WO2013077080A1 - Composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet et procédé de séparation d'un produit polymérisé à base de celle-ci - Google Patents

Composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet et procédé de séparation d'un produit polymérisé à base de celle-ci Download PDF

Info

Publication number
WO2013077080A1
WO2013077080A1 PCT/JP2012/074802 JP2012074802W WO2013077080A1 WO 2013077080 A1 WO2013077080 A1 WO 2013077080A1 JP 2012074802 W JP2012074802 W JP 2012074802W WO 2013077080 A1 WO2013077080 A1 WO 2013077080A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
meth
curable resin
resin composition
ultraviolet curable
Prior art date
Application number
PCT/JP2012/074802
Other languages
English (en)
Japanese (ja)
Inventor
小林　大祐
隼 本橋
雄一朗 松尾
Original Assignee
日本化薬株式会社
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 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to JP2013545831A priority Critical patent/JP5970473B2/ja
Priority to CN201280057253.1A priority patent/CN104024295B/zh
Priority to KR1020147013657A priority patent/KR20140099457A/ko
Publication of WO2013077080A1 publication Critical patent/WO2013077080A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to an ultraviolet curable resin composition useful for peeling a layer formed by curing an ultraviolet curable resin composition present on the surface of an optical substrate and a method for peeling the cured product.
  • This touch panel has a structure in which a display device, a glass plate or a resin film on which a transparent electrode is formed, and a glass or resin transparent protective plate are bonded together.
  • a glass plate on which a display device and transparent electrodes are formed is very expensive. Therefore, after bonding the substrate with the UV curable resin composition, if the bubbles or the bonding position are wrong, it is necessary to return the substrate to the state before bonding and re-paste. is there.
  • the UV curable resin cured product layer is cut, the cured product layer is softened by adding a solvent, the cured product layer is removed from the substrate with a brush, and finally the surface is wiped with a solvent. The material is restored.
  • the present invention relates to an ultraviolet curable resin composition capable of recovering an optical substrate with good productivity from an optical member bonded with an ultraviolet curable resin with little damage to the optical substrate, and a method for peeling the cured product.
  • the purpose is to provide.
  • the present invention relates to the following (1) to (12).
  • Step 1 In the ultraviolet curable resin composition used in the method including the following (Step 1) to (Step 3) for peeling a layer formed by curing an ultraviolet curable resin composition present on the surface of an optical substrate.
  • An ultraviolet curable resin composition comprising (meth) acrylate (A) and a photopolymerization initiator (B).
  • Step 2 The process which makes the base material for peeling contact the layer formed by hardening
  • Step 2 A step of attaching a layer formed by curing the ultraviolet curable resin composition to the substrate for peeling.
  • Step 3 An optical substrate and ultraviolet rays are peeled off from the optical substrate by attaching and collecting a layer formed by curing the ultraviolet curable resin composition on the peeling substrate to the surface of the peeling substrate. The process of peeling the layer formed by hardening
  • the (meth) acrylate (A) is at least one (meth) acrylate selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton, and a (meth) acrylate monomer.
  • the ultraviolet curable resin composition according to (1) comprising: (3)
  • the (meth) acrylate (A) is a urethane (meth) acrylate, and the urethane (meth) acrylate is obtained by reacting a polyol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate. ) Acrylate, wherein the polyol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, propylene oxide-modified bisphenol A, and polyester polyol.
  • the urethane (meth) acrylate (A) is urethane (meth) acrylate, and urethane (meth) acrylate is obtained by reacting polypropylene glycol, polyisocyanate and hydroxyl group-containing (meth) acrylate (The ultraviolet curable resin composition according to (3), which is a (meth) acrylate.
  • the (meth) acrylate is a (meth) acrylate monomer, and the (meth) acrylate is lauryl (meth) acrylate, 2-ethylhexyl carbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth) acrylate, tetrahydro It is one or more selected from the group consisting of furfuryl (meth) acrylate, isostearyl (meth) acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate ( The ultraviolet curable resin composition as described in 2).
  • (Process 1) The process which makes the base material for peeling contact the layer formed by hardening
  • (Step 2) A step of attaching a layer formed by curing the ultraviolet curable resin composition to the substrate for peeling.
  • An optical substrate and ultraviolet rays are peeled off from the optical substrate by attaching and collecting a layer formed by curing the ultraviolet curable resin composition on the peeling substrate to the surface of the peeling substrate. The process of peeling the layer formed by hardening
  • the ultraviolet curable resin composition is an ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B), and (meth) acrylate (A) is a polyol, Urethane (meth) acrylate obtained by reacting polyisocyanate and hydroxyl group-containing (meth) acrylate, wherein the polyol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, propylene oxide modified
  • the peeling method according to (6) or (7), wherein the peeling method is one or more selected from the group consisting of bisphenol A and polyester polyol.
  • the ultraviolet curable resin composition is an ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B), and (meth) acrylate (A) is lauryl ( (Meth) acrylate, 2-ethylhexyl carbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, polypropylene oxide modified nonylphenyl (meth) acrylate, dicyclo
  • the peeling method according to any one of (6) to (8), wherein the peeling method is at least one selected from the group consisting of pentenyloxyethyl (meth) acrylates.
  • the optical substrate is one or more selected from the group consisting of a transparent glass substrate, a transparent resin substrate, a glass substrate with a touch sensor, a liquid crystal display unit, a plasma display unit, and an organic EL display unit.
  • the base material for peeling is at least one selected from the group consisting of a metal roll, a resin roll, a metal substrate, a resin substrate, and a resin film. The peeling method as described in any one of 10).
  • (12) Prior to (Step 1), a layer obtained by curing the ultraviolet curable resin composition present on the surface of the optical substrate is obtained by irradiating with ultraviolet rays at an irradiation dose of 10 to 1000 mJ / cm 2.
  • the optical base material there is little damage to the optical base material, and the optical base material can be recovered economically with good productivity.
  • FIG. 1 is a view showing an optical member to which the peeling method of the present invention can be applied
  • FIG. 2 is a process of peeling a layer formed by curing the ultraviolet curable resin composition of the present invention from the surface of the optical substrate. It is process drawing which shows 1st Embodiment.
  • the optical member has a configuration in which the same or different optical base materials are bonded to both surfaces of a cured resin layer made of an ultraviolet curable resin composition.
  • Various materials can be used as the optical substrate. Specifically, PET, PC, PMMA, composite of PC and PMMA, glass, COC, COP, plastic (acrylic resin, etc.), polarizing plate, lens sheet A prism sheet, ITO glass, or the like can be used.
  • the following sheets, display bodies, and optical functional materials can be used.
  • the sheet include an icon sheet, a decorative sheet, and a protective sheet
  • examples of the plate include a decorative board and a protective plate.
  • or board what was enumerated as a material of a transparent board is applicable.
  • Examples of the display body include display devices such as LCD, EL display, EL illumination, electronic paper, and plasma display in which a polarizing plate is attached to glass.
  • Examples of the optical functional material include transparent plastic plates such as acrylic plates, PC plates, PET plates, and PEN plates, tempered glass, and touch panel input sensors.
  • a layer formed by curing an ultraviolet curable resin composition from an optical member in which a liquid crystal display unit 1 and a glass substrate 2 having a touch sensor are bonded as an optical substrate (hereinafter referred to as a resin)
  • the method will be described based on a method of peeling 3) (also referred to as a cured product layer).
  • the liquid crystal display unit 1 is a liquid crystal display unit in which a liquid crystal material is sealed between a pair of substrates on which electrodes are formed, and a polarizing plate, a driving circuit, a signal input cable, and a backlight unit are provided.
  • the glass substrate 2 having a touch sensor has a transparent electrode formed on the surface of the glass substrate.
  • the resin cured product layer 3 is made of a cutting member such as a wire 4 smaller than the thickness of the resin cured product layer 3, and the blade of the cutting member contacts the surface of the optical substrate. Do not cut, saw, or shear.
  • a known member can be used without any particular problem as long as it is thinner than the cured resin layer 3 and can cut the cured resin layer.
  • a wire, a fine wire, a cutter, a knife, a saw, or the like can be used.
  • any method may be used as long as the cured resin layer 3 can be cut. Specifically, there are a cutting method and a drawing method.
  • the cured resin layer 3 is a layer obtained by curing a resin, and includes not only a layer that is entirely cured but also a layer that is semi-cured with a cured portion and an uncured portion. .
  • Examples of the semi-cured layer include those in which only a specific portion of the layer is intensively cured and the remainder is uncured.
  • cured material layer is formed with respect to the optical base material bonded together, and the method of peeling off are also mentioned,
  • cured material layer 3 is semi-hardened.
  • a method of applying a force and peeling off as described above can be applied as a cutting method.
  • the base material for peeling is made to contact the layer 3 formed by hardening
  • a metal roll 5 is used as the peeling substrate and brought into contact with the surface of the cured resin layer 3.
  • Cylindrical metal materials such as iron, steel, zinc, titanium, aluminum, copper, alloys such as stainless steel and brass, or plastic materials such as PET, PC, PMMA, and a composite of PC and PMMA.
  • Spherical shape, prismatic shape, plate shape, film shape and the like can be used.
  • a metal roll, a resin roll, a glass roll, a metal substrate, a resin substrate, and the like can be used.
  • an easy-adhesive film when a plate-like or film-like shape is used, an easy-adhesive film can be suitably used.
  • Easy-adhesion films include polypropylene film, fluororesin film, polyphenylene sulfide film, polyester film, polyethylene naphthalate film, PET film, polyvinylidene chloride film, and corona discharge to improve the adhesion to the resin.
  • surface activation treatment such as treatment or plasma treatment, processing treatment for forming irregularities, and those subjected to coating treatment with an adhesive layer containing a polymer binder can be preferably used.
  • those having transparency in the ultraviolet region can be suitably used.
  • the cured resin layer 3 can be adhered to the peeling substrate by ultraviolet irradiation in step 2.
  • a film that does not undergo the above surface treatment to a film such as a polypropylene film, a fluororesin film, a polyphenylene sulfide film, a polyester film, a polyethylene naphthalate film, a PET film, or a polyvinyl chloride film.
  • a film such as a polypropylene film, a fluororesin film, a polyphenylene sulfide film, a polyester film, a polyethylene naphthalate film, a PET film, or a polyvinyl chloride film.
  • adding flexibility by adding a softening agent is preferable because adhesion can be easily made to a cured portion or an uncured portion of the cured resin layer 3. It is.
  • the softening agent to be added for example, a fatty acid derivative or the like can be used.
  • the polyvinylidene chloride film obtained by adding a softening agent to the resin include saran wrap (manufactured by Asahi Kasei Chemical Co., Ltd.), clerap (manufactured by Kureha Co., Ltd.), and Riken wrap (manufactured by Riken Technos Co., Ltd.).
  • the film thickness of the easily adhesive film is preferably 1 to 100 ⁇ m, particularly preferably 5 to 20 ⁇ m.
  • the peeling substrate is subjected to a surface treatment.
  • the processing treatment include an uneven portion on the surface of the material, and a coating treatment that coats the surface of the peeling substrate with an easy-adhesive film.
  • the unevenness formed by the processing is preferably fine, and macroscopic unevenness having a height of several ⁇ m to several tens of ⁇ m and a pitch of several tens of ⁇ m to several hundreds of ⁇ m is formed on the surface. It is particularly preferable.
  • an easily adhesive film used for coating treatment in order to improve the adhesion to the resin on the surface of films such as polypropylene film, fluororesin film, polyphenylene sulfide film, polyester film, polyethylene naphthalate film, PET film, etc.
  • films such as polypropylene film, fluororesin film, polyphenylene sulfide film, polyester film, polyethylene naphthalate film, PET film, etc.
  • Those subjected to surface activation treatment such as corona discharge treatment and plasma treatment, processing treatments for forming irregularities, and those subjected to coating treatment with an adhesive layer containing a polymer binder can be preferably used.
  • the surface of the peeling substrate is applied by applying a corrosion inhibitor or the like so that the peeling substrate can be recycled. It is preferable to use a substrate for peeling which has been etched.
  • curing an ultraviolet curable resin composition is made to adhere to a base material for peeling.
  • the metal roll 5 and the surface of the cured resin layer 3 are adhered to each other by, for example, applying a pressure 6 to the metal roll 5.
  • the method for attaching the cured resin layer 3 to the peeling substrate include a method of heating, a method of heating, a method of irradiating with ultraviolet rays, and the like. Further, even if these methods are not adopted, the cured resin layer 3 adheres to the peeling substrate to some extent by allowing the peeling substrate and the cured resin layer 3 to come into contact with each other.
  • process 2 since the contact is an adhesion process (process 2), (process 2) is also achieved by performing (process 1).
  • a method of irradiating with ultraviolet rays is preferably used.
  • the layer 3 formed by curing the ultraviolet curable resin composition on the peeling substrate is attached to the surface of the peeling substrate and collected from the optical substrate.
  • the optical base material and the layer 3 formed by curing the ultraviolet curable resin composition are peeled off.
  • the resin cured product is adhered to a portion where the resin cured product is not adhered, thereby peeling off. Go. That is, the cured resin layer 3 is peeled off from the optical base material by using the rotation of the metal roll 5.
  • the cured resin layer 3 sticks to the peeling base material so as to be caught by the peeling base material.
  • the substrate is peeled off in a form in which the resin is adhered to the peeling substrate by pulling it up in the peeling direction.
  • the resin cured material layer 3 can be removed by employ
  • the cured resin layer 3 can be peeled from the optical substrate.
  • the cured resin layer 3 can be effectively removed from the optical substrate by peeling the cured resin layer 3 from the optical substrate.
  • the optical substrate thus obtained can be used as an optical substrate to be bonded to obtain an optical member again.
  • the optical base material which removed the resin cured material layer 3 in order to obtain the optical base material with few deposits by the resin cured material layer 3, it is preferable to go through the process of wiping a base material with an organic solvent.
  • organic solvent examples include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, and aliphatic solvents such as hexane and heptane.
  • the peeling method of the present invention automatically removes the cured resin from the peeling substrate by a machine by introducing the peeling substrate into the optical member manufacturing apparatus in the removal process that has been performed by the work of a conventional person. Since it is realizable, the manufacturing efficiency of an optical member can be improved significantly and the number of workers can be reduced. Furthermore, it is possible to make the process of using the solvent only the process of wiping the substrate, so it is possible to reduce the amount of the solvent used, which is economical, low cost, and low environmental impact. It is possible to perform a repair process (repair process) including In addition, since the number of separation steps is small, the time required for the repair step can be reduced.
  • an ultraviolet curable resin composition is applied to an optical substrate, and at least two optical substrates are bonded together, and then irradiated with ultraviolet rays to obtain an optical member.
  • a coating material such as a slit coater, a roll coater, a spin coater, or a screen printing method is applied to one substrate so that the thickness of the applied resin is 10 to 300 ⁇ m. It is performed by applying and bonding the other substrate.
  • the optical member obtained in this way it is inspected whether or not defects caused by bonding, such as air bubbles intervening between the optical substrate and the cured resin layer 3, are detected. In the inspection, the presence or absence of a defect is judged. If there is a defect, the cured resin layer 3 is removed from the optical substrate by the peeling method of the present invention.
  • the amount of UV irradiation suitable for peeling the cured resin layer 3 from the optical substrate is usually 10 to 2000 mJ / cm 2 , preferably 10 to 1000 mJ / cm 2 , particularly preferably 50 to 500 mJ / cm 2. Degree. If it is less than 10 mJ / cm 2, the cured resin layer 3 is difficult to adhere to the substrate for peeling, and if it is more than 2000 mJ / cm 2 , the cured product layer 3 may be difficult to peel from the substrate.
  • any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays.
  • a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
  • the irradiation dose here is usually 10 to 2000 mJ / cm 2 , preferably 10 to 2000 mJ / cm 2 , and particularly preferably about 50 to 500 mJ / cm 2 . If it is less than 10 mJ / cm 2, the cured resin layer 3 may be difficult to adhere to the substrate for peeling, and if it is more than 2000 mJ / cm 2 , it may be difficult to peel off.
  • any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays.
  • a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
  • the entire surface of the cured resin layer 3 may be irradiated with ultraviolet rays, or a method of intensively irradiating several portions of the cured resin layer 3 may be employed.
  • a method of irradiating several places intensively it is preferable to irradiate opposite points or sides on the optical base material because the optical base material can be fixed by temporary curing. Specifically, there is a method of irradiating two opposing corners or two sides.
  • a method of intensively irradiating the four corners of the bonded optical base material or a method of intensively irradiating the four sides of the optical base material is based on temporary curing. It can be suitably applied to ensure the fixation of the optical substrate. By doing so, it becomes possible to obtain the semi-cured resin cured product layer 3.
  • an uncured resin surface composed of a cured portion obtained by intensive irradiation after temporary curing and an uncured portion with insufficient irradiation can be formed.
  • the irradiation dose in this step is usually 500 to 5000 mJ / cm 2 , preferably about 1000 to 5000 mJ / cm 2 .
  • the cured resin layer 3 is removed from the optical base material by performing the separation steps (Step 1) to (Step 3), and the optical material from which the deposits are removed.
  • the substrate will be used again to obtain the optical member.
  • the process scheme for obtaining the optical member in which the peeling method of the present invention can be used is not limited to the above process, and for example, defect inspection before temporary curing may be omitted. In that case, inspection is performed after a series of steps from application of resin to provisional curing.
  • the UV curable resin composition of the present invention is applied to one substrate using a coating device such as a slit coater, roll coater, spin coater, screen printing method, etc. Is applied so that the thickness becomes 10 to 300 ⁇ m, the other base material is bonded, and the transparent base material side is irradiated with ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) and cured. it can.
  • the amount of UV irradiation suitable for peeling the cured resin layer 3 from the optical substrate is preferably 10 to 1000 mJ / cm 2 , particularly preferably about 50 to 500 mJ / cm 2 .
  • any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays.
  • a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
  • FIG. 4 is a process diagram showing a second embodiment of a process of peeling the layer 3 formed by curing the ultraviolet curable resin composition of the present invention from the surface of the optical substrate.
  • symbol is attached
  • the base material for peeling is made to contact the layer 3 formed by hardening
  • a resin film 7 is used as a peeling substrate, and is brought into contact with the surface of the cured resin layer 3.
  • the layer 3 formed by curing the ultraviolet curable resin composition on the peeling substrate is attached to the surface of the peeling substrate and collected from the optical substrate.
  • the optical base material and the layer 3 formed by curing the ultraviolet curable resin composition are peeled off.
  • the cured resin layer 3 is peeled from the optical base material by pulling up the cured resin layer 3 in a direction in which the resin film adhered to the surface of the resin film is peeled off.
  • the cured resin layer 3 can be peeled from the optical substrate.
  • FIG. 5 is a process diagram showing a third embodiment of the process of peeling the layer 3 formed by curing the ultraviolet curable resin composition of the present invention from the surface of the optical substrate.
  • symbol is attached
  • cured material layer 3 forms the resin cured material layer 3 semi-hardened so that it may have a hardened part and an unhardened part with respect to the optical base material bonded together. Apply force in the opposite direction to the direction that is being peeled off and split.
  • the base material for peeling is made to contact the layer 3 formed by semi-hardening an ultraviolet curable resin composition.
  • a resin film 7 is used as a peeling substrate, and is brought into contact with the surface of the cured resin layer 3.
  • the layer 3 formed by semi-hardening an ultraviolet curable resin composition is made to adhere to a peeling base material. Specifically, the resin film 7 and the surface of the cured resin layer 3 are attached by curing the uncured portion by irradiating the ultraviolet ray 8 to the semi-cured layer 3.
  • the layer 3 formed by curing the ultraviolet curable resin composition on the peeling substrate is attached to the surface of the peeling substrate and collected from the optical substrate.
  • the optical base material and the layer 3 formed by curing the ultraviolet curable resin composition are peeled off.
  • the cured resin layer 3 is peeled from the optical base material by pulling up the cured resin layer 3 in a direction in which the resin film adhered to the surface of the resin film is peeled off.
  • the cured resin layer 3 can be peeled from the optical substrate.
  • the ultraviolet curable resin of the present invention contains (meth) acrylate (A) and a photopolymerization initiator (B).
  • (meth) acrylate (A) urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton, (meth) acrylate monomer, and the like can be used.
  • Urethane (meth) acrylate is obtained by reacting polyhydric alcohol, polyisocyanate and hydroxyl group-containing (meth) acrylate.
  • an ultraviolet curable resin composition containing urethane (meth) acrylate as the resin cured product layer for the optical member, the resin cured product layer can be easily removed when the peeling process of the present invention is applied. It can be attached to the material. That is, the cured resin layer is non-fragmented (continuously) without leaving fragments or lumps as a residue of the cured resin layer on the optical substrate by adhering in pieces to the peeling substrate. In particular, it can be suitably used in the peeling process of the present invention.
  • polyhydric alcohol examples have 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.
  • polyhydric alcohols and polybasic acids for example, succinic acid, triol such as alkylene glycol, trimethylolpropane, pentaerythritol, alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, etc.
  • polyester polyol obtained by reaction with polyhydric alcohol and ⁇ -caprolactone Alcohol
  • polycarbonate polyol for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate
  • polyether polyol for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.
  • Polypropylene glycol is preferable from the viewpoint of compatibility and adhesion, and polypropylene glycol having a molecular weight of 2000 or more is particularly preferable from the viewpoint of adhesion to the substrate.
  • polypropylene glycol having a molecular weight of 2000 or more is used, the adhesive strength of the cured product layer is improved, and therefore, when two or more optical substrates are bonded, the prevention of peeling due to external pressure or environmental changes is improved. Is preferable.
  • organic polyisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl isocyanate.
  • hydroxyl group-containing (meth) acrylates include hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono ( A (meth) acrylate, a hydroxycaprolactone (meth) acrylate, a hydroxyl group terminal polyalkylene glycol (meth) acrylate, etc. can be used.
  • hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono ( A (meth) acrylate, a hydroxycaprolactone (meth) acrylate, a hydroxyl group terminal polyalkylene glycol (meth) acryl
  • the reaction is performed, for example, as follows. That is, the polyhydric alcohol is mixed with an organic polyisocyanate per equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalent, more preferably 1.1 to 1.5 equivalent. Is preferably reacted at 70 to 90 ° C. to synthesize a urethane oligomer. Next, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and reacted at 70 to 90 ° C. to react with the target urethane (meth). ) Acrylate can be obtained.
  • the weight average molecular weight of urethane (meth) acrylate is preferably about 7,000 to 25,000, and more preferably 10,000 to 20,000. When the weight average molecular weight is less than 7000, shrinkage increases, and when the weight average molecular weight is more than 25,000, curability may be poor.
  • urethane (meth) acrylates can be used alone or in admixture of two or more.
  • the weight ratio of urethane (meth) acrylate in the ultraviolet curable resin composition of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight.
  • the (meth) acrylate having a polyisoprene skeleton has a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule.
  • a (meth) acrylate having a polyisoprene skeleton can be obtained as “UC-203” (manufactured by Kuraray Co., Ltd.).
  • the weight ratio of the (meth) acrylate having a polyisoprene skeleton in the ultraviolet curable resin composition of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight.
  • a (meth) acrylate having one (meth) acryloyl group in the molecule can be preferably used.
  • isooctyl (meth) acrylate, isoamyl (meth) acrylate can be used.
  • Alkyl (meth) acrylates having 5 to 20 carbon atoms such as lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate, tridecyl (meth) acrylate, etc.
  • alkyl (meth) acrylates having 10 to 20 carbon atoms, 2-ethylhexyl carbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate and polypropylene oxide-modified nonylphenyl (meth) acrylate are preferred.
  • alkyl (meth) acrylate having 10 to 20 carbon atoms, dicyclopentenyloxyethyl (meth) Preferred are acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
  • an alkyl (meth) acrylate having 1 to 5 carbon atoms having a hydroxyl group and acryloylmorpholine are preferable, and acryloylmorpholine is particularly preferable.
  • the (meth) acrylate monomer refers to (meth) acrylate excluding urethane (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylate having a polyisoprene skeleton.
  • composition of the present invention can contain a (meth) acrylate monomer other than (meth) acrylate having one (meth) acryloyl group as long as the characteristics of the present invention are not impaired.
  • a (meth) acrylate monomer other than (meth) acrylate having one (meth) acryloyl group for example, tricyclodecane dimethylol di (meth) acrylate, dioxane glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, alkylene oxide modified bisphenol A type di (meth) acrylate Trimethylol C2-C10 alkanes such as caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate and ethylene oxide-modified phosphoric acid di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri
  • (meth) acrylate having a propylene oxide skeleton it is particularly preferable to use (meth) acrylate having a propylene oxide skeleton, from the viewpoint of adhesiveness to the substrate for peeling in Step 2. That is, when a (meth) acrylate having a propylene oxide skeleton is used, the adhesive force to the substrate for peeling is improved, and thus it is preferable to peel off the cured product layer from the optical substrate in Step 3, which is preferable. .
  • the (meth) acrylate having a propylene oxide skeleton include polypropylene glycol (meth) acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, polypropylene glycol di (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth).
  • An acrylate is mentioned.
  • isooctyl (meth) acrylate isoamyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl C5-C20 alkyl (meth) acrylates such as (meth) acrylate, isomyristyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate DOO, polypropylene oxide modified nony
  • these (meth) acrylate monomer components can be used alone or in admixture of two or more at any ratio.
  • the weight ratio of the (meth) acrylate monomer in the ultraviolet curable resin composition of the present invention is usually 5 to 70% by weight, preferably 10 to 50% by weight. If it is less than 5% by weight, the curability may be poor, and if it is more than 70% by weight, shrinkage may increase.
  • Examples of the photopolymerization initiator (B) contained in the ultraviolet curable resin composition of the present invention include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl- [4- ( 1-methylvinyl) phenyl] propanol oligomer (Esacure ONE; manufactured by Lamberti), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959; manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (Irgacure 127; Manufactured by BASF), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; manufactured by BASF), -Hydroxy-2-methyl-1-phenyl-
  • these photopolymerization initiators can be used alone or in admixture of two or more at any ratio.
  • the weight ratio of the photopolymerization initiator in the ultraviolet curable resin composition of the present invention is usually 0.2 to 5% by weight, preferably 0.3 to 3% by weight.
  • amines that can serve as photopolymerization initiation assistants can be used in combination with the above photopolymerization initiator.
  • examples of amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester.
  • the content in the ultraviolet curable resin composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight.
  • epoxy (meth) acrylate can be used as long as the characteristics of the present invention are not impaired.
  • Epoxy (meth) acrylate has a function of improving curability and improving the hardness and curing speed of a cured product. Any epoxy (meth) acrylate can be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid, and preferably used epoxy (meth) acrylate.
  • Examples of the glycidyl ether type epoxy compound to be obtained include diglycidyl ether of bisphenol A or its alkylene oxide adduct, diglycidyl ether of bisphenol F or its alkylene oxide adduct, diglycidyl of hydrogenated bisphenol A or its alkylene oxide adduct.
  • Diglycidyl ether ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether of ether, hydrogenated bisphenol F or its alkylene oxide adduct Neopentyl glycol diglycidyl ether, butanediol diglycidyl ether hexanediol diglycidyl ether to, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol diglycidyl ether.
  • Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.
  • (Meth) acrylic acid is preferably reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound.
  • the reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours.
  • a catalyst such as triphenylphosphine, TAP, triethanolamine, or tetraethylammonium chloride.
  • paramethoxyphenol, methylhydroquinone or the like can be used as a polymerization inhibitor.
  • An epoxy (meth) acrylate that can be suitably used in the present invention is a bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound.
  • the weight average molecular weight of the epoxy (meth) acrylate is preferably 500 to 10,000.
  • the weight ratio of the epoxy (meth) acrylate in the ultraviolet curable resin composition of the present invention is usually 1 to 80% by weight, preferably 5 to 30% by weight.
  • a compound having a structure represented by the general formula (1) can be contained as necessary.
  • n represents an integer of 0 to 40
  • m represents an integer of 10 to 50.
  • R 1 and R 2 may be the same or different.
  • R 1 and R 2 each have 1 to 18 alkyl groups, alkenyl groups having 1 to 18 carbon atoms, alkynyl groups having 1 to 18 carbon atoms, and aryl groups having 5 to 18 carbon atoms.
  • the weight ratio of the compound having the structure represented by the general formula (1) in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.
  • a softening component can be used in the ultraviolet curable resin composition of the present invention as necessary.
  • Specific examples of the softening component that can be used include polyisoprene, (meth) acrylate oligomer having a polybutadiene skeleton or esterified product thereof, polymer, oligomer, phthalate ester, phosphate ester, glycol ester, citrate ester Aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resins, and the like.
  • Examples of oligomers and polymers include polyisoprene-based, polybutadiene-based, and xylene-based oligomers or polymers.
  • the weight ratio of the softening component in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.
  • an antioxidant In the ultraviolet curable resin composition of the present invention, an antioxidant, an organic solvent, a silane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, and a light stabilizer are optionally added. You may add additives, such as an agent (for example, hindered amine compound etc.) and a filler.
  • an agent for example, hindered amine compound etc.
  • antioxidants include, for example, BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, , N-hexamethylenebis (3,5-di-di
  • organic solvent examples include alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, xylene and the like.
  • silane coupling agent examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -mercapropropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltri
  • polymerization inhibitor examples include paramethoxyphenol and methylhydroquinone.
  • the light stabilizer include, for example, 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2, 6,6-pentamethyl-4-piperidyl (meth) acrylate (LA-82, manufactured by ADEKA Corporation), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (2,2,6,6-totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Unde Mixed ester with decanoic acid bis (2,2,6,6-tetramethyl-4-
  • the filler include, for example, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like.
  • examples thereof include powder or beads obtained by spheroidizing these.
  • the weight ratio of the various additives in the ultraviolet curable resin composition is usually 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably 0.02 to 0.5% by weight.
  • the ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the aforementioned components at room temperature to 80 ° C., and if necessary, impurities may be removed by an operation such as filtration.
  • impurities may be removed by an operation such as filtration.
  • the cure shrinkage of the cured product of the ultraviolet curable resin composition of the present invention is preferably 3.0% or less, and particularly preferably 2.0% or less.
  • the transmittance at 400 nm to 800 nm of the cured product of the ultraviolet curable resin composition of the present invention is preferably 90% or more.
  • the transmittance at 400 to 450 nm is preferably 90% or more.
  • the ultraviolet curable resin composition of the present invention can be suitably used as an adhesive for laminating a plurality of optical substrates.
  • the optical substrate having a light shielding part can be used without particular limitation as long as the light shielding part is formed on the surface of the optical substrate made of the above material.
  • the optical base material to be bonded to the optical base material having the light shielding material may have a light shielding portion on the surface or may not have the light shielding material.
  • the ultraviolet curable resin composition of this invention can be used also as an adhesive agent which bonds a sheet
  • examples of the sheet include an icon sheet, a decorative sheet, and a protective sheet
  • examples of the plate include a decorative board and a protective plate.
  • or board what was enumerated as a material of a transparent board is applicable.
  • the material for the touch panel surface include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.
  • the ultraviolet curable resin composition of the present invention can also be suitably used for bonding a display unit of a liquid crystal display device and an optical substrate.
  • the display unit include LCD, EL display, EL illumination, electronic paper, plasma display, and other display devices in which a polarizing plate is attached to glass.
  • the optical functional material include transparent plastic plates such as acrylic plates, PC plates, PET plates, and PEN plates, tempered glass, and touch panel input sensors.
  • the refractive index of the cured product is preferably 1.45 to 1.55 in order to improve visibility.
  • the difference in refractive index from the base material used as the optical base material can be reduced, and the light loss can be reduced by suppressing the irregular reflection of light.
  • An optical member including a display unit and an optical base material bonded together with the ultraviolet curable resin composition of the present invention can be incorporated into an electronic device such as a television, a small game machine, a mobile phone, and a personal computer.
  • UV curable resin compositions having the compositions shown in Table 1 were prepared.
  • each component shown with the abbreviation in Table 1 is as follows.
  • ACMO acryloylmorpholine
  • 4-HBA 4-hydroxybutyl acrylate manufactured by Kojin Co., Ltd.
  • LA lauryl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • FA-512AS manufactured by Osaka Organic Chemical Industry Co., Ltd .
  • THFA Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd.
  • M-117 Propylene oxide 2.5 mol modified nonylphenyl acrylate, Toa Gosei Co., Ltd.
  • NP-5P Propylene oxide 5 mol modified nonylphenyl acrylate, Daiichi Kogyo Seiyaku Co., Ltd.
  • speed cure TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON
  • each obtained ultraviolet curable resin composition of the present invention was produced.
  • Production of Optical Member Having Resin Cured Material Layer of the Present Invention Each ultraviolet curable resin composition of Examples 1 to 5 prepared in a 3.5 inch liquid crystal display unit was applied so as to have a film thickness of 250 ⁇ m.
  • a glass substrate having a touch sensor was placed on each ultraviolet curable resin composition and bonded to a liquid crystal display unit.
  • an ultraviolet ray of 200 mJ / cm 2 is irradiated from the glass substrate side having the touch sensor with an ultra-high pressure mercury lamp (TOSCURE 752, manufactured by Harrison Toshiba Lighting Co., Ltd.), the cured resin layer is cured, and the optical member of the present invention is used.
  • TOSCURE 752 ultra-high pressure mercury lamp
  • the cured resin layer 3 was cut using a metal wire 4 to separate the liquid crystal display unit 1 and the glass substrate 2 having a touch sensor. .
  • Example 6 As shown in FIG. 2 (b), a metal roll (material: stainless steel, shape: cylindrical shape, dimension: bottom diameter 5 cm, axial length 10 cm) 5 is a cured resin layer 3 on the liquid crystal display unit 1. And the cured resin layer 3 on the glass substrate 2 having the touch sensor. Next, as shown in FIG. 2 (c), pressure 6 was applied to the metal roll 5 to adhere the metal roll 5 and the surface of the cured resin layer 3. Finally, as shown in FIG. 2D, the metal roll 5 was rotated, and the cured resin layer 3 was peeled off.
  • a metal roll material: stainless steel, shape: cylindrical shape, dimension: bottom diameter 5 cm, axial length 10 cm
  • Example 7 As shown in FIG. 4B, the resin film (material: PET) 7 is brought into contact with the cured resin layer 3 on the liquid crystal display unit 1 and the cured resin layer 3 on the glass substrate 2 having the touch sensor. did. Next, as shown in FIG. 4C, pressure 6 was applied to the resin film 7 to adhere the resin film 7 and the surface of the cured resin layer 3. Finally, as shown in FIG. 4D, the resin film 7 was pulled up from the end, and the cured resin layer 3 was peeled off.
  • material material: PET
  • the glass substrate 2 having the liquid crystal display unit 1 and the touch sensor after the cured resin layer 3 was peeled off was washed with isopropanol, and the surface was visually observed. Both were the same as the surface state before bonding.
  • FIG. 4A the cured resin layer 3 is cut using a metal wire 4, and the liquid crystal display unit 1 and the glass substrate 2 having the touch sensor are separated, and then FIG.
  • a resin film (material: PET) 7 was brought into contact with the cured resin layer 3 on the liquid crystal display unit 1 and the cured resin layer 3 on the glass substrate 2 having a touch sensor.
  • FIG. 4C pressure 6 was applied to the resin film 7 to adhere the resin film 7 and the surface of the cured resin layer 3.
  • FIG. 4 (d) the resin film 7 is pulled up from the end, the cured resin layer 3 is peeled off, and the cured resin adhered to the resinous film 7 and the glass substrate 2. The condition was observed.
  • UV-curable resin composition A 0.8 mm thick slide glass and an 0.8 mm thick acrylic plate were bonded together so that the film thickness of the obtained UV-curable resin composition was 200 ⁇ m, and a high-pressure mercury lamp ( A sample for evaluation was prepared by irradiating with 2000 mJ / cm 2 of ultraviolet rays at 80 W / cm, ozone-less). This was allowed to stand for 250 hours in an environment of 85 ° C. and 85% RH, and peeling was confirmed visually. However, the ultraviolet curable resin compositions described in Examples 1 to 5 did not peel.
  • the obtained ultraviolet curable resin composition was sufficiently cured, measured for durometer E hardness according to JIS K7215, and evaluated for flexibility.
  • the ultraviolet curable resin described in Examples 1 to 5 The value was less than 10 in the composition.
  • Transparency Two glass slides each having a thickness of 1 mm coated with a fluorine-based release agent were bonded so that the film thickness of the obtained ultraviolet curable resin composition was 200 ⁇ m, and a high-pressure mercury lamp (80 W through the glass). / Cm, ozone-less) was irradiated with ultraviolet rays of 2000 mJ / cm 2 to prepare a cured product for transparency measurement. Transparency was determined by measuring the transmittance at 400 to 800 nm and 400 to 450 nm using a spectrophotometer (U-3310, Hitachi High-Technologies Corporation), and in the ultraviolet curable resin compositions described in Examples 1 to 5. The transmittance at 400 to 800 nm was 90% or more and the transmittance at 400 to 450 nm was 90% or more.
  • Example 8 As shown in FIG. 5 (a), the cured product layer 3 is formed on the optical base material bonded to the resin cured product layer 3 semi-cured so as to have a cured portion and an uncured portion. A force was applied in the direction opposite to the direction in which it was peeled off. Then, as shown in FIG.5 (b), the resin-made film (material: polyvinylidene chloride) 7 is made into the resin cured material layer 3 which exists on a liquid crystal display unit, and the resin cured material layer which exists on the glass substrate 2 which has a touch sensor. 3 was contacted. Next, as shown in FIG.
  • the uncured portion was cured by irradiating ultraviolet rays 8, and the resin film 7 and the surface of the cured resin layer 3 were adhered. Finally, as shown in FIG. 5 (d), the resin film 7 was pulled up from the end, and the cured resin layer 3 was peeled off.
  • the glass substrate having the liquid crystal display unit and the touch sensor after peeling off the cured resin layer 3 was washed with isopropanol, and the surface was visually observed. Then, it was the same as the surface state before bonding.
  • An optical member of the present invention having a cured resin layer 3 that is semi-cured to have And as shown to Fig.5 (a), the hardened
  • the resin cured material (material: polyvinylidene chloride) 7 is placed on the liquid crystal display unit 1 as shown in FIG.
  • the cured resin layer 3 on the glass substrate 2 having the layer 3 and the touch sensor was brought into contact. Next, as shown in FIG.
  • the resin film 7 and the cured resin layer 3 surface were adhered by curing the uncured portion by irradiation.
  • FIG. 5 (d) the resin film 7 is pulled up from the end, the cured resin layer 3 is peeled off, and the cured resin adhered to the resinous film 7 and the glass substrate 2. The condition was observed. The peelability was evaluated according to the following criteria, and the results were as shown in Table 3.
  • the ultraviolet curable resin composition of the present invention can be suitably used for laminating an optical base material for producing an optical member, etc., and the optical member having the laminated structure has little damage to the optical base material and is optically highly productive. The substrate can be restored.
  • SYMBOLS 1 Liquid crystal display unit 2 Glass substrate which has a touch sensor, 3 Resin hardened material layer, 4 Wire, 5 Metal roll, 6 Pressure, 7 Resin film, 8 Ultraviolet

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet permettant la récupération d'un support optique à partir d'un élément optique, lesdits support et élément étant liés au moyen d'une résine polymérisable sous l'effet d'un rayonnement ultraviolet, sans trop endommager le support optique et avec une bonne productivité. L'invention concerne également un procédé de séparation d'un produit polymérisé à base de ladite composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet. La composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet est utilisée dans le cadre d'un procédé de séparation d'une couche présente à la surface d'un support optique et obtenue par polymérisation d'une composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet, ledit procédé comprenant les étapes (1) à (3) décrites ci-dessous. La composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet contient (A) un méthacrylate et (B) un initiateur de photopolymérisation. Etape (1) : étape consistant à mettre en contact un support pour séparation avec une couche obtenue par polymérisation d'une composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet. Etape (2) : étape consistant à faire adhérer au support pour séparation la couche obtenue par polymérisation d'une composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet. Etape (3) : étape consistant à séparer l'un de l'autre un support optique et la couche obtenue par polymérisation d'une composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet en séparant ladite couche dudit support optique, et ce, en faisant adhérer la couche à la surface du support pour séparation, puis en y recueillant ladite couche.
PCT/JP2012/074802 2011-11-21 2012-09-26 Composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet et procédé de séparation d'un produit polymérisé à base de celle-ci WO2013077080A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2013545831A JP5970473B2 (ja) 2011-11-21 2012-09-26 紫外線硬化型樹脂組成物、及びその硬化物の剥離方法
CN201280057253.1A CN104024295B (zh) 2011-11-21 2012-09-26 紫外线固化型树脂组合物及其固化物的剥离方法
KR1020147013657A KR20140099457A (ko) 2011-11-21 2012-09-26 자외선 경화형 수지 조성물, 및 그 경화물의 박리방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011253891 2011-11-21
JP2011-253891 2011-11-21

Publications (1)

Publication Number Publication Date
WO2013077080A1 true WO2013077080A1 (fr) 2013-05-30

Family

ID=48469536

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/074802 WO2013077080A1 (fr) 2011-11-21 2012-09-26 Composition de résine polymérisable sous l'effet d'un rayonnement ultraviolet et procédé de séparation d'un produit polymérisé à base de celle-ci

Country Status (5)

Country Link
JP (1) JP5970473B2 (fr)
KR (1) KR20140099457A (fr)
CN (1) CN104024295B (fr)
TW (1) TWI535745B (fr)
WO (1) WO2013077080A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106536653A (zh) * 2014-07-22 2017-03-22 日本合成化学工业株式会社 活性能量射线固化性粘合剂组合物、使用其而得到的粘合剂和粘合片
US10927276B2 (en) 2015-06-04 2021-02-23 3M Innovative Properties Company Methods of bonding hardware to vehicular glass
JP2021035779A (ja) * 2020-12-04 2021-03-04 デクセリアルズ株式会社 積層体の製造方法、及び光硬化性樹脂組成物

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101891729B1 (ko) * 2015-01-20 2018-08-24 주식회사 엘지화학 경화성 조성물
WO2017039209A1 (fr) 2015-09-03 2017-03-09 동우화인켐 주식회사 Substrat de fenêtre de couverture et dispositif d'affichage d'image comprenant celui-ci
CN106977657A (zh) * 2016-01-19 2017-07-25 杭州吉华高分子材料股份有限公司 一种水性可剥离树脂及其制备方法和应用
CN109476950A (zh) * 2016-07-26 2019-03-15 日产化学株式会社 易剥离性保护膜形成用组合物

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038546A (ja) * 1998-07-24 2000-02-08 Mitsubishi Rayon Co Ltd 光硬化型接着剤組成物およびそれを用いた光学部材
JP2004077887A (ja) * 2002-06-18 2004-03-11 Sony Corp 表示装置および表示装置を有する電子機器
JP2008101105A (ja) * 2006-10-19 2008-05-01 Denki Kagaku Kogyo Kk 硬化性組成物
WO2008111580A1 (fr) * 2007-03-12 2008-09-18 Toagosei Co., Ltd. Stratifié de film optique et dispositif d'affichage utilisant celui-ci
JP2009001655A (ja) * 2007-06-21 2009-01-08 Nippon Kayaku Co Ltd 光硬化型透明接着剤組成物
WO2010027041A1 (fr) * 2008-09-05 2010-03-11 協立化学産業株式会社 Composition de résine photodurcissable pour la stratification d'un matériau optiquement fonctionnel
JP2010122563A (ja) * 2008-11-21 2010-06-03 Hitachi Displays Ltd 表示装置及びその製造方法
JP2011048055A (ja) * 2009-08-26 2011-03-10 Hitachi Displays Ltd 液晶表示装置
JP2011511851A (ja) * 2007-12-28 2011-04-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 化学線硬化型接着剤組成物
JP2011158851A (ja) * 2010-02-04 2011-08-18 Hitachi Displays Ltd 表示装置およびその製造方法
JP2012136557A (ja) * 2010-12-24 2012-07-19 Dic Corp 紫外線硬化型粘着剤用樹脂組成物、粘着剤及び積層体
JP2012172034A (ja) * 2011-02-21 2012-09-10 Jnc Corp 接着した部材からの光硬化性接着剤の除去方法、及び二部材の接着方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4651799B2 (ja) * 2000-10-18 2011-03-16 日東電工株式会社 エネルギー線硬化型熱剥離性粘着シート、及びこれを用いた切断片の製造方法
TW201035134A (en) * 2008-11-05 2010-10-01 Nippon Kayaku Kk Ultraviolet curable resin composition for optical disk and cured product thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038546A (ja) * 1998-07-24 2000-02-08 Mitsubishi Rayon Co Ltd 光硬化型接着剤組成物およびそれを用いた光学部材
JP2004077887A (ja) * 2002-06-18 2004-03-11 Sony Corp 表示装置および表示装置を有する電子機器
JP2008101105A (ja) * 2006-10-19 2008-05-01 Denki Kagaku Kogyo Kk 硬化性組成物
WO2008111580A1 (fr) * 2007-03-12 2008-09-18 Toagosei Co., Ltd. Stratifié de film optique et dispositif d'affichage utilisant celui-ci
JP2009001655A (ja) * 2007-06-21 2009-01-08 Nippon Kayaku Co Ltd 光硬化型透明接着剤組成物
JP2011511851A (ja) * 2007-12-28 2011-04-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 化学線硬化型接着剤組成物
WO2010027041A1 (fr) * 2008-09-05 2010-03-11 協立化学産業株式会社 Composition de résine photodurcissable pour la stratification d'un matériau optiquement fonctionnel
JP2010122563A (ja) * 2008-11-21 2010-06-03 Hitachi Displays Ltd 表示装置及びその製造方法
JP2011048055A (ja) * 2009-08-26 2011-03-10 Hitachi Displays Ltd 液晶表示装置
JP2011158851A (ja) * 2010-02-04 2011-08-18 Hitachi Displays Ltd 表示装置およびその製造方法
JP2012136557A (ja) * 2010-12-24 2012-07-19 Dic Corp 紫外線硬化型粘着剤用樹脂組成物、粘着剤及び積層体
JP2012172034A (ja) * 2011-02-21 2012-09-10 Jnc Corp 接着した部材からの光硬化性接着剤の除去方法、及び二部材の接着方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106536653A (zh) * 2014-07-22 2017-03-22 日本合成化学工业株式会社 活性能量射线固化性粘合剂组合物、使用其而得到的粘合剂和粘合片
US10927276B2 (en) 2015-06-04 2021-02-23 3M Innovative Properties Company Methods of bonding hardware to vehicular glass
US11352524B2 (en) 2015-06-04 2022-06-07 3M Innovative Properties Company Methods of bonding substrates together
US11773295B2 (en) 2015-06-04 2023-10-03 3M Innovative Properties Company Methods of bonding substrates together
JP2021035779A (ja) * 2020-12-04 2021-03-04 デクセリアルズ株式会社 積層体の製造方法、及び光硬化性樹脂組成物
JP7170703B2 (ja) 2020-12-04 2022-11-14 デクセリアルズ株式会社 積層体の製造方法、及び光硬化性樹脂組成物

Also Published As

Publication number Publication date
CN104024295A (zh) 2014-09-03
TWI535745B (zh) 2016-06-01
KR20140099457A (ko) 2014-08-12
JP5970473B2 (ja) 2016-08-17
TW201329122A (zh) 2013-07-16
CN104024295B (zh) 2016-10-19
JPWO2013077080A1 (ja) 2015-04-27

Similar Documents

Publication Publication Date Title
JP6568567B2 (ja) 紫外線硬化型樹脂組成物
JP5331271B1 (ja) 光学部材の製造方法及びそのための紫外線硬化型樹脂組成物の使用
JP5970473B2 (ja) 紫外線硬化型樹脂組成物、及びその硬化物の剥離方法
JP6620092B2 (ja) タッチパネル用紫外線硬化型樹脂組成物、それを用いた貼り合せ方法及び物品
WO2015190552A1 (fr) Composition de résine durcissable par rayonnement ultraviolet pour panneau tactile, et procédé de collage ainsi que composant mettant en œuvre celle-ci
WO2015190561A1 (fr) Composition de résine durcissable par rayonnement ultraviolet pour panneau tactile, et procédé de collage ainsi que composant mettant en œuvre celle-ci
JP6378184B2 (ja) 光学部材の製造方法及びそれに用いる紫外線硬化型樹脂組成物
WO2015190571A1 (fr) Composition de résine durcissable par rayonnement ultraviolet pour panneau tactile, et procédé de collage ainsi que composant mettant en œuvre celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12851717

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013545831

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147013657

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12851717

Country of ref document: EP

Kind code of ref document: A1