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WO2018159260A1 - Composition adhésive durcissable par un rayonnement d'énergie active pour film ou feuille plastique - Google Patents

Composition adhésive durcissable par un rayonnement d'énergie active pour film ou feuille plastique Download PDF

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Publication number
WO2018159260A1
WO2018159260A1 PCT/JP2018/004576 JP2018004576W WO2018159260A1 WO 2018159260 A1 WO2018159260 A1 WO 2018159260A1 JP 2018004576 W JP2018004576 W JP 2018004576W WO 2018159260 A1 WO2018159260 A1 WO 2018159260A1
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Prior art keywords
component
weight
composition
meth
plastic film
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PCT/JP2018/004576
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English (en)
Japanese (ja)
Inventor
和正 稲田
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to CN201880014998.7A priority Critical patent/CN110366587A/zh
Priority to KR1020197025668A priority patent/KR20190120239A/ko
Priority to JP2019502844A priority patent/JPWO2018159260A1/ja
Publication of WO2018159260A1 publication Critical patent/WO2018159260A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to an active energy ray-curable adhesive composition capable of bonding various plastic films or sheets by irradiation with active energy rays such as ultraviolet rays, visible light, or electron beams, and It is suitably used for the production of various optical films or sheets used for liquid crystal displays, organic EL displays and the like, and can be used in these technical fields.
  • acrylic resin and / or methacrylic resin is (meth) acrylic resin
  • acrylate and / or methacrylate is (meth) acrylate
  • acryloyl group and / or methacryloyl group is (meth) acryloyl.
  • the group and acrylic acid and / or methacrylic acid are represented as (meth) acrylic acid.
  • a plastic film or sheet is collectively expressed as “plastic film or the like”, and a film or sheet is collectively expressed as “film or the like”.
  • an ethylene-vinyl acetate copolymer is used in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film is bonded to a thin-layer adherend made of another material.
  • a solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like.
  • the dry laminating method for pressure bonding is mainly performed.
  • the adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem.
  • a solventless adhesive composition has been studied.
  • the solventless adhesive composition a two-component adhesive composition and an active energy ray-curable adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
  • a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent.
  • the composition has a drawback that it takes a long time to cure.
  • the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and thus has been used in recent years.
  • various displays such as a liquid crystal display and an organic EL display are thin, lightweight, and have low power consumption, and mobile devices, personal computers, televisions, and digital devices equipped with touch panels such as mobile phones, smartphones, tablets, and car navigation systems. Widely used in medium and large image display devices such as signage.
  • the active energy ray-curable adhesive composition is widely used for bonding various optical films and the like used for liquid crystal displays and organic EL displays.
  • a hard coat film provided with functionality such as anti-fingerprint and anti-glare, a touch panel front plate, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an anti-reflection film, an anti-glare film, A lens sheet, a diffusion sheet, etc. are mentioned, and various kinds of plastics are used for these.
  • cellulose-based films such as triacetyl cellulose and (meth) acrylic resins such as polymethyl methacrylate are widely used because they have particularly excellent optical properties such as colorless transparency and optical isotropy. .
  • Non-patent Document 1 Non-patent Document 1
  • Patent Document 1 discloses that a photocation curable adhesive containing a polyfunctional aliphatic epoxy monomer as a main component and containing an alicyclic epoxy monomer and / or an oxetane monomer is a cycloolefin even if the adhesive is thin. It is disclosed that it has excellent adhesion to plastic materials such as polymers and triacetylcellulose.
  • the active energy ray-curable adhesive composition disclosed in Patent Document 1 has a problem that it is inferior in productivity because of its poor cationic curability and large energy required for curing. For this reason, it is necessary to slow down the line speed of the bonding process or increase the number of light sources, and sufficient adhesive strength can be exhibited even with an irradiation dose of 200 mJ / cm 2 or less in UV-B (near 310 nm). It was difficult. Furthermore, according to the results of the study by the present inventors, the composition disclosed in Patent Document 1 has insufficient adhesion to (meth) acrylic resins such as polymethyl methacrylate and alkyl (meth) acrylate polymers. There was a problem that there was.
  • the present invention has been made in view of the above problems, has excellent curability, and adheres to cellulose-based films such as triacetyl cellulose and various plastic films including (meth) acrylic resins such as polymethyl methacrylate.
  • An object of the present invention is to provide an active energy ray-curable adhesive composition for plastic films and the like that is excellent in strength and colorless and transparent.
  • an aromatic epoxy compound having a weight average molecular weight of 500 or more, a polyglycidyl ether, an alicyclic epoxy of a polyol having 2 to 10 carbon atoms As a result of diligent studies to solve the above problems, the present inventors have found that an aromatic epoxy compound having a weight average molecular weight of 500 or more, a polyglycidyl ether, an alicyclic epoxy of a polyol having 2 to 10 carbon atoms.
  • an active energy ray-curable adhesive composition containing a group-containing compound and a cationic photopolymerization initiator at a specific ratio can solve the above-mentioned problems.
  • the present invention (A) Component: Aromatic epoxy compound having a weight average molecular weight of 500 or more (B) Component: Polyglycidyl ether (C) component of a polyol having 2 to 10 carbon atoms: Compound having an alicyclic epoxy group ( Component D): a composition containing a cationic photopolymerization initiator, The content ratio of the components (A) to (D) is in the whole composition. (A) Component: 1 to 30% by weight Component (B): 20 to 70% by weight Component (C): 10 to 60% by weight Component (D): 0.5 to 10% by weight
  • the present invention relates to an active energy ray-curable adhesive composition for plastic films and the like.
  • the component (A) a compound having a weight average molecular weight of 1,000 to 20,000 and a number of epoxy groups contained in one molecule of 2 or more is preferable, and a bisphenol A type epoxy resin and / or bisphenol is preferable. It is more preferable that it is F type epoxy resin.
  • the component (B) is preferably a diglycidyl ether of a diol having 2 to 6 carbon atoms, more preferably a diglycidyl ether of an alkane diol having 4 to 6 carbon atoms.
  • C As a component, the compound which has an alicyclic epoxy group shown to following formula (1) is preferable.
  • a sulfonium salt photocationic polymerization initiator is preferable.
  • the content ratio of the components (A) to (D) is 3 to 20% by weight of the component (A), 30 to 60% by weight of the component (B), and 20 to 50% of the component (C). 1% to 5% by weight of the component (D), 100 parts by weight of the component (B), the content of the component (A) is less than 100 parts by weight, and the content of the component (C) is 100 The amount is preferably less than parts by weight.
  • component (E) a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule is contained in the whole composition in an amount of less than 30% by weight.
  • At least one of the plastic film or the like is a cellulose film or a (meth) acrylic resin.
  • the present invention is a laminate composed of a substrate, a cured product of the active energy ray-curable adhesive composition for a plastic film and the like, and another substrate,
  • the present invention relates to a laminate in which both or one of the base material and the other base material is a plastic film or the like.
  • the plastic film or the like it is preferable that at least one of them is a cellulose film or a (meth) acrylic resin.
  • this invention coats the said composition on a base material, bonds another base material to a coating surface, and irradiates an active energy ray from either the said base material or the said other base material side.
  • a method of manufacturing a laminate The present invention relates to a method for producing a laminate in which both or one of the substrate and the other substrate is a plastic film or the like.
  • an active energy ray-curable adhesive having excellent curability, excellent adhesive strength to various plastic films including cellulose-based films and (meth) acrylic resins, and excellent in colorless transparency.
  • a composition can be provided. For this reason, it can use suitably for manufacture of the various optical films etc. which are used for a liquid crystal display, an organic EL display, etc. Moreover, it can be suitably used for various uses other than displays, such as windows and building materials, which require curability, adhesive strength, and transparency.
  • the present invention (A) Component: Aromatic epoxy compound having a weight average molecular weight of 500 or more (B) Component: Polyglycidyl ether (C) component of a polyol having 2 to 10 carbon atoms: Compound having an alicyclic epoxy group ( Component D): a composition containing a cationic photopolymerization initiator, The content ratio of the components (A) to (D) is in the whole composition. (A) Component: 1 to 30% by weight Component (B): 20 to 70% by weight Component (C): 10 to 60% by weight Component (D): 0.5 to 10% by weight
  • the present invention relates to an active energy ray-curable adhesive composition for plastic films and the like.
  • components (A) to (D), other components, and preferred methods of using the composition of the present invention will be described in detail.
  • the component (A) is an aromatic epoxy compound having a weight average molecular weight (hereinafter referred to as “Mw”) of 500 or more.
  • Mw weight average molecular weight
  • the aromatic epoxy compound means an epoxy compound in which a glycidyl ether group or a glycidyl ester group is directly bonded to an aromatic ring, and even a low molecular weight compound is commonly referred to as an “epoxy resin”. It is a compound.
  • Mw of the component (A) is 500 or more, preferably in the range of 500 to 50,000, more preferably in the range of 1,000 to 20,000, and 1,000 to 10,000. The range is more preferable, and the range of 2,000 to 10,000 is particularly preferable. When Mw is less than 500, the adhesive force with a plastic film or the like, in particular, a (meth) acrylic resin is low. For the same reason, Mw is preferably 50,000 or less.
  • Mw means Mw in terms of polystyrene measured by gel permeation chromatography (GPC).
  • an aromatic epoxy compound that is solid at 25 ° C. is preferable, and specifically, an aromatic epoxy compound having a softening point of 40 ° C. or higher is preferable.
  • an aromatic epoxy compound having a softening point of 40 ° C. or higher it is possible to further improve the adhesive force with a plastic film or the like, in particular, a (meth) acrylic resin.
  • the softening point is more preferably 50 ° C. or higher and 200 ° C. or lower, further preferably 60 ° C. or higher and 170 ° C. or lower, and particularly preferably 70 ° C. or higher and 140 ° C. or lower.
  • the softening point means a measured value measured by the ring and ball method of JIS K7234.
  • the number of epoxy groups contained in one molecule of the component (A) is 2 or more in terms of further improving the adhesive force with a plastic film or the like.
  • a glycidyl ether group is preferable to a glycidyl ester group.
  • the component (A) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an epoxy resin obtained by polycondensation of bisphenol A, bisphenol F and epichlorohydrin, a phenol novolac type epoxy resin, having an Mw of 500 or more.
  • examples include cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, and bisphenol F novolac type epoxy resins.
  • a cured product of the resulting composition is further excellent in adhesive strength, and further has excellent colorless transparency, so that it is bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol A and bisphenol.
  • Epoxy resins obtained by polycondensation of F and epichlorohydrin are more preferable, bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
  • the above-described compounds may be used alone, or two or more kinds may be used.
  • the content of component (A) is 1 to 30% by weight in the entire composition.
  • the content rate of (A) component exceeds 30 weight%, the viscosity of a composition will become high too much and coating property will worsen.
  • a preferred content ratio of the component (A) is 3 to 20% by weight, more preferably 5 to 15% by weight in the whole composition.
  • the content ratio of the component (A) is preferably less than 100 parts by weight, preferably less than 50 parts by weight, with 100 parts by weight of the component (B) to be described later, from the point that the adhesive force to the plastic film or the like is more excellent. More preferably.
  • Component (B) is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms.
  • the “carbon number” in a polyol having 2 to 10 carbon atoms means the number of carbons constituting the site obtained by removing the hydroxyl group from the polyol.
  • the component (B) examples include polyglycidyl ether of alkane polyol, polyglycidyl ether of cycloalkane polyol, polyglycidyl ether of polyalkylene glycol, and polyglycidyl ether of aromatic polyol.
  • the component (B) is preferably a diglycidyl ether of a diol having 2 to 6 carbon atoms, and more preferably a diglycidyl ether of an alkane diol having 4 to 6 carbon atoms.
  • component (B) examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane.
  • component (B) ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydroquinone diglycidyl ether More preferred are diglycidyl ethers of diols having 2 to 6 carbon atoms, exemplified by resorcin diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and the like.
  • component (B) examples include 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like, which are alkanediols having 4 to 6 carbon atoms.
  • Diglycidyl ether is particularly preferable in that the resulting composition has a low viscosity, the cured product is more excellent in adhesive strength, and further colorless transparency is further improved.
  • component (B) As a component, an above described compound may be used independently, or 2 or more types may be used.
  • the content of component (B) is 20 to 70% by weight in the entire composition.
  • the adhesive strength of the composition with respect to many plastic films and the like is lowered.
  • the content rate of (B) component exceeds 70 weight%, the sclerosis
  • a preferred content ratio of the component (B) is 30 to 60% by weight, and more preferably 35 to 50% by weight in the entire composition.
  • Component (C) is a compound having an alicyclic epoxy group.
  • component (C) the compound which has a 2 or more alicyclic epoxy group in 1 molecule is preferable.
  • component (C) examples include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3. , 4-epoxycyclohexanecarboxylate modified with caprolactone, esterified product of polycarboxylic acid and 3,4-epoxycyclohexylmethyl alcohol or caprolactone modified product, dicyclopentadiene dioxide, limonene dioxide, and the like.
  • component (C) a compound represented by the following formula (1) is particularly preferable.
  • component (C) As a component, an above described compound may be used independently, or 2 or more types may be used.
  • the content of component (C) is 10 to 60% by weight in the entire composition.
  • the component (C) is less than 10% by weight, the curability of the composition is deteriorated and the adhesive strength is also deteriorated.
  • the content rate of (C) component exceeds 60 weight%, adhesive force will decline with respect to plastic films etc., such as (meth) acrylic-type resin.
  • a preferred content ratio of the component (C) is 20 to 50% by weight, more preferably 25 to 40% by weight in the entire composition.
  • the content ratio of the component (C) is preferably less than 100 parts by weight, with the component (B) being 100 parts by weight, from the viewpoint that the adhesive strength to a plastic film or the like is further improved.
  • Component (D) component is a photocationic polymerization initiator. That is, it is a compound that generates a cation or a Lewis acid upon irradiation with active energy rays such as ultraviolet rays and electron beams, and initiates polymerization of a cationically curable component such as an epoxy compound or an oxetane compound.
  • Specific examples of the component (D) include sulfonium salt photocationic polymerization initiators, iodonium salt photocationic polymerization initiators, diazonium salt photocationic polymerization initiators, and the like.
  • sulfonium salt photocationic polymerization initiators include, for example: Triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phen
  • iodonium salt-based photocationic polymerization initiators include, for example: Diphenyliodonium tetrakis (pentafluorophenyl) borate diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroantimonate, Di (4-t-butylphenyl) iodonium hexafluorophosphate, Di (4-t-butylphenyl) iodonium hexafluoroantimonate, Trilcumyl iodonium tetrakis (pentafluorophenyl) borate, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, Di (4-nonylphenyl) iodonium hexafluorophosphate, Di (4-alkylphenyl) iodonium hexafluorophosphate
  • diazonium salt photocationic polymerization initiators examples include benzenediazonium hexafluoroantimonate, Examples thereof include benzenediazonium hexafluorophosphate.
  • Component (D) is commercially available, Adekaoptomer SP-100, SP-150, SP-152, SP-170, SP-172 (manufactured by ADEKA), photoinitiator 2074 (manufactured by Rhodia), Kayrad PCI-220, PCI-620 (manufactured by Nippon Kayaku Co., Ltd.), Irgacure 250 (manufactured by Ciba Japan), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S [San Apro ( Co., Ltd.), WPI-113, WPI-116 [Wako Pure Chemical Industries, Ltd.]), BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [Midori Chemical Etc.].
  • a sulfonium salt-based photocationic polymerization initiator is preferable, and a triarylsulfonium salt is more preferable because the active energy ray curability is further excellent and the colorless transparency is further excellent.
  • a triarylsulfonium salt triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable.
  • the above-described compounds may be used alone, or two or more kinds may be used.
  • the content ratio of the component (D) is 0.5 to 10% by weight, preferably 1 to 5% by weight in the whole composition.
  • the content of component (D) is less than 0.5% by weight, the curability of the composition deteriorates, and when it exceeds 10% by weight, the adhesive strength of the composition decreases or the cured product of the composition turns yellow. To do.
  • composition of the present invention essentially comprises the components (A) to (D), but various components (hereinafter referred to as “other components”) may be blended depending on the purpose. it can.
  • Other components include cationic curing compounds other than the components (A), (B), and (C) described above (hereinafter referred to as “other cationic curing components”), water, radical curing components, and various types. An additive is mentioned.
  • Other cationic curable components include compounds having an epoxy group, compounds having an oxetanyl group, and vinyl ether groups other than the components (A), (B), and (C). Compounds and the like. When other cationic curable components are included, the total content thereof is preferably less than 30% by weight, more preferably less than 20% by weight, and less than 10% by weight in the entire composition. More preferably.
  • the compound having an epoxy group other than the component (A), the component (B), and the component (C) include diglycidyl ether of bisphenol A (less than Mw500), diglycidyl ether of bisphenol F (less than Mw500), Diglycidyl ether of brominated bisphenol A (Mw less than 500), phenol novolac type epoxy resin (less than Mw500), cresol novolac type epoxy resin (less than Mw500), biphenyl type epoxy resin (less than Mw500), diglycidyl terephthalate, and phthalate Aromatic epoxy resins having an Mw of less than 500 such as acid diglycidyl ester; and polyethylene glycol (repeating number 6 or more) diglycidyl ether, polypropylene glycol (repeating number 4 or more) diglycidyl ether, polytetra Ji glycol (repeated 3 or more) diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether,
  • epoxidized vegetable oil 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, polybutadiene internal epoxidized product, styrene-butadiene copolymer double bond partially epoxidized Compound (for example, “Epofriend” manufactured by Daicel Chemical Industries, Ltd.) and a compound in which the isoprene unit of the block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, manufactured by KRATON) "L-207”) and the like.
  • component (E) a compound having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less.
  • component (E) examples include bis [(3-ethyloxetane-3-yl) methyl] ether, bis [(3-methyloxetane-3-yl) methyl] ether, and bis [(oxetane-3-yl ) Methyl] ether, 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane -3-yl) methoxy] biphenyl, 2,2′-bis [(3-ethyloxetane-3-yl) meth
  • oxetane compound other than the component (E) include alkoxyalkyl group-containing monofunctional oxetanes such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3-phenoxymethyloxetane.
  • vinyl ether compound examples include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and the like.
  • composition of the water present invention in the overall composition, an appropriate amount of water may be intentionally added.
  • the presence or absence and the amount of water added may be optimized depending on the type of film or the like.
  • the water content is preferably less than 3% by weight in the entire composition.
  • the composition of the present invention may contain a radical curable component.
  • the radical curable component When the radical curable component is included, the total amount thereof is preferably 120 parts by weight or less, more preferably 100 parts by weight or less, with respect to 100 parts by weight of the total amount of the cationic curable component. More preferably, it is no more than parts by weight.
  • the radical curable component include a (meth) acryloyl group-containing compound.
  • various molecular weights can be selected, and any of monomers, oligomers, and polymers may be used.
  • the (meth) acryloyl group-containing compound includes a compound having one (meth) acryloyl group in the molecule (hereinafter referred to as “monofunctional (meth) acrylate”) and two or more (meth) acryloyl groups in the molecule. [Hereinafter referred to as “polyfunctional (meth) acrylate”].
  • monofunctional ((meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate -To, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopentani
  • polyfunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate and 1,9 A di (meth) acrylate of an aliphatic diol such as nonanediol di (meth) acrylate; Di (meth) acrylates of alicyclic diols such as cyclohexane dimethylol di (meth) acrylate and tricyclodecane dimethylol di (meth) acrylate; Alkylene glycol di (meth
  • composition of the present invention contains a radical curable component
  • a radical photopolymerization initiator based on the whole composition.
  • the radical photopolymerization initiator those generally available can be used.
  • composition of this invention may contain various additives other than a sclerosing
  • Various additives include thermal cationic polymerization initiator, photosensitizer, UV absorber, light stabilizer, antioxidant, polymerization inhibitor, silane coupling agent, polyol compound, polymer, tackifier, filler, metal Examples thereof include fine particles, metal oxide fine particles, ion trapping agents, antifoaming agents, leveling agents, dyes and pigments.
  • polymer examples include poly (meth) acrylic acid ester, polyvinyl acetate, polystyrene, polyether and polyester.
  • a polymer what contains cationic polymerizable groups, such as an epoxy group, an oxetanyl group, and a vinyl ether group, can also be used in a molecule
  • radically polymerizable groups such as a (meth) acryloyl group and a vinyl group, can also be used in a molecule
  • Plastic films for the active energy ray-curable adhesive composition The present invention relates to the (A) ⁇ (D) of plastic film or the like for the active energy ray-curable adhesive composition comprising a component as an essential component.
  • the total chlorine content in the composition is preferably 0.1% by weight or less.
  • the method for reducing the total chlorine content in the composition include a method using a distilled purified product as the component (B).
  • the conventional method may be followed.
  • the components (A) to (D) are mixed as necessary, and other components are added, followed by stirring according to a conventional method.
  • the viscosity at 25 ° C. is 1,000 mPa ⁇ s or less. Is more preferably 10 to 500 mPa ⁇ s, and particularly preferably 20 to 100 mPa ⁇ s.
  • the viscosity of the composition means a value measured at 25 ° C. using an E-type viscometer.
  • composition of the present invention can be used for adhesion between plastic films and the like, and adhesion between plastic films and the like and various other substrates (hereinafter referred to as “other substrates”). That is, it can be used for bonding two substrates, at least one of which is a plastic film or the like.
  • base material when simply described as “base material”, it means a general term for plastic films and other base materials.
  • Other examples of the substrate include glass, metal oxide, metal, wood and paper.
  • plastic films examples include cellulose film, (meth) acrylic resin, cycloolefin polymer, polystyrene, acrylic / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, ABS resin, and polyamide. , Polyester, polycarbonate, polyurethane, and chlorinated polypropylene.
  • the cellulose film examples include triacetyl cellulose and cellulose acetate butyrate.
  • the (meth) acrylic resin include polymethyl methacrylate, a copolymer containing methyl methacrylate as a main component, and a copolymer not containing methyl methacrylate as a polymerization monomer.
  • the composition of the present invention can be preferably applied to cellulosic films and (meth) acrylic resins.
  • the metal oxide examples include tin oxide, indium oxide, titanium oxide, and zinc oxide.
  • the metal examples include gold, silver, copper, aluminum, iron, nickel, and titanium.
  • the transparency that is one of the characteristics of the composition of the present invention is often required, so that it is more preferably applied.
  • an activation treatment can be performed on one or both surfaces before applying the composition of the present invention.
  • the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment and etching treatment, and flame treatment, and these may be used in combination.
  • Method of use As a method of using the composition of the present invention, it is sufficient to follow a conventional method, and after applying the composition to a substrate, it is bonded to the other substrate and irradiated with an active energy ray. It is done.
  • the composition of the present invention is suitable for bonding a thin layer adherend as a substrate.
  • the method of use for adhering the thin-layer adherend may be in accordance with a method usually used in the production of laminates. For example, a method in which the composition is applied to a first thin-layer adherend, a second thin-layer adherend is bonded to the composition, and irradiation with active energy rays is performed.
  • Coating on the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.
  • the coating thickness of the composition of the present invention may be selected according to the substrate to be used and the application, but is preferably 0.1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • active energy rays examples include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
  • Various light sources can be used as the light source when cured by ultraviolet rays, and examples thereof include a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED. Among these, a high pressure mercury lamp and a metal halide lamp are particularly preferable.
  • the EB irradiation device In the case of curing with an electron beam, various devices can be used as the EB irradiation device that can be used, such as Cockcroft-Walton type, Van de Graaf type and resonant transformer type devices.
  • the absorbed dose of the electron beam is preferably 1 to 200 kGy, more preferably 10 to 100 kGy.
  • the acceleration voltage of the electron beam may be appropriately set in the range of 80 to 300 kV depending on the film thickness of the film or the like, and 200 kV is preferable if the film thickness of the film or the like is 100 ⁇ m.
  • the oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.
  • the composition of this invention can be preferably used for manufacture of a laminated body.
  • the laminate is composed of a base material, a cured product of the above-described composition, and another base material, and both or one of the base material and the other base material is a plastic film. Etc.
  • the plastic film or the like at least one is preferably a cellulose film or a (meth) acrylic resin.
  • the above-described composition is applied to a base material, and another base material is bonded to the coated surface, and either the base material or the other base material is used.
  • a plastic film or the like is used as both the base material and the other base material, or at least one of the base materials.
  • Specific examples and preferred examples of the substrate are as described above.
  • the coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy ray, etc. are also as described above.
  • hard coat films and touch panels provided with functionality such as anti-fingerprint and anti-glare Front plate, polarizing plate, retardation film, viewing angle compensation film, brightness enhancement film, antireflection film, antiglare film, lens sheet and diffusion sheet.
  • parts means parts by weight
  • numerical values indicating the blending ratios in the table mean% by weight
  • Component (A) J-1004: bisphenol A type solid epoxy resin (Mw: 4,500, softening point 97 ° C.), “jER-1004” manufactured by Mitsubishi Chemical Corporation
  • (C) Component C-2021 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, “Celoxide 2021P” manufactured by Daicel Corporation
  • Component (D) 110P Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd.
  • Component (E) OXT-221: Bis [(3-ethyloxetane-3-yl) methyl] ether, “Aron Oxetane (registered trademark) OXT-221” manufactured by Toagosei Co., Ltd.
  • Examples 1 to 2 and Comparative Examples 1 to 2 1) Production of active energy ray-curable composition The components shown in Table 1 were blended in their respective proportions and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition.
  • an ultraviolet irradiation device with a belt conveyor (using a metal halide lamp) manufactured by iGraphics Co., Ltd.
  • an integrated light amount of 100 mJ / cm 2 (UV-B, UV POWER PUCK manufactured by Heraeus Co., Ltd.) is measured from the surface of PMMA. Value) was irradiated with ultraviolet rays to cure the adhesive composition, and the curing rate was evaluated according to the following method.
  • the obtained laminate was allowed to stand for 1 day under conditions of 23 ° C. and 50% relative humidity, and then evaluated for colorless transparency and adhesive strength according to the following methods.
  • Evaluation methods 1) Evaluation of curing speed The film was peeled off immediately after being irradiated with ultraviolet rays in 1.2) and discharged from the conveyor, and evaluated based on the following criteria. A: It was not an adhesive state but was cured. B: Adhesive state. C: It was liquid.
  • Example 2 contains less than 30% by mass of the component (E) and the content of the component (C) is smaller than the component (B).
  • Example 2 has excellent adhesion to both PMMA and CEL films. However, the film was broken.
  • the composition of Comparative Example 1 in which the (A) component was replaced with a bisphenol A type liquid epoxy resin not corresponding to the (A) component had an insufficient curing rate and an extremely low adhesive force.
  • the comparative example 2 which does not contain (C) component had low adhesive force with CEL.
  • composition of the present invention can be used as an adhesive for plastic films and the like, and can be particularly suitably used for bonding optical films used for liquid crystal displays, organic EL displays and the like.

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

Abstract

L'invention concerne une composition adhésive durcissable par rayonnement d'énergie active pour un film ou une feuille plastique, ladite composition présentant une aptitude au durcissement exceptionnelle, une force adhésive exceptionnelle par rapport à divers types de films et de feuilles plastiques comprenant des films de cellulose et des résines (méth)acryliques et une transparence incolore exceptionnelle. La présente invention concerne une composition adhésive durcissable par rayonnement d'énergie active pour un film ou une feuille plastique, la composition comprenant : un constituant (A), qui est un composé époxy aromatique présentant un poids moléculaire moyen en poids de 500 ou plus ; un constituant (B), qui est un polyglycidyléther d'un polyol en C2-10 ; un constituant (C), qui est un composé présentant un groupe époxy alicyclique ; et un constituant (D), qui est un initiateur de polymérisation photo-cationique, les rapports des teneurs en constituants (A) à (D) dans la composition entière étant les suivants : 1 à 30 % en poids de constituant (A) ; 20 à 70 % en poids de constituant (B) ; 10 à 60 % en poids de constituant (C) ; et 0,5 à 10 % en poids de constituant (D).
PCT/JP2018/004576 2017-03-02 2018-02-09 Composition adhésive durcissable par un rayonnement d'énergie active pour film ou feuille plastique Ceased WO2018159260A1 (fr)

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CN201880014998.7A CN110366587A (zh) 2017-03-02 2018-02-09 用于塑料制膜或片的活性能量射线固化型胶粘剂组合物
KR1020197025668A KR20190120239A (ko) 2017-03-02 2018-02-09 플라스틱제 필름 또는 시트용 활성 에너지선 경화형 접착제 조성물
JP2019502844A JPWO2018159260A1 (ja) 2017-03-02 2018-02-09 プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物

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SG11202107968VA (en) * 2019-01-28 2021-08-30 Showa Denko Materials Co Ltd Adhesive composition, film-like adhesive, adhesive sheet and method for producing semiconductor device

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JP2015040283A (ja) * 2013-08-23 2015-03-02 東亞合成株式会社 光硬化性接着剤組成物、偏光板とその製造法、光学部材及び液晶表示装置
JP2015057467A (ja) * 2013-08-09 2015-03-26 東亞合成株式会社 プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物
JP2016004205A (ja) * 2014-06-18 2016-01-12 チェイル インダストリーズ インコーポレイテッド 偏光板およびこれを用いた表示装置
JP2016130277A (ja) * 2015-01-13 2016-07-21 東亞合成株式会社 活性エネルギー線硬化型組成物
WO2016140294A1 (fr) * 2015-03-04 2016-09-09 東亞合成株式会社 Composition d'adhésif durcissable par rayonnement d'énergie active pour film ou feuille en plastique
WO2016140308A1 (fr) * 2015-03-04 2016-09-09 東亞合成株式会社 Composition d'adhésif durcissable par rayonnement d'énergie active pour film ou feuille en plastique
WO2016158522A1 (fr) * 2015-03-27 2016-10-06 株式会社Adeka Composition
JP2016204513A (ja) * 2015-04-22 2016-12-08 Dic株式会社 接着剤組成物、及び、積層体

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JP2015057467A (ja) * 2013-08-09 2015-03-26 東亞合成株式会社 プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物
JP2015040283A (ja) * 2013-08-23 2015-03-02 東亞合成株式会社 光硬化性接着剤組成物、偏光板とその製造法、光学部材及び液晶表示装置
JP2016004205A (ja) * 2014-06-18 2016-01-12 チェイル インダストリーズ インコーポレイテッド 偏光板およびこれを用いた表示装置
JP2016130277A (ja) * 2015-01-13 2016-07-21 東亞合成株式会社 活性エネルギー線硬化型組成物
WO2016140294A1 (fr) * 2015-03-04 2016-09-09 東亞合成株式会社 Composition d'adhésif durcissable par rayonnement d'énergie active pour film ou feuille en plastique
WO2016140308A1 (fr) * 2015-03-04 2016-09-09 東亞合成株式会社 Composition d'adhésif durcissable par rayonnement d'énergie active pour film ou feuille en plastique
WO2016158522A1 (fr) * 2015-03-27 2016-10-06 株式会社Adeka Composition
JP2016204513A (ja) * 2015-04-22 2016-12-08 Dic株式会社 接着剤組成物、及び、積層体

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