WO2012173054A1 - Composition adhésive durcissable par un rayonnement d'énergie active pour film ou feuille de plastique - Google Patents

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

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WO2012173054A1
WO2012173054A1 PCT/JP2012/064786 JP2012064786W WO2012173054A1 WO 2012173054 A1 WO2012173054 A1 WO 2012173054A1 JP 2012064786 W JP2012064786 W JP 2012064786W WO 2012173054 A1 WO2012173054 A1 WO 2012173054A1
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component
meth
acrylate
adhesive composition
compound
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PCT/JP2012/064786
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English (en)
Japanese (ja)
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一樹 大房
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東亞合成株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the present invention relates to an active energy ray-curable adhesive composition capable of adhering various plastic films or sheets by irradiation with active energy rays such as electron beams or ultraviolet rays, and the composition of the present invention.
  • active energy rays such as electron beams or ultraviolet rays
  • the composition of the present invention is suitable for the adhesion of thin-layer adherends such as plastic films or sheets, and is preferably used for the production of various optical films or sheets used for liquid crystal display elements, etc. It can be used in the field.
  • acrylate and / or methacrylate is represented by (meth) acrylate, acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid is represented by (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 between a thin layer adherend such as a plastic film and a thin layer adherend made of another material is bonded.
  • a solvent-type adhesive composition containing a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is pressure-bonded thereto with a nip roller or the like.
  • the dry laminating method is mainly used.
  • 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.
  • the adhesive composition is a thin layer in a post-processing step such as a heat seal for bonding the obtained laminate film and a ruled line step for engraving grooves immediately after the thin layer adherend is bonded. There is a problem that the adherends are separated from each other.
  • a solventless adhesive composition has been studied.
  • the solventless adhesive composition a two-component adhesive composition and an 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, and thus there is a problem in productivity such as being unable to enter a post-processing step such as a ruled line step immediately after laminating the thin layer adherend.
  • the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and has recently attracted attention.
  • liquid crystal display devices are widely used in navigation systems for automobiles, small electronic devices such as mobile phones and PDAs, screens of word processors and personal computers, and even television receivers because of their features such as thinness, light weight, and low power consumption. is doing.
  • an active energy ray-curable adhesive has been used for bonding various optical films and the like used in the liquid crystal display element.
  • optical film examples include a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an antireflection film, an antiglare film, a lens sheet, and a diffusion sheet, and various types of plastics are used. It has been.
  • plastics polyvinyl alcohol and triacetyl cellulose are particularly used as polarizing plates. These plastics contain a hydroxyl group and are characterized by being very hydrophilic compared to ordinary plastics.
  • the active energy ray curable adhesive composition for polarizing plates includes a photo radical polymerization composition utilizing photo radical polymerization, a photo cation polymerization composition utilizing photo cation polymerization, and photo radical polymerization and photo cation polymerization. Hybrid type compositions using a combination of these are known.
  • Patent Document 1 a composition containing a radical polymerizable compound containing a polar group such as a hydroxyl group or a carboxyl group and a radical polymerizable compound not containing a polar group (Patent Document 1) is known. ing. However, the composition has a large shrinkage during curing, and depending on the type of adherend, it has been difficult to obtain sufficient peel strength due to the generation of stress at the interface. In order to solve this problem, a composition containing urethane (meth) acrylate having a large molecular weight has been studied (for example, Patent Document 2). However, since the viscosity increases, the composition has a problem that thin film coating cannot be performed depending on the coating apparatus.
  • a photocationic polymerization type composition a composition containing an epoxy resin containing no aromatic ring as a main component (Patent Document 3) or a composition containing an aliphatic epoxy and an alicyclic epoxy and / or oxetane (Patent Document 4).
  • Etc. a composition containing an epoxy resin containing no aromatic ring as a main component
  • the composition has an advantage that the generation of stress at the interface can be suppressed because the shrinkage at the time of curing is relatively small compared to the radical photopolymerization type composition.
  • photocationic polymerization is generally known to cause polymerization inhibition due to moisture and basic substances. In high humidity environments, substrates with a lot of moisture, and substrates with a basic surface. It was difficult to obtain sufficient peel strength.
  • composition containing a polyfunctional epoxy resin as a main component, it is possible to reduce the effect of curability reduction due to polymerization inhibition, but such a composition increases the viscosity, Depending on the coating apparatus, there is a problem that thin film coating is not possible.
  • a composition containing a (meth) acrylate having an isocyanuric ring skeleton, an alicyclic epoxy compound, a compound containing a hydroxyl group and a photoacid generator (Patent Document 5), having two or more epoxy groups
  • An epoxy resin in which at least one of these groups is an alicyclic epoxy group, an epoxy resin having two or more epoxy groups and no alicyclic epoxy group, a photocationic polymerization initiator and polymerization Composition containing a reactive monomer (Patent Document 6), a compound having two or more (meth) acryl groups, a compound having a hydroxyl group and one (meth) acryl group, a cationic polymerizable compound having a (meth) acryl group, light
  • a composition including a radical polymerization initiator and a photocationic polymerization initiator (Patent Document 7) is known.
  • compositions are intended to solve the problem of shrinkage during curing and polymerization inhibition due to moisture by hybridization, but according to the study of the present inventors, it has been found that there are the following problems.
  • composition disclosed in Patent Document 5 contains a (meth) acrylate compound having an isocyanuric ring skeleton as an essential component, but according to the study of the present inventor, the composition having two or more (meth) acryloyl groups.
  • a large amount of (meth) acrylate is contained in the composition, the shrinkage at the time of curing is not so small that stress generation at the interface cannot be suppressed. For this reason, it is difficult to obtain sufficient peel strength depending on the substrate. It turned out to be.
  • composition disclosed in Patent Document 6 includes a hybridized composition as a concept
  • compositions disclosed in Examples are only compositions composed only of a photocationically polymerizable monomer.
  • the hybridized composition is not specifically disclosed.
  • composition disclosed in Patent Document 7 contains a cationic polymerizable compound having a (meth) acrylic group as an essential component at a specific ratio, but according to the study of the present inventors, the compound is often contained in the composition. If it is included, the shrinkage at the time of curing is not so small that stress generation at the interface cannot be suppressed. For this reason, it has been found that it is difficult to obtain a sufficient peel strength depending on the substrate.
  • JP 2008-009329 A JP 2007-177169 A (Claims) JP 2004-245925 A (Claims) JP 2008-134384 A (Claims) JP 2008-233279 A (Claims) JP 2008-257199 A (Claims) JP 2008-260879 A (Claims)
  • the present invention has been made in view of the above problems, has low viscosity and excellent curability, has excellent adhesion to various plastic films, particularly hydrophilic plastic films, etc., and is sufficient for applications that require strict durability. It is an object to provide an active energy ray-curable adhesive composition for a plastic film or sheet that exhibits excellent performance.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • B an ethylenically unsaturated compound
  • C an active energy ray-curable adhesive composition containing at least a photocationic polymerization initiator has an adhesive force to various plastic films, particularly hydrophilic plastic films such as polyvinyl alcohol polarizer films. It has been found that it is excellent and has low viscosity and exhibits high durability even when cured under high humidity, and the present invention has been completed.
  • seat are laminated
  • the composition of the present invention uses a compound represented by the above formula (1) and an ethylenically unsaturated compound as a curable component and can be cured with at least a photocationic polymerization initiator.
  • the present invention comprises at least a curable component and a polymerization initiator, the curable component comprises at least the following components (A) and (B), and the polymerization initiator comprises at least the following component (C).
  • the present invention relates to an active energy ray-curable adhesive composition suitable for a plastic film or sheet.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • m is an integer of 1 to 20
  • R 2 is a linear chain having 1 to 20 carbon atoms.
  • M-valent residue of a compound selected from the group consisting of compounds may contain —OCH 2 C (OH) (R 1 ) CH 2 O— units.
  • component (A) A compound represented by the following [hereinafter referred to as “component (A)”].
  • component (B) ethylenically unsaturated compound [hereinafter referred to as “component (B)”].
  • component (C) Photocationic polymerization initiator [hereinafter referred to as “component (C)”].
  • the adhesive composition of the present invention may contain (D) a radical photopolymerization initiator (hereinafter referred to as “component (D)”) as desired.
  • component (D) a radical photopolymerization initiator
  • Component (A) is a compound having at least one glycidyl group having an alkyl substituent at the alpha position of the oxirane ring via an ether bond as represented by the formula (1). is there.
  • R 1 in the formula (1) is an alkyl group having 1 to 6 carbon atoms, and this alkyl group may be linear or branched, and considering the convenience of synthesis, a methyl group or an ethyl group is A methyl group is particularly preferable.
  • m is an integer of 1 to 20, preferably 1 to 5, and more preferably 1 to 3.
  • R 2 represents a linear or branched aliphatic alcohol having 1 to 20 carbon atoms, a linear or branched poly (alkyleneoxy), a polyester polyol, an aromatic alcohol and an alkylene oxide modified product thereof, and a phenolic hydroxyl group. And a m-valent residue of a compound selected from the group consisting of modified alkylene oxides thereof, and may contain —OCH 2 C (OH) (R 1 ) CH 2 O— units.
  • the epoxy groups of the obtained epoxy compound may react to form a multimer, but when the multimer is formed, R 2 is —OCH 2 C ( OH) (R 1 ) CH 2 O— units.
  • R 2 is preferably an m-valent residue of a compound selected from the group consisting of a compound having a phenolic hydroxyl group and a modified alkylene oxide thereof.
  • —OCH 2 C (OH) (R 1 ) CH 2 O— units may be included.
  • Component (A) is, for example, an alkyl epichlorohydrin represented by the following formula (2) (hereinafter referred to as compound (2)) having one hydroxyl group such as an alcohol or phenol represented by the following formula (3) in the molecule. It can be easily produced by reacting the above compound with a known method (for example, see JP-A-08-283379).
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • m is an integer of 1 to 20
  • R 2 is a linear or branched aliphatic alcohol having 1 to 20 carbon atoms, linear or branched poly (alkyleneoxy).
  • reaction residue of the compound represented by formula (3) (hereinafter referred to as compound (3)) is R 2 in formula (1). Specific examples of the compound (3) are given below.
  • Linear or branched aliphatic alcohols having 1 to 20 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2- Aliphatic monohydric alcohols which may have 1 to 20 carbon atoms such as ethylhexanol; glycols such as ethylene glycol, propylene glycol and neopentyl glycol; 1,3-propanediol, 1,4-butanediol, Aliphatic polyhydric alcohols such as 1,6-hexanediol, aliphatic polyhydric alcohols such as trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol; alicyclic groups such as norbornane dimethanol Including alipha
  • linear or branched polyalkylene oxide examples include linear or branched polyalkylene oxides such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol. It is done.
  • polyester polyol examples include those obtained by reacting a polyhydric alcohol and a polycarboxylic acid.
  • Aromatic alcohol examples include xylylene glycol and the like, and modified alkylene oxides thereof.
  • O Compound having phenolic hydroxyl group examples include phenol, bisphenol, biphenol, and a phenol resin. Among these, compounds selected from the group consisting of phenol, bisphenol, and phenol resin are preferable.
  • examples of phenol include monovalent compounds such as phenol, divalent or higher compounds such as catechols and pyrogallols, phenol derivatives substituted with hydrogen atoms of aromatic rings such as cumylphenol, and aromatic rings.
  • examples thereof include phenol derivatives in which a hydrogen atom is substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and modified alkylene oxides thereof.
  • Examples of the bisphenol include bisphenol derivatives such as bisphenol A and bisphenol F, and alkylene oxide modified products thereof.
  • Examples of the biphenol include biphenol, biphenol having 1 to 6 chain or branched alkyl groups, and modified alkylene oxides thereof.
  • Examples of the phenol resin include a phenol novolac resin, a cresol novolac resin, and polyvinylphenol.
  • examples of the alkylene oxide modified product include an ethylene oxide modified product and a propylene oxide modified product.
  • Preferred examples of the compound (3) include alkyl alcohols having 1 to 8 carbon atoms which may have branches, ethylene glycol modified products of alkyl alcohols having 1 to 8 carbon atoms which may have branches, ethylene Glycol, propylene glycol, polyethylene glycol, polypropylene glycol, phenol, modified ethylene oxide of catechol, catechol, modified ethylene oxide of catechol, modified ethylene oxide of t-butylcatechol, t-butylcatechol, pyrogallol, ethylene oxide of pyrogallol Modified products, biphenylphenol, ethylene glycol modified products of biphenylphenol, bisphenol A, ethylene glycol modified products of bisphenol A, bisphenol F, ethylene oxide of bisphenol F Id modified products include phenol novolac resin and cresol novolac resin.
  • M in the formula (3) is an integer of 1 to 20, preferably 1 to 5, and more preferably 1 to 3.
  • a known production method for obtaining an epoxy compound can be used.
  • the component (A) when the component (A) is produced from the compound (2) and a polyhydric phenol as the compound (3), it can be obtained by reacting with an alkali compound.
  • alkali compound alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate and the like can be used. Specifically, sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, Sodium hydrogencarbonate etc. are mentioned, These mixtures can also be used.
  • the reaction temperature at this time include 30 to 120 ° C.
  • Examples of such polymers that can be obtained include those wherein m is 2 or more in formula (3), and the actual compounds include resorcinol, bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin and norbornane. Methanol etc. can be illustrated.
  • the component (A) is a compound represented by the above formula (1), wherein m is 1 or 2, and R 2 is a m-valent residue of a compound having a phenolic hydroxyl group and a modified alkylene oxide thereof. , —OCH 2 C (OH) (R 1 ) CH 2 O— units are preferable, and preferred examples of the compound are shown in the following formulas (5) to (9).
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.
  • the compound of the formula (2) may be bonded to any of the o-position, m-position, and p-position, preferably the o-position or m-position.
  • R 1 in the formula (5) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • N in the formula (5) is 0 or a positive number, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 1.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.
  • the compound of the formula (2) may be bonded to any of the o-position, m-position, p-position, o'-position, m'-position or p'-position, preferably the o-position, p-position. Is the position, o′-position, or p′-position (where the o-position, m-position, and p-position are the compounds of the formula (2) bonded to the benzene ring at one end of the formula (6).
  • R 1 in the formula (6) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • N in the formula (6) can be adjusted by, for example, the amount of the compound of the formula (2) used relative to bisphenol F.
  • N in the formula (6) is 0 or a positive number, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 1.
  • bond position between bisphenol F when n of Formula (6) is a positive number may be any, and p, p 'position, o, p' position, o ', p position or o, o' position is preferable. .
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • R 3 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • R 3 may be bonded to any of the o-position, m-position, and p-position, and is preferably the o-position or p-position.
  • R 1 in the formula (7) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • R 3 in the formula (7) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a butyl group, a t-butyl group or a hexyl group, and more preferably a t-butyl group.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • R 1 in the formula (8) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.
  • the formula (1) may be bonded to any of the o-position, m-position, p-position, o′-position, m′-position or p′-position, preferably the o-position, p-position, o′-position or p′-position (note that the o-position, m-position and p-position indicate that the compound of the formula (2) is bonded to the benzene ring at one end of the formula (9).
  • R 1 in the formula (9) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • N in the formula (9) can be adjusted by, for example, the amount of the compound of the formula (2) used relative to bisphenol A.
  • N in the formula (9) is 0 or a positive number, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 1.
  • the bonding position between bisphenol A when n in Formula (9) is a positive number may be any, and p, p ′ position, o, p ′ position, o ′, p position or o, o ′ position is preferable. .
  • the compounds of the formulas (5), (6) and (8) are preferable, and when used for adhesion of hydrophilic plastics or sheets.
  • component (A) only one kind of the aforementioned compounds can be used, or two or more kinds can be used in combination.
  • the blending ratio of the component (A) is 20 to 70% by weight, preferably 30 to 60% by weight in 100% by weight of the total amount of the curable component.
  • the ratio of the component (A) 20% by weight or more, the cured product has excellent heat resistance and water resistance, and by making it 70% by weight or less, the composition has low viscosity and excellent coating properties. It becomes a thing and it becomes the thing excellent in the adhesive force of hardened
  • the component (B) is an ethylenically unsaturated compound, and various compounds can be used as long as the compound has an ethylenically unsaturated group.
  • ethylenically unsaturated groups include (meth) acryloyl groups, vinyl groups, and vinyl ether groups.
  • the proportion of component (B) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on 100% by weight of the total amount of the curable component. By making the ratio of the component (B) 30% by weight or more, it is possible to improve curability and reduce the viscosity, and by making it 80% by weight or less, it is possible to prevent a decrease in the adhesive strength and water resistance of the composition. be able to.
  • component (b1) an ethylenically unsaturated compound having a hydroxyl group (hereinafter referred to as “component (b1)”), a compound having two or more ethylenically unsaturated groups in the molecule [hereinafter referred to as (b2 And a compound other than the components (b1) and (b2) (hereinafter referred to as other monofunctional unsaturated compounds) having one ethylenically unsaturated group in the molecule.
  • component (b1) an ethylenically unsaturated compound having a hydroxyl group
  • the component (b1) is an ethylenically unsaturated compound having a hydroxyl group.
  • the component (b1) is preferably a (meth) acrylate having one hydroxyl group and one ethylenically unsaturated group in the molecule.
  • the (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane Dimethanol monoacrylate, (meth) acrylic acid adduct of cyclohexene oxide, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) ) Acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol Mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2- (meth) acrylate
  • a compound having a molecular weight of less than 300 is preferable in order to make the composition have a low viscosity and excellent adhesiveness.
  • the compound satisfying the molecular weight include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexanedimethanol monoacrylate.
  • 4-hydroxybutyl (meth) acrylate is more preferable from the viewpoint of water resistance.
  • the proportion of the component (b1) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on 100% by weight of the total amount of the curable component.
  • a phenomenon called so-called dark reaction in which the reaction proceeds and cures even after the active energy ray irradiation is completed, may cause problems depending on the application.
  • the dark reaction proceeds and the wound shape remains as it is.
  • marks such as wave undulations and dents are easily attached.
  • it is very effective to include the component (b2) in the component (B) so that the elastic modulus of the adhesive layer is increased immediately after irradiation with the active energy ray.
  • the heat resistance is improved by increasing the crosslinking density.
  • a compound having two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylate”) is preferable.
  • the polyfunctional (meth) acrylate include 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-nonanediol diacrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylo
  • examples of the oligomer that can be used as the component (b2) include polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate. These oligomers are compounds having two (meth) acryloyl groups, but are simply referred to as (meth) acrylates unless otherwise specified.
  • polyester (meth) acrylate examples include a dehydration condensate of polyester polyol and (meth) acrylic acid.
  • polyester polyol examples include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.
  • Polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and their alkylene oxide adducts Etc.
  • dibasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid or anhydrous Thing etc.
  • polyester poly (meth) acrylates other than these include compounds described on pages 74 to 76 of the above-mentioned document “UV / EB Curing Material”.
  • Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin, and examples thereof include compounds as described on pages 74 to 75 of the above-mentioned document “UV / EB Curing Material”. .
  • the epoxy resin examples include aromatic epoxy resins and aliphatic epoxy resins.
  • aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; phenol novolac type epoxy resin and cresol novolac type Examples thereof include novolak-type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
  • aliphatic epoxy resin examples include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc.
  • Diglycidyl ethers of polyalkylene glycols diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts; Of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.
  • Polymer Processing separate volume epoxy resin
  • epoxy compounds having a triazine nucleus in the skeleton such as TEPIC [Nissan Chemical Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.], etc., can be mentioned. Examples thereof include compounds described on pages 289 to 296 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin.
  • the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.
  • polyether (meth) acrylate oligomer examples include polyalkylene glycol (meth) diacrylate, and examples thereof include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. .
  • Examples of compounds other than the component (b2) (meth) acrylate include compounds having two or more allyl groups, such as diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.
  • a (meth) acrylic polymer having a (meth) acryloyloxy group As the polymer that can be used as the component (b2), a (meth) acrylic polymer having a (meth) acryloyloxy group, a (meth) acrylic polymer having a functional group, and a (meth) acryloyl group introduced into the side chain And compounds described on pages 78 to 79 of the above-mentioned document “UV / EB Curing Material”.
  • the component (b2) includes polyalkylene glycol di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, and a modified alkylene oxide of bisphenol A.
  • Di (meth) acrylate, bisphenol F alkylene oxide modified di (meth) acrylate, and isocyanuric acid alkylene oxide modified triacrylate are preferred.
  • Polyalkylene glycol di (meth) acrylate and isocyanuric acid-modified alkylene oxide triacrylate are particularly preferred because they can maintain adhesive strength with hydrophilic plastics.
  • the blending ratio of the component (b2) is preferably 1 to 50% by weight, more preferably 1 to 30% by weight in 100% by weight of the total amount of the curable component.
  • Other monofunctional unsaturated compounds include vinyl compounds and allyl compounds, (meth) acrylamide compounds, compounds having an aromatic or alicyclic skeleton containing one ethylenically unsaturated group in the molecule, aliphatic Examples include (meth) acrylate, carboxylic acid group-containing (meth) acrylate, and phosphoric acid group-containing (meth) acrylate.
  • a compound having an aromatic ring skeleton or alicyclic skeleton having one ethylenically unsaturated group is preferable.
  • Specific examples include alicyclic (meth) acrylates, aromatic (meth) acrylates, and imide (meth) acrylates.
  • Cycloaliphatic (meth) acrylates include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, tetrahydro Examples include furfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
  • aromatic (meth) acrylate phenyl (meth) acrylate, phenol derivative (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, cresol (Meth) acrylate of modified alkylene oxide, (meth) acrylate of modified alkylene oxide of p-cumylphenol, (meth) acrylate of modified alkylene oxide of nonylphenol, (meta) of modified alkylene oxide of o-phenylphenol ) Acrylate, (meth) acrylate of p-phenylphenol modified with alkylene oxide, (meth) acrylate of tribromophenol with modified alkylene oxide, neope Chill glycol (meth) acrylic acid benzoic acid ester.
  • imide (meth) acrylate examples include N- (meth) acryloyloxyethylhexahydrophthalimide, 2- (1,2-cyclohex-1-enecarboximido) ethyl (meth) acrylate, and funkryl FA-502A (Hitachi Chemical Industries). Manufactured) and the like.
  • isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy are used because of their high heat resistance and adhesive strength.
  • vinyl compounds include monofunctional vinyl compounds such as styrene, vinyl toluene, N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole and vinyl pyridine, and vinyl compounds such as divinylbenzene.
  • allyl compounds include monofunctional allyl compounds such as allyl alcohol.
  • Examples of the (meth) acrylamide compound include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like can be mentioned.
  • aliphatic (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth)
  • carboxylic acid group-containing (meth) acrylate examples include (meth) acrylic acid, (meth) acrylic acid dimer, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- Examples thereof include carboxylic acid-containing (meth) acrylates such as (meth) acryloyloxyethyl hexahydrophthalic acid and ⁇ -carboxypolycaprolactone (meth) acrylate.
  • Examples of the phosphoric acid group-containing (meth) acrylate include 2- (meth) acryloyloxyethyl acid phosphate.
  • component (B) that can be used as other monofunctional unsaturated compounds, it is described on pages 53 to 56 of the document "Latest UV Curing Technology" [Printed Information Association, 1991].
  • the ratio of the other monofunctional unsaturated compound is preferably 0 to 40% by weight, more preferably 0 to 30% by weight in 100% by weight of the total amount of the curable component. By making this ratio 40% by weight or less, the heat resistance of the cured product can be increased.
  • Component (C) component is a photocationic polymerization initiator.
  • the component (C) is a compound that generates a cation or a Lewis acid by irradiation with active energy rays and starts polymerization of the component (A) that is a photocationically polymerizable compound.
  • Specific examples of the component (C) include sulfonium salts, iodonium salts, and diazonium salts.
  • sulfonium salts 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) phenylsulfoni
  • iodonium salts 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, Iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, Di (4-nonylphenyl) iodonium hexafluorophosphate, Examples thereof include diaryl iodonium salts such as di (4-alkylphenyl) iodonium
  • diazonium salts examples include benzenediazonium hexafluoroantimonate, Examples thereof include benzenediazonium hexafluorophosphate.
  • Adekaoptomer SP-100, 150, 152, 170, 172 made by ADEKA
  • Photoinitiator 2074 made by Rhodia
  • Kayrad PCI-220, 620 Nippon Kayaku Co., Ltd.
  • Irgacure 250 Ciba Japan
  • WPI-113, 116 Wako Pure Chemical Industries
  • BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 manufactured by Midori Chemical
  • triarylsulfonium salts and diaryliodonium salts are preferred because of their excellent active energy ray curability, cured films having excellent water resistance and no coloring, and diaryliodonium salts are particularly preferred because of their excellent curability.
  • diaryliodonium salts are particularly preferred because of their excellent curability.
  • triarylsulfonium salts triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable.
  • diaryl iodonium salts among those described above, tricumyl iodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluoro Preferred are phosphate, di (4-t-butylphenyl) iodonium hexafluorophosphate, and WPI-113 (manufactured by Wako Pure Chemical Industries).
  • the aforementioned compounds may be used alone or in combination of two or more.
  • the blending ratio of the component (C) is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the total amount of the curable component.
  • a sensitizer in order to improve photocationic sclerosis
  • the sensitizer include anthracene compounds, 4-methoxy-1-naphthol, fluorene, pyrene, stilbene and the like.
  • anthracene compound examples include anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10- Diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 4′-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4′-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate And 4'-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate.
  • 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dipropoxyanthracene are preferable from the viewpoints of solubility and sensitization efficiency.
  • Commercially available products of these sensitizers include Anthracure UVS-1331, 1221, 1101, and ET-2111 (manufactured by Kawasaki Chemical Industries).
  • the blending ratio of the sensitizer is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight with respect to 100 parts by weight of the total amount of the curable component.
  • an anthracene compound is preferably used as a sensitizer.
  • Component (D) is a radical photopolymerization initiator.
  • Component (D) is a compound that generates radicals by irradiation with active energy rays and initiates polymerization of component (B), which is a compound having an ethylenically unsaturated group.
  • component (B) is a compound having an ethylenically unsaturated group.
  • Some types of component (D) function as a sensitizer that promotes photolysis of component (C).
  • component (D) examples include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4- 1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methylpropan-1-one, 2 -Methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-o 2-benzyl-2-dimethylamino-1- (4-morpholinoph
  • thioxanthone compounds are preferred because of the high sensitizing effect of component (C).
  • 2,4-diethylthioxanthone and isopropylthioxanthone are more preferable from the viewpoint of excellent active energy ray curability and small coloration of the cured film.
  • the above-described compounds may be used alone, or two or more kinds may be used in combination.
  • the proportion of component (D) is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the total amount of the curable component.
  • the proportion of the component (D) 0.1 weight or more the active energy ray curability of the composition can be made sufficient and the adhesiveness can be made excellent, while it is made 20 weight% or less.
  • the internal curability of the adhesive layer can be made good and the adhesiveness can be made excellent.
  • Preferable components that can be used in the present invention include compounds other than the component (A) having at least one cationic polymerizable group in the molecule.
  • Applicable compounds include epoxy compounds in which R 1 in formula (1) is hydrogen (hereinafter referred to as unsubstituted epoxy compounds), alicyclic epoxies, oxetane compounds, and vinyl ether compounds.
  • An unsubstituted epoxy compound is divided into an aromatic type and an aliphatic type.
  • aromatic systems include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of brominated bisphenol A, diglycidyl ether of brominated bisphenol F, brominated bisphenol Diglycidyl ether of S, diglycidyl ether of rubber-modified bisphenol A, bisphenol type epoxy resin such as di- or polyglycidyl ether of bisphenolfluorene or its alkylene oxide adduct; phenol novolac type epoxy resin, cresol novolak type epoxy resin, bromination Phenol novolac epoxy resin, brominated cresol novolac epoxy resin, dicyclopentadiene-phenol novolac epoxy resin, etc.
  • Borac type epoxy resin naphthalene type epoxy resin, alkyldiphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ether, phthalic acid diglycidyl ether, styrene -Epoxidized butadiene copolymer, epoxidized styrene-isoprene copolymer, addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin, N, N, N ', N'-tetraglycidyl-m-xylene Examples include diamines.
  • the epoxy resin means a compound or polymer having an average of two or more unsubstituted epoxy groups in the molecule and cured by reaction.
  • a monomer having two or more curable unsubstituted epoxy groups in its molecule may be referred to as an epoxy resin.
  • Aromatic unsubstituted epoxy compounds other than these include Epicoat 5050, 5051, 1031S, 1032H60, 604, 630, 871, 872, 191P, YX310, 545, YL6810, YX8800, YL980 [above, Japan Epoxy Resin ( Etc.].
  • the aliphatic unsubstituted epoxy compound examples include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl of polyethylene glycol and polypropylene glycol Diglycidyl ether of polyalkylene glycol such as ether; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di- or triglycidyl of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct; Polyethers of ethers and polyhydric alcohols such as di, tri or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts.
  • alkylene glycols such as ethylene glycol, propylene glyco
  • the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, can be mentioned.
  • Examples of other aliphatic unsubstituted epoxy compounds include Denarex R-45EPT (manufactured by Nagase ChemteX Corporation), Epofriend AT501, CT310, Epolide PB3600 (above, Daicel Chemical Industries, Ltd.), KL-630. [Kuraray Co., Ltd.], Tetrad C [Mitsubishi Gas Chemical Co., Ltd.], TEPIC [Nissan Chemical Industry Co., Ltd.] and the like.
  • alicyclic epoxy compounds include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, bis (3,4 -Epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like.
  • An oxetane compound is a compound having one or more oxetane rings in the molecule. Specific examples include various oxetane compounds described in JP-A-8-85775 and JP-A-8-134405, and among these, compounds having one or more oxetanyl groups are preferable.
  • Examples of monofunctional oxetanes include 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane and the like.
  • bifunctional oxetane examples include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis ⁇ [1-ethyl (3-oxetanyl)] methyl ⁇ ether, and the like.
  • a vinyl ether compound is a compound having one or more vinyl ether groups in the molecule. Specifically, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl Vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, monofunctional vinyl ethers such as 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, Multifunctional vinyl such as triethylene glycol divinyl ether Ether and the like
  • the compound other than the component (A) having one or more cationically polymerizable groups in the molecule is preferably a low molecular weight compound because it can increase the adhesiveness and can reduce the viscosity.
  • a compound having a molecular weight of 2,000 or less is preferred.
  • Particularly preferred examples include limonene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) Methyl] oxetane and bis (3-ethyl-3-oxetanylmethyl) ether.
  • composition of the present invention can be blended with other components usually used in adhesive compositions.
  • silane coupling agents inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifying resins, leveling agents, antifoaming agents, plasticizers, organic solvents, dyes, pigments, treatments Inactive ingredients such as agents and UV screening agents can be blended.
  • the tackifying resin include rosins such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, and petroleum resin.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N -2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoe
  • the composition of the present invention can be produced by stirring and mixing the components (A) to (C) and, if necessary, the component (D) or other components according to a conventional method. In this case, heating can be performed as necessary.
  • the heating temperature may be appropriately set according to the composition to be used, the substrate, the purpose, etc., but is preferably 30 to 80 ° C.
  • the viscosity of the composition is preferably 10 to 1000 mPa ⁇ s from the viewpoint of excellent coatability on the substrate.
  • the 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).
  • 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 paper and metal.
  • the method of using the composition of the present invention may be in accordance with a conventional method, and specific examples include a method of applying to a base material, pasting with another base material, and irradiating active energy rays.
  • Examples of the material in the plastic film include polyvinyl chloride resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, triacetyl cellulose, cycloolefin polymer, Examples include polymethyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer, and chlorinated polypropylene.
  • Examples of the paper include imitation paper, fine paper, craft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, water resistant paper, glassine paper, and corrugated paper.
  • Examples of the metal foil include aluminum foil.
  • 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 used and the application, but is preferably 0.1 to 100 ⁇ m, more preferably 1 to 25 ⁇ m.
  • the active energy rays 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.
  • various devices can be used as an EB irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device. Those having an energy of 1000 eV are preferred, and more preferably 100 to 300 eV.
  • 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, dried as necessary, and then a second thin-layer adherend is bonded thereto and irradiated with active energy rays. Is mentioned.
  • the thin layer adherend examples include plastic film, paper, metal foil, and the like.
  • the plastic film or the like needs to be capable of transmitting active energy rays, and the film thickness may be selected according to the thin layer adherend to be used and the use, but preferably the thickness is 0.2 mm or less. is there.
  • the composition of the present invention is preferably used for adhesion between plastic films and the like, and more preferably used for hydrophilic plastics, specifically, those made of polyvinyl alcohol or triacetyl cellulose. be able to.
  • an activation treatment can be performed on one or both surfaces in order to increase the interlayer adhesion.
  • 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.
  • Coating on the thin layer adherend may be performed according to a conventionally known method, and examples thereof include the same method as described above.
  • the coating thickness of the composition of the present invention may be selected according to the thin layer adherend to be used and the application, but the same coating thickness as described above is preferable.
  • the bonding can be performed not only in a flat state but also in a curved surface state. That is, there is a method in which the base material is folded into a concave state or a convex state, the composition is applied in this state, the other base material is bonded, and active energy rays are irradiated. As another method, there is a method in which the composition of the present invention is applied in a planar state, the other substrate is bonded, folded into a concave state or a convex state, and irradiated with active energy rays to adhere. Can be mentioned. In this case, as a method for applying the composition in a planar state, the above-described method may be followed. Examples of the method of coating the composition in a curved surface include a method using a spray, dip, curtain flow coater, screen printing, slot die coater and the like.
  • a laminate composed of a plastic film / cured product of the composition of the present invention / plastic film and a laminate composed of a plastic film / cured product of the composition of the present invention / other substrates are produced.
  • the Laminates such as a laminate film obtained from the composition of the present invention are excellent in adhesive strength under high temperature and high humidity conditions. Therefore, optical films such as polarizing plates, protective films and retardation films used in liquid crystal display devices, etc. It can be suitably used for a film.
  • the composition of this invention can be preferably used for manufacture of a polarizing plate and a polarizing plate with retardation film.
  • the manufacturing method of a polarizing plate is demonstrated.
  • a polarizer means a film or film having a polarizing function described later
  • a polarizing plate is a polarizer with a protective layer in which one or both sides of the polarizer are protected by a film or film.
  • a polarizing plate with a retardation film represents a polarizer or a polarizing plate in which a retardation film is bonded or a film having a retardation function is formed by coating.
  • the composition of the present invention can be preferably used for adhesion of hydrophilic plastics.
  • polyvinyl alcohol used as a polarizer and triacetyl cellulose used as a protective film for a polarizer are hydrophilic. Corresponds to plastic.
  • composition of the present invention can be used for adhesion between a polarizer and a protective film and adhesion between a polarizing plate and a retardation film.
  • a polarizer has a function of selectively transmitting linearly polarized light in one direction from natural light.
  • polarizers include iodine polarizers in which iodine is adsorbed and oriented on a polyvinyl alcohol film, dichroic dyes in which dichroic dye is adsorbed and oriented on a polyvinyl alcohol film, and (lyotropic) liquid crystal Examples thereof include a coating type polarizer coated with a dye in a state, oriented and fixed.
  • These iodine-based polarizers, dye-based polarizers, and coating-type polarizers have the function of selectively transmitting one direction of linearly polarized light from natural light and absorbing the other direction of linearly polarized light. It is called a type polarizer.
  • a protective layer is usually provided on one side or both sides thereof, but the composition of the present invention can be used for adhesion between the polarizer and the protective film.
  • protective films used in the protective layer include cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose, acrylic resin films, polyester resin films, polyarylate resin films, polyether sulfone resin films, and cyclic rings such as norbornene.
  • cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose
  • acrylic resin films acrylic resin films
  • polyester resin films polyarylate resin films
  • polyether sulfone resin films polyether sulfone resin films
  • cyclic rings such as norbornene.
  • examples thereof include cyclic polyolefin resin films containing olefin as a monomer.
  • the composition of this invention can also be used for adhesion
  • a polarizing plate having a protective layer on one side or both sides can be used.
  • the protective layer may be one obtained by bonding the protective film or a protective film formed by coating.
  • the surface to be bonded to the retardation film may be a surface with a protective layer or a surface without a protective layer.
  • retardation films can be used.
  • Optical films that have been subjected to processing such as uniaxial or biaxial stretching, or liquid crystal compounds are applied to a substrate, and processed to be oriented and fixed.
  • An optical film or the like is mentioned, and the magnitude relationship (refractive index ellipsoid) of the three-dimensional refractive index is controlled according to the use conditions. It is mainly used to compensate for coloration of the liquid crystal layer of a liquid crystal display and to compensate for changes in phase difference due to viewing angle.
  • retardation films include optical film materials that are subjected to processing such as stretching, such as polyolefins such as polyethylene, polypropylene, and cyclic polyolefins, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polyarylate. And polyamide.
  • the above-mentioned cyclic polyolefin is a general generic name for resins obtained from cyclic olefins such as norbornene, tetracyclododecene, and derivatives thereof. For example, JP-A-3-14882 and JP-A-3-122137. Etc. are mentioned.
  • a cyclic olefin ring-opening polymer, a cyclic olefin addition polymer, a random copolymer of a cyclic olefin and an ⁇ -olefin such as ethylene or propylene, or these are modified with an unsaturated carboxylic acid or a derivative thereof.
  • graft-modified products can be given.
  • these hydrides are mentioned. Examples of the products include ZEONEX and ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, and TOPAS manufactured by TICONA.
  • a method for producing a polarizing plate or a polarizing plate with a retardation film using the composition of the present invention will be described.
  • Examples of the production method include a method including the following steps [1] to [3].
  • [1] A step of applying the composition of the present invention to any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film as an adherend
  • [2] A step of laminating one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film, which is the other adherend, to the film coated with the composition
  • [3] A step of irradiating an active energy ray through a substrate coated with the composition of the present invention after the films are bonded together.
  • a polarizing plate or a polarizing plate with a retardation film can be produced by the above procedure, but when bonding to both sides, the steps [1] and [2 ] May be repeated after repeating step [3], or steps [1], [2] and [3] may be repeated twice.
  • the coating method in the step [1] and the active energy ray irradiation method in the step [3] may be performed by the same method as described above. Further, as described above, it can be bonded in a curved state.
  • a retardation film having a different retardation is further pasted on the retardation film side of the polarizing plate with a retardation film. It can also be combined. Specifically, a method of laminating a retardation film having a 1 ⁇ 2 wavelength with respect to each wavelength and further laminating a retardation film having a 1 ⁇ 4 wavelength with respect to each wavelength to the polarizer film. is there. In this case, step [3] may be performed after steps [1] and [2] are repeated three times, or steps [1], [2] and [3] may be repeated three times.
  • Methyl epichlorohydrin (hereinafter referred to as “MECH”) was produced according to the method described in Synthesis Example 1 of Japanese Patent No. 4251138 (hereinafter referred to as “Patent Document 8”).
  • Tables 1 and 2 the numbers of each component of the composition mean parts.
  • the abbreviations in Tables 1 and 2 mean the following, except for those defined above.
  • DETX-S (trade name) 4
  • Other components jER Diglycidyl ether of bisphenol F, jER-807 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.
  • EX-201 resorcinol diglycidyl ether, Denacol EX-201 (trade name) manufactured by Nagase ChemteX Corporation
  • CEL2021 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, Daicel Chemical Industries, Ltd.
  • Celoxide 2021P (trade name)
  • OXT211 3-ethyl-3-phenoxymethyloxetane
  • Aron Oxetane OXT-211 (trade name) manufactured by Toagosei Co., Ltd.
  • the resulting composition was applied to a 50 ⁇ m thick PET film (trade name Cosmo Shine A-4300, manufactured by Toyobo Co., Ltd.) with a bar coater to a thickness of 2 ⁇ m. A glass plate was bonded to this. Thereafter, from the glass side, using an 80 W / cm condensing type metal halide lamp, ultraviolet rays were irradiated for one pass at a conveyor speed of 30 m / min to cure, thereby producing a laminate.
  • the ultraviolet intensity was 233 mW / cm 2 and the integrated light amount was 114 mJ / cm 2 (both values at 365 nm).
  • composition of the present invention had a low viscosity and an excellent peel strength.
  • composition not containing the component (A) of the present invention Comparative Examples 1 to 5
  • the composition not containing the component (B) Comparative Example 6
  • have at least one of viscosity and peel strength. Was insufficient.
  • each component of the composition means the number of parts.
  • the abbreviations in Tables 3 and 4 mean the following, except for those defined above.
  • M203 Tricyclodecane dimethanol diacrylate, Aronix M-203S (trade name) manufactured by Toagosei Co., Ltd.
  • M325 ⁇ -caprolactone-modified tris (acryloxyethyl isocyanurate), Aronix M-325 (trade name) manufactured by Toagosei Co., Ltd.
  • M-270 Polypropylene glycol (n ⁇ 12) diacrylate, Aronix M-270 (trade name) manufactured by Toagosei Co., Ltd.
  • -PEA Phenoxyethyl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate PO-A (trade name) -IBXA: Isobornyl acrylate, Kyoeisha Chemical Co., Ltd.
  • a dyeing solution was prepared by dissolving 0.05 parts by mass of iodine and 0.5 parts by mass of potassium iodide in 100 parts by mass of water.
  • the dyeing solution was heated to 55 ° C., a PVA film (Kuraray vinylon film VF-PS, 75 ⁇ m) was immersed for 1 minute, and the film was stretched 6 times in one direction. Furthermore, washing after dyeing was performed in an aqueous solution in which 4 parts by mass of boric acid and 6 parts by mass of potassium iodide were dissolved in 90 parts by mass of water, and then dried to prepare a polarizer having a thickness of 30 ⁇ m.
  • UVA-TAC triacetylcellulose film containing UV absorber with a thickness of 80 ⁇ m (trade name: Fujitac, manufactured by Fuji Film Co., Ltd., hereinafter referred to as “UVA-TAC”)
  • corona treatment (Navitas Polydyne 1, output 0. 1 kW, treatment speed 1 second / cm).
  • the active energy ray-curable adhesive composition was applied to the polarizer obtained in Production Example 1 to a thickness of 5 ⁇ m with a bar coater. This was laminated with corona-treated UVA-TAC, then turned over, and similarly coated with an active energy ray-curable adhesive composition and corona-treated UVA-TAC.
  • ultraviolet rays were irradiated on each of the front and back surfaces at a conveyor speed of 5 m / min for curing. Thereafter, it was cured at room temperature for 12 hours or more to produce a TAC polarizing plate as a test specimen.
  • the ultraviolet intensity was 250 mW / cm 2 and the integrated light quantity was 100 mJ / cm 2 (both values at 365 nm).
  • Polarizing plate production example 2 A polarizing plate was prepared in the same manner as in Production Example 1 of the polarizing plate, except that a triacetyl cellulose film (manufactured by LOFO, hereinafter referred to as “TAC”) having a thickness of 100 ⁇ m and containing no UV absorber was used instead of UVA-TAC. Was made.
  • TAC triacetyl cellulose film
  • composition of the present invention has a low viscosity, excellent peel strength and appearance after a high humidity test, and curling of the film derived from a dark reaction after UV curing is also suppressed. Met.
  • compositions (Comparative Examples 8 to 15) that do not contain the component (A) of the present invention and compositions (Comparative Example 7) that do not contain the component (B) At least one of the peel strength and the appearance after the high-humidity test was insufficient.
  • composition of the present invention can be used as an adhesive for various plastic films, especially as an adhesive for hydrophilic plastics, and is particularly suitable for the production of optical films such as liquid crystal display devices, particularly for the production of polarizing plates. Can be used.

Abstract

L'invention porte sur une composition adhésive durcissable par un rayonnement d'énergie active qui a une faible viscosité, une excellente aptitude au durcissement et une excellente aptitude à adhérer à divers films de plastique et similaires, en particulier à des films de plastique hydrophiles, et qui présente une performance suffisante même dans des applications qui requièrent une extrême durabilité. La composition adhésive durcissable par un rayonnement d'énergie active selon l'invention contient les composants (A) et (B) en tant que composants durcissables et un composant (C) en tant qu'initiateur de polymérisation. Le composant (A) est un composé représenté par la formule (1) (dans la formule (1), R1 représente un groupe alkyle en C1-6, m représente un nombre entier de 1 à 20 et R2 représente un résidu de valence m d'un composé choisi dans le groupe constitué par les alcools aliphatiques, les poly(oxydes d'alkylène), les polyols de polyester, les composés renfermant un groupe hydroxyle phénolique et les produits de ceux-ci modifiés par de l'oxyde d'alkylène). Le composant (B) est un composé à insaturation éthylénique. Le composant (C) est un initiateur de polymérisation photocationique.
PCT/JP2012/064786 2011-06-11 2012-06-08 Composition adhésive durcissable par un rayonnement d'énergie active pour film ou feuille de plastique WO2012173054A1 (fr)

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JP2015017146A (ja) * 2013-07-08 2015-01-29 チェイル インダストリーズ インコーポレイテッド 偏光板用接着剤組成物
WO2015194654A1 (fr) * 2014-06-20 2015-12-23 東亞合成株式会社 Composition adhésive durcissable par un faisceau d'énergie d'activation pour film ou feuille plastique
WO2017104165A1 (fr) * 2015-12-18 2017-06-22 古河電気工業株式会社 Composition adhésive, procédé de liaison de parties adhérées l'utilisant et procédé de fabrication de stratifié
US9834708B2 (en) 2013-07-08 2017-12-05 Samsung Sdi Co., Ltd. Adhesive composition for polarizing plate, adhesive film for polarizing plate comprising the same, polarizing plate comprising the same and display device comprising the same
WO2019177134A1 (fr) * 2018-03-15 2019-09-19 東亞合成株式会社 Composition adhésive durcissable par rayonnement d'énergie active pour films et feuilles en plastique, stratifié et plaque de polarisation
JP2020105265A (ja) * 2018-12-26 2020-07-09 三菱ケミカル株式会社 活性エネルギー線硬化性接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、及びそれを用いた偏光板
EP3943563A4 (fr) * 2019-03-18 2022-04-20 ThreeBond Co., Ltd. Composition adhésive, matériau durci et composite

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WO2005085317A1 (fr) * 2004-03-04 2005-09-15 Toagosei Co., Ltd. Composition pour traitement (séchage) aux ultra-violets
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Cited By (15)

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US9834708B2 (en) 2013-07-08 2017-12-05 Samsung Sdi Co., Ltd. Adhesive composition for polarizing plate, adhesive film for polarizing plate comprising the same, polarizing plate comprising the same and display device comprising the same
US20180044563A1 (en) * 2013-07-08 2018-02-15 Samsung Sdi Co., Ltd. Adhesive composition for polarizing plate, adhesive film for polarizing plate comprising the same, polarizing plate comprising the same and display device comprising the same
JP2015017146A (ja) * 2013-07-08 2015-01-29 チェイル インダストリーズ インコーポレイテッド 偏光板用接着剤組成物
US10655037B2 (en) 2013-07-08 2020-05-19 Samsung Sdi Co., Ltd. Adhesive composition for polarizing plate, adhesive film for polarizing plate comprising the same, polarizing plate comprising the same and display device comprising the same
WO2015194654A1 (fr) * 2014-06-20 2015-12-23 東亞合成株式会社 Composition adhésive durcissable par un faisceau d'énergie d'activation pour film ou feuille plastique
JPWO2015194654A1 (ja) * 2014-06-20 2017-05-25 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
US10988646B2 (en) 2015-12-18 2021-04-27 Furukawa Electric Co., Ltd. Adhesive composition, and method of bonding an adherend and method of producing a stack, each of which uses the same
WO2017104165A1 (fr) * 2015-12-18 2017-06-22 古河電気工業株式会社 Composition adhésive, procédé de liaison de parties adhérées l'utilisant et procédé de fabrication de stratifié
WO2019177134A1 (fr) * 2018-03-15 2019-09-19 東亞合成株式会社 Composition adhésive durcissable par rayonnement d'énergie active pour films et feuilles en plastique, stratifié et plaque de polarisation
JPWO2019177134A1 (ja) * 2018-03-15 2021-03-18 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、積層体及び偏光板
JP7331832B2 (ja) 2018-03-15 2023-08-23 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、積層体及び偏光板
JP2020105265A (ja) * 2018-12-26 2020-07-09 三菱ケミカル株式会社 活性エネルギー線硬化性接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、及びそれを用いた偏光板
JP7196596B2 (ja) 2018-12-26 2022-12-27 三菱ケミカル株式会社 活性エネルギー線硬化性接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、及びそれを用いた偏光板
EP3943563A4 (fr) * 2019-03-18 2022-04-20 ThreeBond Co., Ltd. Composition adhésive, matériau durci et composite
JP7401792B2 (ja) 2019-03-18 2023-12-20 株式会社スリーボンド 接着剤組成物、硬化物および複合体

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