WO2020218447A1 - Film stratifié - Google Patents

Film stratifié Download PDF

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Publication number
WO2020218447A1
WO2020218447A1 PCT/JP2020/017556 JP2020017556W WO2020218447A1 WO 2020218447 A1 WO2020218447 A1 WO 2020218447A1 JP 2020017556 W JP2020017556 W JP 2020017556W WO 2020218447 A1 WO2020218447 A1 WO 2020218447A1
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WIPO (PCT)
Prior art keywords
acrylic resin
mass
film
laminated film
acrylic
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PCT/JP2020/017556
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English (en)
Japanese (ja)
Inventor
峻 ▲高▼輪
直人 福原
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株式会社クラレ
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Priority to JP2021516215A priority Critical patent/JP7362729B2/ja
Publication of WO2020218447A1 publication Critical patent/WO2020218447A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

  • the present invention relates to a laminated film containing an acrylic resin film and a layer made of a metal and / or a metal oxide.
  • Patent Document 1 proposes a metal-like decorative film in which an acrylic resin film is provided on the surface of a film in which a metal layer is formed on a polyester-based polymer compound.
  • Acrylic resin has excellent optical properties such as transparency and weather resistance, and its molded body has a beautiful appearance. Therefore, it is attracting attention as a base material for metallic decorative films, such as lighting equipment and signboards. It is used in various applications such as display members, optical members such as display parts, interior members, building members, electronic / electrical members, and medical members. However, when a rubber component is added to improve workability, whitening and clouding occur due to heating and stretching, so that there is a problem that the transparency, which is a characteristic of acrylic, is lowered and the appearance quality is impaired.
  • the present invention has been made in view of the above background, and an object of the present invention is to provide a laminated film suitable for a metallic decorative film whose appearance quality is not impaired even after heat molding. is there.
  • the value of Mw (A) / Mw (b1) is 0.5 to 2.3.
  • the acrylic block copolymer (B) is a diblock containing 20 to 80% by mass of the methacrylic acid ester polymer block (b1) and 80 to 20% by mass of the acrylic acid ester polymer block (b2).
  • the acrylic resin film contains 60 to 99% by mass of the methacrylic polymer (A) and 1 to 40% by mass of the acrylic block copolymer (B).
  • the laminated film according to any one of.
  • the laminated film of the present invention does not impair the appearance quality even after heat molding. Taking advantage of this excellent feature, it can be suitably used for decorative applications and the like where designability is required.
  • the numerical values specified in the present specification indicate values obtained when measured by the method described in Examples described later. Further, the numerical values "A to B" specified in the present specification indicate a range that is larger than the numerical values A and A and satisfies the values smaller than the numerical values B and B. Further, the “film” is not limited to the thickness and the like, but also includes the “sheet” defined in JIS.
  • the acrylic resin film constituting the laminated film of the present invention is a film composed of a (meth) acrylic resin composition containing a methacrylic polymer (A) and an acrylic block copolymer (B).
  • the methacrylic polymer (A) is not particularly limited as long as it is a polymer containing a (meth) acrylic acid ester.
  • examples of the methacrylic polymer (A) include a homopolymer of methyl methacrylate, a random copolymer consisting of a structural unit derived from a methacrylic acid ester and a structural unit derived from an acrylic acid ester, and a structural unit derived from methyl methacrylate. And a random copolymer containing a structural unit having a ring structure in the main chain.
  • Examples of the structural unit having a ring structure in the main chain include a lactone ring unit, a maleic anhydride unit, a glutaric anhydride unit, a glutarimide unit, an N-substituted maleimide unit, and a tetrahydropyran ring structure unit.
  • the heat resistance of the methacrylic polymer (A) is improved by containing a structural unit having a ring structure in the main chain.
  • the methacrylic polymer (A) preferably has a structural unit derived from methyl methacrylate in an amount of 80% by mass or more, more preferably 90% by mass or more. It is more preferably 95% by mass or more, further preferably 99% by mass or more, and particularly preferably 100% by mass. That is, the proportion of the structural unit derived from the monomer other than methyl methacrylate in the methacrylic polymer (A) is 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less. Yes, more preferably 1% by mass or less, and particularly preferably 0% by mass.
  • Examples of monomers other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and tert-acrylate.
  • Olefins conjugated dienes such as butadiene, isoprene, milsen; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene; acrylamide, methacrylicamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl Examples thereof include pyridine, vinyl ketone, vinyl chloride, vinylidene chloride and vinylidene fluoride.
  • the stereoregularity of the methacrylic polymer (A) is not particularly limited, and for example, one having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used.
  • the method for producing the methacrylic polymer (A) is not particularly limited, and a method according to a known method can be adopted.
  • a method of radically polymerizing the monomers constituting each polymer block is generally used.
  • examples of such a radical polymerization method include a method of polymerizing using an azo compound as a polymerization initiator and mercaptan as a chain transfer agent.
  • the methacrylic polymer (A) can be obtained, for example, by polymerizing one or more kinds of monomers containing 80% by mass or more of methyl methacrylate under suitable conditions in consideration of a desired weight average molecular weight. Be done.
  • methacrylic polymer (A) a commercially available product may be used, for example, "Parapet H1000B” (MFR: 22 g / 10 minutes (230 ° C., 37.3 N)), “Parapet GF” (MFR: 15 g / 10 minutes).
  • the acrylic resin film is an acrylic block copolymer (B) containing a methacrylic ester polymer block (b1) and an acrylic ester polymer block (b2) (hereinafter, simply referred to as a block copolymer (B)). Contains.
  • the bonding state of the methacrylic acid ester polymer block (b1) and the acrylic acid ester polymer block (b2) in the block copolymer (B) is not particularly limited, and for example, the diblock represented by (b1)-(b2).
  • n is an arbitrary integer.
  • diblock copolymers represented by (b1)-(b2) are preferable from the viewpoint of adhesion to metals and / or metal oxides and smoothness of the film.
  • other polymer blocks may be contained as long as the effects of the present invention are not lost.
  • the methacrylic acid ester polymer block (b1) has a structural unit derived from a methacrylic acid ester as a main structural unit.
  • the proportion of the structural unit derived from the methacrylic acid ester in the methacrylic acid ester polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass. % Or more, including the case where all structural units are derived from methacrylic acid ester.
  • methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate and methacrylic acid.
  • Amil isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2 methacrylic acid -Hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate and the like can be mentioned.
  • methacrylic acid such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate Alkyl esters are preferred, and methyl methacrylate is more preferred.
  • a methacrylic acid ester polymer block (b1) can be formed by polymerizing one of these methacrylic acid esters alone or in combination of two or more.
  • the methacrylic ester polymer block (b1) may contain a structural unit derived from a monomer other than the methacrylic ester, and the ratio thereof is preferably 20% by mass or less, more preferably from the viewpoint of transparency and heat resistance. Is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • Examples of the monomer other than the methacrylic acid ester include acrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylic acid, vinyl acetate, vinyl pyridine, and vinyl ketone. , Vinyl chloride, vinylidene chloride, vinylidene fluoride and the like, and these can be copolymerized with the above-mentioned methacrylic acid ester either individually or in combination of two or more.
  • the maximum weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) is preferably 5,000 to 150,000, more preferably 10,000 to 100,000, still more preferably 25,000 to. It is 80,000.
  • the weight average molecular weight of the methacrylic acid ester polymer block (b1) is Mw (b1).
  • a plurality of methacrylic acid ester polymer blocks (b1) are contained in the block copolymer (B) and the weight average molecular weights of the plurality of methacrylic acid ester polymer blocks (b1) are the same.
  • the weight average molecular weight of the methacrylic acid ester polymer block (b1) is the intermediate product and the final product (block copolymer weight) measured by sampling during and after the polymerization in the process of producing the block copolymer (B). It is a value calculated from the weight average molecular weight of the coalescence (B)).
  • Each weight average molecular weight is a standard polystyrene conversion value measured by GPC (gel permeation chromatography).
  • the ratio of the methacrylic acid ester polymer block (b1) in the block copolymer (B) is 100% by mass of the block copolymer (B) from the viewpoint of transparency, surface hardness, and appearance of the acrylic resin film.
  • the lower limit is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 43% by mass or more, particularly preferably 47% by mass or more, and the upper limit is preferably 80% by mass or less. It is more preferably 70% by mass or less, further preferably 65% by mass or less, and particularly preferably 60% by mass or less.
  • the acrylic acid ester polymer block (b2) constituting the block copolymer (B) has a structural unit derived from the acrylic acid ester as a main structural unit.
  • the proportion of the structural unit derived from the acrylic acid ester in the acrylic acid ester polymer block (b2) is preferably 50% by mass or more, more preferably 90% by mass or more, and includes a composition of 100% by mass.
  • acrylic acid ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylate.
  • Acrylic acid ester polymer block (b2) can be formed by polymerizing one of these acrylic acid esters alone or in combination of two or more. Of these, those polymerized with n-butyl acrylate alone are preferable from the viewpoint of cost and the like.
  • the acrylic acid ester polymer block (b2) may contain a structural unit derived from a monomer other than the acrylic acid ester, and the proportion thereof is preferably 50% by mass or less, more preferably 10% by mass or less. Including the case where all structural units are monomers derived from acrylic acid ester.
  • Examples of the monomer other than the acrylic acid ester include methacrylic acid ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylic acid, vinyl acetate, vinyl pyridine, and vinyl ketone. , Vinyl chloride, vinylidene chloride, vinylidene fluoride and the like, and one of these can be copolymerized with the above-mentioned acrylic acid ester alone or in combination of two or more.
  • the maximum weight average molecular weight Mw (b2) of the acrylic ester polymer block (b2) is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, still more preferably 20,000 to. It is 60,000. If Mw (b2) is small, the appearance tends to deteriorate. On the other hand, when Mw (b2) is large, the heat resistance of the film tends to decrease. When only one acrylic acid ester polymer block (b2) is contained in the block copolymer (B), the weight average molecular weight of the acrylic acid ester polymer block (b2) is Mw (b2).
  • the weight average molecular weight of the acrylic ester polymer block (b2) is an intermediate product and a final product (block) measured by sampling during and after the polymerization in the process of producing the block copolymer (B). It is a value calculated from the weight average molecular weight of the copolymer (B)).
  • Each weight average molecular weight is a standard polystyrene conversion value measured by GPC (gel permeation chromatography).
  • the upper limit of the ratio of the acrylic acid ester polymer block (b2) in the block copolymer (B) is preferably 100% by mass with respect to 100% by mass of the block copolymer (B) from the viewpoint of transparency, surface hardness and appearance. It is 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferable. Is 40% by mass or more.
  • the block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the end of the molecular chain, if necessary.
  • the method for producing the block copolymer (B) is not particularly limited, and a method according to a known method can be adopted.
  • a method of living-polymerizing the monomers constituting each polymer block is generally used.
  • Examples of such a living polymerization method include a method of anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid such as an alkali metal or an alkaline earth metal salt, and an organic alkali metal compound.
  • a method of anion polymerization using an organic aluminum compound as a polymerization initiator, a method of polymerizing using an organic rare earth metal complex as a polymerization initiator, and a method of polymerizing using an ⁇ -halogen ester compound as an initiator in the presence of a copper compound examples thereof include a method of radical polymerization in. Further, a method of polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent to produce a mixture containing the block copolymer (B) used in the present invention. Can also be mentioned.
  • the block copolymer (B) can be obtained with high purity, the molecular weight and composition ratio can be easily controlled, and it is economical, an organoalkali metal compound is used as a polymerization initiator.
  • a method of anionic polymerization in the presence of an organoaluminum compound is preferred.
  • the content of the methacrylic polymer (A) is preferably 60 to 99% by mass with respect to 100% by mass of the (meth) acrylic resin composition. It is more preferably 60 to 90% by mass, and further preferably 70 to 88% by mass.
  • the content of the block copolymer (B) is preferably 1 to 40% by mass, more preferably 10 to 40% by mass, and further, based on 100% by mass of the (meth) acrylic resin composition. It is preferably 12 to 30% by mass. If the content of the block copolymer (B) in the (meth) acrylic resin composition is more than 40% by mass, the surface hardness of the film tends to decrease. On the other hand, if the content of the block copolymer (B) is less than 1% by mass, the adhesion to the metal is low, and the appearance quality tends to be impaired after molding.
  • the ratio of the weight average molecular weight Mw (A), that is, the value of Mw (A) / Mw (b1) is preferably 0.5 to 2.3, more preferably 0.7 to 2.
  • additives such as antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, antioxidants, colorants, impact-resistant aids, etc. are added to the acrylic resin film as needed. May be good. From the viewpoint of the mechanical properties and surface hardness of the film, it is preferable not to add a large amount of foaming agent, filler, matting agent, light diffusing agent, softening agent or plasticizer.
  • the processing aid is a compound that exerts an effect on thickness accuracy and thinning when molding a (meth) acrylic resin composition.
  • the processing aid is usually polymer particles that can be produced by an emulsion polymerization method.
  • Such polymer particles may be single-layer particles composed of polymers having a single composition ratio and a single extreme viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or extreme viscosities. You may.
  • particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
  • the processing aid preferably has an ultimate viscosity of 3 to 6 dl / g. If the ultimate viscosity is too small, the effect of improving moldability is low. If the ultimate viscosity is too large, the melt fluidity of the (meth) acrylic resin composition tends to decrease.
  • Typical products of processing aids include, for example, Kaneka PA series (manufactured by Kaneka), Metabren P series (manufactured by Mitsubishi Rayon), Pararoid K series (manufactured by Dow Chemical), and the like.
  • the ultraviolet absorber is a compound that has the ability to absorb ultraviolet rays, and is said to have the function of mainly converting light energy into heat energy.
  • the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These can be used alone or in combination of two or more.
  • benzotriazoles and hydroxyphenyltriazines are preferable, and hydroxyphenyltriazines are particularly preferable, because they have a high ability to suppress resin deterioration when irradiated with ultraviolet rays and have high compatibility with the resin.
  • benzotriazoles examples include 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-yl) phenol] (manufactured by Adeca; trade name Adecastab).
  • LA-31 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329)
  • 2- (2H-benzo) Examples thereof include triazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234).
  • hydroxyphenyltriazines examples include 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-butyloxyphenyl) -1,3,5-triazine (manufactured by BASF; commercial products). Name chinubin 460), 2- ⁇ 2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl ⁇ -4,6-bis (2,4-dimethylphenyl)- Examples thereof include 1,3,5-triazine (manufactured by BASF; trade name TINUVIN405), TINUVIN479 and TINVUVIN1477 (all manufactured by BASF).
  • the method for preparing the (meth) acrylic resin composition constituting the acrylic resin film is not particularly limited, but in order to enhance the dispersibility of each component constituting the composition, for example, a method of melt-kneading and mixing is preferable. ..
  • the kneading operation can be performed using, for example, a known mixing or kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer.
  • a twin-screw extruder from the viewpoint of improving the kneadability and compatibility between the methacrylic polymer (A) and the block copolymer (B).
  • the shear rate during melt-kneading is preferably 10 to 1,000 / sec -1 .
  • the temperature at the time of mixing / kneading should be appropriately adjusted according to the melting temperature of the (meth) acrylic resin or the like to be used, and is usually preferably mixed at a temperature within the range of 110 to 300 ° C., preferably 180 to 300. It is recommended to mix at a temperature within the range of ° C.
  • the composition constituting the acrylic resin film can be obtained in any form such as pellets and powder.
  • block copolymer (B) is dissolved in a mixed solution of an acrylic monomer which is a monomer unit of the methacrylic polymer (A) and a solvent such as toluene, and the acrylic monomer is polymerized.
  • a (meth) acrylic resin composition used in the present invention containing the block copolymer (B) can also be prepared.
  • the acrylic resin film can be produced by using a known method such as a T-die method, an inflation method, a melt casting method, or a calendar method. From the viewpoint of obtaining an acrylic resin film with good surface smoothness and low haze, the melt-kneaded product is extruded from a T-die in a molten state, and both surfaces are brought into contact with a mirror roll surface or a mirror belt surface for molding. The method including is preferable. The rolls or belts used at this time are preferably made of metal.
  • the acrylic resin film When both sides of the melt-kneaded product extruded in this way are brought into contact with the mirror surface to form a film, it is preferable to sandwich the acrylic resin film with a mirror surface roll or a mirror surface belt and pressurize the film.
  • the pinching pressure by the mirror surface roll or the mirror surface belt is preferably high, and the linear pressure is preferably 10 N / mm or more, and more preferably 30 N / mm or more.
  • an extruder type melt extruder equipped with a single-screw or twin-screw extrusion screw can be used.
  • the melt extrusion temperature is preferably 200 ° C. or higher, more preferably 220 ° C. or higher. Further, the temperature is preferably 300 ° C. or lower, more preferably 270 ° C. or lower. Further, from the viewpoint of suppressing coloration, it is preferable to use a vent to perform melt extrusion under reduced pressure or melt extrusion under a nitrogen stream.
  • the surface temperature of the mirror roll or mirror belt sandwiching the acrylic resin film is preferably 60 ° C. or higher. , 70 ° C. or higher is more preferable. Further, the temperature is preferably 130 ° C. or lower, more preferably 100 ° C. or lower. When the surface temperature of the mirror surface roll or the mirror surface belt sandwiching the acrylic resin film is less than 60 ° C., the surface smoothness of the obtained acrylic resin film decreases, and the haze tends to increase.
  • the acrylic resin film and the mirror roll or the mirror belt are in close contact with each other too much, so that the surface of the acrylic resin film tends to be rough when the film is peeled off from the mirror roll or the mirror belt.
  • the appearance of the acrylic resin film tends to be spoiled due to wrinkles.
  • the laminated film of the present invention is provided with a layer made of a metal and / or a metal oxide on at least one surface of the acrylic resin film described above. Further, the laminated film of the present invention is formed by providing a base material layer made of a thermoplastic resin, a wooden base material, a non-wood fiber such as kenaf, on one side or both sides of the acrylic resin film described above. There may be.
  • metal oxides include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, and titanium oxide.
  • Iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide and the like can be used.
  • metals and metal oxides may be used alone or as a mixture of two or more kinds.
  • indium is preferable because it has excellent designability and its luster is not easily lost even when the laminate is deep-drawn.
  • aluminum has excellent designability and can be obtained industrially at low cost, and is particularly preferable when a particularly deep drawing is not required.
  • the vacuum vapor deposition method is usually used as a method for providing these metal and / or metal oxide layers, but a method such as ion plating, sputtering, or CVD (Chemical Vapor Deposition) may also be used. ..
  • the thickness of the thin-film film made of metal and / or metal oxide is generally about 5 to 100 nm. When deep drawing is performed after layer formation, 5 to 250 nm is preferable.
  • the 20-degree mirror surface gloss on the acrylic resin film side does not decrease by 300 Gloss Unit (GU) or more, preferably 200 GU. It is a laminated film that does not decrease more than that, more preferably does not decrease by 100 GU or more, and more preferably 20 degrees mirror surface gloss increases by 70 GU or more.
  • GU Gloss Unit
  • the laminated film of the present invention has a 20-degree mirror glossiness of 1000 GU or more, preferably 1100 GU or more, and more preferably 1200 GU or more on the acrylic resin film side before heating under the above conditions.
  • the laminated film of the present invention has an acrylic acid ester polymer block (b2) of a block copolymer (B) in a cross section parallel to the extrusion direction (MD direction) and parallel to the thickness direction (hereinafter referred to as "MD cross section"). ) Preferably form a spherical phase having a diameter of 10 to 100 nm.
  • the acrylic ester polymer block (b2) forms a columnar phase having a major axis of 1 ⁇ m or more, it tends to show a fluctuating appearance and lose metallic luster due to the relaxed flow between the phases during heat molding. It becomes.
  • the cross section of the acrylic resin film or flat extruded product obtained by melt-extruding the (meth) acrylic resin composition is dyed with phosphotensive acid, and a transmission electron microscope (TEM) is used. It can be confirmed by observing with.
  • the ratio of the acrylic acid ester polymer block (b2) is preferably 5 to 15% by mass, preferably 8 to 15% by mass, based on the (meth) acrylic resin composition. More preferably, it is 12% by mass.
  • the upper limit of the thickness of the acrylic resin film is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, further preferably 200 ⁇ m or less, and the lower limit is preferably 40 ⁇ m or more, more preferably 50 ⁇ m or more. .. If it is thicker than 500 ⁇ m, secondary processability such as laminateability, handleability, cutability and punching property will deteriorate, making it difficult to use as an acrylic resin film, and increasing the unit price per unit area, making it economical. It is not preferable because it is disadvantageous to.
  • the acrylic resin film may be stretched. By the stretching treatment, the mechanical strength is increased, and a film that is hard to crack can be obtained.
  • the stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tuber stretching method, and a rolling method.
  • the lower limit of the stretching temperature is 5 ° C. higher than the glass transition temperature of the (meth) acrylic resin composition from the viewpoint that the acrylic resin film can be uniformly stretched and a high strength acrylic resin film can be obtained, and the upper limit is ( Meta)
  • the temperature is 40 ° C. higher than the glass transition temperature of the acrylic resin composition. If the stretching temperature is too low, the molded product is likely to break during stretching.
  • the stretching temperature is too high, the effect of the stretching treatment is not sufficiently exhibited and the strength of the molded product is difficult to increase. Stretching is usually performed at 100-5,000% / min. If the stretching speed is low, the strength is unlikely to increase, and the productivity also decreases. Further, if the stretching speed is high, the molded body may be broken and uniform stretching may be difficult. It is preferable to perform heat fixation after stretching. By heat fixing, a film with less heat shrinkage can be obtained. The thickness of the film obtained by stretching is preferably 10 to 200 ⁇ m.
  • the acrylic resin film may be colored.
  • the coloring method include a method of adding a colorant to the (meth) acrylic resin composition; a method of immersing the acrylic resin film in a liquid in which a dye is dispersed, but the method is not particularly limited thereto. Absent.
  • the surface of at least one surface of the acrylic resin film is preferably B or harder than the pencil hardness measured by the JIS-A method of JIS K6253, and more preferably HB or harder than that. Since an acrylic resin film having a hard surface is not easily scratched, it is preferably used as a film having both decorativeness and protection on the surface of a molded product that requires design.
  • the laminated film of the present invention may be further laminated with another thermoplastic resin, if necessary.
  • Other thermoplastic resins include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resin, and acrylonitrile-butadiene-styrene copolymer (ABS). ) Resin, ethylene vinyl alcohol resin, polyvinyl butyral resin, polyvinyl acetal resin, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, acrylic-based thermoplastic elastomer and the like.
  • the layer made of another thermoplastic resin can function as an adhesive layer and an adhesive layer. It is preferably in contact with the metal and / or metal oxide layer.
  • the method of laminating the thermoplastic resin layer is not particularly limited.
  • Acrylic resin film and other thermoplastic resin film are prepared separately and laminated continuously between heating rolls, thermocompression bonding with a press, pressure air or vacuum forming at the same time.
  • Method, laminating method with an adhesive layer intervening (wet lamination);
  • a method of laminating another thermoplastic resin melt-extruded from a T-die using an acrylic resin film as a base material (3) Examples thereof include a method of coextruding the (meth) acrylic resin composition and the thermoplastic resin.
  • a surface treatment such as a corona treatment may be applied to the bonded surface side of the acrylic resin film or the thermoplastic resin film before laminating.
  • the acrylic resin film used in the present invention may be used for the inner layer or a part thereof, or may be used for the outermost layer.
  • the other resin used for laminating a transparent resin is preferable from the viewpoint of film design.
  • the outermost layer preferably has high surface hardness and weather resistance, and for example, a film made of (meth) acrylic resin is preferable.
  • the laminated film of the present invention covers the surface of an adherend such as another thermoplastic resin, thermosetting resin, wood base material or non-wood fiber base material, thereby covering the surface of the molded product. Can be decorated.
  • an adherend such as another thermoplastic resin, thermosetting resin, wood base material or non-wood fiber base material
  • thermoplastic resins used in the molded product include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resin, and acrylonitrile-butadiene.
  • -Serethane copolymer (ABS) resin ethylene vinyl alcohol resin, polyvinyl butyral resin, polyvinyl acetal resin, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, acrylic-based thermoplastic elastomer and the like can be mentioned.
  • thermosetting resins include epoxy resins, phenolic resins, and melamine resins.
  • the laminated film of the present invention may be provided on the surface of a base material made of a non-wood fiber such as a wooden base material or kenaf.
  • the method of coating the molded product with the laminated film of the present invention is not particularly limited.
  • the laminated film of the present invention is vacuum-formed, vacuum-formed, or compression-molded on the surface of another thermoplastic resin, thermosetting resin, wooden base material, or non-wood fiber base material under heating to form a molded product.
  • the molded product in which the laminated film of the present invention is provided on the outermost surface layer of the adherend is excellent in surface smoothness, surface hardness, etc., and can obtain gloss like a metal.
  • the method generally called the injection molding simultaneous bonding method is preferable.
  • the laminated film of the present invention is inserted between male and female molds for injection molding, and a molten thermoplastic resin is injected into the mold from one side of the film to form an adherend. At the same time as forming, the film is attached to the adherend.
  • the film to be inserted into the mold may be a flat one, or may be preformed by vacuum forming, compressed air forming, or the like and shaped into an uneven shape.
  • the premolding of the film may be performed by a separate molding machine, or may be premolded in the mold of the injection molding machine used in the injection molding simultaneous bonding method.
  • the latter method that is, a method of pre-molding a film and then injecting a molten resin onto one side of the film, is called an insert molding method.
  • the (meth) acrylic resin composition was melt-extruded at an extrusion temperature of 260 ° C. and a shear rate of 122 sec -1 using a capillograph (capillograph 1C manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a slit die having a width of 7 mm and a thickness of 1 mm.
  • a flat extruded product was prepared.
  • a cross-sectional section of the MD cross section was prepared for such a flat extruded product using an ultramicrotome (Leica EM UC7rt manufactured by JEOL Ltd.).
  • a cross section is stained with a 10% aqueous solution of phosphotungstate, and a transmission electron detector (STEM) (manufactured by JEOL Ltd., main body: JSM-7600F, detector: SM-74240RTED) of a Schottky field emission scanning electron microscope is used.
  • STEM transmission electron detector
  • the shape (morphology) of the stained part was observed using. It is considered that the acrylic acid ester portion in the cross-sectional section is stained with the phosphotungstic acid aqueous solution.
  • the compound was dried and purified by a conventional method and degassed with nitrogen.
  • the transfer and supply of the compound was carried out in a nitrogen atmosphere.
  • Synthesis Example 1 [Synthesis of methacrylic polymer (A-1)] Polymerization initiator (2,2'-azobis (2-methylpropionitrile), hydrogen extraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.1 on a monomer consisting of 100 parts by mass of methyl methacrylate A raw material solution was obtained by adding 0.21 part by mass and 0.21 part by mass of a chain transfer agent (n-octyl mercaptan) and dissolving the mixture. 100 parts by mass of ion-exchanged water, 0.03 part by mass of sodium sulfate and 0.45 parts by mass of suspension dispersant were mixed to obtain a mixed solution.
  • a chain transfer agent n-octyl mercaptan
  • Synthesis Example 2 [Synthesis of methacrylic polymer (A-2)]
  • the monomer was changed from 100 parts by mass of methyl methacrylate to 99.3 parts by mass of methyl methacrylate and 0.7 parts by mass of methyl acrylate, and the amount of the chain transfer agent was changed from 0.21 parts by mass to 0.
  • a methacrylic polymer (A-2) having a weight average molecular weight Mw (A) of 80,000 was produced in the same manner as in Synthesis Example 1 except that the content was changed to .24 parts by mass.
  • the obtained block copolymer had a diblock structure of (b1)-(b2), and the composition ratio of (b1)-(b2) was 50% by mass-50% by mass.
  • the weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) was 60,000
  • the weight average molecular weight Mw of the acrylic acid ester polymer block (b2). (B2) was 60,000.
  • the weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) is 80,000
  • the Mw (b2) was 80,000.
  • the weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) is 45,000
  • the weight average molecular weight of the acrylic acid ester polymer block (b2) was 45,000.
  • Synthesis Example 6 [Synthesis of block copolymer (B-4)] The molecular weight is adjusted by adjusting the polymerization initiator under the same solvent and catalytic conditions as in Synthesis Example 3, the amount of the polymerizable monomer is adjusted, and it is composed of methyl methacrylate (b1-1) -n-acrylic acid.
  • the composition ratio of (b1-1)-(b2)-(b1-2) was 15% by mass-50% by mass-35% by mass.
  • the weight average molecular weight Mw (b2) of the acrylic acid ester polymer block (b2) was 30,000.
  • Example 1 80 parts by mass of methacrylic polymer (A-1) and 20 parts by mass of block copolymer (B-1) are melt-kneaded at 260 ° C. using a twin-screw extruder, extruded into strands, and cut with a pelletizer. By doing so, pellets of the (meth) acrylic resin composition were produced. The obtained pellets were melt-extruded at an extrusion temperature of 260 ° C. and a shear rate of 122 sec -1 using a capillograph equipped with a slit die having a width of 7 mm and a thickness of 1 mm to prepare a flat extruded product. As shown in FIG.
  • the morphology of the dyed portion in the MD cross section of the flat extruded product was spherical.
  • the pellets of the obtained (meth) acrylic resin composition are melted by a 65 mm ⁇ vent type single-screw extruder, extruded from a die having a width of 620 mm at an extrusion temperature of 260 ° C. and a discharge rate of 25 kg / h, and a metal having a surface temperature of 70 ° C. It was sandwiched between a roll and a metal roll having a surface temperature of 90 ° C. and taken up at a rate of 6.7 m / min to produce a transparent film having a thickness of 75 ⁇ m.
  • the obtained base film was subjected to corona treatment under the condition of 14 kV using a corona treatment device (Corona Cassner ASA-4, manufactured by Shinko Denki Keiso Co., Ltd.), and then a vacuum vapor deposition device (Synchron Co., Ltd., vacuum vapor deposition).
  • An indium layer having a thickness of 50 nm was formed by vacuum vapor deposition using an apparatus BMC-850CS (resistive heating method) to obtain a laminated film which is a metallic decorative film.
  • a basket heater alumina 92%) was used for resistance heating, and an indium having a purity of 99.99% and a particle size of 1 mm was used.
  • the vapor deposition conditions were a vacuum degree of 8 ⁇ 10 -3 Pa and a speed of 10 ⁇ / sec.
  • the evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a metallic luster equivalent to that of plating.
  • the obtained laminated film was heated in an oven set at 130 ° C. for 30 seconds and taken out of the oven.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had the same metallic luster as plating as before heating.
  • Example 2 A flat extruded product and an acrylic resin film were prepared in the same manner as in Example 1 except according to the formulation shown in Table 1. As shown in FIG. 2, the morphology of the dyed portion in the MD cross section of the flat extruded product was spherical.
  • Example 1 Using the obtained acrylic resin film, a laminated film was obtained in the same manner as in Example 1. The evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a metallic luster equivalent to that of plating.
  • the obtained laminated film was heated in the same manner as in Example 1.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had the same metallic luster as plating as before heating.
  • Example 3 A flat extruded product and an acrylic resin film were prepared in the same manner as in Example 1 except according to the formulation shown in Table 1. As shown in FIG. 3, the morphology of the dyed portion in the MD cross section of the flat extruded product was spherical.
  • Example 1 Using the obtained acrylic resin film, a laminated film was obtained in the same manner as in Example 1. The evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a metallic luster equivalent to that of plating.
  • the obtained laminated film was heated in the same manner as in Example 1.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had the same metallic luster as plating as before heating.
  • Example 4 A flat extruded product and an acrylic resin film were prepared in the same manner as in Example 1 except according to the formulation shown in Table 1. The morphology of the dyed portion in the MD cross section of the flat extruded product was spherical.
  • Example 1 Using the obtained acrylic resin film, a laminated film was obtained in the same manner as in Example 1. The evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a metallic luster equivalent to that of plating.
  • the obtained laminated film was heated in the same manner as in Example 1.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had the same metallic luster as plating as before heating.
  • Example 1 A flat extruded product and an acrylic resin film were prepared in the same manner as in Example 1 except according to the formulation shown in Table 1. As shown in FIG. 4, the morphology of the dyed portion in the MD cross section of the flat extruded product was columnar.
  • Example 1 Using the obtained acrylic resin film, a laminated film was obtained in the same manner as in Example 1. The evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a metallic luster equivalent to that of plating.
  • the obtained laminated film was heated in the same manner as in Example 1.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had a lot of fluctuating texture and lost the metallic luster equivalent to plating.
  • Example 2 Pellets of the (meth) acrylic resin composition and the flat extruded product were produced in the same manner as in Example 1 except according to the formulation shown in Table 1.
  • the morphology of the dyed part in the MD cross section of the flat extruded product was columnar.
  • the pellets of the obtained (meth) acrylic resin composition are melted by a single-screw extruder with a ⁇ 20 mm vent, extruded from a die having a width of 150 mm at an extrusion temperature of 260 ° C. and a discharge rate of 3 kg / h, and a metal having a surface temperature of 80 ° C.
  • the film was brought into close contact with a cast roll and cooled, and the film was taken up at a rate of 2 m / min to produce a transparent film having a thickness of 125 ⁇ m.
  • Example 1 Using the obtained acrylic resin film, a laminated film was obtained in the same manner as in Example 1. The evaluation results of the laminated film are shown in Table 1. When the obtained laminated film was observed from the acrylic resin film side, it had a flickering texture because it was not sandwiched between the metal rolls when the acrylic resin film was produced, and the metallic luster was low.
  • the obtained laminated film was heated in the same manner as in Example 1.
  • Table 1 shows the evaluation results of the laminated film after heating. When the obtained laminated film after heating was observed from the acrylic resin film side, it had a lot of flickering texture and a low metallic luster.
  • the block copolymer has a structure of (b1-1) made of methyl methacrylate (b2) made of n-butyl acrylate (b1-2) made of methyl methacrylate (b1).
  • a triblock copolymer having a composition ratio of -1)-(b2)-(b1-2) of 6% by mass-50% by mass-42% by mass may be used.
  • the laminated film of the present invention and the molded product using the same have excellent metallic luster and good appearance quality even after heat molding, and take advantage of the features that require designability, that is, an advertising tower. It can be suitably used for signboard parts such as stand signboards; interior parts such as furniture, pendants, mirrors; and transport machine-related parts such as automobile interior members, emblems, bumpers and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film stratifié approprié en tant que film décoratif à teinte métallique dont la qualité d'apparence ne se détériore pas même après thermoformage. Le film stratifié selon l'invention comprend une couche constituée d'un métal et/ou d'un oxyde métallique et un film de résine acrylique contenant un polymère méthacrylique (A) et un copolymère séquencé acrylique (B), la valeur de Mw(A)/Mw(b1), qui est le rapport du poids moléculaire moyen en poids Mw(A) du polymère méthacrylique (A) au poids moléculaire moyen en poids le plus élevé Mw(b1) parmi les blocs polymères d'ester d'acide méthacrylique (b1) du copolymère séquencé acrylique (B), est de 0,5 à 2,3, et le brillant spéculaire à 20° du côté film de résine acrylique du film stratifié ne diminue pas de 300 GU ou plus lorsque le film de résine acrylique est chauffé pendant 30 secondes à une température de 20 °C supérieure à son point de ramollissement.
PCT/JP2020/017556 2019-04-24 2020-04-23 Film stratifié WO2020218447A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015076398A1 (fr) * 2013-11-25 2015-05-28 株式会社クラレ Film de résine acrylique
WO2018021449A1 (fr) * 2016-07-29 2018-02-01 株式会社クラレ Composition de résine de méthacrylate, son procédé de production, corps moulé, film, film stratifié et corps moulé stratifié

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015076398A1 (fr) * 2013-11-25 2015-05-28 株式会社クラレ Film de résine acrylique
WO2018021449A1 (fr) * 2016-07-29 2018-02-01 株式会社クラレ Composition de résine de méthacrylate, son procédé de production, corps moulé, film, film stratifié et corps moulé stratifié

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