized.
  • the film according to the first embodiment may be formed with a single layer, or may be formed with multiple layers, but it is desirable that the total average thickness is within the above average thickness.
  • the average thickness of the film can be calculated as an average value when the thickness is measured at multiple locations by observing the cross section of the film using a confocal laser microscope.
  • crosslinked (meth)acrylic acid ester resin particles include, but are not limited to, crosslinked polymethyl acrylate, crosslinked polyethyl acrylate, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, crosslinked polyn-butyl methacrylate, and the like. These can be used alone or in combination of two or more. Among them, it is preferable to contain crosslinked polymethyl methacrylate because the difference in refractive index from that of the methacrylic acid ester resin constituting the matrix is small.
  • the crosslinked (meth)acrylic acid ester-based resin particles are easily maintained without being compatible with the methacrylic acid ester-based resin in which the fine particles constitute the matrix due to the crosslinked structure even when heat is applied during film production.
  • the amount of the crosslinked (meth)acrylic acid ester-based resin particles in the film according to the first embodiment can improve transparency, while a larger amount can improve blocking resistance. Therefore, from the viewpoint of achieving both transparency and blocking resistance, the amount of the crosslinked (meth)acrylic acid ester-based resin particles is 0.1 parts by mass or more with respect to 100 parts by mass of the methacrylic acid ester-based resin. It is preferably 2 parts by mass or less, more preferably 0.3 parts by mass or more and 1.5 parts by mass or less, and even more preferably 0.5 parts by mass or more and 1 part by mass or less.
  • the lower limit of the glass transition point (Tg) of the methacrylic acid ester resin is preferably 70°C or higher, more preferably 80°C or higher.
  • the upper limit of the Tg of the methacrylic acid ester resin is preferably 120°C or less.
  • the Tg of the methacrylic acid ester resin can be measured by heat flux differential scanning calorimetry (heat flux DSC).
  • heat flux DSC heat flux differential scanning calorimetry
  • a sample mass of 1.5 mg is heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min DSC curve (first run) can be obtained from
  • the haze of the film according to the first embodiment is preferably 5% or less, more preferably 4% or less, from the viewpoint of enhancing transparency. It can range from 1 to 5%.
  • the film according to the first embodiment has a clarity (CLR) calculated from the following formula of 97% or more, preferably 98% or more, more preferably 99% or more. , 97-99.5%.
  • CLR 100 ⁇ (Ic ⁇ Ir)/(Ic+Ir)
  • Ic is the amount of light that has passed through the film and travels straight with respect to the optical axis of the parallel light incident perpendicularly to the surface of the film
  • Ir is the angle of the parallel light with respect to the optical axis. It represents the amount of narrow-angle scattered light within ⁇ 2.5°.
  • a CIE-D65 light source is used as the light source.
  • Clarity is a parameter similar to haze, but good haze does not necessarily mean good clarity (CLR).
  • Haze is a parameter that evaluates the optical properties of a film perceived by an observer using wide-angle scattered light (transmitted light that deviates from the incident light by 2.5° or more due to forward scattering).
  • Clarity is a parameter that evaluates the optical properties of a film perceived by an observer using narrow-angle scattered light. Therefore, it can be said that the haze evaluates the degree of turbidity of the film, while the clarity evaluates the sharpness of the outline of the article when the article is viewed through the film.
  • high clarity in addition to haze means that when the film is applied to the surface of an article for use, the design displayed on the surface of the article can be visually recognized faithfully.
  • the article is a substrate for a metallic decorative film
  • the metallic luster of the surface of the substrate can be clearly visually recognized even after the film is attached.
  • the total light transmittance of the film according to the first embodiment measured based on JIS K7361-1:1997 is preferably 80% or more, more preferably 85% or more, from the viewpoint of increasing transparency. is more preferable, and 90% or more is even more preferable, and can be, for example, 80 to 95%.
  • the film according to the first embodiment contains, in addition to the methacrylic acid ester-based resin and the crosslinked (meth)acrylic acid ester-based resin particles, an ultraviolet absorber, another resin, and a plasticizer to the extent that the object of the present invention is not impaired. , a heat stabilizer, an antioxidant, a light stabilizer, a crystal nucleating agent, an antiblocking agent, a sealability improver, a release agent, a coloring agent, a pigment, a foaming agent, a flame retardant, and the like.
  • the total content of the methacrylic acid ester-based resin and the crosslinked (meth)acrylic acid ester-based resin particles in the film according to the first embodiment is 90% by mass or more, typically 95% by mass. % or more, more typically 97 mass % or more, and may be 100 mass %.
  • the film according to the first embodiment does not contain a vinylidene fluoride resin.
  • the film according to the first embodiment preferably contains an ultraviolet absorber.
  • ultraviolet absorbers include, but are not limited to, hydroquinone-based, triazine-based, benzotriazole-based, benzophenone-based, cyanoacrylate-based, oxalic acid-based, hindered amine-based, salicylic acid derivatives, and the like. Two or more kinds can be used in combination. Among them, it is preferable to contain a triazine-based compound, a benzotriazole-based compound, or a mixture thereof from the standpoint of the durability of the ultraviolet shielding effect.
  • the blending amount of the ultraviolet absorber in the film according to the first embodiment is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the methacrylic acid ester resin. More preferably, the amount of the ultraviolet absorber in the resin composition is 0.1 parts by mass or more, preferably 1 part by mass or more, with respect to 100 parts by mass of the methacrylic acid ester-based resin. is 2 parts by mass or more, it is possible to expect an ultraviolet absorption effect along with the effect of improving weather resistance, and the amount of the ultraviolet absorber in the resin composition is By adjusting the amount to 10 parts by mass or less, preferably 5 parts by mass or less, it is possible to prevent the ultraviolet absorber from bleeding out onto the film surface, thereby achieving cost reduction.
  • the film according to the first embodiment can be produced by, for example, carrying out the following steps.
  • Step 1 A resin composition containing a methacrylic acid ester-based resin and 0.1 parts by mass or more and 2 parts by mass or less of crosslinked (meth)acrylic acid ester-based resin particles with respect to 100 parts by mass of the methacrylic acid ester-based resin, A step of melt extrusion molding into a film having an average thickness of 10 to 100 ⁇ m from a T-die at a temperature of 200 to 260°C.
  • Step 2 After being extruded from the outlet of the T-die, at least one surface of the melt-extruded film is brought into contact with the surface of a metal roll whose temperature is adjusted to 30 to 60°C to cool it.
  • a method of adjusting the temperature of the metal roll surface for example, a method of circulating a cooling medium such as cooling water inside the metal roll can be mentioned.
  • Melt extrusion molding methods include the T-die method of forming a film using a T-die and the method of using an inflation die.
  • a rubber touch roll is arranged to face the metal roll, and the molten resin composition extruded from the exit of the die is pinched between the metal roll (cast roll) and the touch roll. It is more preferable from the viewpoint of transferring the smooth surface of the metal roll to the film.
  • the surface temperature of the rubber touch roll is preferably 0 to 70° C., more preferably 0 to 30° C., from the viewpoint of suppressing transfer of the surface shape of the rubber roll.
  • the surface roughness of the metal roll is small, and that the surface roughness of the touch roll is also small. Reducing the surface roughness of the film is advantageous for reducing the haze value and increasing the clarity of the film. This is because the surface roughness of the metal roll and the touch roll is reflected in the surface roughness of the film. Therefore, the arithmetic mean roughness Ra measured based on JIS B0601:2001 on the surface of the metal roll is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less.
  • the arithmetic mean roughness Ra of the touch roll surface measured according to JIS B0601:2001 is preferably 150 nm or less, more preferably 120 nm or less, and can be, for example, 100 to 150 nm.
  • FIG. 1 shows a schematic cross-sectional view showing the laminated structure of a film 1 according to the second embodiment.
  • the film 1 has a laminated structure comprising at least a surface layer 10 and a back layer 20 laminated on the surface layer 10 in this order.
  • the surface layer 10 and the back layer 20 are directly bonded without any other resin layer interposed between them.
  • the surface layer is composed of a film containing a vinylidene fluoride resin.
  • the film constituting the surface layer preferably contains a vinylidene fluoride-based resin and a methacrylate ester-based resin.
  • the vinylidene fluoride-based resin is 50 parts by mass or more with respect to the total of 100 parts by mass of the vinylidene fluoride-based resin and the methacrylic acid ester-based resin, properties such as chemical resistance, weather resistance, and stain resistance are improved. be able to.
  • methacrylate ester resin in the film constituting the surface layer, the adhesiveness and adhesion to the back surface layer can be improved.
  • the vinylidene fluoride-based resin refers to homopolymers of vinylidene fluoride, as well as copolymers of vinylidene fluoride and monomers copolymerizable with vinylidene fluoride.
  • monomers copolymerizable with vinylidene fluoride include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, hexafluoroisobutylene, trifluoroethylene chloride, various fluorinated alkyl vinyl ethers, and styrene, ethylene, butadiene.
  • vinyl monomers such as propylene, which can be used alone or in combination of two or more.
  • at least one selected from vinyl fluoride, tetrafluoroethylene, hexafluoropropylene and trifluoroethylene chloride is preferred, and hexafluoropropylene is more preferred.
  • the film constituting the surface layer is one or two selected from a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride (PVDF homopolymer) (A), and a methacrylate ester-based
  • PVDF homopolymer a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride
  • a total of 50 parts by mass to 80 parts by mass of (A) and 20 parts by mass to 50 parts by mass of (B) are preferably contained with respect to a total of 100 parts by mass of the resin (B). It is more preferable to contain 60 to 75 parts by mass in total and 25 to 40 parts by mass of (B).
  • the polymerization reaction for obtaining the vinylidene fluoride resin includes known polymerization reactions such as radical polymerization and anionic polymerization. Further, the polymerization method includes known polymerization methods such as suspension polymerization and emulsion polymerization. The mechanical properties and the like of the obtained resin change depending on the polymerization reaction and/or polymerization method.
  • the lower limit of the melting point of the vinylidene fluoride resin is preferably 150°C or higher, more preferably 160°C or higher.
  • the upper limit of the melting point of the vinylidene fluoride resin is preferably 170° C. or less, which is equal to the melting point of polyvinylidene fluoride (PVDF).
  • the lower limit of the glass transition point (Tg) of the methacrylic acid ester resin is preferably 70°C or higher, more preferably 80°C or higher.
  • the upper limit of the Tg of the methacrylic acid ester resin is preferably 120°C or less.
  • the melting point of the vinylidene fluoride-based resin and the Tg of the methacrylic acid ester-based resin can be measured by heat flux differential scanning calorimetry (heat flux DSC).
  • heat flux DSC heat flux differential scanning calorimetry
  • a sample mass of 1.5 mg is heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min DSC curve (first run) can be obtained from
  • the film that constitutes the surface layer may contain other resins, plasticizers, heat stabilizers, antioxidants, light stabilizers, etc., as long as the objects of the present invention are not impaired. agents, crystal nucleating agents, anti-blocking agents, sealing improvers, release agents, coloring agents, pigments, foaming agents, flame retardants, and the like.
  • the total content of the vinylidene fluoride-based resin and the methacrylic acid ester-based resin in the film constituting the surface layer is 80% by mass or more, typically 90% by mass or more, and more Typically, it is 95% by mass or more, and can be 100% by mass.
  • the total content of the methacrylic acid ester-based resin (B) is 80% by mass or more, typically 90% by mass or more, more typically 95% by mass or more, and may be 100% by mass. can.
  • a UV absorber may be added to the film constituting the surface layer, but it is preferable not to add it from the viewpoint of cost and bleed-out.
  • the average thickness of the film constituting the surface layer is preferably 1-40 ⁇ m, more preferably 5-35 ⁇ m, even more preferably 8-30 ⁇ m, and particularly preferably 10-20 ⁇ m.
  • the film constituting the surface layer may be formed of a single layer or a plurality of layers, but it is desirable that the total average thickness is within the above-mentioned average thickness.
  • the average thickness of the film can be calculated as an average value when the thickness is measured at multiple locations by observing the cross section of the film using a confocal laser microscope.
  • the composition, the average particle size of the crosslinked (meth)acrylic acid ester resin particles, the average thickness, the haze, the clarity, and the total light transmittance of the first embodiment Since the same description as that of the embodiment of the film according to is applied, the description is omitted.
  • the haze of the film according to the second embodiment is preferably 5% or less, more preferably 4% or less, from the viewpoint of enhancing transparency. It can range from 1 to 5%.
  • the film according to the second embodiment has, in one embodiment, the clarity (CLR) described for the film according to the first embodiment of 97% or more, preferably 98% or more, more preferably 99%. It is more than that, and can be, for example, 97 to 99.5%.
  • CLR clarity
  • the 60° specular glossiness of the outer surface side of the surface layer (film containing vinylidene fluoride resin) measured based on JIS Z8741: 1997 of the film according to the second embodiment enhances transparency. From this point of view, it is preferably 100 or more, more preferably 110 or more, and even more preferably 120 or more.
  • a laminated film in which a surface layer and a back layer are laminated can be produced, for example, by a melt coextrusion molding method in which a plurality of resins are adhered and laminated in a molten state using a plurality of extruders.
  • the melt co-extrusion molding method includes a multi-manifold die method in which each layer is contacted and bonded at the tip of the T-die after making multiple resins into sheets, and a method in which multiple resins are bonded in a confluence device (feed block) and then There is a feed block die method that spreads into a sheet, and a dual slot die method that adheres each layer by contacting each layer at the tip of the outside of the T die after molding a plurality of resins into a sheet. It can also be manufactured by an inflation molding method using a round die.
  • the film according to the second embodiment can be produced by, for example, carrying out the following steps.
  • Step 1 a first resin composition containing a vinylidene fluoride resin, and A methacrylic acid ester-based resin and a second resin composition containing 0.1 parts by mass or more and 2 parts by mass or less of crosslinked (meth)acrylic acid ester-based resin particles with respect to 100 parts by mass of the methacrylic acid ester-based resin,
  • the average thickness of the first resin composition is 1 to 40 ⁇ m
  • the average thickness of the second resin composition is 10 to 100 ⁇ m. process.
  • Step 2 After being extruded from the outlet of the T-die, at least the surface of the first resin composition side of the melt-coextruded film is brought into contact with the surface of a metal roll whose temperature is adjusted to 30 to 60 ° C. and cooled. process.
  • a method of adjusting the temperature of the metal roll surface for example, a method of circulating a cooling medium such as cooling water inside the metal roll can be mentioned.
  • a rubber touch roll is arranged to face the metal roll, and the laminate of the first resin composition and the second resin composition in a molten state extruded from the exit of the T die is transferred to the metal roll (cast From the viewpoint of transferring the smooth surface of the metal roll to the film, pinching between the roll) and the touch roll is more preferable.
  • the surface temperature of the rubber touch roll is preferably 0 to 70° C., more preferably 0 to 30° C., from the viewpoint of suppressing transfer of the surface shape of the rubber roll.
  • the surface roughness of the metal roll is small, and that the surface roughness of the touch roll is also small. Reducing the surface roughness of the film is advantageous for reducing the haze value and increasing the clarity of the film. This is because the surface roughness of the metal roll and the touch roll is reflected in the surface roughness of the film. Therefore, the arithmetic mean roughness Ra measured based on JIS B0601:2001 on the surface of the metal roll is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less.
  • the arithmetic mean roughness Ra of the touch roll surface measured according to JIS B0601:2001 is preferably 150 nm or less, more preferably 120 nm or less, and can be, for example, 100 to 150 nm.
  • a substrate may be laminated on each of the films according to the first embodiment and the second embodiment. Accordingly, in one embodiment, the present invention provides a film having a substrate laminated on one side of the film according to the first embodiment. In another embodiment of the present invention, a film is provided in which a substrate is laminated on the surface layer and/or the back layer of the film according to the second embodiment.
  • the average value of the total thickness of the film laminated with the base material is 50 to 1000 ⁇ m, it is preferable from the viewpoint of the workability and cost of bonding to automobile interior parts.
  • base materials include layers such as decorative layers, protective layers, adhesive layers, printed layers, and metal deposition layers.
  • One substrate may be used as a single layer, or a combination of two or more substrates may be used as a laminate.
  • the films according to the first and second embodiments can have high transparency. Therefore, this property can be effectively utilized by applying the film to a substrate surface having a high glossiness. Therefore, in a preferred embodiment, the 60° specular gloss measured based on JIS Z8741: 1997 on the surface of the substrate to be bonded to the film is 100 to 600, typically 300 to 550. Yes, and L* at an acceptance angle of 15° in the L*a*b* color space based on JIS Z8781-4:2013 is 0-20, typically 0-5.
  • a metallic decorative film in which the film according to the first embodiment is laminated as the outermost layer, or the film according to the second embodiment is a surface layer (containing vinylidene fluoride resin A metal-like decorative film laminated as the outermost layer with the film having the outermost layer facing outward is provided.
  • the metallic decorative film comprises the film according to the first embodiment, an anchor layer, a metal deposition layer, and an adhesive layer in this order, and the film according to the first embodiment constitutes the outermost layer.
  • the metal-tone decorative film comprises the film according to the second embodiment, an anchor layer, a metal vapor deposition layer, and an adhesive layer in this order, and the film according to the second embodiment comprises a surface layer (a surface layer). The film containing the vinylidene chloride resin) is placed outside to constitute the outermost layer.
  • the anchor layer may be made of, but not limited to, acrylic resins, nitrocellulose resins, polyurethane resins (including polyol resin as the main ingredient and cured with isocyanate resin as a curing agent), acrylic urethane resins (acrylic polyol resin as the main ingredient and cured with isocyanate resin as a curing agent), polyester resin, styrene-maleic acid resin, chlorinated PP resin, and the like.
  • the anchor layer contains an acrylic resin from the viewpoint that the adhesiveness of the obtained film is more excellent.
  • the metal deposition layer can contain, but is not limited to, metal such as indium.
  • the metal deposition layer may contain various non-metals, metals, metal oxides and metal nitrides.
  • the adhesive layer can contain various adhesives, adhesives, pressure sensitive adhesives (PSA: Pressure Sensitive Adhesive), and the like.
  • PSA Pressure Sensitive Adhesive
  • Examples of methods for laminating substrates on the films according to the first embodiment and the second embodiment include adhesive lamination and thermal lamination. Other known lamination methods can also be employed. Also, the films according to the first embodiment and the second embodiment can be heat-molded. As a method of thermoforming, for example, a method of laminating a substrate on one side or both sides of a film, followed by vacuum forming, pressure forming, and vacuum pressure forming can be used.
  • Methods for coating the surface of articles such as automobile interior parts with a decorative film, especially a metallic decorative film include, for example, film insert molding, in-mold molding, and vacuum lamination molding (such as TOM molding). (including vacuum and pressure molding). Film insert molding, in particular, performs preforming by heating the decorative film. There is an advantage that a surface covering state can be realized.
  • the average particle size is the D50 value (volume basis) of particle size distribution measured using a laser diffraction/scattering method.
  • the D50 value is sometimes called a median diameter, and is a particle diameter at which the cumulative particle size distribution from the smaller particle diameter side is 50%.
  • Examples of the measuring device include Mastersizer 2000 (manufactured by Malvern Panalytical).
  • each compound was obtained after kneading with a ⁇ 30 mm twin-screw extruder.
  • Each compound obtained is melt-extruded using a T-die single-screw extruder having a diameter of 40 mm, and the extruded film-shaped resin composition is conveyed at a conveying speed of 4.5 m / min while cooling water is introduced into the inside.
  • the film was sandwiched between a metal roll (surface temperature: about 40°C) and a rubber touch roll (surface temperature: about 20°C) and cooled to obtain a film having an average thickness shown in Table 1.
  • Laminated film> (2-1. Materials) ⁇ For surface layer (film containing vinylidene fluoride resin)>> ⁇ Vinylidene fluoride resin> The following materials were prepared as vinylidene fluoride resin (PVDF). ⁇ “Kynar 1000HD” manufactured by Arkema (PVDF homopolymer with a melting point of 168 ° C.) ⁇ Methacrylate ester resin> The following materials were prepared as the methacrylic acid ester-based resin. ⁇ Sumitomo Chemical Co., Ltd.
  • each compound for the surface layer and the back layer was obtained according to the compounding recipe shown in Table 2 according to the test number.
  • the compound for the surface layer and the compound for the back layer are melted and co-extruded using two single-screw extruders of ⁇ 40 mm and a feed block type T-die multilayer extruder with a feed block and a T-die attached to the tip, While conveying the extruded film-shaped resin composition at a conveying speed of 6.7 m / min, a metal roll (surface temperature: about 20 ° C.) and a rubber touch roll (surface temperature: (approximately 40° C.) and cooled to obtain a laminate film having an average thickness shown in Table 2.
  • the back layer (film containing methacrylic acid ester-based resin as a main component) contains a vinylidene fluoride-based resin having a significantly different refractive index from the crosslinked (meth)acrylic acid ester-based resin particles. Transparency was insufficient due to the inclusion of The films of Comparative Examples 2-6 to 2-9 contained crosslinked (meth)acrylic acid ester-based resin particles, but their sizes were inappropriate, resulting in insufficient transparency.

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PCT/JP2022/028095 2021-08-06 2022-07-19 メタクリル酸エステル系樹脂を主成分とするフィルム Ceased WO2023013404A1 (ja)

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