WO2020235164A1 - Film multicouche - Google Patents

Film multicouche Download PDF

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Publication number
WO2020235164A1
WO2020235164A1 PCT/JP2020/007376 JP2020007376W WO2020235164A1 WO 2020235164 A1 WO2020235164 A1 WO 2020235164A1 JP 2020007376 W JP2020007376 W JP 2020007376W WO 2020235164 A1 WO2020235164 A1 WO 2020235164A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
cured resin
laminated film
mass
elastic modulus
Prior art date
Application number
PCT/JP2020/007376
Other languages
English (en)
Japanese (ja)
Inventor
弘行 谷山
敦子 小西
剛司 加藤
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020217041767A priority Critical patent/KR20220013391A/ko
Priority to JP2021520055A priority patent/JP7302656B2/ja
Priority to CN202080034261.9A priority patent/CN113795375B/zh
Publication of WO2020235164A1 publication Critical patent/WO2020235164A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a laminated film having excellent surface hardness and repeated bending characteristics.
  • the surface protective film for display screens used for such applications requires not only surface protective properties such as high hardness, scratch prevention, stain resistance, and abrasion resistance, but also high durability in terms of bendability. It was said that further performance improvement was requested.
  • Patent Document 1 in a hard coat layer having a laminated structure, the intermediate layer has a larger elastic modulus than the surface layer to improve the surface hardness and damage to the hard coat film due to stress concentration.
  • the technical contents regarding the hard coat film which prevents the stress and is hard to be scratched are disclosed.
  • Patent Document 2 discloses a hard coat layer having a laminated structure in which a radical material is used for the surface layer and a cationic material is used for the intermediate layer, and the interlayer adhesion is good.
  • Patent Document 3 discloses a technical content for controlling the elastic modulus of a hard coat coating film by including silica particles in the coating film.
  • the surface layer has a larger elastic modulus than the intermediate layer, and the abrasion resistance and flexibility are excellent by setting the elongation rate of the cured coating film within a specific range.
  • the technical contents related to the hard coat film are disclosed.
  • the present invention proposes a new laminated film that not only has excellent surface hardness but also has excellent practical repeated bending characteristics.
  • the present invention has a configuration in which a cured resin layer (A) and a cured resin layer (B) are sequentially laminated on the surface of a base film.
  • the elastic modulus measured by the micro-hardness meter measurement JIS Z 2255
  • the elastic modulus of the cured resin layer (B) is larger than the elastic modulus of the cured resin layer (A)
  • the cured resin layer (A) We propose a laminated film characterized in that the difference between the elastic modulus of the above and the elastic modulus of the cured resin layer (B) is larger than 0 (MPa) and smaller than 220 (MPa).
  • the present invention is characterized in that, as an example of the method for producing a laminated film, the cured resin layer (A) is formed by applying a curable composition onto a base film and curing the curable composition.
  • a method for producing a laminated film characterized in that the mass average molecular weight is in the range of 1,000 to 500,000.
  • the laminated film proposed by the present invention has a structure in which a cured resin layer (A) and a cured resin layer (B) are sequentially laminated on the surface of a base film, and the elastic modulus and curing of the cured resin layer (A) are provided.
  • the difference in elastic modulus of the resin layer (B) ((B)-(A)) is larger than 0 (MPa) and smaller than 220 (MPa). Therefore, it is possible to improve the practical repetitive bending characteristics while maintaining the surface hardness, and specifically, it is possible to obtain excellent repetitive bending characteristics that do not cause any problem even if the surface is repeatedly bent 200,000 times or more.
  • the laminated film (referred to as "the present laminated film") according to an example of the embodiment of the present invention has a cured resin layer (A) and a cured resin layer (A) on at least one side surface of the base film (referred to as the "main base film”). It is a laminated film having a structure in which a resin layer (B) is sequentially laminated.
  • the laminated film may have other layers as long as it has the above structure.
  • the material and composition of the base film are not limited as long as the film can obtain the necessary and sufficient rigidity and repeatability.
  • the base film may have a single-layer structure or a multi-layer structure.
  • the base film may have four or more layers as long as the gist of the present invention is not exceeded in addition to the two-layer and three-layer structure.
  • the main component resin of each layer is preferably polyester or polyimide (PI).
  • PI polyimide
  • the "main component resin” means the resin having the highest content ratio among the resins constituting the present base film, for example, 50% by mass or more, particularly 70% by mass of the resins constituting the present base film. % Or more, especially 80% by mass or more (including 100% by mass).
  • each layer constituting this base film may contain other resin other than polyester or polyimide, or component other than resin, as long as the main component resin is polyester or polyimide.
  • polyester The polyester (referred to as “the present polyester”) as the main component resin of each layer constituting the present base film may be a homopolyester or a copolymerized polyester.
  • the present polyester is made of a homopolyester, it is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol.
  • aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • aliphatic glycol include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like.
  • examples of the dicarboxylic acid component include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid and the like. be able to.
  • examples of the glycol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like.
  • polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene terephthalate (PBN), polyethylene furanoate (PEF), and the like. Can be done. Of these, PET and PEN are preferable in terms of handleability.
  • PET and PEN are preferable in terms of handleability.
  • the film is referred to as "polyethylene terephthalate film". The same applies when the other resin is the main component resin.
  • a polyimide film is also suitable in addition to the polyester film.
  • the imidization of the polyimide for example, a method of imidizing after polyamic acid polymerization of diamine and dianehydride, particularly aromatic dianhydride and aromatic diamine at a 1: 1 equivalent ratio is exemplified.
  • aromatic dianhydride examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6FDA), 4- (2,5-dioxotetraki-yl) -1, 2,3,4-Tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic dianhydride, PMDA), benzophenonetetra
  • TDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride
  • TDA 4- (2,5-dioxotetraki-yl) -1, 2,3,4-Tetrahydronaphthalene-1,2-dicarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • benzophenonetetra examples thereof include carboxylic acid dianhydride (BTDA), biphenylte
  • aromatic diamine examples include oxydianiline (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMADA), Examples thereof include bistrifluoromethylbenzidine (TFDB), cyclohexanediamine (13CHD, 14CHD), and bisaminohydroxyphenylhexafluoropropane (DBOH). These may be used alone or in combination of two or more.
  • ODA oxydianiline
  • pPDA p-phenylenediamine
  • mPDA m-phenylenediamine
  • pMDA p-methylenedianiline
  • mMADA m-methylenedianiline
  • TFDB bistrifluoromethylbenzidine
  • DBOH bisaminohydroxyphenylhexafluoropropane
  • Each layer constituting the base film may contain a resin other than polyester and polyimide as a main component resin.
  • the main component resins include, for example, epoxy, polyarylate, polyethersulphon, polycarbonate, polyetherketone, polysulphon, polyphenylene sulfide, polyester-based liquid crystal polymer, triacetyl cellulose, cellulose derivative, polypropylene, polyamides, and poly. Cycloolefins and the like can be exemplified.
  • the base film may contain particles for the purpose of imparting slipperiness to the film surface and for the main purpose of preventing scratches in each step.
  • the type of the particles is not particularly limited as long as the particles can be easily slippery.
  • inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, titanium oxide, acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, benzoguanamine.
  • organic particles such as resin. These may be used alone or in combination of two or more of them.
  • precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed can also be used.
  • the shape of the particles is not particularly limited. For example, it may be spherical, lumpy, rod-shaped, flat-shaped, or the like. Further, the hardness, specific gravity, color and the like of the particles are not particularly limited. Two or more kinds of these series of particles may be used in combination, if necessary.
  • the average particle size of the particles is preferably 5 ⁇ m or less, more preferably 0.01 ⁇ m or more or 3 ⁇ m or less, and more preferably 0.5 ⁇ m or more or 2.5 ⁇ m or less. If it exceeds 5 ⁇ m, the surface roughness of the base film may become too rough, and a problem may occur when a cured resin layer made of various cured compositions is formed in a subsequent step.
  • the particle content is preferably 5% by mass or less of the present base film, particularly 0.0003% by mass or more or 3% by mass or less, and among them, 0.01% by mass or more or 2% by mass or less. More preferred. If the average particle size of the particles is within the above range, the surface roughness of the base film is not too coarse, so that a problem occurs when a cured resin layer made of various cured compositions is formed in a subsequent step. Can be suppressed.
  • the method of adding particles to the base film is not particularly limited, and a conventionally known method can be adopted.
  • it can be added at any stage in the production of a raw material resin such as polyester.
  • polyester it is preferable to add it after the esterification or transesterification reaction is completed.
  • the base film may contain, for example, conventionally known antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments, ultraviolet absorbers, and the like as other components. ..
  • the thickness of the base film is preferably, for example, 9 ⁇ m to 125 ⁇ m, more preferably 12 ⁇ m or more or 100 ⁇ m or less, and among them, 20 ⁇ m or more or 75 ⁇ m or less, from the viewpoint that necessary and sufficient rigidity and repeatability can be obtained. Is more preferable.
  • the base film can be formed, for example, by forming a resin composition into a film shape by a melt film forming method or a solution film forming method. In the case of a multi-layer structure, co-extrusion may be performed. Further, it may be uniaxially stretched or biaxially stretched, and a biaxially stretched film is preferable from the viewpoint of rigidity.
  • the tensile elastic modulus (JIS K 7161) of the base film is preferably 2.0 GPa or more, particularly 9.0 GPa or less, and 3 among them, from the viewpoint of obtaining necessary and sufficient rigidity and repetitive bendability. More preferably, it is 0.0 GPa or more or 8.0 GPa or less, and more preferably 3.0 GPa or more or 7.0 GPa or less.
  • the laminated film has a laminated structure in which a cured resin layer (A) is provided on at least one side surface of the base film, and a cured resin layer (B) is further provided on the surface side thereof.
  • the crosslinked resin layer means a layer having a crosslinked resin structure. Whether or not it has a crosslinked resin structure can be determined by analyzing the crystal structure using an apparatus such as TOFSIMS or IR to determine the presence or absence of the crosslinked resin structure. However, the method is not limited to this method.
  • Each of these cured resin layers (A) and (B) is a layer containing a cured resin, in other words, a resin having a crosslinked structure, and the elasticity of the cured resin layer (A) is higher than the elastic modulus of the cured resin layer (B). It is preferable that the rate is lower. Further, regarding the elastic modulus measured by the micro-hardness meter measurement (JIS Z 2255), the difference between the elastic modulus of the cured resin layer (A) and the elastic modulus of the cured resin layer (B) (elastic modulus of the cured resin layer (B)).
  • the elastic modulus of the cured resin layer (A) is preferably larger than 0 (MPa) and smaller than 220 (MPa).
  • MPa 0
  • MPa 220
  • the elastic modulus of the cured resin layer (A) is lower than that of the cured resin layer (B), and the difference between the elastic modulus of the cured resin layer (A) and the elastic modulus of the cured resin layer (B).
  • the difference in elastic modulus between the cured resin layer (A) and the cured resin layer (B) is more preferably 50 MPa or more, particularly 100 MPa or more, and particularly 150 MPa or more from the viewpoint of bendability. Is even more preferable.
  • the difference is preferably 210 MPa or less, more preferably 200 MPa or less, and more preferably 190 MPa or less.
  • the cured resin layer (A) satisfying the condition of the cured resin layer (B)> the cured resin layer (A) ⁇ 10 MPa exists as the lower layer of the cured resin layer (B), so that the stress It is possible to avoid concentration. Further, the cured resin layer (A) can be deformed to absorb an external force. Therefore, it is possible to obtain a laminated film having excellent repetitive bending characteristics.
  • the elastic modulus of the cured resin layer (A) is more preferably 20 MPa or more, particularly preferably 50 MPa or more, and particularly preferably 100 MPa or more.
  • the upper limit is preferably 495 MPa or less, more preferably 400 MPa or less, and more preferably 350 MPa or less.
  • the elastic modulus of the cured resin layer (B) is preferably 100 MPa or more, more preferably 200 MPa or more, and even more preferably 300 MPa or more, from the viewpoint of surface hardness. On the other hand, it is preferably 900 MPa or less, and more preferably 800 MPa or less, and more preferably 700 MPa or less.
  • the elastic properties of the cured resin layer (A) and the cured resin layer (B) are the thickness of each layer, the particle content, the selection of the curable monomer, the composition ratio of the curable monomer, and the crosslinkable monomer. It can be adjusted by changing the content ratio, the cross-linking density (molecular weight between the cross-linking points), the molecular weight of the base polymer forming each layer, the molecular weight of the cured resin composition forming each layer, and the like. However, the method is not limited to these methods.
  • the "base polymer” refers to a resin having the highest mass ratio among the resins constituting each layer.
  • the thickness of the cured resin layer (A) is preferably 10 to 300% of the thickness of the cured resin layer (B), particularly 20% or more or 200% or less, and among them, 30% or more or 100% or less. It is more preferable to have it.
  • the thickness of the cured resin layer (A) is preferably 1.0 ⁇ m or more and 30.0 ⁇ m or less. If it is 1.0 ⁇ m or more, for example, when the cured resin layer (A) is cured by irradiating with ultraviolet rays, insufficient curing due to oxygen inhibition or the like can be prevented. On the other hand, if it is 30.0 ⁇ m or less, it becomes easy to secure the surface smoothness of the laminated film, and it becomes easy to secure the transparency. From this point of view, the layer thickness is preferably 1.0 ⁇ m or more and 30.0 ⁇ m or less, and more preferably 20.0 ⁇ m or less, particularly 10.0 ⁇ m or less, and particularly 5.0 ⁇ m or less.
  • the layer thickness of the cured resin layer (B) is preferably 1.0 ⁇ m or more and 30.0 ⁇ m or less, more preferably 20.0 ⁇ m or less, of which 10.0 ⁇ m or less, and particularly 5 ⁇ m or less. Is even more preferable.
  • the total thickness of the cured resin layer (A) and the cured resin layer (B) is 20.0 ⁇ m or less, preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, and particularly 6 among them, from the viewpoint of bendability. It is preferably 0.0 ⁇ m or less, and 5.0 ⁇ m or less.
  • the cured resin layer (B) may contain particles, or the particle content of the cured resin layer (A) may be adjusted to the cured resin layer (B). It can be adjusted so that the elastic modulus of the cured resin layer (B) is higher than that of the cured resin layer (A). As a specific example of the latter, the particle content of the cured resin layer (A) is 1% by mass to 20% by mass, while the particle content of the cured resin layer (B) is 20% by mass to 60% by mass. The elastic modulus of can be adjusted.
  • the particle content of the cured resin layer (A) is more preferably 1% by mass or more, particularly 2% by mass or more, and more preferably 5% by mass or more, while 20% by mass or less, particularly 15% by mass or less. Among them, it is more preferably 10% by mass or less.
  • the particle content of the cured resin layer (B) is more preferably 20% by mass or more, particularly 25% by mass or more, and more preferably 30% by mass or more, while 60% by mass or less, particularly 55% by mass or less. Above all, it is more preferably 50% by mass or less.
  • the types of particles contained in the cured resin layer (A) and the cured resin layer (B) will be described later.
  • the surface of the cured resin layer (A) may be uneven or flat. Above all, it is preferable that it is flat from the viewpoint of appearance (surface gloss).
  • the surface of the cured resin layer (B) may also be uneven or flat. Above all, it is preferable that it is flat from the viewpoint of appearance (surface gloss).
  • Both the cured resin layers (A) and (B) are preferably transparent in consideration of optical applications.
  • the difference in refractive index between the cured resin layer (A) and the cured resin layer (B) is preferably 0.15 or less.
  • the difference in refractive index between the cured resin layer (A) and the cured resin layer (B) is 0.15 or less, the visibility can be improved.
  • the difference in refractive index between the cured resin layer (A) and the cured resin layer (B) is preferably 0.15 or less, more preferably 0.10 or less, and more preferably 0.05 or less. ..
  • the lower limit of the refractive index difference is 0.
  • Both the cured resin layer (A) and the cured resin layer (B) can be formed by curing a curable composition, that is, a composition having a ability to be cured. More specifically, a curable composition is applied and cured on at least one side surface of the base film to form a cured resin layer (A), and then the curable composition is applied and cured on the curable resin layer (A).
  • This laminated film can be manufactured by forming the cured resin layer (B). At this time, the cured resin layer (A) and the cured resin layer (B) may be cured at the same time.
  • the film is once wound into a roll, the film is unwound again, and the curable composition is applied onto the cured resin layer (A) and cured.
  • the cured resin layer (B) may be formed by forming the cured resin layer (B), or after the cured resin layer (A) is formed on the surface of the base film, the curable composition is continuously applied and cured to form the cured resin layer. (B) may be formed.
  • the method for producing the present laminated film is not limited to such a method.
  • the curable composition for forming the curable resin layer (A) and the curable resin layer (B) includes a curable monomer, a photopolymerization initiator, a solvent, particles, a cross-linking agent, and the like, if necessary. It is preferable to contain the components of. Each will be described below.
  • the cured resin layer (B) is formed by setting the mass average molecular weight of the base polymer forming the cured resin layer (A), that is, the curable monomer to the mass average molecular weight of the curable resin composition forming the cured resin layer (A).
  • the mass average molecular weight of the base polymer, that is, the curable monomer, or the mass average molecular weight of the curable resin composition forming the cured resin layer (B) larger than that of the cured resin layer (A), the cured resin layer It can be adjusted so that the elastic coefficient of (B) becomes high.
  • the total thickness of the cured resin layers (A) and (B) is 30 ⁇ m or less, particularly 20 ⁇ m or less, and among them, 10 ⁇ m or less.
  • the molecular weight is increased by an order of magnitude or more, that is, 10 times or more, from the mass average molecular weight of the base polymer forming the cured resin layer (B) to the mass average molecular weight of the curable resin composition forming the cured resin layer (B). Therefore, the elastic ratio of the cured resin layer (B) can be adjusted to be higher than that of the cured resin layer (A).
  • the mass average molecular weight of the base polymer forming the cured resin layer (A), that is, the curable monomer, or the mass average molecular weight of the curable resin composition forming the cured resin layer (A) is 1,000 or more. It is preferably 3,000 or more, and more preferably 5,000 or more. On the other hand, it is preferably 500,000 or less, more preferably 400,000 or less, and more preferably 250,000 or less.
  • the mass average molecular weight of the base polymer forming the cured resin layer (B), that is, the curable monomer, or the mass average molecular weight of the curable resin composition forming the cured resin layer (B) is preferably 100 or more. Above all, it is more preferably 200 or more, and among them, 400 or more. On the other hand, it is preferably 500,000 or less, more preferably 400,000 or less, and more preferably 250,000 or less.
  • the curable monomer may be any compound that can be cured.
  • those containing at least one selected from the group consisting of crosslinkable monomers, acrylic acid esters, and methacrylic acid esters are preferable from the viewpoint of achieving both excellent surface hardness and repetitive bendability.
  • it is it a comixture consisting of at least two kinds selected from crosslinkable monomers and (meth) acrylic acid esters from the viewpoint of handleability, industrial availability, and cost?
  • it is preferably a mixture consisting of at least two types selected from methacrylic acid esters and vinyl-based monomers.
  • the blending ratio (a / b) is preferably in the range of 90/10 to 10/90 in terms of mass ratio, and more preferably. , 80/20 to 40/60, and more preferably 70/30 to 40/60.
  • (meth) acrylic when used, it means one or both of “acrylic” and “methacrylic”. The same applies to “(meth) acrylate” and “(meth) acryloyl”.
  • (poly) propylene glycol shall mean one or both of “propylene glycol” and “polypropylene glycol”. “(Poly) ethylene glycol” has the same meaning.
  • each main component it is preferable to select each main component so that each of the cured resin layer (A) and the cured resin layer (B) can satisfy at least the elastic modulus and the refractive index described above.
  • the curable monomer used in the curable composition for forming the cured resin layer (A) is preferably selected so as to satisfy the above-mentioned elastic modulus and refractive index.
  • the curable monomer used in the curable composition for forming the cured resin layer (B) is preferably selected so as to satisfy the above-mentioned elastic modulus and refractive index.
  • the crosslinkable monomer refers to a monomer having one or more polymerizable functional groups in one molecule.
  • examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-acryroxy-3-butane, 1-methacryloxy-3-butane, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, and the like.
  • hydroxyl group-containing (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6.
  • -Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylates, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalates, caprolactone-modified 2-hydroxyethyl (meth) acrylates, Dipropylene glycol (meth) acrylate, fatty acid-modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate , Etc.
  • (meth) acrylate-based compound containing one ethylenically unsaturated group; containing two ethylenically unsaturated groups such as glycerindi (meth) acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate.
  • (Meta) acrylate compounds pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol Examples thereof include (meth) acrylate-based compounds containing three or more ethylenically unsaturated groups such as penta (meth) acrylate and ethylene oxide-modified dipentaerythritol penta (meth) acrylate.
  • crosslinkable monomer having a vinyl group examples include glycidyl (meth) acrylate, ⁇ -methylglucidyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.
  • examples thereof include ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, and ⁇ -methyl-p-vinylbenzyl glycidyl ether, among which o-vinylbenzyl glycidyl ether and m.
  • acrylic esters examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylic.
  • Acrylic acid acyclic alkyl esters such as amyl acid, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; cyclic alkyl acrylates such as cyclohexyl acrylate and isobornyl acrylate; Acrylic acid aryl esters such as phenyl acrylate and naphthyl acrylate; functional group-containing acrylic acid acyclic alkyl esters such as 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, and glycidyl acrylate can be exemplified.
  • methacrylic acid esters examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate and methacrylic acid.
  • Amilic methacrylic acid such as amyl acid, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate; cyclic alkyl methacrylate such as cyclohexyl methacrylate and isobornyl methacrylate; Arylmethacrylic acid esters such as phenyl methacrylate; functional group-containing acyclic alkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, and glycidyl methacrylate can be exemplified. These may be used alone or in combination of two or more.
  • Photopolymerization initiator When the curable composition is photocured, it is preferable to add a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited, and examples thereof include a ketone-based photopolymerization initiator and an amine-based photopolymerization initiator.
  • a ketone-based photopolymerization initiator and an amine-based photopolymerization initiator.
  • a sensitizer may be used in combination with the photocuring initiator, if necessary.
  • the sensitizer include aliphatic amines such as n-butylamine, triethylamine, and ethyl p-dimethylaminobenzoate, and aromatic amines.
  • the content of the photopolymerization initiator is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curable composition. More preferably, the range is 1 to 5 parts by mass.
  • the content of the photopolymerization initiator is 1 part by mass or more, the desired polymerization initiation effect can be obtained, and when the content of the photopolymerization initiator is 10 parts by mass or less, the resin layer turns yellow. Can be suppressed.
  • the photocurable initiator and sensitizer are preferably used in a proportion of 20% by mass or less based on the solid content of the photocurable composition.
  • solvent examples include ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and acetone; alcohol solvents such as pentanol, hexanol, heptanol and octanol; ethylene glycol monoethyl.
  • ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and acetone
  • alcohol solvents such as pentanol, hexanol, heptanol and octanol
  • ethylene glycol monoethyl examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl propyl ketone,
  • Ether solvents such as ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, ethyl lactate, methyl lactate, Ester-based solvents such as butyl lactate; organic solvents such as hydrocarbon solvents such as toluene, xylene, solventnaphtha, hexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, and decane can be exemplified. These organic solvents may be used alone or in combination of two or more.
  • the curable composition can contain a predetermined amount of particles in order to improve slipperiness and blocking, and further to adjust the elastic modulus of each layer.
  • the particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, titanium oxide, acrylic resin, styrene resin, urea resin, and phenol resin.
  • Organic particles such as epoxy resin and benzoguanamine resin can be mentioned. These may be used alone or in combination of two or more of them. Further, during the polyester manufacturing process, precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed can also be used.
  • the shape of the particles is not particularly limited. For example, it may be spherical, lumpy, rod-shaped, flat-shaped, or the like. Further, the hardness, specific gravity, color and the like of the particles are not particularly limited. Two or more kinds of these series of particles may be used in combination, if necessary.
  • the thickness is preferably 5 ⁇ m or less, more preferably 0.01 ⁇ m or more or 3 ⁇ m or less, and more preferably 0.5 ⁇ m or more or 2.5 ⁇ m or less.
  • Cross-linking agent From the viewpoint of improving chemical resistance or elastic modulus, it is preferable to add a cross-linking agent.
  • the cross-linking agent referred to here means a cross-linking agent other than the above-mentioned cross-linking monomer.
  • examples of the cross-linking agent include oxazoline compounds, isocyanate compounds, epoxy compounds, melamine compounds, and carbodiimide compounds. Above all, from the viewpoint of improving adhesion, it is more preferable to use at least one of an oxazoline compound or an isocyanate compound.
  • the above-mentioned oxazoline compound used as a cross-linking agent is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and it is prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. be able to.
  • the addition polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-.
  • Examples thereof include oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and one or a mixture of two or more thereof can be used. .. Among them, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
  • the other monomer is not limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (the alkyl group is a methyl group, an ethyl group, an n-propyl group, or an isopropyl).
  • (Meta) acrylic acid esters such as group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid , Unsaturated carboxylic acids such as styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N- Alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2
  • the amount of the oxazoline group of the oxazoline compound is preferably 0.5 to 10 mmol / g, particularly 1 mmol / g or more or 9 mmol / g or less, and 3 mmol / g or more or 8 mmol / g or less among them. Among them, it is more preferably 4 mmol / g or more or 6 mmol / g or less.
  • the isocyanate compound used as a cross-linking agent is, for example, an isocyanate or a compound having an isocyanate derivative structure typified by blocked isocyanate.
  • the isocyanate has, for example, aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyldiisocyanate, phenylenedi isocyanate and naphthalenedi isocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanates, methylene diisocyanates, propylene diisocyanates, lysine diisocyanates, trimethylhexamethylene diisocyanates, hexamethylene diisocyanates, cyclohexane diisocyanates, methylcyclohexane diisocyanates, isophorone diisocyanates, methylenebis (4-cyclohexylisocyanates), isopropyridene dicyclohexyldiisocyanates, etc.
  • the alicyclic isocyanate of the above can be exemplified.
  • polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimides of these isocyanates can also be mentioned. These may be used alone or in combination of two or more.
  • isocyanates aliphatic isocyanates or alicyclic isocyanates are preferable as measures against yellowing due to ultraviolet irradiation.
  • the blocking agent When used in the state of blocked isocyanate, the blocking agent includes, for example, phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol, and alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol.
  • phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol
  • alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol.
  • Compounds, active methylene compounds such as methyl isobutanoyl acetate, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, ⁇ -caprolactam, ⁇ -valerolact
  • Lactam compounds such as diphenylaniline, aniline, ethyleneimine, acetoanilide, acid amide compounds of acetate amide, formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime and other oxime compounds. These can be used alone or in combination of two or more.
  • the isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. From the viewpoint of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.
  • the epoxy compound used as a cross-linking agent is a compound having an epoxy group in the molecule, and is, for example, a condensate of epichlorohydrin and a hydroxyl group or an amino group such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, or bisphenol A. Examples thereof include polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds.
  • polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyltris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane.
  • polyglycidyl ether and the diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
  • Polypropylene glycol diglycidyl ether, Polytetramethylene glycol diglycidyl ether, Monoepoxy compounds include, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenylglycidyl ether, glycidylamine compounds N, N, N', N ′ -Tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like can be mentioned. From the viewpoint of improving adhesion, a polyether epoxy compound is preferable. Further, as the amount of the epoxy group, a polyepoxy compound having trifunctional or higher functionalities is preferable to bifunctional.
  • the above-mentioned melamine compound used as a cross-linking agent is a compound having a melamine skeleton in the compound, for example, an alkylolated melamine derivative or a compound obtained by reacting an alkylolated melamine derivative with an alcohol to partially or completely etherify. , And a mixture thereof can be used.
  • the alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
  • the melamine compound may be either a monomer or a multimer of a dimer or more, or a mixture thereof may be used.
  • a type in which urea or the like is copolymerized with a part of melamine, or a catalyst can be used in combination to improve the reactivity of the melamine compound.
  • the content of the cross-linking agent is preferably 10 parts by mass or more, particularly 20 parts by mass or more, and 25 parts by mass among them, with respect to 100 parts by mass of the curable monomer, from the viewpoint of obtaining good coating film strength.
  • the above is more preferable.
  • it is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and more preferably 40 parts by mass or less.
  • the carbodiimide compound used as a cross-linking agent is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule.
  • a polycarbodiimide-based compound having two or more in the molecule is more preferable for better adhesion and the like.
  • This carbodiimide compound can be synthesized by a conventionally known technique, and a condensation reaction of a diisocyanate compound is generally used.
  • the diisocyanate compound is not particularly limited, and any aromatic or aliphatic type can be used.
  • tolylene diisocyanate xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, etc.
  • examples thereof include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanis, and dicyclohexylmethane diisocyanate.
  • the content of the carbodiimide group contained in the carbodiimide compound is a carbodiimide equivalent (weight [g] of the carbodiimide compound for giving 1 mol of the carbodiimide group), preferably 100 to 1000, and more than 250 or 800 or less. Among them, it is more preferably 300 or more or 700 or less. By using in the above range, the durability of the coating film is improved.
  • polyol compound examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,4-butane.
  • Diol 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2,2-dimethylolheptan, tri Methylene glycol, 1,4-tetramethylene glycol, dipropylene glycol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 2,4-diethyl-1,5-pentamethylenediol, water Additive bisphenol A, hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 2,2,4-trimethyl-1,3-pentanediol, N, N-bis- (2-hydroxy) Low molecular weight diols such as ethyl) dimethyl hydantin; polyether polyols, polyester
  • polyether polyol examples include oxyalkylene structure-containing polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block co-weights of these polyalkylene glycols. Coalescence is mentioned.
  • an oxyalkylene structure-containing polyether polyol is preferable, and the number of carbon atoms in the alkylene structure is preferably 2 to 6, particularly preferably 2 to 4, and even more preferably 4.
  • polyester-based polyol examples include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Examples thereof include reactants.
  • the polyhydric alcohol examples include the low molecular weight diols mentioned above.
  • polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecandioic acid; 1,4 An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid can be mentioned.
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and a phosgene; a transesterification reaction product of a carbonic acid ester and a polyhydric alcohol.
  • Examples of the polyhydric alcohol include the low molecular weight diol and the like, and examples of the alkylene carbonate include ethylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Examples include diphenyl carbonate.
  • the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.
  • Examples of the curable composition for forming the cured resin layers (A) and (B) include a combination of a hydroxyl group-containing (meth) acrylate compound and an isocyanate compound, or a hydroxyl group-containing (meth) acrylate compound and an isocyanate. Examples thereof include urethane (meth) acrylate compounds obtained by combining a compound and a polyol compound.
  • a combination of acrylic acid esters and a crosslinkable monomer having a vinyl group a combination of methacrylic acid esters and a crosslinkable monomer having a vinyl group, acrylic acid esters and a hydroxyl group-containing (meth) acrylate type.
  • examples thereof include a combination with a compound, a combination of methacrylic acid esters and a hydroxyl group-containing (meth) acrylate-based compound, and the like. However, it is not limited to these.
  • the curable composition for forming the cured resin layers (A) and (B) preferably has a viscosity at 25 ° C. of 10 to 60 mPa ⁇ s as measured by an E-type viscometer in order to improve coatability. Above all, it is more preferably 30 mPa ⁇ s or less, among them 20 mPa ⁇ s or less, among them 15 mPa ⁇ s or less, and among them 12 mPa ⁇ s or less.
  • the cured resin layer (A) is coated with a curable composition using a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, and inkjet, and then light. It is preferably formed by irradiation, for example, irradiation with ultraviolet rays and curing.
  • a curable composition is applied by using a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, and inkjet. After that, it is preferably formed by irradiating with light, for example, ultraviolet rays and curing.
  • the surface hardness of the film specifically, the pencil hardness on the surface of the cured resin layer (B) can be 2H or more, and in particular, 3H or more.
  • the laminated film having the above structure is provided with a cured resin layer (A) on the surface of the base film, and the elasticity of the cured resin layer (A) is higher than that of the cured resin layer (B).
  • R repeated bendability
  • the film haze is preferably 5.0% or less, more preferably 4.0% or less, and particularly preferably 3.0% or less. ..
  • a resin component composed of an acrylic monomer which has been considered difficult to use, can also be used, which has an advantage of increasing the degree of freedom when designing a laminated film. .. Furthermore, it is presumed that the two-layer structure of the cured resin layer (A) and the cured resin layer (B) can be expected to disperse stress in the thickness direction, which can contribute to further improvement of bending durability.
  • the elastic modulus of the cured resin layer (A) is set to be lower than the elastic modulus of the cured resin layer (B)
  • the base film used is constructed as necessary. It was necessary to review the structural design of the raw material and further increase the tensile elastic modulus.
  • a target surface hardness for example, 2H or more
  • the base film used is constructed as necessary. It was necessary to review the structural design of the raw material and further increase the tensile elastic modulus.
  • the two-layer structure of the cured resin layer (A) and the cured resin layer (B) as described above it is possible to appropriately select a general-purpose base film on the market. It has the advantage of increasing the degree of freedom in terms of selecting the base film.
  • This laminated film has excellent surface hardness, practical repetitive bendability, and can also obtain transparency, so it is used for surface protection, displays, and especially for front panels. Can be used for. For example, it can be suitably used as a surface protective film, particularly a surface protective film for a display, and among them, a surface protective film for a flexible display. However, the use of this laminated film is not limited to these uses.
  • X to Y (X, Y are arbitrary numbers) is described, it means “X or more and Y or less” and “preferably larger than X” or “preferably Y”, unless otherwise specified. It also includes the meaning of “smaller”.
  • X or more (X is an arbitrary number) is described, it includes the meaning of "preferably larger than X” and is described as “Y or less” (Y is an arbitrary number) unless otherwise specified. In this case, unless otherwise specified, it also includes the meaning of "preferably smaller than Y”.
  • a borazon cutting edge having a width of 300 ⁇ m is set in the sample in which a notch having a width of 300 ⁇ m is made in advance, and each cured resin layer is measured at an arbitrary depth, a horizontal speed of 1 ⁇ m / s, and a vertical speed of 0.5 ⁇ m / s.
  • the film thickness was measured.
  • a boron nitride blade having a blade width dimension of 0.3 mm, a squeeze angle of 20 °, and a niger angle of 10 ° was used. The material strength was measured from the vertical displacement position and the cutting force, and the thickness of each layer was confirmed.
  • Pencil hardness (hard coat property) The pencil hardness was evaluated with a pencil hardness tester (manufactured by Yasuda Seiki Co., Ltd.) under a load condition of 750 g in accordance with JIS K 5600-5-4. Based on the result, it was judged according to the following criteria. (Criteria) A (good): Pencil hardness is 3H or more. B (little good): Pencil hardness is 2H or more and less than 3H. C (poor): Pencil hardness is less than 2H.
  • Refractive index of the cured resin layer (A) and the cured resin layer (B) The refractive index of each layer was determined by Abbe measurement. Based on the result, it was judged according to the following criteria.
  • a (good) The difference in refractive index between the cured resin layer (A) and the cured resin layer (B) is 0.15 or less.
  • Adhesion between the cured resin layer (A) and the cured resin layer (B) In accordance with JIS K 5600-5-6, the cured resin layer (A) and the cured resin layer (A) are subjected to the cross-cut method (10 x 10 100 squares). The adhesion with the cured resin layer (B) was evaluated. Based on the result, it was judged according to the following criteria. (Criteria) A (good): Good adhesion on the entire surface (area of adhesion: 100%) B (little good): Partially peeled off. (Area in close contact: 50% or more and less than 100%) C (poor): Partial peeling or total peeling occurs. (Area in close contact: less than 50%)
  • C (poor): Transparency, hard coat property, repetitive bendability, bend direction, refractive index difference between the cured resin layer (A) and the cured resin layer (B), the cured resin layer (A) and the cured resin layer (B), the cured resin layer (A) and the cured resin layer (B) (
  • the adhesion of B at least one of the hard coat property, the repeat bendability and the bend directionability is C, and the rest is A or B.
  • ⁇ Base film F2> Made by Teijin: Polyethylene naphthalate biaxially stretched film (grade name "Theonex W51”), thickness: 50 ⁇ m, tensile modulus (JIS K 7161) 6.4 GPa.
  • V-65 2,2'-azobis (2,4-dimethylvaleronitrile)
  • Fuji Film Wako Pure Chemical Industries, Ltd. the temperature inside the system was raised to 65 ° C.
  • 0.5 parts by mass of V-65 was further added and the mixture was stirred at 65 ° C. for 3 hours.
  • Example 1 The curable composition a prepared as described below is applied onto the base film F2 with a bar coater at 25 ° C. so that the coating thickness (after drying) is 2.0 ⁇ m, and 1 min at 90 ° C. It was dried by heating.
  • the curable composition b prepared as described below was applied with a bar coater so as to coat the cured resin layer (A) so that the coating thickness (after drying) was 3.0 ⁇ m, and 90 After drying by heating at ° C.
  • the cured resin layers (A) and (B) are cured by irradiating with ultraviolet rays of 400 mJ / cm 2 in an integrated light amount, and the base film F2 / cured resin layer (A) / A laminated film having a laminated structure of the cured resin layer (B) was obtained.
  • curable composition a A curable composition a was prepared by adding 5 parts by mass of a photopolymerization initiator to 100 parts by mass of the acrylate (A). The mass average molecular weight of the curable composition a was 15,000, and the refractive index of the cured resin layer (A) was 1.53.
  • Example 2 A laminated film was obtained in the same manner as in Example 1 except that the thicknesses of the cured resin layer (A) and the cured resin layer (B) were changed in Example 1.
  • Example 3 In Example 1, the curable composition b was changed to the next curable composition b1 and produced in the same manner as in Example 1 to obtain a laminated film.
  • curable composition b1 67 parts by mass of alumina particles (ALTPGDA manufactured by CIK Nanotech Co., Ltd.) and 5 parts by mass of a photopolymerization initiator were added to 100 parts by mass of acrylate (A) to prepare a curable composition b1.
  • the mass average molecular weight of the curable composition b1 was 15,000, and the refractive index of the cured resin layer (B) was 1.54.
  • Example 4 In Example 1, a laminated film was obtained in the same manner as in Example 1 except that the base film F2 was changed to the above base film F1.
  • Example 5 In Example 1, a laminated film was obtained in the same manner as in Example 1 except that the base film F2 was changed to the base film F3.
  • Example 1 Similar to Example 1, the curable composition a is applied onto the base film F2 with a bar coater at 25 ° C. so that the coating thickness (after drying) is 5.0 ⁇ m, and heated at 90 ° C. for 1 min. After drying, a cured resin layer (A) having a thickness (after drying) of 5.0 ⁇ m was formed by irradiating ultraviolet rays of 400 mJ / cm 2 with an integrated light amount to obtain a laminated film. At this time, the cured resin layer (B) was not formed.
  • Example 2 Similar to Example 1, the curable composition b was applied onto the base film F2 with a bar coater so that the coating thickness (after drying) was evenly 5.0 ⁇ m, and heated at 90 ° C. for 1 min. After drying, a cured resin layer (B) having a thickness (after drying) of 5.0 ⁇ m was formed by irradiating ultraviolet rays of 400 mJ / cm 2 with an integrated light amount to obtain a laminated film. At this time, the cured resin layer (A) was not formed.
  • curable composition a1 A curable composition a1 was prepared by adding 5 parts by mass of a photopolymerization initiator to 100 parts by mass of urethane acrylate (Shikou "UV-6640B” manufactured by Mitsubishi Chemical Corporation). The curable composition a1 had a mass average molecular weight of 5,000 and the refractive index of the cured resin layer (A) was 1.51.
  • curable composition b2 was prepared by adding 80 parts by mass of DPHA and 5 parts by mass of a photopolymerization initiator to 100 parts by mass of urethane acrylate (Shikou "UV-1700B” manufactured by Mitsubishi Chemical Corporation).
  • the curable composition b2 had a mass average molecular weight of 2,000, and the refractive index of the cured resin layer (B) was 1.51.
  • DPHA Aronix M-404 (dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd.
  • Example 4 A laminated film was obtained in the same manner as in Example 1 except that the order of applying the curable composition a and the curable composition b was reversed in Example 1.
  • curable composition a2 was prepared by adding 100 parts by mass of 6 molEO-modified DPHA, 200 parts by mass of silica particles (MEK-AC-2140Y manufactured by Nissan Chemical Industries, Ltd.), and 5 parts by mass of a photopolymerization initiator to 100 parts by mass of the above DPHA. ..
  • the mass average molecular weight of the curable composition a2 was 790, and the refractive index of the cured resin layer (A) was 1.50.
  • curable composition b3 was prepared by adding 100 parts by mass of pentaerythritol triacrylate and 5 parts by mass of a photopolymerization initiator to 100 parts by mass of urethane acrylate (Shikou "UV-7650B” manufactured by Mitsubishi Chemical Corporation).
  • the curable composition b3 had a mass average molecular weight of 2,300, and the refractive index of the cured resin layer (B) was 1.51.
  • curable composition a3 To 100 parts by mass of the following (meth) acrylic polymer solution, 6 parts by mass of the following polyisocyanate and 23 parts by mass of DPHA were added to prepare a curable composition a3.
  • the mass average molecular weight of the curable composition a3 was 15,000, and the refractive index of the cured resin layer (A) was 1.50.
  • ((Meta) acrylic polymer solution) 283 parts by mass of methylisobutylketone, 149 parts by mass of glycidyl methacrylate, 276 parts by mass of methyl methacrylate, and 25 parts by mass of t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Emulsifier Co., Ltd., trade name: Perbutyl O) was synthesized to obtain a precursor, and 76 parts by mass of acrylic acid was added thereto for synthesis to obtain 1000 parts by mass (50.0% by mass) of a methylisobutylketone solution of a (meth) acrylic polymer.
  • the property values of the (meth) acrylic polymer were as follows. Weight Average Molecular Weight (Mw): 15,000, Theoretical acryloyl group equivalent in terms of solid content: 478 g / eq, Hydroxy group value: 117 mgKOH / g.
  • curable composition b4 was prepared by adding 6 parts by mass of the following polyisocyanate and 8 parts by mass of the DPHA to 100 parts by mass of the following (meth) acrylic polymer solution.
  • the curable composition b4 had a mass average molecular weight of 40,000, and the refractive index of the cured resin layer (B) was 1.52.
  • ((Meta) acrylic polymer solution) 229 parts by mass of methyl isobutyl ketone was charged into a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, and the temperature was raised to 110 ° C. with stirring, and then glycidyl methacrylate 309
  • a mixed solution consisting of 10 parts by mass of mass, 34 parts by mass of methyl methacrylate, and 10 parts by mass of t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Emulsifier Co., Ltd., product name: perbutyl O) was added dropwise over 3 hours. After further dropping, the mixture was kept at 110 ° C. for 15 hours.
  • the cured resin layer (A) and the cured resin layer (B) are sequentially laminated on the surface of the base film, and the elastic modulus is described.
  • By having the characteristics of being larger than MPa) and smaller than 220 (MPa), it has a high level of surface hardness (for example, 2H or more in pencil hardness evaluation) and repetitive bendability (under the condition of R 2.5, 200,000).
  • the elastic modulus of each of the cured resin layers (A) and (B) should be adjusted by adjusting the thickness and composition of each of the cured resin layers (A) and (B), for example, the particle content.
  • a resin component composed of an acrylic monomer which has been considered difficult to use, can also be used, which has an advantage of increasing the degree of freedom when designing a laminated film. ..
  • the difference ((B)-(A)) between the elastic modulus of the cured resin layer (A) and the elastic modulus of the cured resin layer (B) is larger than 0 (MPa) and smaller than 220 (MPa), it can be used. It was also found that it is not necessary to make the tensile elastic modulus of the base film to be extremely large. Conventionally, in a laminated film having a surface layer having a high surface hardness, when designing a target surface hardness to a desired level (for example, 2H or more), the base film used is constructed as necessary. The structural design of the raw material had to be reviewed to further increase the tensile modulus.
  • the base film can be appropriately selected. It has the advantage of increasing the degree of freedom in terms of selection.
  • the elastic modulus of the cured resin layer (A) measured by the micro-hardness meter measurement (JIS Z 2255) is 330 MPa is examined.
  • JIS Z 2255 micro-hardness meter measurement

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film multicouche agencé de sorte qu'une couche de résine durcie (A) et une couche de résine durcie (B) soient séquentiellement superposées sur la surface d'un film de matériau de base, et qui est caractérisé en ce que, par rapport au module élastique tel que déterminé par mesure à l'aide d'une jauge de microdureté (JIS Z 2255), le module élastique de la couche de résine durcie (B) est supérieur au module élastique de la couche de résine durcie (A), et la différence entre le module élastique de la couche de résine durcie (A) et le module élastique de la couche de résine durcie (B) est supérieure à 0 (MPa), mais inférieure à 220 (MPa).
PCT/JP2020/007376 2019-05-22 2020-02-25 Film multicouche WO2020235164A1 (fr)

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JP2021520055A JP7302656B2 (ja) 2019-05-22 2020-02-25 積層フィルム
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CN115404020A (zh) * 2022-10-14 2022-11-29 深圳市高仁电子新材料有限公司 一种用于全贴合和柔性折叠屏的三层结构的丙烯酸类光学胶膜及其制备方法
WO2023085184A1 (fr) * 2021-11-11 2023-05-19 味の素株式会社 Feuille de résine multicouche

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WO2016163554A1 (fr) * 2015-04-10 2016-10-13 富士フイルム株式会社 Film transparent, plaque polarisante, et dispositif d'affichage d'image
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WO2023085184A1 (fr) * 2021-11-11 2023-05-19 味の素株式会社 Feuille de résine multicouche
CN115404020A (zh) * 2022-10-14 2022-11-29 深圳市高仁电子新材料有限公司 一种用于全贴合和柔性折叠屏的三层结构的丙烯酸类光学胶膜及其制备方法
CN115404020B (zh) * 2022-10-14 2023-06-30 深圳市高仁电子新材料有限公司 一种用于全贴合和柔性折叠屏的三层结构的丙烯酸类光学胶膜及其制备方法

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JPWO2020235164A1 (fr) 2020-11-26
KR20220013391A (ko) 2022-02-04
CN113795375A (zh) 2021-12-14
TW202106501A (zh) 2021-02-16
JP7302656B2 (ja) 2023-07-04

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