Classifications

• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • 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
• • 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
• • 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
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating

Definitions

• the present invention relates to a laminated base film for vapor deposition, a metal-like sheet, and the like. More specifically, the present invention provides a laminated substrate film for vapor deposition, which is used to provide a vapor deposition layer on a layer made of a methacrylic copolymer, which has high heat resistance, low water absorption, high mechanical strength, and high wetting tension.
• the present invention relates to a vapor-deposited laminated film having excellent adhesion to the vapor-deposited layer, which comprises the laminated base film for vapor-deposition and a vapor-deposited layer.
• Methacrylic resin has excellent transparency, scratch resistance, and weather resistance.
• Laminated films using methacrylic resin as the surface layer material are used in applications that require high appearance, surface strength, durability, etc., such as walls of houses, furniture, home appliances, electronic devices, and display devices.
• a laminated film further provided with a metal vapor-deposited layer for the purpose of imparting functions such as design, scratch resistance, antistatic properties, electrical conductivity, and gas barrier properties.
• Patent Document 1 discloses an acrylic resin using a heat-resistant acrylic resin as a base material obtained by copolymerizing methyl methacrylate units, maleic anhydride units, and aromatic vinyl compound units. We are proposing a type resin laminate. Copolymerization of maleic anhydride units improves adhesion, but the resulting laminate is brittle.
• Patent Document 2 discloses a resin containing a copolymer of a styrene monomer and an alnicel cyanide on at least one surface of a thermoplastic resin layer (A) made of a resin composition (a) containing a methacrylic resin.
• Patent Document 3 proposes a base film obtained by forming a glutarimide acrylic resin having a glutarimide structural unit and a methyl methacrylate structural unit to obtain a film, and then biaxially stretching the film. Although adhesion is improved by including the glutarimide structural unit, water absorption is high and dimensional stability is poor. As described above, there is room for consideration of methods for improving adhesion with the vapor deposited layer and achieving a high level of balance between heat resistance, flexibility, and dimensional stability.
• the object of the present invention is to provide a laminated base film that has high heat resistance, flexibility, and dimensional stability, and that is used for providing a vapor deposition layer on at least one surface thereof, and a laminated base film that has high heat resistance, flexibility, and dimensional stability.
• An object of the present invention is to provide a vapor-deposited laminated film comprising a layer.
• R 1 is each independently a hydrogen atom or a methyl group
• R 2 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic It is an organic group containing a ring and having 6 to 15 carbon atoms.
• a vapor-deposited laminated film characterized in that a vapor-deposited layer is provided on either side of the film.
• a metal-like sheet comprising a thermoplastic resin sheet laminated on the vapor-deposited layer side surface of the vapor-deposited laminated film according to [7] or [8].
• the metal-like sheet according to [9] wherein the vapor deposition layer and the thermoplastic resin sheet are laminated via an adhesive layer.
• the metallic sheet according to [9] wherein the vapor deposited layer and the thermoplastic resin sheet are laminated by dry lamination.
• a metal-like molded product characterized in that the vapor-deposited layer side surface of the vapor-deposited laminated film according to [7] or [8] is bonded to a molded product.
• a metal-like molded product characterized in that the surface of the metal-like sheet according to [9] on which the thermoplastic resin sheet is laminated is bonded to a molded product.
• a metal-like molded product characterized in that the surface of the metal-like sheet described in [10] on which the thermoplastic resin sheet is laminated is bonded to a molded product.
• a metal-like molded product characterized in that the surface of the metal-like sheet according to [11] on which the thermoplastic resin sheet is laminated is bonded to a molded product.
• the laminated substrate film for vapor deposition of the present invention has high heat resistance, flexibility, and dimensional stability.
• the laminated substrate film for vapor deposition of the present invention can be suitably used in vapor deposition processes.
• the laminated substrate film for vapor deposition of the present invention has high adhesion with the vapor deposition layer, and can be provided with high performance functions in various uses.
• Metal-like sheets and metal-like molded products, which are an embodiment of the laminated substrate film for vapor deposition of the present invention, have an excellent metallic appearance and are therefore suitable for use in interior and exterior materials for vehicles, interior and exterior materials for electronic devices, and building materials. It is useful in the field of architecture and construction materials such as sizing and resin sashes, and as housing for home appliances.
• the laminated substrate film for vapor deposition of the present invention is a film used for vapor deposition.
• Vapor deposition includes physical vapor deposition and chemical vapor deposition.
• the laminated substrate film for vapor deposition of the present invention may be produced by a conventionally known physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method. Among these, the vacuum evaporation method is preferably used.
• the methacrylic resin composition (I) used in the laminated base film for vapor deposition of the present invention contains a methacrylic copolymer (a).
• the methacrylic resin composition (I) contains a methacrylic copolymer (a) and a methacrylic resin.
• the content of the methacrylic copolymer (a) in the methacrylic resin composition (I) is preferably 51% by mass or more, more preferably 65% by mass or more, and 80% by mass or more. is more preferable, particularly preferably 90% by mass or more, and may be composed only of the methacrylic copolymer (a).
• the methacrylic copolymer (a) contains 5 to 73% by mass of methyl methacrylate units, 25 to 70% by mass of structural units (r), 1 to 48% by mass of ⁇ -methylstyrene units, and styrene. It contains 1 to 48% by mass of at least one selected from the group consisting of maleic anhydride units and maleic anhydride units, and 0 to 20% by mass of unsubstituted or N-substituted maleimide units.
• the methacrylic copolymer (a) also includes those containing 0% by mass of unsubstituted or N-substituted maleimide units, ie, containing no unsubstituted or N-substituted maleimide units.
• the methacrylic copolymer (a) used in the present invention may further contain other vinyl monomer units copolymerizable with methyl methacrylate.
• the structural unit in a polymer means a repeating unit constituting the polymer or a unit obtained by derivatizing at least a portion of the repeating unit (for example, an unsubstituted or N-substituted glutarimide unit). do.
• the term "structural unit" may be used to collectively refer to methyl methacrylate units, structural units (r), ⁇ -methylstyrene units, styrene units, and other vinyl monomer units. be.
• the proportion of methyl methacrylate units is 5 to 73% by mass, preferably 6 to 70% by mass, and 6 to 60% by mass based on the total structural units. is more preferable, and even more preferably 6 to 50% by mass. From the viewpoint of transparency and heat decomposition resistance of the obtained methacrylic copolymer, it is preferable that the proportion of methyl methacrylate units is within the above range.
• the proportion of ⁇ -methylstyrene units is 1 to 48% by mass, preferably 3 to 40% by mass, and 5 to 35% by mass based on the total structural units. % is more preferable, and 7 to 30% by mass is even more preferable.
• the proportion of ⁇ -methylstyrene units is preferably within the above range from the viewpoint of suppressing the inhibition of the glutarimidation reaction due to oxidation and the dimensional stability of the laminated base film.
• the proportion of styrene units or maleic anhydride units is 1 to 48% by mass, preferably 3 to 40% by mass, based on the total structural units. It is more preferably 35% by mass, and even more preferably 7% to 30% by mass.
• the proportion of styrene units is within the above range from the viewpoint of suppressing this, the appearance of the laminated base film, and the like.
• the proportion of maleic anhydride units is within the above range.
• the total proportion of ⁇ -methylstyrene units and styrene units is preferably 2 to 40% by mass, and 5 to 35% by mass based on the total structural units. %, and even more preferably 10 to 30% by mass.
• the total ratio of ⁇ -methylstyrene units and styrene units is within the above range, it is difficult to inhibit the glutarimidation reaction due to intramolecular cyclization of two adjacent structural units derived from (meth)acrylic acid, which will be described later.
• the proportion of ⁇ -methylstyrene units is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, based on the total proportion of ⁇ -methylstyrene units and styrene units, More preferably, it is 40 to 85% by mass.
• the proportion of ⁇ -methylstyrene units is within the above range, the methacrylic copolymer used in the present invention has an excellent balance between heat resistance and low water absorption, and the resulting film has good dimensional stability.
• the structural unit (r) is a structural unit having a ring structure in its main chain selected from the group consisting of N-substituted or unsubstituted glutarimide units.
• the N-substituted or unsubstituted glutarimide unit is a unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure.
• Examples of the unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure include a structural unit represented by formula (I).
• R 1 is each independently a hydrogen atom or a methyl group, and preferably both R 1 are methyl groups.
• R 2 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms containing an aromatic ring, preferably a methyl group or an n-butyl group. , cyclohexyl group or benzyl group, more preferably methyl group, n-butyl group or cyclohexyl group, most preferably methyl group.
• the structural unit (r) can be formed, for example, by an imide cyclization reaction in which an imidizing agent is added to a precursor polymer in an extruder, kneaded, and reacted.
• the structural unit represented by formula (I) is formed by reacting the corresponding acid anhydride (IIa) with an imidizing agent represented by R 2 NH 2 as shown in scheme (i), for example.
• it may be produced by an intramolecular cyclization reaction of a copolymer having a partial structure of formula (III). It is preferable to heat the structural unit represented by formula (III) to convert it into the structural unit represented by formula (I) by an intramolecular cyclization reaction.
• the N-substituted or unsubstituted glutarimide unit can be prepared by the method described in WO2005/10838A1, JP2010-254742A, JP2008-273140A, JP2008-274187A, etc.
• Ammonia, methylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine are added to two matching structural units derived from methyl methacrylate or glutaric anhydride units.
• Amines containing aliphatic hydrocarbon groups such as aniline, toluidine, trichloroaniline, amines containing aromatic hydrocarbon groups such as N-methylbenzylamine, and alicyclic hydrocarbon groups such as cyclohexylamine, N-methylcyclohexylamine, etc. It can be obtained by reacting an imidizing agent such as amine, urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea. Among these, primary amines are essential, and secondary amines may be used in combination, with methylamine being preferred as the primary amine.
• a part of the methyl methacrylate unit may be hydrolyzed to become a carboxyl group, and this carboxyl group is converted to the original methyl methacrylate unit by the esterification reaction treated with an esterification agent. It is preferable to return it.
• the esterifying agent is not particularly limited as long as it can exhibit the effects of the present application, but dimethyl carbonate and the like can be suitably used.
• tertiary amines such as trimethylamine, triethylamine, and tributylamine can also be used as a catalyst.
• the proportion of the structural unit (r) is 25 to 70% by mass, preferably 30 to 68% by mass, and 35 to 65% by mass based on the total structural units. % is more preferable, and 40 to 60% by mass is even more preferable.
• the structural unit (r ) is preferably within the above range.
• the methacrylic copolymer (a) according to the present invention may contain an N-substituted or unsubstituted maleimide unit in addition to the structural unit (r) and the like.
• the N-substituted or unsubstituted maleimide unit is a unit having an N-substituted or unsubstituted 2,5-pyrrolidinedione structure.
• Examples of the unit having an N-substituted or unsubstituted 2,5-pyrrolidinedione structure include a structural unit represented by formula (VI).
• R 10 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms containing an aromatic ring.
• the structural unit represented by formula (VI) can be obtained by a method of polymerizing a monomer mixture containing a monomer represented by formula (VI), or a reaction product obtained by polymerizing a monomer mixture containing maleic anhydride. It can be incorporated into the methacrylic copolymer by a reaction between maleic anhydride contained therein and an imidizing agent represented by R 3 NH 2 .
• the N-substituted or unsubstituted maleimide unit can be prepared by the method described in Japanese Patent Publication No. 61-026924, Japanese Patent Publication No. 7-042332, Japanese Patent Application Publication No. 9-100322, Japanese Patent Application Publication No. 2001-329021, etc. is a maleic anhydride unit containing an aliphatic hydrocarbon group-containing amine such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine, or aniline.
• an aliphatic hydrocarbon group-containing amine such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine, or aniline.
• toluidine amines containing aromatic hydrocarbon groups such as trichloroaniline, amines containing alicyclic hydrocarbon groups such as cyclohexylamine, urea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-dipropyl It can be obtained by reacting with an imidizing agent such as urea. Among these, methylamine is preferred.
• the methacrylic copolymer (a) according to the present invention may contain a lactone ring unit as a structural unit derived from other vinyl monomer units.
• >C in the formula means that carbon atom C has two bonds.
• the ⁇ -valerolactonediyl structural unit includes a structural unit represented by formula (IV).
• R 6 , R 7 and R 8 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms, more preferably a hydrogen atom or It is an organic group having 1 to 5 carbon atoms.
• the organic group is not particularly limited as long as it has 1 to 20 carbon atoms, and includes, for example, a linear or branched alkyl group, a linear or branched aryl group, -OCOCH3 group, -CN group, etc. can be mentioned.
• the organic group may also contain a heteroatom such as an oxygen atom.
• R 6 and R 7 are preferably methyl groups, and R 8 is preferably a hydrogen atom.
• the lactone ring unit can be obtained by the methods described in JP-A-2000-230016, JP-A 2001-151814, JP-A 2002-120326, JP-A 2002-254544, JP-A 2005-146084, etc.
• it can be incorporated into a methacrylic copolymer by intramolecular cyclization of a structural unit derived from 2-(hydroxyalkyl)acrylate and a structural unit derived from methyl (meth)acrylate.
• the methacrylic copolymer (I) according to the present invention may contain a glutaric anhydride unit as a structural unit derived from other vinyl monomer units.
• the glutaric anhydride unit is a unit having a 2,6-dioxodihydropyrandiyl structure.
• Examples of the unit having a 2,6-dioxodihydropyrandiyl structure include a structural unit represented by formula (V).
• each R 9 is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group.
• a unit having a 2,6-dioxodihydropyrandiyl structure is derived from two adjacent (meth)acrylic acids by the method described in JP-A No. 2007-197703, JP-A No. 2010-96919, etc. It can be incorporated into methacrylic copolymers by intramolecular cyclization of structural units, intramolecular cyclization of structural units derived from (meth)acrylic acid and structural units derived from methyl (meth)acrylate, etc. can.
• the methacrylic copolymer (a) according to the present invention may contain other vinyl monomer units copolymerizable with the methyl methacrylate unit.
• Materials for the other vinyl monomer units can be selected as appropriate depending on the properties required of the methacrylic copolymer (a), including thermal stability, fluidity, chemical resistance, and optical properties. , if properties such as compatibility with other resins are particularly required, it may consist of acrylic acid ester monomer units, aromatic vinyl monomer units other than styrene and ⁇ -methylstyrene, and cyanide vinyl monomer units. At least one selected from the group is preferred.
• At least one selected from the group consisting of methyl acrylate, ethyl acrylate, and acrylonitrile is preferred from the viewpoint of easy availability.
• vinyl monomer units that can be copolymerized with methyl methacrylate include, for example, methacrylic acid amide units represented by the following formula (A), and 2-(hydroxyalkyl) units represented by the following formula (B). Also included are acrylic acid ester units and the like.
• R 3 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms containing an aromatic ring, preferably a hydrogen atom, A methyl group, n-butyl group, cyclohexyl group or benzyl group, more preferably a methyl group, n-butyl group or cyclohexyl group.
• R 4 and R 5 are each independently a hydrogen atom or a carbon number of 1 to 20 is an organic group, preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 5 carbon atoms.
• the organic group is an organic group having 1 to 20 carbon atoms. is not particularly limited, and includes, for example, a straight-chain or branched alkyl group, a straight-chain or branched aryl group, an -OCOCH3 group, a -CN group, etc.
• the organic group does not contain a heteroatom such as an oxygen atom.
• R4 is preferably a methyl group
• R5 is preferably a hydrogen atom.
• the proportion of other vinyl monomer units copolymerizable with methyl methacrylate units is preferably 0 to 20% by mass based on the total structural units. , more preferably 0 to 15% by weight, even more preferably 0 to 10% by weight.
• a methacrylic copolymer in which the proportion of other vinyl monomer units copolymerizable with methyl methacrylate units exceeds 20% by mass has reduced heat resistance and rigidity. Note that the proportion of each monomer unit can be measured by 1 H-NMR, 13 C-NMR, infrared spectroscopy, or the like.
• the methacrylic copolymer (a) according to the present invention has a weight average molecular weight (Mw) of preferably 40,000 to 250,000, more preferably 50,000 to 200,000, even more preferably 60,000 to 180,000.
• Mw weight average molecular weight
• the methacrylic resin composition (I) according to the present invention has excellent impact resistance.
• Mw is 250,000 or less, the fluidity of the methacrylic resin composition (I) related to the present invention improves, and the moldability improves.
• the weight average molecular weight (Mw) is a value calculated by converting a chromatogram measured by gel permeation chromatography into the molecular weight of standard polystyrene.
• the methacrylic copolymer (a) related to the present invention preferably has a glass transition temperature of 135°C or higher, more preferably 140°C, and even more preferably 145°C, and although the upper limit is not particularly limited, it is preferable. is 170°C.
• glass transition temperature (Tg) is measured in accordance with JIS K7121. Specifically, the DSC curve is measured under the conditions that the temperature is raised once to 250°C, then cooled to room temperature, and then the temperature is raised from room temperature to 250°C at a rate of 10°C/min. The midpoint obtained from the DSC curve measured during the second heating is determined as the "glass transition temperature (Tg)."
• the methacrylic copolymer (a) according to the present invention preferably has a melt flow rate (hereinafter referred to as "MFR") in the range of 1.0 to 30 g/10 minutes.
• MFR melt flow rate
• the lower limit of this MFR is more preferably 1.5 g/10 minutes or more, and even more preferably 2.0 g/10 minutes.
• the upper limit of the MFR is more preferably 25 g/10 minutes or less, and even more preferably 20 g/10 minutes or less.
• the MFR of the methacrylic copolymer (a) in this specification is a value measured using a melt indexer at a temperature of 230° C. and a load of 3.8 kg in accordance with JIS K7210.
• the saturated water absorption rate of the methacrylic copolymer (a) related to the present invention can be measured under the following conditions.
• the methacrylic copolymer is press-molded into a sheet with a thickness of 1.0 mm.
• a test piece of 50 mm x 50 mm is cut out from the center of the obtained press-formed sheet and dried in a dryer at 90° C. for 16 hours or more. After cooling the dried test piece to room temperature in a desiccator, the weight is measured to the nearest 0.1 mg, and this weight is defined as the initial weight W 0 .
• the saturated weight WS is defined as the saturated weight WS .
• the saturated water absorption rate can be calculated from equation (1).
• the saturated water absorption rate is preferably 3.0% by mass or less, more preferably 2.7% by mass or less, even more preferably 2.5% by mass or less.
• the methacrylic resin composition (I) according to the present invention may contain a methacrylic resin.
• the content of methacrylic resin is preferably 1 to 49% by weight, more preferably 5 to 40% by weight, and even more preferably 10 to 30% by weight.
• the methacrylic resin composition (I) according to the present invention has improved fluidity by containing a methacrylic resin.
• the above-mentioned methacrylic resin is a resin containing a structural unit derived from methacrylic acid ester.
• methacrylate esters include methyl methacrylate (hereinafter referred to as "MMA"), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, Alkyl methacrylates such as pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cyclomethacrylate Methacrylic acid cycloalkyl esters such as heptyl,
• MMA ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred. , MMA are most preferred.
• Methacrylic acid esters can be used alone or in combination of two or more.
• the content of structural units derived from methacrylic esters in the methacrylic resin is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and contains only structural units derived from methacrylic esters. Good too.
• the lower limit of the syndiotacticity (rr) of the methacrylic resin is preferably 56% or more, more preferably 57% or more, and even more preferably 58% or more.
• the methacrylic resin composition (I) according to the present invention has excellent heat resistance.
• syndiotacticity (rr) in triad representation is a chain of three consecutive structural units (triad, triad). ) has two chains (diad) that are both racemo (denoted as rr).
• a chain of structural units (diad) in a polymer molecule having the same configuration is called meso, and the opposite is called racemo, and is expressed as m and r, respectively.
• the syndiotacticity (rr) (%) of methacrylic resin is determined by measuring the 1 H-NMR spectrum in deuterated chloroform at 30°C, and based on the spectrum, when tetramethylsilane (TMS) is set to 0 ppm, The area (Y) of the 0.6 to 0.95 ppm region and the area (Z) of the 0.6 to 1.35 ppm region can be measured and calculated using the formula: (Y/Z) x 100. .
• the weight average molecular weight (hereinafter referred to as "Mw") of the methacrylic resin is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, and even more preferably 80,000 to 200,000.
• Mw weight average molecular weight
• the methacrylic resin composition (I) according to the present invention has excellent mechanical strength, and when it is 500,000 or less, it has good fluidity.
• the glass transition temperature of the methacrylic resin is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 110°C or higher. Since the glass transition temperature is 100° C. or higher, the methacrylic resin composition (I) according to the present invention has excellent heat resistance.
• the saturated water absorption rate of the methacrylic resin in water at 23°C is preferably 2.5% by mass or less, more preferably 2.3% by mass or less, and even more preferably 2.1% by mass or less.
• the saturated water absorption rate is 2.5% by mass or less, the methacrylic resin composition (I) according to the present invention has excellent moisture resistance, and warping of the laminate due to moisture absorption can be suppressed.
• the MFR of the methacrylic resin is preferably in the range of 1 to 20 g/10 minutes.
• the lower limit of the MFR is more preferably 1.2 g/10 minutes or more, and even more preferably 1.5 g/10 minutes or more.
• the upper limit of the MFR is more preferably 15 g/10 minutes or less, and even more preferably 10 g/10 minutes or less.
• the methacrylic resin composition (I) has a glass transition temperature of 135°C or higher, preferably 140°C, more preferably 145°C, and the upper limit is not particularly limited, but is preferably 170°C. Since the glass transition temperature is 135° C. or higher, the laminated base film for vapor deposition of the present invention has good dimensional stability.
• the methacrylic resin composition (I) according to the present invention preferably has a melt flow rate (hereinafter referred to as "MFR") in the range of 1.0 to 30 g/10 minutes.
• MFR melt flow rate
• the lower limit of this MFR is more preferably 1.5 g/10 minutes or more, and even more preferably 2.0 g/10 minutes.
• the upper limit of the MFR is more preferably 25 g/10 minutes or less, and even more preferably 20 g/10 minutes or less.
• the methacrylic resin composition (I) according to the present invention has a saturated water absorption rate of preferably 3.0% by mass or less, more preferably 2.5% by mass or less, and still more preferably 2.0% by mass or less. Since the saturated water absorption is 3.0% by mass or less, the laminated base film for vapor deposition of the present invention has good dimensional stability.
• the methacrylic resin composition (I) according to the present invention may contain a filler as necessary to the extent that the effects of the present invention are not impaired.
• a filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
• the amount of filler that can be contained in the resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.
• the methacrylic resin composition (I) according to the present invention may contain other polymers as long as the effects of the present invention are not impaired.
• Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; Methyl methacrylate-styrene copolymer; Polyester resin such as polyethylene terephthalate and polybutylene terephthalate; Nylon 6, Nylon 66, polyamide elastomer Polyamides such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylid
• Plastic elastomers examples include olefin rubbers such as IR, EPR, and EPDM.
• the amount of other polymers that may be contained in the methacrylic resin composition (I) according to the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass.
• the methacrylic resin composition (I) according to the present invention includes antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymers, etc., to the extent that the effects of the present invention are not impaired. It may contain additives such as processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes, matting agents, and phosphors.
• additives may be used alone or in combination of two or more. Further, these additives may be added to the polymerization reaction solution when producing the methacrylic copolymer (a), or may be added to the produced methacrylic copolymer (a). may be added when preparing the methacrylic resin composition (I) related to the present invention.
• the total amount of additives contained in the methacrylic resin composition (I) of the present invention is preferably 7% by mass based on the methacrylic resin composition (I) from the viewpoint of suppressing poor appearance of the molded article.
• the content is more preferably 5% by mass or less, further preferably 4% by mass or less.
• the method for preparing the methacrylic resin composition (I) of the present invention is not particularly limited.
• a method in which methacrylic copolymer (a) is produced by polymerizing a monomer mixture containing methyl methacrylate etc. in the presence of methacrylic resin or a method in which methacrylic copolymer (a) and methacrylic resin are melt-kneaded.
• methacrylic copolymer (a) and methacrylic resin are melt-kneaded.
• other polymers and additives may be mixed as necessary, or the methacrylic copolymer (a) may be mixed with other polymers and additives and then mixed with the methacrylic resin.
• the methacrylic resin may be mixed with other polymers and additives and then mixed with the methacrylic copolymer (a), or other methods may be used. Kneading can be carried out using a known mixing or kneading device, such as a kneader, extruder, mixing roll, Banbury mixer, or the like. Among these, a twin screw extruder is preferred.
• the resin composition (T) used in the laminated base film for vapor deposition of the present invention contains a thermoplastic resin (b).
• the thermoplastic resin (b) may be appropriately selected depending on the use of the metal-deposited laminated film obtained using the laminated substrate film for deposition of the present invention, and is not particularly limited. Examples include methacrylic resins, polyester resins, polycarbonate resins, polycyclic olefin resins, styrene resins such as ABS resins and AAS resins, polyvinylidene fluoride resins, and polycarbonate resins are preferred from the viewpoint of transparency and moldability.
• the polycarbonate resin is preferably obtained by copolymerizing a dihydric phenol such as bisphenol A and a carbonate precursor.
• the Mw of the polycarbonate resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 70,000.
• the laminated base film for vapor deposition of the present invention has excellent impact resistance and heat resistance, and when it is 100,000 or less, the polycarbonate resin has excellent moldability, and the present invention The productivity of laminated base film for vapor deposition can be increased.
• the above-mentioned polycarbonate resin may be a commercially available product, such as "SD Polycarbonate (registered trademark)” manufactured by Sumika Polycarbonate Co., Ltd., “Iupilon/Novarex (registered trademark)” manufactured by Mitsubishi Engineering Plastics Co., Ltd., or manufactured by Idemitsu Kosan Co., Ltd. "Taflon (registered trademark)", “Panlite (registered trademark)” manufactured by Teijin Kasei Ltd., etc. can be suitably used.
• the polycarbonate resin may contain other polymers as long as the effects of the present invention are not impaired.
• other polymers the same ones as the methacrylic resin and other polymers that may be contained in the above-mentioned methacrylic resin composition (I) can be used. These other polymers may be used alone or in combination.
• the content of these other polymers in the resin composition (T) is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
• the resin composition (T) may contain various additives as necessary.
• the same additives as those that may be contained in the above-mentioned methacrylic resin composition (I) can be used.
• the content of these additives can be set as appropriate within a range that does not impair the effects of the present invention.
• the content of antioxidant is 0.01 to 1 part by mass
• the content of ultraviolet absorber is 0.01 to 1 part by mass per 100 parts by mass.
• Content is 0.01 to 3 parts by mass
• light stabilizer content is 0.01 to 3 parts by mass
• lubricant content is 0.01 to 3 parts by mass
• dye/pigment content is 0.01 to 3 parts by mass. 3 parts by mass is preferred.
• the resin composition (T) used in the present invention preferably has a glass transition temperature of 120 to 160°C. Further, the resin composition (T) preferably has a glass transition temperature comparable to that of the methacrylic resin composition (I). Specifically, the absolute value of the difference between the glass transition temperature of the resin composition (T) and the glass transition temperature of the methacrylic resin composition (I)
• is preferably 15°C or less, more preferably 10°C or less It is. When
• the resin composition (T) used in the present invention preferably has a saturated water absorption rate of 0.1 to 1.0% by mass in water at 80°C. Further, the resin composition (T) preferably has a saturated water absorption rate comparable to that of the methacrylic resin composition (I). Specifically, the absolute value of the difference between the saturated water absorption of the resin composition (T) and the saturated water absorption of the methacrylic resin composition (I)
• the MFR of the resin composition (T) used in the present invention is preferably in the range of 1 to 30 g/10 minutes, more preferably in the range of 3 to 20 g/10 minutes, and more preferably in the range of 5 to 10 g/10 minutes. More preferably, the range is within the range.
• the MFR is in the range of 1 to 30 g/10 minutes, the stability of hot melt molding is good.
• the MFR of the resin composition (T) in this specification is measured using a melt indexer at a temperature of 300° C. and under a load of 1.2 kg.
• the laminated substrate film for vapor deposition of the present invention has a layer made of methacrylic resin composition (I) and a layer made of resin composition (T).
• the laminated substrate film for vapor deposition of the present invention may have one layer each consisting of the methacrylic resin composition (I) and one layer consisting of the resin composition (T), or may have one layer each consisting of the methacrylic resin composition (I) and one layer consisting of the resin composition (T). It may each have a plurality of layers made of (I) and/or a plurality of layers made of resin composition (T).
• the laminated substrate film for vapor deposition of the present invention has a layer made of another resin (another resin layer) in addition to the layer made of the methacrylic resin composition (I) and the layer made of the resin composition (T). You can leave it there.
• the resin contained in the other resin layer include various thermoplastic resins other than the methacrylic resin composition (I) and the resin composition (T); thermosetting resins; energy ray-curing resins; and the like.
• Examples of the other resin layers mentioned above include a scratch-resistant layer, an antistatic layer, an antifouling layer, a friction reduction layer, an antiglare layer, an antireflection layer, an adhesive layer, an impact strength imparting layer, an anchor layer, and the like.
• the number of these other resin layers may be one or more. Furthermore, when there are a plurality of these other resin layers, they may be made of the same resin or different resins. In the laminated substrate film for vapor deposition of the present invention, there is no particular restriction on the order in which the other resin layers are arranged, and they may be on the surface or in the inner layer.
• the thickness of the laminated base film for vapor deposition of the present invention is preferably in the range of 0.03 to 0.5 mm, and preferably in the range of 0.05 to 0.5 mm, from the viewpoint of manufacturing with high productivity while maintaining an excellent appearance. It is more preferably 4 mm, and even more preferably in the range of 0.07 to 0.3 mm.
• the thickness of the layer made of methacrylic resin composition (I) in the laminated substrate film for vapor deposition of the present invention is preferably in the range of 0.01 to 0.1 mm, and preferably in the range of 0.015 to 0.09 mm. It is more preferably within the range of 0.02 to 0.08 mm. If the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. Moreover, if it exceeds 0.1 mm, impact resistance may be insufficient.
• the thickness of the layer made of the resin composition (T) in the laminated substrate film for vapor deposition of the present invention is preferably in the range of 0.02 to 0.4 mm, and preferably in the range of 0.035 to 0.31 mm. is more preferable, and even more preferably in the range of 0.08 to 0.27 mm. From the viewpoint of impact resistance and productivity, it is preferable that the thickness of the layer made of the resin composition (T) is within the above range.
• the thickness of the layer made of methacrylic resin composition (I) in the laminated substrate film for vapor deposition of the present invention is preferably in the range of 2 to 20% of the thickness of the laminated substrate film for vapor deposition. , more preferably in the range of 3 to 17%, and even more preferably in the range of 4 to 15%. From the viewpoints of scratch resistance, weather resistance, and impact resistance, it is preferable that the thickness of the layer made of methacrylic resin composition (I) is within the above range.
• the thickness of the layer made of the resin composition (T) in the laminated substrate film for vapor deposition of the present invention is preferably in the range of 80 to 98%, and 83 to 97% of the thickness of the laminate. It is more preferably within the range of 85% to 96%. From the viewpoint of impact resistance and weather resistance, it is preferable that the ratio of the thickness of the layer made of the resin composition (T) to the thickness of the laminated base material film for vapor deposition of the present invention is within the above range.
• the lamination order of the laminated base film for vapor deposition of the present invention is (1)-(2); (1)-(2)-( 1); (2)-(1)-(2); (1)-(2)-(1)-(2)-(1); )-(2); (1)-(2)-(1); (1)-(2)-(1)-(2)-(1); at least one surface is made of a methacrylic resin composition. It is preferable that the layers are laminated to form a layer consisting of (I).
• the lamination order of the laminate of the present invention is (1). -(2)-(3);(3)-(1)-(2);(3)-(1)-(2)-(3);(3)-(1)-(2)-( 1)-(3); (1)-(2)-(3)-(2)-(1); and the like.
• (3) is an anchor layer
• the lamination order of the laminated substrate film for vapor deposition of the present invention is (3') - (1) - (2); (3')-(1)-(2)-(3'), (3')-(1)-(2)-(1)-(3'), etc.
• they are laminated to form an anchor layer.
• the stacking order of the laminate of the present invention is (1)-(2)-(3)-(4); (4)-(3 )-(1)-(2);(4)-(3)-(1)-(2)-(3);(4)-(1)-(2)-(3);(4)- (3)-(1)-(2)-(3)-(4);(4)-(3)-(1)-(2)-(1)-(3)-(4); etc. Can be mentioned.
• the laminated base film for vapor deposition of the present invention has a lamination order that is symmetrical in the thickness direction, and furthermore, the thickness of each layer is also symmetrical. It is more preferable to be present.
• the total light transmittance of the laminated substrate film for vapor deposition of the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. Since the total light transmittance is 80% or more, the laminated base film for vapor deposition obtained by the present invention has excellent appearance quality.
• the total light transmittance can be measured by a method according to JIS K7105.
• the surface wetting tension of the layer made of methacrylic resin composition (I) is preferably 38 mN/m or more, more preferably 39 mN/m or more, and even more preferably 40 mN/m. That's all.
• the surface wetting tension is at least 38 mN/m or more, the adhesive strength between the laminated substrate film for vapor deposition of the present invention and the vapor deposition layer is improved.
• corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other conventionally known surface treatments can be performed. Wetting tension can be measured by a method according to JIS K6768.
• the lamination of the layer consisting of the methacrylic resin composition (I) and the layer consisting of the resin composition (T) is usually carried out by multilayer molding. It is preferable to do so.
• multilayer molding include bonding methods such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, and insert injection molding, and multilayer extrusion molding is preferred from the viewpoint of productivity.
• Methods for further laminating other resin layers include a method of multi-layer molding by the method described above together with a layer made of methacrylic resin composition (I) and a layer made of resin composition (T), a method of multilayer molding using the method described above, and a method of multi-layer molding with a layer made of methacrylic resin composition (I) and a layer made of resin composition (T); A method of applying another fluid resin to the surface of a layer consisting of composition (I) or a layer consisting of resin composition (T) and drying or curing it, consisting of a pre-prepared methacrylic resin composition (I). Examples include a method of bonding the layer or the surface of the resin composition (T) via an adhesive layer.
• the method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for manufacturing a multilayer laminate of thermoplastic resin can be preferably employed, and more preferably a flat T-die and polishing with a mirror-finished surface. It is formed by a device equipped with rolls.
• the T-die method includes a feed block method in which methacrylic resin composition (I) and resin composition (T) in a heated and molten state are laminated before flowing into the T-die, and It is possible to adopt a multi-manifold method in which objects (T) are stacked inside a T die.
• a multi-manifold method is preferable from the viewpoint of improving the smoothness of the interface between each layer constituting the laminated base material film for vapor deposition.
• examples of the polishing roll in this case include a metal roll and an elastic roll having a metal thin film on the outer periphery (hereinafter sometimes referred to as metal elastic roll).
• the metal roll is not particularly limited as long as it has high rigidity, and examples thereof include drilled rolls, spiral rolls, and the like.
• the surface condition of the metal roll is not particularly limited, and may be, for example, a mirror surface, or may have a pattern, unevenness, or the like.
• a metal elastic roll includes a substantially cylindrical rotatable shaft roll, a cylindrical metal thin film arranged to cover the outer peripheral surface of the shaft roll and in contact with a film-like object, and these shafts.
• the shaft roll is not particularly limited, and is made of, for example, stainless steel.
• the metal thin film is made of, for example, stainless steel, and preferably has a thickness of about 2 to 5 mm.
• the metal thin film preferably has bendability, flexibility, etc., and preferably has a seamless structure without welded joints.
• Elastic metal rolls with such metal thin films have excellent durability, and if the metal thin film is mirror-finished, they can be handled in the same way as ordinary mirror-finished rolls, and if the metal thin film is given a pattern or unevenness, It becomes a roll that can transfer the shape, so it is easy to use.
• the methacrylic resin composition (I) and the resin composition (T) are preferably melt-filtered using a filter before and/or during multilayer molding.
• a filter By performing multilayer molding using each melt-filtered resin composition, a laminate with few defects caused by foreign matter or gel can be obtained.
• the filter material used, and it is selected appropriately depending on the operating temperature, viscosity, and filtration accuracy, such as nonwoven fabric made of glass fiber, etc.; phenol resin impregnated cellulose film; metal fiber nonwoven sintered film; metal powder sintered film. ; wire mesh; or a combination of these can be used.
• the filtration accuracy of the filter is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the anchor layer will be described in detail as an example of a layer made of another resin composition.
• the anchor layer is provided to improve the adhesion layer between the layer made of methacrylic resin composition (I) and the vapor deposited layer.
• the anchor layer is not particularly limited.
• the anchor layer may be any raw material that has good adhesion to the layer made of the methacrylic resin composition (I) and has good receptivity to the material constituting the vapor deposited layer, such as acrylic resin, nitrocellulose, etc. resins, polyurethane resins (including those cured with polyol resin as the main ingredient and isocyanate resin as the curing agent), acrylic urethane resins (including those cured with acrylic polyol resin as the main ingredient and isocyanate resin as the curing agent) polyester resins, styrene-maleic acid resins, chlorinated PP resins, etc.
• the anchor layer contains an acrylic resin, since the resulting laminated film (laminated base film for vapor deposition, laminated film for vapor deposition) has better adhesion.
• the acrylic resin is not particularly limited, and may be included in the category of the methacrylic resin described above.
• the thickness of the anchor layer is preferably 0.1 to 3 ⁇ m. When the thickness of the anchor layer is within the above range, the laminated film has excellent adhesion between the layer made of the methacrylic resin composition (I) and the vapor deposited layer.
• the anchor layer may be given a design by adding a colorant or a metal pigment. For example, by incorporating a yellow pigment as a colorant, the film can exhibit a golden appearance. The type and content of the colorant can be adjusted as appropriate depending on the desired metallic appearance. Further, the anchor layer may be provided with a function such as an antistatic effect by incorporating an antistatic agent. Furthermore, the anchor layer may be mixed with a curing agent having an isocyanate resin. By mixing a curing agent containing an isocyanate-based resin, the resulting laminated film can have further improved heat resistance, weather resistance, and water resistance.
• the anchor layer is made of a methacrylic resin composition (I) using a roll coater or the like to apply a resin solution constituting the anchor layer dissolved in an appropriate solvent (for example, methyl ethyl ketone, toluene, ethyl acetate, etc.). It can be formed by applying a layer and then drying at about 80 to 100°C for 30 seconds to 1 minute.
• an appropriate solvent for example, methyl ethyl ketone, toluene, ethyl acetate, etc.
• the vapor-deposited laminated film of the present invention is a laminated base film for vapor deposition in which a layer made of a methacrylic resin composition (I) is laminated on one side of a layer made of a resin composition (T).
• a vapor deposition layer is provided on one side of the laminated base material film for vapor deposition.
• the vapor deposited layer is provided to impart various functions to the film.
• Such functions include, for example, decoration, scratch resistance, antistatic, antifouling, friction reduction, antifogging, antiglare, antireflection, high light reflection, adhesiveness, impact resistance, antisticking, gas barrier, and transparent conductivity. can be mentioned.
• the material constituting the vapor deposition layer is not particularly limited, and examples thereof include elemental metals, elemental metalloids, inorganic compounds, and organic compounds.
• the inorganic compound oxides and oxynitrides of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, etc. are preferable.
• the organic compound an organic polymer compound is preferable.
• One or more vapor deposition layers using at least one selected from these materials can be provided on one or both surfaces of the laminated base film for vapor deposition.
• Deposited layers made of silicon oxide, silicon oxynitride, aluminum oxide, etc. have excellent light transmittance and are suitable for optical applications.
• Polysiloxane is produced, for example, by introducing vapor obtained by heating and evaporating hexamethyldisiloxane into a parallel plate type plasma device using RF electrodes, and depositing it on a base film while causing a polymerization reaction in the plasma.
• a vapor deposited layer made of polysiloxane can be easily made hydrophilic by oxygen plasma or the like, has good adhesion to an inorganic vapor deposited layer, and has excellent bending resistance.
• Polypara-xylylene can be produced, for example, by heating and vaporizing di-para-xylylene in a high vacuum, and heating the vapor to 650° C. to 700° C. to thermally decompose the di-para-xylylene to generate radicals.
• these radicals are introduced into a chamber in which a base film is installed, the radicals are adsorbed by the base film, and at the same time, radical polymerization proceeds to form a polyparaxylylene film.
• a vapor deposited layer made of polyparaxylylene has excellent mechanical strength, thermal strength, chemical strength, etc.
• the addition polymer is formed into a film by, for example, adding and polymerizing the monomers above in a vacuum and depositing them on a base film.
• polyurea is preferred from the viewpoint of transparency, material cost, and the like.
• a vapor deposited layer with a refractive index lower than that of the base film may be provided on the surface of the base film, or a vapor deposited layer with a high refractive index and a vapor deposited layer with a low refractive index may be provided on the surface of the base film. They are provided on the surface of the base film in this order.
• a vapor deposited layer so dense that barrier target gas molecules such as water molecules and oxygen molecules cannot pass through is provided on the surface of the base film.
• Materials constituting the gas barrier deposited layer include, for example, metal alloys consisting of elemental metals such as aluminum, nickel, chromium, iron, cobalt, zinc, gold, silver, copper, and combinations thereof; silicon, germanium, carbon (diamond), etc.; Elemental metalloids such as carbon-like carbon, graphite, etc.; oxides such as silicon oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, zinc oxide, cerium oxide, hafnium oxide, barium oxide, etc.
• nitrides such as silicon nitride, aluminum nitride, boron nitride, and magnesium nitride; carbides such as silicon carbide; oxide carbides; nitride carbides; oxynitrides; oxynitride carbides; sulfides.
• an indium oxide film containing at least one of tin, germanium, zinc, gallium, and magnesium can be used.
• the vapor-deposited layer containing indium has excellent moldability of the obtained film and is easily processed into various three-dimensional shapes, so it is also suitable for metallic decoration.
• Indium may be included as an oxide or nitride. In addition to indium, it may also contain various nonmetals, metals, metal oxides, and metal nitrides.
• the obtained vapor deposited layer can be analyzed using, for example, a surface analysis device such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (XPS), or a secondary ion mass spectrometer (SIMS). These devices can perform analysis in the thickness direction of a deposited layer using ion etching.
• a surface analysis device such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (XPS), or a secondary ion mass spectrometer (SIMS). These devices can perform analysis in the thickness direction of a deposited layer using ion etching.
• the thickness of the vapor deposited layer can be set depending on the function to be imparted, but is preferably 5 to 2000 nm, more preferably 10 to 1500 nm, still more preferably 20 to 1000 nm, and most preferably 30 to 500 nm. When the thickness of the vapor-deposited layer is within the above range, the vapor-deposited layer can easily achieve both its function, productivity, and moldability.
• the vapor deposition layer can be formed by a known vapor deposition method.
• Vapor deposition methods include physical vapor deposition methods (PVD methods) such as vacuum evaporation method, sputtering method, and ion plating method; chemical vapor deposition methods (CVD method) such as reduced pressure chemical vapor deposition method, catalytic chemical vapor deposition method, and plasma chemical vapor deposition method. can be mentioned.
• PVD methods physical vapor deposition methods
• CVD method chemical vapor deposition methods
• the vacuum evaporation method is preferred because of its high productivity.
• the vapor deposition conditions conventionally known conditions may be appropriately adopted based on the desired thickness of the vapor deposited layer.
• the surface of the base film may be subjected to surface treatment within a range that does not impair the purpose of the present invention.
• the surface treatment include discharge treatment methods such as low-temperature plasma treatment and corona discharge treatment; chemical treatment methods such as acid treatment, alkali treatment, and organic solvent treatment; and treatment methods by applying a primer paint. It seems that the electric discharge treatment method can increase the number of carbonyl groups, carboxyl groups, hydroxyl groups, etc., and the chemical treatment method can increase the number of polar groups such as amino groups, hydroxyl groups, carbonyl groups, etc.
• the vapor-deposited laminated film of the present invention may further have a coating film on the surface of the vapor-deposited layer.
• a coating film is a film formed by applying a coating composition, drying it as necessary, and curing it.
• Various functions can be imparted by the coating film. Such functions include, for example, decoration, scratch resistance, antistatic, antifouling, friction reduction, antifogging, antiglare, antireflection, high light reflection, adhesiveness, impact resistance, antisticking, gas barrier, and transparent conductivity. can be mentioned.
• There is no particular restriction on the method of applying the coating composition and for example, methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating can be used.
• the metal-like sheet of the present invention is obtained by laminating a thermoplastic resin sheet as a backing material on the vapor-deposited layer side surface of the vapor-deposited laminated film of the present invention.
• the resin constituting the thermoplastic resin sheet is not particularly limited, but examples include ABS (acrylonitrile-butadiene-styrene copolymer) resin, polycarbonate resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester Examples include resins and polyolefin resins.
• the thickness of the thermoplastic resin sheet is not particularly limited, and may be the thickness of the so-called film region. Specifically, the thickness of the thermoplastic resin sheet is usually 0.2 to 2 mm.
• the vapor deposition layer and the thermoplastic resin sheet are preferably laminated with an adhesive layer interposed therebetween.
• the presence of the adhesive layer provides good adhesion between the vapor deposited layer and the thermoplastic resin sheet, making it suitable for use as a metallic sheet.
• the adhesive forming the adhesive layer may be appropriately selected so that it can withstand the heating temperature during molding and exhibits good adhesiveness depending on the type of metal vapor deposited layer or thermoplastic resin sheet. .
• polyurethane type polyester type, polyethylene type, polyamide type, polyvinyl chloride type, polychloroprene type, carboxylated rubber type, thermoplastic styrene-butadiene rubber type, acrylic type, styrene type, cellulose type, alkyd type, polyacetic acid type.
• Adhesives made of one or more resins such as vinyl, ethylene vinyl acetate copolymer, polyvinyl alcohol, epoxy, silicone, natural rubber, and synthetic rubber are used.
• additives such as pigments, dyes, metal powders, mica, and the like may be added to these adhesives for the purpose of adjusting the color tone, taking into consideration the influence of metallic luster on the color tone.
• the thickness of the adhesive layer is preferably 1 to 20 ⁇ m, more preferably 2 to 8 ⁇ m. If the thickness of the adhesive layer is less than 1 ⁇ m, the adhesive force may be insufficient. On the other hand, if it exceeds 20 ⁇ m, it will take a long time to dry the adhesive layer, which is preferable in terms of the process. It also tends to be disadvantageous in terms of cost. Furthermore, in the metallic sheet of the present invention, the metal vapor deposited layer and the thermoplastic resin sheet are preferably laminated by dry lamination.
• the above-mentioned adhesive is made into a solution or emulsion state using a solvent as necessary, and this is coated by known means such as a gravure coater, reverse coater, die coater, knife coater, roll coater, etc. It may be applied to the metal vapor deposited layer, the thermoplastic resin sheet, or both, and dried as appropriate.
• the metal-like molded product of the present invention is obtained by laminating the vapor-deposited laminated film or metal-like sheet of the present invention onto a molded product such that the surface opposite to the vapor-deposited layer side is placed on the front side.
• the molded product to which the vapor-deposited laminated film or metal-like sheet is laminated is, for example, made of thermoplastic resin such as ABS resin, polycarbonate resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, or polyolefin resin. It is preferable that the thermoplastic resin such as ABS resin, polycarbonate resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, or polyolefin resin. It is preferable that the thermoplastic resin such as ABS resin, polycarbonate resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, or polyolefin resin. It is preferable that the thermoplastic resin such as ABS resin, polycarbonate resin,
• the vapor deposition layer and the molded article are bonded together via an adhesive layer.
• the presence of the adhesive layer provides good adhesion between the vapor deposited layer and the molded article.
• the type of adhesive forming the adhesive layer and the thickness of the adhesive layer are the same as the adhesive layer in the metal-like sheet of the present invention, but the adhesive layer is usually sticky after drying. It is selected as appropriate so that it does not have.
• Methods for obtaining the metal-like molded product of the present invention include film (sheet) in-mold molding, laminate injection press molding, film (sheet) insert molding, vacuum-pressure molding, TOM (Three Dimension Overlay Method) molding, and hot stamping. Examples include molding.
• the film (sheet) insert injection molding method is advantageously employed.
• a vapor-deposited laminated film or metal-like sheet is preformed by vacuum forming or pressure forming, then trimmed using a Thomson mold, etc., and then inserted into an injection mold.
• This is a method in which an injection molded product is formed by injecting molten resin, and at the same time, a molded film or metal-like sheet is laminated to the molded product.
• conventionally known techniques such as those described in, for example, JP-A-2005-254531 may be followed.
• the vapor-deposited laminated film of the present invention can be used, for example, in the interior and exterior of automobiles, the interior and exterior of personal computers, the interior and exterior of mobile terminals, the interior and exterior of wearable terminals, the interior and exterior of solar cells, solar cell backsheets, light guide plates for liquid crystals, diffusion plates, backsheets, reflective Films for liquid crystal displays such as sheets, polarizer protective films and retardation films, information equipment fields such as surface protection films, optical communication fields such as optical fibers, optical switches, and optical connectors, automobile headlight and tail lamp lenses, inner lenses, Vehicle fields such as instrument covers, sunroofs, glazing, eyeglasses, contact lenses, endoscope lenses, road signs, bathroom equipment, flooring, road transparent plates, lenses for double glazing, lighting windows, carports, and lighting.
• It can be used in the field of architecture and building materials such as lenses, lighting covers, and sizing for building materials, microwave cooking containers (tableware), housings for home appliances, toys, sunglasses, stationery, and solar light-concentrating films. It can also be used as an alternative to molded products using transfer sheets.
• metal-like molded products formed from the vapor-deposited laminated film of the present invention can be used, for example, as metal-like signboards, metal-like interior and exterior parts for vehicles, metal-like home appliances, metal-like amusement products, and metal-like building materials. etc.
• metal-like molded products are suitably used as interior and exterior members for metal-like vehicles.
• the metallic interior and exterior members for vehicles are not particularly limited.
• metal interior and exterior parts for vehicles include instrument panel garnishes and ornaments, audio panels, auto air conditioner panels, steering ornaments, door trim ornaments, power window switch bezels, operation knobs, switches, and various caps or covers.
• radiator grilles include radiator grilles, pillar garnishes, back door ornaments, side mirror covers, outer panels, rear spoilers, inside or outside door handles, side visors, wheel covers, cowlings for motorcycles, etc.
• the metal interior/exterior member for a vehicle of this embodiment is more suitable when applied to a steering wheel, a handle, etc.
• each unit composition of precursor polymer The carbon ratio of the phenyl group of the ⁇ -methylstyrene unit, the carbonyl group of the methyl methacrylate unit, the phenyl group of the styrene unit, and the carbonyl group of the maleic anhydride unit was determined by 13C -NMR, and the composition of each unit was calculated from this. did.
• the weight average molecular weight (Mw) of each resin obtained in the production example was determined by GPC (gel permeation chromatography).
• a sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran.
• the temperature of the column oven was set at 40° C., 20 ⁇ l of the sample solution was injected into the device at an eluent flow rate of 0.35 ml/min, and the chromatogram was measured.
• Ten points of standard polystyrene having a molecular weight in the range of 400 to 5,000,000 were measured by GPC, and a calibration curve showing the relationship between retention time and molecular weight was created.
• the Mw of the resin to be measured was determined based on this calibration curve.
• the value corresponding to the molecular weight of standard polystyrene from the chromatogram measured by GPC was determined as the molecular weight of the copolymer.
• Equipment Tosoh GPC equipment
• Eluent Tetrahydrofuran Eluent flow rate: 0.35ml/min
• each unit composition in methacrylic copolymer The ⁇ -methylstyrene unit and styrene unit had the same composition as each unit composition of the precursor polymer.
• 1 H-NMR measurement of the methacrylic copolymer was performed using 1 H-NMR (manufactured by Bruker; trade name: ULTRA SHIELD 400 PLUS), and the imide units (glutarimide and maleimide) in the methacrylic copolymer were detected.
• the content (mol%) of each monomer unit such as methyl methacrylate unit and aromatic vinyl ( ⁇ -methylstyrene and styrene) unit is determined, and the content (mol%) is calculated by calculating the content (mol%) of each monomer unit.
• the molecular weight was used to convert into content (% by weight).
• the imidization rate (R m ) of the acid anhydride was determined. From the amount of maleic anhydride (m) in the precursor polymer determined by 13C -NMR and the imidization rate (R m ), the value determined by the following formula was taken as the amount of maleic anhydride (M) in the methacrylic copolymer. .
• Amount of maleic anhydride (M) m x (100-Rm)/100
• M m x (100-Rm)/100
• the ratio of glutarimide units to maleimide units in the methacrylic copolymer was determined from the absorption intensity of the peak derived from the carbonyl unit of maleimide.
• the content of glutarimide units and maleimide units in the methacrylic copolymer was determined from the amount of imide units in the methacrylic copolymer determined by 1 H-NMR and the ratio of glutarimide units to maleimide units.
• Total light transmittance Tt
• the methacrylic resin composition obtained in the production example was press-molded to form a sheet with a thickness of 3 mm.
• the total light transmittance of the press plate was measured using a haze meter (manufactured by Murakami Color Research Institute; trade name HM-150).
• Glass transition temperature Tg
• the methacrylic resin composition obtained in the production example was dissolved in chloroform and reprecipitated with methanol, and the precipitated resin was vacuum-dried at 100° C. for 12 hours or more.
• the vacuum-dried resin was heated to 250°C in accordance with JIS K7121 using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50 (product number)), then cooled to room temperature, and then cooled to room temperature.
• the DSC curve was measured under conditions of increasing the temperature from 10°C to 200°C at a rate of 10°C/min.
• the midpoint glass transition temperature determined from the DSC curve measured during the second temperature rise was defined as the glass transition temperature in the present invention.
• thermogravimetric reduction temperature The methacrylic resin composition obtained in the production example was heated at a rate of 10°C/min in a nitrogen atmosphere using a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50), and when the starting point was 200°C. The temperature at which the weight decreased by 1% was defined as the 1% thermoweight loss temperature.
• a test piece with a thickness of 4 mm, a length of 80 mm, and a width of 10 mm was obtained by cutting the methacrylic resin composition obtained in the production example after press molding.
• Each test piece was measured under the conditions of 23° C. and 50% relative humidity according to the method described in JIS K7111-1/1eU. The measurements were performed 10 times, and the average value was adopted as the Charpy impact value.
• the methacrylic resin composition obtained in the production example was dissolved in chloroform and reprecipitated with methanol, and the precipitated resin was vacuum-dried at 100° C. for 12 hours or more.
• the vacuum-dried resin was measured in accordance with JIS K7210 at 230° C. and a load of 3.8 kg.
• the methacrylic resin composition obtained in the production example was press-molded to form a sheet with a thickness of 3 mm.
• Wet tension was measured using a mixed liquid for wetting tension test (manufactured by Wako Pure Chemical Industries, Ltd.) under conditions of 23° C. and 50% relative humidity in accordance with JIS K6768.
• the laminated base film for vapor deposition of Examples and Comparative Examples was cut into a rectangle with the long side parallel to the extrusion flow direction and the short side perpendicular to the extrusion flow direction, and the long side was 200 mm.
• a test piece with a short side of 120 mm was prepared. Place the test piece on a surface plate so that both ends of the test piece are in contact with the surface plate (that is, the test piece has an upward convex shape), and use a gap gauge to measure the maximum gap between the test piece and the surface plate. was measured and used as the initial amount of warpage.
• each test piece was left in a hot air dryer set at a temperature of 100°C for 1 hour, and then the test piece with its short side clipped was placed in an environmental testing machine set at a temperature of 85°C and a relative humidity of 85%. After hanging it and leaving it in that state for 72 hours, it was allowed to cool and control humidity for 120 hours in an environment of 23° C. and 50% relative humidity. As a result, all the test pieces were warped in an arch-like manner along the long sides of the test piece, with the layer made of methacrylic resin composition (I) on the outside and the layer made of resin composition (T) on the inside. occured.
• the maximum value of the gap with the surface plate was measured and used as the amount of warpage under high temperature and high humidity.
• the amount of change in warpage under high temperature and high humidity was calculated from the following formula, and the quality of dimensional stability was determined from the amount of change.
• Amount of change in warpage under high temperature and high humidity Amount of warpage under high temperature and high humidity - Initial amount of warpage ⁇ : Amount of change in warpage under high temperature and high humidity is 10 mm or less ⁇ : Amount of change in warpage under high temperature and high humidity is 10 mm Larger but less than 20mm ⁇ : Warpage change amount under high temperature and high humidity is greater than 20mm
• precursor polymer The precursor polymers (p-1) to (p-5) of this production example were produced by the following method.
• Precursor polymer (p-1) to (p-2) In an autoclave equipped with a stirrer, 68.0 parts by mass of purified methyl methacrylate (MMA), 28.0 parts by mass of ⁇ -methylstyrene ( ⁇ MSt), 7.0 parts by mass of styrene (St), and 2,2'-azobis. 0.05 parts by mass of (2-methylpropionitrile) (AIBN) and 0.01 parts by mass of n-octylmercaptan (n-OM) were charged and uniformly dissolved to obtain a polymerization raw material.
• MMA purified methyl methacrylate
• ⁇ MSt ⁇ -methylstyrene
• St 7.0 parts by mass of styrene
• 2,2'-azobis 0.05 parts by mass of (2-methylpropionitrile) (AIBN) and 0.01 parts by mass of n
• Nitrogen gas was blown into the reaction raw material to remove dissolved oxygen to 3 ppm.
• the interior of the continuous flow tank reactor equipped with a brine cooling condenser was replaced with nitrogen gas.
• the polymerization raw material was continuously fed into the tank reactor at a constant flow rate so that the average residence time was 3.0 hours, and bulk polymerization was carried out at a polymerization temperature of 140°C, and the precursor was removed from the tank reactor.
• the liquid containing the polymer was continuously discharged. Note that the pressure inside the tank reactor was regulated by a pressure regulating valve connected to a brine cooling condenser.
• the polymerization conversion rate reached the values shown in Table 1.
• the liquid discharged from the reactor was heated to 210°C and supplied to a twin-screw extruder controlled at 230°C.
• the twin-screw extruder volatile components mainly consisting of unreacted monomers were separated and removed, and the precursor polymer was extruded into strands.
• the strand was cut with a pelletizer to obtain a precursor polymer (p-1).
• the weight average molecular weight Mw of the obtained precursor polymer (p-1) was measured. The results are shown in Table 1.
• Precursor polymer (p-3) In an autoclave with a stirrer, 60.0 parts by mass of purified methyl methacrylate (MMA), 25.0 parts by mass of ⁇ -methylstyrene ( ⁇ MSt), 15.0 parts by mass of maleic anhydride (Mah), 2,2' -0.005 parts by mass of azobis(2-methylpropionitrile) (AIBN) and 0.02 parts by mass of n-octylmercaptan (n-OM) were charged and uniformly dissolved to obtain a polymerization raw material. Nitrogen gas was blown into the reaction raw material to remove dissolved oxygen to 3 ppm. Next, the interior of the continuous flow tank reactor equipped with a brine cooling condenser was replaced with nitrogen gas.
• MMA purified methyl methacrylate
• ⁇ MSt ⁇ -methylstyrene
• Mih maleic anhydride
• AIBN 2,2' -0.005 parts by mass of azobis(2-methylpropionitrile)
• the polymerization raw material was continuously fed into the tank reactor at a constant flow rate so that the average residence time was 2 hours, and bulk polymerization was carried out at a polymerization temperature of 130°C, and the precursor polymer was removed from the tank reactor.
• the containing liquid was continuously discharged.
• the pressure inside the tank reactor was regulated by a pressure regulating valve connected to a brine cooling condenser.
• the polymerization conversion rate reached the values shown in Table 1.
• the liquid discharged from the reactor was heated to 230°C and supplied to a twin-screw extruder controlled at 240°C. In the twin-screw extruder, volatile components mainly consisting of unreacted monomers were separated and removed, and the precursor polymer was extruded into strands.
• the strand was cut with a pelletizer to obtain a precursor polymer (p-3).
• the weight average molecular weight Mw of the obtained precursor polymer (p-3) was measured. The results are shown in Table 1.
• Precursor polymer (p-4) In an autoclave equipped with a stirrer, 75.0 parts by mass of purified methyl methacrylate (MMA), 25.0 parts by mass of ⁇ -methylstyrene ( ⁇ MSt), and 2,2′-azobis(2-methylpropionitrile) (AIBN ) and 0.02 parts by mass of n-octylmercaptan (n-OM) were charged and uniformly dissolved to obtain a polymerization raw material. Nitrogen gas was blown into the reaction raw material to remove dissolved oxygen to 3 ppm. Next, the interior of the continuous flow tank reactor equipped with a brine cooling condenser was replaced with nitrogen gas.
• MMA purified methyl methacrylate
• ⁇ MSt ⁇ -methylstyrene
• AIBN 2,2′-azobis(2-methylpropionitrile)
• n-OM n-octylmercaptan
• the polymerization raw material was continuously fed into the tank reactor at a constant flow rate so that the average residence time was 3 hours, and bulk polymerization was carried out at a polymerization temperature of 130°C, and the precursor polymer was removed from the tank reactor. Containing liquid was continuously discharged. Note that the pressure inside the tank reactor was regulated by a pressure regulating valve connected to a brine cooling condenser. The polymerization conversion rate reached the values shown in Table 1. Next, the liquid discharged from the reactor was heated to 230°C and supplied to a twin-screw extruder controlled at 240°C.
• Precursor polymer (p-5) MS resin (copolymer of methyl methacrylate (MMA) and styrene (St)) was polymerized according to the method for producing copolymer (A) described in the [Examples] section of JP-A-2003-231785. did. By changing the mass ratio of MMA and St charged into the autoclave, a precursor polymer (p-5) containing 20% by mass of styrene monomer units was obtained. The weight average molecular weight Mw of the obtained precursor polymer (p-5) was measured. The results are shown in Table 1.
• a twin-screw extruder (manufactured by Nippon Steel Corporation; trade name: TEX30 ⁇ -77AW-3V) consisting of a transport section, a melt-kneading section, a devolatilizing section, and a discharge section, and set at a screw rotation speed of 150 rpm and a temperature of 210 to 270°C.
• the precursor polymer (p-1) was supplied to the transport section at a rate of 15 kg/hr, and in the melt-kneading section equipped with a kneading block, monomethylamine was mixed so as to have the content of structural units derived from glutarimide shown in Table 1.
• the amount added was adjusted and injected from the additive supply port of the twin-screw extruder to cause the precursor polymer (p-1) and monomethylamine to react.
• the melt-kneading section is mostly composed of kneading disks, and seal elements are attached to both ends of the kneading disks.
• the devolatilization section by-products and excess monomethylamine were volatilized from the molten resin that had passed through the melt-kneading section and discharged through a plurality of vents.
• the molten resin extruded as a strand from the die installed at the end of the discharge section of the twin-screw extruder is cooled in a water tank, and then cut with a pelletizer to obtain pellet-shaped methacrylic copolymer (a-1). Obtained.
• the content of structural units derived from glutarimide in the methacrylic copolymer (a-1) was 53 wt%.
• Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-1).
• Example 2 A methacrylic copolymer (a-2) was obtained in the same manner as in Example 1, except that the amount of monomethylamine added was changed so that the content of structural units derived from glutarimide was 70 wt%. .
• Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-2).
• Example 3 Methacryl was added in the same manner as in Example 1, except that the precursor polymer (p-2) was used and the amount of monomethylamine added was changed so that the content of structural units derived from glutarimide was 38 wt%. A copolymer (a-3) was obtained. Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-3).
• Example 5 Methacryl was added in the same manner as in Example 1, except that the precursor polymer (p-2) was used and the amount of monomethylamine added was changed so that the content of structural units derived from glutarimide was 15 wt%. A copolymer (a-5) was obtained. Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-5).
• Example 6 Methacryl was added in the same manner as in Example 1, except that the precursor polymer (p-4) was used and the amount of monomethylamine added was changed so that the content of structural units derived from glutarimide was 30 wt%. A copolymer (a-8) was obtained. Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-8).
• Methacryl was prepared in the same manner as in Example 1, except that the precursor polymer (p-5) was used and the amount of monomethylamine added was changed so that the content of structural units derived from glutarimide was 48 wt%.
• a copolymer (a-9) was obtained.
• Table 1 shows the composition and weight average molecular weight Mw of the methacrylic copolymer (a-9).
• Example 1 Two types of resins, one for the layer consisting of the resin composition (T) and the other for the layer consisting of the methacrylic resin composition (I), were processed using separate 25 mm ⁇ vented single screw extruders (manufactured by GM ENGINEER JNG; VGM25). -28EX) and melted and kneaded, these resin compositions were introduced into a junction block and extruded using a multi-manifold die at an extrusion temperature of 25. Coextrusion was carried out at 0°C. The thickness of each layer was adjusted by adjusting the discharge amount of each resin composition.
• the coextruded resin composition in a molten state is sandwiched between a first cooling roll and a second cooling roll that are adjacent to each other, and wound around the second cooling roll. It was cooled by sandwiching it between them and winding it around a third cooling roll.
• the thermoplastic resin layer obtained after cooling was taken off by a pair of take-off rolls. Note that the layer made of methacrylic resin composition (I) was brought into contact with the third cooling roll. In this way, a two-layer laminated base film for vapor deposition was produced.
• Table 3 shows the evaluation results of the laminated base material film for vapor deposition.
• Examples 2 to 6 and Comparative Examples 1 to 7 The deposition method described in Examples 2 to 6 and Comparative Examples 1 to 7 was performed in the same manner as in Example 1, except that the resin composition (T) and methacrylic resin composition (I) listed in Table 3 were used. A laminated base film was manufactured. Table 3 shows the evaluation results of the laminated base material film for vapor deposition.
• the laminated films obtained in Examples 1 to 6 had high total light transmittance, high Charpy impact strength, excellent fluidity, and a heat-resistant and low water absorption methacrylic resin composition (I-1 ) to (I-5) provides excellent appearance quality, dimensional stability, and flexibility. Furthermore, since the resin composition has high wet tension, the laminated film of the present invention has excellent adhesion to the vapor deposited layer. From the above, the laminated films of Examples 1 to 6 are suitable as substrates for vapor deposition. In contrast, laminated films using methacrylic resin compositions (I-6), (I-8), (I-9), and (I-12) that do not have sufficient heat resistance or low water absorption (comparison Examples 1, 3, 4, and 7) have poor dimensional stability.
• laminated films (Comparative Examples 2, 3, 6 ), which tends to cause poor appearance. Furthermore, a laminate film using a methacrylic resin composition (I-6) with low wet tension (Comparative Example 1) and a laminate using a resin composition (I-10) with low Charpy impact strength (Comparative Example 5) In this case, the adhesion and flexibility with the vapor deposited layer are reduced.

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