WO2024128122A1 - 延伸フィルムとその製造方法、光学フィルム、および加飾フィルム - Google Patents

延伸フィルムとその製造方法、光学フィルム、および加飾フィルム Download PDF

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WO2024128122A1
WO2024128122A1 PCT/JP2023/043818 JP2023043818W WO2024128122A1 WO 2024128122 A1 WO2024128122 A1 WO 2024128122A1 JP 2023043818 W JP2023043818 W JP 2023043818W WO 2024128122 A1 WO2024128122 A1 WO 2024128122A1
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Prior art keywords
film
glutarimide
resin
stretched film
stretching
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English (en)
French (fr)
Japanese (ja)
Inventor
仁聡 谷口
祐作 野本
侑史 大澤
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to CN202380081125.9A priority Critical patent/CN120187781A/zh
Priority to JP2024564332A priority patent/JPWO2024128122A1/ja
Publication of WO2024128122A1 publication Critical patent/WO2024128122A1/ja
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    • 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
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • This disclosure relates to stretched films and their manufacturing methods, optical films, and decorative films.
  • Liquid crystal display devices use various resin films such as polarizer protective films.
  • triacetyl cellulose (TAC) film has been mainly used for polarizer protective films.
  • TAC film has high moisture permeability, and there is a risk of causing a deterioration in the quality of the polarizer, especially when it is thin.
  • an amorphous thermoplastic resin film mainly composed of glutarimide resin is being considered. If no special treatment is applied, this film tends to become brittle and its mechanical properties deteriorate as the film becomes thinner, so it is generally stretched to increase its toughness.
  • Patent Document 1 discloses a stretched film obtained by stretching a film made of a glutarimide resin containing 20 mol % or more of glutarimide units and (meth)acrylic acid alkyl ester units such as methyl methacrylate units, in a range of 1.2 to 5.0 times at a temperature range of 2 to 50° C. higher than the glass transition temperature of the resin (claim 1, paragraphs 0007 and 0012, the section [Examples], etc.).
  • Patent Document 2 discloses a stretched film containing an imidized resin composition having glutarimide units and (meth)acrylic acid alkyl ester units such as methyl methacrylate units, and having an imidization rate of 30 to 90% and an acid value of 0.01 to 0.2 mmol/g, as an optical film suitable as a polarizer protective film (claims 1, 2, 4, 6, etc.).
  • Patent Document 3 relates to a method for producing a stretched film containing an acrylic resin such as a glutarimide resin, and discloses a method for producing a stretched film including a first axial stretching step in which an unstretched film is stretched at a temperature equal to or higher than 5° C. lower than the glass transition temperature of the film, and a second axial stretching step in which the film is stretched at a temperature equal to or higher than the glass transition temperature of the film and within a temperature range of the glass transition temperature of the film plus 10° C. (claims 1, 3, etc.).
  • Patent Document 4 relates to a method for producing a stretched film containing an acrylic resin such as a glutarimide resin and acrylic rubber particles, and discloses a method for producing a stretched film in which the stretching temperature in the stretching step is Tg+20°C to Tg+55°C (claims 1, 6, etc.).
  • the inventors of the present invention have found that, depending on the polymer composition, etc., glutarimide resins have poor stretchability, making it impossible to stably produce stretched films with good thickness uniformity, and may break depending on the stretch ratio. If there is thickness unevenness, there is a risk of reduced impact resistance due to the presence of thin parts.
  • the stretched film disclosed in Patent Document 4 contains acrylic rubber particles.
  • the addition of a rubber component such as acrylic rubber particles can improve mechanical properties such as impact resistance, but the dimensional stability of the stretched film against temperature tends to deteriorate, and the shrinkage rate in a high-temperature environment tends to increase.
  • a coating layer such as a hard coat layer may be formed on a raw film or a stretched film containing a thermoplastic resin.
  • a film containing a glutarimide resin preferably has good coating adaptability, so that a coating layer can be formed with good adhesion without causing poor appearance such as warping or curling when a coating layer is formed thereon.
  • Patent Documents 1 to 4 are silent about optimizing the rheological properties, such as the uniaxial extensional viscosity property, of glutarimide resins.
  • This disclosure has been made in consideration of the above circumstances, and aims to provide a stretched film with good thickness uniformity, impact resistance, dimensional stability against temperature, and coating adaptability, and a method for producing the same.
  • the present disclosure provides a stretched film, a manufacturing method thereof, an optical film, and a decorative film as set forth in the following items [1] to [10].
  • a stretched film comprising a glutarimide resin (G) containing a glutarimide unit and a methyl methacrylate unit
  • the glutarimide resin (G) has a glutarimide cyclization rate (R) defined as the ratio of the content of glutarimide units to the total amount of glutarimide units and methyl methacrylate units of 50 to 90 mass%, a product (Tg ⁇ R) of the glass transition temperature (Tg) [° C.] and the glutarimide cyclization rate (R) [mass %] of 7,500 to 15,000, and a strain hardening degree (K) of the uniaxial elongation viscosity of the film determined by the following measurement method is 0.50 to 3.00.
  • R glutarimide cyclization rate
  • the glutarimide resin (G) is press molded to obtain a film having a thickness of 200 ⁇ m.
  • the uniaxial extensional viscosity ( ⁇ ) of the film is measured at 190° C. in a constant strain rate mode under two conditions: a low strain rate condition in which the strain rate is 0.1 sec ⁇ 1 and a high strain rate condition in which the strain rate is 10.0 sec ⁇ 1 .
  • the ratio ( ⁇ exp / ⁇ 1 ) of the uniaxial extensional viscosity ( ⁇ exp ) under the high strain rate condition to the uniaxial extensional viscosity ( ⁇ 1 ) under the low strain rate condition is calculated as the nonlinear parameter ( ⁇ n ). Furthermore, the natural logarithm (ln( ⁇ n )) of ⁇ n is calculated.
  • Tg glass transition temperature of the glutarimide resin
  • the method for producing a stretched film according to [7] wherein the stretching temperature is +20 to +55° C. higher than the glass transition temperature (Tg) of the glutarimide resin (G).
  • the present disclosure provides a stretched film with good thickness uniformity, impact resistance, dimensional stability against temperature, and coating adaptability, and a method for producing the same.
  • FIG. 1 is a graph showing an example of a linear approximation equation obtained by plotting the relationship between elongation strain ( ⁇ ) and ln( ⁇ n ) in the section [Examples].
  • FIG. 1 is an explanatory diagram of a method for evaluating thickness uniformity.
  • film and “sheet” are used for thin film molded bodies depending on their thickness, but there is no clear distinction between them.
  • film includes “sheet.”
  • the stretched film of the present disclosure contains a glutarimide resin (G) that contains glutarimide (GI) units and methyl methacrylate (MMA) units, and the content of the glutarimide units relative to the total amount of the glutarimide units and the methyl methacrylate units is 50 to 90 mass%.
  • G glutarimide resin
  • GI glutarimide
  • MMA methyl methacrylate
  • the glutarimide (GI) can be a unit represented by the following general formula (I).
  • R 1s are each independently a hydrogen atom or a methyl group, and it is preferable that both R 1s 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 and containing an aromatic ring, preferably a methyl group, an n-butyl group, a cyclohexyl group, or a benzyl group, more preferably a methyl group, an n-butyl group, or a benzyl group, and particularly preferably a methyl group.
  • the glutarimide cyclization rate (R) [mass %] is defined as the ratio of the content [mass %] of glutarimide units to the total amount of glutarimide units and methyl methacrylate units in the glutarimide resin (G) (100 mass %). Since a stretched film having good thickness uniformity, impact resistance, dimensional stability, and coating adaptability can be obtained, the glutarimide cyclization rate (R) of the glutarimide resin (G) is 50 to 90 mass %.
  • the lower limit is preferably 55 mass %, more preferably 58 mass %, and particularly preferably 60 mass %, and the upper limit is preferably 88 mass %, more preferably 86 mass %.
  • the glutarimide cyclization rate (R) [mass %] can be measured by the method described in the section [Examples] below.
  • the glutarimide resin (G) has a strain hardening (K) of the uniaxial elongation viscosity of the film, determined by the following measurement method, of 0.50 to 3.00.
  • the lower limit is preferably 0.55, more preferably 0.58, and particularly preferably 0.60
  • the upper limit is preferably 2.80, more preferably 2.50, even more preferably 2.00, particularly preferably 1.50, and most preferably 1.00.
  • ⁇ Method for measuring strain hardening (K) of uniaxial extensional viscosity The glutarimide resin (G) is press molded to obtain a film having a thickness of 200 ⁇ m.
  • the uniaxial extensional viscosity ( ⁇ ) of the film is measured at 190° C. in a constant strain rate mode under two conditions: a low strain rate condition in which the strain rate is 0.1 sec ⁇ 1 and a high strain rate condition in which the strain rate is 10.0 sec ⁇ 1 .
  • the ratio ( ⁇ exp / ⁇ 1 ) of the uniaxial extensional viscosity ( ⁇ exp ) under the high strain rate condition to the uniaxial extensional viscosity ( ⁇ 1 ) under the low strain rate condition is calculated as the nonlinear parameter ( ⁇ n ). Furthermore, the natural logarithm (ln( ⁇ n )) of ⁇ n is calculated. The relationship between the elongational strain ( ⁇ ) and ln( ⁇ n ) when the elongational strain ( ⁇ ) under the high strain rate condition is changed within a range of 0.7 to 2.0 in increments of at least 0.04 is plotted, and a linear approximation equation represented by the following equation (A) is determined by the least squares method.
  • the strain hardening degree (K) of the uniaxial elongational viscosity is a parameter that indicates the degree of strain hardening. Films containing resins that exhibit strain hardening develop elasticity when stretched, allowing uniform deformation. In films containing glutarimide resins (G) whose strain hardening degree (K) of the uniaxial elongational viscosity is within the above range, when strain is increased in the constant strain rate mode, the increase in uniaxial elongational viscosity is highly nonlinear, and a rapid increase in uniaxial elongational viscosity is observed in response to an increase in strain.
  • This glutarimide resin (G) has superior stretchability compared to glutarimide resins whose strain hardening degree (K) of the uniaxial elongational viscosity is less than the lower limit above, and by using this glutarimide resin (G), stretched films with good thickness uniformity can be stably produced.
  • glutarimide resins (G) whose uniaxial elongational viscosity strain hardening (K) is within the above range can have the properties of a higher glass transition temperature (Tg) and a higher film wetting tension than glutarimide resins whose uniaxial elongational viscosity strain hardening (K) is less than the above lower limit.
  • Glutarimide resin (G) has excellent stretchability and a high glass transition temperature (Tg), so by using glutarimide resin (G), it is possible to stably produce stretched films with good thickness uniformity without film breakage even under conditions of relatively high stretching temperatures and/or relatively high stretch ratios.
  • a stretched film containing a glutarimide resin (G) has good thickness uniformity and is therefore free of locally thin portions, and can have good impact resistance.
  • a rubber component such as acrylic rubber particles can improve the mechanical properties of the film, such as impact resistance, but it also tends to deteriorate the dimensional stability of the film and increase the shrinkage rate in a high-temperature environment.
  • a stretched film containing glutarimide resin (G) can have good impact resistance even without containing a rubber component such as acrylic rubber particles. Since glutarimide resin (G) has a high glass transition temperature (Tg) and does not require the addition of a rubber component such as acrylic rubber particles, the use of glutarimide resin (G) can provide a stretched film with good dimensional stability against temperature.
  • a coating layer such as a hard coat layer may be formed on the original film or stretched film.
  • Films (original film or stretched film) containing glutarimide resin (G) have a high glass transition temperature (Tg) and good dimensional stability against temperature, so that when a coating layer is formed on them, even if they are exposed to high temperatures in the drying and curing processes, the occurrence of poor appearance such as warping or curling is suppressed.
  • Films (original film or stretched film) containing glutarimide resin (G) have high surface wetting tension, so a coating layer can be formed on them with good adhesion. In other words, stretched films containing glutarimide resin (G) can have good coating adaptability.
  • the glutarimide resin (G) may contain one or more copolymerizable vinyl monomer units other than the glutarimide unit and the methyl methacrylate unit, if necessary.
  • the vinyl monomer unit is preferably at least one selected from the group consisting of (meth)acrylic acid ester monomer units other than the methyl methacrylate unit, aromatic vinyl monomer units, and vinyl cyanide monomer units, and among these, aromatic vinyl monomer units are preferred.
  • (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylic acid, (meth)acrylonitrile, etc.
  • Examples of the (meth)acrylic acid ester monomer include methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate, from the viewpoints of heat resistance, fluidity, thermal stability, productivity, etc.
  • the content of (meth)acrylic acid ester monomer units other than methyl methacrylate units in the glutarimide resin (G) is preferably 0 to 20 mass % from the viewpoint of heat resistance and thermal stability.
  • the upper limit is more preferably 10 mass %.
  • aromatic vinyl monomers include, from the viewpoints of heat resistance, fluidity, thermal stability, and productivity, styrene (St), ⁇ -methylstyrene ( ⁇ MSt), o-, m-, or p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, o-, m-, or p-ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylbenzylbenz
  • the content of aromatic vinyl monomer units in the glutarimide resin (G) (the total amount when multiple types are contained) is preferably 0 to 40 mass % from the viewpoint of heat resistance and thermal stability.
  • the upper limit is more preferably 30 mass %, particularly preferably 25 mass %.
  • Examples of the vinyl cyanide monomer include (meth)acrylonitrile and vinylidene cyanide from the viewpoints of heat resistance, fluidity, thermal stability, chemical resistance, productivity, etc. Among them, acrylonitrile and the like are preferred from the viewpoints of availability and chemical resistance.
  • the content of vinyl cyanide monomer units in the glutarimide resin (G) (the total amount when multiple types are contained) is preferably 0 to 20% by mass from the viewpoints of heat resistance and thermal stability. The upper limit is more preferably 10% by mass.
  • the glutarimide resin (G) may contain one or more vinyl monomer units other than those mentioned above.
  • the vinyl monomer other than those mentioned above include amides such as (meth)acrylamide; various polyfunctional monomers; and the like.
  • the content (total amount in the case of a plurality of types) of vinyl-based monomer units other than (meth)acrylic acid ester monomer units, aromatic vinyl monomer units, and vinyl cyanide monomer units in the glutarimide resin (G) is preferably 0 to 20% by mass from the viewpoint of heat resistance and thermal stability.
  • the upper limit is more preferably 10% by mass.
  • the weight average molecular weight (Mw) of the glutarimide resin (G) is preferably 40,000 to 250,000, more preferably 50,000 to 200,000, and particularly preferably 55,000 to 180,000.
  • Mw is equal to or greater than the lower limit
  • the strength and toughness of the stretched film of the present disclosure are improved.
  • the Mw is equal to or less than the upper limit
  • the melt fluidity of the glutarimide resin (G) is improved, and the film formability of the raw film containing the glutarimide resin (G) is improved.
  • the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the glutarimide resin (G) is preferably 1.6 to 3.0, more preferably 1.7 to 2.8, and particularly preferably 1.8 to 2.5. When the molecular weight distribution is within the above range, the film formability of the film raw material containing the glutarimide resin (G) is improved.
  • the "weight average molecular weight (Mw)” is the weight average molecular weight calculated based on standard polymethyl methacrylate (PMMA) determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the "number average molecular weight (Mn)” is the number average molecular weight calculated based on standard polymethyl methacrylate (PMMA) determined by GPC.
  • the acid value of the glutarimide resin (G) is preferably 0.01 to 0.30 mmol/g, more preferably 0.05 to 0.28 mmol/g.
  • the acid value is a value proportional to the content of carboxylic acid units and carboxylic anhydride units in the glutarimide resin (G).
  • the acid value can be calculated, for example, by the method described in JP-A-2005-23272. When the acid value is within the above range, a good balance of heat resistance, mechanical properties, and moldability is achieved.
  • the lower limit of the glass transition temperature (Tg) of the glutarimide resin (G) is preferably 135° C., more preferably 138° C., particularly preferably 140° C., and most preferably 145° C.
  • the upper limit of Tg is not particularly limited, and is preferably 170° C., more preferably 165° C., particularly preferably 160° C., and most preferably 155° C.
  • the "glass transition temperature (Tg)" is a value measured in accordance with JIS K7121. For specific measurement methods, see the section [Examples] below.
  • the glutarimide resin (G) has a product (Tg ⁇ R) of the glass transition temperature (Tg) [°C] and the glutarimide cyclization rate (R) [mass %] of 7,500 to 15,000.
  • the lower limit is preferably 7,600, more preferably 7,700, even more preferably 7,800, particularly preferably 8,000, and most preferably 8,500.
  • the upper limit is preferably 14,500, more preferably 14,000, even more preferably 13,500, even more preferably 13,000, particularly preferably 12,000, and most preferably 10,000.
  • the balance between the glass transition temperature (Tg) and the glutarimide cyclization rate (R) is important.
  • the stretchability may be adversely affected, such as the imide cyclized portion not being able to be sufficiently oriented during stretching.
  • a glutarimide resin (G) having a Tg/R value within the above range can have high stretchability compared to a glutarimide resin having a Tg/R value below the above lower limit, because intermolecular forces such as hydrogen bonds act appropriately with adjacent molecules with appropriate strength during stretching.
  • the glutarimide resin (G) having a Tg ⁇ R value within the above range can also have a high film wet tension.
  • a stretched film containing the glutarimide resin (G) having a Tg ⁇ R value within the above range can have good coating adaptability.
  • the melt flow rate (MFR) of the glutarimide resin (G) is preferably 0.3 to 20 g/10 min.
  • the lower limit of the MFR is more preferably 0.4 g/10 min, and particularly preferably 0.5 g/10 min.
  • the upper limit of the MFR is more preferably 15 g/10 min, particularly preferably 10 g/10 min, and most preferably 5 g/10 min. When the MFR is within the above range, the stability of hot melt molding is good.
  • MFR is a value measured in accordance with JIS K7210. For specific measurement methods, see the section "Examples" below.
  • the surface wet tension of a film (raw film or stretched film) containing glutarimide resin (G) is high, and can be, for example, 38 mN/m or more, or 39 mN/m or more, even without any special surface treatment.
  • the upper limit can be, for example, 50 mN/m, 45 mN/m, or 40 mN/m.
  • the wet tension is equal to or higher than the lower limit, the adhesion (adhesive strength) between the film containing glutarimide resin (G) and various coating layers is improved. Since the surface of a film containing a glutarimide resin (G) has a high wet tension, no special surface treatment is required to adjust the wet tension.
  • the surface of the film may be subjected to a known surface treatment such as corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, or chemical treatment.
  • a known surface treatment such as corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, or chemical treatment.
  • the "wet tension" can be measured in accordance with JIS K6768. For a specific measurement method, see the section [Examples] below.
  • Glutarimide resin (G) can be produced by known methods described in International Publication No. 2005/108438, JP 2010-254742 A, JP 2008-273140 A, and JP 2008-274187 A, etc.
  • the first production method includes an imide cyclization reaction step in which an imidizing agent is added to a precursor resin having two adjacent methyl methacrylate units to cause a reaction.
  • the imidizing agent include ammonia, aliphatic hydrocarbon group-containing amines such as methylamine (also called monomethylamine), ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, and n-hexylamine, aromatic hydrocarbon group-containing amines such as aniline, toluidine, trichloroaniline, and n-methylbenzylamine, alicyclic hydrocarbon group-containing amines such as cyclohexylamine and n-methylcyclohexylamine, and urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea
  • methyl methacrylate units may be hydrolyzed to form carboxy groups.
  • esterification agent include dimethyl carbonate and trimethyl acetate.
  • a tertiary amine such as trimethylamine, triethylamine, or tributylamine may be used in combination as a catalyst.
  • the second production method includes a method in which an imidizing agent represented by the general formula R 2 NH 2 is added to a precursor resin having an acid anhydride unit (glutaric anhydride unit) represented by the following formula (IIa) and reacted.
  • an imidizing agent represented by the general formula R 2 NH 2 is added to a precursor resin having an acid anhydride unit (glutaric anhydride unit) represented by the following formula (IIa) and reacted.
  • the reaction between the precursor resin and the imidizing agent can be carried out in a continuous manner, in which the precursor resin is melted using an extruder or the like, and the imidizing agent is added to the melt to carry out the reaction, or in a batch manner, in which a precursor resin solution is prepared using a solvent that is capable of dissolving the precursor resin but is unreactive in the imidization reaction, and the imidizing agent is added to the melt to carry out the reaction.
  • a precursor resin is charged into the raw material charging section of the extruder, and the precursor resin is melted to fill the cylinder. Then, an imidization agent is injected into the extruder using an addition pump, and the imidization reaction can be carried out in the extruder.
  • the region between the injection position of the imidizing agent and the resin discharge port (die portion) is also called the "reaction zone in the extruder.”
  • the extruder include a single screw extruder, a twin screw extruder, a multi-screw extruder, and a combination thereof. From the viewpoint of promoting the mixing of the imidizing agent with the precursor resin, a twin screw extruder is preferred.
  • twin screw extruder examples include a non-intermeshing co-rotating type, an intermeshing co-rotating type, a non-intermeshing counter-rotating type, and an intermeshing counter-rotating type.
  • the intermeshing co-rotating type is preferred from the viewpoint of promoting the mixing of the imidizing agent with the precursor resin, since it is capable of high-speed rotation.
  • the resin temperature (also referred to as the reaction temperature) in the reaction zone in the extruder is preferably 180 to 300° C., more preferably 200 to 290° C.
  • the reaction time in the reaction zone of the extruder is preferably 10 to 600 seconds, more preferably 30 to 300 seconds.
  • the resin pressure in the extruder is preferably from atmospheric pressure to 50 MPa, more preferably from 1 MPa to 30 MPa.
  • the extruder preferably has a vent hole capable of reducing the pressure to below atmospheric pressure in order to remove unreacted imidizing agent and by-products such as methanol.
  • a horizontal twin-screw reactor e.g., "Bivolac” manufactured by Sumitomo Heavy Industries, Ltd.
  • a vertical twin-screw agitator e.g., "Superblend” manufactured by Sumitomo Heavy Industries, Ltd.
  • other reactor capable of handling high viscosity materials.
  • a third manufacturing method includes a method including an intramolecular cyclization reaction step of a copolymer having a unit represented by the following formula (III).
  • this method it is preferable to carry out the reaction under heating at an appropriate temperature in order to promote the intramolecular cyclization reaction.
  • R 1 and R 2 are as defined above. Me represents a methyl group.
  • the stretched film of the present disclosure may consist only of the glutarimide resin (G), and may contain one or more optional components, as necessary, within a range that does not impair the effects of the present disclosure.
  • the content of the glutarimide resin (G) in the stretched film of the present disclosure is not particularly limited, but is preferably 90 to 100% by mass. The lower limit is more preferably 95% by mass.
  • the stretched film of the present disclosure may contain one or more other polymers other than the glutarimide resin (G) as an optional component.
  • the other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; styrene-based resins such as polystyrene, methyl methacrylate-styrene copolymer (MS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-maleic anhydride-methyl methacrylate copolymer (SMM resin), high impact polystyrene, acrylonitrile-styrene copolymer (AS resin), ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon
  • a stretched film containing a glutarimide resin (G) can have good impact resistance even without containing a rubber component such as acrylic rubber particles.
  • the content of the rubber component such as acrylic rubber particles (total amount in the case of multiple types) in the stretched film of the present disclosure is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0% by mass.
  • the content of other polymers in the stretched film of the present disclosure is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0% by mass.
  • the stretched film of the present disclosure may contain a filler as an optional component.
  • fillers include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
  • the content of the filler in the glutarimide resin (G) (the total amount when multiple types of filler are used) is preferably 0 to 3 mass%. The upper limit is more preferably 1.5 mass%.
  • the stretched film of the present disclosure may contain, as optional components, one or more additives other than those described above, such as antioxidants, heat degradation inhibitors, UV absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, dyes, organic dyes, pigments, light diffusing agents, matting agents, and phosphors.
  • additives other than the filler in the stretched film of the present disclosure is preferably 0 to 7% by mass from the viewpoint of suppressing defective appearance, etc.
  • the upper limit is more preferably 5% by mass, and particularly preferably 4% by mass.
  • the method for producing a stretched film according to the present disclosure includes: A step (S1) of preparing a raw film (also referred to as an unstretched film) containing a glutarimide resin (G); The method further comprises the step (S2) of uniaxially or biaxially stretching the raw film.
  • Step (S1) can be a process for producing a raw film.
  • the raw film can be produced by melt casting and solution casting, and from the viewpoint of productivity, the melt casting is preferred.
  • the melt casting can be exemplified by inflation, extrusion, calendaring, and cutting, and the extrusion is preferred.
  • the extrusion methods the T-die method is preferred.
  • the T-die method will be described below.
  • the resin material for the film roll which contains the glutarimide resin (G) and, if necessary, one or more optional components, is melt-kneaded using an extruder and extruded in a molten state from a T-die having a wide discharge port.
  • the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and combinations thereof.
  • the melting temperature of the resin material is higher than the glass transition temperature (Tg) of the glutarimide resin (G), and is preferably 180 to 350° C., more preferably 200 to 300° C., particularly preferably 200 to 280° C., and most preferably 210 to 270° C. From the viewpoint of suppressing coloration, it is preferable to perform melt kneading under reduced pressure using a vent or under a nitrogen stream.
  • the filter material of the filter is appropriately selected depending on the use temperature, viscosity, filtration accuracy, etc.
  • nonwoven fabric made of glass fiber, etc. sheet-like material made of cellulose impregnated with phenolic resin
  • sintered sheet-like material of nonwoven metal fiber fabric sintered sheet-like material of metal powder; wire mesh; and combinations thereof.
  • a filter made of a plurality of laminated sheets of sintered nonwoven metal fiber fabric is preferable.
  • the filtration accuracy of the filter is not particularly limited, and is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • a gear pump may be installed in the extrusion molding line to carry out film production.
  • the molten resin extruded into a film shape from the T-die is cooled by a plurality of cooling rolls, such as rigid metal rolls and elastic metal rolls.
  • the rigid metal roll is a roll having no elasticity and made of a metal such as stainless steel, and examples of such rolls include a drilled roll and a spiral roll.
  • the surface of the rigid metal roll is preferably a mirror surface, since it is possible to produce a raw film having high surface smoothness.
  • the metal elastic roll is a roll having an elastic outer cylinder made of a thin metal film on the outer periphery.
  • the metal elastic roll is composed of, for example, a metal shaft roll made of stainless steel or the like, a thin metal film (elastic outer cylinder) made of stainless steel or the like covering the outer periphery of the shaft roll, and a fluid sealed between the shaft roll and the thin metal film (elastic outer cylinder), and can exhibit elasticity in the presence of the fluid.
  • the fluid include water and oil.
  • the thickness of the metal thin film of the metal elastic roll is not particularly limited, and is preferably about 2 to 8 mm.
  • the metal thin film preferably has bending properties and flexibility, and is preferably a seamless structure without welded joints.
  • a metal elastic roll equipped with such a metal thin film is excellent in durability, and if the metal thin film is mirror-finished, it can be handled in the same way as a normal mirror-finished roll, and can produce a film raw material with high surface smoothness.
  • the film web obtained after cooling is taken up by a take-up roll. The above steps of extrusion, cooling, and taking up are carried out continuously.
  • the solution casting method is a method in which an organic solvent is added to a resin material for a film roll containing a glutarimide resin (G) and, if necessary, one or more optional components, to obtain a resin solution, which is then cast onto a support and dried by heating to produce a film roll.
  • G glutarimide resin
  • the organic solvent is not particularly limited, and examples thereof include halogenated hydrocarbon solvents such as methylene chloride and trichloroethane, highly polar non-halogenated solvents such as dimethylformamide and dimethylacetamide, aromatic solvents such as toluene, xylene, and anisole, cyclic ether solvents such as dioxane, dioxolane, tetrahydrofuran, and pyran, ketone solvents such as methyl ethyl ketone, and combinations thereof.
  • halogenated hydrocarbon solvents such as methylene chloride and trichloroethane are preferred because they easily dissolve the glutarimide resin (G) and have a low boiling point.
  • the amount of organic solvent used may be any amount as long as it can dissolve the glutarimide resin (G) to an extent that casting can be sufficiently performed.
  • "dissolved” refers to a state in which the resin is present in the solvent in a homogeneous state to an extent that casting can be sufficiently performed. It is not necessary that the solute is completely dissolved in the solvent.
  • the resin concentration in the solution is preferably 1 to 90% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 50% by mass.
  • the support is not particularly limited, and examples thereof include an endless belt made of stainless steel; and resin films made of polyimide, polyethylene terephthalate (PET), and the like.
  • the thickness of the original film is not particularly limited, and is preferably, for example, 10 to 500 ⁇ m. Since a stretched film having good thickness uniformity can be obtained, the thickness distribution of the raw film is preferably within ⁇ 10%, more preferably within ⁇ 5%, and particularly preferably within ⁇ 3% of the average value. The thickness distribution of the raw film can be evaluated in the same manner as in the "Thickness uniformity of stretched film" described in the section [Examples] below.
  • the process (S1) for producing the film roll and the process (S2) may be carried out continuously or discontinuously.
  • Step (S2) can be carried out by a known method, and preferably includes a preheating step (also called a heating step), a stretching step, a heat setting step, and a cooling step in that order.
  • a relaxation step may be carried out between the heat setting step and the cooling step. These steps may be carried out continuously or discontinuously.
  • Step (S2) enhances the heat resistance and mechanical strength of the film, and a film having good heat resistance, impact resistance, and handleability can be obtained.
  • the preheating step is a step of preheating the raw film to a temperature for the stretching step.
  • the stretching method in the stretching step is not particularly limited, and examples thereof include uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and tubular stretching, with simultaneous biaxial stretching and sequential biaxial stretching being preferred.
  • the stretching temperature in the stretching step is preferably +10 to +55° C., more preferably +20 to +55° C., relative to the glass transition temperature (Tg) of the glutarimide resin (G).
  • Tg glass transition temperature
  • G glutarimide resin
  • the stretching ratio in the stretching direction is preferably 2.0 to 4.0 times, more preferably 2.2 to 4.0 times.
  • the "stretching direction" referred to here is the longitudinal direction of the film (the direction in which the film travels, MD (Machine Direction)) or the width direction of the film (the direction perpendicular to the direction in which the film travels, TD (Transverse Direction)).
  • MD Machine Direction
  • TD Transverse Direction
  • the stretching ratio in each stretching direction is preferably 2.0 to 4.0 times, more preferably 2.2 to 4.0 times.
  • a tenter is generally used as a simultaneous biaxial stretching device.
  • both ends in the width direction of the film are held by a pair of tenter clamps, and the film is stretched in the longitudinal direction and the width direction simultaneously.
  • Each tenter clamp includes a stretchable pantograph that runs along one end of the film in the width direction, and a plurality of clips that are provided on the pantograph and hold one end of the film.
  • the longitudinal direction of the film (the direction of travel of the film, MD) is stretched by widening the distance between two adjacent clips.
  • the width direction of the film (the direction perpendicular to the direction of travel of the film, TD) is stretched by widening the distance between a pair of tenter clamps.
  • the distance between the pair of tenter clamps is adjusted by the distance between a pair of rails on which they run.
  • the stretching speed in the longitudinal direction and the stretching speed in the transverse direction are expressed by the following formulas.
  • [Longitudinal stretching speed (%/min)] ⁇ ([Separation distance between two adjacent clips after stretching (mm)] ⁇ [Separation distance between two adjacent clips before stretching (mm)])/[Separation distance between two adjacent clips before stretching (mm)]/[Time required for stretching (min)] ⁇ 100
  • [Stretching speed in width direction (%/min)] ⁇ ([Separation distance between a pair of tenter clamps after stretching] ⁇ [Separation distance between a pair of tenter clamps before stretching])/[Separation distance between a pair of tenter clamps before stretching]/[Time required for stretching (min)] ⁇ 100
  • stretching in the longitudinal direction and the width direction is performed separately and sequentially. Stretching in the longitudinal direction can be performed, for example, by utilizing the difference in conveying speed between a pair of conveying rolls.
  • a tenter is generally used for stretching in the transverse direction. The method and stretching speed for stretching the film in the transverse direction using a tenter are the same as those for coaxial and biaxial stretching.
  • the stretching speed is preferably 50 to 5,000%/min, more preferably 100 to 3,000%/min.
  • the stretching speed may be the same or different in each stretching direction, and is preferably 100 to 5,000%/min, more preferably 100 to 3,000%/min, and particularly preferably 500 to 1,000%/min.
  • the stretching temperature is preferably (Tg+10° C.) to (Tg+55° C.) based on the glass transition temperature (Tg) of the glutarimide resin (G).
  • the lower limit is preferably Tg+15° C., more preferably Tg+20° C.
  • the upper limit is preferably Tg+40° C., more preferably Tg+30° C.
  • the stretching ratio in both the longitudinal direction and the transverse direction is preferably 2.0 to 4.0 times.
  • the lower limit is more preferably 2.2 times, particularly preferably 2.3 times, and most preferably 2.4 times.
  • the upper limit is more preferably 3.5 times, and particularly preferably 3.0 times.
  • the thickness of the stretched film obtained after the stretching step is preferably 10 to 50 ⁇ m, more preferably 15 to 45 ⁇ m, and particularly preferably 20 to 40 ⁇ m.
  • the heat setting process is a process in which the stretched film obtained after the stretching process is held within a certain temperature range for a specified time while restraining both ends of the film in at least one direction under a specified temperature range condition.
  • the relaxation step is a step of relaxing the stretched film.
  • Relaxation may be carried out in both the longitudinal direction and the width direction, or only in the direction in which it is desired to reduce the amount of thermal shrinkage.
  • the relaxation rate in the relaxation step is preferably 5 to 10% in both the longitudinal and transverse directions with respect to the stretched film immediately before the relaxation step.
  • the cooling step is a step in which the stretched film is cooled to room temperature (20 to 25° C.). Thereafter, a trimming step may be performed to remove both ends of the stretched film in the width direction, if necessary. Finally, a winding step is performed to wind the stretched film onto a winding roll, if necessary.
  • the stretched film of the present disclosure has low thermal shrinkage and excellent dimensional stability, so that wrinkles, winding slippage, and tight winding are suppressed, and winding can be performed without problems. In this manner, a biaxially stretched film is produced.
  • the present disclosure can provide a laminated film having the stretched film of the present disclosure described above and one or more other layers.
  • the present disclosure can provide laminates having various substrates and the above-described stretched film of the present disclosure.
  • the stretched film of the present disclosure may have, for example, an adhesive layer or a pressure-sensitive adhesive layer on at least one surface thereof for laminating another film or substrate, and can be used in the form of a stretched film with an adhesive layer or a pressure-sensitive adhesive layer.
  • the stretched film of the present disclosure can be used, for example, in the form of a coated stretched film having one or more coating layers on at least one surface thereof.
  • the coating layer include various functional layers such as a hard coat layer (also called a scratch-resistant layer), a low-reflection layer, an anti-fogging layer, an anti-reflection layer, an anti-glare layer, an anti-fingerprint layer, a transparent conductive layer, an electromagnetic wave shielding layer, and a gas barrier layer.
  • the timing of forming the coating layer is not particularly limited, and the coating layer may be formed on the original film and then the stretching step may be carried out, or the coating layer may be formed on the obtained stretched film.
  • the coating layer can be formed by a coating method or the like. Since the surface wetting tension of a film (raw film or stretched film) containing the glutarimide resin (G) is high, it is not particularly necessary to provide an adhesion improving layer, such as an easy-adhesion layer containing inorganic fine particles, a primer layer, or an anchor layer, between the film containing the glutarimide resin (G) and the coating layer in order to improve the adhesion of the coating layer.
  • an adhesion improving layer such as an easy-adhesion layer containing inorganic fine particles, a primer layer, or an anchor layer, between the film containing the glutarimide resin (G) and the coating layer in order to improve the adhesion of the coating layer.
  • the hard coat layer (scratch-resistant layer) and the low reflectivity layer can be cured films.
  • Materials for the cured coating include inorganic, organic, organic-inorganic, and silicone-based materials, with the organic and organic-inorganic materials being preferred from the viewpoint of productivity.
  • the inorganic hardened coating can be formed, for example, by depositing an inorganic material such as a metal oxide such as SiO 2 , Al 2 O 3 , TiO 2 , or ZrO 2 by vapor phase deposition such as vacuum deposition or sputtering.
  • the organic cured coating can be formed, for example, by applying a paint containing a resin such as a melamine resin, an alkyd resin, a urethane resin, or an acrylic resin and then heating and curing it, or by applying a paint containing a polyfunctional acrylic resin and then curing it with ultraviolet light.
  • the organic/inorganic cured coating film can be formed, for example, by applying an ultraviolet-curable hard coat paint containing inorganic ultrafine particles such as silica ultrafine particles having photopolymerization reactive functional groups introduced on the surface and a curable organic component, and then polymerizing the curable organic component with the photopolymerization reactive functional groups of the inorganic ultrafine particles by ultraviolet irradiation.
  • This method produces a crosslinked coating film in the form of a network in which the inorganic ultrafine particles are dispersed in the organic matrix while being chemically bonded to the organic matrix.
  • the silicone-based cured coating can be formed, for example, by polycondensing partial hydrolysates of carbon functional alkoxysilane, alkyltrialkoxysilane, tetraalkoxysilane, and the like, or materials obtained by mixing these with colloidal silica.
  • examples of the material coating method include dip coating, various roll coating methods such as gravure roll coating, flow coating, rod coating, blade coating, spray coating, die coating, and bar coating.
  • the anti-fogging layer can be formed, for example, by applying a curable composition containing fine particles of silica, melamine resin, acrylic resin, etc., by a known method, and curing (thermal curing or photocuring).
  • the anti-reflection layer include an inorganic layer made of a metal oxide, a metal fluoride, a metal silicide, a metal boride, a metal nitride, a metal sulfide, or a combination thereof; a resin layer having a single layer structure or a laminate structure using a plurality of resins having different refractive indices, such as a combination of an acrylic resin and a fluororesin; and a thin layer containing composite fine particles of an inorganic compound and an organic compound.
  • Films (original film or stretched film) containing glutarimide resin (G) have little thermal shrinkage and excellent dimensional stability against temperature, so when a coating layer is formed on them, even if they are exposed to high temperatures in the drying and curing processes, the occurrence of defects in appearance such as warping or curling is suppressed. Films (original film or stretched film) containing glutarimide resin (G) have high surface wetting tension, so a coating layer can be formed on them with good adhesion.
  • the stretched film of the present disclosure can be used in the form of a laminated film, for example, by laminating it with any other resin film.
  • the stretched film of the present disclosure has small thermal shrinkage and excellent dimensional stability against temperature, so that when it is laminated with another resin film, the occurrence of warping or curling of the film is suppressed.
  • the stretched film of the present disclosure can be used in the form of a laminate by, for example, laminating it onto a non-resin material such as metal, wood, etc.
  • the stretched film of the present disclosure has small thermal shrinkage and excellent dimensional stability against temperature, so that when it is laminated onto a non-resin material, peeling of the film due to temperature change is suppressed.
  • the present disclosure can provide a stretched film with good thickness uniformity, impact resistance, dimensional stability against temperature, and coating adaptability, and a method for producing the same.
  • the uses of the stretched film of the present disclosure are not particularly limited. Suitable applications include optical films such as polarizer protective films, quarter-wave plates, half-wave plates, viewing angle control films, liquid crystal optical compensation films, liquid crystal protective plates, surface materials for portable information terminals, display window protective films for portable information terminals, light-guiding films used in various displays, transparent conductive films having silver nanowires or carbon nanotubes applied to their surfaces, and front panels for various displays.
  • a polarizer protective film etc.
  • a polarizing plate can be obtained by laminating the polarizer protective film to a known polarizer (for example, a polarizer obtained by adding iodine to stretched polyvinyl alcohol, etc.). This polarizing plate may further be laminated with various optical films as necessary.
  • Such a polarizing plate can be used in various products such as various displays (liquid crystal displays, organic EL displays, etc.).
  • Another suitable application is as a decorative film.
  • hot air drying may be performed, preferably at a temperature of about 80°C, for the purpose of volatilizing the solvent components or improving adhesive strength.
  • the stretched film of the present disclosure which has small thermal shrinkage and excellent dimensional stability, as the decorative film, it is possible to suppress thermal shrinkage of the film during the hot air drying process, and to suppress product defects such as misalignment due to thermal shrinkage.
  • the stretched film disclosed herein is also suitable for applications such as infrared-blocking film, security film, shatterproof film, solar cell backsheet, flexible solar cell front sheet, shrink film, and in-mold label film.
  • the evaluation items and evaluation methods are as follows. (Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn)) The weight average molecular weight (Mw) and the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) were determined by GPC (gel permeation chromatography).
  • the measurement device used was a GPC device "HLC-8320" manufactured by Tosoh Corporation.
  • the separation column used was a series connection of "TSKguardcolumnSuperHZ-H", “TSKgelHZM-M” and “TSKgelSuperHZ4000” manufactured by Tosoh Corporation.
  • the detector used was a differential refractive index detector (RI detector). 4 mg of the resin to be measured was dissolved in 5 ml of tetrahydrofuran. A sample solution was prepared by dissolving the resin. The temperature of the column oven was set to 40°C. Tetrahydrofuran was used as the eluent, the eluent flow rate was set to 0.35 ml/min, 20 ⁇ l of the sample solution was injected into the device, and the chromatogram was measured. GPC measurement was performed on 10 standard polymethyl methacrylate (PMMA) points with molecular weights in the range of 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw and Mw/Mn converted to standard PMMA were obtained from the chromatogram of the resin to be measured. The measurement conditions were as follows.
  • the glutarimide resin was subjected to 1 H-NMR measurement using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker).
  • a sample solution was prepared by dissolving 0.04 g of the resin to be measured in 0.55 ml of deuterated chloroform, and the 1 H-NMR spectrum was measured under conditions of room temperature and 64 accumulations, and the following two peaks were identified.
  • the glass transition temperature (Tg) was measured using a differential scanning calorimeter (Shimadzu Corporation "DSC-50") in accordance with JIS K7121. 10 mg of the resin to be measured was placed in an aluminum pan and set in the above-mentioned device. After nitrogen replacement for 30 minutes or more, the temperature was raised from room temperature (20 to 25 ° C.) to 230 ° C. at a rate of 20 ° C. / min in a nitrogen flow of 10 ml / min, held for 5 minutes, and cooled to room temperature (primary scan). Next, the temperature was raised to 230 ° C. at a rate of 10 ° C. / min (secondary scan), and the DSC curve was measured. The midpoint glass transition temperature obtained from the DSC curve obtained by the secondary scan was taken as the glass transition temperature (Tg).
  • DSC-50 differential scanning calorimeter
  • melt flow rate (Melt Flow Rate (MFR)) The melt flow rate (MFR) was measured in accordance with JIS K7210 under conditions of 230° C. and a load of 3.8 kg.
  • the resin to be measured was press molded to obtain a film having a thickness of 200 ⁇ m, and a test piece having a size of 18 mm ⁇ 10 mm was cut out.
  • a rotational rheometer (TA Instruments'"DHR-2")
  • the test piece was uniaxially elongated at 190° C. (standby time 30 seconds) in a constant strain rate mode under two conditions: low strain rate condition (strain rate 0.1 sec ⁇ 1 ) and high strain rate condition (strain rate 10.0 sec ⁇ 1 ).
  • the cross-sectional area (S) and load of the test piece were measured, and the uniaxial elongation viscosity ( ⁇ ) was calculated.
  • the cross-sectional area (S) of the test piece at a certain measurement time (t) can also be calculated from the initial cross-sectional area (S 0 ) and strain rate ( ⁇ ) of the test piece based on the formula: S 0 ⁇ exp( ⁇ t).
  • the ratio ( ⁇ exp / ⁇ 1 ) of the uniaxial extensional viscosity under high strain rate conditions ( ⁇ exp ) to the uniaxial extensional viscosity under low strain rate conditions ( ⁇ 1 ) was calculated as the nonlinear parameter ( ⁇ n ).
  • the resin to be measured was press-molded to obtain a sheet having a thickness of 3 mm.
  • the wet tension was measured using a mixture for wet tension testing (manufactured by Wako Pure Chemical Industries, Ltd.) at 23° C. and a relative humidity of 50% in accordance with JIS K6768.
  • Thickness uniformity A 180 mm x 180 mm test piece was cut out from the stretched film, and the thickness was measured with a digital micrometer at nine points shown by black dots in Figure 2 to determine the maximum thickness, minimum thickness, and average thickness.
  • Figure 2 is a schematic plan view of the test piece, with the symbol S indicating the test piece and the symbol MP indicating the measurement points.
  • the thickness unevenness represented by the following formula was calculated, and the thickness uniformity was evaluated according to the following criteria.
  • [Thickness unevenness] (%) [(maximum thickness - minimum thickness) / (average thickness)] x 100 ⁇ Criteria> Excellent: thickness unevenness is less than 30%. Good: Thickness unevenness is 30% or more and less than 50%. Acceptable: Thickness unevenness is 50% or more but less than 70%. Poor: Thickness unevenness of 70% or more.
  • test piece measuring 20 mm in length and 5 mm in width was cut out from the stretched film, with the longitudinal direction of the test piece parallel to the transverse direction (TD) of the original film. Both ends of the test piece in the longitudinal direction (parts 5 mm from both ends) were held by a pair of film chucks. The distance between the pair of film chucks was 10 mm.
  • a tensile load of 2 g was applied to the stretched film by the pair of film chucks, and the stretched film was attached to a stress/strain controlled thermomechanical analyzer (TMA). With the test piece set as described above, the test piece was heated from 25° C. to 85° C.
  • [Deformation rate] (%) [ ⁇ L (mm) / 10 (mm)] x 100 ⁇ Criteria> Excellent: deformation rate is 0.5% or less; Good: deformation rate is more than 0.5% and 1.5% or less; Poor: Deformation rate exceeds 1.5%.
  • a solution for the hard coat layer was prepared by adding 35 parts by mass of a urethane acrylate resin ("DPHA-40H” manufactured by Nippon Kayaku Co., Ltd.) and 1.75 parts by mass of a photoradical polymerization initiator ("Irgacure 184" manufactured by BASF Corporation) to a mixed solvent consisting of 70 parts by mass of methyl isobutyl ketone and 30 parts by mass of isopropyl alcohol and dissolving them.
  • the above-mentioned solution for hard coat layer was applied onto one surface of the stretched film using a bar coater #6, and after standing for 10 minutes, it was dried for 5 minutes at 80° C.
  • This film was irradiated with ultraviolet light at an integrated light quantity of 300 mJ/cm 2 using a high-pressure mercury lamp to cure the coating film, thereby forming a hard coat layer having a thickness of 6 ⁇ m.
  • the appearance of the obtained stretched film with a hard coat layer was visually observed, and the presence or absence of warping and/or curling of the film was evaluated.
  • the obtained stretched film with hard coat layer was left to stand for 6 hours under conditions of temperature 23 ° C. and relative humidity 50%, and then a checkerboard test was performed as an adhesion test according to JIS K5400 3.5. Using a checkerboard peeling test tool, the hard coat layer was cross-cut into 100 checkers of 1 mm2 .
  • a 25 mm wide cellophane tape conforming to JIS Z1522 was attached thereon and pressed uniformly overall using a wooden spatula. The cellophane tape was then peeled off in the 180 ° direction. The number of remaining checkers that were not peeled off was visually counted. In each example, this test was performed a total of 5 times, and the average number of remaining squares was calculated. Coating suitability was evaluated according to the following criteria. ⁇ Criteria> Excellent: 70 to 100 checkered patterns remained, and the film did not warp or curl. Good: 70 to 100 grids remained, but warping and/or curling of the film occurred. Poor: 69 or less check marks remained, and warping and/or curling of the film occurred.
  • the relationship between the elongational strain ( ⁇ ) and ln( ⁇ n ) for the methacrylic resin (PM1) was plotted, and the resulting linear approximation equation is shown in Figure 1.
  • the strain hardening factor (K) of the uniaxial elongational viscosity of the methacrylic resin (PM1) was 0.03.
  • a continuous flow tank reactor equipped with a brine cooling condenser was prepared, and the inside of the reactor was replaced with nitrogen gas.
  • the above polymerization raw materials were continuously fed into the 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 140°C, and a liquid containing a methacrylic resin was continuously discharged from the reactor.
  • the pressure in the reactor was adjusted by a pressure regulating valve connected to the brine cooling condenser.
  • the polymerization conversion rate was 35%.
  • the liquid discharged from the reactor was then heated to 210°C and fed to a twin-screw extruder adjusted to 230°C. Volatiles mainly composed of unreacted monomers were separated and removed.
  • the resin was extruded into strands and cut with a pelletizer to obtain pellets of methacrylic resin (PM2) (MMA/ ⁇ MSt/St copolymer).
  • PM2 methacrylic resin
  • PET1 A twin-screw extruder (manufactured by Nippon Steel Corporation, "TEX30 ⁇ -77AW-3V") having a transport section, a melt-kneading section, a devolatilizing section, and a discharge section, with the screw speed set to 150 rpm and the temperature set to 210 to 270°C, was prepared.
  • a methacrylic resin (PM1) was supplied as a precursor resin to the transport section of this twin-screw extruder at a flow rate of 15 kg/hr, and monomethylamine was injected as an imidizing agent from the additive supply port of the twin-screw extruder in an amount such that the glutarimide cyclization rate (R) was the value shown in Table 1.
  • the methacrylic resin (PM1) was reacted with monomethylamine. From the obtained molten resin, by-products and excess monomethylamine were volatilized in the devolatilizing section and discharged through multiple vents.
  • the molten resin was extruded in the form of strands from a die provided at the end of the discharge section of the twin-screw extruder, cooled in a water tank, and cut with a pelletizer to obtain a pellet-shaped glutarimide resin (G-1).
  • the relationship between the extensional strain ( ⁇ ) and ln( ⁇ n ) of the obtained glutarimide resin (G-1) was plotted, and the obtained linear approximation equation is shown in Figure 1.
  • the strain hardening factor (K) of the uniaxial extensional viscosity of the glutarimide resin (G-1) was 0.96.
  • the type of precursor resin, as well as the polymer composition and physical properties of the resulting glutarimide resin (G-1) are shown in Table 1.
  • Glutarimide resins (G-2), (GC-3), and (GC-7) were obtained in the same manner as in Production Example (PE1), except that the amount of monomethylamine added was changed.
  • the type of precursor resin, as well as the polymer composition and polymer properties of the obtained glutarimide resins, are shown in Table 1.
  • Glutarimide resin (GC) indicates a glutarimide resin for comparison.
  • Example (E1) The glutarimide resin (G-1) was dried for 12 hours at 90° C. Using a 20 mm ⁇ single screw extruder (manufactured by OCS Corporation), the glutarimide resin (G-1) was extruded from a 150 mm wide T-die at a resin temperature of 260° C., and taken up with a roll having a surface temperature of 110° C. to obtain a film roll having a width of 110 mm and a thickness of 160 ⁇ m. A test piece of 90 mm x 90 mm was cut out from the obtained film roll, and sequential biaxial stretching was performed at a stretching temperature of glass transition temperature (Tg) + 10 ° C.
  • Tg glass transition temperature
  • glutarimide resin (G) having a glutarimide cyclization rate (R) of 50 to 90 mass% and a product (Tg ⁇ R) of the glass transition temperature (Tg) [° C.] and the glutarimide cyclization rate (R) [mass %] of 7,500 to 15,000 had a high glass transition temperature (Tg), a large strain hardening degree (K) of the uniaxial extensional viscosity (nonlinearity of the uniaxial extensional viscosity), excellent extensibility, and high wetting tension on the surface of the film.
  • the stretched films obtained in Examples (E1) to (E7) also had good dimensional stability because the glutarimide resin (G) has a high glass transition temperature (Tg). Since the glutarimide resin (G) has a high glass transition temperature (Tg) and a high wetting tension on the surface of the film, the stretched films obtained in Examples (E1) to (E7) also had good coating adaptability.
  • the stretched films obtained in Examples (E1) to (E7) were suitable for use as optical films, decorative films, and the like.
  • the comparative glutarimide resin (GC) having a glutarimide cyclization rate (R) of less than 50% by mass had insufficient nonlinearity of the uniaxial elongational viscosity and poor stretchability.
  • R glutarimide cyclization rate

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PCT/JP2023/043818 2022-12-13 2023-12-07 延伸フィルムとその製造方法、光学フィルム、および加飾フィルム Ceased WO2024128122A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06256537A (ja) * 1992-02-26 1994-09-13 Kuraray Co Ltd 延伸フィルムまたはシート
JPH07138389A (ja) * 1993-11-12 1995-05-30 Ube Ind Ltd 二軸延伸フィルムまたはシート
WO2012114718A1 (ja) * 2011-02-21 2012-08-30 株式会社カネカ アクリル系樹脂フィルム
WO2018168960A1 (ja) * 2017-03-15 2018-09-20 株式会社カネカ 延伸フィルムおよび延伸フィルムの製造方法
WO2022114194A1 (ja) * 2020-11-27 2022-06-02 株式会社カネカ グルタルイミド樹脂

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06256537A (ja) * 1992-02-26 1994-09-13 Kuraray Co Ltd 延伸フィルムまたはシート
JPH07138389A (ja) * 1993-11-12 1995-05-30 Ube Ind Ltd 二軸延伸フィルムまたはシート
WO2012114718A1 (ja) * 2011-02-21 2012-08-30 株式会社カネカ アクリル系樹脂フィルム
WO2018168960A1 (ja) * 2017-03-15 2018-09-20 株式会社カネカ 延伸フィルムおよび延伸フィルムの製造方法
WO2022114194A1 (ja) * 2020-11-27 2022-06-02 株式会社カネカ グルタルイミド樹脂

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