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WO2019021557A1 - Corps stratifié et dispositif souple pourvu dudit corps stratifié - Google Patents

Corps stratifié et dispositif souple pourvu dudit corps stratifié Download PDF

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Publication number
WO2019021557A1
WO2019021557A1 PCT/JP2018/016763 JP2018016763W WO2019021557A1 WO 2019021557 A1 WO2019021557 A1 WO 2019021557A1 JP 2018016763 W JP2018016763 W JP 2018016763W WO 2019021557 A1 WO2019021557 A1 WO 2019021557A1
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WIPO (PCT)
Prior art keywords
group
adhesive
laminate
cationically polymerizable
compound
Prior art date
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PCT/JP2018/016763
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English (en)
Japanese (ja)
Inventor
西尾直高
水田智也
岩谷真男
中村敏和
Original Assignee
株式会社ダイセル
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
Priority claimed from JP2018073646A external-priority patent/JP2019025899A/ja
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Priority to EP18839370.6A priority Critical patent/EP3659799A4/fr
Priority to US16/634,491 priority patent/US20200230925A1/en
Priority to KR1020207005395A priority patent/KR20200037301A/ko
Priority to CN201880048685.3A priority patent/CN111093978A/zh
Publication of WO2019021557A1 publication Critical patent/WO2019021557A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils

Definitions

  • the present invention relates to a laminate including a thinned glass plate, and a laminate having excellent bending durability, and a flexible device including the laminate.
  • the present application is related to Japanese Patent Application No. 2017-147077 filed on July 28, 2017, Japanese Patent Application No. 2018-73646 filed on April 6, 2018, Japanese Patent Application No. 2018-73647, Japanese Patent Application No. 2018- Priority is claimed on Japanese Patent Application No. 73648, Japanese Patent Application No. 2018-73649, Japanese Patent Application No. 2018-73650, Japanese Patent Application No. 2018-73651, and Japanese Patent Application No. 2018-73652, the contents of which are incorporated herein by reference.
  • glass plates have been used as touch panels for portable information terminals such as smartphones and tablets, and displays such as organic EL displays, for reasons of high hardness, transparency, superior texture, etc., but glass plates are flexible. The problem is that it lacks sex and is easily broken.
  • Patent Document 1 describes a thinned glass plate, and describes that the thinned glass plate is excellent in flexibility (that is, it has flexibility and can be slowly bent).
  • the thinned glass plate has flexibility, it is easily broken and difficult to handle, and the bending durability is poor.
  • the inventors of the present invention are laminates in which a thinned glass plate and a resin film are bonded by an adhesive, and the flexibility, bending durability, curl resistance, And the laminated body which is excellent in handleability was found.
  • the present invention has been completed based on these findings.
  • the present invention provides a laminate having a configuration in which a glass plate having a thickness of 150 ⁇ m or less and a resin film are laminated via an adhesive layer, and the bending durability according to the following test is 10 or more.
  • Flexural endurance test When the laminate is stretched, it is bent 180 ° so that the bending radius is 3 mm in the direction in which the surface of the glass plate is concave, and the operation of extending again is regarded as one set, and the operation is performed at a speed of 43 sets per minute. The number of sets before the crack is generated in the laminate at the time of installation is used as an index of bending durability
  • the present invention also provides the above laminate wherein the adhesion (based on JIS K 5600-5-6) of the adhesive layer to the glass plate is classified into 0 to 2 in the 6-step classification test.
  • the present invention also provides the above laminate, wherein the storage elastic modulus at 20 ° C. of the adhesive layer is 10 MPa or more, which is measured using a dynamic viscoelasticity measurement device.
  • the present invention also provides the above laminate wherein the glass transition temperature of the adhesive layer is less than 5 ° C., which is measured using a dynamic viscoelasticity measurement device.
  • the present invention also provides the above laminate wherein the total thickness of the laminate is 300 ⁇ m or less.
  • the present invention also provides the above laminate wherein the total light transmittance of the laminate is 80% or more.
  • the present invention also provides the above laminate wherein the adhesive layer is a cured product of the following adhesive (1).
  • Adhesive (1) containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule And a compound having at least one hydroxyl group in an amount of 10% by weight or more of the total amount of the cationically polymerizable monomer, and the following formula (b) (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more) And 5 wt% or more of the total amount of the cationically polymerizable monomers.
  • the adhesive (1) is further added as a cationically polymerizable monomer, and the following formula (b ′) (Wherein, X represents a single bond or a linking group)
  • the above-mentioned laminate contains the compound represented by 10% by weight or more of the total amount of the cationically polymerizable monomers.
  • the present invention also provides the above laminate, wherein the adhesive layer is a cured product of an acrylic urethane adhesive (2) containing urethane (meth) acrylate or a polymer thereof.
  • the present invention also provides the laminate, wherein the adhesive layer is a cured product of a vinyl acetate adhesive (3) containing a vinyl acetate polymer.
  • the present invention also provides the above laminate, wherein the minimum bending radius of the glass sheet is 3 mm or less.
  • the present invention also provides the above laminate wherein the resin film is laminated such that the MD direction of the resin film is along the bending direction of the laminate.
  • the present invention also provides a laminate having a configuration in which a glass plate having a thickness of 150 ⁇ m or less and a resin film are laminated via an adhesive layer made of a cured product of the following adhesive.
  • Adhesive containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule, and a hydroxyl group 10% by weight or more of the total amount of the cationically polymerizable monomers, containing a compound having at least one, and the following formula (b) (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more) And 5 wt% or more
  • the present invention also provides a wound body obtained by winding the above laminate in a roll.
  • the present invention also provides a member for a flexible device comprising the above-mentioned laminate.
  • the present invention also provides a flexible device provided with the above laminate.
  • the present invention also includes a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule.
  • a compound having at least one hydroxyl group in an amount of 10% by weight or more of the total amount of the cationically polymerizable monomer and the following formula (b) (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more)
  • R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more
  • the adhesive for glass which contains the compound represented by these 5 weight% or more of the cationically polymerizable monomer whole quantity is provided.
  • the present invention also includes a glass plate and a resin film having a thickness of 150 ⁇ m or less, a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, a vinyl ether group, an epoxy group, and one molecule in one molecule.
  • a compound having at least one cationically polymerizable group selected from oxetanyl groups and at least one hydroxyl group is contained in an amount of 10% by weight or more of the total amount of cationically polymerizable monomers, and the following formula (b) (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more) Are bonded with an adhesive (1), an acrylic urethane adhesive (2), or a vinyl acetate adhesive (3) containing 5% by weight or more of the compound represented by the following formula: There is provided a method of producing a laminate, wherein the laminate is obtained by curing an agent.
  • the laminate of the present invention is excellent in flexibility and bending durability, and further excellent in curl resistance. Moreover, it is hard to be cracked compared with thin glass single-piece
  • the adhesive (1) can form a cured product having excellent adhesion to glass. Therefore, it can be suitably used as an adhesive for glass (that is, an adhesive used for bonding glass).
  • the adhesive (1) has a low viscosity and excellent coatability before being irradiated with ultraviolet light, and is thus irradiated with ultraviolet light, It is possible to cure rapidly even in the presence of oxygen and form a cured product having excellent adhesion to glass, so there is no need to perform primer treatment etc. on the surface of glass in advance, it is possible It can be applied and adhered, and it is excellent in workability. In addition, since the film has low cure shrinkage, the occurrence of curling in the laminate can also be prevented.
  • FIG. 1 It is a schematic diagram which shows the measuring method of the floating amount of a test piece at the time of evaluating curl resistance.
  • Test method of bending durability (R bending method) in the present invention one set of operation of bending the laminate 180 ° so that the bending radius (R) is 3 mm in the direction in which the surface of the glass plate is concave and extending
  • R bending method Test method of bending durability
  • side view It is the figure which expanded and showed (4) of FIG.
  • the laminate of the present invention has a configuration in which a glass plate having a thickness of 150 ⁇ m or less and a resin film are laminated via an adhesive layer. That is, it has at least a three-layer laminated structure of thinned glass plate / adhesive layer / resin film.
  • the laminate of the present invention may have other layers in addition to the three layers of the thinned glass plate / adhesive layer / resin film, and the surface of the thinned glass plate on the side opposite to the adhesive layer laminating surface Furthermore, one or more other layers may be laminated, and one or more other layers may be laminated on the surface of the resin film opposite to the adhesive layer laminated surface. It is good.
  • the layered product of the present invention has the above-mentioned composition, stress load to a glass board at the time of making it bend can be eased by the above-mentioned adhesion layer, and it can exhibit outstanding bending endurance. That is, generation of cracks in the glass plate can be suppressed even if the bending and stretching are repeated.
  • the bending durability according to the following test is 10 or more, preferably 100 or more, particularly preferably 1000 or more, more preferably 2000 or more, and most preferably 10000 or more.
  • Flexural endurance test When the laminate is stretched, it is bent 180 ° so that the bending radius is 3 mm in the direction in which the surface of the glass plate is concave, and the operation of extending again is regarded as one set, and the operation is performed at a speed of 43 sets per minute. The number of sets before the crack is generated in the laminate at the time of installation is used as an index of bending durability
  • the total thickness of the laminate is, for example, 300 ⁇ m or less, preferably 250 ⁇ m or less, particularly preferably 200 ⁇ m or less, and most preferably 150 ⁇ m or less, in that the bending durability is extremely excellent.
  • the lower limit of the total thickness is, for example, 50 ⁇ m, preferably 75 ⁇ m, and particularly preferably 100 ⁇ m.
  • the laminate of the present invention is excellent in transparency, and the total light transmittance is, for example, 80% or more, preferably 85% or more, particularly preferably 88% or more, and most preferably 90% or more.
  • a wound body can be formed by winding in a roll.
  • the wound body can be stored without bulk and is easy to carry.
  • the laminate of the present invention is, for example, a member for a flexible device [an electronic material / electronic component requiring flexibility, for example, a touch panel such as a portable information terminal (for example, a smartphone, a tablet), a display such as an organic EL display, Can be suitably used as a protective film etc.].
  • a touch panel such as a portable information terminal (for example, a smartphone, a tablet), a display such as an organic EL display, Can be suitably used as a protective film etc.
  • the thickness of the glass plate constituting the laminate of the present invention is 150 ⁇ m or less, preferably 100 ⁇ m or less, particularly preferably 75 ⁇ m or less, and most preferably 50 ⁇ m or less. Moreover, in terms of extremely excellent bending durability, the thickness is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
  • a laminate having excellent bending durability by using a glass plate having a minimum bending radius of 3 mm or less that is, a glass plate which can be bent at least once until the bending radius becomes 3 mm or less
  • the glass plate Is preferable in that the probability of obtaining is dramatically improved.
  • Glass plates with a minimum bending radius of more than 3 mm often have small scratches on the surface or end face of the glass plate that can not be visually confirmed, and if such a glass plate is used, the resulting laminate will be refracted There is a tendency for the possibility of insufficient durability to increase.
  • resin film As a resin film which comprises the laminated body of this invention, it is preferable to use a plastic film which is excellent in transparency (total light transmittance is 80% or more, for example).
  • thermoplastic plastics examples include thermoplastic plastics and thermosetting plastics.
  • thermoplastics include polyethylene, polypropylene, polyethylene terephthalate (PET), polyvinyl chloride, acrylonitrile butadiene styrene (ABS), polyvinylidene chloride, cellulose acetate (eg, triacetyl cellulose (TAC)), polyethylene General-purpose plastics such as naphthalate (PEN); engineering plastics such as polyamide, polycarbonate and polyvinylidene fluoride; polysulfone, polyethersulfone, polyphenylene sulfide, polyamidoimide (PAI), polyimide (PI), polyetheretherketone (PEEK), etc. Super engineering plastics etc. are included.
  • the thermosetting plastic includes, for example, phenol resin, melamine resin, polyurethane, silicone resin and the like.
  • a plastic film made of at least one material selected from PET, PAI, PI, cellulose acetate (especially TAC), and PEN is preferable as the resin film, in particular, in that it is extremely excellent in bending durability.
  • the plastic film which consists of, PET or PI is preferable.
  • the thickness of the resin film is, for example, 150 ⁇ m or less, preferably 140 ⁇ m or less, particularly preferably 120 ⁇ m or less, most preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, particularly preferably 70 ⁇ m or less.
  • 10 micrometers or more are preferable at the point which is very excellent in bending
  • the thickness of the adhesive layer constituting the laminate of the present invention is, for example, 100 ⁇ m or less, preferably 80 ⁇ m or less, particularly preferably 50 ⁇ m or less, and most preferably 30 ⁇ m or less.
  • the lower limit of the thickness is, for example, 1 ⁇ m, preferably 5 ⁇ m.
  • the adhesive layer is in the above range, it is preferable in that it has both adhesiveness and resistance to bending, and transparency (total light transmittance is, for example, 80% or more).
  • the thickness of the adhesive layer is excessive, the adhesion is improved but the bending durability and the transparency tend to be lowered.
  • the said contact bonding layer (preferably, the contact bonding layer which consists of a hardened
  • the adhesion of the adhesive layer (or the cured product of the adhesive) to the glass plate and / or the resin film is classified, for example, in the six-step classification test of the cross cut method (based on JIS K 5600-5-6). It is ⁇ 2.
  • the elastic modulus (for example, Young's modulus at 25 ° C.) of the adhesive layer is, for example, 0.01 MPa to 1000 GPa.
  • the laminate is preferably from the viewpoint of imparting excellent bending durability to the laminate, particularly preferably 1 MPa to 100 GPa, most preferably 5 MPa to 50 GPa, and particularly preferably 5 MPa to 10 GPa.
  • the adhesive layer is excellent in heat resistance so that the bending durability of the laminate of the present invention can be kept high even under high temperature environment, and it can be used for in-vehicle devices.
  • the glass transition temperature (Tg) or the melting point (Tm) of the adhesive layer comprising the cured product of the adhesive (1) described later is preferably 70 ° C. or more, particularly preferably 80 ° C. or more.
  • an upper limit is 150 degreeC, for example.
  • the glass transition temperature (Tg) or the melting point (Tm) can be measured by, for example, thermal analysis such as DSC or TGA or dynamic viscoelasticity measurement.
  • the surface hardness of the glass plate surface of the laminate of the present invention is, for example, H or more, preferably 2H or more, particularly preferably 2H or more, particularly preferably 3H or more, most preferably pencil hardness (JIS K5600-5-4 (ISO / DIN 15184)). Is 5H or more.
  • the surface hardness in particular, the surface hardness of the bent portion
  • the surface hardness can be maintained high as described above.
  • the storage elastic modulus at 20 ° C. of the adhesive layer (or the cured product of the later-described acrylic urethane adhesive (2) constituting the adhesive layer) formed of the cured product of the later-described acrylic urethane adhesive (2) is From the viewpoint of imparting excellent bending durability to the laminate of the present invention, 10 MPa or more is preferable, more preferably 50 MPa or more, particularly preferably 80 MPa or more, and most preferably 120 MPa or more.
  • the storage elastic modulus in this specification is the value measured using the dynamic-viscoelasticity measuring apparatus.
  • a dynamic viscoelasticity measuring device of an adhesive layer (or a cured product of an acrylic urethane adhesive (2) described later constituting the adhesive layer) comprising a cured product of an acrylic urethane adhesive (2) described later
  • the glass transition temperature (Tg) measured by using it is preferably 0 to 100 ° C., more preferably 0 to 70 ° C., particularly preferably 0 to 30 in that the laminate of the present invention has excellent bending durability. ° C.
  • the glass transition temperature is, for example, a method according to JIS K7244-4, more specifically, dynamic viscoelasticity measurement (for example, temperature rising rate: 5 ° C./minute, measurement temperature: 20 to 350 ° C., deformation mode: It can be determined as the temperature at the peak top of tan ⁇ (loss tangent) measured in dynamic viscoelasticity measurement under the conditions of tensile mode.
  • the storage elastic modulus at 20 ° C. of the adhesive layer (or the cured product of the vinyl acetate adhesive (3) described below constituting the adhesive layer) comprising the cured product of the vinyl acetate adhesive (3) described later Is preferably 10 to 200 MPa, more preferably 30 to 150 MPa, and particularly preferably 30 to 100 MPa from the viewpoint of imparting excellent bending durability to the laminate of the present invention.
  • a dynamic viscoelasticity measuring device of an adhesive layer (or a cured product of a vinyl acetate adhesive (3) described below constituting the adhesive layer) comprising a cured product of a vinyl acetate adhesive (3) described later
  • the glass transition temperature (Tg) measured using it is preferably 5 ° C. or less, more preferably less than ⁇ 5 ° C., particularly preferably ⁇ 10 ° C. or less, from the viewpoint of imparting excellent bending durability to the laminate of the present invention It is.
  • the lower limit of the glass transition temperature is, for example, preferably -30.degree. C., particularly preferably -20.degree.
  • the adhesive layer comprises a cured product of an adhesive.
  • an adhesive agent for forming the said contact bonding layer an ultraviolet curing adhesive, a thermosetting adhesive, a thermoplastic adhesive etc. are mentioned, for example.
  • UV curing adhesives are preferable in that they are excellent in quick curing and can be used for resin films with low heat resistance.
  • “curing” includes curing with polymerization of monomers of a radical curing type or cation curing type adhesive described later, and curing by cooling a heated and softened thermoplastic adhesive (or , Solidified).
  • UV-curable adhesives include radical-curable and cationic-curable adhesives.
  • a radical curing adhesive is excellent in that it has fast curing properties and is rich in monomer types.
  • a cationically curable adhesive is less susceptible to inhibition of curing by oxygen and is excellent in that it cures rapidly even in the presence of oxygen.
  • the curing shrinkage is small, the dimensional stability is also excellent.
  • the cationically curable adhesive contains a cationically polymerizable monomer and a curing catalyst.
  • cationically polymerizable monomer examples include compounds containing at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group.
  • a compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and at least one hydroxyl group as a cationically polymerizable monomer, among others Or 10% by weight or more of the total amount of the cationically polymerizable monomers, which may be referred to as “the compound (I)”, and the following formula (b) (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more) It is preferable to contain 5 weight% or more of the compound (Hereafter, it may be called "compound (b)”) represented by these with respect to the cationically polymerizable monomer whole quantity.
  • Adhesive (1) an adhesive containing 10% by weight or more of the compound (I) and 5% by weight or more of the compound (b) based on the total amount of the cationically polymerizable monomers as the cationically curable adhesive (hereinafter referred to as , “Adhesive (1)” may be preferred).
  • the adhesive (1) is excellent in adhesion to the glass plate, and the glass plate and resin have extremely excellent adhesion even if the surface of the glass plate is not pretreated (for example, primer treatment, plasma treatment, corona treatment, etc.)
  • the film can be glued. Therefore, the adhesive (1) can be suitably used as an adhesive for glass, that is, an adhesive used for bonding glass.
  • the adhesive (1) since it has excellent adhesive strength, it is possible to bond the glass plate and the resin film by using a very small amount, and when the glass plate and the resin film are transparent, they can be bonded without losing the transparency. And a laminate (total light transmittance of, for example, 80% or more) excellent in transparency can be formed.
  • the cured product of the adhesive (1) has extremely low brittleness and excellent toughness.
  • the compound (I) is a compound having at least two functional groups in one molecule.
  • it is a compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and at least one hydroxyl group.
  • the cured product obtained by curing the adhesive containing the compound (I) has high hardness because the two types of functional groups polymerize to form a highly crosslinked structure.
  • the compound (I) cationic polymerization selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule from the viewpoints of, among others, higher hardness, lower cure shrinkage, and improved adhesion of the obtained cured product
  • the compound (i) which has one sexing group and one hydroxyl group is preferable.
  • i-1 compound having one vinyl ether group and one hydroxyl group
  • i compound having one epoxy group and one hydroxyl group
  • i-3 having one oxetanyl group and one hydroxyl group
  • the compound (i) is represented, for example, by the following formula.
  • HO-R a -Y (i) (Wherein, R a represents a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which these are linked via a single bond or a linking group.
  • R a represents a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which these are linked via a single bond or a linking group.
  • Y is a vinyl ether group, an epoxy group, And a cationically polymerizable group selected from oxetanyl groups
  • the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • divalent aliphatic hydrocarbon group for example, a linear or branched alkylene group having 1 to 18 carbon atoms such as methylene group, methyl methylene group, dimethyl methylene group, ethylene group, propylene group and trimethylene group
  • Linear or branched alkenylene groups having 2 to 18 carbon atoms such as vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, etc.
  • ethynylene, propynylene, 3- Examples thereof include C2-C18 linear or branched alkynylene groups such as methyl-1-propynylene, butynylene and 1,3-butadiynylene groups.
  • the alicyclic ring constituting the divalent alicyclic hydrocarbon group includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring, and the polycyclic hydrocarbon ring includes a spiro hydrocarbon ring and a ring Included are an aggregate hydrocarbon ring, a bridged cyclic hydrocarbon ring, a fused cyclic hydrocarbon ring, and a bridged fused cyclic hydrocarbon ring.
  • a bivalent alicyclic hydrocarbon group the group which remove
  • Examples of the monocyclic hydrocarbon ring include C 3-12 cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like; C 3-12 cycloalkene rings such as cyclopentene and cyclohexene Can be mentioned.
  • spiro hydrocarbon ring examples include C 5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, spirobicyclohexane and the like.
  • the ring assembly hydrocarbon ring etc. which contain 2 or more of C5-12 cycloalkane rings, such as bicyclohexane, etc. are mentioned, for example.
  • bridged cyclic hydrocarbon ring examples include pinane, bornane, norpinane, norbornane, norbornene, bicycloheptane, bicycloheptene, bicyclooctane (bicyclo [2.2.2] octane, bicyclo [3.2.1] octane, etc. And the like) bicyclic hydrocarbon rings such as homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon such as tricyclo [4.3.1.1 2, 5 ] undecane Ring; tetracyclo [4.4.0.1 2,5 . 1 7,10] dodecane, perhydro-1,4-methano-5,8 methanolate 4 cyclic hydrocarbon ring such as a naphthalene.
  • bicyclic hydrocarbon rings such as homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon such as
  • fused cyclic hydrocarbon ring examples include a plurality of 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene and perhydroindene.
  • decalin perhydronaphthalene
  • perhydroanthracene perhydrophenanthrene
  • perhydroacenaphthene perhydrofluorene
  • perhydroindene perhydroindene
  • crosslinked fused cyclic hydrocarbon ring examples include dimers of dienes (for example, dimers of cycloalkadienes such as cyclopentadiene, cyclohexadiene, cycloheptadiene and the like), hydrogenated products thereof and the like.
  • divalent aromatic hydrocarbon group examples include arylene groups having 6 to 18 carbon atoms, such as phenylene group, biphenylene group and naphthylene group.
  • the above-mentioned hydrocarbon group can be selected from various substituents [for example, a halogen atom, an oxo group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group etc.), a carboxyl group, a substituted oxycarbonyl group (alkoxy Carbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group etc., substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group etc.] Good.
  • substituents for example, a halogen atom, an oxo group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group etc.), a carboxyl group, a
  • the carboxyl group may be protected by a conventional protecting group in the field of organic synthesis.
  • an aromatic or non-aromatic heterocyclic ring may be fused to a ring constituting an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
  • linking group examples include a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), an amide bond (-CONH-), and a carbonate bond (-OCOO-) and the like.
  • heterocyclic ring constituting the divalent heterocyclic group examples include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a four-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, 5-membered ring such as ⁇ -butyrolactone ring; 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, Fused ring such as isochroman ring; 3-oxatricyclo [4.3.1.1 4,8 ] undecane-2-one ring, 3-oxatricyclo [4.2.1.0 4,8 ] nonane- Bridging ring such as
  • the above-mentioned heterocyclic group is, besides the substituent which the above-mentioned hydrocarbon group may have, an alkyl group (for example, a C 1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (For example, it may have a phenyl group, a naphthyl group, etc.) and the like.
  • Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the structural formula of the heterocyclic ring.
  • R a inter alia a divalent hydrocarbon group, or a divalent group is preferably two or more are bonded through a linking group of a hydrocarbon group, particularly preferably a divalent aliphatic hydrocarbon group, Or a divalent group in which two or more of the aliphatic hydrocarbon groups are linked via a linking group, most preferably a linear or branched alkylene group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms
  • two or more of the linear or branched alkylene groups of the above are bonded via a linking group.
  • an ether bond is preferable.
  • a compound (i-1) having one vinyl ether group and one hydroxyl group and / or a compound (i-3) having one oxetanyl group and one hydroxyl group It is preferable at the point from which the hardened
  • the compound (i) preferably contains at least one selected from the compounds represented by the following formulas (i-1-1) to (i-1-3) (i-3-1), In particular, it is preferable to contain at least a compound represented by the following formula (i-3-1).
  • the compound (b) is a compound represented by the following formula (b). (Wherein R represents an s-valent linear or branched saturated aliphatic hydrocarbon group, or two or more linear or branched saturated aliphatic hydrocarbon groups linked via an ether bond represents an s-valent group, and s represents an integer of 2 or more)
  • s represents an integer of 2 or more and is, for example, an integer of 2 to 6, preferably an integer of 2 to 4, particularly preferably an integer of 2 to 3, particularly preferably 2.
  • examples of the divalent linear or branched saturated aliphatic hydrocarbon group include a methylene group, a methyl methylene group, and a dimethyl group.
  • Linear or branched alkylene having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms, particularly preferably 3 to 6 carbon atoms) such as methylene, ethylene, propylene, trimethylene and tetramethylene Groups are mentioned.
  • the trivalent or higher linear or branched saturated aliphatic hydrocarbon group may be a (s-2) hydrogen according to the structural formula of a divalent linear or branched saturated aliphatic hydrocarbon group. And groups other than.
  • the total carbon number of the group represented by R is, for example, 1 to 20, preferably 2 to 15, particularly preferably 2 to 10, and most preferably 3 to 8.
  • the compound (b) among others, compounds represented by the following formulas (b-1) to (b-5), trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, and dipentamer At least one selected from erythritol hexaglycidyl ether is preferable, and in particular, at least at least one selected from compounds represented by the following formulas (b-1) to (b-5) from the viewpoint of low viscosity and excellent coatability. It is one kind, and most preferably at least one kind selected from the compounds represented by the following formulas (b-1) to (b-4).
  • Vinyl ether compound (A) In the adhesive (1), as a cationically polymerizable monomer, in addition to the above-mentioned compound (I), a compound having at least one vinyl ether group in one molecule and having no hydroxyl group (herein, One or two or more of the vinyl ether compounds (A) may be contained.
  • the vinyl ether compound (A) may have another cationically polymerizable group (for example, an epoxy group, an oxetanyl group, etc.) in addition to the vinyl ether group.
  • R c- (O-CH CH 2 ) t (a) (Wherein, R c represents a t-valent hydrocarbon group, a t-valent heterocyclic group, or a t-valent group in which these are linked via a single bond or a linking group, and t is an integer of 1 or more) Show)
  • the t is an integer of 1 or more, for example, an integer of 1 to 10, preferably an integer of 1 to 5, and particularly preferably an integer of 2 to 5.
  • Examples of the t-valent hydrocarbon group and the t-valent heterocyclic group in R c include a t-valent group corresponding to the divalent hydrocarbon group and the divalent heterocyclic group in R a .
  • the t-valent hydrocarbon group and the t-valent heterocyclic group may have a substituent, and examples of the substituent include a divalent hydrocarbon group and a divalent heterocyclic group in Ra .
  • examples of the linking group include the same examples as the linking group in R a . Among them, a t-valent group having an alicyclic or heterocyclic skeleton is preferable as R c .
  • vinyl ether compounds (A) compounds represented by the following formulas (a-1) to (a-2), cyclohexyldimethanol monovinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexylethyl vinyl ether, menthyl vinyl ether, tetrahydroful Preferred are furyl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether and the like.
  • the adhesive (1) is a compound having at least one epoxy group in one molecule and no hydroxyl group in addition to the compound (I) and the compound (b) described above as cationically polymerizable monomers
  • the epoxy compound (B) may have another cationically polymerizable group (for example, oxetanyl group) in addition to the epoxy group.
  • the epoxy group includes two adjacent carbon atoms constituting an alicyclic ring (eg, a 3- to 8-membered alicyclic ring) such as a cyclohexene oxide group represented by the following formula (e-1), and an oxygen atom And an ethylene oxide group represented by the following formula (e-2).
  • R 1 represents a hydrogen atom or a C 1-3 alkyl group.
  • a compound having two or more epoxy groups in one molecule is preferable in that it is excellent in curability, and in particular, a compound having two or more alicyclic epoxy groups in one molecule, ethylene oxide At least one selected from a compound having two or more groups in one molecule, and a compound having one or more each of an alicyclic epoxy group and one or more ethylene oxide groups in one molecule is preferable.
  • the compound represented by following formula (b ') is preferable.
  • X represents a single bond or a linking group.
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of carbon-carbon double bonds are epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples thereof include an ester bond (-COO-), a carbonate group (-O-CO-O-), an amide group (-CONH-), and a group in which a plurality of these are linked.
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, and a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene group, methyl methylene group, dimethyl methylene group, ethylene group, propylene group and trimethylene group.
  • Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group and a 1,2-cyclohexylene group.
  • cycloalkylene groups (including cycloalkylidene groups) such as 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group and the like.
  • alkenylene group in the above-mentioned alkenylene group (sometimes referred to as “epoxidized alkenylene group”) in which part or all of the carbon-carbon double bond is epoxidized is, for example, vinylene group, propenylene group, 1-butenylene group And C2-C8 linear or branched alkenylene groups such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
  • an alkenylene group in which all of carbon-carbon double bonds are epoxidized is preferable, and more preferably, all of carbon-carbon double bonds are epoxidized and has 2 to 4 carbon atoms It is an alkenylene group.
  • a substituent may be bonded to the cyclohexene oxide group in the above formula (b ′), and examples of the substituent include a halogen atom, a C 1-10 alkyl group, a C 1-10 alkoxy group, C 2-10 alkenyloxy group, C 6-14 aryloxy group, C 7-18 aralkyloxy group, C 1-10 acyloxy group, C 1-10 alkoxycarbonyl group, C 6-14 aryloxycarbonyl group, C 7- 18 aralkyloxycarbonyl group, epoxy group-containing group, oxetanyl group-containing group, C 1-10 acyl group, isocyanate group, sulfo group, carbamoyl group, oxo group and the like.
  • Representative examples of the compound represented by the above formula (b ′) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2 -Epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexan-1-yl) propane, 1,2-bis (3,4 And -epoxycyclohexan-1-yl) ethane, and compounds represented by the following formulas (b'-1) to (b'-8), and the like.
  • L in the following formula (b'-5) is an alkylene group having 1 to 8 carbon atoms (for example, a linear or branched chain having 1 to 3 carbon atoms such as methylene, ethylene, propylene or isopropylene) Chained alkylene group) is shown.
  • n 1 and n 2 in the following formulas (b′-5) and (b′-7) each represent an integer of 1 to 30.
  • the compound having two or more alicyclic epoxy groups in one molecule further includes a compound represented by the following formula (b'-9) (b'-10).
  • N 3 to n 8 in the following formula (b′-9) (b′-10) are the same or different and each represents an integer of 1 to 30.
  • R ′ ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol, and p and n 9 each represent a natural number .
  • the p-valent alcohol [R ′ (OH) p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (polyhydric alcohols having 1 to 15 carbon atoms, etc.) and the like.
  • n 9 is 1 to case 30 is preferably .p is 2 or more, n 9 in groups in each [] (outside the square brackets) may be different may be the same Specifically, as the compound represented by the above formula (b ′ ′), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [For example, a trade name "EHPE 3150" (manufactured by Daicel Co., Ltd., etc.) and the like can be mentioned. Can be mentioned.
  • Examples of the compound having one or more alicyclic epoxy group and one or more ethylene oxide groups in one molecule include, for example, 1,2: 8,9-diepoxylimonene and the like.
  • epoxy compound (B) containing a compound having two or more alicyclic epoxy groups in one molecule (in particular, a compound represented by the formula (b ′)) has fast curability. It is preferable at the point from which the hardened
  • the adhesive (1) is, as a cationically polymerizable monomer, a compound having at least one oxetanyl group in one molecule other than the above-mentioned compound (I) and having no hydroxyl group (vinyl ether group and / or One or two or more kinds of compounds may be contained except for compounds having an epoxy group; sometimes referred to herein as “oxetane compounds (C)”.
  • the oxetane compound (C) is represented, for example, by the following formula (c). (Wherein, R a represents a monovalent organic group, R b represents a hydrogen atom or an ethyl group, and m represents an integer of 0 or more)
  • the monovalent organic group for R a is, for example, a monovalent hydrocarbon group, a monovalent heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group Etc.), substituted carbamoyl groups (N-alkylcarbamoyl group, N-arylcarbamoyl group etc.), acyl groups (aliphatic acyl groups such as acetyl group; aromatic acyl groups such as benzoyl group), and two or more of them are It includes monovalent groups bonded through a single bond or a linking group.
  • Examples of the monovalent hydrocarbon group and the monovalent heterocyclic group include the divalent hydrocarbon group and the monovalent group corresponding to the divalent heterocyclic group in the above R a .
  • As the connecting group the same examples as the linking group in the above R a and the like. These groups may have a substituent, and examples of the substituent include the same examples as the substituent which the hydrocarbon group in R a may have.
  • the m represents an integer of 0 or more and is, for example, an integer of 0 to 20, preferably an integer of 0 to 1.
  • a compound having two or more oxetanyl groups in one molecule as the oxetane compound (C) in that a cured product having fast curing property and high hardness can be obtained, for example,
  • the compound represented by the following formula (c-1), the compound represented by the following formula (c-2) and the like are preferable.
  • commercially available products such as “Aron oxetane OXT-221” and “Aron oxetane OXT-121” (all manufactured by Toagosei Co., Ltd.) can be used.
  • the adhesive (1) contains the cationically polymerizable monomer, for example, 50 to 99.9% by weight (preferably 70 to 98% by weight) of the total amount (100% by weight) of the adhesive.
  • the adhesive (1) contains at least the compound (I) and the compound (b) as cationically polymerizable monomers, and further, the vinyl ether compound (A), the epoxy compound (B), and the oxetane compound (C) It may contain one or more selected from
  • the content of the compound (I) is preferably 10% by weight or more (for example, 10 to 65% by weight) of the total amount of the cationically polymerizable monomers contained in the adhesive (1).
  • a cured product having excellent adhesion to a resin film The lower limit is preferably 25% by weight, more preferably 30% by weight, particularly preferably 33% by weight, and most preferably 35% by weight.
  • the upper limit is preferably 55% by weight, particularly preferably 50% by weight, and most preferably 45% by weight, in order to obtain a cured product having particularly high hardness.
  • the content of the compound (i-1-1) having at least one vinyl ether group and at least one hydroxyl group and the compound (i-3-1) having at least one oxetanyl group and at least one hydroxyl group is an adhesive.
  • 25 wt% or more (e.g. 25 to 65 wt%) of the total amount of cationically polymerizable monomers contained in (1) is that a cured product having excellent adhesion to a resin film and high hardness can be obtained
  • the content is preferably 25% by weight or more and less than 60% by weight, particularly preferably 25 to 55% by weight, and particularly preferably 25 to 45% by weight, from the viewpoint of excellent curability.
  • the content of the compound (i-1-1) having one vinyl ether group and one hydroxyl group is, for example, 30% by weight or less, preferably 25% by weight or less, of the total amount of the cationically polymerizable monomers contained in the adhesive (1). Particularly preferably, it is at most 18% by weight.
  • the content of the compound (i-3-1) having one oxetanyl group and one hydroxyl group is excellent in adhesion to a resin film, and a cured product having high hardness can be obtained, so an adhesive (1) It is preferable that it is 15 weight% or more of the cationically polymerizable monomer whole contained in, More preferably, it is 20 weight% or more, Especially preferably, it is 25 weight% or more. Further, from the viewpoint of curability, the upper limit of the content is, for example, 55% by weight, preferably 45% by weight, and particularly preferably 40% by weight.
  • the content of the compound (b) is preferably 5% by weight or more of the total amount of the cationically polymerizable monomers contained in the adhesive (1), and has rapid curability and high hardness with excellent adhesion to glass. More preferably, it is 5 to 45% by weight, particularly preferably 12 to 40% by weight, and most preferably 18 to 30% by weight from the viewpoint of obtaining a cured product of If the content of the compound (b) is below the above range, the crack resistance of the resulting cured product tends to be reduced and it tends to become brittle.
  • the weight ratio of the compound (I) to the compound (b) is, for example, at least 0.5, preferably at least 1.0, particularly preferably 1 in that a cured product having excellent adhesion to glass can be obtained. 1 or more, most preferably 1.3 or more.
  • the upper limit of the weight ratio is, for example, 6.5, preferably 5.5, particularly preferably 3.0, most preferably 2.5, particularly preferably 2.0.
  • the content of the compound other than the compound (I) and the compound (b) is a compound having two or more cationically polymerizable groups selected from a vinyl ether group, an epoxy group and an oxetanyl group in one molecule
  • the total amount of cationically polymerizable monomers contained in the adhesive (1) is, for example, 15% by weight or more, preferably 20% by weight or more, particularly preferably 25% by weight or more, and most preferably 30% by weight or more is there.
  • the upper limit of the content is, for example, 55% by weight, preferably 50% by weight in that a cured product having high hardness and excellent adhesion to glass can be obtained.
  • the cationic polymerizable monomer contained in the adhesive (1) is particularly preferable in that the content of the compound represented by the formula (b ′) is fast curing and a cured product of high hardness is obtained.
  • the total amount is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 25% by weight or more.
  • the upper limit of the content is, for example, 50% by weight, preferably 45% by weight, and particularly preferably 43% by weight in that a cured product having high hardness and excellent adhesion to glass can be obtained.
  • the content of the compound having two or more vinyl ether groups in one molecule and no hydroxyl group is, for example, 20% by weight or less of the total amount of the cationically polymerizable monomers contained in the adhesive (1), preferably It is 15% by weight or less.
  • the content of the compound having two or more oxetanyl groups in one molecule and no hydroxyl group is, for example, 20% by weight or less of the total amount of the cationically polymerizable monomers contained in the adhesive (1), preferably It is 15% by weight or less.
  • the content of the compound having one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and having no hydroxyl group is an adhesive (1 Is preferably less than 30% by weight, more preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably 5% by weight or less, and most preferably 1% by weight or less. It is below.
  • the radical curable adhesive contains a radical polymerizable monomer and a curing catalyst.
  • radically polymerizable monomers examples include olefins (for example, chain olefins such as ethylene, propylene, 1-butene, butadiene and the like (particularly, C 2-12 alkene); cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2 Cyclic olefins such as norbornene and tetracyclododecene], aromatic vinyl compounds (eg, styrene, vinyl toluene, ⁇ -methylstyrene, 1-propenylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-vinylpyridine, C 6-14 aromatic vinyl compounds such as 3-vinylfuran, 3-vinylthiophene, 3-vinylquinoline), (meth) acrylic acid esters (eg, ethyl acrylate, butyl acryl
  • the thermoplastic adhesive contains at least one thermoplastic resin.
  • thermoplastic resin examples include homopolymers or copolymers of (meth) acrylic acid esters, (meth) acrylic urethane copolymers (in particular, (meth) acrylic urethane graft copolymers), styrene (meth) ) Acrylic acid ester copolymer, vinyl acetate-(meth) acrylic acid ester copolymer, ethylene-(meth) acrylic acid ester copolymer, ethylene-(meth) acrylic acid copolymer, (meth) acrylic acid ester -(Meth) acrylic acid copolymer, styrene-acrylonitrile-(meth) acrylic acid ester copolymer, styrene-(meth) acrylic acid ester-(meth) acrylic acid copolymer, styrene-acrylonitrile-(meth) acrylic acid Acid ester-(meth) acrylic acid copolymer, ethylene-vinyl acetate-(meth) acrylic acid ester Acrylic poly
  • the adhesive layer is preferably an adhesive layer comprising a cured product of an acrylic urethane adhesive (2) containing a urethane (meth) acrylate or its (co) polymer, and particularly an adhesive comprising a cured product of the adhesive (2)
  • An adhesive layer which is a layer and whose storage elastic modulus at 20 ° C. is, for example, 10 MPa or more (preferably 50 MPa or more, more preferably 80 MPa or more, particularly preferably 120 MPa or more) measured using a dynamic viscoelasticity measuring device However, it is preferable at the point from which the laminated body which is excellent in bending
  • an adhesive layer comprising a cured product of a vinyl acetate adhesive (3) (especially ethylene-vinyl acetate copolymer) containing a vinyl acetate polymer is preferable, and in particular, the adhesive (3) And a glass transition temperature (Tg) of, for example, 5 ° C. or less (preferably less than ⁇ 5 ° C., particularly preferably ⁇ 10 ° C. or less), which is measured using a dynamic viscoelasticity measuring apparatus.
  • Tg glass transition temperature
  • the lower limit of the glass transition temperature is, for example, ⁇ 30 ° C., preferably ⁇ 20 ° C.), which is preferable in that a laminate excellent in bending durability can be obtained.
  • the curing catalyst includes known or commonly used photo cationic polymerization initiator and photo radical polymerization initiator.
  • the cationically curable adhesive preferably contains at least a photocationic polymerization initiator as a curing catalyst, and in particular, containing both a photocationic polymerization initiator and a photoradical polymerization initiator makes the curing reaction of the adhesive more It is preferable at the point which can be made to advance efficiently and the hardened
  • the radical curable adhesive preferably contains at least a photoradical polymerization initiator as a curing catalyst.
  • photo cationic polymerization initiator examples include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromine salt compounds. Etc.
  • trade names “CPI-101A”, “CPI-100P”, “CPI-110P” all available from San-Apro Co., Ltd.
  • photoradical polymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, and 1- (4-isopropylphenyl) -2-.
  • the cationically curable adhesive preferably uses a cationic photopolymerization initiator as a curing catalyst, and the amount thereof used is, for example, 0.1 to 20 parts by weight, preferably 0 based on 100 parts by weight of the cationically polymerizable monomer.
  • the content is preferably 5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.
  • the amount of the photo radical polymerization initiator used is 0.1 to 5 parts by weight with respect to 100 parts by weight of the cationically polymerizable monomer.
  • the amount is preferably, particularly preferably 0.5 to 3 parts by weight, most preferably 0.5 to 2 parts by weight.
  • the radical curable adhesive preferably uses a photo radical polymerization initiator as a curing catalyst, and the amount thereof used is, for example, 0.1 to 20 parts by weight, preferably 0 based on 100 parts by weight of the radical polymerizable monomer.
  • the content is preferably 5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.
  • the adhesive may further contain a solvent, but being non-solvent, that is, containing no solvent can improve the drying property, and is also applicable to a resin film which is easily deteriorated by the solvent.
  • the content of the solvent is, for example, 10% by weight or less, preferably 5% by weight or less, based on the total amount of the adhesive (100% by weight). Particularly preferably, it is at most 1% by weight.
  • the adhesive When the adhesive is a cation- or radical-curable adhesive, it may contain other components as necessary in addition to the monomer and the curing catalyst.
  • a well-known and commonly used sensitizer eg, acridine compound
  • sensitizers antioxidants
  • stabilizers such as amines, and the like.
  • the adhesive when used for curing by irradiating UV-LEDs, containing a sensitizer and, if necessary, a sensitizer, makes it possible to use the ultraviolet light absorptivity of the curing catalyst.
  • these are preferable in that they can be improved to improve the curability, and their content (the total amount of two or more) is, for example, 0.05 to 10 parts by weight, preferably 100 parts by weight of the monomer. Is 0.1 to 5 parts by weight.
  • the compounding ratio of the compound [compound represented by formula (d-1) / compound represented by formula (d-2); weight ratio] is preferably 0.01 to 1. It is 0, preferably 0.1 to 0.5, and particularly preferably 0.2 to 0.5.
  • a compound represented by the following formula (d-1) for example, trade name “Antracure UVS-1331” (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) can be used.
  • a trade name “Antracure UVS-581” manufactured by Kawasaki Kasei Kogyo Co., Ltd.
  • the surface tension (at 30 ° C. under 1 atm) of the adhesive is preferably, for example, 10 to 50 mN / m.
  • the viscosity [at 25 ° C., shear rate 100 (1 / s)] of the adhesive is excellent in fluidity, and when applied using an inkjet printer or the like, it is 1 to 1000 mPa ⁇ in terms of excellent dischargeability.
  • s is preferred, more preferably 5 to 500 mPa ⁇ s, particularly preferably 10 to 100 mPa ⁇ s, most preferably 10 to 50 mPa ⁇ s, particularly preferably 10 to 30 mPa ⁇ s.
  • the surface tension of the adhesive can be measured, for example, by the Wilhelmy method (plate method) using a high accuracy surface tension meter “DY-700” (manufactured by Kyowa Interface Science Co., Ltd.).
  • the laminate of the present invention can be produced, for example, by bonding the above-mentioned glass plate and a resin film with an adhesive and then curing the adhesive.
  • the MD direction of the resin film is the bending direction of the laminate (or Or parallel to the direction of refraction of the laminate (the crossing angle between the MD direction of the resin film and the direction of bending of the laminate is, for example, 30 ° or less, preferably 20).
  • the MD direction of the resin film is substantially perpendicular to the fold line generated when the laminate is bent in the bending direction (MD direction of resin film And the broken line crosses the bonding direction so as to intersect, for example, 60 to 120 °, preferably 70 to 110 °, particularly preferably 80 to 100 °, and most preferably 85 to 95 °). It is preferable to adjust and laminate in that a laminate having particularly excellent bending durability can be obtained (see FIG. 4).
  • the MD direction is a direction in which the molten resin flows when the resin film is manufactured by injection molding, and is superior in mechanical strength to the TD direction (a direction perpendicular to the MD direction and in the width direction).
  • the MD direction and the TD direction of the resin film can be confirmed by, for example, the orientation direction of birefringence measured using a two-dimensional birefringence apparatus (PA-100, manufactured by Photonic Lattice, Inc.).
  • the laminate in the present invention preferably has a bending durability of 10 or more (more preferably 100 or more, particularly preferably 1000 or more, still more preferably 2000 or more, most preferably 10000 or more) according to the following test.
  • Flexural endurance test From the extended state of the laminate, in the direction in which the surface of the glass plate is recessed, and in the direction along the MD direction of the resin film, bend 180 ° so that the bending radius is 3 mm. When the above-mentioned operation is performed at a speed of 43 sets per minute, the number of sets until a crack is generated in the laminated body is used as an index of bending durability.
  • a laminate having excellent bending durability by using a glass plate having a minimum bending radius of 3 mm or less that is, a glass plate which can be bent at least once until the bending radius becomes 3 mm or less
  • Glass plates with a minimum bending radius of more than 3 mm often have small scratches on the glass surface or end face that can not be visually confirmed, and if such glass plates are used, the resulting laminate has a refractive durability
  • the suitability of the glass sheet can be judged instantly and extremely easily, and the working efficiency and the yield can be improved.
  • the curing of the adhesive can be carried out in a manner depending on the type of adhesive. For example, when using an ultraviolet curing adhesive as the adhesive, it can be cured by irradiation with ultraviolet light, and when using a thermoplastic adhesive as the adhesive, the adhesive softened by heating is cooled. It can be hardened (or solidified) by
  • the light source of the ultraviolet light for example, a UV-LED, a mercury lamp such as low, medium or high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a tungsten lamp, an arc lamp, an excimer lamp, an excimer laser, a semiconductor laser, YAG A laser, a laser system combining a laser and a non-linear optical crystal, a high frequency induced ultraviolet light generator, or the like can be used.
  • the ultraviolet irradiation amount integrated light amount is, for example, 10 to 5000 mJ / cm 2 .
  • heat treatment may be performed.
  • the heat treatment can further improve the degree of curing.
  • the heating temperature is about 40 to 200 ° C.
  • the heating time is about 1 minute to 15 hours.
  • the degree of curing can also be improved by leaving it to stand at room temperature (20 ° C.) for about 1 to 48 hours after irradiation with ultraviolet light.
  • the member for flexible devices (or parts for flexible devices) of the present invention includes the above-mentioned laminate as its component.
  • the flexible device member includes, for example, a display (for example, a display used for a touch panel, a wearable terminal, an organic EL display, etc.), a protective film, a barrier film, a TFT substrate, and the like. Since the member for a flexible device of the present invention is provided with the above-mentioned laminate excellent in bending durability, no cracks occur in the laminate even if bending-extension is repeated, and the reliability is excellent. Moreover, the display and protective film provided with the said laminated body which are excellent in transparency are excellent in visibility.
  • the flexible device of the present invention comprises the above-mentioned laminate as its component.
  • Flexible devices include, for example, portable information terminals such as smartphones, tablets, and wearable terminals. Since the flexible device of the present invention is provided with the above-mentioned laminate excellent in bending durability, no cracks occur in the laminate even if bending and extension are repeated, and the reliability is excellent. Moreover, the portable information terminal provided with the said laminated body which is excellent in transparency is excellent in visibility.
  • Example 1 preparation of adhesive
  • the components were mixed as described in Table 1 (units by weight) to obtain an adhesive.
  • the viscosity of the obtained adhesive at a shear rate of 100 (1 / s) was measured using an E-type viscometer (trade name "VISCOMETER TV-25, manufactured by Toki Sangyo Co., Ltd.), It was 22.6 mPa ⁇ s.
  • the adhesive obtained in the examples and comparative examples is applied to a glass plate (trade name "S9112" manufactured by Matsunami Glass Industry Co., Ltd.) (film thickness: 5 ⁇ m), and an LED irradiator is used as a light source under an air atmosphere. It was used and irradiated with light of 365 nm to obtain a cured product / glass plate laminate.
  • the obtained laminate was subjected to an adhesion test (cross-cut method; in accordance with JIS K5600-5-6 (ISO 2409)), and adhesion was evaluated by a six-step classification test.
  • the floating amount is less than 1 mm ⁇ : The floating amount is 1 mm or more and less than 2 mm ⁇ : The floating amount is 2 mm or more and less than 5 mm ⁇ : The floating amount is 5 mm or more
  • HEVE ethylene glycol monovinyl ether
  • HBVE 4-hydroxybutyl vinyl ether
  • DEGMVE diethylene glycol monovinyl ether
  • OXT 101 3-ethyl-3-hydroxymethyl oxetane, trade name "Aron oxetane OXT-101, manufactured by Toagosei Co., Ltd.
  • OXT 221 bis [1-one Le (3-oxetanyl)] methyl ether, trade name "ARON OXT-221", manufactured by Toagosei Co., Ltd.
  • DCPA tricyclodecanedimethanol diacrylate
  • DPGDA dipropylene glycol diacrylate
  • VEEA 2- (2-vinyloxyethoxy) ethyl acrylate
  • CPI-110P Mixture of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and thiodi-p-phenylene bis (diphenylsulfonium) bis (hexafluorophosphate) (99.5 / 0.5), trade name "CPI-110P", San-Apro Co., Ltd.
  • UVS1331 9,10-dibutoxyanthracene, trade name "Antracure UVS-1331”, manufactured by Kawasaki Chemical Industries, Ltd. , Manufactured by Kawasaki Kasei Kogyo Co., Ltd.
  • Example 31 preparation of laminate
  • a TAC / adhesive layer / G-leaf laminate was obtained. It was 9H when the pencil hardness of the G-leaf surface of the obtained laminated body was measured by the method based on JISK5600-5-4 (ISO / DIN15184).
  • Example 32 (Preparation of Laminated Body)
  • PET polyethylene terephthalate film
  • a PET / adhesive layer / G-leaf laminate was obtained.
  • the pencil hardness of the G-leaf surface of the obtained laminate was 9H.
  • Total light transmittance The transparency of the laminate obtained in Examples 31 and 32 was evaluated by measuring the total light transmittance (in accordance with JIS-K7361). Moreover, as Comparative Example 4, a total ray of PET / adhesive layer / G-leaf laminate (trade name “Lamion”, manufactured by Nippon Electric Glass Co., Ltd., PET thickness 38 ⁇ m / adhesive layer thickness 25 ⁇ m / G-leaf thickness 50 ⁇ m) The transmittance was measured as well. The pencil hardness of the Lamion G-leaf surface was 9H. Furthermore, as Comparative Example 5, the total light transmittance of only G-leaf (thickness 50 ⁇ m) was similarly measured. The pencil hardness of the G-leaf surface was 9H.
  • Laminates obtained in Examples 31 and 32, PET / adhesive layer / G-leaf laminate as Comparative Example 4 (trade name “Lamion”, manufactured by Nippon Electric Glass Co., Ltd., PET thickness 38 ⁇ m / adhesive layer thickness 25 ⁇ m / G-leaf thickness 50 ⁇ m) and G-leaf (50 ⁇ m thickness) as Comparative Example 5 are used as test pieces, and at 25 ° C., the test pieces are placed horizontally on a plane and stretched.
  • Example 33 to 41 (Preparation of Laminated Body)
  • the adhesive obtained in Example 8 was coated on the resin film described in the following table so that the thickness after drying was 15 ⁇ m, and a glass plate having the minimum bending radius described in the following table (trade name “G- leaf, “50 ⁇ m thick, manufactured by Nippon Electric Glass Co., Ltd., the bending direction of the laminate to be obtained from this is 45 ° to the MD direction, TD direction, or birefringence alignment direction of the resin film.
  • the resin film / adhesion layer / G-leaf laminated body (irradiated amount: 2000 mJ / cm 2 ) is irradiated with light of 365 nm using an LED irradiator in an air atmosphere, after bonding so as to be parallel to the direction of For each example, 10 samples were obtained. The minimum bending radius was measured by the same method as described above (flexibility evaluation).
  • PET biaxially stretched PET film, trade name "Cosmo Shine A4300", manufactured by Toyobo Co., Ltd.
  • TAC biaxially stretched triacetyl cellulose film, trade name “Fujitac TG 60UL”, manufactured by Fujifilm Corp.
  • PEN biaxially stretched polyethylene Naphthalate film, trade name “Theonex Q65HA”, manufactured by Teijin Film Solutions Ltd.
  • PAI biaxially stretched polyamide imide film, trade name “Taimide OT-050”, manufactured by Taimide Tech. Inc.
  • Examples 42 to 48, Comparative Example 6 Preparation of Laminated Body
  • the adhesive described in the following table is coated on a PET film (biaxially stretched PET film, trade name "Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) so that the thickness after drying becomes as described in the following table.
  • a glass plate having a minimum bending radius of 3 mm or less (trade name "G-leaf” manufactured by Nippon Electric Glass Co., Ltd., thickness 50 ⁇ m) in a laminated body which is to be obtained from the MD direction of the PET film After bonding so as to be parallel to the bending direction, the adhesive was cured by the following method to obtain a PET / adhesive layer / G-leaf laminate.
  • Examples 42, 45, 47, 48 cured by heating and drying a solvent
  • Example 43 cured by irradiation with ultraviolet light
  • Example 44 after heating and drying a solvent, irradiation and curing by ultraviolet light
  • Example 46 After the sheet adhesive was sandwiched between glass and PET, it was cured by vacuum heating and pressure bonding Comparative example 6: it was allowed to stand at normal temperature for 24 hours to be cured
  • the storage elastic modulus and Tg of the adhesive layer were measured by cutting out the cured product of the adhesive (thickness: 0.5 mm) to a width of 4 mm and a length of 3 cm, and using this as a sample of dynamic viscoelasticity measurement (DMA) , Implemented under the following conditions.
  • DMA dynamic viscoelasticity measurement
  • Laminates obtained in Examples 42 to 48 and Comparative Example 6 PET / adhesive layer / G-leaf laminate as Comparative Example 7 (trade name “Lamion”, manufactured by Nippon Electric Glass Co., Ltd., PET thickness 38 ⁇ m / Adhesive layer thickness 25 ⁇ m / G-leaf thickness 50 ⁇ m) and G-leaf (50 ⁇ m thickness) as Comparative Example 8 are used as test pieces, and the evaluation of the bending durability thereof is the same as the above-mentioned bending durability evaluation (1) It went in the way of.
  • UAl composition containing urethane-modified acrylic polymer and solvent (ethyl acetate / isopropyl alcohol) (trade name "Akrit 8UA-017" manufactured by Taisei Fine Chemical Co., Ltd.)
  • UA2 A composition obtained by blending 5 parts by weight of Irgacure-184 with 100 parts by weight of a UV-curable urethane acrylate (trade name "Akrit 8UX-077A” manufactured by Taisei Fine Chemical Co., Ltd.)
  • UA3 UV-curable urethane acrylic A composition obtained by blending 0.2 parts by weight of Irgacure-184 with 100 parts by weight of a polymer (trade name “Akrit 8 BR-600”, manufactured by Taisei Fine Chemical Co., Ltd.)
  • EVA1 Vinyl acetate and ethylene-vinyl acetate co-weight Composition containing coalescing and solvent (water) (trade name “Akrit 8 BR-600”, manufactured by Taisei Fine
  • Flexural endurance test From the stretched state, turn the surface of the glass plate inward and bend it 180 ° so that the bending radius is 3 mm in the concave direction, and set the operation to extend again as one set, at a speed of 43 sets per minute The number of sets before cracks occur in the laminated body at the time of the above operation is used as an index of bending durability [2] A glass plate having a thickness of 150 ⁇ m or less and a minimum bending radius of 3 mm or less, and a resin film A laminate having a configuration laminated via an adhesive layer.
  • the adhesion of the adhesive layer to the glass plate (according to JIS K 5600-5-6) is classified 0 to 2 in a six-step classification test.
  • Stacks [5] The laminate according to any one of [1] to [3], wherein the storage elastic modulus at 20 ° C. of the adhesive layer is 10 MPa or more, which is measured using a dynamic viscoelasticity measurement device.
  • Adhesive (1) containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule And a compound having at least one hydroxyl group in an amount of 10% by weight or more of the total amount of the cationically polymerizable monomer, and a compound represented by the formula (b) in an amount of 5% by weight or more of the total amount of the cationically polymerizable monomer.
  • a compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and at least one hydroxyl group is a compound of formulas (i-1-1) to (i -1-3)
  • [11] [compound having at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule and at least one hydroxyl group] / [compound represented by formula (b) ]
  • the adhesive (1) further contains, as a cationically polymerizable monomer, a compound represented by the formula (b ′) in an amount of 10% by weight or more of the total amount of cationically polymerizable monomers
  • the laminated body as described in any one.
  • the compound represented by the formula (b ′) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1
  • the layered product according to [12] which is at least one compound selected from -yl) propane and 1,2-bis (3,4-epoxycyclohexan-1-yl) ethane.
  • the adhesive layer comprises a cured product of an acrylic urethane adhesive (2) containing urethane (meth) acrylate or a polymer thereof, and the cured product is measured using a dynamic viscoelasticity measuring device, 20
  • the laminate according to any one of [1] to [6] which has a storage elastic modulus at 10 ° C. of 10 MPa or more.
  • the adhesive layer comprises a cured product of a vinyl acetate adhesive (3) containing a vinyl acetate polymer, and the cured product has a glass transition temperature (Tg measured using a dynamic viscoelasticity measuring device)
  • Tg glass transition temperature
  • the laminate according to any one of [1] to [6] which has a temperature of 5 ° C. or less.
  • the adhesive It contains a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule, and at least one hydroxyl group. 10% by weight or more of the total amount of the cationically polymerizable monomers, and 5% by weight or more of the compounds represented by the formula (b). [19] The laminate according to any one of [1] to [18], wherein the total thickness of the laminate is 300 ⁇ m or less. [20] The laminate according to any one of [1] to [19], wherein the thickness of the glass plate is 150 ⁇ m or less.
  • a flexible device comprising the laminate according to any one of [1] to [26].
  • a portable information terminal comprising the laminate according to any one of [1] to [26].
  • a cationically polymerizable monomer and a curing catalyst wherein as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule, and a hydroxyl group
  • An adhesive containing 10% by weight or more of a compound having at least one of the cationically polymerizable monomers and 5% by weight or more of a compound represented by the formula (b).
  • the adhesive according to [32] which is a glass adhesive.
  • Adhesive (1) containing a cationically polymerizable monomer and a curing catalyst, and as the cationically polymerizable monomer, at least one cationically polymerizable group selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule
  • Adhesive (3) vinyl acetate adhesive
  • a display, a protective film, a barrier film, or a TFT substrate provided with [38]
  • the laminate of the present invention is excellent in curl resistance, flexibility, and bending durability. Moreover, it is hard to be cracked compared with thin glass single-piece

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un corps stratifié comprenant une plaque de verre amincie et un film de résine qui sont collés ensemble grâce à un adhésif et ayant une excellente résistance à la flexion. Un corps stratifié selon la présente invention présente une configuration dans laquelle une plaque de verre ayant une épaisseur inférieure ou égale à 150 µm et un film de résine sont stratifiés ensemble grâce à une couche adhésive, et présente une résistance à la flexion supérieure ou égale à 10 selon le test suivant. Test de résistance à la flexion : un jeu d'opérations consiste à courber le corps stratifié à 180° à partir d'un état étiré de façon à avoir un rayon de courbure de 3 mm dans une direction dans laquelle une surface de la plaque de verre devient concave, puis étirer le corps stratifié à nouveau. L'opération est effectuée à la vitesse de 43 jeux par minute, et le nombre de jeux lorsqu'une fissure s'est produite dans le corps stratifié est considéré comme un indice de la résistance à la flexion.
PCT/JP2018/016763 2017-07-28 2018-04-25 Corps stratifié et dispositif souple pourvu dudit corps stratifié WO2019021557A1 (fr)

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EP18839370.6A EP3659799A4 (fr) 2017-07-28 2018-04-25 Corps stratifié et dispositif souple pourvu dudit corps stratifié
US16/634,491 US20200230925A1 (en) 2017-07-28 2018-04-25 Laminated body and flexible device provided with said laminated body
KR1020207005395A KR20200037301A (ko) 2017-07-28 2018-04-25 적층체 및 상기 적층체를 구비한 플렉시블 디바이스
CN201880048685.3A CN111093978A (zh) 2017-07-28 2018-04-25 层叠体及具备所述层叠体的柔性设备

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110191604A (zh) * 2019-06-27 2019-08-30 Oppo广东移动通信有限公司 壳体组件及其制备方法、电子设备
CN110267478A (zh) * 2019-06-27 2019-09-20 Oppo广东移动通信有限公司 壳体组件及制备方法、电子设备
CN110290658A (zh) * 2019-06-27 2019-09-27 Oppo广东移动通信有限公司 壳体组件及其制备方法、电子设备
WO2020153258A1 (fr) * 2019-01-25 2020-07-30 株式会社ダイセル Support, et procédé de fabrication d'un condensateur céramique multicouche utilisant ledit support
WO2020153259A1 (fr) * 2019-01-25 2020-07-30 株式会社ダイセル Élément de recouvrement
CN114586087A (zh) * 2019-10-28 2022-06-03 住友化学株式会社 光学层叠体和显示装置
WO2023236349A1 (fr) * 2022-06-06 2023-12-14 韦尔通科技股份有限公司 Composition adhésive époxyde présentant une tg élevée, une adhérence élevée et une résistance au vieillissement, son procédé de préparation et son utilisation

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010105900A (ja) 2008-10-01 2010-05-13 Nippon Electric Glass Co Ltd ガラスロール及びその製造方法
JP2013214544A (ja) * 2012-03-30 2013-10-17 Sekisui Chem Co Ltd フレキシブル太陽電池モジュールの製造方法
WO2015005210A1 (fr) * 2013-07-09 2015-01-15 株式会社Adeka Composition polymérisable par voie cationique
JP2015042713A (ja) * 2013-08-26 2015-03-05 株式会社Adeka エネルギー線感受性組成物
JP2016203515A (ja) * 2015-04-23 2016-12-08 三菱樹脂株式会社 ガラス積層体
JP2016216554A (ja) * 2015-05-18 2016-12-22 藤森工業株式会社 接着性樹脂層及び接着性樹脂フィルム
JP2017080970A (ja) * 2015-10-27 2017-05-18 三菱樹脂株式会社 ガラス積層体、電子デバイス用基板、及び電子デバイス
JP2017147077A (ja) 2016-02-16 2017-08-24 株式会社豊田自動織機 蓄電装置
JP2018073647A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073652A (ja) 2016-10-31 2018-05-10 住友電装株式会社 端子台
JP2018073649A (ja) 2016-10-31 2018-05-10 昭和電工パッケージング株式会社 蓄電デバイス用外装材、蓄電デバイス用外装ケースおよび蓄電デバイス
JP2018073650A (ja) 2016-10-31 2018-05-10 Jnc株式会社 リチウム吸蔵放出材料、電極、リチウムイオン二次電池およびリチウム吸蔵放出材料の製造方法
JP2018073648A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073646A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073651A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 燃料電池用高分子電解質の製造方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010105900A (ja) 2008-10-01 2010-05-13 Nippon Electric Glass Co Ltd ガラスロール及びその製造方法
JP2013214544A (ja) * 2012-03-30 2013-10-17 Sekisui Chem Co Ltd フレキシブル太陽電池モジュールの製造方法
WO2015005210A1 (fr) * 2013-07-09 2015-01-15 株式会社Adeka Composition polymérisable par voie cationique
JP2015042713A (ja) * 2013-08-26 2015-03-05 株式会社Adeka エネルギー線感受性組成物
JP2016203515A (ja) * 2015-04-23 2016-12-08 三菱樹脂株式会社 ガラス積層体
JP2016216554A (ja) * 2015-05-18 2016-12-22 藤森工業株式会社 接着性樹脂層及び接着性樹脂フィルム
JP2017080970A (ja) * 2015-10-27 2017-05-18 三菱樹脂株式会社 ガラス積層体、電子デバイス用基板、及び電子デバイス
JP2017147077A (ja) 2016-02-16 2017-08-24 株式会社豊田自動織機 蓄電装置
JP2018073647A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073652A (ja) 2016-10-31 2018-05-10 住友電装株式会社 端子台
JP2018073649A (ja) 2016-10-31 2018-05-10 昭和電工パッケージング株式会社 蓄電デバイス用外装材、蓄電デバイス用外装ケースおよび蓄電デバイス
JP2018073650A (ja) 2016-10-31 2018-05-10 Jnc株式会社 リチウム吸蔵放出材料、電極、リチウムイオン二次電池およびリチウム吸蔵放出材料の製造方法
JP2018073648A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073646A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 蓄電デバイス用外装材
JP2018073651A (ja) 2016-10-31 2018-05-10 凸版印刷株式会社 燃料電池用高分子電解質の製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
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WO2020153258A1 (fr) * 2019-01-25 2020-07-30 株式会社ダイセル Support, et procédé de fabrication d'un condensateur céramique multicouche utilisant ledit support
WO2020153259A1 (fr) * 2019-01-25 2020-07-30 株式会社ダイセル Élément de recouvrement
CN110191604A (zh) * 2019-06-27 2019-08-30 Oppo广东移动通信有限公司 壳体组件及其制备方法、电子设备
CN110267478A (zh) * 2019-06-27 2019-09-20 Oppo广东移动通信有限公司 壳体组件及制备方法、电子设备
CN110290658A (zh) * 2019-06-27 2019-09-27 Oppo广东移动通信有限公司 壳体组件及其制备方法、电子设备
CN110267478B (zh) * 2019-06-27 2020-10-02 Oppo广东移动通信有限公司 壳体组件及制备方法、电子设备
CN110290658B (zh) * 2019-06-27 2021-03-09 Oppo广东移动通信有限公司 壳体组件及其制备方法、电子设备
CN114586087A (zh) * 2019-10-28 2022-06-03 住友化学株式会社 光学层叠体和显示装置
CN114586087B (zh) * 2019-10-28 2024-05-07 住友化学株式会社 光学层叠体和显示装置
WO2023236349A1 (fr) * 2022-06-06 2023-12-14 韦尔通科技股份有限公司 Composition adhésive époxyde présentant une tg élevée, une adhérence élevée et une résistance au vieillissement, son procédé de préparation et son utilisation

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