WO2024019169A1 - 蒸着用基材フィルム、および蒸着フィルム - Google Patents

蒸着用基材フィルム、および蒸着フィルム Download PDF

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Publication number
WO2024019169A1
WO2024019169A1 PCT/JP2023/026859 JP2023026859W WO2024019169A1 WO 2024019169 A1 WO2024019169 A1 WO 2024019169A1 JP 2023026859 W JP2023026859 W JP 2023026859W WO 2024019169 A1 WO2024019169 A1 WO 2024019169A1
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Prior art keywords
mass
film
units
methacrylic
vapor deposition
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PCT/JP2023/026859
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English (en)
French (fr)
Japanese (ja)
Inventor
祐作 野本
公俊 中村
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2024535162A priority Critical patent/JPWO2024019169A1/ja
Priority to CN202380054144.2A priority patent/CN119487109A/zh
Priority to KR1020257004112A priority patent/KR20250041129A/ko
Publication of WO2024019169A1 publication Critical patent/WO2024019169A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • 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
    • C08F8/48—Isomerisation; Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention relates to a substrate film for vapor deposition, and a vapor deposited film in which the substrate film for vapor deposition is provided with a vapor deposited film. More specifically, the present invention relates to a film that is excellent in dimensional stability, adhesion to a vapor deposited film, and flexibility and is suitable for vapor deposition applications, and a vapor deposited film in which a conductive layer or a gas barrier layer is formed by vapor deposition.
  • a technique is known in which a metal such as tin-doped indium oxide is vapor-deposited in order to impart design properties, conductivity, etc. to a base film (for example, Patent Document 1).
  • a technique is known in which an inorganic compound such as silicon oxide is vapor-deposited in order to impart gas barrier properties, antireflection properties, etc. to a base film (for example, Patent Document 2).
  • the base film may be further required to have excellent light transmittance.
  • Methacrylic resin is a resin with extremely excellent light transmittance.
  • methacrylic resin films generally have low adhesion to vapor deposited films, making it difficult to use them as base films for vapor deposition.
  • Patent Document 3 discloses that a styrene monomer and an alkenyl cyanide are added to at least one surface of a thermoplastic resin layer (A) made of a resin composition (a) containing a methacrylic resin.
  • a laminated film for direct metal deposition which is formed by laminating a styrene resin layer (B1) made of a resin composition (b1) containing a copolymer of
  • Patent Documents 4 and 5 propose an acrylic resin film for metal deposition formed by molding a (meth)acrylic resin composition having an acid value of 0.2 to 1.5 mmol/g.
  • Patent Document 6 proposes a base film obtained by molding a glutarimide acrylic resin having a glutarimide structural unit and a methyl methacrylate structural unit to obtain a film, and biaxially stretching the film.
  • Patent Document 7 proposes a base material for a transparent conductive film made of a mixed resin of a polymethylmethacrylimide resin and an acrylic elastomer.
  • the above-mentioned film had a problem in that it had a high water absorption rate, and the physical properties deteriorated and dimensional changes were large due to water absorption.
  • Japanese Unexamined Patent Publication No. 2-6126 Japanese Patent Application Publication No. 2004-276566 Japanese Patent Application Publication No. 2011-143584 Japanese Patent Application Publication No. 2012-57067 Japanese Patent Application Publication No. 2010-236085 Japanese Patent Application Publication No. 6-256537 Japanese Patent Application Publication No. 2020-122125
  • an object of the present invention is to provide a base film that has high heat resistance, flexibility, and dimensional stability and that is used for providing a vapor deposited film on at least one surface thereof, and a combination of the base film and the vapor deposited film.
  • An object of the present invention is to provide a vapor-deposited film comprising:
  • the present inventor has completed the present invention, which includes the following embodiments.
  • methacrylic copolymer (a) having 1 to 48% by mass of at least one selected from the group consisting of physical units and 0 to 20% by mass of unsubstituted or N-substituted maleimide units, and having a glass transition temperature
  • a substrate film for vapor deposition comprising a methacrylic resin composition (I) having a temperature of 135° C.
  • 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 film comprising the base film according to [1] and a vapor deposited film provided on at least one surface of the base film.
  • methacrylic copolymer (a) having 1 to 48% by mass of at least one selected from the group consisting of physical units and 0 to 20% by mass of unsubstituted or N-substituted maleimide units, and having a glass transition temperature is 135° C. or higher, forming the methacrylic resin composition (I) to obtain a film, and biaxially stretching the film to an area ratio of 1.5 to 8 times.
  • Method of manufacturing material film
  • 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.
  • the base film of the present invention has high heat resistance, flexibility, and dimensional stability.
  • the base film of the present invention can be suitably used in a vapor deposition process.
  • the vapor-deposited film of the present invention has high adhesion to the vapor-deposited film, and can be provided with high-performance functions in various uses.
  • the transparent conductive film which is an embodiment of the vapor-deposited film of the present invention, is used for window electrodes of photoelectric conversion elements of solar cells, electromagnetic shielding films of electromagnetic shields, transparent radio wave absorbers, electrodes of input devices such as transparent touch panels, and liquid crystal displays. It is useful as a base material for organic EL displays, transparent electrodes for touch panels, and the like.
  • gas barrier film which is another embodiment of the vapor-deposited film of the present invention, is useful as a packaging material for foods, medicines, etc., and as a sealing material for organic EL elements, organic thin-film solar cells, organic transistors, flexible liquid crystals, etc. be.
  • the base film of the present invention is a film used for vapor deposition.
  • Vapor deposition includes physical vapor deposition and chemical vapor deposition.
  • conventionally known physical vapor deposition methods such as vacuum evaporation methods, sputtering methods, and ion plating methods, or chemical vapor deposition methods can be appropriately employed.
  • the vacuum evaporation method is preferably used.
  • the methacrylic resin composition (I) used in the 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 glutarimidization reaction due to oxidation, the heat shrinkage rate of the base film, and the dimensional stability of the deposited 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 stretchability of the unstretched 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 methacrylic copolymer (a) related 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 methacrylic resin composition (I) according to the present invention has excellent moisture resistance and can suppress curling caused by moisture absorption.
  • 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.
  • the base film of the present invention can reduce the heat shrinkage rate.
  • 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.
  • the saturated water absorption rate is 3.0% by mass or less, the base film of the present invention has excellent dimensional stability.
  • the methacrylic resin composition (I) according to the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more, and even more preferably 90% or more.
  • the total light transmittance of the methacrylic resin composition is a value measured in accordance with JIS K7361-1 using a haze meter using a press sheet with a thickness of 3 mm.
  • 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 base film for vapor deposition of the present invention can be produced by molding the methacrylic resin composition (I).
  • the base film of the present invention can be obtained by molding the methacrylic resin composition (I) to obtain a raw film, and then subjecting the raw film to a stretching treatment. can be manufactured.
  • the method for molding the methacrylic resin composition is not particularly limited.
  • the molding method include a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, and a calendar molding method.
  • extrusion molding is preferred from the viewpoint of productivity.
  • the temperature set in the extruder for the methacrylic resin composition discharged from the extruder is preferably 180 to 280°C, more preferably 200 to 260°C.
  • thermoplastic resin film molding As the extrusion molding method, a known method used for ordinary thermoplastic resin film molding can be adopted. For example, from the viewpoints of good surface smoothness, good gloss, and low haze, molding can be performed using a device equipped with a flat T-die and two or more metallic polishing rolls or belts with mirror-finished surfaces. can.
  • the linear pressure between the pair of mirror-finished rolls or mirror-finished belts is preferably 10 N/mm or more, more preferably 30 N/mm.
  • the surface temperature of both the mirror-finished roll or the mirror-finished belt is 130°C or less. Moreover, it is preferable that the surface temperature of at least one of the pair of mirror-finished rolls or mirror-finished belts is 60° C. or higher.
  • the surface temperature is set to such a value, the methacrylic resin composition discharged from the extruder can be cooled at a faster rate than natural cooling, making it easy to obtain a film with excellent surface smoothness and low haze.
  • the methacrylic resin composition is preferably melt-filtered using a filter before molding.
  • a filter By molding using a melt-filtered methacrylic resin composition, it is easy to obtain a film with fewer defects caused by foreign matter, gel, and the like.
  • the filter used for melt filtration is not particularly limited.
  • the filter is appropriately selected from known filters in terms of operating temperature, viscosity, required filtration accuracy, and the like. Specific examples of the filter include a nonwoven fabric made of glass fiber or the like; a phenol resin-impregnated cellulose film; a sintered metal fiber nonwoven film; a sintered metal powder film; a wire mesh; or a combination of these.
  • the filtration accuracy of the filter it is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the stretching treatment methods used in the field of resin films can be adopted.
  • the stretching process is usually performed through the steps of heating, stretching, heat setting, and cooling in this order.
  • This stretching treatment increases mechanical strength and makes it possible to obtain a base film that is less likely to crack.
  • Examples of the stretching method include uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and tubular stretching.
  • the temperature during stretching is preferably 100 to 200°C, more preferably 120 to 160°C, from the viewpoint of uniform stretching and obtaining a film with high strength.
  • the tensile speed during stretching is preferably 100 to 5000%/min based on the length.
  • the stretching ratio in biaxial stretching is preferably 1.5 to 8 times in terms of area ratio. After stretching, a base film with little heat shrinkage can be obtained by heat-setting or relaxing the stretched film.
  • the stretching ratio in biaxial stretching can be measured from the length and width of the film before and after stretching.
  • the thickness of the base film for vapor deposition of the present invention is 10 to 50 ⁇ m, preferably 15 to 40 ⁇ m.
  • the total light transmittance of the base 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 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 wetting tension of the surface 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 base film for vapor deposition of the present invention and the vapor deposited film 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 vapor-deposited film of the present invention comprises the base film of the present invention and a vapor-deposited film provided on at least one surface of the base film.
  • the deposited film is provided to impart various functions to the film. Examples of such functions include decoration, scratch resistance, antistatic, antifouling, friction reduction, antiglare, antireflection, high light reflection, adhesiveness, impact resistance, antisticking, conductivity, and gas barrier. can.
  • the vapor-deposited film of the present invention can also be considered as having a vapor-deposited film laminated on at least one surface of the base film of the present invention, so the vapor-deposited film of the present invention can also be referred to as the laminated film of the present invention. You can also do it.
  • the material used for the deposited film is not particularly limited, and examples 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-deposited films using at least one selected from these materials can be provided on one or both sides of the base film.
  • Deposited films 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 deposited film made of polysiloxane can be easily made hydrophilic with oxygen plasma or the like, has good adhesion to an inorganic deposited film, 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 deposited film 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 film 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 film with a high refractive index and a vapor deposited film 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 conductive layer containing a metal oxide is provided on the base film. If necessary, it may have an index matching layer, a hard coat layer and/or an anti-blocking hard coat layer.
  • the index matching layer, hard coat layer, and anti-blocking layer configurations well known in the industry can be adopted, so detailed explanations will be omitted.
  • Examples of the material constituting the conductive layer include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite oxide, etc. be able to. Among them, indium-tin composite oxide (ITO) is preferred.
  • ITO indium-tin composite oxide
  • a vapor deposited film 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 film include, for example, metal alloys made 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.
  • At least one inorganic compound selected from the group consisting of oxides, nitrides, carbides, oxycarbides, nitride carbides, oxynitrides, and oxynitride carbides is preferred.
  • Such inorganic compounds include silicon compounds (Si), aluminum compounds (Al), indium compounds (In), tin compounds (Sn), zinc compounds (Zn), titanium compounds (Ti), copper compounds (Cu), or tantalum compounds.
  • Ti titanium compound
  • Si silicon compound
  • Al aluminum compound
  • In indium compound
  • Sn tin compound
  • Zn zinc compound
  • Ti titanium compound
  • Si silicon compound or aluminum
  • silicon compound or aluminum Most preferred are compounds. These materials can be used alone or in combination of two or more.
  • the inorganic compound and an elemental metal or elemental metalloid can be used in combination.
  • the obtained deposited film can be analyzed using 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 film 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 film using ion etching.
  • the vapor deposited film in the vapor deposited film of the present invention may be a stack of two or more films made of different or similar materials.
  • One example is a configuration in which a transparent conductive film is provided on a gas barrier vapor-deposited film in order to improve resistance value stability and heat resistance stability of the transparent conductive film.
  • the thickness of such a gas barrier vapor deposited film is not particularly limited, but is preferably 0.001 to 1 ⁇ m, more preferably 0.002 to 0.1 ⁇ m, and even more preferably 0.003 to 0.05 ⁇ m.
  • a specific example of such a vapor-deposited film having gas barrier properties is preferably a thin film made of a metal oxide, a metal nitride, or a mixture thereof.
  • one or more vapor deposited films may be further provided on the gas barrier vapor deposited film in order to protect the gas barrier vapor deposited film or improve gas barrier properties.
  • the thickness of such a protective vapor deposited film is not particularly limited, but is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.03 ⁇ m to 5 ⁇ m, and even more preferably 0.05 ⁇ m to 1 ⁇ m.
  • Specific examples of the protective deposited film include a deposited film made of a metal oxide or metal oxynitride, and a deposited film made of an organic polymer material.
  • the thickness of the deposited film can be set depending on the function to be imparted, but is preferably 30 to 2000 nm, more preferably 50 to 1500 nm, still more preferably 100 to 1000 nm, and most preferably 200 to 800 nm. It is preferable that the thickness of the vapor deposited film is within the above range from the viewpoint of suppressing the tendency for spots and defects to occur in the vapor deposited film if it is too thin, suppressing costs, suppressing a decrease in light transmittance, and suppressing coloring.
  • the vapor deposited film 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.
  • PVD methods physical vapor deposition methods
  • CVD method chemical vapor deposition methods
  • plasma chemical vapor deposition is more preferred, since high-speed film formation is possible and good adhesion to the substrate is achieved.
  • Plasma source methods used in plasma chemical vapor deposition include capacitively coupled plasma using parallel plate electrodes (parallel plate type), inductively coupled plasma (coil type), microwave excited plasma using surface waves, etc. Can be done. An inductive coupling method that can efficiently convert source gas molecules into plasma is preferred.
  • the vapor deposition may be performed using a combination of plasma chemical vapor deposition and other types of chemical vapor deposition (for example, catalytic chemical vapor deposition).
  • plasma chemical vapor deposition method and the catalytic chemical vapor deposition method together, it becomes possible to perform processing with extremely small plasma damage and processing with a high film formation rate.
  • 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.
  • Surface treatments include, for example, 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; treatment methods by applying a primer paint (formation of an anchor layer); etc. can be mentioned. 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 anchor layer is not particularly limited.
  • the anchor layer may be any raw material that has good adhesion to the layer made of methacrylic resin composition (I) and has good receptivity to the constituent materials of the deposited film, 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 from the viewpoint of better adhesion.
  • the acrylic resin is not particularly limited, and may be included in the category of methacrylic resins described above.
  • the thickness of the anchor layer is preferably 0.1 to 3 ⁇ m. Since the thickness of the anchor layer is within the above range, the vapor deposited film has excellent adhesion between the layer made of the methacrylic resin composition (I) and the vapor deposited film.
  • 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 vapor-deposited 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 film of the present invention may further have a coating film on the surface of the vapor deposited film.
  • 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 vapor-deposited film of the present invention can be applied, for example, to 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 back sheets, light guide plates for liquid crystals, diffusion plates, back sheets, and reflective sheets.
  • liquid crystal display films such as 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, automotive headlight and tail lamp lenses, inner lenses, and instruments.
  • Vehicle fields such as covers, sunroofs, glazing, glasses and contact lenses, endoscope lenses, road signs, bathroom equipment, flooring materials, road transmissive plates, lenses for double glazing, lighting windows, carports, and lighting lenses. It can be used in the field of architecture and building materials such as lighting covers, sizing for building materials, microwave cooking containers (tableware), housings for home appliances, toys, sunglasses, stationery, solar light-concentrating films, etc. It can also be used as an alternative to molded products using transfer sheets.
  • transparent conductive films with conductive vapor deposited films include window electrodes of photoelectric conversion elements in solar cells, electromagnetic shielding films for electromagnetic shields, transparent radio wave absorbers, electrodes of input devices such as transparent touch panels, and liquid crystals.
  • Examples include base materials such as transparent electrodes for displays, organic EL displays, and touch panels.
  • 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) method.
  • 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 (Rm) of the acid anhydride was determined. From the maleic anhydride amount (m) and imidization rate (Rm) of the precursor polymer determined by 13 C-NMR, the value determined by the following formula was taken as the maleic anhydride amount (M) in the methacrylic copolymer.
  • Amount of maleic anhydride (M) m ⁇ (100-Rm)/100
  • methacrylic The ratio of glutarimide units to maleimide units in the copolymer was determined.
  • 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.
  • ⁇ Biaxial stretchability> The following evaluations were performed on 10 base films (biaxially stretched films) of Examples and Comparative Examples. A: Out of 10 film pieces, there are 5 or more film pieces with no cracks or cracks. B: Out of 10 film pieces, there are 4 or less film pieces with no cracks or cracks. Uniaxial stretchability and Based on the evaluation results of biaxial stretchability, the quality of stretchability was determined based on the following criteria. ⁇ : Uniaxial stretchability and biaxial stretchability are both graded A. ⁇ : Uniaxial stretchability or biaxial stretchability is graded A. ⁇ : Uniaxial stretchability and biaxial stretchability are graded B.
  • Curl value B The value obtained by subtracting the curl value B from the curl value (AB) was used as the curl value and was used as a criterion for determining dimensional stability.
  • ⁇ Curl value is within the range of 0 to 50 mm
  • ⁇ Curl value is outside of the range of 0 to 50 mm
  • methacrylic copolymer (a), styrene-maleic anhydride copolymer, and methacrylic resin related to the present invention The following materials were used for the methacrylic copolymer (a), styrene-maleic anhydride copolymer, and methacrylic resin related to the present invention.
  • 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.
  • 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-4).
  • the weight average molecular weight Mw of the obtained precursor polymer (p-4) was measured. The results are shown in Table 1.
  • 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 The methacrylic resin composition (I-1) was dried at 80° C. for 12 hours. Using a 20 mm ⁇ single-screw extruder (manufactured by OCS), the methacrylic copolymer (a-1) was extruded through a 150 mm wide T-die at a resin temperature of 260°C, and then rolled using a roll with a surface temperature of 110°C. An unstretched film having a width of 110 mm and a thickness of 160 ⁇ m was obtained.
  • the obtained unstretched film was cut into 100 mm x 100 mm, and stretched using a pantograph biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.) at a stretching temperature of 10° C. above the glass transition temperature, a stretching speed of 500%/min in one direction, and a stretching speed of 500%/min in one direction.
  • the film was sequentially biaxially stretched at a stretching ratio of 2 times (4 times the area ratio), cooled to 100° C. or lower over 2 minutes, and taken out to obtain a biaxially stretched film (substrate film) with a thickness of 40 ⁇ m.
  • Table 3 shows the evaluation results of the obtained base film.
  • the base films obtained in Examples 1 to 5 used methacrylic resin compositions (I-1) to (I-5), which have high Charpy impact strength and excellent fluidity. It has excellent stretchability. Furthermore, since the resin composition is heat resistant and has low water absorption, the base films of Examples 1 to 5 have low heat shrinkage rates and excellent dimensional stability. Furthermore, since the wetting tension is high, the base films of Examples 1 to 5 have excellent adhesion to the deposited film. From the above, the base films of Examples 1 to 5 are suitable as base materials for vapor deposition.
  • base films using methacrylic resin compositions (I-6) to (I-9) and (I-12) that do not have sufficient heat resistance or low water absorption have a high heat shrinkage rate and poor dimensional stability.
  • a base film using a methacrylic resin composition (I-6) with low wet tension (Comparative Example 1) and a base film using a resin composition (I-10) with low Charpy impact strength (Comparative Example In 5)
  • the base film (Comparative Example 6) using the methacrylic resin composition (I-11) with low heat decomposition resistance has poor stretchability.

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WO2020100913A1 (ja) * 2018-11-13 2020-05-22 株式会社クラレ 変性メタクリル樹脂および成形体
WO2021193922A1 (ja) * 2020-03-26 2021-09-30 株式会社クラレ アクリル系組成物及び成形体
WO2021235393A1 (ja) * 2020-05-19 2021-11-25 株式会社クラレ 逆波長分散性位相差フィルム用メタクリル系共重合体、組成物、フィルム、フィルムの製造方法および積層体
WO2022202965A1 (ja) * 2021-03-24 2022-09-29 株式会社クラレ メタクリル系共重合体、メタクリル系樹脂組成物およびその製造方法、並びに成形体

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JP4249520B2 (ja) 2003-03-19 2009-04-02 大日本印刷株式会社 ガスバリア性積層材の製造方法
JP5489663B2 (ja) 2009-03-10 2014-05-14 株式会社カネカ アクリル系樹脂フィルム
JP5087092B2 (ja) 2010-01-13 2012-11-28 住友化学株式会社 金属直接蒸着用積層フィルム
JP2012057067A (ja) 2010-09-09 2012-03-22 Kaneka Corp 金属蒸着用艶消しアクリル系樹脂フィルム
JP2020122125A (ja) 2019-01-31 2020-08-13 日東電工株式会社 透明導電性フィルム用基材および透明導電性フィルム

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JPH06256537A (ja) * 1992-02-26 1994-09-13 Kuraray Co Ltd 延伸フィルムまたはシート
WO2020100913A1 (ja) * 2018-11-13 2020-05-22 株式会社クラレ 変性メタクリル樹脂および成形体
WO2021193922A1 (ja) * 2020-03-26 2021-09-30 株式会社クラレ アクリル系組成物及び成形体
WO2021235393A1 (ja) * 2020-05-19 2021-11-25 株式会社クラレ 逆波長分散性位相差フィルム用メタクリル系共重合体、組成物、フィルム、フィルムの製造方法および積層体
WO2022202965A1 (ja) * 2021-03-24 2022-09-29 株式会社クラレ メタクリル系共重合体、メタクリル系樹脂組成物およびその製造方法、並びに成形体

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