WO2008056751A1 - Composition adhésive durcissable par rayonnement actinique - Google Patents

Composition adhésive durcissable par rayonnement actinique Download PDF

Info

Publication number
WO2008056751A1
WO2008056751A1 PCT/JP2007/071741 JP2007071741W WO2008056751A1 WO 2008056751 A1 WO2008056751 A1 WO 2008056751A1 JP 2007071741 W JP2007071741 W JP 2007071741W WO 2008056751 A1 WO2008056751 A1 WO 2008056751A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
component
adhesive composition
compound
active energy
Prior art date
Application number
PCT/JP2007/071741
Other languages
English (en)
Japanese (ja)
Inventor
Yasuyuki Sanai
Mikihide Osoegawa
Miki Tachibana
Original Assignee
Toagosei Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to JP2008543129A priority Critical patent/JPWO2008056751A1/ja
Publication of WO2008056751A1 publication Critical patent/WO2008056751A1/fr

Links

Classifications

    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • Active energy ray-curable adhesive composition Active energy ray-curable adhesive composition
  • the present invention relates to an active energy ray-curable adhesive composition capable of adhering various substrates by irradiation with active energy rays such as an electron beam or ultraviolet rays, and the composition of the present invention Is suitable for laminating and bonding thin-layer adherends such as plastic films or plastic sheets used as optical components.
  • active energy rays such as an electron beam or ultraviolet rays
  • the composition of the present invention Is suitable for laminating and bonding thin-layer adherends such as plastic films or plastic sheets used as optical components.
  • liquid crystal display elements, EL (electric aperture luminescence) display elements, projection display elements, FED ( Field emission (field emission) display) It is suitably used for the production of various optical films or sheets used for display elements, plasma display elements, etc., and can be used in these technical fields.
  • thin-layer adherends such as plastic films or sheets, or thin-layer adherends such as plastic films or sheets, and thin-layer adherends made of other materials are bonded together.
  • a solvent-type adhesive composition containing an ethylene acetate butyl copolymer or a polyurethane-based polymer is applied to the first thin layer adherend and dried, and then the second thin layer is added thereto.
  • the dry laminating method is mainly used in which the adherend is pressed with a nip roller.
  • the adhesive composition used in this method is generally a force that contains a large amount of solvent in order to make the coating amount of the composition uniform, and therefore 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 a two-component adhesive composition and an adhesive composition that is cured by active energy rays such as ultraviolet rays or electron beams are widely used.
  • the two-component adhesive composition is mainly composed of a polymer having a hydroxyl group at the terminal and a polyisocyanate compound having an isocyanate group at the terminal as a curing agent.
  • a urethane-based adhesive composition is used.
  • the composition has the disadvantage that it takes too much time to cure!
  • liquid crystal display devices are widely used as display elements for televisions, portable personal computers, mobile phones and mobile phones, as well as simple display devices for digital watches and various electrical appliances. It has been. In recent years, active energy ray-curable adhesives have also been used for bonding various optical films used in the liquid crystal display elements.
  • the adhesive composition used in the optical film is required to have the ability to maintain its adhesive strength under severe conditions under high temperature and high humidity conditions.
  • most of the conventional active energy ray-curable adhesive compositions are excellent in the initial adhesive strength, but the adhesive strength decreases when used for a long time under high temperature or high humidity conditions. May cause peeling or whitening due to moisture absorption.
  • Patent Document 1 containing a polymer having a glass transition temperature of 40 ° C or higher in the composition, or using a compound having an imide group.
  • Patent Document 2 Proposes an adhesive (Patent Document 2) that has excellent adhesion at high temperatures and high humidity!
  • Patent Document 3 an adhesive between a polymethylmetatalylate (PMMA) plate and a film, but when used as a laminate adhesive between films, the adhesive strength is insufficient.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2000-072833 (Claims)
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-064594 (Claims)
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-272775 (Claims)
  • the present inventors have found an adhesive composition having an active energy ray-curable adhesive composition that is excellent in adhesive strength under both high temperature and high humidity conditions, and has little coloring even when used for a long time! For this reason, we conducted an intensive study.
  • composition comprising a urethane (meth) acrylate having a specific structure, a phenol compound having a specific structure, and a phenolic antioxidant has either high temperature or high humidity. It was found that the adhesive strength was excellent even under conditions, and there was little coloring, and that it was at a practical level, and the present invention shown in ⁇ 1> below was completed.
  • A Urethane (meth) acrylate having a polyester skeleton or a polycarbonate skeleton, (B) at least one group in the phenyl group — C (CH 2) R (R represents an alkyl group or a phenyl group)
  • An active energy ray-curable adhesive comprising: a phenolic compound having a hydrogen atom; (C) a thio-based antioxidant; and (D) a compound having an ethylenically unsaturated group other than the component (A). Composition.
  • the active energy ray-curable adhesive composition of the present invention it is possible to maintain an excellent adhesive force even under high temperature or high humidity! Few . Therefore, the active energy ray-curable adhesive composition of the present invention is effective for adhesion of thin-layer adherends such as plastic films used as various optical members, and particularly for the production of optical films used for liquid crystal display devices and the like. Can be suitably used.
  • attalylate and / or metatalylate is referred to as (meth) atalylate
  • attalyloyl group and / or methacryloylole group is referred to as (meth) atalyleunole group
  • acrylic acid and / or methacrylic acid as (meth) acrylic acid. Expressed as acid.
  • the active energy ray-curable adhesive composition of the present invention includes (A) a urethane (meth) acrylate (hereinafter referred to as component (A)) having a polyester skeleton or a polycarbonate skeleton, and (B) a phenyl. At least one group in the group — C (CH 2) R (R represents an alkyl group or a phenyl group. ) Phenol compounds (hereinafter referred to as component (B)), (C) xio antioxidants (hereinafter referred to as component (C) and! /, U), and (D) ethylene other than component (A). And a compound having an unsaturated group (hereinafter referred to as component (D)).
  • each compound described later is used alone or in combination of two or more.
  • Component (A) is a urethane (meth) acrylate having a polyester skeleton or a polycarbonate skeleton.
  • the cured product obtained has excellent adhesion even if it is subjected to high temperature or high humidity!
  • the adhesive strength of the obtained cured product under high temperature conditions and high humidity conditions decreases. End up.
  • both oligomers and polymers can be used, and those having a weight average molecular weight of 500 to 50,000 are more preferable, and those having 3,000 to 40,000 are more preferable.
  • the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.
  • component (A) various compounds can be used.
  • a polyester skeleton or polycarbonate that is preferably a urethane (meth) atrelate (hereinafter referred to as a bifunctional urethane (meth) acrylate) having two (meth) attaroyl groups. It is more preferable that the reaction product of a diol having a skeleton and an organic diisocyanate is a bifunctional urethane (meth) acrylate in which a hydroxyl group-containing (meth) acrylate is reacted.
  • examples of the polyol having a polyester skeleton include an esterification reaction product of a diol such as a low molecular weight diol or polyprolacton diol and an acid component such as a dibasic acid or an anhydride thereof.
  • examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexane dimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like.
  • dibasic acid or its anhydride examples include adipic acid, succinic acid, phthalic acid, tetrahidrphthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
  • polycarbonate polyol examples include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.
  • organic polyisocyanates include tolylene diisocyanate, 1,6-hexanediisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, 1,6 San diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, paraphenol dirange Isocyanate, Tolylene diisocyanate dimer, 1,5-Naphthalene diisocyanate, Hexamethylene diisocyanate cross-adduct, 4, 4'-dicyclohexylmethane diisocyanate, Trimethylolpropane Examples include tris (tolylene diisocyanate) adduct and isophorone diisocyanate. Organic diisocyanates are preferred as organic polyisocyanates.
  • Hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) atereloxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy octyl (meth) acrylate, pentaerythritol Examples thereof include hydroxyalkyl (meth) acrylates such as tri, di or mono (meth) acrylate and trimethylolpropane di or mono (meth) acrylate.
  • the organic isocyanate to be used and the polyol component are subjected to an addition reaction by heating and stirring, and further, a hydroxyalkyl (meth) acrylate is added, followed by heating and stirring to cause an addition reaction. Can be obtained.
  • an addition catalyst such as dibutyltin dilaurate
  • the adhesive strength under high humidity is particularly excellent, and the adhesive after curing is time-dependent.
  • Urethane acrylate using non-aromatic polyester polyols and polycarbonate polyols is preferred because it is less colored!
  • Component (B) is a phenol compound having at least one group — C (CH 2) R (wherein R represents an alkyl group or a phenyl group) in the phenyl group.
  • R represents an alkyl group or a phenyl group
  • coloring over time can be remarkably suppressed.
  • alkyl group for R examples include those having 1 to 10 carbon atoms, and more preferred is a methyl group, preferably an alkyl group having carbon atoms;!
  • the number of the group C (CH 3) 2 R in the phenyl group is preferably 1 or 2.
  • the component (B) preferably contains a compound represented by the following formula (1), more preferably only one or more compounds represented by the formula (1). .
  • R represents an alkyl group or a phenyl group
  • R 1 represents a hydrogen atom, an alkyl group or a phenyl group
  • R 2 and R 3 represent a hydrogen atom or a methyl group
  • X represents an m-valent group
  • m represents an integer of 1 to 4.
  • X is preferably a monovalent or divalent group, and m is preferably an integer of 1 or 2.
  • alkyl group for R 1 in formula (1) is preferably an alkyl group having 1 to 20 carbon atoms.
  • X include the following monovalent to tetravalent groups.
  • Examples of the monovalent group include an alkyl group, a group having one or more ester bonds (COO and / or OCO), a benzotriazol group, and a group containing a hindered amino skeleton.
  • an alkyl group having 2 or more carbon atoms is preferred, and the cured product is preferably prevented from being colored.
  • Examples of the group having one or more ester bonds include an alkoxycarbonylalkyl group, and a group represented by I ⁇ COOR 1 is preferable.
  • R 7 is an alkylene group having 1 to 12 carbon atoms such as an ethylene group
  • R 1 represents an alkyl group having 1 to 20 carbon atoms.
  • R 7 is preferably an alkylene group having 2 to 6 carbon atoms! /.
  • Examples of the divalent group include an alkylene group and a group having one or more ester bonds.
  • the group having one or more ester bonds includes two or more structures selected from the group consisting of monovalent to tetravalent alkyl groups, ester bonds, and ether bonds, and one or more ester bonds.
  • a divalent group having a spiro orthoether ring and one or more ester bonds is preferable.
  • trivalent group examples include isocyanur groups (1, 3, 5 triazine 1, 2, 4, 6 (1H, 3H, 5H) -trione 1, 3, 5-triyl group).
  • tetravalent group examples include groups having one or more ester bonds, and two or more structures selected from the group consisting of monovalent to tetravalent alkyl groups, ester bonds, and ether bonds are linked. And tetravalent groups having one or more ester bonds are preferred. More specifically, C (CH OCOR 7 ) and the like can be mentioned. R 7 has the same carbon number as described above!
  • X has one or more ester bonds.
  • the compound (Bl) which is a group [hereinafter referred to as component (B1)] is more preferred.
  • preferred examples of the monophenol compound include a compound represented by the following formula (2).
  • R 4 represents an alkyl group having 1 to 20 carbon atoms.
  • the solubility in the composition is sufficient, and if the carbon number is 20 or less, a desired effect can be obtained with a small amount. A uniform composition can be obtained.
  • diphenol compound examples include compounds represented by the following formula (3).
  • At least one group in the phenyl group known as an ultraviolet absorber — C (CH 2) R R (R is an alkyl group or a phenyl group)
  • component (B2) a benzotriazole group (hereinafter referred to as component (B2)
  • component (B2) a known light stabilizer
  • the product (B3) [hereinafter referred to as the component (B3)] can also be mentioned.
  • various compounds can be used as long as they are compounds having at least one group C (CH 3) R in the phenyl group and further having a benzotriazole group.
  • Such compounds are commercially available, and examples thereof include TINUVIN series manufactured by Ciba Specialty Chemicals.
  • R 7 represents an alkyl group or a phenyl group having carbon atoms;! -10].
  • R 7 an alkyl group having 4 carbon atoms or a phenyl group is commercially available and can be suitably used.
  • various compounds can be used as long as they are compounds having at least one group C (CH 3) R in the phenyl group and further having a hindered amino group.
  • Such compounds are commercially available and can mention the TINUVIN series manufactured by Chino 'Specialty' Chemicals.
  • any of the components (B1) to (B3) described above can be used.
  • the component (B1) is essential, and the combination of the component (B2) and / or the component (B3) can be used by transmitting light through the adhesive layer to the substrate. When it reaches, it is preferable because coloring of the substrate can be suppressed.
  • Component (C) is a xio antioxidant.
  • the component (C) by including the component (C), there is an effect of suppressing coloring particularly when light and heat are simultaneously applied to the laminate.
  • various compounds can be used as long as they have a thio atom and have an antioxidant function, and the diester-type thioether compound and / or the tetraester-type thiocarbonate are excellent because of excellent coloring suppression effect. Compounds are preferred.
  • the diester type thioether compound and / or the tetraester type carbonate compound in the component (C) various compounds can be used, and the diester type thioether compound is represented by the formula because it has low volatility.
  • the diester type thioether compound in which the compound represented by (6) is preferred a compound represented by the formula (7) is preferred.
  • R 5 represents an alkyl group having 1 to 20 carbon atoms.
  • R 6 represents an alkyl group having 1 to 20 carbon atoms.
  • R 5 and R 6 are alkyl groups having 1 to 20 carbon atoms.
  • R When the carbon number of R 6 is 1 or more, the solubility in the composition is sufficient, and when the carbon number is 20 or less, the desired effect can be obtained with a small amount, and a uniform composition can be obtained. can get.
  • diester type thioether compound examples include dioctylthiodipropionate, dimyristyl-3,3-thiodipropionate, and the like.
  • tetraester type thiocarbonate compound examples include pentaerythritol tetrakis (/ 3-laurylthiopropionate).
  • Non-patent Document 1 it is a fact widely known in the field of plastic molding materials that the heat-resistant oxidative degradation of plastic materials can be suppressed by using a phenol compound and a thioether compound in combination.
  • Non-patent literature l Japan Energy & Technology Intelligence), Vol. 44,
  • composition of the present invention a compound having an ethylenically unsaturated group is blended for the purpose of adjusting the viscosity of the composition or adjusting the desired physical properties.
  • component (D) various compounds can be used as long as they are compounds having an ethylenically unsaturated group other than the component (A).
  • Component (D) includes monomers, oligomers and polymers.
  • Examples of the monomer include a compound having one (meth) attalyloyl group.
  • Such compounds include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate and 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxy ethyl (meth) acrylate and hydroxypropyl (meth) acrylate; benzyl (meth) acrylate, o—Fueyurphenyle Aromatic group-containing (meth) acrylates such as chill (meth) acrylate and P-tamylphenylethyl (meth) acrylate; and cycloaliphatic (meth) acrylates
  • (meth) acrylamide derivatives such as N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide and attalyloylmorpholine N-Bureformamide, N-Buyl N-Methylformamide, N-Bulucecetamide, N-Buyl N-Methylacetamide, N-Buylpyrrolidone and N-Buyl Force Prolatatum, etc. Can be mentioned.
  • a hydroxyl group-containing (meth) acrylate is preferable because adhesion to the substrate can be improved.
  • the aromatic compound-containing (meth) acrylate has two aromatic groups (meta) which is preferable in that the cured product has an excellent refractive index. ) Atari rate is preferred!
  • Examples of the compound having two or more (meth) atalyloyl groups include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and tripropylene glycol di Alkylene Dalicol Di (meth) atarylate such as (meth) atallylate; 1,6-Hexanediol di (meth) talylate and glycol di (meth) atalylate such as neopentylglycol di (meth) attalylate; Enolole A Di (meth) atarylate or its halogen aromatic nucleus substitution and bisphenol F di (meth) atalylate or its halogen aromatic nucleus substitution bisphenol type di (meth) talylate; dimethylol tricyclodecandi (Meta) Atarilate, Trimethylo Polyol poly, such as lepropantri (meth) acrylate
  • oligomer examples include polyester (meth) acrylate, epoxy (meth) acrylate and polyether (meth) acrylate.
  • polyester (meth) acrylate oligomer 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.
  • polyol examples include ethylene glycol, diethylene glycol, triethylene glycol monoole, tetraethylene glycol monoole, polyethylene glycol mononore, propylene glycol monole, dipropylene glycol monole, tripropylene glycol monole, polypropylene glycol monole, butylene glycol monole, polybutylene glycol monole.
  • Tetramethylene glycol Tetramethylene glycol, hexamethylene glycol, neopentino glycol, cyclohexane dimethanol, 3-methanol, 1,5-pentanediol, 1,6-hexanediol, trimethylone lepronone,
  • low molecular weight polyols such as glycerin, pentaerythritol and dipentaerythritol, and adducts thereof with these alkylene oxides.
  • Carboxylic acids or anhydrides include dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid.
  • dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid.
  • the anhydride etc. are mentioned.
  • polyester poly (meth) acrylate examples 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 is described in pages 74 to 75 of the above-mentioned document “UV'EB Curing Material”. Etc.
  • epoxy resin examples include aromatic epoxy resins and aliphatic epoxy resins.
  • aromatic epoxy resin examples include resorcinol diglycidyl ether; Di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adducts; nopolac epoxy resins such as phenol novolac epoxy resin and cresol nopolac epoxy resin Glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
  • aliphatic epoxy resin examples include ethylene glycol, propylene glycol, 1,4-monobutanediol and alkyleneglycol such as 1,6-hexanediol; Diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of glycolenole and polypropylene glycolenoles; diglycidyl ethers of neopentinoleglycolanol, dibromoneopentylglycol and its alkylene oxides; trimethylolethane, trimethylolpropane , Di- or triglycidyl ethers of glycerin and its alkylene oxide adducts, and divalent, tri- or tetraglycidinyl ethers of pentaerythritol and its alkylene oxide adducts Polyglycidyl ethers of alcohols; hydrogenated bisphenol A and di- or polyglycol
  • the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.
  • Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) di
  • atarylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate.
  • Examples of the polymer include 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.
  • Examples include compounds described on pages 78 to 79 of the document “UV'EB Curing Material”.
  • the total amount of the components (A), (B), (C) and (D) is 100% by weight.
  • the adhesive strength is excellent at high temperatures, and when it is 50% by weight or less, the initial adhesive strength or adhesive strength under high humidity is excellent. It becomes.
  • the component (B) and the component (C) are each 0.01% by weight or more, in the cured product obtained by curing the composition, the coloring by heat or light is less than 5% by weight. A uniform composition is obtained and the curability is excellent.
  • the component (D) is 90% by weight or less, the initial adhesive strength and the adhesive strength at high temperature or high humidity are excellent.
  • the composition of the present invention contains 2 to 30 wt.% Of the metatalylate compound in the total amount of the components (A) and (D) in order to prevent appearance defects such as wrinkles and warpage of the base film for shelling. % Is preferable.
  • the curing rate of the composition can be adjusted. When it is 2% by weight or more, it has excellent adhesive strength, and when it is 30% by weight or less, it has excellent curability and productivity.
  • the metatalylate compound may be appropriately selected from the aforementioned components (A) and (D).
  • the components (A) and (D) The total amount of the component is less than 50% by weight of the compound having an aromatic group and an ethylenically unsaturated group, preferably S, more preferably less than 30% by weight, most preferably including the compound. There is nothing.
  • the refractive index of the cured product 50% by weight or more of the compound having an aromatic group and an ethylenically unsaturated group is contained in the total amount of the component (A) and the component (D). It is preferable to be less than% by weight!
  • the compound having an aromatic group and an ethylenically unsaturated group may be appropriately selected from the components (D) described above.
  • composition of the present invention is cured by ultraviolet rays
  • a photopolymerization initiator may be combined as necessary.
  • photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and their alkyl ethers; acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2-Diethoxy 2-phenylenoacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1 [4 (methylthio) phenyl] — 2-morpholinopropane-1-acetophenone such as 1-one; 2-methyl haloanthraquinone and 2-amylanthraquinone and other anthraquinones; 2,4 dimethyl thixanthone, 2,4 jetylthioxanthone, 2-clothioxanthone and 2,4-diiso Thioxane such as pyrthioxanthone Down; ket
  • a preferable blending ratio of the photopolymerization initiator is 0.1% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 5% by weight or less with respect to 100% by weight of the composition.
  • An ⁇ -hydroxyacetophenone-based or phosphine oxide-based photopolymerization initiator is preferred because of less coloring over time.
  • composition of the present invention contains other antioxidants in an amount of up to 5% by weight per 100% by weight of the total of the components (A) to (D) and, if necessary, the component (i). , UV absorbers other than the component (B2), light stabilizers other than the component (B3) (HALS (hindered amine light stabilizer), etc.) Leveling agents and antifoaming agents to suppress foaming can be added.
  • the production method of the composition of the present invention is not particularly limited, and can be obtained by stirring or mixing the essential components of the present invention, or the essential components and other components as necessary, by a commonly performed method.
  • the glass transition temperature (hereinafter referred to as Tg) after curing of the composition is preferably 10 ° C or higher and 70 ° C or lower.
  • Tg glass transition temperature
  • Tg means a temperature at which the main peak of the loss tangent (tan ⁇ ) of the viscoelastic spectrum of the cured product measured at 1 Hz becomes maximum.
  • composition of the present invention can be used for adhesion of various substrates, and as a method of use, a method of irradiating active energy rays after applying to a good substrate according to a conventional method, etc. Is mentioned.
  • ultraviolet rays are preferable because an inexpensive device including ultraviolet rays, X-rays, and electron beams can be used.
  • Various light sources can be used for curing with ultraviolet rays, such as pressurized or high-pressure mercury lamps, methano, ride lamps, xenon lamps, electrodeless discharge lamps, and carbon arc lamps.
  • various devices can be used as an irradiation device such as a Cockloft-Walton type, a bandegraph type, and a resonance transformer type device. 1 and those having an energy of OOOeV are preferred, and more preferably 100 to 300 eV.
  • the composition of the present invention can be preferably used in the production of a laminate. What is necessary is just to follow the method currently performed normally. For example, there is a method in which the composition is applied to a first base material, and a second base material is bonded to the first base material, and then V, an active energy ray is irradiated from the surface of one of the base materials. In this case, at least one of the first base material and the second base material is transparent.
  • composition of the present invention can be preferably used as an adhesive composition for optical materials, and more preferably used as an adhesive composition for optical film lamination.
  • a thin layer adherend used as an optical member can be used, and a laminate can be produced according to the same method as described above.
  • the thin-layer adherend used as the optical member is mainly made of a plastic film and must be capable of transmitting active energy rays.
  • the thin-layer adherend to be used is used as the film thickness.
  • the thickness may be selected depending on the body and application, but preferably has a thickness of 0.1 lm or more and 1 mm or less.
  • plastic in the plastic film examples include polychlorinated bur resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), polyamide, polyester, polycarbonate, polyurethane, and polybule.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • examples thereof include alcohol, ethylene acetate butyl copolymer, and chlorinated polypropylene.
  • Knife-on blanket spray, dip, kisslow nore, squeeze rolle, sroll, air blade, curtain flow coater and gravure coater.
  • the coating thickness of the composition of the present invention may be selected according to the thin-layer adherend to be used and the use, but is preferably 0 ⁇ 1,000 m, more preferably; m
  • the laminate film or sheet obtained from the adhesive composition of the present invention is excellent in adhesive strength under high temperature conditions and high humidity conditions
  • the polarizing film used in a liquid crystal display device or the like is used. It can be suitably used for optical films or sheets such as films, retardation films, prism sheets, brightness enhancement films, light guide plates, and diffusion plates.
  • Table 1 summarizes the ratio (% by weight) (hereinafter also referred to as “MA ratio”) of metatarates in the total number of components (A) and (D) of each composition.
  • each number means the number of copies, and each abbreviation means the following.
  • M-1200 Urethane acrylate with a non-aromatic polyester skeleton, weight average molecular weight of about 5,000 [Aronix M-1 200 manufactured by Toagosei Co., Ltd.]
  • UN-9200 Urethane acrylate with a non-aromatic polycarbonate skeleton, weight average molecular weight of about 20,000 [Negami Kogyo Art Resin UN-9200A]
  • AO-50 Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO-50 manufactured by Asahi Denka Kogyo Co., Ltd., where R 1 is an octadecyl group) Compound)
  • AO-80 3,9bis [2— ⁇ 3— (3— t-butyl 4-hydroxy-5-methylphenyl] ) Propionyloxy ⁇ -1,1-dimethylethyl] —2, 4, 8, 10 Tetraoxaspiro [5 • 5] undecane (AO-80 manufactured by Asahi Denka Kogyo Co., Ltd., compound of formula (4))
  • TV900 2-(2H benzotriazole 2 yl) 4, 6 bis (1 methyl 1-phenol cinole) fenenore [TINUVIN900, manufactured by Specialty Chemicals,
  • AO-412 Pentaerythritol tetrakis (/ 3-laurylthiopropionate) [AO_412S manufactured by Asahi Denka Kogyo Co., Ltd.]
  • IBXA Isobornyl attalylate (Kyoeisha Chemical Co., Ltd. Light Atrelay HB-XA)
  • HEMA Hydroxyethyl methacrylate (Light Ester HO manufactured by Kyoeisha Chemical Co., Ltd.)
  • OPPA Orthophenylphenol Atarylate [Aronix TO-2 344 manufactured by Toagosei Co., Ltd.]
  • Irgl84 1-Hydroxycyclohexyl phenyl ketone [Tinoku's Specialty ⁇ Inregacure 184, manufactured by Chemicals
  • TPO 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO)
  • the obtained composition was applied to a thickness of 10 m by a bar coater on a 75-am-thick triacetylcellulose (hereinafter abbreviated as TAC) film.
  • TAC triacetylcellulose
  • a 75-mm thick TAC film was pasted onto this with a nip roll, and this was placed at 120 W / cm, 10 cm from the bottom of the concentrating metal halide lamp, and under the lamp at a conveyor speed of 5 m / min.
  • the laminate film was manufactured by repeatedly passing the film and bonding the films together. This is called Specimen A.
  • a laminate film was produced in the same manner as described above except that the TAC film was changed to a 50 m thick polyethylene terephthalate (hereinafter abbreviated as PET) film and the coating thickness was changed to 50 m. This is called Specimen B.
  • PET polyethylene terephthalate
  • the obtained specimen A was used and allowed to stand under the following conditions, and then the peel strength was evaluated.
  • the obtained specimen B was allowed to stand under the following conditions and then evaluated for coloring. • After high temperature test: 500 hours at 90 ° C
  • Specimen A is subjected to a high temperature test or high humidity test under the above conditions and then peeled off under the following conditions The strength was measured with a tensile tester.
  • Test piece 25mm X 100mm
  • ⁇ difference between the YI value of specimen B after each test and the YI value of specimen B before each test.
  • An active energy one-line curable adhesive composition was produced in the same manner as in the Examples except that the components shown in Table 4 below were used. Table 5 summarizes the MA ratio of each composition.
  • M-1600 Polyether urethane acrylate, weight average molecular weight of about 3,000 [Aronix M-1600, manufactured by Toagosei Co., Ltd.]

Landscapes

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

Abstract

L'invention concerne une composition adhésive durcissable par rayonnement actinique, ladite composition présentant une excellente force de liaison en conditions quelconques de température élevée et d'humidité élevée et une faible décoloration, même après une longue utilisation. La composition adhésive durcissable par rayonnement actinique selon l'invention est caractérisée en ce qu'elle comprend (A) un (méth)acrylate d'uréthanne ayant un squelette polyester ou polycarbonate, (B) un composé de phénol ayant au moins un groupement -C(CH3)2R (R représentant un alkyle ou phényle) dans le groupement phényle, (C) un antioxydant contenant du soufre et (D) un composé comprenant un groupement à insaturation éthylénique à l'exception du composant (A).
PCT/JP2007/071741 2006-11-09 2007-11-08 Composition adhésive durcissable par rayonnement actinique WO2008056751A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008543129A JPWO2008056751A1 (ja) 2006-11-09 2007-11-08 活性エネルギー線硬化型接着剤組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-303722 2006-11-09
JP2006303722 2006-11-09

Publications (1)

Publication Number Publication Date
WO2008056751A1 true WO2008056751A1 (fr) 2008-05-15

Family

ID=39364562

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/071741 WO2008056751A1 (fr) 2006-11-09 2007-11-08 Composition adhésive durcissable par rayonnement actinique

Country Status (3)

Country Link
JP (1) JPWO2008056751A1 (fr)
TW (1) TW200837167A (fr)
WO (1) WO2008056751A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001855A1 (fr) * 2008-06-30 2010-01-07 東亞合成株式会社 Composition d’adhésif durcissable sous rayonnement énergétique actif
WO2011065546A1 (fr) * 2009-11-30 2011-06-03 日立化成工業株式会社 Composition de résine photosensible, vernis à partir de résine photosensible, pellicule de résine photosensible et produit durci en résine photosensible
JP2012093708A (ja) * 2010-09-30 2012-05-17 Hitachi Chem Co Ltd 可視光導光路用感光性樹脂組成物、その硬化物及び可視光導光路
WO2012137828A1 (fr) * 2011-04-04 2012-10-11 株式会社ダイセル Composition photodurcissable, pellicule composite conductrice et leur procédé de fabrication
JP2013035920A (ja) * 2011-08-05 2013-02-21 Dic Corp 紫外線硬化型粘着剤用樹脂組成物、粘着剤及び積層体
WO2013073363A1 (fr) * 2011-11-17 2013-05-23 株式会社スリーボンド Composition thermodurcissable
JP2018100403A (ja) * 2016-12-20 2018-06-28 荒川化学工業株式会社 紫外線硬化型粘着剤、硬化物、及び粘着シート

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256228A (ja) * 2001-03-01 2002-09-11 Nippon Kayaku Co Ltd 光ディスク用接着剤組成物、硬化物および物品
JP2004059773A (ja) * 2002-07-30 2004-02-26 Dainippon Ink & Chem Inc 紫外線硬化型組成物および貼り合わせ型光ディスク
JP2005126724A (ja) * 2004-11-24 2005-05-19 Nippon Kayaku Co Ltd 光ディスク用接着剤組成物、硬化物、物品及び接着方法
JP2005272495A (ja) * 2004-03-23 2005-10-06 Jsr Corp 接着剤用液状硬化性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256228A (ja) * 2001-03-01 2002-09-11 Nippon Kayaku Co Ltd 光ディスク用接着剤組成物、硬化物および物品
JP2004059773A (ja) * 2002-07-30 2004-02-26 Dainippon Ink & Chem Inc 紫外線硬化型組成物および貼り合わせ型光ディスク
JP2005272495A (ja) * 2004-03-23 2005-10-06 Jsr Corp 接着剤用液状硬化性樹脂組成物
JP2005126724A (ja) * 2004-11-24 2005-05-19 Nippon Kayaku Co Ltd 光ディスク用接着剤組成物、硬化物、物品及び接着方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001855A1 (fr) * 2008-06-30 2010-01-07 東亞合成株式会社 Composition d’adhésif durcissable sous rayonnement énergétique actif
CN102076806A (zh) * 2008-06-30 2011-05-25 东亚合成株式会社 活性能量线固化型粘合剂组合物
JPWO2010001855A1 (ja) * 2008-06-30 2011-12-22 東亞合成株式会社 活性エネルギー線硬化型接着剤組成物
WO2011065546A1 (fr) * 2009-11-30 2011-06-03 日立化成工業株式会社 Composition de résine photosensible, vernis à partir de résine photosensible, pellicule de résine photosensible et produit durci en résine photosensible
JPWO2011065546A1 (ja) * 2009-11-30 2013-04-18 日立化成株式会社 感光性樹脂組成物、感光性樹脂ワニス、感光性樹脂フィルム、及び感光性樹脂硬化物
JP5716672B2 (ja) * 2009-11-30 2015-05-13 日立化成株式会社 感光性樹脂組成物、感光性樹脂ワニス、感光性樹脂フィルム、及び感光性樹脂硬化物
JP2012093708A (ja) * 2010-09-30 2012-05-17 Hitachi Chem Co Ltd 可視光導光路用感光性樹脂組成物、その硬化物及び可視光導光路
WO2012137828A1 (fr) * 2011-04-04 2012-10-11 株式会社ダイセル Composition photodurcissable, pellicule composite conductrice et leur procédé de fabrication
JP2013035920A (ja) * 2011-08-05 2013-02-21 Dic Corp 紫外線硬化型粘着剤用樹脂組成物、粘着剤及び積層体
WO2013073363A1 (fr) * 2011-11-17 2013-05-23 株式会社スリーボンド Composition thermodurcissable
JP2013107932A (ja) * 2011-11-17 2013-06-06 Three Bond Co Ltd 熱硬化性組成物
JP2018100403A (ja) * 2016-12-20 2018-06-28 荒川化学工業株式会社 紫外線硬化型粘着剤、硬化物、及び粘着シート

Also Published As

Publication number Publication date
TW200837167A (en) 2008-09-16
JPWO2008056751A1 (ja) 2010-02-25

Similar Documents

Publication Publication Date Title
JP4900241B2 (ja) 活性エネルギー線硬化型接着剤組成物
JP5733175B2 (ja) 活性エネルギー線硬化型接着剤組成物
TWI585175B (zh) Resin composition and adhesive for UV hardening adhesive
US20110108191A1 (en) Active energy beam-curable adhesive composition
JP5822052B1 (ja) 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法
CN107722916B (zh) Uv固化型树脂组合物
WO2008056751A1 (fr) Composition adhésive durcissable par rayonnement actinique
JP5641382B1 (ja) 紫外線硬化型粘着剤組成物及び粘着剤
JP5652380B2 (ja) 硬化型接着剤組成物
JP3640149B2 (ja) 活性エネルギー線硬化型接着剤組成物
WO2016092971A1 (fr) Composition d'agent adhésif durcissable par des rayons ultraviolets, procédé pour la production de feuille adhésive durcissable par des rayons ultraviolets et procédé pour la production de stratifié
WO2012141275A1 (fr) Composition adhésive durcissable par un rayonnement d'énergie active
JP7111155B2 (ja) 光硬化性樹脂組成物及びそれを用いた粘接着剤
JP5105065B2 (ja) 位相差フィルム付き偏光板の製造方法
WO2014188767A1 (fr) Composition adhésive durcissable par ultraviolet, adhésif et film adhésif
JP6410092B2 (ja) 接着シート、物品ならびに物品の製造方法
WO2015098307A1 (fr) Composition adhésive durcissable aux ultraviolets, film adhésif et son procédé de production
JP2014009339A (ja) 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
JP6524655B2 (ja) 紫外線硬化型粘着剤組成物、紫外線硬化型粘着シート、及び、積層体
JP7318366B2 (ja) 触媒層用活性エネルギー線硬化型組成物及び積層体
JP6120073B2 (ja) 紫外線硬化型粘着剤組成物、粘着剤及び粘着フィルム
JP2009078380A (ja) 水圧転写体及び水圧転写体の製造方法
KR102587767B1 (ko) 점착 시트 및 점착제 조성물
WO2019069621A1 (fr) Composition de résine photodurcissable et feuille adhésive
JP6863378B2 (ja) 光硬化性樹脂組成物及びそれを用いた粘・接着剤

Legal Events

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

Ref document number: 07831472

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008543129

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07831472

Country of ref document: EP

Kind code of ref document: A1