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WO2017208882A1 - Matériau lamellé en résine avec film protecteur - Google Patents

Matériau lamellé en résine avec film protecteur Download PDF

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Publication number
WO2017208882A1
WO2017208882A1 PCT/JP2017/019005 JP2017019005W WO2017208882A1 WO 2017208882 A1 WO2017208882 A1 WO 2017208882A1 JP 2017019005 W JP2017019005 W JP 2017019005W WO 2017208882 A1 WO2017208882 A1 WO 2017208882A1
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WIPO (PCT)
Prior art keywords
resin
film
protective film
laminate
resin laminate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/019005
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English (en)
Japanese (ja)
Inventor
一喜 大松
美保 大関
山下　恭弘
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to CN201780033201.3A priority Critical patent/CN109219517B/zh
Priority to KR1020187037739A priority patent/KR102008476B1/ko
Publication of WO2017208882A1 publication Critical patent/WO2017208882A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • 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
    • B32B2363/00—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Definitions

  • This invention relates to the resin laminated body with a protective film used suitably, for example in a display apparatus.
  • Patent Document 1 discloses a transparent sheet containing a methacrylic resin and a vinylidene fluoride resin as a plastic sheet as a substitute for a glass sheet, and this transparent sheet sufficiently satisfies transparency and relative dielectric constant. It is described.
  • an object of this invention is to provide the resin laminated body which can avoid the appearance defects, such as a dent, used suitably in a display apparatus etc.
  • the present inventors have studied in detail about a resin laminate suitably used in a display device, and have completed the present invention.
  • At least a film substrate is provided on both surfaces of a resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A).
  • Protective film (D) and (E) are each laminated resin laminate with protective film,
  • the intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A).
  • the film base of the protective films (D) and (E) is at least one selected from the group consisting of a low density polyethylene film, a high density polyethylene film, a polypropylene film, a polyethylene terephthalate film, an acrylic resin film, and a polycarbonate film.
  • the resin laminate with a protective film according to any one of [1] to [3], which is a seed film.
  • the intermediate layer (A) contains 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 8 carbon atoms when R 1 is a hydrogen atom
  • R 2 represents an alkyl group having 2 to 2 carbon atoms when R 1 is a methyl group.
  • the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at a load of 3.8 kg and 230 ° C., according to any one of the above [1] to [10] Resin laminate.
  • the average value of the film thickness of the resin laminate is 100 to 2000 ⁇ m, and the average value of the film thickness of the thermoplastic resin layers (B) and (C) is 10 to 200 ⁇ m, respectively.
  • thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer.
  • thermoplastic resin layers (B) and (C) each contain 50% by mass or more of a (meth) acrylic resin based on the total resin contained in each thermoplastic resin layer.
  • the resin laminate with a protective film as described in [15] above, wherein the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) has a weight average molecular weight of 50,000 to 300,000. .
  • the resin laminate with a protective film of the present invention is less susceptible to appearance defects such as dents in the manufacturing / distribution process, and is suitably used in display devices and the like.
  • the resin laminate with a protective film of the present invention includes a resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) respectively present on both sides of the intermediate layer (A).
  • the resin laminate in the resin laminate with a protective film of the present invention is a resin having at least a constitution in which the thermoplastic resin layer (B) / intermediate layer (A) / thermoplastic resin layer (C) are laminated in this order. It is a laminate.
  • the intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A).
  • the amount of (meth) acrylic resin is lower than the above lower limit, sufficient transparency of the resin laminate cannot be obtained, and when the amount of (meth) acrylic resin is higher than the above upper limit, sufficient dielectric constant is obtained. Absent.
  • the amount of vinylidene fluoride resin is lower than the above lower limit, a sufficient dielectric constant cannot be obtained, and when the amount of vinylidene fluoride resin is higher than the above upper limit, the durability of the resin laminate and sufficient transparency are obtained. I can't get it.
  • the intermediate layer (A) has a (meth) acrylic resin of 30 to 60% by mass based on the total resin contained in the intermediate layer (A) from the viewpoint of easily increasing the dielectric constant and enhancing the transparency of the resin laminate. And 70 to 40% by mass of vinylidene fluoride resin, more preferably 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin, more preferably 37 to 45% by mass. % Of (meth) acrylic resin and 63 to 55% by mass of vinylidene fluoride resin are more preferable, and 38 to 45% by mass of (meth) acrylic resin and 62 to 55% by mass of vinylidene fluoride resin are included. It is particularly preferable to include 38 to 43% by mass of (meth) acrylic resin and 62 to 57% by mass of vinylidene fluoride resin.
  • Examples of the (meth) acrylic resin contained in the intermediate layer (A) of the resin laminate with a protective film of the present invention include homopolymers of (meth) acrylic monomers such as (meth) acrylic acid esters and (meth) acrylonitrile. Examples include copolymers of two or more kinds of (meth) acrylic monomers, copolymers of (meth) acrylic monomers and monomers other than (meth) acrylic monomers, and the like.
  • the term “(meth) acryl” means “acryl” or “methacryl”.
  • the (meth) acrylic resin is preferably a methacrylic resin from the viewpoint of easily increasing the hardness, weather resistance, and transparency of the resin laminate.
  • a methacrylic resin is a polymer of a monomer mainly composed of a methacrylic acid ester (alkyl methacrylate).
  • a homopolymer of a methacrylic acid ester polyalkyl methacrylate
  • a copolymer of two or more methacrylic acid esters And a copolymer of a monomer other than 50% by mass of a methacrylic acid ester and a monomer other than 50% by mass of a methacrylic acid ester.
  • copolymer of a methacrylic acid ester and a monomer other than the methacrylic acid ester from the viewpoint of easily improving optical properties and weather resistance, 70% by mass or more of the methacrylic acid ester and 30% relative to the total amount of the monomers. Copolymers with other monomers of less than or equal to mass% are preferred, and copolymers of more than 90 mass% of methacrylic acid esters with other monomers of less than or equal to 10 mass% are more preferred.
  • Examples of monomers other than methacrylic acid esters include acrylic acid esters and monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule.
  • monofunctional monomers examples include styrene monomers such as styrene, ⁇ -methylstyrene and vinyltoluene; alkenyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; N-substituted Maleimide; and the like.
  • the (meth) acrylic resin may be copolymerized with N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide, or in the molecular chain (in the main skeleton or in the polymer).
  • N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide
  • a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced into the main chain).
  • (meth) acrylic resin specifically, 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, based on (a1) methyl methacrylate homopolymer and / or (a2) all structural units constituting the copolymer
  • each structural unit can be calculated by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 8 carbon atoms when R 1 is a hydrogen atom
  • R 2 represents an alkyl group having 2 to 2 carbon atoms when R 1 is a methyl group. Represents an alkyl group of 8;
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 8 carbon atoms
  • R 2 represents the number of carbon atoms
  • the alkyl group having 2 to 8 carbon atoms include ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
  • R 2 is preferably an alkyl group having 2 to 4 carbon atoms from the viewpoint of heat resistance, and more preferably an ethyl group.
  • the weight average molecular weight of the (meth) acrylic resin contained in the intermediate layer (A) (hereinafter sometimes referred to as Mw) is 100,000 to 300,000. When Mw is lower than the above lower limit, transparency when exposed to a high temperature and high humidity environment is not sufficient, and when Mw is higher than the above upper limit, film formability when producing a resin laminate cannot be obtained. .
  • the Mw of the (meth) acrylic resin is preferably 120,000 or more, and more preferably 150,000 or more, from the viewpoint of easily increasing transparency when exposed to a high temperature and high humidity environment.
  • the Mw of the (meth) acrylic resin is preferably 250,000 or less, and more preferably 200,000 or less, from the viewpoint of film formability when producing a resin laminate.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.
  • the (meth) acrylic resin is usually 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, more preferably 0.5 to 3 g / 10, as measured at a load of 3.8 kg and 230 ° C. Minute melt mass flow rate (hereinafter sometimes referred to as MFR).
  • MFR Minute melt mass flow rate
  • the MFR is preferably not more than the above upper limit because it is easy to increase the strength of the resin laminate, and is preferably not less than the above lower limit from the viewpoint of film formability of the resin laminate.
  • the MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastics—Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics”. This JIS stipulates that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C. and a load of 3.80 kg (37.3 N).
  • the (meth) acrylic resin preferably has a Vicat softening temperature (hereinafter sometimes referred to as VST) of preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 102 ° C. or higher.
  • VST Vicat softening temperature
  • the upper limit of VST is not specifically limited, Usually, it is 150 degrees C or less.
  • VST can be measured by the B50 method described in accordance with JIS K 7206: 1999. VST can be adjusted to the above range by adjusting the type of monomer and its ratio.
  • (Meth) acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization or bulk polymerization.
  • MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent.
  • the chain transfer agent an appropriate commercial product can be used. What is necessary is just to determine the addition amount of a chain transfer agent suitably according to the kind of monomer, its ratio, the characteristic to obtain
  • Examples of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate with a protective film of the present invention include a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and other monomers.
  • the vinylidene fluoride resin is at least one selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene from the viewpoint of easily improving the transparency of the resin laminate.
  • a copolymer of a seed monomer and vinylidene fluoride and / or a homopolymer of vinylidene fluoride is preferable, and polyvinylidene fluoride is more preferable.
  • the weight average molecular weight (Mw) of the vinylidene fluoride resin contained in the intermediate layer (A) is preferably 100,000 to 500,000, more preferably 150,000 to 450,000, still more preferably 200,000 to 450,000, particularly preferably 350,000 to 450,000. It is easy for the transparency of the resin laminate to be increased when the resin laminate of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C. and relative humidity 90%) that Mw is equal to or more than the above lower limit. preferable. Moreover, it is preferable that Mw is not more than the above upper limit because the film-forming property of the resin laminate is easily improved.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.
  • the vinylidene fluoride resin is preferably 0.1 to 40 g / 10 min, more preferably 0.1 to 30 g / 10 min, even more preferably 0.1 to 25 g, as measured at a load of 3.8 kg and 230 ° C. It has a melt mass flow rate (MFR) of / 10 minutes.
  • MFR melt mass flow rate
  • the MFR is more preferably 0.2 g / 10 min or more, and even more preferably 0.5 g / 10 min or more. Further, the MFR is more preferably 20 g / 10 min or less, even more preferably 5 g / 10 min or less, and particularly preferably 2 g / 10 min or less.
  • MFR is not more than the above upper limit because it is easy to suppress a decrease in transparency when the resin laminate is used for a long period of time. It is preferable that the MFR is not less than the above lower limit because the film formability of the resin laminate can be easily improved.
  • the MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastics—Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics”.
  • the vinylidene fluoride resin is industrially produced by a suspension polymerization method or an emulsion polymerization method.
  • the suspension polymerization method is carried out by using water as a medium, dispersing the monomer as droplets in the medium with a dispersant, and polymerizing an organic peroxide dissolved in the monomer as a polymerization initiator, A granular polymer of 100 to 300 ⁇ m is obtained.
  • Suspension polymers are preferred because they have a simpler manufacturing process than powdered emulsions, have excellent powder handling properties, and do not contain an emulsifier or salting-out agent containing an alkali metal unlike emulsion polymers.
  • a commercially available vinylidene fluoride resin may be used.
  • examples of preferable commercially available products include “KF Polymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300 from Kureha Corporation.
  • the intermediate layer (A) may further contain another resin different from the (meth) acrylic resin and the vinylidene fluoride resin.
  • the amount of other resins is preferably 15% by mass or less, preferably 10% by mass or less, based on the total resin contained in the intermediate layer (A). Is more preferable, and it is still more preferable that it is 5 mass% or less.
  • other resins include polycarbonate resin, polyamide resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, and polyethylene terephthalate.
  • the intermediate layer (A) may further contain another resin, but from the viewpoint of transparency, the amount of the other resin is preferably 1% by mass or less, and the resin contained in the intermediate layer (A) is ( More preferably, it is only a (meth) acrylic resin and a vinylidene fluoride resin.
  • the content of alkali metal in the intermediate layer (A) is preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, particularly preferably 1 ppm or less, based on the total resin contained in the intermediate layer (A). It is. It is preferable that the content of alkali metal in the intermediate layer (A) is not more than the above upper limit because it is easy to suppress a decrease in transparency when the resin laminate is used for a long time in a high temperature and high humidity environment.
  • the lower limit of the content of alkali metal in the intermediate layer (A) is 0, and it is extremely preferable that the content is not substantially contained from the viewpoint of easily suppressing the decrease in transparency of the resin laminate.
  • the intermediate layer (A) contains, for example, 0.05 ppm or more of alkali metal such as sodium or potassium derived from the remaining emulsifier.
  • alkali metal such as sodium or potassium derived from the remaining emulsifier.
  • the amount of the emulsifier remaining in the resin increases, and the intermediate layer (A) The alkali metal content is also increased. From the viewpoint of easily suppressing a decrease in transparency of the resin laminate, it is preferable to use a resin having a low alkali metal content as the (meth) acrylic resin and vinylidene fluoride resin contained in the intermediate layer (A). .
  • the amount of the compound containing the alkali metal is reduced during the polymerization of the resin, or the compound containing the alkali metal is increased by increasing the washing step after the polymerization. Remove it.
  • the alkali metal content can be determined by, for example, inductively coupled plasma mass spectrometry (ICP / MS).
  • ICP / MS inductively coupled plasma mass spectrometry
  • examples of inductively coupled plasma mass spectrometry include sample pellets to be measured such as a high temperature ashing melting method, a high temperature ashing acid dissolution method, a Ca-added ashing acid dissolution method, a combustion absorption method, and a low temperature ashing acid dissolution method.
  • the sample may be ashed by an appropriate method, dissolved in an acid, and the volume of the dissolved solution may be determined, and the content of alkali metal may be measured by inductively coupled plasma mass spectrometry.
  • the resin laminate with a protective film of the present invention has at least thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A).
  • the thermoplastic resin layer (B) and the thermoplastic resin layer (C) may be the same layer or different layers.
  • the thermoplastic resin layers (B) and (C) contain at least one thermoplastic resin.
  • the thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass, based on the total resin contained in each thermoplastic resin layer, from the viewpoint of easily improving moldability. As described above, even more preferably, 80% by mass or more of thermoplastic resin is included. The upper limit of the amount of the thermoplastic resin is 100% by mass.
  • the thermoplastic resin include (meth) acrylic resin, polycarbonate resin, and cycloolefin resin.
  • the thermoplastic resin is preferably a (meth) acrylic resin or a polycarbonate resin from the viewpoint of easily improving the adhesion between the thermoplastic resin layers (B) and (C) and the intermediate layer (A).
  • the thermoplastic resin layers (B) and (C) may contain the same thermoplastic resin or may contain different thermoplastic resins.
  • the thermoplastic resin layers (B) and (C) preferably contain the same thermoplastic resin from the viewpoint of easily suppressing war
  • the thermoplastic resin contained in the thermoplastic resin layers (B) and (C) is preferably 100 to 160 ° C., more preferably 102 to 155 ° C., and still more preferably 102 to 150 ° C. from the viewpoint of heat resistance of the resin laminate. It has a Vicat softening temperature of 152 ° C.
  • the Vicat softening temperature is the Vicat softening temperature of the resin when the thermoplastic resin layer contains one kind of thermoplastic resin, and the thermoplastic resin layer contains two or more kinds of thermoplastic resins. Is the Vicat softening temperature of a mixture of a plurality of thermoplastic resins.
  • the Vicat softening temperature of the thermoplastic resin is measured in accordance with the B50 method defined in JIS K 7206: 1999 “Plastics—Thermoplastic—Vicat Softening Temperature (VST) Test Method”.
  • the Vicat softening temperature can be measured using a heat distortion tester (for example, “148-6 continuous type” manufactured by Yasuda Seiki Seisakusho Co., Ltd.).
  • the measurement may be performed using a test piece obtained by press-molding each raw material to a thickness of 3 mm.
  • thermoplastic resin layers (B) and (C) are provided with other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin for the purpose of increasing the strength and elasticity of the thermoplastic resin layer. May be included.
  • the amount of the other resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total resin contained in each thermoplastic resin layer. .
  • the lower limit of the amount of other resins is 0% by mass.
  • thermoplastic resin layers (B) and (C) are preferably a (meth) acrylic resin layer or a polycarbonate resin layer from the viewpoint of good molding processability and easy enhancement of adhesion to the intermediate layer (A). .
  • thermoplastic resin layers (B) and (C) are (meth) acrylic resin layers
  • the thermoplastic resin layers (B) and (C) contain one or more (meth) acrylic resins.
  • the thermoplastic resin layers (B) and (C) are preferably 50% by mass or more based on the total resin contained in each thermoplastic resin layer, more preferably 60% by mass or more, and even more, from the viewpoint of surface hardness. Preferably 70 mass% or more of (meth) acrylic resin is included.
  • Examples of the (meth) acrylic resin include the resins described for the (meth) acrylic resin contained in the intermediate layer (A). Unless it mentions specially, the preferable (meth) acrylic resin described about the intermediate
  • the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) and the (meth) acrylic resin contained in the intermediate layer (A) may be the same or different.
  • the weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, more preferably 70,000 to 250, from the viewpoint of good moldability and easy increase in mechanical strength. 1,000.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.
  • the thermoplastic resin layers (B) and (C) may further contain a thermoplastic resin other than one or more (meth) acrylic resins.
  • a thermoplastic resin compatible with the (meth) acrylic resin is preferable.
  • methyl methacrylate-styrene-maleic anhydride copolymer for example, “Resphi” manufactured by Denki Kagaku Kogyo
  • methyl methacrylate-methacrylic acid copolymer for example, “Altglass HT121” manufactured by Arkema
  • polycarbonate resin Is mentioned.
  • the thermoplastic resin other than the (meth) acrylic resin is preferably 115 ° C.
  • thermoplastic resin layer (B) and (C) does not contain a vinylidene fluoride resin substantially from a viewpoint of heat resistance and surface hardness.
  • the pencil hardness of the thermoplastic resin layers (B) and (C) is preferably HB or more, more preferably F or more, and more preferably H or more, from the viewpoint of enhancing scratch resistance. Is even more preferred.
  • thermoplastic resin layers (B) and (C) are polycarbonate resin layers
  • the thermoplastic resin layers (B) and (C) contain one or more polycarbonate resins.
  • the thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass or more based on the total resin contained in each thermoplastic resin layer, from the viewpoint of impact resistance. More preferably, 80% by mass or more of polycarbonate resin is included.
  • polycarbonate resin examples include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted.
  • a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) can be mentioned.
  • dihydroxydiaryl compound examples include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1 Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4
  • Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
  • Polycarbonate resins other than the above polycarbonate resins include polycarbonates synthesized from isosorbite and aromatic diols.
  • An example of the polycarbonate is “DURABIO (registered trademark)” manufactured by Mitsubishi Chemical Corporation.
  • polycarbonate resin Commercially available products may be used as the polycarbonate resin.
  • the weight average molecular weight (Mw) of the polycarbonate resin is preferably 20,000 to 70,000, more preferably 25,000 to 60,000, from the viewpoint of easily improving impact resistance and moldability. It is.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.
  • MVR melt volume rate
  • MVR melt volume rate
  • the thermoplastic resin layers (B) and (C) may further contain a thermoplastic resin other than one or more polycarbonate resins.
  • a thermoplastic resin compatible with the polycarbonate resin is preferable, a (meth) acrylic resin is more preferable, and a methacrylic resin having an aromatic ring or a cycloolefin in the structure is still more preferable.
  • the thermoplastic resin layers (B) and (C) contain a polycarbonate resin and the above (meth) acrylic resin, the surface hardness of the thermoplastic resin layers (B) and (C) includes only the polycarbonate resin. It is preferable because it can be made higher than that.
  • At least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) in the resin laminate with a protective film of the present invention is variously used as long as the effects of the present invention are not impaired.
  • the additive may be further included.
  • additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, and flame retardant aids.
  • coloring agents such as reinforcing agents, nucleating agents, and bluing agents.
  • Examples of the colorant include compounds having an anthraquinone skeleton, compounds having a phthalocyanine skeleton, and the like. Among these, a compound having an anthraquinone skeleton is preferable from the viewpoint of heat resistance.
  • the content of the colorant in each layer is appropriately determined according to the purpose, the type of the colorant, and the like. You can choose.
  • a bluing agent used as the colorant, the content thereof can be about 0.01 to 10 ppm based on the total resin contained in each layer containing the bluing agent. This content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, and preferably 7 ppm or less, more preferably 5 ppm or less, even more preferably 4 ppm or less, Especially preferably, it is 3 ppm or less.
  • Known bluing agents can be used as appropriate.
  • Macrolex (registered trademark) Blue RR manufactured by Bayer
  • Macrolex (registered trademark) Blue 3R manufactured by Bayer
  • Sumiplast registered trademark
  • Viloet B manufactured by Sumika Chemtex Co., Ltd.
  • Polycinslen registered trademark
  • Blue RLS manufactured by Clariant
  • Dialesin Violet D Dialesin Blue G
  • Dialesin Blue N aboveve, manufactured by Mitsubishi Chemical Corporation
  • the ultraviolet absorber is not particularly limited, and various conventionally known ultraviolet absorbers may be used.
  • an ultraviolet absorber having an absorption maximum at 200 to 320 nm or 320 to 400 nm can be mentioned. Specific examples include triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
  • an ultraviolet absorber you may use 1 type of these ultraviolet absorbers individually or in combination of 2 or more types.
  • Use of at least one ultraviolet absorber having an absorption maximum at 200 to 320 nm and at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm in combination can more effectively prevent damage from ultraviolet rays To preferred.
  • UV absorber such as “Kemisorb 102” (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-N-octyl) manufactured by Chemipro Kasei Co., Ltd.
  • Oxyphenyl) -1,3,5-triazine) (absorbance 0.1), “ADEKA STAB LA-F70” (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methyl) manufactured by ADEKA Corporation Phenyl) -1,3,5-triazine) (absorbance 0.6), “Adekastab LA-31, LA-31RG, LA-31G” (2,2′-methylenebis (4- (1,1,3,3 -Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) (absorbance 0.2), “ADEKA STAB LA-46” (2- (4,6) manufactured by ADEKA Corporation Diphenyl-1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or “TINUVIN 1577” manufactured by BASF Japan Ltd.
  • the absorbance of the exemplified ultraviolet absorber is at 380 nm. This is absorbance, which can be measured using a spectrophotometer (for example, a spectrophotometer U-4100 manufactured by HITACHI) after dissolving an ultraviolet absorber in chloroform at a concentration of 10 mg / L.
  • a spectrophotometer for example, a spectrophotometer U-4100 manufactured by HITACHI
  • the content of the UV absorber in each layer depends on the purpose, the type of the UV absorber, etc. You may select suitably according to it.
  • the content of the ultraviolet absorber can be about 0.005 to 2.0% by mass based on the total resin contained in each layer containing the ultraviolet absorber.
  • the content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more. Further, the content of the ultraviolet absorber is preferably 1.5% by mass or less, more preferably 1.0% by mass or less.
  • the content of the ultraviolet absorber is not less than the above lower limit from the viewpoint of easily enhancing the ultraviolet absorption effect, and being not more than the above upper limit prevents a change in the color (for example, yellowness YI) of the resin laminate. It is preferable because it is easy to do. For example, it is preferable to use the above-mentioned commercially available “ADK STAB LA-31, LA-31RG, LA-31G” in the above amounts.
  • thermoplastic resin layers (B) and (C) are polycarbonate resin layers, and 0.005 to 2.0 mass% based on the total resin contained in each thermoplastic resin layer. It is preferable to contain a UV absorber because it is easy to obtain a resin laminate having excellent light resistance.
  • the average value of the thickness of the intermediate layer (A) is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, and even more preferably 300 ⁇ m or more, from the viewpoint of dielectric constant. Moreover, from a viewpoint of transparency, Preferably it is 1500 micrometers or less, More preferably, it is 1200 micrometers or less, More preferably, it is 1000 micrometers or less.
  • the average value of the thickness of the intermediate layer (A) is obtained by cutting the resin laminate perpendicularly to the surface direction, polishing the cross section with sandpaper, and then using a microscope (for example, a microscope manufactured by Micro Square). It can be measured by observing. Let the average value which performed the said measurement in arbitrary 10 points
  • the average values of the film thicknesses of the thermoplastic resin layers (B) and (C) are each preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, from the viewpoint of easily increasing the surface hardness. Even more preferably, it is 50 ⁇ m or more. From the viewpoint of dielectric constant, each is preferably 200 ⁇ m or less, more preferably 175 ⁇ m or less, and even more preferably 150 ⁇ m or less.
  • the average value of the film thickness of the thermoplastic resin layer can be measured in the same manner as described above for the intermediate layer.
  • the average value of the film thickness of the resin laminate is 100 to 2000 ⁇ m, and the average value of the film thickness of the thermoplastic resin layers (B) and (C) is 10 to 200 ⁇ m, respectively. It is preferable from the viewpoint of easily suppressing warpage of the laminate.
  • the average value of the film thickness is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, and even more preferably 300 ⁇ m or more, from the viewpoint of easily increasing the rigidity of the resin laminate. Further, from the viewpoint of transparency of the laminate after peeling, it is preferably 2000 ⁇ m or less, more preferably 1500 ⁇ m or less, and even more preferably 1000 ⁇ m or less.
  • the film thickness is measured with a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.
  • the resin laminate in the resin laminate with a protective film of the present invention is preferably 3.5 or more, more preferably 4.0 or more, and even more preferably from the viewpoint of obtaining a function sufficient for use in a display device such as a touch panel.
  • the upper limit value of the dielectric constant is not particularly limited, but is usually 20.
  • the dielectric constant can be adjusted by adjusting the kind and amount of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention, or by adding a high dielectric constant compound such as ethylene carbonate or propylene carbonate. Can be adjusted within the range.
  • the dielectric constant conforms to JIS K-6911: 1995, and the resin laminate after peeling off the protective films (D) and (E) is allowed to stand for 24 hours at 23 ° C. in an environment with a relative humidity of 50%.
  • the resin laminate is a value measured at 3 V and 100 kHz by the automatic equilibrium bridge method.
  • a commercially available instrument may be used, for example, “precision LCR meter HP4284A” manufactured by Agilent Technologies, Inc. may be used.
  • the resin laminate is preferably transparent when visually observed.
  • the resin laminate after peeling off the protective films (D) and (E) is preferably 85% or more, more preferably 88% or more, more preferably measured according to JIS K7361-1: 1997. More preferably, it has a total light transmittance (Tt) of 90% or more. The upper limit of the total light transmittance is 100%. It is preferable that the laminate after exposure for 120 hours in an environment of 60 ° C. and 90% relative humidity still has a total light transmittance in the above range.
  • the resin laminate after peeling off the protective films (D) and (E) is measured according to JIS K7136: 2000 using the laminate after exposure for 120 hours in an environment of 90% relative humidity at 60 ° C.
  • the haze is preferably 2.0% or less, more preferably 1.8% or less, and still more preferably 1.5% or less.
  • the resin laminate after peeling off the protective films (D) and (E) was measured according to JIS Z 8722: 2009 using the resin laminate after exposure for 120 hours in an environment with a relative humidity of 90% at 60 ° C.
  • the yellowness (Yellow Index: YI value) is preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less.
  • the resin laminate after peeling off the protective films (D) and (E) having the haze and yellowness described above is less likely to warp even when used in an environment such as high temperature and high humidity, it has transparency. It is preferable because it is easy to maintain and suppress yellowing.
  • the resin laminate may further include at least one functional layer in addition to the intermediate layer (A) and the thermoplastic resin layers (B) and (C).
  • the functional layer is preferably present on the surface of the thermoplastic resin layer (B) and / or (C) opposite to the intermediate layer (A).
  • the protective film may be bonded to the surface of the functional layer.
  • the functional layer include a hard coat layer, an antireflection layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer.
  • These functional layers may be laminated on the resin laminate via an adhesive layer, or may be a coating layer laminated by coating.
  • a cured film described in JP 2013-86273 A may be used as the functional layer.
  • the functional layer is, for example, coated on one side or both sides of at least one functional layer selected from the group consisting of a hard coat layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer by a coating method, a sputtering method, a vacuum deposition method, or the like.
  • the antireflection layer may be a further coated layer, or may be a layer in which an antireflection sheet is bonded to one side or both sides of the at least one functional layer.
  • the thickness of the functional layer may be appropriately selected according to the purpose of each functional layer, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more from the viewpoint of easily expressing the function. From the viewpoint of easily preventing cracking, the thickness is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
  • the resin laminate with a protective film of the present invention further has protective films (D) and (E) having at least a film substrate, which are bonded to both surfaces of the resin laminate.
  • the protective film may be bonded to both surfaces of the resin laminate by, for example, electrostatic attraction, or may be bonded via an adhesive layer. It is preferable that the protective film further has an adhesive layer and is bonded to both surfaces of the resin laminate via the adhesive layer.
  • the protective films (D) and (E) may be the same film or different films.
  • the protective films (D) and (E) may have the same film substrate and adhesive layer as each other, It may have different film bases and adhesive layers, may have the same film bases and mutually different adhesive layers, may have different film bases and mutually identical adhesive layers Good.
  • the protective films (D) and (E) are bonded to the surfaces of the thermoplastic resin layers (B) and (C), respectively, for the purpose of protecting the surfaces. Since the resin laminate having at least the intermediate layer (A) and the thermoplastic resin layers (B) and (C) in the resin laminate with a protective film of the present invention is soft, dust in the air is formed on the surface of the resin laminate. A dent is likely to occur due to foreign matters such as. From the viewpoint of easily avoiding such dents, it is preferable that each of the protective films (D) and (E) satisfy the following relationship. [In formula, E represents the tensile elasticity modulus (MPa) of a protective film, L represents the average value (mm) of the film thickness of the film base material of a protective film. ]
  • the protective film satisfying the above relationship has rigidity particularly suitable for protecting the surface of the resin laminate.
  • the elastic modulus is a numerical value determined by the type of resin constituting the film substrate or the type of adhesive layer when the protective film has an adhesive layer. Therefore, the protective film which satisfy
  • the tensile elastic modulus of the protective film can be measured according to JIS-K7127, for example, by an electromechanical universal testing machine manufactured by Instron. When the protective film has an adhesive layer, the tensile elastic modulus is measured using the protective film including the adhesive layer. The average value of the film thickness of the film substrate is measured with a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.
  • the film base material of the protective films (D) and (E) is not particularly limited as long as the surface of the resin laminate can be protected, but is preferably a plastic film from the viewpoint of easily improving the protection of the surface of the resin laminate. , At least one selected from the group consisting of a low density polyethylene (LDPE) film, a high density polyethylene (HDPE) film, a polypropylene (PP) film, a polyethylene terephthalate (PET) film, an acrylic resin film, and a polycarbonate (PC) film More preferably a film.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PC polycarbonate
  • the film substrate of the protective films (D) and (E) is more preferably an HDPE film, a PP film, or a PET film, and an HDPE film or a PET film.
  • the film substrate of the protective films (D) and (E) may be a single layer or a multilayer in which a plurality of plastic films are laminated.
  • the multilayer film substrate examples include, for example, a film substrate having the following constitution: LLDPE (linear low density polyethylene) / LDPE / PP, LLDPE / HDPE / PP, EVA (ethylene- Vinyl acetate copolymer) / HDPE / PP, EVA / HDPE / LDPE, and the like.
  • LLDPE linear low density polyethylene
  • LLDPE / HDPE / PP LLDPE / HDPE / PP
  • EVA ethylene- Vinyl acetate copolymer
  • HDPE / PP EVA ethylene- Vinyl acetate copolymer
  • the tensile elastic modulus of the protective films (D) and (E) is preferably 100 MPa or more, more preferably 150 MPa or more, and even more preferably 200 MPa or more, from the viewpoint of easily improving the protective properties of the surface of the resin laminate. Further, the tensile elastic modulus of the film base material of the protective films (D) and (E) is preferably 5 from the viewpoint of easily maintaining the protective properties of the surface of the resin laminate even when large foreign matter is present. 000 MPa or less, more preferably 4,500 MPa or less, and even more preferably 4,000 MPa or less. The method for measuring the tensile modulus of the protective film is as described above.
  • the average value of the film bases of the protective film (D) and (E) is preferably 45 ⁇ m or more, more preferably 50 ⁇ m or more, and even more preferably from the viewpoint of easily improving the surface protection of the resin laminate. 60 ⁇ m or more.
  • the average film thickness of the protective film (D) and (E) film base is preferably 200 ⁇ m or less, more preferably 175 ⁇ m or less, and even more preferably 150 ⁇ m or less, from the viewpoint of easy bonding. is there.
  • the method for measuring the average value of the film thickness of the film substrate is as described above.
  • the average value of the film substrate thickness is from the viewpoint of easily enhancing the surface protection of the resin laminate.
  • the thickness is preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more, and even more preferably 70 ⁇ m or more.
  • the average film thickness of the film substrate is preferably 200 ⁇ m or less, more preferably 175 ⁇ m or less, and even more preferably 150 ⁇ m or less, from the viewpoint of easy bonding.
  • the method for measuring the average value of the film thickness of the film substrate is as described above.
  • the average value of the film thicknesses of the protective films (D) and (E) increases the protective properties of the surface of the resin laminate. From an easy viewpoint, it is preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more, and even more preferably 70 ⁇ m or more. In this embodiment, the average value of the film thicknesses of the protective films (D) and (E) is preferably 200 ⁇ m or less, more preferably 175 ⁇ m or less, and even more preferably 150 ⁇ m or less, from the viewpoint of easy bonding. is there.
  • the measuring method of the average value of the film thickness of a protective film is the same as the method shown above about the film base material.
  • the protective films (D) and (E) are bonded to the surface of the resin laminate.
  • the protective films (D) and (E) are films bonded together for the purpose of protecting the surface of the resin laminate in, for example, a manufacturing process or a distribution process. Therefore, in the manufacturing process of the display device, the protective films (D) and (E) are peeled off from the surfaces of the thermoplastic resin layers (B) and (C), and the intermediate layer (A) and the thermoplastic resin layer (B). And the resin laminated body which has at least (C) is integrated in a display apparatus as a component.
  • the adhesive layer has, for example, sufficient adhesiveness to maintain the state in which the protective films (D) and (E) are bonded to the surface of the resin laminate in the manufacturing process, distribution process, and the like, and from the surface of the resin laminate. It is required that the protective films (D) and (E) have easy releasability. From such a viewpoint, it is preferable that the protective films (D) and (E) have a low adhesive strength that can be peeled by hand from the surface of the resin laminate, specifically, preferably 0.4 N / 25 mm.
  • the peel strength is 0.35 N / 25 mm or less, and still more preferably 0.3 N / 25 mm or less.
  • it has a peel strength of 0.03 N / 25 mm or more. The peel strength is measured according to JIS-Z0237 at a peel rate of 0.3 mm / min, a peel angle of 180 °, and a measurement width of 25 mm.
  • the adhesive layers of the protective films (D) and (E) are not particularly limited as long as they have the above-mentioned adhesiveness and peelability.
  • acrylic resins, rubber resins, ethylene vinyl acetate copolymer resins, polyester resins It is preferable to contain an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, or the like as an adhesive.
  • the adhesive layer more preferably contains an acrylic resin or an ethylene vinyl acetate copolymer resin as an adhesive.
  • the adhesive layer of the protective films (D) and (E) may contain other components of the adhesive.
  • other components include an antistatic agent, a colorant, and an ultraviolet absorber.
  • the resin laminate in the resin laminate with a protective film of the present invention comprises a resin composition (A) that provides the intermediate layer (A), a resin composition (B) that provides the thermoplastic resin layers (B) and (C), and It can be manufactured from (C).
  • the resin compositions (B) and (C) need only contain at least a resin that gives the thermoplastic resin layers (B) and (C).
  • a composition containing more than one kind of component may be used, or a single type of resin may be used.
  • Resin composition (A) is usually obtained by kneading (meth) acrylic resin and vinylidene fluoride resin.
  • the kneading can be performed, for example, by a method including a step of melt kneading at a temperature of 150 to 350 ° C. at a shear rate of 10 to 1000 / sec.
  • the temperature at the time of melt kneading is preferably 150 ° C. or higher because the resin can be sufficiently melted, and is preferably 350 ° C. or lower because it is easy to suppress thermal decomposition of the resin. Furthermore, it is preferable that the shear rate at the time of melt-kneading is 10 / second or more because the resin can be sufficiently kneaded, and it is preferably 1000 / second or less because the decomposition of the resin is easily suppressed.
  • the melt-kneading is preferably performed at a temperature of 180 to 300 ° C., more preferably 200 to 300 ° C., preferably 20 to 700 / second, and more. Preferably, it is carried out at a shear rate of 30 to 500 / sec.
  • an ordinary mixer or kneader can be used as an apparatus used for melt kneading.
  • Specific examples include a single-screw kneader, a twin-screw kneader, another-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill.
  • a high shearing device or the like may be used.
  • Resin compositions (B) and (C) can also be produced in the same manner as resin composition (A), for example, by melt kneading under the above temperature and shear rate.
  • the resin laminate may be manufactured by melt extrusion described later without melt-kneading in advance.
  • the additives may be included in advance in the resin contained in each layer, and are added when the resin is melt-kneaded. Alternatively, the resin may be added after melt-kneading, or may be added when a resin laminate is produced using the resin composition.
  • the resin laminate having at least the intermediate layer (A) and the thermoplastic resin layers (B) and (C) respectively present on both sides of the intermediate layer (A) is, for example, a melt extrusion molding method or a solution casting film forming method.
  • the layers (A) to (C) are separately prepared from the resin compositions (A) to (C) by a hot press method, an injection molding method, etc., and these are bonded via, for example, an adhesive or an adhesive.
  • the resin compositions (A) to (C) may be laminated and integrated by melt coextrusion molding.
  • Resin laminates can be produced by melt coextrusion molding of the resin compositions (A) to (C), and are usually easier to secondary mold than resin laminates produced by bonding. Since a laminated body is obtained, it is preferable.
  • the resin composition (A) and the resin compositions (B) and (C) are separately fed into two or three uniaxial or biaxial extruders and melted respectively.
  • the intermediate layer (A) formed from the resin composition (A) and the thermoplastic resin layers (B) and (C) are laminated and integrated through a feed block die, a multi-manifold die, and the like. This is a molding method.
  • the resin compositions (B) and (C) are the same composition, one composition melt-kneaded in one extruder is divided into two via a feed block die or the like, and a thermoplastic resin is obtained. Layers (B) and (C) may be formed.
  • the obtained film is preferably cooled and solidified by, for example, a roll unit.
  • the protective films (D) and (E) are coated on one surface of the film substrate with a coating solution containing, for example, an adhesive and optionally other components, and a solvent such as water, and dried. It can be manufactured by forming an adhesive layer. Or it can also manufacture by sticking the adhesive layer previously shape
  • Commercially available protective films include, for example, polyolefin film “PAC-2 type” manufactured by Sanei Kaken Co., Ltd., “PET base marking SAT116 type”, and “E-2035” manufactured by Sumilon.
  • the resin laminate with a protective film of the present invention can be produced by laminating the protective film to the resin laminate produced as described above.
  • the size of the resin laminate with a protective film of the present invention is not particularly limited, for example, it is distributed in the form of a resin laminate with a protective film having a width of 500 to 3000 mm and a length of 500 to 3000 mm.
  • the resin laminate with protective film of the present invention can be used in various display devices in the form of a resin laminate obtained by peeling off the protective film.
  • a display device is a device having a display element and includes a light-emitting element or a light-emitting device as a light-emitting source.
  • a liquid crystal display device As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device) (SED)), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection display device (for example, a grating light valve (GLV) display device, a display having a digital micromirror device (DMD)) Apparatus) and a piezoelectric ceramic display.
  • EL organic electroluminescence
  • EL inorganic electroluminescence
  • touch panel display device As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device)
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices may be a display device that displays a two-dimensional image, or may be a stereoscopic display device that displays a three-dimensional image.
  • the resin laminate in the resin laminate with a protective film of the present invention is suitably used, for example, as a front plate or a transparent electrode.
  • a transparent conductive sheet is produced by forming a transparent conductive film on at least one surface of the resin laminate, and the transparent conductive A transparent electrode can be produced from the sheet.
  • the transparent conductive film may be directly formed on the surface of the resin laminate, or a plastic film on which a transparent conductive film has been previously formed is laminated with resin. It may be laminated on the surface of the body.
  • the film base material of the plastic film on which the transparent conductive film is formed in advance is not particularly limited as long as it is a transparent film and can form a transparent conductive film.
  • a transparent film for example, polyethylene terephthalate, polyethylene naphthalate , Polycarbonate, acrylic resin, polyamide, a mixture or laminate thereof.
  • the film may be coated for the purpose of improving surface hardness, preventing Newton's ring, imparting antistatic properties, and the like.
  • the method of laminating a film, on which a transparent conductive film has been previously formed, on the surface of the resin laminate may be any method as long as it is free from bubbles and provides a uniform and transparent sheet.
  • a method of laminating using an adhesive that is cured by normal temperature, heating, ultraviolet light, or visible light may be used, or a transparent adhesive tape may be used for bonding.
  • a vacuum deposition method As a method for forming a transparent conductive film, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and these methods are appropriately used depending on a required film thickness. Can do.
  • the sputtering method for example, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, or means such as ozone addition, plasma irradiation, or ion assist may be used in combination. If necessary, a bias such as direct current, alternating current, and high frequency may be applied to the substrate.
  • the transparent conductive metal oxide used for the transparent conductive film is indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite. An oxide etc. are mentioned. Of these, indium-tin composite oxide (ITO) is preferable from the viewpoint of environmental stability and circuit processability.
  • a coating agent containing various conductive polymers capable of forming a transparent conductive film is applied to the surface of the resin laminate and irradiated with ionizing radiation such as heat or ultraviolet rays.
  • ionizing radiation such as heat or ultraviolet rays.
  • a method for curing the coating can be applied.
  • the conductive polymer polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.
  • the thickness of the transparent conductive film is not particularly limited, but when a transparent conductive metal oxide is used, it is usually 50 to 2000 mm, preferably 70 to 000 mm. If it is this range, it will be excellent in both electroconductivity and transparency.
  • the thickness of the transparent conductive sheet is not particularly limited, and an optimum thickness can be selected according to the demand for the product specifications of the display.
  • the resin laminate in the resin laminate with a protective film of the present invention can be used as a display panel face plate, and a transparent conductive sheet produced from the resin laminate can be used as a transparent electrode such as a touch screen to produce a touch sensor panel.
  • the resin laminate of the present invention can be used as a touch screen window sheet, and the transparent conductive sheet can be used as an electrode substrate for a resistive film type or capacitive type touch screen.
  • An external touch sensor panel having a touch screen function can be obtained by arranging the touch screen on the front surface of a liquid crystal display device, an organic EL display device or the like.
  • FIG. 2 is a schematic cross-sectional view showing a preferred embodiment of a liquid crystal display device including a resin laminate in the resin laminate with a protective film of the present invention.
  • the resin laminate 10 in the resin laminate with a protective film of the present invention is laminated on the polarizing plate 11 via the optical adhesive layer 12, and this laminate can be disposed on the viewing side of the liquid crystal cell 13.
  • a polarizing plate 11 is usually disposed on the back side of the liquid crystal cell 13.
  • the liquid crystal display device 14 is composed of such members.
  • FIG. 2 is an example of a liquid crystal display device, and the display device of the present invention is not limited to this configuration.
  • Vicat softening temperature, alkali metal content, MFR, MVR, total light transmittance, haze, and YI value were measured by the following methods.
  • VST Vinyl softening Temperature
  • MFR melt mass flow rate
  • MVR melt volume flow rate
  • the film thickness of the resin laminate was measured with a digital micrometer.
  • the average value obtained by performing the above measurement at 10 points was defined as the average value of the film thickness of the resin laminate.
  • the thickness of each layer of the intermediate layer (A), the thermoplastic resin layer (B) and (C) is measured after cutting the resin laminate perpendicularly to the surface direction and polishing the cross section with sandpaper It was measured by observing with a microscope manufactured by Micro Square.
  • the average value obtained by performing the above measurement at 10 points was defined as the average value of the film thickness of each layer.
  • the obtained pellet-like methacrylic resin composition was analyzed by pyrolysis gas chromatography under the following conditions, and each peak area corresponding to methyl methacrylate and acrylate ester was measured.
  • the structural unit derived from methyl methacrylate was 97.0% by mass
  • the structural unit derived from methyl acrylate was 3.0% by mass.
  • a standard product of a methacrylic resin having a weight ratio of acrylic ester units to methyl methacrylate units of W 0 (known) is pyrolyzed under the above pyrolysis conditions, and the generated decomposition product is subjected to the above gas chromatography analysis conditions.
  • a pellet-like methacrylic resin (ii) was prepared in the same manner as in Production Example 1 except that 98.9 parts by weight of methyl methacrylate, 1.1 parts by weight of methyl acrylate, and 0.16 parts by weight of the chain transfer agent were changed. And the content of the structural unit was measured.
  • the structural unit derived from methyl methacrylate was 97.5% by mass, and the structural unit derived from methyl acrylate was 2.5% by mass.
  • Table 1 shows the physical properties of the methacrylic resins (i) and (ii) obtained in Production Examples 1 and 2.
  • Vinylidene fluoride resin (i): Polyvinylidene fluoride resin produced by suspension polymerization (ii): Polyvinylidene fluoride vinylidene fluoride resin produced by suspension polymerization (iii): Produced by emulsion polymerization Polyvinylidene fluoride
  • the weight average molecular weight (Mw) of the vinylidene fluoride resin was measured by GPC.
  • Mw weight average molecular weight
  • polystyrene was used as a standard reagent
  • a calibration curve was created from the elution time and molecular weight, and the weight average molecular weight of each resin was measured.
  • 40 mg of resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample.
  • NMP N-methylpyrrolidone
  • two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and an RI detector was used as a detector.
  • polycarbonate (i) was used as the polycarbonate resin of the thermoplastic resin layer.
  • Table 3 shows the physical properties of the resin.
  • the weight average molecular weight of the polycarbonate resin was measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • To create a GPC calibration curve use a methacrylic resin made by Showa Denko KK with a narrow molecular weight distribution and known molecular weight as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the weight average of each resin composition.
  • the molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample.
  • THF tetrahydrofuran
  • As the measuring apparatus two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and an RI detector was used as a detector.
  • the resin composition (A) is 65 mm ⁇ single screw extruder 2 (manufactured by Toshiba Machine Co., Ltd.), and the resin compositions (B) and (C) are 45 mm ⁇ single screw extruders 1 and 3 (manufactured by Hitachi Zosen Corporation). ] To melt each.
  • the B layer and the C layer are layers having the same composition. Then, the obtained film-like molten resin 6 is sandwiched between the first cooling roll 7 and the second cooling roll 8 that are arranged to face each other, and then wound around the second roll 8 while the second roll 8 and the third roll.
  • the product was wound around a third cooling roll 9, molded and cooled to obtain a resin laminate 10 having a three-layer structure in which each layer has an average thickness shown in Table 5.
  • Each of the obtained resin laminates 10 had a total film thickness of about 800 ⁇ m, and was visually transparent when visually observed.
  • a protective film having physical properties shown in Table 5 was bonded to both surfaces of the obtained resin laminate while applying pressure to obtain a resin laminate with a protective film.
  • the dielectric constants of the resin laminates in the resin laminates with protective films of Examples 1 to 10 and Comparative Example 1 are 5.2 in Examples 1 to 9, 5.3 in Example 10, and Comparative Example 1 Then it was 4.4. It was confirmed that any of the resin laminates has a dielectric constant sufficient for use in a display device such as a touch panel.
  • the resin laminate with a protective film of the present invention shown in Examples 1 to 10 has high transparency and hardly causes appearance defects such as dents. Furthermore, it was confirmed that high transparency was maintained even after the durability test under high temperature and high humidity conditions.

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  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne un matériau lamellé en résine doté d'un film protecteur qui est avantageusement utilisé dans des dispositifs d'affichage et analogues et dans lesquels des défauts d'aspect tels que des bosses ne sont pas susceptibles de se produire lors des processus de fabrication et de distribution qui sont avantageusement utilisés dans des dispositifs d'affichage. À cet effet, l'invention concerne un matériau lamellé en résine comportant au moins une couche intermédiaire (A) et des couches de résine thermoplastique (B) et (C) qui sont présentes sur les deux faces de la couche intermédiaire (A), et des films protecteurs (D) et (E) ayant au moins un substrat de film sont collés sur les deux surfaces du matériau lamellé en résine, la couche intermédiaire (A) contenant 10 à 90 % en masse d'une résine (méth)acrylique et 90 à 10 % en masse d'une résine de fluorure de vinylidène par rapport à toutes les résines incluses dans la couche intermédiaire (A), et la masse moléculaire moyenne en poids de la résine (méth)acrylique (Mw) étant de 100 000 à 300 000.
PCT/JP2017/019005 2016-05-30 2017-05-22 Matériau lamellé en résine avec film protecteur Ceased WO2017208882A1 (fr)

Priority Applications (2)

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CN201780033201.3A CN109219517B (zh) 2016-05-30 2017-05-22 带保护膜的树脂层叠体
KR1020187037739A KR102008476B1 (ko) 2016-05-30 2017-05-22 보호 필름을 구비하는 수지 적층체

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JP2022048309A (ja) * 2017-12-28 2022-03-25 大日本印刷株式会社 保護フィルム付き光透過性フィルムおよび保護フィルム
EP3960417A4 (fr) * 2019-04-23 2023-01-25 Sumitomo Chemical Company Limited Corps multicouche et procédé de production de corps multicouche

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TW202112542A (zh) * 2019-08-08 2021-04-01 日商住友化學股份有限公司 積層體
JP7604132B2 (ja) * 2020-08-13 2024-12-23 デンカ株式会社 積層体、建造物用フィルム、膜構造物、建造物、膜構造物の建築方法及び膜構造物の補修方法

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JP2017213880A (ja) 2017-12-07
TW201808639A (zh) 2018-03-16
CN109219517A (zh) 2019-01-15

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