WO2023149169A1 - Corps stratifié optique - Google Patents

Corps stratifié optique Download PDF

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Publication number
WO2023149169A1
WO2023149169A1 PCT/JP2023/000788 JP2023000788W WO2023149169A1 WO 2023149169 A1 WO2023149169 A1 WO 2023149169A1 JP 2023000788 W JP2023000788 W JP 2023000788W WO 2023149169 A1 WO2023149169 A1 WO 2023149169A1
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Prior art keywords
mass
meth
film
acrylate
damping portion
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PCT/JP2023/000788
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English (en)
Japanese (ja)
Inventor
啓人 小長
奈々恵 藤枝
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コニカミノルタ株式会社
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Publication of WO2023149169A1 publication Critical patent/WO2023149169A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to an optical laminate.
  • a flexible display is composed of a cover glass unit intended to protect the flexible display unit and a display unit including a polarizing plate.
  • the glass substrate used in the cover glass unit is required to be flexible, it is necessary to change to a resin substrate or make the glass substrate itself thinner. From the viewpoint of (durability) and the like, thin-film glass has become mainstream.
  • Thin-film glass is extremely fragile, and the development of displays that support pen input is progressing, so there is a need for a cover glass unit that can withstand the impact of pen input. It is In addition, due to device characteristics, further thinning of the cover glass unit is required.
  • JP-A-2020-139108 discloses an organic An adhesive layer for an EL display is disclosed.
  • the present invention has been made based on the circumstances as described above, and an object of the present invention is to provide a means for making it possible to reduce the thickness of an optical laminated body containing a thin film glass and to improve both impact resistance and flexibility. intended to provide
  • the present invention provides an optical laminate comprising a restraining portion, a damping portion 1, a damping portion 2, and a thin film glass having a thickness of 10 to 40 ⁇ m in this order, wherein tan ⁇ of the restraining portion is tan ⁇ 1, tan ⁇ 2 of the vibration damping portion 1, and tan ⁇ 3 of the vibration damping portion 2, wherein the tan ⁇ 1, the tan ⁇ 2, and the tan ⁇ 3 satisfy the following formula (1): is.
  • FIG. 1 is a schematic diagram showing an example of a method of manufacturing a thin film glass.
  • Reference numeral 21 is a carrier substrate
  • 22 is a thin film glass
  • 23 is a contact film
  • 24 is electromagnetic radiation.
  • the present invention provides an optical laminate comprising a restraining portion, a damping portion 1, a damping portion 2, and a thin film glass having a thickness of 10 to 40 ⁇ m in this order, wherein tan ⁇ of the restraining portion is tan ⁇ 1.
  • tan ⁇ of the vibration damping portion 1 is tan ⁇ 2
  • tan ⁇ of the vibration damping portion 2 is tan ⁇ 3
  • the tan ⁇ 1, the tan ⁇ 2, and the tan ⁇ 3 satisfy the following formula (1). .
  • optical layered body of the present invention having such a configuration, it is possible to reduce the thickness and improve both impact resistance and flexibility.
  • optical layered body of the present invention achieves the above effects are unknown, it is believed to be due to the following mechanism.
  • the mechanism described below is based on speculation, and the present invention is not limited to the mechanism described below.
  • an optical laminate such as a cover glass unit is composed of a constraining layer such as a PET film, a single adhesive layer with vibration damping properties, and thin glass.
  • the optical layered body having such a structure lacked impact resistance against pen input. The reason for this is considered as follows. When the pen is input (dropped), energy (impact) is applied from the constrained part to the glass direction and lateral direction, and it reaches the adhesive part. Misalignment occurs at the interface of each part. If the deflection is a certain amount, the displacement at the interface can be absorbed, but as the deflection increases, the displacement (stress) at the interface cannot be absorbed, and the displacement (stress) is transmitted in the direction of the glass, causing the thin film glass to crack. it is conceivable that.
  • the present inventors conducted extensive studies, and found that two damping portions were provided between the constraining portion, which is the outermost layer of the optical laminate, and the thin film glass having a specific thickness, Moreover, it was discovered that an optical laminate having a specific relationship between the tan ⁇ (loss tangent) of the restraining portion and the tan ⁇ of the two damping portions exhibits high impact resistance against the impact of pen input.
  • the restraining portion, the damping portion 1, the damping portion 2, and the thin glass are laminated in this order. 2 in order of increasing size.
  • the two vibration damping sections deform so that only the center portion follows the deformation of the restraining section, which is the outermost layer, when pen input is performed.
  • X to Y indicating a range means “X or more and Y or less”.
  • operations and measurements of physical properties are performed under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.
  • the optical laminated body of the present invention comprises a restraining portion, damping portion 1, damping portion 2, and thin film glass in this order.
  • "provided in this order” means that the restraining portion, the damping portion 1, the damping portion 2, and the thin film glass are arranged in this order, and other portions are arranged between each portion and the thin film glass. may have been
  • tan ⁇ is different between the upper portion and the lower portion of a certain portion and the relationship of the above formula (1) holds, it is included in the present invention.
  • tan ⁇ measured within 30% of the thickness from the top of a specific portion and tan ⁇ measured within 30% of the thickness from the bottom differ by 20% or more, and the above formula (1) is included in the present invention as long as it satisfies the relationship of
  • a portion having tan ⁇ larger than the above tan ⁇ 1 is provided on the surface of the restraining portion opposite to the surface facing the damping portion 1. Good too. Further, if the relationship of the above formula (1) is satisfied, a portion having tan ⁇ smaller than the above tan ⁇ 3 is provided on the surface of the damping portion 2 opposite to the surface on the damping portion 1 side.
  • the restraining portion according to the present invention may be an article that can be wound like a film made of a thermoplastic resin or the like, or a coating layer formed by coating on a support, but it is in the form of a film. is preferred.
  • the film used for the restraint part is preferably a resin film.
  • the resin material constituting the resin film include polyester resins such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate (abbreviation: PBT), and polyethylene naphthalate (abbreviation: PEN); polyolefin resins such as polyethylene and polypropylene; Cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose esters such as cellulose nitrate and derivatives thereof; polyvinylidene chloride , polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate (abbreviation: PC), norbornene resin, polymethylpentene, polyetherketone, polyimide (including transparent polyimide (abbreviation
  • PET polyethylene terephthalate
  • TAC cellulose diacetate
  • TAC cellulose triacetate
  • CPI transparent polyimide
  • UV curable or thermal A curable acrylate resin or the like is preferable.
  • the above resin film may be an unstretched film or a stretched film.
  • a resin film that can be applied to the restraint part can be manufactured by a conventionally known general film-forming method.
  • a substantially amorphous, non-oriented and unstretched resin substrate can be produced by melting a material resin with an extruder, extruding it with an annular die or a T-die, and quenching it.
  • an unstretched resin substrate is subjected to a known method such as uniaxial stretching, tenter-type successive biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like, in the conveying direction of the resin substrate (longitudinal direction).
  • a stretched resin film can be produced.
  • the draw ratio in this case can be appropriately selected according to the resin that is the raw material of the resin base material, but is preferably within the range of 2 to 10 times in each of the vertical and horizontal directions.
  • the film used for the restraining portion may be manufactured by a solution casting method.
  • the thickness of the constraining portion is preferably 5 to 60 ⁇ m, more preferably 15 to 50 ⁇ m, and even more preferably 25 to 40 ⁇ m, in consideration of thinning of the optical layered body.
  • the weight average molecular weight of the resin material used in the restraining portion is preferably 5,000 to 4,000,000, more preferably 100,000 to 4,000,000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin material can be measured in terms of polystyrene by gel permeation chromatography (GPC). It can be measured by the method described in the examples.
  • the glass transition temperature of the restraining portion is preferably 70 to 170°C, more preferably 120 to 170°C.
  • the glass transition temperature can be obtained from a DSC curve obtained by differential scanning calorimetry (DSC). More specifically, it is determined by the "extrapolated glass transition start temperature” described in the method for determining the glass transition temperature in JIS K 7121 (2012) “Method for measuring the transition temperature of plastics”.
  • the storage elastic modulus of the restraining portion is preferably 2.0 to 7.0 GPa, more preferably 4.0 to 7.0 GPa.
  • Tan ⁇ (tan ⁇ 1) of the restraint portion is not particularly limited as long as it satisfies the relationship of the above formula (1), but is preferably 0.001 to 0.1, more preferably 0.01 to 0.05. more preferred.
  • the storage elastic modulus and tan ⁇ of each part and each material adopt values measured by a dynamic viscoelasticity measuring device, and more specifically, adopt values measured under the following test conditions.
  • tan ⁇ of the restraining portion and damping portion 1 and damping portion 2 which will be described later, can be controlled by appropriately selecting the type of material used, the thickness of each portion, and the like.
  • the storage elastic modulus and tan ⁇ of the restraint part and the damping part 1 are measured using a dynamic viscoelasticity measuring device (product number: RSA-3) manufactured by TA Instruments Japan Co., Ltd. under the following test conditions.
  • the measured 25° C. storage modulus and tan ⁇ values were taken: ⁇ Test conditions (dynamic viscoelasticity test)
  • Tester Dynamic viscoelasticity measuring device (product number: RSA-3) manufactured by TA Instruments Japan Co., Ltd.
  • Deformation method tension Preload load: 55 g Temperature range: -70 to 200°C Frequency: 1.0Hz Displacement: ⁇ 0.1% Sample: width 5mm Distance between chucks: 20 mm.
  • the storage elastic modulus and tan ⁇ of the vibration damping portion 2 were measured using a nanoindenter device (product number: G200XP) manufactured by Keysight Technologies, Inc. under the following test conditions at 25°C. We adopted the value of : ⁇ Test conditions (dynamic viscoelasticity test) Tester: Keysight Technologies, Nanoindenter device (product number: G200XP) Deformation method: Push type Temperature range: -100°C to 100°C Frequency: 1Hz Displacement: 100nm Sample size (morphology, etc.): 10 ⁇ 10 mm Thickness about 1 mm.
  • each part may be peeled off by leaving the optical layered body under high temperature and high humidity, for example, and the measurement may be performed.
  • the peeled portion for example, the damping portion 1 and the damping portion 2
  • the peeled portion may be turned to the upper surface and tan ⁇ may be obtained by performing the same measurement as that used for the vibration damping section 2 .
  • the value of tan ⁇ may be obtained by performing the measurement described for either the vibration damping section 1 or the vibration damping section 2 according to the state of each part.
  • vibration damping portion 1 may be either an article that can be wound like a film made of a thermoplastic resin or the like, or a coating layer formed by coating on the restraining portion, but the film preferably in the form of In other words, both the restraining portion and the damping portion 1 are preferably films.
  • the material contained in the damping portion 1 is not particularly limited, and examples thereof include thermoplastic (meth)acrylic resins, cycloolefin resins, resin materials such as transparent polyurethane resins, and rubber materials such as graft copolymers. can be used.
  • the damping portion 1 preferably contains at least a thermoplastic (meth)acrylic resin and a graft copolymer, or contains a transparent polyurethane resin.
  • the film preferably contains at least an acrylic resin and a graft copolymer.
  • (meth)acryl refers to a generic term for acryl and methacryl.
  • the preferred range of the weight-average molecular weight of the resin material contained in the damping portion 1 varies depending on the type of material, and cannot be generalized.
  • the resin material preferably has a weight average molecular weight of 5,000 to 4,000,000.
  • thermoplastic (meth)acrylic resin, graft copolymer, cycloolefin resin, and transparent polyurethane resin which are preferable materials for the damping portion 1, will be described below.
  • the weight average molecular weight (Mw) of the thermoplastic (meth)acrylic resin is preferably 1,000,000 or more.
  • Mw weight average molecular weight of the thermoplastic (meth)acrylic resin
  • the toughness of the obtained damping portion 1 can be enhanced.
  • the weight average molecular weight of the thermoplastic (meth)acrylic resin is more preferably 1,500,000 to 3,000,000.
  • the weight average molecular weight (Mw) of the thermoplastic (meth)acrylic resin can be measured in terms of polystyrene by gel permeation chromatography (GPC). Specifically, it can be measured by the method described in Examples.
  • the thermoplastic (meth)acrylic resin preferably contains at least a structural unit derived from methyl methacrylate.
  • the thermoplastic (meth)acrylic resin preferably further contains a structural unit derived from phenylmaleimide from the viewpoint of increasing the storage elastic modulus of the vibration damping portion 1 and improving the storage stability of the film, which is a preferred form.
  • thermoplastic (meth)acrylic resin preferably contains a structural unit derived from methyl methacrylate, a structural unit derived from phenylmaleimide, and a structural unit derived from alkyl acrylate.
  • the content of structural units derived from methyl methacrylate is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, based on the total structural units constituting the thermoplastic (meth)acrylic resin. more preferred.
  • a structural unit derived from phenylmaleimide has a relatively rigid structure, and therefore can increase the storage elastic modulus of the damping portion 1 .
  • the structural unit derived from phenylmaleimide has a relatively bulky structure and can have microscopic voids that allow the graft copolymer (rubber particles) to move in the resin matrix. rubber particles) can be easily unevenly distributed on the surface layer portion of the damping portion 1 .
  • the content of structural units derived from phenylmaleimide is preferably 1 to 25% by mass with respect to all structural units constituting the thermoplastic (meth)acrylic resin.
  • the content of structural units derived from phenylmaleimide is 1% by mass or more, the storage elastic modulus of the vibration damping portion 1 tends to be increased, and when it is 25% by mass or less, the brittleness of the vibration damping portion 1 is excessively impaired. not easy to fall off.
  • the content of structural units derived from phenylmaleimide is more preferably 7 to 15% by mass.
  • Structural units derived from acrylic acid alkyl esters can impart moderate flexibility to resins, so fragility due to inclusion of structural units derived from phenylmaleimide, for example, can be improved.
  • the alkyl acrylate is preferably an alkyl acrylate in which the alkyl portion has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
  • acrylic acid alkyl esters include methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), propyl acrylate (propyl acrylate), butyl acrylate (butyl acrylate), 2-hydroxyethyl acrylate (2- hydroxyethyl acrylate), hexyl acrylate (hexyl acrylate), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), and the like.
  • the content of structural units derived from acrylic acid alkyl esters is preferably 1 to 25% by mass with respect to all structural units constituting the thermoplastic (meth)acrylic resin.
  • the thermoplastic (meth)acrylic resin can be imparted with appropriate flexibility, so that the vibration damping portion 1 does not become too brittle. Not easy to break.
  • the content of the structural unit derived from the acrylic acid alkyl ester is 25% by mass or less, the Tg of the thermoplastic (meth)acrylic resin is not excessively lowered, so that the heat resistance and storage elastic modulus of the damping portion 1 are improved. It is difficult to decrease excessively.
  • the content of the structural unit derived from the acrylic acid alkyl ester is more preferably 5 to 15% by mass.
  • the ratio of the structural unit derived from phenylmaleimide to the total amount of the structural unit derived from phenylmaleimide and the structural unit derived from the acrylic acid alkyl ester is preferably 20 to 70% by mass.
  • the ratio is 20% by mass or more, the storage elastic modulus of the damping portion 1 can be easily increased, and when the ratio is 70% by mass or less, the damping portion 1 does not become too fragile.
  • the glass transition temperature (Tg) of the thermoplastic (meth)acrylic resin is preferably 100°C or higher, more preferably 120 to 150°C.
  • Tg of the thermoplastic (meth)acrylic resin is within the above range, the heat resistance of the damping portion 1 can be easily increased.
  • the graft copolymer (rubber particles) can have a function of imparting toughness (flexibility) to the damping portion 1 .
  • a graft copolymer is a particle containing a rubber-like polymer.
  • a rubber-like polymer is a soft crosslinked polymer having a glass transition temperature of 20° C. or lower.
  • crosslinked polymers include butadiene crosslinked polymers, (meth)acrylic crosslinked polymers, and organosiloxane crosslinked polymers. Among them, a (meth)acrylic crosslinked polymer is preferable, and an acrylic crosslinked polymer (acrylic rubber-like polymer) is more preferred.
  • the graft copolymer is preferably particles containing an acrylic rubber-like polymer.
  • the acrylic rubber-like polymer (a) is a crosslinked polymer containing a structural unit derived from an acrylic acid ester as a main component.
  • "containing as a main component” means that the content of the structural unit derived from the acrylic acid ester falls within the range described below.
  • the acrylic rubber-like polymer (a) comprises a structural unit derived from an acrylic acid ester, a structural unit derived from another monomer copolymerizable therewith, and two or more radically polymerizable groups in one molecule ( It is preferably a crosslinked polymer containing a structural unit derived from a polyfunctional monomer having a non-conjugated reactive double bond.
  • Acrylic acid esters include methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-propyl acrylate (n-propyl acrylate), n-butyl acrylate (n-butyl acrylate), sec-butyl acrylate.
  • acrylic acid n It is preferably an acrylic acid alkyl ester having 1 to 12 carbon atoms of an alkyl group such as -octyl (n-octyl acrylate). Acrylic acid esters may be used singly or in combination of two or more.
  • the content of structural units derived from an acrylic acid ester is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total structural units constituting the acrylic rubber-like polymer (a). is more preferred.
  • the acrylic acid ester content is within the above range, it is easy to impart sufficient toughness to the protective film.
  • copolymerizable monomers are monomers copolymerizable with acrylic acid esters other than polyfunctional monomers. That is, the copolymerizable monomer does not have two or more radically polymerizable groups.
  • copolymerizable monomers include methacrylic acid esters such as methyl methacrylate; styrenes such as styrene and methylstyrene; (meth)acrylonitriles; (meth)acrylamides; and (meth)acrylic acid.
  • the other copolymerizable monomer preferably contains styrenes.
  • Other copolymerizable monomers may be of one type or two or more types.
  • the content of structural units derived from other copolymerizable monomers is preferably 5 to 55% by mass with respect to all structural units constituting the acrylic rubber-like polymer (a), and is preferably 10 to 55% by mass. It is more preferably 45% by mass.
  • polyfunctional monomers examples include allyl (meth)acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol di(meth)acrylate, diethylene glycol ( meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetromethylolmethane tetra(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate .
  • the content of the structural unit derived from the polyfunctional monomer is preferably 0.05 to 10% by mass with respect to the total structural units constituting the acrylic rubber-like polymer (a), and 0.1% by mass. It is more preferably ⁇ 5% by mass.
  • the content of the polyfunctional monomer is 0.05% by mass or more, the degree of cross-linking of the obtained acrylic rubber-like polymer (a) can be easily increased, so that the vibration damping portion 1 obtained has high hardness and rigidity. If the content is not excessively impaired and is 10% by mass or less, the toughness of the vibration damping portion 1 is less likely to be impaired.
  • composition of the monomers constituting the acrylic rubber-like polymer (a) can be measured, for example, by the peak area ratio detected by pyrolysis GC-MS.
  • the glass transition temperature (Tg) of the acrylic rubber-like polymer (a) is preferably 0°C or lower, more preferably -10°C or lower.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the acrylic rubber-like polymer (a) is measured by the same method as described above.
  • the glass transition temperature (Tg) of the acrylic rubbery polymer (a) can be adjusted by the composition of the acrylic rubbery polymer (a). For example, in order to lower the glass transition temperature (Tg) of the acrylic rubber-like polymer (a), an acrylic ester/copolymer having an alkyl group having 4 or more carbon atoms in the acrylic rubber-like polymer (a) It is preferable to increase the mass ratio of the other polymerizable monomer (for example, 3 or more, preferably 4 to 10).
  • the particles containing the acrylic rubbery polymer (a) are particles made of the acrylic rubbery polymer (a), or a hard layer made of a hard crosslinked polymer (c) having a glass transition temperature of 20° C. or higher, It may be a particle having a soft layer composed of the acrylic rubber-like polymer (a) arranged around it; Particles made of an acrylic graft copolymer obtained by polymerizing a mixture of monomers in at least one step or more may also be used.
  • the particles made of the acrylic graft copolymer may be core-shell type particles having a core portion containing the acrylic rubber-like polymer (a) and a shell portion covering the core portion.
  • the core part contains an acrylic rubber-like polymer (a), and may further contain a hard crosslinked polymer (c) as necessary. That is, the core portion may have a soft layer made of the acrylic rubber-like polymer (a) and a hard layer made of the hard crosslinked polymer (c) disposed inside the soft layer.
  • the crosslinked polymer (c) can be a crosslinked polymer containing methacrylic acid ester as a main component. That is, the crosslinked polymer (c) comprises a structural unit derived from a methacrylic acid alkyl ester, a structural unit derived from another monomer copolymerizable therewith, and a structural unit derived from a polyfunctional monomer. It is preferably a crosslinked polymer containing.
  • the methacrylic acid alkyl ester may be the methacrylic acid alkyl ester described above; other copolymerizable monomers may be the styrenes and acrylic acid esters described above; Examples thereof are the same as those mentioned above as the polyfunctional monomer.
  • the content of the structural unit derived from the methacrylic acid alkyl ester can be 40 to 100% by mass based on the total structural units constituting the crosslinked polymer (c).
  • the content of structural units derived from other copolymerizable monomers may be 60 to 0% by mass based on the total structural units constituting the other crosslinked polymer (c).
  • the content of the structural units derived from the polyfunctional monomer may be 0.01 to 10% by mass based on the total structural units constituting the other crosslinked polymer.
  • the shell portion preferably contains a methacrylic polymer (b) (another polymer) graft-bonded to the acrylic rubber-like polymer (a) and containing a structural unit derived from a methacrylic acid ester as a main component.
  • “Contained as a main component” means that the content of the structural unit derived from the methacrylic acid ester falls within the range described below.
  • the methacrylic acid ester constituting the methacrylic polymer (b) is preferably a methacrylic acid alkyl ester having an alkyl group of 1 to 12 carbon atoms, such as methyl methacrylate.
  • One type of methacrylic acid ester may be used, or two or more types may be used.
  • the content of the methacrylic acid ester is preferably 50% by mass or more with respect to all structural units constituting the methacrylic polymer (b).
  • the content of the methacrylic acid ester is 50% by mass or more, compatibility with a methacrylic resin containing a structural unit derived from methyl methacrylate as a main component is likely to be obtained.
  • the content of the methacrylic acid ester is more preferably 70% by mass or more based on the total structural units constituting the methacrylic polymer (b).
  • the methacrylic polymer (b) may further contain structural units derived from other monomers copolymerizable with the methacrylic acid ester.
  • other copolymerizable monomers include acrylic acid esters such as methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-butyl acrylate (n-butyl acrylate); Alicyclics such as benzyl acrylate (benzyl (meth)acrylate), dicyclopentanyl (meth)acrylate (dicyclopentanyl (meth)acrylate), phenoxyethyl (meth)acrylate (phenoxyethyl (meth)acrylate) , heterocyclic or aromatic ring-containing (meth)acrylic monomers (ring-containing (meth)acrylic monomers).
  • the content of structural units derived from copolymerizable monomers is preferably 50% by mass or less and 30% by mass or less with respect to all structural units constituting the methacrylic polymer (b). is more preferred.
  • the ratio (graft ratio) of the graft component in the graft copolymer (rubber particles) is preferably 10 to 250% by mass, more preferably 15 to 150% by mass.
  • the proportion of the graft component that is, the methacrylic polymer (b) whose main component is a structural unit derived from a methacrylic acid ester, is moderately high. It is easy to improve compatibility, and it is more difficult to agglomerate rubber particles. In addition, the rigidity of the film is less likely to be impaired.
  • the proportion of the acrylic rubber-like polymer (a) does not become too small, so that the effect of improving the toughness and brittleness of the film is less likely to be impaired.
  • the graft rate is measured by the following method.
  • the shape of the rubber particles is not particularly limited, it is preferably a shape close to a perfect sphere.
  • the nearly spherical shape means a shape in which the aspect ratio of the rubber particles is in the range of about 1 to 2 when the cross section or surface of the vibration damping portion 1 is observed.
  • the laminated body is more resistant to deformation due to contact with rolls during transport and internal stress during winding, and resistance to deformation can be easily obtained.
  • the average particle size of the graft copolymer (rubber particles) is preferably 100-400 nm.
  • the average particle size of the rubber particles is 100 nm or more, it is easy to impart sufficient toughness and stress relaxation to the vibration damping portion 1, and when it is 400 nm or less, the transparency of the vibration damping portion 1 is less likely to be impaired.
  • the average particle size of the rubber particles is more preferably 150 to 300 nm.
  • the average particle size of the graft copolymer (rubber particles) can be calculated by the following method.
  • the average particle size of the graft copolymer can be measured as the average value of circle-equivalent diameters of 100 particles obtained by SEM or TEM imaging of the surface or section of the laminate.
  • the equivalent circle diameter can be obtained by converting the projected area of the particle obtained by photographing into the diameter of a circle having the same area.
  • rubber particles observed by SEM observation and/or TEM observation at a magnification of 5000 are used for calculating the average particle size.
  • the content of the thermoplastic (meth)acrylic resin is 5 to 5 with respect to the total mass of the film. It is preferably 95% by mass, more preferably 10 to 60% by mass, even more preferably 10 to 50% by mass, and particularly preferably 10 to 40% by mass.
  • the content of the graft copolymer (rubber particles) is 5 to 5 with respect to the total mass of the film. It is preferably 95% by mass, more preferably 40 to 90% by mass, even more preferably 50 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the size of the agglomerates is sufficient and substantially uniform, foreign matter is less likely to be mixed into the film, and a film with improved optical properties and mechanical properties can be obtained.
  • the cycloolefin resin used for the damping portion 1 is preferably a polymer of cycloolefin monomers or a copolymer of cycloolefin monomers and other copolymerizable monomers.
  • the cycloolefin monomer is preferably a cycloolefin monomer having a norbornene skeleton, and a cycloolefin monomer having a structure represented by the following general formula (A-1) or (A-2) It is more preferable to have
  • R 1 to R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a polar group.
  • p represents an integer of 0 to 2; However, R 1 to R 4 do not all represent a hydrogen atom at the same time, R 1 and R 2 do not represent a hydrogen atom at the same time, and R 3 and R 4 do not represent a hydrogen atom at the same time. do.
  • the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 4 in the general formula (A-1) is preferably, for example, a hydrocarbon group having 1 to 10 carbon atoms. ⁇ 5 hydrocarbon groups are more preferred.
  • a hydrocarbon group having 1 to 30 carbon atoms may further have a linking group containing, for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Examples of such linking groups include divalent polar groups such as carbonyl groups, imino groups, ether bonds, silyl ether bonds and thioether bonds. Examples of hydrocarbon groups having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group and the like.
  • Examples of the polar groups represented by R 1 to R 4 in general formula (A-1) above include a carboxy group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, and A cyano group is included. Among them, a carboxy group, a hydroxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group are preferred, and an alkoxycarbonyl group and an aryloxycarbonyl group are preferred from the viewpoint of ensuring solubility during solution film formation.
  • p in the above general formula (A-1) is preferably 1 or 2. This is because when p is 1 or 2, the resulting polymer becomes bulky and the glass transition temperature tends to be improved. In addition, there is also the advantage that it becomes possible to slightly respond to humidity, making it easier to control the curl balance as a laminate.
  • R 5 represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms.
  • R6 represents a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, a cyano group, or a halogen atom (fluorine, chlorine, bromine, or iodine atom).
  • p represents an integer of 0 to 2;
  • R 5 in general formula (A-2) above preferably represents a hydrocarbon group having 1 to 5 carbon atoms, and more preferably represents a hydrocarbon group having 1 to 3 carbon atoms.
  • R 6 in general formula (A-2) above preferably represents a carboxy group, a hydroxy group, an alkoxycarbonyl group and an aryloxycarbonyl group, and from the viewpoint of ensuring solubility during solution film formation, an alkoxycarbonyl group and An aryloxycarbonyl group is more preferred.
  • p in the above general formula (A-2) is preferably 1 or 2. This is because when p is 1 or 2, the resulting polymer becomes bulky and the glass transition temperature tends to be improved.
  • a cycloolefin monomer having a structure represented by the general formula (A-2) is preferable from the viewpoint of improving the solubility in organic solvents.
  • breaking the symmetry of an organic compound lowers the crystallinity, thereby improving the solubility in an organic solvent.
  • R 5 and R 6 in general formula (A-2) are substituted only on one ring-constituting carbon atom with respect to the symmetry axis of the molecule, the symmetry of the molecule is low, that is, general formula (A- Since the cycloolefin monomer having the structure represented by 2) is highly soluble, it is suitable for manufacturing the damping portion 1 by a solution casting method.
  • the content of the cycloolefin monomer having the structure represented by the general formula (A-2) in the cycloolefin monomer polymer is based on the total of all cycloolefin monomers constituting the cycloolefin resin. For example, it is 70 mol % or more, preferably 80 mol % or more, more preferably 100 mol %.
  • the cycloolefin monomer having the structure represented by the general formula (A-2) is included in a certain amount or more, the orientation of the resin is enhanced, so that the retardation value tends to increase.
  • copolymerizable monomers copolymerizable with cycloolefin monomers examples include copolymerizable monomers capable of ring-opening copolymerization with cycloolefin monomers and addition copolymerization with cycloolefin monomers. possible copolymerizable monomers and the like.
  • copolymerizable monomers capable of ring-opening copolymerization include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.
  • Examples of addition-copolymerizable copolymerizable monomers include unsaturated double bond-containing compounds, vinyl-based cyclic hydrocarbon monomers, and (meth)acrylates.
  • Examples of unsaturated double bond-containing compounds include olefinic compounds having 2 to 12 carbon atoms (preferably 2 to 8 carbon atoms), examples of which include ethylene, propylene, butene, and the like.
  • Examples of vinyl-based cyclic hydrocarbon monomers include vinylcyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene.
  • (meth)acrylates include C1-C20 alkyl (meth)acrylates such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
  • the content of the cycloolefin monomer in the copolymer of the cycloolefin monomer and the copolymerizable monomer is, for example, 20 to 80 mol with respect to the total of all monomers constituting the copolymer. %, preferably 30-70 mol %.
  • the cycloolefin resin is obtained by polymerizing or polymerizing a cycloolefin monomer having a norbornene skeleton, preferably a cycloolefin monomer having a structure represented by the general formula (A-1) or (A-2).
  • Polymers obtained by copolymerization examples of which include: 1) A ring-opening polymer of a cycloolefin monomer 2) A ring-opening copolymer of a cycloolefin monomer and a copolymerizable monomer capable of ring-opening copolymerization with it 3) The above 1) or 2) Hydrogenated ring-opening (co)polymer 4) A (co)polymer obtained by cyclizing the ring-opening (co)polymer of 1) or 2) above by Friedel-Crafts reaction and then hydrogenating it 5) Cycloolefin Saturated copolymers of monomers and unsaturated double bond-containing compounds 6) Addition copolymers of cycloolefin monomers with vinyl-based cyclic hydrocarbon monomers and hydrogenated products thereof 7) Cycloolefin monomers Alternating copolymers of monomers and (meth)acrylates.
  • the above polymers 1) to 7) can all be obtained by known methods, for example, the methods described in JP-A-2008-107534 and JP-A-2005-227606.
  • the catalyst and solvent used in the ring-opening copolymerization of 2) above can be those described in paragraphs 0019 to 0024 of JP-A-2008-107534.
  • the catalyst used for hydrogenation in 3) and 6) above for example, those described in paragraphs 0025 to 0028 of JP-A-2008-107534 can be used.
  • As the acidic compound used in the Friedel-Crafts reaction of 4) above, for example, those described in paragraph 0029 of JP-A-2008-107534 can be used.
  • the catalyst used for the addition polymerization of 5) to 7) above for example, those described in paragraphs 0058 to 0063 of JP-A-2005-227606 can be used.
  • the alternating copolymerization reaction of 7) above can be carried out, for example, by the method described in paragraphs 0071 to 0072 of JP-A-2005-227606.
  • the cycloolefin resin has a structural unit represented by the following general formula (B-1) and the following general formula It preferably contains at least one of the structural units represented by (B-2), and contains only the structural unit represented by general formula (B-2), or represented by general formula (B-1) More preferably, it contains both a structural unit and a structural unit represented by general formula (B-2).
  • the structural unit represented by general formula (B-1) is a structural unit derived from the cycloolefin monomer represented by general formula (A-1) described above, and is represented by general formula (B-2). is a structural unit derived from the cycloolefin monomer represented by the general formula (A-2) described above.
  • R 1 to R 4 and p have the same definitions as R 1 to R 4 and p in general formula (A-1) above, respectively.
  • R 5 to R 6 and p have the same definitions as R 5 to R 6 and p in general formula (A-2), respectively.
  • the cycloolefin resin used in the present invention may be a commercially available product.
  • examples of commercially available cycloolefin resins include ARTON (registered trademark, hereinafter the same) G (eg, G7810, etc.) manufactured by JSR Corporation, ARTON F, ARTON R (eg, R4500, R4900, R5000, etc.). , and Arton RX (eg, RX4500, etc.).
  • the intrinsic viscosity [ ⁇ ] inh of the cycloolefin resin is preferably 0.2 to 5 cm 3 /g, more preferably 0.3 to 3 cm 3 /g, more preferably 0.4 when measured at 30°C. More preferably ⁇ 1.5 cm 3 /g.
  • the number average molecular weight (Mn) of the cycloolefin resin is preferably 8,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 12,000 to 50,000.
  • the weight average molecular weight (Mw) of the cycloolefin resin is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, even more preferably 40,000 to 200,000.
  • the cycloolefin resin has good heat resistance, water resistance, chemical resistance, mechanical properties, and moldability as a base film. becomes.
  • the glass transition temperature (Tg) of the cycloolefin resin is usually 110°C or higher, preferably 110 to 350°C, more preferably 120 to 250°C, and further preferably 120 to 220°C. preferable.
  • Tg is 110° C. or higher, deformation under high temperature conditions is easily suppressed.
  • the Tg is 350° C. or less, the molding process becomes easy, and deterioration of the resin due to heat during the molding process can be easily suppressed.
  • the content is preferably 70% by mass or more, more preferably 80% by mass or more, relative to the total mass of the damping portion 1.
  • vibration damping portion 1 contains a cycloolefin resin, it is also preferable to further contain fine particles.
  • fine particles to be used include inorganic compounds such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, silica Mention may be made of aluminum phosphates, magnesium silicates, and calcium phosphates. Fine particles of organic compounds can also be preferably used.
  • organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resins, silicone resins, polycarbonate resins, benzoguanamine resins, and melamine resins.
  • polyolefin powder, polyester resin, polyamide resin, polyimide resin, polyfluoroethylene resin, pulverized classified products of organic polymer compounds such as starch, and polymer compounds synthesized by suspension polymerization can be used. can.
  • Fine particles containing silicon are preferable in terms of lowering turbidity, and silicon dioxide is particularly preferable.
  • fine particles include trade names of Aerosil (registered trademark, hereinafter the same) R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) It is commercially available and can be used.
  • the transparent polyurethane resin used for the vibration damping portion 1 is preferably formed from a polyurethane resin-forming composition.
  • the polyurethane resin-forming composition according to the present invention is composed of polyisocyanate (A) and polyol (B). Either or both of the polyisocyanate (A) and the polyol (B) contain ethylene oxide units, and the content of the ethylene oxide units is 3 to 15% by mass based on the total amount of (A) and (B). is preferred, and 3 to 10% by mass is more preferred.
  • a polyether compound (b) having a terminal active hydrogen functional group and an average of 6 or more ethylene oxide units in one molecule is used as a method for introducing the ethylene oxide unit. It can be introduced by causing a chemical reaction, or it can be introduced by blending it with the polyol (B) and causing a urethanization reaction during curing.
  • the polyether compound (b) used in the present invention is a compound having a terminal active hydrogen functional group such as a hydroxy group or an amino group and an average of 6 or more ethylene oxide units per molecule.
  • Examples of the polyether compound (b) used in the present invention include alkylene oxide adducts of alcohols, phenols and amines.
  • EO ethylene oxide
  • PO propylene oxide
  • THF tetrahydrofuran
  • EO is used as an essential component and used in any combination. can.
  • an alkylene oxide other than EO it is necessary to increase the amount of the polyether compound (b) introduced in order to improve the whitening resistance of the resulting polyurethane resin, which leads to deterioration of weather resistance. is preferably used alone.
  • the alcohols include water, monohydric alcohols (methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, etc.), dihydric alcohols (ethylene glycol , diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butylene glycol, neopentyl glycol, etc.), 3 Hydric alcohols (glycerin, trimethylolpropane, etc.), tetrahydric to octahydric alcohols (pentaerythritol, diglycerin, ⁇ -methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose, etc.), and these Combinations of two or more are included.
  • phenols examples include hydroquinone, bisphenols (bisphenol A, bisphenol F, etc.), formalin low condensates of phenol compounds (number average molecular weight of 1000 or less) (novolac resins, resol - intermediates), and combinations of two or more thereof.
  • amines examples include ammonia, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, aminoethylethanolamine, etc.), alkylamines having 1 to 20 carbon atoms (methyl amine, ethylamine, n-butylamine, octylamine, etc.), alkylenediamines having 2 to 6 carbon atoms (ethylenediamine, hexamethylenediamine, etc.), polyalkylenepolyamines having an alkylene group having 2 to 6 carbon atoms (polymerization degree 2 to 8) (diethylenetriamine, triethylenetetramine, etc.), aromatic amines having 6 to 20 carbon atoms (aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine, etc.), 4 to 15 carbon atoms cycloaliphatic amines (is
  • Polyisocyanate (A) used in the present invention includes aliphatic and / or alicyclic diisocyanate monomer (a1) and isocyanurate, allophanate, adduct, prepolymer derived from them, Among these, one type can be used alone or two or more types can be used in combination.
  • Aliphatic and/or alicyclic diisocyanate monomers (a1) include, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate , lysine diisocyanate, trioxyethylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated naphthalene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, etc.
  • aliphatic and/or alicyclic diisocyanates can be used alone or in combination of two or more.
  • hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate are preferred, and hexamethylene diisocyanate is most preferred, from the viewpoint of physical properties, durability, and practicality.
  • the polyisocyanate (A) When an isocyanurate, allophanate, or adduct is used as the polyisocyanate (A), it is preferable to remove unreacted isocyanate monomers to a residual content of 1.0% by mass or less by a process such as distillation. .
  • the EO unit can be incorporated into the polyisocyanate (A) by subjecting the polyisocyanate and the polyether compound (b) to a urethanization reaction in advance.
  • the average number of NCO functional groups of the polyisocyanate (A) is preferably in the range of 2.5-5.0, more preferably in the range of 3.0-4.5.
  • polyol (B) used in the present invention examples include polycarbonate-based polyols, polyester-based polyols, polycaprolactone-based polyols, polyether-based polyols, and the like.
  • polycarbonate-based polyols used in the present invention include ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butane.
  • diol diethylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,
  • short-chain polyols such as 2-dimethylolheptane, glycerin and trimethylolpropane with low-molecular-weight carbonates such as ethylene carbonate, dimethyl carbonate, diethyl carbonate and diphenyl carbonate.
  • a copolycarbonate polyol obtained by polycondensing two or more of the above short-chain polyols and a low-molecular-weight carbonate may also be used. Mixtures of the above polycarbonate-based polyols can also be used.
  • polyester-based polyol used in the present invention those obtained by polycondensation of the above short-chain polyol and polycarboxylic acids such as adipic acid, succinic acid, malonic acid, pimelic acid, sebacic acid and trimellitic acid. mentioned.
  • a copolyester polyol obtained by polycondensing two or more of the above short-chain polyols and a polycarboxylic acid may also be used. Mixtures of the above polyester polyols can also be used.
  • cyclic esters such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -valerolactone are developed using the above short-chain polyol as an initiator. Examples thereof include those obtained by cycloaddition. Mixtures of the above polycaprolactone-based polyols can also be used.
  • Polyether-based polyols used in the present invention include poly(ethylene ether) glycols and poly(propylene ethers) obtained by ring-opening polymerization of the above short-chain polyols and cyclic ethers such as EO, PO, and THF. ) glycol, polytetramethylene ether glycol, and the like. A copolymerized polyether-based polyol using two or more of the above cyclic ethers can also be used. Mixtures of these polyether-based polyols can also be used.
  • the above-mentioned polycarbonate-based polyols, polyester-based polyols, polycaprolactone-based polyols, and polyether-based polyols can be used singly or in combination of two or more.
  • polycarbonate-based polyols, polyester-based polyols, and polycaprolactone-based polyols are preferably used from the viewpoint of the weather resistance of the resulting polyurethane resin.
  • the weather resistance deteriorates, so it is preferable to use it in the minimum necessary amount.
  • the polyether compound (b) described above can be used in combination as an EO unit source.
  • polyol (B) a polyol having an average number of OH functional groups of 3 or more can be used together as a cross-linking agent.
  • examples of polyols having an average number of OH functional groups of 3 or more and used as a cross-linking agent in the present invention include triols such as glycerin and trimethylolpropane, and tetraols such as ditrimethylolpropane, diglycerin and pentaerythritol. can be used alone or in combination of two or more.
  • glycol can be used as a chain extender as the polyol (B).
  • examples of glycols used as chain extenders in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol and 1,4-cyclohexyl. Dimethanol, hydroquinone-bis-(2-hydroxyethyl) ether (including various isomers), etc., may be used alone or in combination of two or more.
  • the hydroxyl value of the polyol (B) is preferably 300 mgKOH/g to 700mgKOH/g, more preferably 400mgKOH/g to 600mgKOH/g. Furthermore, the average OH functional group number of the polyol (B) is preferably 2.1 to 3.0.
  • a urethanization catalyst can be used in the step of reacting the polyisocyanate (A) and the polyol (B) to obtain a polyurethane resin.
  • the urethanization catalyst include known amine compounds (e.g., triethylenediamine), organometallic compounds (e.g., dibutyltin dilaurate) and quaternary ammonium salts. It is preferred to use compounds. From the viewpoint of workability, the catalyst is preferably mixed with the polyol (B) in advance.
  • Antioxidants, ultraviolet absorbers, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic agents, dispersants, storage stabilizers, etc. may be added to the polyurethane resin-forming composition, if necessary. Additives can be appropriately blended.
  • a polyurethane resin obtained using the above polyurethane resin-forming composition is produced, for example, by the following method.
  • the above polyisocyanate (A) and polyol (B) are put into separate tanks of a two-liquid mixing urethane casting machine, and after defoaming and heat retention, the two liquids are mixed at a predetermined ratio in the mixer section.
  • the mixed liquid discharged from the casting machine is poured into a mold whose temperature is adjusted to 50 to 150° C., and when the green strength is obtained so that it can be removed from the mold, the cured product is removed from the mold. Generally, it is often demolded in about 5 to 60 minutes. After performing secondary curing as necessary, it is often further processed as an optical component and incorporated into a device.
  • the mixed liquid discharged from the casting machine is continuously poured and spread on a release film such as a PET film, and the other side is spread before the resin hardens.
  • a release film such as a PET film
  • the film is passed through a curing furnace heated to 50 to 150° C. and wound up with a roll.
  • the manufacturing method (forming method) of the vibration damping part 1 is not particularly limited, but after preparing a dope containing a resin material, a rubber material, a solvent, and optionally other components, the dope is applied to a base material, It is preferable to use a method of obtaining the vibration damping portion 1 in the form of a film by a method of drying after that.
  • a transparent polyurethane resin is used as the vibration damping part 1, it is preferably a polyurethane resin film obtained by the manufacturing method (forming method) described in the above ⁇ Method for manufacturing polyurethane resin>>.
  • the solvent used for the dope is not particularly limited as long as it can satisfactorily disperse the resin material and the rubber material.
  • solvents include alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, tert-butanol, cyclohexanol, ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone, acetone, ethyl acetate, acetic acid.
  • Esters such as methyl, ethyl lactate, isopropyl acetate, amyl acetate, ethyl butyrate, ethers such as tetrahydrofuran (THF) and 1,4-dioxane, glycol ethers (propylene glycol mono (C1-C4) alkyl ether (specifically Propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, etc.), propylene glycol mono (C1-C4) alkyl ether ester ( propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate)), toluene, benzene, cyclohexane, n-hexane and other hydrocarbons.
  • glycol ethers prop
  • solvents can be used singly or in combination of two or more.
  • methyl ethyl ketone, ethyl acetate, acetone, and tetrahydrofuran are preferable from the viewpoints of easily dissolving the resin material, having a low boiling point, and easily increasing the drying speed and productivity.
  • a solvent such as dichloromethane may be further mixed with the solvents listed above.
  • the solid content concentration of the dope is preferably, for example, 5 to 20% by mass from the viewpoint of facilitating adjustment of the viscosity.
  • the dope may further contain other components than those described above, if necessary.
  • other components include matting agents (fine particles), ultraviolet absorbers, surfactants, and the like.
  • a matting agent can be added from the viewpoint of imparting slipperiness to the film.
  • matting agents include inorganic fine particles such as silica particles and organic fine particles having a glass transition temperature of 80° C. or higher.
  • UV absorbers examples include benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers.
  • surfactants include anionic surfactants such as carboxylic acid type, sulfonic acid type, sulfate ester type, and phosphate ester type; cationic surfactants such as alkylamine salt type and quaternary ammonium salt type. Any of amphoteric surfactants such as carboxybetaine type, 2-alkylimidazoline derivative type, glycine type and amine oxide type surfactants can be used.
  • the mixing order of each component contained in the dope is not particularly limited.
  • the method of mixing each component is not particularly limited, either, and for example, it may be stirred using a stirrer or the like.
  • the mixing time is not particularly limited, but is, for example, 1 to 10 hours.
  • the mixing temperature is not particularly limited, but is, for example, 20 to 50°C.
  • the viscosity of the dope is not particularly limited as long as it can form the desired thickness of the damping portion 1, but is preferably 5 to 5000 mPa ⁇ s, for example. When the viscosity of the dope is 5 mPa ⁇ s or more, it is easy to form the vibration damping portion 1 with an appropriate thickness. From the same viewpoint, the viscosity of the dope is more preferably 100 to 1000 mPa ⁇ s. The viscosity of the dope can be measured at 25° C. with an E-type viscometer.
  • the obtained dope may be filtered as necessary.
  • the filtration method is not particularly limited, and conventionally known methods can be appropriately employed.
  • Step of forming a film The dope obtained as described above is applied to the surface of the substrate. After that, the film is formed by removing the solvent from the dope to form a film (laminate) including the substrate and the damping portion 1 .
  • the step of applying the dope to the substrate and the step of forming the damping portion 1 (drying step) will be described below.
  • the dope obtained as described above is applied to the surface of the substrate. Specifically, the dope is applied to the surface of the substrate.
  • the base material is not particularly limited as long as it can support the vibration damping section 1, but can usually include a resin film.
  • resin films examples include polyester resin films (e.g., polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.). , cycloolefin resin film (COP), acrylic film, cellulose resin film (eg, cellulose triacetate film (TAC), etc.).
  • PET film, cellulose triacetate film (TAC), and cycloolefin resin film are preferable from the viewpoint of versatility and high tensile modulus.
  • the resin film may be thermally relaxed or stretched.
  • the thermal relaxation temperature is not particularly limited, but it can be performed at (Tg+60) to (Tg+180)° C., where Tg is the glass transition temperature of the resin constituting the resin film. Thermal relaxation may be performed before forming the release layer, or may be performed after forming the release layer.
  • the stretching process can increase the orientation of the resin molecules, thereby increasing the tensile modulus of the resin film and, in turn, the base material.
  • the stretching treatment may be performed, for example, in the uniaxial direction of the base material, or may be performed in the biaxial direction.
  • the stretching treatment can be performed under arbitrary conditions, for example, at a stretching ratio of about 120 to 900%.
  • the draw ratio is a value obtained by multiplying the draw ratio in each direction. Whether or not the resin film is stretched (whether or not it is a stretched film) can be confirmed by, for example, whether or not there is an in-plane slow axis (an axis extending in the direction in which the refractive index is maximized).
  • the substrate preferably further has a release layer provided on the surface of the resin film.
  • the release layer can make it easier to separate the vibration damping section 1 from the base material.
  • the release layer may contain a known release agent or release agent, and is not particularly limited.
  • release agents contained in the release layer include silicone release agents and non-silicone release agents.
  • silicone-based release agents include known silicone-based resins.
  • non-silicone release agents include long-chain alkyl pendant type polymers obtained by reacting long-chain alkyl isocyanate with polyvinyl alcohol or ethylene-vinyl alcohol copolymer, olefin-based resins (e.g.
  • copolymerized polyethylene cyclic polyolefin, polymethylpentene
  • polyarylate resin e.g., polycondensate of aromatic dicarboxylic acid component and dihydric phenol component
  • fluororesin e.g., polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), PFA (copolymer of tetrafluoroethylene and perfluoroalkoxyethylene
  • FEP copolymer of tetrafluoroethylene and hexafluoropropylene
  • ETFE copolymer of tetrafluoroethylene and ethylene
  • the release layer may further contain additives as necessary.
  • additives include fillers, lubricants (waxes, fatty acid esters, fatty acid amides, etc.), stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), flame retardants, viscosity modifiers, thickeners, Contains defoamer and UV absorber.
  • the thickness of the release layer is not particularly limited as long as it can exhibit the desired releasability, but is preferably 0.1 to 1.0 ⁇ m, for example.
  • the thickness of the substrate is not particularly limited, it is preferably 10 to 100 ⁇ m, more preferably 25 to 50 ⁇ m.
  • the method of applying the dope is not particularly limited, and may be a known method such as a back coating method, gravure coating method, spin coating method, wire bar coating method, or roll coating method.
  • the back coating method is preferable from the viewpoint of forming a coating film having a thin and uniform thickness.
  • the damping portion 1 is formed by removing the solvent from the dope applied to the substrate.
  • the dope applied to the substrate is dried. Drying can be carried out, for example, by blowing air or heating. Above all, it is preferable to dry by blowing air from the viewpoint of easily suppressing curling of the laminate.
  • the drying conditions eg, drying temperature, solvent concentration in the atmosphere, drying time, etc.
  • the distribution state of the graft copolymer (rubber particles) in the damping portion 1 can be adjusted depending on the drying conditions. Specifically, from the viewpoint of facilitating uneven distribution of the graft copolymer (rubber particles), it is preferable to use a solvent that has a good affinity with the graft copolymer (rubber particles) and to increase the drying temperature.
  • the solvent concentration in the atmosphere is preferably low.
  • the drying temperature is preferably (Tb-50) to (Tb+50)°C, more preferably (Tb-40) to (Tb+40)°C, where Tb (°C) is the boiling point of the solvent.
  • Tb (°C) is the boiling point of the solvent.
  • the drying temperature is at least the lower limit, the evaporation rate of the solvent can be increased, so that the graft copolymer (rubber particles) tends to be unevenly distributed. can be done
  • the drying temperature can be 40° C. or higher.
  • the solvent concentration in the atmosphere during drying is preferably 0.10 to 0.30% by mass, more preferably 0.10 to 0.20% by mass.
  • concentration of the solvent in the atmosphere is 0.10% by mass or more, the solvent does not evaporate too much, so cracks and the like are less likely to occur in the coating film.
  • the solvent concentration is 0.30% by mass or less, the evaporation rate of the solvent from the coating film tends to be moderately high, so that the rubber particles tend to be unevenly distributed on the surface.
  • the solvent concentration in the atmosphere can be adjusted by the drying temperature and the dew point temperature in the drying furnace. Also, the solvent concentration in the atmosphere can be measured with an infrared gas concentration meter.
  • the in-plane retardation (R 0 ) represented by the following formula (A) of the damping portion 1 is preferably ⁇ 10 to 10 nm.
  • Nx is the maximum refractive index in the plane of the damping portion 1
  • Ny is the minimum refractive index in the plane of the damping portion 1
  • d is the thickness of the damping portion 1. It is.
  • the in-plane retardation (R 0 ) can be measured using an automatic birefringence meter.
  • an automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd.
  • it can be determined at a wavelength of 590 nm under an environment of a temperature of 23° C. and a humidity of 55% RH.
  • the thickness of the vibration damping portion 1 is preferably 10 to 60 ⁇ m, more preferably 15 to 50 ⁇ m, and even more preferably 25 to 40 ⁇ m, in consideration of thinning of the optical layered body.
  • the glass transition temperature of the damping portion 1 is preferably -30°C to 180°C from the viewpoint of impact resistance. In addition, when a plurality of glass transition temperatures are observed when measuring the glass transition temperature of the vibration damping portion 1 , the lowest glass transition temperature measured is taken as the glass transition temperature of the vibration damping portion 1 .
  • the storage elastic modulus of the vibration damping portion 1 is preferably 0.1 to 3.0 GPa, more preferably 0.1 to 1.0 GPa, from the viewpoint of impact resistance and flexibility.
  • Tan ⁇ (tan ⁇ 2) of the vibration damping portion 1 is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 0.01 to 0.3, more preferably 0.05 to 0.3. is more preferable.
  • the elastic modulus 1 and elastic modulus 2 preferably satisfy the relationship of the following formula (2).
  • the effects of the present invention can be exhibited more efficiently.
  • An adhesive portion may be provided between the restraint portion and the damping portion 1.
  • the material used for such an adhesive portion is not particularly limited, and examples thereof include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, and polyvinyl alcohol-based adhesives. adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like.
  • a more specific example is an adhesive layer obtained by irradiating an active energy ray-curable adhesive material disclosed in JP-A-2009-242633 with an active energy ray.
  • the vibration damping portion 2 may be either an article that can be wound like a film made of a thermoplastic resin or the like, or a coating layer formed by coating on the vibration damping portion 1. It is preferably in the form of layers.
  • an adhesive there are no particular restrictions on the material that constitutes the vibration damping portion 2, it is preferably made of an adhesive.
  • an adhesive there are no particular restrictions on the type of adhesive, and examples include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, and polyvinylpyrrolidone-based adhesives. , polyacrylamide-based adhesives, cellulose-based adhesives, and the like.
  • acrylic pressure-sensitive adhesives are preferable because they are excellent in transparency, exhibit appropriate adhesion, cohesiveness, and adhesive properties, and are excellent in weather resistance, heat resistance, and the like.
  • An acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer.
  • the vibration damping part 2 using an acrylic pressure-sensitive adhesive is, for example, a monomer component containing an alkyl (meth) acrylate and / or a partial polymer of the monomer component, an ultraviolet absorber, and light having an absorption band at a wavelength of 400 nm or more. It is preferably formed by subjecting an ultraviolet-curable acrylic pressure-sensitive adhesive composition containing a polymerization initiator to ultraviolet polymerization.
  • alkyl (meth)acrylates examples include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester end.
  • Alkyl (meth)acrylates can be used singly or in combination of two or more.
  • Alkyl (meth)acrylate is a general term for alkyl acrylate and alkyl methacrylate.
  • alkyl (meth)acrylates examples include alkyl (meth)acrylates having a linear or branched alkyl group with 4 to 9 carbon atoms. Specifically, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate and the like. These can be used singly or in combination of two or more.
  • Alkyl (meth)acrylate having an alkyl group having 1 to 24 carbon atoms at the ester end is preferably 40% by mass or more with respect to the total mass of the monofunctional monomer component forming the (meth)acrylic polymer, 50% by mass or more is more preferable, and 60% by mass or more is even more preferable.
  • the monomer component can contain a copolymerizable monomer other than alkyl (meth)acrylate as a monofunctional monomer component.
  • a copolymerizable monomer can be used as the remainder of the alkyl (meth)acrylate in the monomer component.
  • copolymerizable monomers examples include cyclic nitrogen-containing monomers.
  • cyclic nitrogen-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation.
  • the cyclic nitrogen structure preferably has a nitrogen atom within the cyclic structure.
  • cyclic nitrogen-containing monomers examples include lactam vinyl monomers such as N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinyl Vinyl-based monomers having a nitrogen-containing heterocyclic ring such as pyrrole, vinylimidazole, vinyloxazole, and vinylmorpholine are included. Also included are (meth)acrylic monomers containing a heterocyclic ring such as a morpholine ring, piperidine ring, pyrrolidine ring and piperazine ring.
  • lactam vinyl monomers such as N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone
  • vinylpyridine vinylpiperidone
  • vinylpyrimidine vinylpiperazine
  • vinylpyrazine vinyl Vinyl-based monomers
  • N-acryloylmorpholine N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.
  • lactam vinyl monomers are preferred.
  • the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by mass, preferably 0.5 to 40% by mass, based on the total mass of the monofunctional monomer component forming the (meth)acrylic polymer. %, more preferably 0.5 to 30% by mass.
  • the monomer component used in the present invention can contain a hydroxy group-containing monomer as a monofunctional monomer component.
  • a hydroxy group-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a hydroxy group can be used without particular limitation.
  • hydroxy group-containing monomers examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth)acrylates such as meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate; (4 - hydroxyalkylcycloalkane (meth)acrylates such as hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • hydroxyethyl (meth)acrylamide examples include hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and the like. These can be used singly or in combination of two or more. Among these, hydroxyalkyl (meth)acrylates are preferred.
  • the content of the hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 2% by mass or more, relative to the total mass of the monofunctional monomer component forming the (meth)acrylic polymer. , more preferably 3% by mass or more.
  • the vibration damping portion 2 may become hard and the adhesive strength may be lowered.
  • the hydroxyl group-containing monomer is 30 mass with respect to the total amount of the monofunctional monomer component forming the (meth)acrylic polymer. % or less, more preferably 27 mass % or less, and even more preferably 25 mass % or less.
  • the monomer component forming the (meth)acrylic polymer may contain other functional group-containing monomers as monofunctional monomers, such as carboxy group-containing monomers and cyclic ether group-containing monomers. mentioned.
  • any monomer having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a carboxy group can be used without particular limitation.
  • carboxy group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. These can be used singly or in combination of two or more. Anhydrides of itaconic acid and maleic acid can also be used. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is particularly preferred. Any carboxy group-containing monomer can be used as the monomer component for producing the (meth)acrylic polymer of the present invention, and the carboxy group-containing monomer need not be used.
  • the monomer having a cyclic ether group those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a cyclic ether group such as an epoxy group or an oxetane group are used. It can be used without any particular limitation.
  • epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and the like.
  • oxetane group-containing monomers examples include 3-oxetanylmethyl (meth)acrylate, 3-methyl-oxetanylmethyl (meth)acrylate, 3-ethyl-oxetanylmethyl (meth)acrylate, and 3-butyl-oxetanylmethyl (meth)acrylate. , 3-hexyl-oxetanylmethyl (meth)acrylate, and the like. These can be used singly or in combination of two or more.
  • the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by mass or less with respect to the total mass of the monofunctional monomer component forming the (meth)acrylic polymer. It is more preferably 25% by mass or less, more preferably 25% by mass or less.
  • components forming the (meth)acrylic polymer of the present invention include, for example, CH 2 ⁇ C(R 1 )COOR 2 (R 1 is a hydrogen atom or a methyl group, and R 2 is a substituted polymer having 1 to 3 carbon atoms). or a cyclic cycloalkyl group).
  • Examples of such monomers represented by CH 2 ⁇ C(R 1 )COOR 2 include phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (Meth)acrylate, isobornyl (meth)acrylate and the like. These can be used singly or in combination of two or more.
  • copolymerizable monomers include vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, (meth)acrylate, Glycol-based acrylic ester monomers such as methoxypolypropylene glycol acrylate; acrylic ester-based monomers such as tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, silicone (meth)acrylate and 2-methoxyethyl acrylate; amide group-containing Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like can also be used.
  • a monomer having a cyclic structure such as terpene (meth)acrylate and dicyclopentanyl (meth)acryl
  • silane-based monomers containing silicon atoms can also be used.
  • silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane.
  • the monomer components forming the (meth)acrylic polymer of the present invention include, if necessary, polyfunctional monomers for adjusting the cohesive force of the vibration damping portion 2. can contain
  • a polyfunctional monomer is a monomer having at least two polymerizable functional groups with unsaturated double bonds such as (meth)acryloyl groups or vinyl groups.
  • Specific examples include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri (meth)acrylates, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, Ester compounds of polyhydric alcohols such as trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate and (meth)acrylic acid;
  • trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used.
  • the polyfunctional monomers can be used singly or in combination of two or more.
  • the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, with respect to the total 100 parts by mass of the monofunctional monomers. It is preferably 1 part by mass or less, and more preferably 1 part by mass or less. Moreover, the amount of the polyfunctional monomer used is preferably more than 0 parts by mass, and more preferably 0.001 parts by mass or more. By setting the amount of the polyfunctional monomer to be used within the above range, the adhesive strength can be improved.
  • the damping portion 2 may contain a partial polymer of the monomer component.
  • the UV absorber contained in the UV-curable acrylic pressure-sensitive adhesive composition is not particularly limited. , salicylic acid ester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like, and these can be used alone or in combination of two or more. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferred. Also, at least one ultraviolet absorber selected from the group consisting of a triazine-based ultraviolet absorber having two or less hydroxy groups in one molecule, and a benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule.
  • the agent is preferable because it has good solubility in the monomer used for forming the UV-curable acrylic pressure-sensitive adhesive composition and has a high UV-absorbing ability in the vicinity of a wavelength of 380 nm.
  • the ultraviolet absorbers can be used singly or in combination of two or more.
  • the content of the ultraviolet absorber is preferably 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, with respect to 100 parts by weight of the monofunctional monomer component forming the (meth)acrylic polymer. It is more preferable to have By setting the amount of the ultraviolet absorber to be added within the above range, the ultraviolet absorbing function of the vibration damping portion 2 can be sufficiently exhibited and the ultraviolet polymerization is not hindered, which is preferable.
  • the ultraviolet-curable acrylic pressure-sensitive adhesive composition used in the present invention preferably contains a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more.
  • A photopolymerization initiator
  • the pressure-sensitive adhesive composition contains an ultraviolet absorber
  • the ultraviolet light is absorbed by the ultraviolet absorber, resulting in insufficient polymerization.
  • the ultraviolet-curable acrylic pressure-sensitive adhesive composition used in the present invention has a photopolymerization initiator having an absorption band at a wavelength of 400 nm or more, it can be sufficiently polymerized despite containing an ultraviolet absorber. It is.
  • the photopolymerization initiator having an absorption band at a wavelength of 400 nm or more include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available products are Omnirad (registered trademark) 819, IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available products are Omnirad (registered trademark) TPO H, IGM Resins B.V.), and the like. can.
  • the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used alone or in combination of two or more.
  • the amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but is preferably less than the amount of the ultraviolet absorber. It is preferably about 0.005 to 1 part by mass, more preferably about 0.02 to 0.5 part by mass, relative to 100 parts by mass of the monofunctional monomer component forming the polymer. It is preferable that the amount of the photopolymerization initiator (A) to be added is within the above range because the ultraviolet polymerization can sufficiently proceed.
  • the UV-curable acrylic pressure-sensitive adhesive composition can contain a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm.
  • the photopolymerization initiator (B) preferably does not have an absorption band at a wavelength of 400 nm or longer.
  • the photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays and initiates photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any initiator can be suitably used.
  • benzoin ether-based photopolymerization initiator acetophenone-based photopolymerization initiator, ⁇ -ketol-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzyl-based photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and the like can be used.
  • the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be used singly or in combination of two or more.
  • the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within a range that does not impair the effects of the present invention. It is preferably 0.005 to 0.5 parts by mass, more preferably 0.02 to 0.1 parts by mass, based on 100 parts by mass of the monomer component.
  • a partially polymerized product prepolymer It is preferable to add the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more and an ultraviolet absorber to the composition) and perform ultraviolet polymerization.
  • the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more to a partially polymerized monomer component (prepolymer composition) partially polymerized by ultraviolet irradiation
  • the photopolymerization initiator It is preferred to add A) after dissolving it in the monomer.
  • the UV-curable acrylic pressure-sensitive adhesive composition used in the present invention can contain a silane coupling agent.
  • the amount of the silane coupling agent used is preferably 1 part by mass or less, more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the monofunctional monomer component forming the (meth)acrylic polymer. 0.02 to 0.6 parts by mass is more preferable.
  • silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4- Epoxy group-containing silane coupling agents such as epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene)propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane (Meth)acrylic group-containing silane coupling agents such as 3-isocyanatopropyltri
  • the UV-curable acrylic pressure-sensitive adhesive composition used in the present invention can contain a cross-linking agent.
  • cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, silicone-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl-etherified melamine-based cross-linking agents, and metal chelate-based cross-linking agents. and cross-linking agents such as peroxides.
  • cross-linking agents can be used singly or in combination of two or more. Among these, isocyanate-based cross-linking agents are preferably used.
  • the content of the cross-linking agent is preferably 5 parts by mass or less, more preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the monofunctional monomer component forming the (meth)acrylic polymer. It is preferably from 0.01 to 4 parts by mass, and particularly preferably from 0.02 to 3 parts by mass.
  • An isocyanate-based cross-linking agent refers to a compound having two or more isocyanate groups (including isocyanate regenerative functional groups in which isocyanate groups are temporarily protected by blocking agents or multimerization, etc.) in one molecule.
  • the isocyanate-based crosslinking agent includes aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
  • the UV-curable acrylic pressure-sensitive adhesive composition used in the present invention may appropriately contain other additives depending on the application.
  • additives include, for example, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenolic resins, etc., which are solid, semi-solid, or liquid at room temperature); hollow glass; Fillers such as balloons; plasticizers; anti-aging agents; antioxidants and the like.
  • the viscosity of the UV-curable acrylic pressure-sensitive adhesive composition it is preferable to adjust the viscosity of the UV-curable acrylic pressure-sensitive adhesive composition to suit the application work.
  • the viscosity of the UV-curable acrylic pressure-sensitive adhesive composition can be adjusted, for example, by adding various polymers such as thickening additives, polyfunctional monomers, etc., or by partially adjusting the monomer components in the UV-curable acrylic pressure-sensitive adhesive composition. It is carried out by polymerizing. The partial polymerization may be performed before or after adding various polymers such as thickening additives, polyfunctional monomers, and the like.
  • the viscosity of the UV-curable acrylic pressure-sensitive adhesive composition varies depending on the amount of additives, etc.
  • the polymerization rate when partially polymerizing the monomer components in the UV-curable acrylic pressure-sensitive adhesive composition should be uniquely determined. However, as a guide, it is preferably about 20% or less, more preferably about 3 to 20%, and even more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes too high, which may make coating difficult.
  • the damping portion 2 is formed by applying the ultraviolet-curable acrylic pressure-sensitive adhesive composition described above onto the damping portion 1 and irradiating the ultraviolet-curable acrylic pressure-sensitive adhesive composition with ultraviolet rays. be able to. Further, the ultraviolet-curable acrylic pressure-sensitive adhesive composition described above is applied onto the base material, and then the ultraviolet-curable acrylic pressure-sensitive adhesive composition is irradiated with ultraviolet rays to form a film-like vibration damping portion 2. can be formed.
  • the base material is not particularly limited, and various base materials such as release films and transparent resin film base materials can be suitably used.
  • Materials constituting the release film include, for example, resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, laminates thereof, and the like. Although suitable thin sheets and the like can be mentioned, resin films are preferably used from the viewpoint of excellent surface smoothness.
  • resin films examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene- A vinyl acetate copolymer film and the like can be mentioned.
  • the thickness of the release film is usually 5-200 ⁇ m, preferably about 5-100 ⁇ m.
  • a release agent such as a silicone, fluorine, long-chain alkyl or fatty acid amide release agent, silica powder, etc.
  • for release and antifouling treatment, coating type, kneading type, vapor deposition Antistatic treatment can also be applied to the mold or the like.
  • a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment, the releasability from the damping portion 2 can be further enhanced.
  • the transparent resin film substrate is not particularly limited, but various transparent resin films are used.
  • the resin film substrate is formed of a single-layer film.
  • the material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth)acrylic resins.
  • polyester-based resins particularly preferred are polyester-based resins, polyimide-based resins and polyethersulfone-based resins.
  • the thickness of the transparent resin film substrate is preferably 15-200 ⁇ m, more preferably 25-188 ⁇ m.
  • the method of applying the UV-curable acrylic pressure-sensitive adhesive composition includes a roll coating method, a kiss roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, a dip roll coating method, a bar coating method,
  • a conventionally known method such as a knife coating method, an air knife coating method, a curtain coating method, a lip coating method, a die coater method, or the like can be used as appropriate, and is not particularly limited.
  • the illuminance of the ultraviolet rays with which the ultraviolet-curable acrylic pressure-sensitive adhesive composition is irradiated is preferably 5 mW/cm 2 or more. When the illuminance of the ultraviolet rays is less than 5 mW/cm 2 , the polymerization reaction time becomes long, which may lead to poor productivity.
  • the illuminance of the ultraviolet rays is preferably 200 mW/cm 2 or less. When the illuminance of the ultraviolet rays exceeds 200 mW/cm 2 , the photopolymerization initiator is rapidly consumed, resulting in a decrease in the molecular weight of the polymer and a reduction in holding power, especially at high temperatures. Further, it is preferable that the cumulative light quantity of ultraviolet rays is 100 mJ/cm 2 to 5000 mJ/cm 2 .
  • the ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Since the LED lamp emits less heat than other ultraviolet lamps, the temperature of the damping part 2 during polymerization can be suppressed. Therefore, it is possible to prevent the polymer from having a low molecular weight, prevent a decrease in the cohesive force of the vibration damping portion 2, and increase the holding power at high temperatures when used as an adhesive sheet. It is also possible to combine a plurality of ultraviolet lamps. It is also possible to intermittently irradiate ultraviolet rays and provide a light period during which ultraviolet rays are irradiated and a dark period during which ultraviolet rays are not irradiated.
  • the final polymerization rate of the monomer component in the UV-curable acrylic pressure-sensitive adhesive composition is preferably 90% or higher, more preferably 95% or higher, and even more preferably 98% or higher.
  • the peak wavelength of the ultraviolet rays with which the ultraviolet-curable acrylic pressure-sensitive adhesive composition is irradiated is preferably within the range of 200-500 nm, more preferably within the range of 300-450 nm. If the peak wavelength of ultraviolet rays exceeds 500 nm, the photopolymerization initiator may not decompose and the polymerization reaction may not start. Moreover, when the peak wavelength of the ultraviolet rays is less than 200 nm, the polymer chain may be cut and the adhesiveness may be lowered.
  • a release film or the like is formed on the coating layer of the UV-curable acrylic pressure-sensitive adhesive composition, or the photopolymerization reaction is carried out under a nitrogen atmosphere. It is preferable to go with Examples of the release film include those described above.
  • the thickness of the vibration damping portion 2 is preferably 5 to 60 ⁇ m, more preferably 15 to 50 ⁇ m, and even more preferably 25 to 40 ⁇ m, taking into account thinning of the optical layered body.
  • the weight average molecular weight of the resin material used in the vibration damping portion 2 is preferably 100,000 to 5,000,000, more preferably 200,000 to 1,000,000 from the viewpoint of tan ⁇ control.
  • the glass transition temperature of the damping portion 2 is preferably 0°C or lower, more preferably -20°C or lower, from the viewpoint of impact resistance and flexibility in a low-temperature environment.
  • the storage elastic modulus of the vibration damping portion 2 is preferably 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 3 GPa from the viewpoint of impact resistance and flexibility, and 1.0 ⁇ 10 ⁇ 6 to More preferably, it is 1.0 ⁇ 10 ⁇ 4 GPa.
  • Tan ⁇ (tan ⁇ 3) of the vibration damping portion 2 is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 0.01 to 1.0, more preferably 0.1 to 1.0. is more preferable.
  • the weight average molecular weight of the resin material used in the vibration damping section 1 is preferably larger than the weight average molecular weight of the resin material used in the vibration damping section 2 .
  • Thin film glass Materials for thin film glass according to the present invention include lithium aluminosilicate glass, soda lime glass, borosilicate glass, alkali metal aluminosilicate glass, and low alkali content aluminosilicate glass.
  • the glass that constitutes the thin-film glass is preferably alkali-free glass that does not substantially contain alkali components.
  • the content of alkaline components in the thin glass is preferably 500 ppm or less, more preferably 300 ppm or less.
  • a thin film glass containing a large amount of alkaline components is susceptible to the phenomenon of soda blowing due to substitution of cations on the surface. This is because the density of the surface layer of the glass tends to decrease, and the thin-film glass may break.
  • Thin-film glass can be formed by commonly known methods such as the float method, down-draw method, overflow down-draw method, and the like. Among them, the overflow down-draw method or the float method is preferable because the surface of the thin film glass does not come into contact with the molding member during molding and the surface of the obtained thin film glass is less likely to be damaged.
  • the thin glass used in the present invention can also be obtained by grinding thick glass, such as borosilicate glass, to the desired thickness, but grinding and polishing a thick glass sheet results in a thickness of less than 200 ⁇ m. It is difficult to obtain a thin film glass of Therefore, it is preferable to employ the float method to obtain the thin film glass according to the present invention.
  • the thin-film glass is temporarily adhered to a thicker support substrate (hereinafter also referred to as "carrier substrate") for processing, and the support substrate is peeled off as a post-processing step. It has been proposed to obtain thin glass by
  • soda-lime glass with a thickness of less than 100 ⁇ m can be produced by the following steps.
  • Step 1 A thin film glass is formed on a glass carrier substrate having a bonding surface so that the first surface of the thin film glass is in contact, and the second surface opposite to the first surface has an adhesive force.
  • the step of depositing a contact film also called “contact film”).
  • the thin film glass manufacturing method involves pouring a material for thin film glass formation into a desired thickness onto a carrier substrate 21 having sufficient strength and a thickness that is easy to process. After forming the first surface of the thin film glass 22 so as to be in contact with the carrier substrate 21, there is a step of adhering the contact film 23 to the second surface opposite to the first surface.
  • Step 2 a step of separating the thin film glass 22 from the carrier substrate 21 by the contact film 23 having a high adhesive strength (FIG. 1 (step 2)).
  • Step 3 A step of removing the contact film 23 from the second surface of the thin film glass 22 peeled from the carrier substrate by a weakening treatment (electromagnetic radiation irradiation 24) that weakens the adhesion of the contact film (FIG. 1 (Step 3). )).
  • the use of the contact film 23 for safely holding the thin film glass 22 can have a protective function for the thin film glass 22, thereby allowing the exposed surface of the thin film glass 22, for example, to can be protected from mechanical damage that can occur and can be handled safely and conveniently.
  • the contact film can include hard or soft materials, and polyolefins (PO) such as polyethylene terephthalate (PET) or polyethylene (PE) can be used as preferred materials.
  • PO polyolefins
  • PET polyethylene terephthalate
  • PE polyethylene
  • the contact film is usually adhered to the thin glass with an adhesive layer made of adhesive provided on one side of the substrate.
  • the contact film may be directly adhered to the thin glass by the adhesiveness of the contact film itself.
  • the adhesion force between the contact film and the second surface of the thin film glass transfers sufficient force to the thin film glass upon delamination by the delamination device to overcome the bonding force between the carrier substrate and the thin film glass upon crimping. selected to be able to
  • the contact film can be provided as a foil or tape, which can be wound from a roll, for example, or provided as a sheet.
  • the thickness of the contact film is 50 ⁇ m or more, more preferably 80 ⁇ m or more, still more preferably 125 ⁇ m or more, particularly preferably 150 ⁇ m or more.
  • the thin film glass is preferably produced by the aforementioned down-draw method, overflow down-draw method, float method, or the like.
  • the carrier substrate preferably has a thickness of at least 100 ⁇ m or more, preferably 300 ⁇ m or more, more preferably 500 ⁇ m or more, and a thickness of at least 3 inches (1 inch is 2.54 cm) or more, preferably 6 inches or more, more preferably 8 inches or more. It has a maximum dimension of 12 inches or more, particularly preferably 12 inches or more.
  • the carrier substrate can have a glass substrate 1st generation size or larger, such as a 2nd to 8th generation size, or a larger size such as 1 ⁇ 1 m to 3 ⁇ 3 m.
  • the carrier substrate can have various shapes such as rectangular, oval, or circular.
  • the thin film glass is separated from the carrier substrate together with the contact film by the adhesive force of the contact film. After that, the contact film is peeled off, and the thin film glass alone can be obtained.
  • the adhesive force before removing the contact film from the thin glass, it is preferable to reduce the adhesive force by subjecting the contact film to weakening treatment for adhesive force.
  • the weakening treatment is preferably chosen such that the adhesion can be reduced to 0.5 N/25 mm or less.
  • electromagnetic radiation such as infrared rays, ultraviolet rays, or visible light can be selected as appropriate.
  • the electromagnetic radiation selected may be narrow band, broad band coverage, or laser radiation, depending on the adhesive material used.
  • electromagnetic radiation with wavelengths outside the visible spectrum is selected so that the adhesive strength does not deteriorate under exposure to visible light.
  • adhesive materials that can be at least partially deactivated by exposure to such electromagnetic radiation and can be selected as contact films.
  • heat treatment may be employed as the embrittlement treatment.
  • the electromagnetic radiation is preferably applied from the outside of the contact film, that is, from the side to which the thin film glass is not adhered.
  • a preferred contact film is, for example, the one commercially available from Domei Optical Co., Ltd. under the trade name "NDS4150-20", and a corresponding weakening treatment includes ultraviolet irradiation with a wavelength of 365 nm.
  • thin-film glass A specific method for manufacturing thin-film glass will be described in the Examples section.
  • the thin film glass commercially available products such as those manufactured by SCHOTT and Nippon Electric Glass Co., Ltd. can be used.
  • the thickness of the thin film glass is 10-40 ⁇ m. If the thickness of the thin film glass is less than 10 ⁇ m, the impact resistance of the optical layered body is lowered. On the other hand, when the thickness of the thin film glass exceeds 40 ⁇ m, the flexibility of the optical layered body is lowered. In addition, it becomes difficult to reduce the thickness of the optical layered body.
  • the thickness of the thin film glass is preferably 15-40 ⁇ m, more preferably 15-30 ⁇ m.
  • the thickness of the thin film glass is A (unit: ⁇ m), and the total thickness of the restraining portion, the damping portion 1, and the damping portion 2 is B (unit: ⁇ m). ⁇ m), it is preferable to satisfy the relationship of the following formula (3). Within such a range, the effects of the present invention can be exhibited more efficiently.
  • an adhesive portion may be further provided on the surface of the thin glass opposite to the surface provided with the damping portion 2 .
  • this adhesive portion the same material as the material described for the vibration damping portion 2 can be exemplified.
  • the adhesive portion has a two-layer structure such as thin glass/adhesive portion 3/adhesive portion 4
  • the storage elastic modulus of the adhesive portion 3 is preferably higher than the storage elastic modulus of the adhesive portion 4.
  • the method for manufacturing the optical layered body according to the present invention is not particularly limited, and includes a method of sequentially arranging the restraining portion, the damping portion 1, the damping portion 2, and the thin film glass. Between each part, there may be an adhesive part as described above, or each part may be adhered using a UV adhesive or the like.
  • the optical layered body according to the present invention is suitably used for a display device having a light-emitting device. That is, according to another embodiment of the present invention, there is provided a display device including a light emitting device and the optical layered body of the present invention. Furthermore, according to another preferred embodiment of the present invention, a display device comprising a light-emitting device and the optical layered body of the present invention, wherein the constraining portion of the optical layered body is disposed closest to the viewing side. I will provide a.
  • the light-emitting device is not particularly limited, and includes, for example, a plasma display device, an electroluminescence light-emitting device, and the like.
  • the present invention includes the following aspects and forms: 1.
  • An optical laminate comprising a restraining portion, a damping portion 1, a damping portion 2, and a thin film glass having a thickness of 10 to 40 ⁇ m in this order,
  • the tan ⁇ of the restraint portion is tan ⁇ 1
  • the tan ⁇ of the damping portion 1 is tan ⁇ 2
  • the tan ⁇ of the damping portion 2 is tan ⁇ 3
  • the tan ⁇ 1, the tan ⁇ 2, and the tan ⁇ 3 have a relationship of the following formula (1)
  • the damping portion 1 is a film containing at least a thermoplastic (meth)acrylic resin and a graft copolymer. ⁇ 4.
  • the content of the graft copolymer with respect to the total weight of the film is 60 to 90% by weight.
  • the optical laminate according to: 7. A light emitting device and the above 1. ⁇ 6. and the optical layered body according to any one of the above, wherein the restraint portion of the optical layered body is arranged on the most viewing side.
  • Glass-transition temperature The glass transition temperature (Tg) of each part constituting the optical laminate was measured using DSC (Differential Scanning Calorimetry) in accordance with JIS K 7121 (2012).
  • the weight-average molecular weight (Mw) of the polymer constituting the optical laminate was measured by gel permeation chromatography (manufactured by Tosoh Corporation, HLC8220GPC) and column (manufactured by Tosoh Corporation, TSK-GEL G6000, HXL-G5000, HXL-G5000). , HXL-G4000, HXL-G3000HXL in series). 20 mg ⁇ 0.5 mg of sample was dissolved in 10 ml of tetrahydrofuran and filtered through a 0.45 mm filter. 100 ml of this solution was injected into a column (temperature: 40°C), measured at a detector RI temperature of 40°C, and the value converted to styrene was used.
  • the storage elastic modulus and tan ⁇ of the vibration damping portion 2 were measured using a nanoindenter device (product number: G200XP) manufactured by Keysight Technologies, Inc. under the following test conditions at 25°C. We adopted the value of : ⁇ Test conditions (dynamic viscoelasticity test) Tester: Keysight Technologies, Nanoindenter device (product number: G200XP) Deformation method: Push type Temperature range: -100°C to 100°C Frequency: 1Hz Displacement: 100nm Sample size (morphology, etc.): 10 ⁇ 10 mm Thickness about 1 mm.
  • Example 1 [Formation of restraint part] (Preparation of dope) A dope was prepared by placing the following materials in a closed container, heating and stirring until completely dissolved and filtered: (Dope composition) Cellulose triacetate (acetyl substitution degree 2.88) 100 parts by mass Triphenyl phosphate 8 parts by mass Ethylphthalyl ethyl glycolate 2 parts by mass Tinuvin (registered trademark) 326 1 part by mass Aerosil (registered trademark) 200V 0.1 parts by mass Methylene chloride 418 parts by mass Ethanol 23 parts by mass.
  • Dope composition Cellulose triacetate (acetyl substitution degree 2.88) 100 parts by mass Triphenyl phosphate 8 parts by mass Ethylphthalyl ethyl glycolate 2 parts by mass Tinuvin (registered trademark) 326 1 part by mass Aerosil (registered trademark) 200V 0.1 parts by mass Methylene chloride 418 parts by mass Ethanol 23 parts by mass.
  • a cellulose triacetate film was produced using a solution casting film forming apparatus. That is, as a support for casting the above dope, an endless belt made of SUS316 and polished to a super-mirror surface having an average three-dimensional surface roughness (Ra) of 1.0 nm by a scanning atomic force microscope (AFM) was used. Using.
  • the dope filtered as described above was uniformly cast at a dope temperature of 35°C on an endless belt support made of SUS316 at a temperature of 20°C by a casting die 3 consisting of a coat hanger die.
  • the web formed on the support is dried with dry air having a constant temperature of 30° C. while being transported on the support, then peeled off from the support with a peeling roll, and then, with a tenter, the amount of residual solvent is After stretching 1.06 times in the width direction in an atmosphere of 100°C at 10%, the width holding was released, drying was completed with a drying device at 125°C while being conveyed by rolls, and was wound up with a winding device. .
  • the resulting cellulose triacetate film had a film thickness of 30 ⁇ m, a film width of 2000 mm, and a film winding length of 3000 m.
  • damping portion 1 ⁇ Thermoplastic (meth)acrylic resin> MMA (methyl methacrylate) / PMI (phenylmaleimide) / MA (methyl acrylate) copolymer (85/10/5 mass ratio, Mw: 2 million, Tg: 122 ° C.) as a thermoplastic (meth) acrylic resin ) was prepared.
  • a monomer mixture (a') 39 consisting of 80.0% by mass of n-butyl acrylate (n-butyl acrylate), 18.5% by mass of styrene, and 1.5% by mass of allyl methacrylate (allyl methacrylate)
  • a mixture of 0.25 parts by mass of polyoxyethylene lauryl ether phosphate and 0.25 parts by mass of polyoxyethylene lauryl ether phosphate was added continuously over 117 minutes.
  • the glass transition temperature (Tg) of the soft layer calculated by averaging according to the composition ratio using the glass transition temperature of the homopolymer of each monomer constituting the acrylic rubber-like polymer (a) is -30 ° C. Met.
  • the obtained methacrylic polymer (b) was put into a 3% by mass hot sodium sulfate aqueous solution to salt out and solidify. Next, after repeating dehydration and washing, the particles were dried to obtain acrylic graft copolymer particles (rubber particles) having a three-layer structure.
  • the average particle size of the obtained rubber particles was 200 nm when measured with a zeta potential/particle size measuring system (ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd.).
  • a surfactant solution was prepared by dissolving 2 parts by mass of Phosphanol ML-220 (polyoxyethylene lauryl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.) in 98 parts by mass of methyl ethyl ketone (MEK).
  • Phosphanol ML-220 polyoxyethylene lauryl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.
  • a PET film (manufactured by Toyobo Co., Ltd., TN100, thickness 50 ⁇ m, with a release layer containing a non-silicone release agent) was prepared as a base material.
  • a dope is applied using a die by a back coating method, and then dried at 80 ° C. in an atmosphere with a solvent concentration of 0.18% by volume.
  • a film with a thickness of 20 ⁇ m was obtained.
  • the resulting film-shaped damping portion 1 is adhered to the restraint portion prepared above using a UV adhesive (manufactured by Toagosei Co., Ltd., product number: Aronix (registered trademark) UV-3610), and then The substrate was peeled off.
  • the glass transition temperature (Tg) of the damping portion 1 thus obtained was 10°C.
  • damping part 2 (Production of UV-curable acrylic pressure-sensitive adhesive composition (a-1)) A monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 4 parts by weight of 2-hydroxyethyl acrylate (HEA) was added as a photopolymerization initiator.
  • EHA 2-ethylhexyl acrylate
  • NDP N-vinyl-2-pyrrolidone
  • HSA 2-hydroxyethyl acrylate
  • 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad (registered trademark) 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by IGM Resins B.V.) 0.035 parts by mass, 2,2-dimethoxy-1 , 2-diphenylethan-1-one (trade name: Omnirad (registered trademark) 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by IGM Resins B.V.) was blended. After that, ultraviolet rays are irradiated until the viscosity (measurement conditions: BH viscometer No.
  • the obtained ultraviolet-curable acrylic pressure-sensitive adhesive composition (a-1) is applied to the surface of the damping portion 1 obtained above on the side opposite to the surface on which the restraint portion is formed, and the thickness after curing is applied.
  • the coating was applied so that the thickness was 25 ⁇ m, and a release film was laminated on the surface thereof.
  • ultraviolet irradiation was performed under the conditions of illuminance: 6.5 mW/cm 2 and integrated light amount: 1500 mJ/cm 2 to cure the composition to form vibration damping portion 2 (Adhesive 1 in Table 1 below).
  • the release film was peeled off to obtain a laminate a including the restraining portion, damping portion 1 and damping portion 2 in this order.
  • the Tg of the damping portion 2 was -20°C.
  • the type of vibration damping portion 2 produced by such a method is indicated as "Adhesive 1" in Table 1 below.
  • a thin film glass (soda lime glass) with a dimension of 12 inches was made according to the following steps: (Step 1) A thin film glass is formed on a carrier substrate having a bonding surface so that the first surface of the thin film glass is in contact with the thin film glass, and adhesive strength is applied to the second surface opposite to the first surface of the thin film glass. (Step 2) Next, a step of peeling the thin glass from the carrier substrate with a contact film having a high adhesive strength (Step 3) Weakening the adhesion of the contact film removing the contact film from the second surface of the thin glass stripped from the carrier substrate by a chemical treatment (electromagnetic radiation);
  • the contact film was a 150 ⁇ m-thick film containing polyolefin (PO) and further had a 10 ⁇ m-thick adhesive layer, and was commercially available under the trade name “NDS4150-20”.
  • the exposed contact film was then embrittled to reduce adhesion.
  • the embrittlement treatment was performed by irradiating the contact film with ultraviolet light having a wavelength of 365 nm for 10 seconds.
  • the illuminance of the ultraviolet rays was 500 mW/cm 2 and the cumulative amount of light was 500 mJ/cm 2 .
  • the adhesive strength before the weakening treatment was 11 N/25 mm, but the adhesive strength after the weakening treatment was reduced to 0.4 N/25 mm.
  • the contact film was easily separated from the thin film glass, and a thin film glass having a thickness of 30 ⁇ m was obtained (Step 3).
  • Example 2 An optical layered body 2A was obtained in the same manner as in Example 1, except that instead of the UV adhesive, an adhesive portion 2 was provided between the restraining portion and the damping portion 1 by the method described below.
  • Adhesive part 2 99 parts by mass of butyl acrylate, 1 part by mass of acrylic acid, and 0.03 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator are added to 200 parts by mass of ethyl acetate and stirred under reflux for 5 hours. Thus, a solution containing an acrylic acid ester copolymer having a weight average molecular weight of 1,800,000 was obtained.
  • the coating liquid was applied to the constraining portion with a knife coater and dried at 90°C for 1 minute to form the adhesive portion 2 before photocuring.
  • an electrodeless lamp V bulb manufactured by Fusion Co., Ltd.
  • the wavelength is 365 nm.
  • an adhesive portion 2 having a thickness of 25 ⁇ m was formed.
  • Example 3 A TAC film having a thickness of 10 ⁇ m was produced in the same manner as in [Formation of Restricted Portion], and this film was used as a restricted portion. Further, in the same manner as in Example 1, except that the thickness of the damping portion 1 was changed to 17 ⁇ m, the thickness of the damping portion 2 was changed to 10 ⁇ m, and the thickness of the thin film glass was changed to 15 ⁇ m. An optical laminate 3A was produced.
  • Example 4 An optical laminate 4A was produced in the same manner as in Example 1, except that a COP film produced by the following method was used as the damping portion 1.
  • a dope having the following composition was prepared. Dichloromethane and ethanol were first added to the pressurized dissolution tank. A cycloolefin resin, an additive (a compound of the following chemical formula (A)), and a fine particle additive liquid were put into this pressurized dissolution tank while being stirred. The mixture was heated and completely dissolved with stirring, and filtered through Azumi Filter Paper No. 1 manufactured by Azumi Filter Paper Co., Ltd.
  • the dope was uniformly cast on a stainless steel belt support at a temperature of 31°C and a width of 1800 mm.
  • the temperature of the stainless steel belt was controlled at 28°C.
  • the conveying speed of the stainless steel belt was 20 m/min.
  • the solvent was evaporated on a stainless steel belt support until the amount of residual solvent in the cast film reached 30% by mass. Then, it was peeled off from the stainless steel belt support with a peeling tension of 128 N/m. The peeled film was stretched 1.1 times in the width direction at 160°C. The residual solvent at the start of stretching was 5% by mass. Next, drying was completed while transporting the drying zone with a large number of rollers, and the ends sandwiched between the tenter clips were slit with a laser cutter and then wound up to obtain a COP film with a thickness of 20 ⁇ m. The glass transition temperature of the obtained COP film was 160°C.
  • Example 5 A TAC film having a thickness of 15 ⁇ m was produced in the same manner as in [Formation of the restraint part], and this was used as the restraint part. Thus, an optical layered body 5A was produced.
  • Example 6 A TAC film with a thickness of 50 ⁇ m was prepared in the same manner as in [Formation of the restraint part], this was used as the restraint part, and the thickness of the damping part 1 and the damping part 2 was set to 50 ⁇ m.
  • An optical laminate 6A was produced in the same manner as in Example 1.
  • Example 7 An optical laminate 7A was produced in the same manner as in Example 1, except that a polyurethane resin film formed by the following method was used as the damping portion 1.
  • NCO-TR isocyanurate derived from hexamethylene diisocyanate> 1000 parts by mass of hexamethylene diisocyanate (manufactured by Tosoh Corporation, NCO content: 49.9%, hereinafter abbreviated as HDI) in a four-necked flask with a capacity of 1000 ml equipped with a stirrer, a thermometer, and a cooling tube, 1.0 part by mass of phenol and 16 parts by mass of 1,3-butanediol (manufactured by Daicel Co., Ltd.) were charged, and a urethanization reaction was carried out at 80° C.
  • NCO-TR isocyanurate derived from hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • NCO-TR was a clear viscous liquid with an NCO content of 21.1%, a GPC number average molecular weight of 697, and a free HDI content of 0.2%.
  • a terminal NCO group-containing polyisocyanate (A) temperature-controlled to 40° C., a polyol (B) temperature-controlled to 40° C., and dioctyltin dilaurate as a catalyst were added to the system so that the content (concentration with respect to the entire resin) in the system was 0.5.
  • a polyurethane resin-forming composition was prepared by adding and mixing so as to obtain 01 parts by mass. After sufficiently defoaming this composition under a reduced pressure of 5 mmHg, it is applied onto a heat-resistant polystyrene film (Oidys (registered trademark), manufactured by Kurashiki Boseki Co., Ltd.) and cured in an atmosphere of 120° C. for 30 minutes. and then dried in an atmosphere of 80° C. for 4 hours to obtain a polyurethane resin film having a thickness of 20 ⁇ m.
  • Example 8 Optical laminate 8A was prepared in the same manner as in Example 1 except that E5000 (manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m, glass transition temperature of PET film: 80 ° C.) was used as the restraint portion instead of the TAC film. was made.
  • E5000 manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m, glass transition temperature of PET film: 80 ° C.
  • Example 9 In ⁇ Preparation of dope> in [Formation of damping part 1], the amount of acrylic graft copolymer particles added was changed to 2.2 parts by mass, and the amount of thermoplastic (meth)acrylic resin added was changed to 8 parts.
  • An optical laminate 9A was produced in the same manner as in Example 1, except that the content was changed to .8 parts by mass.
  • the glass transition temperature of the damping portion 1 was 10°C.
  • Example 10 In ⁇ Preparation of dope> in [Formation of damping part 1], the amount of acrylic graft copolymer particles added was changed to 5.5 parts by mass, and the amount of thermoplastic (meth)acrylic resin added was changed to 5 parts by mass.
  • An optical layered body 10A was produced in the same manner as in Example 1, except that the content was changed to 0.5 parts by mass.
  • the glass transition temperature of the damping portion 1 was 10°C.
  • Example 11 In ⁇ Preparation of dope> in [Formation of damping part 1], the amount of acrylic graft copolymer particles added was changed to 9.9 parts by mass, and the amount of thermoplastic (meth)acrylic resin added was changed to 1.
  • An optical layered body 11A was produced in the same manner as in Example 1, except that the content was changed to 1 part by mass.
  • the glass transition temperature of the damping portion 1 was 10°C.
  • Example 12 An optical layered body 12A was produced in the same manner as in Example 1, except that a thin film glass having a thickness of 15 ⁇ m formed by the same method as [Production of thin film glass] was used.
  • Example 13 A TAC film having a thickness of 5 ⁇ m was produced in the same manner as in [Formation of the restraint part], and this was used as the restraint part.
  • An optical layered body 13A was produced in the same manner as in Example 1 except for the above.
  • Comparative example 1 A comparative optical laminate 1A was produced in the same manner as in Example 1, except that a transparent polyimide film (CPI, thickness 30 ⁇ m) produced as follows was used instead of the thin glass.
  • CPI transparent polyimide film
  • stirring was continued for an additional 20 hours while adjusting the temperature in the container to be in the range of 20 to 30° C. using an oil bath, and the mixture was reacted to produce polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by mass. Furthermore, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and imidization was carried out by stirring at room temperature for 10 hours. The polyimide varnish was removed from the reaction vessel.
  • the resulting polyimide varnish was dropped into methanol for reprecipitation, and the resulting powder was dried by heating to remove the solvent to obtain a transparent polyimide resin as a solid content.
  • GPC measurement of the resulting polyimide resin revealed a weight average molecular weight of 360,000.
  • the obtained coating film was peeled off from the polyester substrate to obtain a self-supporting film.
  • the self-supporting film was fixed to a metal frame and dried in air at 200° C. for 40 minutes to obtain a transparent polyimide film having a thickness of 30 ⁇ m.
  • Comparative Example 3 A comparative optical laminate 3A was produced in the same manner as in Comparative Example 2, except that E5000 (75 ⁇ m thick, PET film manufactured by Toyobo Co., Ltd.) was used as the restraining portion instead of the TAC film.
  • E5000 75 ⁇ m thick, PET film manufactured by Toyobo Co., Ltd.
  • Example 5 A TAC film with a thickness of 22 ⁇ m was produced in the same manner as in [Formation of the restraint part], and this was used as the restraint part, the thickness of the damping part 1 was set to 40 ⁇ m, and the thickness of the damping part 2 was set to 50 ⁇ m.
  • a comparative optical laminate 5A was produced in the same manner as in Example 1, except that the thickness of the thin film glass was 45 ⁇ m.
  • Comparative Example 6 A comparative optical laminate 6A was produced in the same manner as in Example 1, except that E5000 (manufactured by Toyobo Co., Ltd., thickness 20 ⁇ m, PET film) was used as the damping portion 1 .
  • Example 7 A damping portion 1 was formed with a thickness of 20 ⁇ m by the same method as described in [Formation of damping portion 2] above. Also, the vibration damping portion 2 was formed with a thickness of 25 ⁇ m by the same method as described in [Formation of the vibration damping portion 1]. A comparative optical laminate 7A was produced in the same manner as in Example 1 except for the above.
  • the bent inner side of the sample was placed on a flat surface, and the haze of the bent portion was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH4000).
  • a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH4000.
  • a rating of 3 or higher is practical: 5: less than 0.1 4: 0.1 or more and less than 0.3 3: 0.3 or more and less than 0.8 2: 0.8 or more and less than 1.1 1: 1.1 or more.
  • ⁇ Pen drop test> The optical layered body obtained above was placed on a bakelite substrate manufactured by Sunhayato Co., Ltd. so that the thin film glass and the substrate were in contact with each other, and the surface of the constraining portion was facing upward.
  • a rating of 3 or higher is actionable: 5: Does not crack when dropped from 30 cm 4: Does not crack when dropped from 25 cm 3: Does not crack when dropped from 15 cm 2: Microscopic cracks can be seen when dropped from 15 cm 1 : Cracks can be visually confirmed when dropped from 15 cm.

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Abstract

La présente invention concerne un moyen qui, dans un corps stratifié optique comportant un verre à film mince, permet l'amincissement et rend possible l'amélioration à la fois de la résistance aux chocs et de la flexibilité.　La présente invention est un corps stratifié optique comprenant, dans l'ordre suivant, une partie de restriction, une partie d'amortissement (1), une partie d'amortissement (2), et un verre à film mince présentant une épaisseur dans la plage de 10 à 40 µm. Lorsque la tanδ de la partie de restriction est définie comme étant tanδ1, la tanδ de la partie d'amortissement (1) est définie comme étant tanδ2, et la tanδ de la partie d'amortissement (2) est définie comme étant tanδ3, la relation dans l'expression (1) est satisfaite par tanδ1, tanδ2, et tanδ3. (1) : tanδ1 < tanδ2 < tanδ3
PCT/JP2023/000788 2022-02-07 2023-01-13 Corps stratifié optique WO2023149169A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0433019U (fr) * 1990-07-16 1992-03-18
JP2003246015A (ja) * 2002-02-25 2003-09-02 Matsushita Electric Ind Co Ltd 平面型ディスプレイパネル用耐衝撃フィルム及び平面型ディスプレイパネル
WO2006011461A1 (fr) * 2004-07-27 2006-02-02 Jsr Corporation Absorbeur de chocs, structure laminée pour l'absorption de chocs, structure laminée pour l'absorption de chocs pour affichage à cristaux liquides, structure laminée pour l'absorption de chocs pour affichage plasma, structure laminée pour l'absorption de chocs pour affic
JP2008191336A (ja) * 2007-02-02 2008-08-21 Toshiba Corp 平面型画像表示装置
JP2011140187A (ja) * 2010-01-08 2011-07-21 Teijin Chem Ltd 積層フィルム、透明導電性積層フィルムおよび電子部品
JP2019532356A (ja) * 2016-09-21 2019-11-07 スリーエム イノベイティブ プロパティズ カンパニー ガラスを含む保護ディスプレイフィルム
WO2021193599A1 (fr) * 2020-03-23 2021-09-30 大日本印刷株式会社 Dispositif d'affichage à électroluminescence organique flexible et plaque de surface avant pour dispositif d'affichage
WO2022113400A1 (fr) * 2020-11-24 2022-06-02 日東電工株式会社 Stratifié optique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0433019U (fr) * 1990-07-16 1992-03-18
JP2003246015A (ja) * 2002-02-25 2003-09-02 Matsushita Electric Ind Co Ltd 平面型ディスプレイパネル用耐衝撃フィルム及び平面型ディスプレイパネル
WO2006011461A1 (fr) * 2004-07-27 2006-02-02 Jsr Corporation Absorbeur de chocs, structure laminée pour l'absorption de chocs, structure laminée pour l'absorption de chocs pour affichage à cristaux liquides, structure laminée pour l'absorption de chocs pour affichage plasma, structure laminée pour l'absorption de chocs pour affic
JP2008191336A (ja) * 2007-02-02 2008-08-21 Toshiba Corp 平面型画像表示装置
JP2011140187A (ja) * 2010-01-08 2011-07-21 Teijin Chem Ltd 積層フィルム、透明導電性積層フィルムおよび電子部品
JP2019532356A (ja) * 2016-09-21 2019-11-07 スリーエム イノベイティブ プロパティズ カンパニー ガラスを含む保護ディスプレイフィルム
WO2021193599A1 (fr) * 2020-03-23 2021-09-30 大日本印刷株式会社 Dispositif d'affichage à électroluminescence organique flexible et plaque de surface avant pour dispositif d'affichage
WO2022113400A1 (fr) * 2020-11-24 2022-06-02 日東電工株式会社 Stratifié optique

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