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WO2020096032A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

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Publication number
WO2020096032A1
WO2020096032A1 PCT/JP2019/043810 JP2019043810W WO2020096032A1 WO 2020096032 A1 WO2020096032 A1 WO 2020096032A1 JP 2019043810 W JP2019043810 W JP 2019043810W WO 2020096032 A1 WO2020096032 A1 WO 2020096032A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
pressure
sensitive adhesive
mass
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/043810
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English (en)
Japanese (ja)
Inventor
文弥 戸村
賢 大橋
直輝 名取
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ajinomoto Co Inc
Original Assignee
Ajinomoto Co Inc
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 Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Publication of WO2020096032A1 publication Critical patent/WO2020096032A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to an adhesive composition, and specifically to an adhesive composition suitable for a sealing material, an adhesive material, a transparent optical adhesive film (OCA), etc. in a flexible electronic device.
  • OCA transparent optical adhesive film
  • Organic EL devices are light-emitting devices that use organic substances as light-emitting materials, and have recently been in the spotlight because they can emit light with high brightness at low voltage.
  • an adhesive composition for shielding an organic EL element from moisture in the outside air one having an adhesive property with a substrate having an electronic element (hereinafter also abbreviated as “element substrate”) is used (for example, Patent Documents 1 and 2).
  • a flexible and bendable flexible electronic device (hereinafter, also simply referred to as “flexible device”) has been actively developed, but an adhesive used for a flexible device such as a flexible organic EL device is used.
  • the composition is required to have excellent flexibility.
  • an object of the present invention is to provide a pressure-sensitive adhesive composition that uses hydrogenated nitrile rubber having excellent flexibility and that also has excellent adhesiveness.
  • an adhesive composition containing a hydrogenated nitrile rubber having an epoxy group and an acid anhydride can be a composition having excellent adhesiveness, Has been completed.
  • the present invention includes the following contents.
  • An adhesive composition containing (A) a hydrogenated nitrile rubber having an epoxy group and (B) an acid anhydride.
  • the tackifier (D) contains at least one resin selected from aromatic hydrocarbon resins, aliphatic / aromatic copolymer hydrocarbon resins and coumarone-indene resins.
  • a pressure-sensitive adhesive sheet comprising a support and the layer of the pressure-sensitive adhesive composition according to any one of [1] to [12] formed on the support.
  • a flexible composition comprising the pressure-sensitive adhesive composition according to any one of [1] to [12], wherein the pressure-sensitive adhesive composition has a crosslinked structure formed by a reaction between an acid anhydride group and an epoxy group.
  • Electronic device [20] The flexible electronic device according to [18] or [19], which is a flexible organic EL device.
  • the pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention can be excellent as a sealing material, adhesive material, transparent optical pressure-sensitive adhesive film (OCA), etc., especially for flexible electronic devices.
  • the hydrogenated nitrile rubber having an epoxy group in the present invention preferably has a plurality of epoxy groups of at least 2 and more preferably 3 or more.
  • the hydrogenated nitrile rubber having such an epoxy group is, for example, an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether.
  • the thing obtained by graft-modifying under conditions is mentioned.
  • Hydrogenated nitrile rubber is one in which the main chain double bond of nitrile rubber is hydrogenated at an arbitrary ratio.
  • Nitrile rubber is a copolymer of acrylonitrile and butadiene, and includes methacrylonitrile, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, divinylbenzene, methacrylic acid, It may be a copolymer with other components such as acrylic acid. Two or more kinds of hydrogenated nitrile rubber having an epoxy group may be used in combination.
  • the acrylonitrile content (bound AN amount) in the hydrogenated nitrile rubber having an epoxy group is preferably 10 to 40% by mass, and 10 to 30% by mass from the viewpoint of solubility in an organic solvent and cold resistance during varnish production. More preferably, it is more preferably 10 to 20% by mass.
  • the acrylonitrile content (bound AN content) the value of hydrogenated nitrile rubber before epoxy modification may be used.
  • the hydrogenation rate of the hydrogenated nitrile rubber having an epoxy group can be evaluated by the residual double bond amount (which can be quantified according to ASTM D5670-95). From the viewpoint of heat resistance, ozone resistance, etc., it is preferable to use one having a residual double bond content of 0 to 20%, more preferably 0 to 10%, and further preferably 0 to 1%.
  • the hydrogenation rate the value of hydrogenated nitrile rubber before epoxy modification may be used.
  • the Mooney viscosity [ML1 + 4 (100 ° C.)] of the hydrogenated nitrile rubber having an epoxy group is preferably 30 to 100, more preferably 30 to 90, and particularly preferably 30 to 80 from the viewpoint of handleability at the time of coating. Is.
  • the Mooney viscosity can be obtained by a measuring method according to JIS K6300.
  • the number average molecular weight of the hydrogenated nitrile rubber having an epoxy group is preferably 2000 to 8000, more preferably 3000 to 7000, and particularly preferably 4000 to 6000 from the viewpoint of bending resistance and the like.
  • the number average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion).
  • GPC method polystyrene conversion
  • the number average molecular weight by GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and toluene as a mobile phase. It can be measured using a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
  • the concentration of the epoxy group of the hydrogenated nitrile rubber having an epoxy group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g from the viewpoint of optical characteristics such as total light transmittance and haze. ..
  • the epoxy group concentration is calculated from the epoxy equivalent obtained according to JIS K 7236-1995.
  • Examples of commercially available hydrogenated nitrile rubbers include 3406 (acrylonitrile content 34% by mass, residual double bond amount max 0.9%, Mooney viscosity 63), 3407, as THERBAN (registered trademark) series manufactured by Alanseo Co., Ltd.
  • the component (A) epoxy group-containing hydrogenated nitrile rubber of the pressure-sensitive adhesive composition of the present invention is a known method described in German Patent Application Publication No. 19921415, for example, these hydrogenated nitrile rubbers are It can be produced by a method such as graft modification with an unsaturated compound having an epoxy group under radical reaction conditions.
  • Examples of commercially available hydrogenated nitrile rubber having an epoxy group include ER859 (manufactured by Seikou PMC, glycidyl methacrylate modified hydrogenated nitrile rubber, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 4825) and the like. ..
  • the content of the hydrogenated nitrile rubber (A) having an epoxy group in the pressure-sensitive adhesive composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited, but optical properties such as total light transmittance and haze are obtained.
  • the content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less with respect to 100% by mass of the nonvolatile component of the adhesive composition.
  • the content is preferably 30% by mass or more, and more preferably 40% by mass or more with respect to 100% by mass of the nonvolatile components of the adhesive composition. Is more preferably 50% by mass or more.
  • the acid anhydride (B) in the present invention means a compound in which two carboxylic acids are dehydrated and condensed intermolecularly or intramolecularly. Two or more acid anhydrides may be used in combination.
  • the acid anhydride include phthalic acid-based acid anhydride, succinic acid-based acid anhydride, maleic acid-based anhydride, trimellitic acid-based acid anhydride, norbornene-based acid anhydride, and nitrile rubber having an acid anhydride group.
  • phthalic acid anhydrides examples include phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride and 3 , 3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride and the like.
  • succinic acid anhydrides include succinic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride and the like.
  • maleic anhydride examples include maleic anhydride.
  • trimellitic acid acid anhydride examples include ethylene glycol / bisanhydrotrimellitate and glycerinbis / anhydrotrimellitate / monoacetate.
  • norbornene-based acid anhydrides include methyl-5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride and bicyclo [2.2.1] heptane-2,3- Examples thereof include dicarboxylic acid anhydride and methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride.
  • nitrile rubber having an acid anhydride group examples include succinic anhydride-modified hydrogenated nitrile rubber and maleic anhydride-modified hydrogenated nitrile rubber.
  • Particularly preferred acid anhydrides include phthalic acid anhydrides.
  • nitrile rubber having an acid anhydride group as an acid anhydride
  • a hydrogenated nitrile rubber having an acid anhydride group may be used.
  • the hydrogenated nitrile rubber having an acid anhydride group preferably has at least two or more acid anhydride groups, and more preferably has three or more acid anhydride groups.
  • the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from phthalic anhydride, and the like.
  • the acid anhydride group can have 1 type (s) or 2 or more types.
  • Examples of such hydrogenated nitrile rubber having an acid anhydride group include unsaturated compounds having an acid anhydride group, which are obtained by graft-modifying hydrogenated nitrile rubber under radical reaction conditions. Be done.
  • the hydrogenated nitrile rubber and nitrile rubber have the same meanings as described above.
  • Acrylonitrile content (bound AN amount) of hydrogenated nitrile rubber having an acid anhydride group, hydrogenation rate, Mooney viscosity, preferable range of number average molecular weight, calculation method is the same as in the case of hydrogenated nitrile rubber having an epoxy group. Is.
  • the concentration of the acid anhydride group of the hydrogenated nitrile rubber having the acid anhydride group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g.
  • the concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin, according to the description of JIS K2501.
  • RIKACID TH (1,2,3,6-tetrahydrophthalic anhydride
  • RIKACID HH hexahydrophthalic anhydride
  • RIKACID HNA-100 methyl
  • the content of the (B) acid anhydride in the pressure-sensitive adhesive composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of optical characteristics such as total light transmittance and haze, 90 mass% or less is preferable with respect to 100 mass% of non-volatile components of an adhesive composition, 40 mass% or less is more preferable, 30 mass% or less is further more preferable, and 25 mass% or less is especially preferable. Further, from the viewpoint of accelerating the curing of the adhesive composition, the content is preferably 2% by mass or more, more preferably 5% by mass or more, and 7% by mass or more with respect to 100% by mass of the nonvolatile components of the adhesive composition. More preferable.
  • the content is 85 mass% with respect to 100 mass% of the nonvolatile components of the adhesive composition.
  • the following is preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, and 50% by mass or less is particularly preferable.
  • the content is preferably 10% by mass or more, more preferably 20% by mass or more, and 25% by mass or more with respect to 100% by mass of the nonvolatile components of the adhesive composition. More preferable.
  • the content of the (B) acid anhydride in the pressure-sensitive adhesive composition of the present invention is preferably 5 to 90% by mass relative to 100% by mass of the non-volatile component of the pressure-sensitive adhesive composition. , And more preferably 10 to 85% by mass.
  • the pressure-sensitive adhesive composition of the present invention can form a crosslinked structure by reacting a hydrogenated nitrile rubber having an epoxy group with an acid anhydride by heating. For this reason, the pressure-sensitive adhesive composition of the present invention can form a sealing layer having further improved adhesive moist heat resistance.
  • the blending ratio of the (B) acid anhydride to the (A) epoxy group-containing hydrogenated nitrile rubber is preferably 1/99 to 50/50 by mass ratio, and 10/90 to 45 / 55 is more preferable.
  • the molar ratio of the epoxy group and the acid anhydride group is preferably 100: 10 to 100: 200, more preferably 100: 50. ⁇ 100: 150, particularly preferably 100: 90 to 100: 110.
  • the pressure-sensitive adhesive composition of the present invention further contains (C) a curing agent or / a curing accelerator (hereinafter sometimes abbreviated as “(C) component”) from the viewpoint of improving the curing performance of the pressure-sensitive adhesive composition.
  • (C) component a curing agent or / a curing accelerator
  • the acid anhydride of the component (B) can also function as a curing agent, but the component (C) in the present invention means a curing agent or / a curing accelerator other than the component (B).
  • the component (C) may be used in combination of two or more kinds.
  • the pressure-sensitive adhesive composition of the present invention preferably contains a curing accelerator because the acid anhydride as the component (B) can function as a curing agent. Even if the component (B) is the same compound, it may function as a curing agent or a curing accelerator depending on the system.
  • Examples of the curing agent (curing agent other than acid anhydride) in the component (C) include ionic liquids, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, organic acid dihydrazide compounds, organic phosphine compounds. , Dicyandiamide compounds, primary / secondary amine compounds, phenol compounds, thiol compounds and the like.
  • Examples of the curing accelerator in the component (C) include ionic liquids, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, and organic phosphine compounds.
  • the component (C) curing agent and / or curing accelerator may be used alone or in combination of two or more.
  • ionic liquid as the curing agent and the curing accelerator in the present invention examples include those described in JP-A-2016-186843.
  • Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium tritate.
  • imidazole compound as the curing agent and the curing accelerator in the present invention examples include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-ethyl-4-methyl-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- (2 '-Undecylimidazolyl- (1'))-ethyl-s-triazine, 2-phenyl-4,5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 2-phenyl-imidazole, 2-dodecyl- Midazole, 2-heptadecyl
  • imidazole compound examples include cuazole. 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A, 2MA-OK ( Both are manufactured by Shikoku Kasei Kogyo Co., Ltd. and the like.
  • Examples of the tertiary amine compound as the curing agent and the curing accelerator in the present invention include DBN (1,5-diazabicyclo [4.3.0] non-5-ene) and DBU (1,8-diazabicyclo [ 5.4.0] undec-7-ene), 2-ethylhexanoate of DBU, phenol salt of DBU, p-toluenesulfonate of DBU, U-CAT SA 102 (manufactured by San-Apro: DBU octylic acid) Salt), DBU-organic acid salt such as DBU formate, 2,4,6-tris (dimethylaminomethyl) phenol (TAP), and the like.
  • DBN 1,5-diazabicyclo [4.3.0] non-5-ene
  • DBU 1,8-diazabicyclo [ 5.4.0] undec-7-ene
  • 2-ethylhexanoate of DBU 2-ethylhexanoate of DBU
  • dimethylurea compound used as the curing agent and the curing accelerator in the present invention examples include aromatics such as DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro).
  • aromatics such as DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro).
  • aliphatic dimethylurea such as group dimethylurea and U-CAT3503N (manufactured by San-Apro).
  • aromatic dimethyl urea is preferably used from the viewpoint of curability.
  • Examples of the amine adduct compound as the curing agent and the curing accelerator in the present invention include, for example, an epoxy adduct compound obtained by stopping the addition reaction of the tertiary amine to the epoxy resin on the way.
  • Specific examples of the amine adduct compound include Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40 and Amicure.
  • Examples include PN-40J (all manufactured by Ajinomoto Fine-Techno Co., Inc.).
  • Examples of the organic acid dihydrazide compound as the curing agent in the present invention include Amicure VDH-J, Amicure UDH, Amicure LDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.
  • organic phosphine compound as the curing agent and the curing accelerator in the present invention examples include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane and the like can be mentioned.
  • organic phosphine compound examples include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, TPP-S (manufactured by Kitako Chemical Co., Ltd.) and the like.
  • Examples of the dicyandiamide compound as the curing agent in the present invention include dicyandiamide.
  • Specific examples of the dicyandiamide compound include dicyandiamide finely pulverized products DICY7 and DICY15 (both manufactured by Mitsubishi Chemical Corporation).
  • Examples of the primary and secondary amine compounds as the curing agent in the present invention include aliphatic amines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, and 1 , 3-bisaminomethylcyclohexane, propylenediamine, diethylaminopropylamine, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like, alicyclic amines N-aminoethylpiverazine, 1 , 4-bis (3-aminopropyl) piperazine and other aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphe Rusuruhon,
  • Examples of the phenolic compound as the curing agent in the present invention include a triazine skeleton-containing phenolic curing agent, a triazine skeleton-containing phenol novolac curing agent, MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), and NHN.
  • triazine skeleton-containing phenolic curing agent examples include LA3018 (manufactured by DIC).
  • triazine skeleton-containing phenol novolac curing agent examples include LA7052, LA7054, LA1356 (manufactured by DIC).
  • Examples of the thiol compound as a curing agent in the present invention include trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate).
  • the adhesive composition of the present invention contains a curing agent and / or a curing accelerator as the component (C), it is preferably 0.01% by mass or more based on 100% by mass of the nonvolatile component of the adhesive composition, 0.05 mass% or more is more preferable, 0.1 mass% or more is still more preferable, and 0.2 mass% or more is particularly preferable. Moreover, 10 mass% or less is preferable, 8 mass% or less is more preferable, 5 mass% or less is further preferable, and 3 mass% or less is particularly preferable.
  • the content of the curing agent (C) and / or the curing accelerator in the pressure-sensitive adhesive composition of the present invention is preferably 0.
  • the amount is 1 to 10% by mass, and more preferably 0.2 to 8% by mass.
  • the pressure-sensitive adhesive composition of the present invention may contain (D) a tackifier for the purpose of further improving the adhesiveness.
  • Tackifiers are also called tackifiers, and include, for example, terpene-based resins, rosin-based resins, alicyclic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic / aromatic copolymerized hydrocarbon resins, and aromatic resins. Hydrocarbon resins, coumarone / indene resins, etc. may be mentioned. You may use a tackifier in combination of 2 or more types. More preferable tackifiers include aliphatic / aromatic copolymer hydrocarbon resins, aromatic hydrocarbon resins, coumarone / indene resins and the like.
  • the content of the component (D) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but from the viewpoint of not impairing the properties of the rubber of the component (A), the pressure-sensitive adhesive composition 35 mass% or less is preferable with respect to 100 mass% of non-volatile components, 30 mass% or less is more preferable, and 25 mass% or less is still more preferable.
  • the amount thereof is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, with respect to 100% by mass of the nonvolatile component of the adhesive composition. 6 mass% or more is particularly preferable.
  • the content of the (D) tackifier in the pressure-sensitive adhesive composition of the present invention is preferably 5 to 30% by mass relative to 100% by mass of the nonvolatile component of the pressure-sensitive adhesive composition. , And more preferably 6 to 25% by mass.
  • Examples of commercially available tackifiers include Alcon P-90 (Arakawa Chemical Industry Co., Ltd.), Alcon P-100 (Arakawa Chemical Industry Co., Ltd.), Alcon P-115 (Arakawa Chemical Industry Co., Ltd.), Pine Crystal ME.
  • the adhesive composition of the present invention may contain (E) a plasticizer for the purpose of further improving the adhesiveness.
  • a plasticizer for the purpose of further improving the adhesiveness.
  • the plasticizer used in the present invention include phthalic acid ester-based, adipic acid ester-based, phosphoric acid ester-based, trimellitic acid ester-based, sulfonic acid ester-based, paraffin oil-based, and naphthene oil-based plasticizers. .. More preferable plasticizers include sulfonate ester plasticizers. You may use a plasticizer in combination of 2 or more type.
  • the content of the component (E) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but from the viewpoint of mechanical properties such as tensile strength, 100% by mass of the nonvolatile component of the pressure-sensitive adhesive composition.
  • 35 mass% or less is preferable, 30 mass% or less is more preferable, and 25 mass% or less is further preferable.
  • the amount thereof is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, with respect to 100% by mass of the nonvolatile components of the adhesive composition.
  • a mass% or more is particularly preferable.
  • the content of the (E) plasticizer in the pressure-sensitive adhesive composition of the present invention is preferably 5 to 30 mass% with respect to 100 mass% of non-volatile components of the pressure-sensitive adhesive composition, It is more preferably 10 to 25% by mass.
  • plasticizers examples include mesamoll (manufactured by LANXESS), mesamoll2 (manufactured by LANXESS), BXA-N (manufactured by Daihachi Chemical Industry Co., Ltd.), Sanso Sizer DOA (manufactured by Shin Nihon Rika Co., Ltd.), and Sanso Sizer.
  • examples include DINA (manufactured by Shin Nippon Rika Co., Ltd.) and Sanso Sizer DIDA (manufactured by Shin Nihon Rika Co., Ltd.).
  • the adhesive composition of the present invention may further contain other additives different from the above components.
  • additives include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and titanium.
  • Inorganic fillers such as strontium acid salt, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate; calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, calcined dolomite (oxidation Hygroscopic metal oxides such as a mixture containing calcium and magnesium oxide), calcined hydrotalcite (a double oxide of aluminum and magnesium, etc.), semi-calcined hydrotalcite; rubber particles, silicon powder, Organic fillers such as iron powder and fluorine powder; Thickeners such as Orben and Benton; Silicone-based, fluorine-based and polymer-based defoamers or leveling agents; Triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds, etc.
  • Inorganic fillers such as strontium acid salt, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate; calcium oxide, magnesium oxide, strontium oxide
  • Adhesion imparting agents and the like can be mentioned.
  • the inorganic filler or the hygroscopic metal oxide can be surface-treated with a surface treating agent to improve its moisture resistance.
  • a surface treating agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, vinylsilane coupling agents, imidazolesilane coupling agents, organosilazane compounds, titanate coupling agents, and the like.
  • the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, vinylsilane coupling agents, imidazolesilane coupling agents, organosilazane compounds, titanate coupling agents, and the like.
  • the pressure-sensitive adhesive composition of the present invention may contain an organic solvent from the viewpoint of coatability of the pressure-sensitive adhesive composition when producing a pressure-sensitive adhesive sheet in which a layer of the pressure-sensitive adhesive composition is formed on a support described later. it can.
  • the organic solvent include acetone, methyl ethyl ketone (hereinafter also abbreviated as “MEK”), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and other acetic acid esters.
  • Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
  • organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent is not particularly limited, but from the viewpoint of coatability, it is preferable to use an amount such that the viscosity (25 ° C.) of the pressure-sensitive adhesive composition is 300 to 2000 mPa ⁇ s.
  • the pressure-sensitive adhesive composition of the present invention can be produced by mixing the components using a kneading roller or a rotary mixer.
  • the pressure-sensitive adhesive composition of the present invention has excellent flexibility and adhesiveness, it can be an excellent pressure-sensitive adhesive composition particularly as a sealing material for flexible electronic devices such as flexible organic EL devices. Particularly preferably, it is used in the form of a pressure-sensitive adhesive sheet in which a layer of the pressure-sensitive adhesive composition is formed on a support.
  • a pressure-sensitive adhesive composition of the present invention is prepared by coating an organic solvent in the form of a varnish on a support, and drying the resulting coating film by heating or blowing hot air.
  • An adhesive sheet which is a sheet on which a product layer is formed, is obtained.
  • the acid anhydride group of the component (B) is reacted with the epoxy group of the component (A) to form a crosslinked structure.
  • An excellent adhesive sheet can be obtained.
  • the thickness of the layer of the pressure-sensitive adhesive composition in the pressure-sensitive adhesive sheet is preferably 5 ⁇ m to 200 ⁇ m, more preferably 15 to 180 ⁇ m, and further preferably 20 ⁇ m to 150 ⁇ m, from the viewpoint of the balance between the light absorption performance and the transmittance.
  • the support used for the pressure-sensitive adhesive sheet is not particularly limited, but examples thereof include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate. , Plastic films such as polycarbonate and polyimide. PET is particularly preferable as the plastic film. Further, the support may be a metal foil such as an aluminum foil, a stainless steel foil and a copper foil.
  • a support having moisture resistance can be used as the support used for the pressure-sensitive adhesive sheet.
  • a layer of a circularly polarizing plate is provided on the device, a circularly polarizing plate can be used as the support used for the pressure-sensitive adhesive sheet.
  • the support used for the pressure-sensitive adhesive sheet may be a support containing both the moisture-proofing support and the circularly polarizing plate.
  • Examples of the moisture-proof support include a moisture-proof plastic film and metal foil such as copper foil and aluminum foil.
  • Examples of the moisture-proof plastic film (barrier film) include a plastic film having a surface deposited with an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon.
  • examples of the plastic film on the surface of which the inorganic substance is vapor-deposited include polyolefin (eg, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (eg, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”).) , Polyethylene naphthalate, etc.), polycarbonate, polyimide, and other plastic films are preferable, and PET films are particularly preferable.
  • examples of commercially available plastic films having moisture resistance include Tech Barrier HX, AX, LX, L series (manufactured by Mitsubishi Chemical Corp.) and more moistureproof effect than the Tech Barrier HX, AX, LX, L series.
  • Examples include an enhanced X-BARRIER (manufactured by Mitsubishi Chemical Corporation) and the like.
  • a support having a multilayer structure of two or more layers for example, a support obtained by laminating the above plastic film and the above metal foil with an adhesive can be used. This is inexpensive and is advantageous from the viewpoint of handleability.
  • a support having no moisture-proof property for example, a single plastic film in which an inorganic substance is not vapor-deposited on the surface
  • Circular polarizing plate is generally composed of a polarizing plate and a quarter wave plate.
  • a quarter wave plate is generally arranged on the pressure-sensitive adhesive composition layer side.
  • the moisture-proof support is preferably placed on the pressure-sensitive adhesive composition layer side, and the quarter-wave plate of the circularly polarizing plate is placed on the moisture-proof support side. Will be placed.
  • the moisture-proof support and the circularly polarizing plate can be bonded with an adhesive or the like.
  • the support may be subjected to matte treatment, corona treatment, or release treatment. That is, the support may be a peelable support.
  • the mold release treatment include a mold release treatment with a mold release agent such as a silicone resin type mold release agent, an alkyd resin type mold release agent, and a fluororesin type mold release agent.
  • the release layer is also regarded as a part of the support.
  • the thickness of the support is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 20 to 125 ⁇ m from the viewpoint of handleability and the like.
  • the layer of the pressure-sensitive adhesive composition may be protected by a protective film.
  • a protective film By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the layer of the pressure-sensitive adhesive composition and prevent scratches.
  • the protective film it is preferable to use the same plastic film as the support. Further, the protective film may be subjected to a mold release treatment in addition to the matte treatment and the corona treatment.
  • the thickness of the protective film is not particularly limited, but is usually 1 to 150 ⁇ m, preferably 10 to 100 ⁇ m.
  • LT1707VP manufactured by Alantheo Co., hydrogenated nitrile rubber (HNBR), acrylonitrile content 17%, residual double bond amount max 0.9%, Mooney viscosity 74
  • ER859 manufactured by Seikou PMC, glycidyl methacrylate modified hydrogenated nitrile rubber ( GMA-modified HNBR), acrylonitrile content 17%, residual double bond amount max 0.9%, epoxy group concentration: 0.64 mmol / g, Mooney viscosity 7.58, number average molecular weight: 4825
  • ER659 manufactured by SEIKO PMC
  • Maleic anhydride modified hydrogenated nitrile rubber MA modified HNBR
  • maleic anhydride concentration 0.46 mmol / g, number average molecular weight: 6,963
  • RIKACID MH-700G Nippon Rika Co., Ltd .:
  • the varnish and pressure-sensitive adhesive sheet of each pressure-sensitive adhesive composition of Examples and Comparative Examples were prepared by the following procedure. The compounding was carried out in the amounts shown in Table 1. The amounts of the components other than the organic solvent listed in Table 1 are values (parts by mass) converted into non-volatile components.
  • the pressure-sensitive adhesive sheet prepared in Example 1 or Example 4 was laminated on a polyimide film (thickness 25 ⁇ m) using a batch type vacuum laminator (V-160 manufactured by Nichigo Morton Co., Ltd.) to obtain a laminated film.
  • the PET film on the pressure-sensitive adhesive sheet side of the laminated film was peeled off, and a polyimide film (thickness: 25 ⁇ m) was further placed on the exposed layer of the pressure-sensitive adhesive composition using a batch type vacuum laminator (Nichigo-Morton V-160).
  • the films were attached to each other to obtain a film for evaluating flexibility.
  • Example 1 467 parts of glycidyl methacrylate modified hydrogenated nitrile rubber (ER859, 15% ipsol solution) to 266 parts of maleic anhydride modified hydrogenated nitrile rubber (ER659, 15% ipsol solution), 1 part of amine curing agent (TAP) and 4 parts of toluene was blended, and the resulting mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of the adhesive composition. The resulting varnish was applied uniformly on a release-treated surface of a PET film (thickness 50 ⁇ m) treated with a silicone-based release agent with a die coater and heated at 120 ° C. for 30 minutes to give a thickness of 25 ⁇ m. A pressure-sensitive adhesive sheet having a layer of the pressure-sensitive adhesive composition was obtained.
  • Example 2 A varnish and an adhesive sheet of an adhesive composition were prepared in the same manner as in Example 1 except that 9 parts of a phthalic acid anhydride (MH-700G) was used instead of the maleic anhydride-modified hydrogenated nitrile rubber (ER659). It was made.
  • MH-700G phthalic acid anhydride
  • ER659 maleic anhydride-modified hydrogenated nitrile rubber
  • Example 3 A varnish of the pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that 18 parts of alkyl sulfonic acid phenyl ester (mesamoll2) was additionally compounded.
  • Example 4 A varnish and a pressure-sensitive adhesive sheet of a pressure-sensitive adhesive composition were produced in the same manner as in Example 2 except that 15 parts of an aromatic hydrocarbon resin (Neopolymer L-90) and 10 parts of toluene were additionally added.
  • an aromatic hydrocarbon resin Neopolymer L-90
  • Example 5 Varnish of adhesive composition in the same manner as in Example 2 except that 10 parts of an aromatic hydrocarbon resin (Neopolymer L-90), 7 parts of toluene and 4 parts of alkylsulfonic acid phenyl ester (mesamoll2) were additionally added. And the adhesive sheet was produced.
  • an aromatic hydrocarbon resin Neopolymer L-90
  • 7 parts of toluene 7 parts of toluene
  • 4 parts of alkylsulfonic acid phenyl ester (mesamoll2) were additionally added.
  • the adhesive sheet was produced.
  • Example 6 A varnish and a pressure-sensitive adhesive sheet were prepared in the same manner as in Example 1 except that 9 parts of norbornene-based acid anhydride (HNA-100) was used in place of the maleic anhydride-modified hydrogenated nitrile rubber (ER659). did.
  • HNA-100 norbornene-based acid anhydride
  • ER659 maleic anhydride-modified hydrogenated nitrile rubber
  • ⁇ Comparative example 2> A varnish and a pressure-sensitive adhesive sheet of a pressure-sensitive adhesive composition were produced in the same manner as in Example 1 except that the maleic anhydride-modified hydrogenated nitrile rubber (ER659, 15% Ipsol solution) was not used.
  • V-160 was laminated on the aluminum surface of an aluminum foil / PET composite film [AL1N30 with PET] having a length of 150 mm * a width of 25 mm (Aluminum foil 30 ⁇ m, PET 25 ⁇ m: product of Toyo Aluminum Sales Co., Ltd.).
  • the lamination conditions were a temperature of 80 ° C., a pressure reduction time of 30 seconds, and a pressure of 0.3 MPa for 30 seconds.
  • the PET film of the pressure-sensitive adhesive sheet was peeled off, and a glass plate (length 76 mm * width 26 mm * thickness 1.2 mm, micro slide glass) was laminated on the exposed layer of the pressure-sensitive adhesive composition under the same conditions as above. Then, a laminated body was produced.
  • the adhesive strength (peeling strength) to the glass plate surface when peeled at a pulling rate of 300 mm / min in a 180 degree direction with respect to the length direction of the aluminum foil / PET composite film was measured. Then, the adhesiveness was evaluated according to the following criteria. In addition, the obtained laminate was stored in a thermo-hygrostat at 85 ° C. and a humidity of 85% RH for 24 hours, and then the adhesiveness was similarly evaluated according to the following criteria.
  • Adhesive strength is 0.2 [kgf / cm] or more Poor x: Adhesive strength is less than 0.2 [kgf / cm]
  • the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition having excellent flexibility using a hydrogenated nitrile rubber having excellent flexibility, and therefore a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive composition of the present invention and a layer of the pressure-sensitive adhesive composition, In particular, it can be excellent as a sealing material, an adhesive material, a transparent optical adhesive film (OCA), etc. for flexible electronic devices.
  • OCA transparent optical adhesive film

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

Abstract

L'invention concerne une composition adhésive qui présente une excellente aptitude au pliage, utilise un caoutchouc nitrile hydrogéné, et présente également une excellente adhésivité. La composition adhésive contient : (A) un caoutchouc nitrile hydrogéné comprenant un groupe époxy ; et (B) un anhydride d'acide.
PCT/JP2019/043810 2018-11-09 2019-11-08 Composition adhésive Ceased WO2020096032A1 (fr)

Applications Claiming Priority (2)

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JP2018211618 2018-11-09
JP2018-211618 2018-11-09

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04224818A (ja) * 1990-03-30 1992-08-14 Shell Internatl Res Maatschappij Bv 粉末被覆組成物用のエラストマー改質エポキシ樹脂
JPH04370183A (ja) * 1991-06-18 1992-12-22 Nippon Zeon Co Ltd 接着剤組成物
JPH05230315A (ja) * 1992-02-18 1993-09-07 Nippon Zeon Co Ltd ゴム組成物
JP2001322184A (ja) * 2000-05-16 2001-11-20 Mitsuboshi Belting Ltd 伝動ベルト用心線の接着処理方法
JP2003155464A (ja) * 2001-11-19 2003-05-30 Mitsui Chemicals Inc エポキシ樹脂組成物からなる極薄金属膜付き接着シート
JP2009029843A (ja) * 2007-07-24 2009-02-12 Sekisui Chem Co Ltd 半導体用接着剤及び半導体用接着テープ
WO2011062167A1 (fr) * 2009-11-18 2011-05-26 味の素株式会社 Composition de résine
WO2013108731A1 (fr) * 2012-01-16 2013-07-25 味の素株式会社 Composition de résine pour faire étanchéité
JP2014532107A (ja) * 2011-10-11 2014-12-04 ランクセス・ドイチュランド・ゲーエムベーハー エポキシ基を有するニトリルゴムを主成分とする加硫可能な組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04224818A (ja) * 1990-03-30 1992-08-14 Shell Internatl Res Maatschappij Bv 粉末被覆組成物用のエラストマー改質エポキシ樹脂
JPH04370183A (ja) * 1991-06-18 1992-12-22 Nippon Zeon Co Ltd 接着剤組成物
JPH05230315A (ja) * 1992-02-18 1993-09-07 Nippon Zeon Co Ltd ゴム組成物
JP2001322184A (ja) * 2000-05-16 2001-11-20 Mitsuboshi Belting Ltd 伝動ベルト用心線の接着処理方法
JP2003155464A (ja) * 2001-11-19 2003-05-30 Mitsui Chemicals Inc エポキシ樹脂組成物からなる極薄金属膜付き接着シート
JP2009029843A (ja) * 2007-07-24 2009-02-12 Sekisui Chem Co Ltd 半導体用接着剤及び半導体用接着テープ
WO2011062167A1 (fr) * 2009-11-18 2011-05-26 味の素株式会社 Composition de résine
JP2014532107A (ja) * 2011-10-11 2014-12-04 ランクセス・ドイチュランド・ゲーエムベーハー エポキシ基を有するニトリルゴムを主成分とする加硫可能な組成物
WO2013108731A1 (fr) * 2012-01-16 2013-07-25 味の素株式会社 Composition de résine pour faire étanchéité

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