WO2019069872A1 - 紫外線硬化型接着剤組成物、その硬化物および紫外線硬化型接着剤組成物を用いた光学部材の製造方法 - Google Patents

紫外線硬化型接着剤組成物、その硬化物および紫外線硬化型接着剤組成物を用いた光学部材の製造方法 Download PDF

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WO2019069872A1
WO2019069872A1 PCT/JP2018/036748 JP2018036748W WO2019069872A1 WO 2019069872 A1 WO2019069872 A1 WO 2019069872A1 JP 2018036748 W JP2018036748 W JP 2018036748W WO 2019069872 A1 WO2019069872 A1 WO 2019069872A1
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curable adhesive
meth
adhesive composition
acrylate
ultraviolet
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PCT/JP2018/036748
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English (en)
French (fr)
Japanese (ja)
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隼 本橋
伸彦 内藤
理子 植原
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日本化薬株式会社
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Priority to CN201880064099.8A priority Critical patent/CN111164170B/zh
Priority to JP2019546705A priority patent/JPWO2019069872A1/ja
Priority to KR1020207006236A priority patent/KR20200064061A/ko
Publication of WO2019069872A1 publication Critical patent/WO2019069872A1/ja

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    • 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a UV-curable adhesive composition for bonding at least two optical substrates, a cured product thereof, and a method for producing an optical member using the UV-curable adhesive composition.
  • a display device in which a touch panel is attached to a display screen of a display device such as a liquid crystal display, a plasma display, an organic EL display, etc. to enable screen input has been widely used.
  • a glass plate or a resin film on which a transparent electrode is formed is attached facing each other with a slight gap, and if necessary, a transparent protective plate made of glass or resin on the touch surface Has a laminated structure.
  • a display device such as a liquid crystal display or an organic EL display, a touch sensor, a glass plate for protection or a film.
  • a display device such as a liquid crystal display or an organic EL display, a touch sensor, a glass plate for protection or a film.
  • Various efforts have been made to reduce the thickness of each member, and a wide variety of materials have been used for the members.
  • a PET film has been mainly used as a substrate for a film type touch panel sensor on which a transparent electrode is formed
  • a cycloolefin polymer, a transparent polyimide film or the like is used at present.
  • the conventional adhesive causes poor adhesion to the base material, insufficient adhesion, and deterioration of the optical base material, causing a crack in the base material. There is.
  • Patent Document 1 mentions a method of lowering the viscosity of the adhesive composition by diluting with a reactive monomer, but the reactivity There is no mention at all about the problem that occurs when the viscosity is reduced by dilution with a monomer.
  • the prior art alone, as the content of the reactive monomer in the composition increases, it becomes difficult to achieve both flexibility and curability. When the flexibility is increased, the curability is deteriorated, and when the curability is improved, the flexibility and the adhesiveness are reduced. If the flexibility or adhesion is low, peeling may occur due to external stress, deformation of the optical substrate, thermal expansion or the like, and if the curability is poor, mass productivity may be reduced.
  • the present invention is an ultraviolet curable resin which has less damage to an optical substrate, is capable of bonding at least two optical substrates even in a thin film thickness, and has good curability, flexibility, and adhesiveness.
  • An object of the present invention is to provide an adhesive composition, a cured product thereof, and a method for producing an optical member using a UV-curable adhesive composition.
  • the present inventors completed the present invention as a result of earnest research in order to solve the above-mentioned subject. That is, the present invention relates to the following (1) to (12).
  • a resin composition used to bond at least two optical substrates which is an intramolecular hydrogen abstraction type photopolymerization initiator (A), a photopolymerizable oligomer (B), and a (meth) acrylate monomer ( C)
  • the content of the solvent in the resin composition is 5% by weight or less
  • the weight average molecular weight of the photopolymerizable oligomer (B) is in the range of 7000 to 100000
  • a UV-curable adhesive composition having a light transmittance of 85% or more in a wavelength range of 450 to 800 nm.
  • the photopolymerizable oligomer (B) has at least one skeleton selected from the group consisting of urethane (meth) acrylates, or polypropylene, polybutadiene, hydrogenated polybutadiene, polyisoprene and hydrogenated polyisoprene (meta )
  • the ultraviolet-curable adhesive composition according to (1) which is an acrylate.
  • the photopolymerizable oligomer (B) is a urethane (meth) acrylate having at least one skeleton selected from the group consisting of polypropylene, polybutadiene, hydrogenated polybutadiene, polyisoprene and hydrogenated polyisoprene ( 1) or the ultraviolet curable adhesive composition as described in (2).
  • a glass substrate, a transparent resin substrate, a glass substrate on which a transparent electrode is formed, a substrate in which a glass substrate or a film on which a transparent electrode is formed is bonded to a transparent substrate, the liquid crystal display unit.
  • the ultraviolet-curable adhesive composition according to any one of (1) to (8) which is at least one optical substrate selected from the group consisting of a plasma display unit and an organic EL display unit.
  • a method of producing an optical member in which at least two optical substrates having the following steps 1 to 2 are bonded, (Step 1) A UV curable adhesive composition according to any one of (1) to (10) is applied to at least one optical substrate to form a coating layer, and UV light is applied to the coating layer. Step of obtaining an optical substrate having a cured product layer by irradiating (step 2) bonding the other optical substrate to the cured product layer of the optical substrate obtained in step 1 or A step of bonding the cured product layers of the other optical substrates obtained in 1.
  • the present invention it is possible to bond at least two optical substrates with a thin film thickness with less damage to the optical substrate, and further to use ultraviolet light with good curability, flexibility, and adhesiveness. It is possible to provide a curable adhesive composition, a cured product thereof, and a method for producing an optical member using an ultraviolet curable adhesive composition.
  • the ultraviolet-curable adhesive composition of the present invention is a resin composition used to bond at least two optical substrates together, and includes an intramolecular hydrogen abstraction type photopolymerization initiator (A) and a photopolymerizable oligomer (B). And a (meth) acrylate monomer (C), the content of the solvent in the resin composition is 5% by weight (wt%) or less, and the weight average molecular weight of the photopolymerizable oligomer (B) is 7,000 to 100,000.
  • the light transmittance of the cured product of the resin composition in the wavelength range of 450 to 800 nm is 85% or more.
  • the other component which can be added to the ultraviolet curable adhesive composition used for an optical member as an arbitrary component can be included.
  • (meth) acrylate is a term referring to either or both of acrylate and methacrylate.
  • (meth) acryloyl group” described below is a term that refers to either or both of an acryloyl group and a methacryloyl group.
  • octyl (meth) acrylate refers to either or both of octyl acrylate and octyl methacrylate.
  • a preferred average transmittance of the sheet in the wavelength region of 450 to 800 nm is It is at least 85% or more, more preferably 90% or more.
  • the composition ratio of the ultraviolet-curable adhesive composition is preferably 0.1 to 5% by weight of the intramolecular hydrogen abstraction type photopolymerization initiator (A) and 5 to 50% by weight of the photopolymerizable oligomer (B).
  • %, (Meth) acrylate monomer (C) is 20 to 94% by weight, and the other components are the balance.
  • the intramolecular hydrogen abstraction type photopolymerization initiator (A) in the ultraviolet ray curable adhesive composition of the present invention is not particularly limited, and any one which is generally sold can be used.
  • the intramolecular hydrogen abstraction type photopolymerization initiator By using the intramolecular hydrogen abstraction type photopolymerization initiator, the surface curability can be improved and film formation can be easily performed. For this reason, it is possible to form a cured film predominantly even in a thin film or in a resin having poor curability. Even if the hydrogen abstraction initiator is not an intramolecular hydrogen abstraction initiator, the curability and adhesion are inferior, but if it is an intramolecular hydrogen abstraction initiator, it exhibits excellent functions in both curability and adhesiveness. Can.
  • the intramolecular hydrogen-abstraction photopolymerization initiator (A) contained in the UV-curable adhesive composition of the present invention is not particularly limited, and, for example, methyl benzoyl formate (IRGACURE MBF; manufactured by BASF), oxy Oxyphenyl photopolymerization, such as a mixture of phenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxy-ethoxy) ethyl ester (IRGACURE 754; made by BASF) An initiator etc. are mentioned and you may use together 2 or more types as needed.
  • the photopolymerization initiator contained in the ultraviolet-curable adhesive composition of the present invention may contain a photopolymerization initiator other than the intramolecular hydrogen abstraction type photopolymerization initiator (A), and the intramolecular hydrogen abstraction is
  • the photopolymerization initiators other than the photopolymerization initiator (A) are not particularly limited, and, for example, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl ethoxy phosphine oxide Bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, bis (2,6-dimethoxy benzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184; manufactured by BASF), 2-hydroxy-2-methyl- [4- (1-methyl) Nyl) phenyl] propanol oligo
  • one or two photopolymerization initiators other than the intramolecular hydrogen abstraction type photopolymerization initiator (A) and the intramolecular hydrogen abstraction type photopolymerization initiator (A) are used.
  • the species or more may be mixed and used in any proportion.
  • the weight ratio of the intramolecular hydrogen abstraction type photopolymerization initiator (A) in the ultraviolet-curable adhesive composition of the present invention is usually 0.1 to 5% by weight, preferably 0.3 to 3% by weight. If it is more than 5% by weight, the transparency of the cured resin layer may be deteriorated. If the amount is less than 0.1% by weight, curing may be poor.
  • an acyl phosphine oxide compound for example, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6- trimethyl benzoyl phenyl ethoxy phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, etc. may be mentioned.
  • the acyl phosphine oxide compound is preferably used in combination since it can absorb a wide range of wavelengths because the light absorption region is different from the intramolecular hydrogen abstraction type photopolymerization initiator.
  • the weight ratio of the intramolecular hydrogen abstraction type photopolymerization initiator (A): acyl phosphine oxide compound is preferably 20: 1 to 1: 5, and more preferably 10: 1 to 1: 1.
  • the photopolymerizable oligomer (B) in the ultraviolet curable adhesive composition of the present invention is not particularly limited as long as the weight average molecular weight is in the range of 7,000 to 100,000, but urethane (meth) acrylate, or polypropylene, polybutadiene, water It is preferable to use a (meth) acrylate having at least one or more skeleton selected from the group consisting of added polybutadiene, polyisoprene and hydrogenated polyisoprene.
  • urethane (meth) acrylate is preferable from the viewpoint of adhesive strength, and urethane (meth) having at least one or more skeleton selected from the group consisting of polypropylene, polybutadiene, hydrogenated polybutadiene, polyisoprene and hydrogenated polyisoprene ) Acrylate is more preferred.
  • the weight average molecular weight of the photopolymerizable oligomer (B) is preferably 7,000 to 100,000, more preferably 9,000 to 80,000, and particularly preferably 11,000 to 70000.
  • the weight average molecular weight can be measured using GPC (gel permeation chromatography) under the following conditions.
  • the content ratio of the photopolymerizable oligomer (B) is usually 5 to 50% by weight, preferably 5 to 30% by weight, and more preferably 5 to 25% by weight in the ultraviolet-curable adhesive composition. 5 to 20% by weight is particularly preferred.
  • the weight ratio of the photopolymerizable oligomer (B) to the (meth) acrylate monomer (C) is preferably 1: 1 to 1:25, more preferably 4: 6 to 1:20, 3: 7 To 1:20 is more preferable, and 1: 4 to 1:20 is particularly preferable.
  • the urethane (meth) acrylate is obtained, for example, by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate.
  • polyhydric alcohols examples include polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, hydrogenated polyisoprene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4 Alkylene glycol having 1 to 10 carbon atoms such as butanediol and 1,6-hexanediol, triol such as trimethylolpropane and pentaerythritol, tricyclodecane dimethylol and cyclic skeleton such as bis- [hydroxymethyl] -cyclohexane
  • polyhydric alcohols and polybasic acids eg, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.
  • polypropylene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, hydrogenated polyisoprene glycol are preferable, and from the viewpoint of transparency and flexibility, weight average molecular weight Particularly preferred are polypropylene glycols of at least 2000, hydrogenated polybutadiene glycols and hydrogenated polyisoprene glycols. Hydrogenated polybutadiene glycol or polypropylene glycol is preferable from the viewpoint of color-changing properties such as heat-resistant colorability and compatibility. On the other hand, polypropylene glycol is preferable from the viewpoint of compatibility with other components.
  • the upper limit of the weight average molecular weight at this time is not particularly limited, it is preferably 10000 or less, more preferably 5000 or less. Moreover, you may use together 2 or more types of polyhydric alcohol as needed.
  • polyisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl isocyanate.
  • isophorone diisocyanate is preferable from the viewpoint of toughness.
  • hydroxyl group-containing (meth) acrylate for example, hydroxy C2 to C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc., dimethylol cyclohexyl mono ( Meta) acrylate, hydroxycaprolactone (meth) acrylate, hydroxyl group-terminated polyalkylene glycol (meth) acrylate and the like can be used.
  • the reaction for obtaining the urethane (meth) acrylate is performed, for example, as follows. That is, polyisocyanate is mixed with polyhydric alcohol per equivalent of hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents, and the reaction temperature is The reaction is preferably performed at 70 to 90 ° C. to synthesize a urethane oligomer. Next, a hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of isocyanate groups of the urethane oligomer, and the reaction is carried out at 70 to 90 ° C. ) Acrylates can be obtained.
  • the weight average molecular weight of the urethane (meth) acrylate is preferably about 7,000 to 100,000, more preferably 9,000 to 80000, and still more preferably 11,000 to 70000. If the weight average molecular weight is less than 7,000, the flexibility may be impaired, and if the weight average molecular weight is greater than 100,000, the curability may be poor.
  • the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is preferably 1.5 or more.
  • the urethane (meth) acrylate can be used by mixing one or two or more in any ratio.
  • the weight ratio of the urethane (meth) acrylate in the ultraviolet curable adhesive composition of the present invention is usually 5 to 50% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight, 20% by weight is particularly preferred.
  • the (meth) acrylate having a polybutadiene backbone has a (meth) acryloyl group at the terminal or side chain of the polybutadiene molecule.
  • a (meth) acrylate having a polybutadiene backbone can be obtained as "BAC-45" (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
  • the weight average molecular weight of the (meth) acrylate having a polybutadiene skeleton is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.
  • the weight ratio of the (meth) acrylate having a polybutadiene skeleton in the ultraviolet curable adhesive composition of the present invention is usually 5 to 50% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight. Preferably, 5 to 20% by weight is particularly preferred.
  • the (meth) acrylate having a polyisoprene backbone has a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule.
  • a (meth) acrylate having a polyisoprene backbone can be obtained as "UC-203" (manufactured by Kuraray Co., Ltd.).
  • the weight average molecular weight of the (meth) acrylate having a polyisoprene skeleton is preferably 7,000 to 100,000, and more preferably about 20,000 to 50,000.
  • the weight ratio of the (meth) acrylate having a polyisoprene skeleton in the ultraviolet curable adhesive composition of the present invention is usually 5 to 50% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight. Preferably, 5 to 20% by weight is particularly preferred.
  • the UV curable adhesive composition of the present invention may contain a photopolymerizable oligomer having a weight average molecular weight outside the range of 7,000 to 100,000, as long as the properties of the present invention are not impaired.
  • the (meth) acrylate monomer (C) contained in the ultraviolet-curable adhesive composition of the present invention is not particularly limited, but preferably has one (meth) acryloyl group in the molecule (meth) Acrylate can be suitably used.
  • the (meth) acrylate monomer (C) is at least one skeleton selected from the group consisting of urethane (meth) acrylate, or polypropylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.
  • eliminated the (meth) acrylate which has is shown.
  • (meth) acrylate monomers having one (meth) acryloyl group in the molecule include octyl (meth) acrylate, isooctyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate and isodecyl (Meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, etc.
  • the monofunctional (meth) acrylate monomer (C-1) represented by (wherein X represents an acryloyl group or a methacryloyl group, and R 1 represents an alkyl group having 8 to 18 carbon atoms) Is preferred. Furthermore, from the viewpoint of volatility and reactivity, normal octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate and isostearyl (meth) acrylate are more preferable.
  • a monofunctional (meth) acrylate monomer (C-2) having an alicyclic or heterocyclic ring examples include tetrahydrofurfuryl (meth) acrylate, acryloyl morpholine, dicyclopentenyl (meth) acrylate, cyclic trimethylolpropane Formal acrylate, dicyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate 1-adamantyl methacrylate, dicyclopentadiene oxyethyl (meth) acrylate and the like.
  • acryloyl morpholine, dicyclopentanyl (meth) acrylate and isobornyl (meth) acrylate are more preferable from the viewpoint of compatibility with other materials, and acryloyl morpholine and dicyclopentanyl (meth) acrylate are preferable from the viewpoint of adhesiveness. More preferable.
  • the (meth) acrylate monomer which has a hydroxyl group as a (meth) acrylate monomer (C) from a viewpoint of the tolerance of high temperature and / or high humidity.
  • a (meth) acrylate monomer which has a hydroxyl group hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate etc. can be mentioned.
  • the (meth) acrylate monomer (C-1) represented by the above formula (1), the monofunctional (meth) acrylate monomer (C-2) having an alicyclic or heterocyclic ring, and (meth) having a hydroxyl group It is preferable to contain two or more kinds of different classifications selected from the group consisting of acrylates. Moreover, it is more preferable to contain three or more types of different classifications. When two or more kinds are contained, any (meth) acrylate monomer is preferably contained in an amount of 4 to 90% by weight, more preferably 4 to 80% by weight, in the ultraviolet-curable adhesive composition.
  • (meth) acrylate monomer represented by the above-mentioned formula (1) (monofunctional (meth) acrylate monomer having an alicyclic or heterocyclic ring + having a hydroxyl group (meth).
  • the weight ratio of (a) acrylate monomer) is preferably 1: 2 to 20: 1, and more preferably 1: 1 to 10: 1.
  • the (meth) acrylate monomer (C) is preferably an acrylate monomer.
  • the ultraviolet curable adhesive composition of the present invention contains (meth) acrylates other than (meth) acrylates having one (meth) acryloyl group in the molecule within the range that the characteristics of the present invention are not impaired.
  • Can 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 to C10 alkanes such as caprolactone modified hydroxypivalate neopentyl glycol di (meth) acrylate and ethylene oxide modified phosphoric acid di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, etc.
  • these (meth) acrylate monomer (C) components can be used by mixing one kind or two or more kinds in an arbitrary ratio.
  • the proportion by weight of the (meth) acrylate monomer (C) in the ultraviolet-curable adhesive composition of the present invention is usually 20 to 95% by weight, preferably 25 to 95% by weight, more preferably 30 to 95% by weight. When the amount is less than 20% by weight, the curability is poor, and when the amount is more than 95% by weight, the shrinkage is large.
  • Epoxy (meth) acrylate can be used for the ultraviolet curable adhesive composition of the present invention as long as the properties of the present invention are not impaired.
  • Epoxy (meth) acrylates have the function of improving the curability and improving the hardness and curing speed of the cured product.
  • any epoxy (meth) acrylate obtained by reacting a glycidyl ether type epoxy compound and (meth) acrylic acid can be used, but preferably used epoxy (meth) acrylate
  • a glycidyl ether type epoxy compound for obtaining 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 Ether, diglycidyl ether of hydrogenated bisphenol F or its alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether Neopentyl glycol diglycidyl ether, butanediol diglycidyl ether hexanediol diglycidyl ether to, cyclohexanedimethanol digly
  • the 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 reacted in a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per equivalent of the 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, tetraethylammonium chloride and the like.
  • paramethoxyphenol, methylhydroquinone and the like can be used as a polymerization inhibitor to prevent polymerization during the reaction.
  • the epoxy (meth) acrylate which can be suitably used in the present invention is bisphenol A 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 proportion by weight of the epoxy (meth) acrylate in the ultraviolet-curable adhesive composition of the present invention is usually 1 to 20% by weight, preferably 5 to 15% by weight.
  • the UV-curable adhesive composition of the present invention can contain, as other components, a softening component described later, an additive described later, and the like.
  • the content ratio of the other components to the total amount of the ultraviolet-curable adhesive composition of the present invention is the remainder obtained by reducing the total amount of the components (A), (B) and (C) from the total amount. , It is a ratio to the total amount.
  • the content ratio of the other components with respect to the total amount of the ultraviolet curable adhesive composition of the present invention is preferably 5 to 75% by weight, more preferably 15 to 75% by weight, particularly preferably 35 It is about 65% by weight.
  • a softener is a compound which does not have a (meth) acryloyl group here.
  • amines and the like that can be a photopolymerization initiation aid can be used in combination with the above-mentioned photopolymerization initiator.
  • examples of amines which can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester and p-dimethylaminobenzoic acid isoamyl ester.
  • the content ratio in the ultraviolet curable adhesive composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight. .
  • a softening component can be used in the ultraviolet-curable adhesive composition of the present invention as required.
  • Specific examples of the softening component that can be used include polymers compatible with the composition, oligomers, phthalic esters, phosphoric esters, glycol esters, citric esters, aliphatic dibasic esters, fatty acids Esters, epoxy plasticizers, castor oils, terpene resins, hydrogenated terpene resins, rosin resins, hydrogenated rosin resins, liquid terpenes and the like can be mentioned.
  • oligomers and polymers examples include oligomers or polymers having a polyisoprene backbone, a hydrogenated polyisoprene backbone, a polybutadiene backbone, a hydrogenated polybutadiene backbone or a xylene backbone, and esters thereof, polybutenes and the like. From the viewpoint of transparency, hydrogenated terpene resins, hydrogenated polyisoprene, hydrogenated polybutadiene, polybutene, and liquid terpenes are preferable.
  • hydrogenated terpene resins containing a hydroxyl group at the end or side chain hydrogenated polyisoprene containing a hydroxyl group at the end or side chain, or a hydroxyl group
  • hydroxyl group-containing polymers such as hydrogenated polybutadiene, which are contained in side chains, hydrogenated rosin resins, and liquid terpene resins are particularly preferable.
  • the proportion by weight of such a softening component in the UV-curable adhesive composition is usually 5 to 40% by weight, preferably 10 to 35% by weight when a solid softening component is used.
  • a liquid softening component is used, it is generally 10 to 70% by weight, preferably 20 to 60% by weight.
  • the total proportion by weight of the solid and liquid softening components in the UV-curable adhesive composition is usually 5 to 90% by weight, preferably 10 to 75% by weight.
  • the amount of the solvent is 0% by weight or more and 5% by weight or less in the ultraviolet curable adhesive composition. This is because, if the solvent is contained in a large amount, film formation becomes difficult, and in addition, a concave portion is generated in the cured product and the curability is adversely affected.
  • 0 weight% or more and 3 weight% or less are preferable in a ultraviolet curable adhesive composition, and 0 weight% or more and 2 weight% or less are more preferable.
  • 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-diethylene bis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-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-hexamethylene bis (3,5-di-t-t
  • silane coupling agent examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxy
  • polymerization inhibitor paramethoxyphenol, methylhydroquinone and the like can be mentioned.
  • 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 (Adeka Co., Ltd.
  • Beta.-lauryloxycarbonyl) ethyl-7-oxa-3,20-diazadispiro [5.1.11.2] heneicosane-21-one, .beta.-alanine, N,-(2,2,6,6 -Tetramethyl-4 Piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4, 4-Tetramethyl-7-oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11] -Heneicosan-20-propanoic acid dodecyl ester / tetradecyl ester, propanedi
  • the weight ratio of various additives in the ultraviolet-curable adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably It is 0.02 to 0.5% by weight.
  • the ultraviolet-curable adhesive composition of the present invention can be obtained by mixing and dissolving the above-described components at normal temperature to 80 ° C., and if necessary, impurities may be removed by an operation such as filtration.
  • the “25 ° C. viscosity” of the composition is measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).
  • TV-200 manufactured by Toki Sangyo Co., Ltd.
  • the viscosity of 25 ° C. is 1 to 300 mPa ⁇ s.
  • the range of s is more preferable, and the viscosity at 25 ° C. is more preferably in the range of 1 to 100 mPa ⁇ s.
  • the viscosity at 25 ° C. is particularly preferably in the range of 1 to 80 mPa ⁇ s, very preferably in the range of 1 to 60 mPa ⁇ s, and the viscosity at 25 ° C. in the range of 1 to 30 mPa ⁇ s. Is most preferred.
  • the viscosity is higher than 10000 mPa ⁇ s, the coating property to the substrate is deteriorated, and the application of the ultraviolet curable adhesive composition is impossible, for example, the thin dispenser, the bar coater method, the ink jet method, etc. The method is limited.
  • the elongation at break of the cured product at 25 ° C. is preferably 200% or more, and more preferably 400% or more.
  • “Elongation at break of cured product at 25 ° C.” using a tensile tester (RTG-1210, manufactured by A & D Co., Ltd.), under the conditions of 25 ° C., the tensile speed is 100 mm / min, width 10 mm, length 30 mm It is measured by pulling the cured product of the UV curable adhesive composition of the present invention. Specifically, the elongation at break (%) is calculated by ([displacement length at break] / [length between chucks at start of measurement]) ⁇ 100.
  • the cured product of the UV curable adhesive composition is prepared, for example, by the following method. First, two release films are prepared, the composition is dropped onto one of them, the release films are bonded together so that the thickness of the resin layer is 500 ⁇ m, and then a high pressure mercury lamp (80 W / cm, ozone-less) Then, the resin composition is cured by irradiating an ultraviolet ray with a cumulative light amount of 3000 mJ / cm 2 . Subsequently, the cured resin is cut out into a width of 10 mm and a length of 30 mm, and the two release films are peeled to obtain a cured product. When the elongation at break is lower than 200%, it becomes difficult to follow the deformation of the substrate, and peeling is likely to occur when the substrate is curved or when a temperature environment such as low temperature or high temperature occurs. turn into.
  • Step 1 it is preferable that at least two optical substrates be bonded by the following (Step 1) to (Step 3).
  • Step 3 When it is judged that sufficient adhesive strength can be secured at the stage of (Step 2), it is possible to omit (Step 3).
  • Step 1 The ultraviolet curable adhesive composition is applied to at least one optical substrate to form a coated layer, and the coated layer is irradiated with ultraviolet light to form an optical layer in the coated layer.
  • the cured portion (hereinafter referred to as "cured portion of the cured product layer” or simply “cured portion”) present on the substrate side (the lower side of the coated layer) and the opposite side to the optical substrate side (the upper portion of the coated layer)
  • a step of obtaining an optical substrate having a cured product layer having an uncured portion (hereinafter referred to as "uncured portion of the cured product layer” or simply “uncured portion") present on the side, usually the atmospheric side) .
  • the curing rate of the coated layer after ultraviolet irradiation is not particularly limited, and an uncured portion exists on the surface opposite to the optical substrate (upper side of the coated layer, usually the air side). I wish I had it.
  • Step 2 Another optical substrate is bonded to the uncured portion of the cured product layer of the optical substrate obtained in Step 1, or the other optical substrate obtained in Step 1 is cured A process of bonding together the uncured portions of the product layer.
  • Step 3 A step of irradiating the cured material layer having an uncured portion in the bonded optical substrate with ultraviolet light through the optical substrate having a light shielding portion to cure the cured material layer.
  • the UV curable adhesive composition of the present invention is applied in the state of liquid resin to at least one substrate when bonding two or more substrates together, and to the other substrate. It is applied in a liquid resin state or in a state having an uncured portion. In the case of curing with ultraviolet light after these are pasted together, a particularly excellent bonding effect can be obtained, and the presence of air can be prevented. Therefore, it is particularly preferable to use in such a case.
  • FIG. 1 is a process chart showing a first embodiment of a manufacturing process of an optical member using the ultraviolet curable adhesive composition of the present invention.
  • This method is a method of obtaining an optical member by bonding the liquid crystal display unit 1 and the transparent substrate 2.
  • the liquid crystal display unit 1 refers to one in which a liquid crystal material is sealed between a pair of substrates on which electrodes are formed, and in which a polarizing plate, a drive circuit, a signal input cable, and a backlight unit are provided.
  • the transparent substrate 2 is a transparent substrate such as a glass plate, a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate, and an alicyclic polyolefin polymer (COP) plate.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • COP alicyclic polyolefin polymer
  • the transparent substrate 2 one having a black frame-shaped light shielding portion 4 on the surface of the transparent substrate can be suitably used, and the light shielding portion 4 is formed by sticking of a tape, coating of paint, printing or the like.
  • the present invention can be applied to those not having the light shielding portion 4, in the following description of the first to third embodiments, the case where the light shielding portion 4 is provided will be described as a specific example. In the case where the light shielding portion 4 is not provided, if “a transparent substrate having a light shielding portion” is read as a “transparent substrate”, it can be considered as an example where the light shielding portion is not provided.
  • an ultraviolet-curable adhesive composition is applied to the display surface of the liquid crystal display unit 1 and the surface of the transparent substrate 2 having the light shielding portion on which the light shielding portion is formed.
  • the coating method may, for example, be a slit coater, a roll coater, a spin coater, a screen printing method, a bar coater, a doctor blade method or an inkjet method.
  • the UV curable adhesive composition applied to the surface of the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion may be the same, or different UV curable adhesive compositions may be used. Absent. It is usually preferred that both be the same UV curable adhesive composition.
  • the film thickness of the cured product of each ultraviolet curable adhesive composition is adjusted so that the cured resin layer 7 after bonding is 10 to 500 ⁇ m, preferably 20 to 350 ⁇ m, and more preferably 30 to 150 ⁇ m. .
  • the film thickness of the cured product layer of the ultraviolet curable adhesive composition present on the surface of the transparent substrate 2 having the light shielding part depends on the film thickness, it is usually present on the surface of the liquid crystal display unit 1 It is preferable that the thickness is as large as or thicker than the thickness of the cured layer of the UV curable adhesive composition. This is to minimize the portion remaining uncured even after irradiation with ultraviolet light in step 3 described later, thereby eliminating the possibility of curing failure.
  • the UV curable adhesive composition layer 5 after application is irradiated with UV light 8 to cure the lower portion of the coated layer (on the liquid crystal display unit side or the transparent substrate side as viewed from the UV curable adhesive composition) (
  • the uncured part (not shown in the figure) present on the upper side of the coating layer (the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side) (air side when performed in the atmosphere)
  • a cured product layer 6 is obtained.
  • the irradiation dose is preferably 5 to 2000 mJ / cm 2 , particularly preferably 10 to 1000 mJ / cm 2 . If the amount of irradiation is too small, the degree of curing of the ultraviolet curable adhesive composition of the finally bonded optical member may be insufficient.
  • uncured refers to a fluidizable state at 25 ° C. environment.
  • any light source may be used as long as it is a lamp that emits ultraviolet to near-ultraviolet light.
  • the wavelength of the ultraviolet light irradiated to the ultraviolet curable adhesive composition is not particularly limited, but when the maximum illuminance in the wavelength region of 320 nm to 450 nm is 100, the wavelength region of 200 to 320 nm 30 or less is preferable and, as for the ratio (illuminance ratio) of the largest illumination intensity in, it is especially preferable in it being 10 or less.
  • the adhesive strength of the finally obtained optical member is inferior. There is a risk of This is because if the illuminance at a low wavelength is high, the curing of the ultraviolet curable adhesive composition proceeds excessively at the time of curing in Step 1, and the contribution to the adhesion at the time of curing in ultraviolet irradiation in Step 3 decreases. It is thought that it is because it does.
  • a method of irradiating the ultraviolet ray so as to obtain the above illumination ratio for example, a method of applying a lamp satisfying the condition of the illumination ratio as a lamp for irradiating ultraviolet to near-ultraviolet light rays;
  • a base material for example, a short wave ultraviolet cut filter, a glass plate, a film, etc.
  • a base material for example, a short wave ultraviolet cut filter, a glass plate, a film, etc.
  • step 1 irradiation with ultraviolet light is usually performed in the air at the upper surface on the coating side (the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side from the ultraviolet curable adhesive composition) (normal air) It is preferable to irradiate from surface.
  • UV curable adhesive composition When the ultraviolet curable adhesive composition is cured in the air, the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side is the air side.
  • ultraviolet rays may be irradiated in a vacuum environment or environment of a gas such as nitrogen that does not cause curing inhibition.
  • a gas for example, nitrogen
  • the state of the uncured portion and the film thickness of the uncured portion can be adjusted. That is, by blowing oxygen or ozone to the surface of the coating layer, oxygen inhibition of the curing of the ultraviolet curable adhesive composition occurs on the surface, so that the uncured portion of the surface is ensured, or uncured.
  • the film thickness of the portion can be increased.
  • Step 2 Next, as shown in FIG. 1B, the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion are bonded to each other such that the uncured portions face each other. Bonding can be performed either in the air or in a vacuum. Here, in order to prevent the formation of air bubbles during bonding, bonding in vacuum is preferable. As described above, when the cured product of the ultraviolet curable adhesive composition having the cured portion and the uncured portion on each of the liquid crystal display unit and the transparent substrate is obtained and then bonded, improvement in adhesion can be expected. Bonding can be performed by pressing, pressing or the like.
  • UV rays 8 are irradiated to the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 from the side of the transparent substrate 2 having the light shielding portion.
  • the adhesive composition (coated layer) is cured.
  • the dose of ultraviolet rays is preferably about 100 ⁇ 4000mJ / cm 2 in accumulated light quantity, particularly preferably 200 ⁇ 3000mJ / cm 2 approximately.
  • any light source may be used as long as it is a lamp that irradiates ultraviolet to near-ultraviolet light.
  • low-pressure, high-pressure or ultra-high pressure mercury lamps, metal halide lamps, (pulsed) xenon lamps, LED lamps or electrodeless lamps etc. may be mentioned.
  • an optical member as shown in FIG. 4 can be obtained.
  • the optical member of the present invention may be manufactured by the following modified second embodiment.
  • the details of each step are the same as those in the first embodiment described above, and thus the description of the same parts will be omitted.
  • Step 1 First, as shown in FIG. 2 (a), an ultraviolet-curable adhesive composition is applied to the surface of the transparent substrate 2 having the light shielding portion on which the light shielding portion 4 is formed, and then the obtained applied layer (ultraviolet light
  • the curable adhesive composition layer 5) is irradiated with ultraviolet light 8, and the cured portion present on the lower side of the coated layer (the transparent substrate side as viewed from the ultraviolet curable adhesive composition) and the upper side of the coated layer (transparent)
  • a cured product layer 6 having an uncured portion present on the side opposite to the substrate side is obtained.
  • the wavelength of the ultraviolet light irradiated to the ultraviolet curable adhesive composition is not particularly limited, but when the maximum illuminance in the wavelength region of 320 nm to 450 nm is 100, the ratio of the maximum illuminance in the wavelength region of 200 to 320 nm Is preferably 30 or less, and more preferably 10 or less. Assuming that the maximum illuminance in the wavelength region of 320 nm to 450 nm is 100, if the ratio of the maximum illuminance in the wavelength region of 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member may be inferior. is there.
  • Step 2 Next, as shown in FIG. 2 (b), the transparent substrate 2 having the liquid crystal display unit 1 and the light shielding portion is formed in such a manner that the uncured portion of the obtained cured product layer 6 and the display surface of the liquid crystal display unit 1 face each other. to paste together. Bonding can be performed either in the air or in a vacuum.
  • Step 3 Next, as shown in FIG. 2 (c), ultraviolet rays 8 are irradiated to the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 from the side of the transparent substrate 2 having the light shielding portion.
  • the cured product layer 6 having the uncured portion of the adhesive composition is cured.
  • optical member shown in FIG. 4 can be obtained.
  • FIG. 3 is a process chart showing a third embodiment of a method for producing an optical member using the ultraviolet-curable adhesive composition of the present invention.
  • the details of each step are the same as those in the first embodiment described above, and thus the description of the same parts will be omitted.
  • the same members as those in the first embodiment described above are designated by the same reference numerals in the drawings, and the description thereof will not be repeated here.
  • Step 1 First, as shown in FIG. 3A, an ultraviolet-curable adhesive composition was applied to the surface of the liquid crystal display unit 1. Thereafter, the ultraviolet curable adhesive composition layer 5 is irradiated with the ultraviolet light 8 so that the cured portion existing on the lower side of the coated layer (the transparent substrate side as viewed from the ultraviolet curable adhesive composition) and the upper portion of the coated layer A cured product layer 6 having uncured portions present on the side (opposite to the transparent substrate side) is obtained.
  • the wavelength of the ultraviolet light irradiated to the ultraviolet curable adhesive composition is not particularly limited, but when the maximum illuminance in the wavelength range of 320 nm to 450 nm is 100, the maximum illuminance in the wavelength range of 200 to 320 nm is 30. The following is preferable, and 10 or less is particularly preferable. Assuming that the maximum illuminance in the wavelength region of 320 nm to 450 nm is 100, if the maximum illuminance in the wavelength region of 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member is inferior.
  • Step 2 Next, as shown in FIG. 3 (b), the liquid crystal display unit 1 is formed such that the surface on which the light shielding portion is formed on the transparent substrate 2 having the light shielding portion and the uncured portion of the obtained cured product layer 6 is opposed. And the transparent substrate 2 having the light shielding portion are attached. Bonding can be performed either in the air or in a vacuum.
  • Step 3 As shown in FIG. 3C, the ultraviolet curing is performed by irradiating the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 with ultraviolet light 8 from the transparent substrate 2 side having the light shielding portion.
  • the cured product layer 6 having the uncured portion of the adhesive composition is cured.
  • optical member shown in FIG. 4 can be obtained.
  • each of the above-described embodiments describes some of the embodiments of the method for producing an optical member of the present invention with one specific optical substrate.
  • each embodiment has been described using a transparent substrate having a liquid crystal display unit and a light shielding portion, in the manufacturing method of the present invention, various members described later can be used as an optical substrate instead of the liquid crystal display unit.
  • various members described later can be used as an optical substrate.
  • optical substrates such as a liquid crystal display unit and a transparent substrate, a film bonded to these various members with another optical substrate layer (for example, a cured product layer of a UV curable adhesive composition) Or what laminated
  • the coating method of the ultraviolet curable adhesive composition, the film thickness of the resin cured product, the irradiation amount and the light source at the time of ultraviolet irradiation, and the ultraviolet curable adhesive composition described in the section of the first embodiment is not limited to the above embodiment, but may be applied to any manufacturing method included in the present invention. it can.
  • At least one optical substrate having a light shielding portion is selected from the group consisting of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, and a glass substrate on which a light shielding portion and a transparent electrode are formed.
  • An optical substrate, and an optical substrate to be bonded to the optical substrate is at least one display unit selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL unit, and an obtained optical member has the light shielding portion
  • One of the optical substrates is a protective substrate having a light shielding portion
  • the other optical substrate to be bonded thereto is a touch panel or a display unit having a touch panel, and at least two optical substrates are bonded to each other
  • the aspect whose optical member is a touch panel which has a protection base material which has a light-shielding part, or a display body unit which has it.
  • the ultraviolet curable adhesive composition as described above is applied to the surface provided with the light shielding portion of the protective substrate having the light shielding portion, or to one or both surfaces of the touch surface of the touch panel. Is preferably applied.
  • One optical base is an optical base having a light shielding portion, another optical base to be bonded thereto is a display unit, and an optical member to which at least two optical bases are bonded is a light shielding portion
  • the above-mentioned UV-curable adhesive is applied to the optical substrate having the light shielding portion on the side provided with the light shielding portion, the display surface of the display unit, or both of them. It is preferred to apply the agent composition.
  • the optical substrate having a light shielding portion for example, a protective plate for a display screen having a light shielding portion or a touch panel provided with a protective substrate having a light shielding portion can be mentioned.
  • the optical substrate having the light shielding portion is a protective plate for a display screen having the light shielding portion
  • the light shielding portion has a light shielding portion. It is the surface on the side where the part is provided.
  • the surface having the light shielding portion is bonded to the touch surface of the touch panel.
  • the surface on the side on which the light shielding portion of the optical base material having the light shielding portion is provided means the substrate surface of the touch panel opposite to the touch surface of the touch panel.
  • the light shielding portion of the optical substrate having the light shielding portion may be in any of the optical substrates, but is usually formed in a frame shape around the transparent plate-like or sheet-like optical substrate, and its width is 0. It is about 1 mm to 10 mm, preferably about 1 to 8 mm, and more preferably about 1.5 to 5 mm.
  • the optical member is It can be used in the method of manufacturing.
  • the cure shrinkage of the cured product of the ultraviolet-curable adhesive composition of the present invention is preferably 10.0% or less, and particularly preferably 6.0% or less.
  • the transmittance of the cured product of the ultraviolet curable adhesive composition of the present invention in the wavelength range of 450 nm to 800 nm is preferably 85% or more, and more preferably 90% or more.
  • the transmittance is less than 85%, it is difficult for light to be transmitted, and when used in a display device, the visibility is reduced.
  • the UV curable adhesive composition of the present invention can be suitably used as an adhesive for producing an optical member by laminating a plurality of optical substrates according to the above (Step 1) to (Step 3).
  • an optical base material used in the manufacturing method of the optical member of this invention a transparent plate, a sheet
  • optical substrate means both an optical substrate having no light shielding portion on the surface and an optical substrate having a light shielding portion on the surface.
  • at least one of a plurality of optical substrates used is an optical substrate having a light shielding portion.
  • a transparent plate or sheet is a sheet or transparent plate obtained by laminating a plurality of films or sheets such as polarizing plates, a sheet or transparent plate not laminated, and a transparent plate made of inorganic glass Plates (inorganic glass plates and their processed products such as lenses, prisms, ITO glass) and the like can be used.
  • the optical base material used in the present invention is a laminate comprising a plurality of functional plates or sheets such as a touch panel (touch panel input sensor) or a display unit described below in addition to the above-mentioned polarizing plate etc. Also referred to as "body”.
  • a sheet which can be used as an optical base material used for the present invention an icon sheet, a makeup sheet, and a protection sheet are mentioned.
  • a board (transparent board) which can be used for the manufacturing method of the optical member of the present invention a decorative board and a guard board are mentioned.
  • materials of these sheets or plates those listed as materials of the transparent plate can be applied. Examples of the material of the touch panel surface that can be used as an optical substrate used in the present invention include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.
  • the thickness of the plate-like or sheet-like optical substrate such as a transparent plate or sheet is not particularly limited, and usually about 5 ⁇ m to about 5 cm, preferably about 10 ⁇ m to about 10 mm, more preferably about 50 ⁇ m to about 3 mm It is a thickness.
  • the optical base material that can be used as the optical base material used in the present invention can be any of a plate-like rigid base material and a thin and sheet-like base material that can be curved or rolled.
  • a display unit with an optical functional material is used by using a display unit such as a liquid crystal display as one of the optical substrates and using an optical functional material as another optical substrate.
  • a display panel it can also be referred to as a display panel.
  • display apparatuses such as LCD which stuck the polarizing plate to glass, EL display, EL illumination, a quantum dot display, electronic paper, a plasma display, are mentioned, for example.
  • transparent plastic boards such as an acrylic board, PC board, a PET board, a PEN board, a cycloolefin board, a transparent polyimide resin, reinforced glass, a touch panel input sensor are mentioned.
  • the refractive index of the cured product is preferably 1.45 to 1.55 in order to improve the visibility. If it is in the range of the said refractive index, the difference of the refractive index with the base material used as an optical base material can be reduced, and it becomes possible to suppress irregular reflection of light and to reduce an optical loss.
  • An optical substrate having a light shielding portion is a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, a glass substrate on which a light shielding object and a transparent electrode are formed, a light shielding object and a transparent electrode.
  • the optical member according to the above (i), which is an optical substrate selected from the group consisting of transparent resin substrates, and the functional laminate is a display unit or a touch panel.
  • the optical member including the display body knit obtained by the manufacturing method of the present invention and the optical base having the light shielding portion may be incorporated into an electronic device such as a television, a small game machine, a mobile phone, a personal computer, or a wearable device. it can.
  • the composition obtained is applied to a PET film of 100 ⁇ m thickness to a thickness of 100 ⁇ m, and bonded to a COP (cycloolefin polymer) film of 100 ⁇ m thickness, and then a high pressure mercury lamp (80 W / cm from the PET film side)
  • the resin composition was cured by irradiating an ultraviolet ray with an integrated light amount of 3000 mJ / cm 2 with no ozone.
  • the obtained test piece was put into an 80 ° C. environment for 200 hours, and the presence or absence of cracks (breaks, cracks, etc.) of the COP film was confirmed using a microscope. The results are shown in Table 2.
  • ⁇ There is no crack in the COP film.
  • X The COP film is torn or cracked.
  • the composition obtained is applied to a 100 ⁇ m thick COP (cycloolefin polymer) film (4 sides 50 mm each) so as to be 100 ⁇ m thick, and the 100 ⁇ m thick PET film (width 60 mm, length 100 mm) Then, the resin composition was cured by irradiating an ultraviolet ray with a cumulative light quantity of 3000 mJ / cm 2 from a PET film side with a high pressure mercury lamp (80 W / cm, ozone-less).
  • COP cycloolefin polymer
  • compositions A to H, J to L compositions A to H, J to L
  • thickness might be set to 200 micrometers.
  • two slide glasses were pasted together so that each release agent application side might face each other.
  • the resin composition was cured by irradiating ultraviolet rays with a cumulative light quantity of 2000 mJ / cm 2 through a glass with a high pressure mercury lamp (80 W / cm, ozone-free). Then, two slide glasses were exfoliated and the hardened material for transparency measurement was produced.
  • the light transmittance in the wavelength region of 450 to 800 nm was measured using a spectrophotometer (U-3310, Hitachi High-Technologies Corporation). As a result, the light transmittance in the wavelength range of 450 to 800 nm was 85% or more.
  • a slide glass of 0.8 mm in thickness and an acrylic plate of 0.8 mm in thickness are prepared, and the composition A obtained on one side is coated to a film thickness of 200 ⁇ m, and then the other is attached to the coated surface
  • the resin composition was irradiated with ultraviolet light with an integrated light quantity of 3000 mJ / cm 2 through a glass with a high pressure mercury lamp (80 W / cm, ozone-less) to cure the resin composition, and a sample for evaluating adhesion was prepared. This was left for 250 hours in an 85 ° C., 85% RH environment. In the evaluation sample, peeling of the slide glass or the acrylic plate from the cured resin was confirmed visually, but no peeling was observed.
  • Composition A is formed on each of the substrates on the display surface of the liquid crystal display unit having an area of 3.5 inches and the surface on which the light shielding portion is formed on the transparent substrate having the light shielding portion (width 5 mm) in the outer peripheral portion.
  • Weight 5 mm the surface on which the light shielding portion is formed on the transparent substrate having the light shielding portion (width 5 mm) in the outer peripheral portion.
  • the coated layer obtained using an electrodeless ultraviolet lamp (D bulb, manufactured by Heraeus Noble Light Fusion, Inc., D-bulb) on the coated layer obtained, the accumulated light amount from the atmosphere side through an ultraviolet cut filter that blocks light of wavelength 320 nm or less It was irradiated with ultraviolet light of 500 mJ / cm 2 to form a cured product layer having a cured portion and an uncured portion present on the atmosphere side.
  • the ratio of the maximum illuminance in the wavelength region of 200 to 320 nm was 3 when the maximum illuminance in the wavelength region of 320 nm to 450 nm was 100, and the ultraviolet light irradiated to the composition at this time was 100.
  • the transparent substrate which has a liquid crystal display unit and a light-shielding part was bonded together in the form which an unhardened part opposes.
  • the resin cured product layer is cured by irradiating ultraviolet rays of an integrated light quantity of 3000 mJ / cm 2 from a glass substrate side having a light shielding part with an ultra-high pressure mercury lamp (TOSCURE 752, manufactured by Harrison Toshiba Lighting Co., Ltd.), Made.
  • TOSCURE 752 manufactured by Harrison Toshiba Lighting Co., Ltd.
  • (Flexibility) Durability was evaluated by measuring durometer E hardness using a durometer hardness meter (type E) according to the method according to JIS K7215. More specifically, the obtained composition A was poured into a cylindrical mold so as to have a film thickness of 1 cm, and was irradiated with ultraviolet light to sufficiently cure the resin composition. The hardness of the obtained cured product was measured with a durometer hardness meter (type E). As a result, the measured value was less than 10 and the flexibility was excellent.
  • SYMBOLS 1 liquid crystal display unit 2 transparent substrate which has a light shielding part, 3 transparent substrate, 4 light shielding part, 5 ultraviolet curable resin composition (ultraviolet curable adhesive composition), 6 cured material layer which has 6 uncured parts, 7 resin Hardened layer, 8 UV rays

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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