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
  • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
  • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
• • 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
  • 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
  • C08G18/675—Low-molecular-weight compounds
  • C08G18/6755—Unsaturated carboxylic acids
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
  • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• • 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
• • 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
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups

Definitions

• the present invention relates to a urethane (meth)acrylate suitable for adhesives, a method for producing the same, a curable composition containing the urethane (meth)acrylate, and a cured product thereof.
• urethane (meth)acrylate By using urethane (meth)acrylate as a monomer, functional polymers with excellent properties such as flexibility, toughness, impact resistance, and adhesion can be obtained. It is a highly versatile compound. As an example of its use, it can be used as an adhesive component in places where impact resistance is required, such as the periphery of a touch panel of an image display device.
• a common method for synthesizing urethane (meth)acrylate is to react an isocyanate-terminated prepolymer with a compound having a hydroxyl group and a (meth)acryloyloxy group (eg, 2-hydroxyethyl acrylate, etc.).
• a synthesis method is also known in which a polyol is reacted with a compound having an isocyanate group and a (meth)acryloyloxy group.
• the type of raw material polyol greatly affects the difference in the properties of the cured product obtained using the urethane (meth)acrylate as a monomer.
• Patent Document 1 discloses a (meth)acryloyl-modified polyether (urethane ( meth) acrylate) are described.
• devices with a structure that can be folded on the surface such as flexible displays and foldable devices, are required to have shape recoverability when folded.
• the urethane (meth)acrylate specifically described in Patent Document 1 has a number average molecular weight of at most 15,500. However, a good shape recovery property upon bending could not be obtained.
• the present invention has been made in view of such circumstances, and by curing, urethane ( The purpose is to provide meth)acrylates.
• the present invention is based on the discovery that a cured product obtained from a urethane (meth)acrylate having a specific diol-derived structure has a small residual strain and exhibits good shape recovery upon bending.
• the present invention provides the following means.
• [1] Represented by the following formula (1), having a number average molecular weight (Mn) of 16,000 to 60,000, and a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 1.0 ⁇ 1.2 and the ratio of the mass of the urethane groups to the total mass of the urethane (meth)acrylate is 0.18 to 0.73% by mass.
• R 2 is a residue obtained by removing two hydroxyl groups from one molecule of a diol selected from polyether diols, polyester diols and polycarbonate diols, and R 2 and R 3 are each independently It is a residue obtained by removing an isocyanate group from a monoisocyanate having one or more (meth)acryloyloxy groups in one molecule.
• a method for producing a urethane (meth)acrylate in which a reaction product obtained by a urethanization reaction of 1 mol part of a diol and 2 mol parts of a monoisocyanate is obtained, wherein the number average molecular weight (Mn) of the urethane (meth)acrylate is 16000 to 60000, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1.2, and the urethane group to the total mass of urethane (meth)acrylate is 0.18 to 0.73% by mass, and is represented by the following formula (1), a method for producing a urethane (meth)acrylate.
• R 2 is a residue obtained by removing two hydroxyl groups from one molecule of a diol selected from polyether diols, polyester diols and polycarbonate diols, and R 2 and R 3 are each independently It is a residue obtained by removing an isocyanate group from a monoisocyanate having one or more (meth)acryloyloxy groups in one molecule.
• R 6 The method for producing a urethane (meth)acrylate according to [5], wherein the diol has a hydroxyl value-equivalent molecular weight of 16,000 or more.
• the urethane (meth)acrylate of the present invention is useful for applications such as adhesives, intermediate coatings, ink binders, etc., which can be applied to flexible displays, foldable devices, and the like.
• (Meth)acryloyloxy is a generic term for acryloyloxy and methacryloyloxy.
• (meth)acryl is a generic term for acrylic and methacrylic
• (meth)acrylate is a generic term for acrylate and methacrylate.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene equivalent molecular weights determined by gel permeation chromatography (GPC) based on a calibration curve prepared using a standard polystyrene sample.
• the urethane bond concentration indicates the ratio of the mass of the urethane group to the total mass of the urethane (meth)acrylate, and the total amount (x moles) of the isocyanate groups in the isocyanate compound of the reaction raw material forms the urethane bond (formula weight 59). It is a value (unit: mass %) calculated by the formula of x ⁇ 59/(mass of urethane (meth)acrylate) ⁇ 100.
• the "hydroxyl value equivalent molecular weight” is a value calculated from the formula: 56100 x (number of hydroxyl groups in one molecule)/(hydroxyl value [mgKOH/g]).
• a hydroxyl value is calculated
• Viscosity is a value measured with an E-type viscometer at 25°C.
• the "NCO index” is the equivalent ratio of the isocyanate group of the isocyanate compound to the hydroxyl group of the polyol expressed as a percentage.
• the urethane (meth)acrylate of the present invention is represented by the following formula (1), Mn is 16000 to 60000, the ratio of Mw to Mn (Mw/Mn) is 1.0 to 1.2, and the urethane bond concentration is is 0.18 to 0.73% by mass.
• R1 is a residue obtained by removing two hydroxyl groups from one molecule of a diol selected from polyether diols, polyester diols and polycarbonate diols.
• R 2 and R 3 are each independently a residue obtained by removing an isocyanate group from a monoisocyanate having one or more (meth)acryloyloxy groups in one molecule.
• Such a urethane (meth)acrylate has a skeleton derived from a high-molecular-weight diol and has a narrow molecular weight distribution. Therefore, a cured product obtained by using this as a monomer tends to form a uniform crosslinked network. it is conceivable that. Therefore, a cured product having a large tensile elongation, a small storage shear modulus and residual strain, excellent elongation, flexibility and bendability, and excellent shape recovery upon bending can be obtained.
• the urethane (meth)acrylate of the present invention is a compound represented by the formula (1).
• Urethane (meth)acrylate is preferably urethane acrylate from the viewpoint of rapid polymerization.
• R1 is a residue obtained by removing two hydroxyl groups from one molecule of a diol selected from polyether diols, polyester diols and polycarbonate diols.
• a diol selected from polyether diols, polyester diols and polycarbonate diols.
• diol polyether diol is preferable from the viewpoint of shape recovery when the cured product obtained from the urethane (meth)acrylate is bent.
• the polyether diol is preferably a polymer having two hydroxyl groups and an oxyalkylene group as a structural unit.
• a polyether diol can be obtained by ring-opening polymerization of a compound having a cyclic ether structure with an initiator having two active hydrogens. Moreover, a commercial item can also be used.
• the oxyalkylene group preferably contains a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms.
• the oxyalkylene group may be used singly or in combination of two or more.
• the oxyalkylene group is preferably one or more selected from an oxyethylene group, an oxypropylene group and an oxytetramethylene group, and more preferably includes an oxypropylene group.
• the oxypropylene group is preferably 50% by mass or more, more preferably 60 to 100% by mass, in 100% by mass of all oxyalkylene groups.
• the content of oxypropylene groups in all the oxyalkylene groups corresponds to the amount by mass of propylene oxide blended with respect to 100 parts by mass of the total blended amount of the originating raw materials constituting the oxyalkylene groups when synthesizing the polyether diol. regarded as a thing.
• Examples of compounds having a cyclic ether structure include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, hexyl Glycidyl ether, tetrahydrofuran can be mentioned.
• ethylene oxide and propylene oxide are preferred.
• the group having active hydrogen in the initiator includes, for example, a hydroxyl group, a carboxy group, and an amino group having a hydrogen atom bonded to a nitrogen atom.
• a hydroxyl group is preferred, and an alcoholic hydroxyl group is more preferred.
• initiators having two active hydrogens include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, tripropylene glycol, Glycols such as polyoxyalkylene diols (polyethylene glycol, polypropylene glycol, etc.); bisphenols such as bisphenol A, bisphenol F, bisphenol AD; dihydroxybenzenes such as catechol, resorcin, hydroquinone, methylamine, ethylamine, propylamine, butylamine and other primary amines. Among these, glycols are preferred.
• Ring-opening polymerization is carried out using, for example, an alkali catalyst such as potassium hydroxide, a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin, a double metal cyanide complex catalyst, or a catalyst comprising a phosphazene compound. It can be carried out using a known catalyst such as. Among these catalysts, a double metal cyanide complex (DMC) catalyst is preferred because it yields a polyether diol with a narrow molecular weight distribution.
• DMC double metal cyanide complex
• a known compound can be used as the double metal cyanide complex, and examples thereof include a zinc hexacyanocobaltate complex with tert-butanol as a ligand.
• Production of polyether diol by ring-opening polymerization using a DMC catalyst can be carried out by a known method, for example, International Publication No. 2003/062301, International Publication No. 2004/067633, and JP-A-2004-269776.
• the production methods described in JP-A-2005-15786, WO-A-2013/065802, and JP-A-2015-10162 can be applied.
• polyester diol one obtained by a known production method such as polycondensation of dibasic acid and glycol or ring-opening polymerization of cyclic ester such as ⁇ -caprolactone can be used. Moreover, a commercial item can also be used.
• dibasic acids examples include aliphatic dibasic acids such as succinic acid, adipic acid, maleic acid and fumaric acid; alicyclic dibasic acids such as 1,4-cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid and terephthalic acid.
• Aromatic dibasic acids such as acids and acid anhydrides thereof can be mentioned.
• Dibasic acids may be used singly or in combination of two or more.
• Glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, tripropylene glycol, and polyoxyalkylenediol.
• One type of glycol may be used alone, or two or more types may be used.
• polycarbonate diol one obtained by a known production method such as polycondensation of a glycol and a carbonate compound can be used. Moreover, a commercial item can also be used.
• glycols include those similar to the glycols used in the production of the polyester diol described above.
• One type of glycol may be used alone, or two or more types may be used.
• carbonate compounds include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and neopentylene carbonate.
• the carbonate compound may be used singly or in combination of two or more.
• R 2 and R 3 are each independently a residue obtained by removing an isocyanate group from a monoisocyanate having one or more (meth)acryloyloxy groups in one molecule.
• R 2 and R 3 may be the same or different. From the viewpoint of efficient synthesis of urethane (meth)acrylate, R 2 and R 3 are preferably the same.
• the monoisocyanate having a (meth)acryloyloxy group is preferably a compound in which one or more (meth)acryloyloxy groups are bonded to a hydrocarbon skeleton having an isocyanate group.
• the number of (meth)acryloyloxy groups may be one or two or more.
• the hydrocarbon skeleton is preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
• the number of carbon atoms in the aliphatic hydrocarbon group or alicyclic hydrocarbon group is preferably 8 or less, more preferably 2-6, still more preferably 2-4.
• Examples of monoisocyanates having a (meth) acryloyloxy group include compounds having one (meth) acryloyloxy group such as isocyanate methyl (meth) acrylate and 2-isocyanate ethyl (meth) acrylate; 1,1-(bis Compounds having two (meth)acryloyloxy groups such as (meth)acryloyloxymethyl)ethylisocyanate and 1,1-(bis(meth)acryloyloxymethyl)propylisocyanate can be mentioned.
• AOI (2-isocyanatoethyl acrylate
• Karenzu MOI (2-isocyanatoethyl methacrylate
• Karenzu BEI (1,1-(bis acryloyloxymethyl)ethyl isocyanate) (manufactured by Showa Denko KK).
• the urethane (meth)acrylate has an Mn of 16,000 to 60,000, preferably 17,000 to 55,000, and more preferably 18,000 to 50,000. When the Mn is within the above range, the cured product of the urethane (meth)acrylate has good elongation and excellent shape recovery property when bent.
• Mw/Mn is 1.0 to 1.2, preferably 1.02 to 1.17, more preferably 1.05 to 1.15.
• Mw/Mn is an index representing the degree of dispersion (breadth) of the molecular weight distribution, where 1 indicates monodispersity, and the closer to 1, the narrower the molecular weight distribution. If the molecular weight distribution is within the above range, the urethane (meth)acrylate has a relatively low viscosity even if it has a high molecular weight of 16000 or more Mn, and is used during operations such as mixing a curable composition using it. is easy to handle. Moreover, the cured product of the urethane (meth)acrylate has a small residual strain, easily forms a uniform crosslinked network, and is excellent in shape recoverability when bent.
• the urethane (meth)acrylate has a urethane bond concentration of 0.18 to 0.73% by mass, preferably 0.40 to 0.72% by mass, more preferably 0.55 to 0.70% by mass.
• the urethane bond concentration is within the above range, the cured product of the urethane (meth)acrylate has good elongation and excellent shape recovery property when bent.
• urethane (meth)acrylate is liquid at room temperature (25°C) and has a viscosity at 25°C of preferably 50 Pa ⁇ s or less, more preferably 40 Pa ⁇ s or less, and even more preferably 30 Pa ⁇ s. s or less.
• the urethane (meth)acrylate of the present invention is obtained as a reaction product of urethanization reaction between 1 mol part of diol and 2 mol parts of monoisocyanate. That is, the urethane (meth)acrylate is a reaction product of the diol derived from R1 in formula ( 1 ) and the monoisocyanate derived from R2 and R3 .
• the hydroxyl value-equivalent molecular weight of the diol is preferably 16,000 or more, more preferably 16,500 to 60,000, and still more preferably 17,000 to 55,000 from the viewpoint of ensuring that the Mn of the urethane (meth)acrylate is within the above range.
• the urethanization reaction can be carried out by a known method, usually by mixing a diol and a monoisocyanate and using a urethanization catalyst in a nitrogen gas or inert gas atmosphere.
• urethanization catalysts include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and tin 2-ethylhexanoate; iron compounds such as iron acetylacetonate and ferric chloride; and 2-ethylhexane.
• lead compounds such as acid lead; bismuth compounds such as bismuth 2-ethylhexanoate; and tertiary amines such as triethylamine and triethylenediamine.
• bismuth compounds such as bismuth 2-ethylhexanoate
• tertiary amines such as triethylamine and triethylenediamine.
• organic tin compounds, lead 2-ethylhexanoate, and bismuth 2-ethylhexanoate are preferred.
• the urethanization catalyst may be used alone or in combination of two or more.
• the amount of the urethanization catalyst used is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.5 part by mass, and still more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the diol that is the reactant. It is 0.1 part by mass.
• the reaction temperature for the urethanization reaction is preferably 20 to 100°C, more preferably 30 to 90°C, still more preferably 40 to 80°C.
• the curable composition of the invention contains the urethane (meth)acrylate of the invention described above.
• a polymerization initiator and, if necessary, other components are preferably blended into the curable composition.
• the content of urethane (meth)acrylate in the curable composition is preferably 50% by mass or more, more preferably 70% by mass or more and less than 100% by mass, from the viewpoint of obtaining a cured product having excellent shape recovery property when bent. , more preferably 80% by mass or more and less than 100% by mass.
• Each compounding component in the curable composition is preferably uniformly mixed, for example, using a known mixing device such as a rotation-revolution stirring deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. Mixable. Each compounding component may be mixed at the same time or may be mixed by successive addition.
• the polymerization initiator is preferably a radical polymerization initiator, and may be a photopolymerization initiator or a thermal polymerization initiator, and known ones can be used. From the viewpoint of ease of control of the polymerization reaction, the photopolymerization initiator is preferably one that can be used by ultraviolet irradiation with a wavelength of 380 nm or less, and the thermal polymerization initiator can be used by heating within the range of 50 to 120 ° C. things are preferred.
• photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropanone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropanone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone-4-methoxybenzophenone, thioxanth
• thermal polymerization initiators include azo compounds; organic peroxides such as hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides.
• azobisisobutyronitrile benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane , tert-butyl peroxybenzoate, tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4 -dichlorobenzoyl peroxide, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1 , 1,3,3-tetramethylbutyl peroxy-2-ethylhex
• the content of the polymerization initiator in the curable composition is preferably 0.001 to 20 parts by mass, more preferably 0.01, per 100 parts by mass of urethane (meth)acrylate, from the viewpoint of a suitable polymerization rate. to 10 parts by mass, more preferably 0.1 to 7 parts by mass.
• the light source can be appropriately set according to the light absorption ability of the photopolymerization initiator to be blended.
• the integrated amount of light is, for example, approximately 0.01 to 50 J/cm 2 . From the viewpoint of stabilizing the physical properties of the cured product, heat treatment may be further performed after light irradiation.
• the heating temperature is about 40 to 200° C.
• the heating time is about 1 minute to 15 hours.
• the physical properties of the cured product can also be stabilized by allowing it to stand at room temperature (about 15 to 25° C.) for about 1 to 48 hours.
• the heating temperature is usually about 40 to 250°C, and the heating time is about 5 minutes to 24 hours.
• the heating time is shortened when the heating temperature is high, and the heating time is lengthened when the heating temperature is low.
• the curable composition may contain other components in addition to the urethane (meth)acrylate and the polymerization initiator, depending on the ease of handling and its intended use.
• Other components include, for example, monomer components other than the urethane (meth)acrylate of the present invention, catalysts, coloring agents such as pigments and dyes, silane coupling agents, tackifying resins, antioxidants, light stabilizers, agents, metal deactivators, rust inhibitors, anti-aging agents, moisture absorbers, anti-hydrolysis agents, anti-foaming agents, and fillers. It may also contain a solvent.
• These other components in the curable composition may be blended within a range that does not impair the effects of the present invention.
• the other monomer component is a compound that can be copolymerized with the urethane (meth)acrylate.
• (meth)acrylates such as acrylates and amino group-containing (meth)acrylates.
• Other monomer components may be used singly or in combination of two or more.
• the curable composition containing the urethane (meth)acrylate of the present invention is suitable for use as, for example, an adhesive, an intermediate coating for paints, and an ink binder. Due to its excellent recoverability, it is suitable for use as an adhesive for bending portions of flexible displays, foldable devices, and the like.
• the cured product of the present invention is obtained by curing the curable composition containing the urethane (meth)acrylate described above, and has a large tensile elongation, a small storage shear modulus and residual strain, elongation, flexibility and bending. It has excellent flexibility and excellent shape recovery property when bent. Therefore, according to the present invention, since these properties are exhibited in the above applications, various articles such as coated articles, printed matters, and adhesives, especially flexible displays and the like, provided with the cured product of the present invention Articles with foldable portions, such as foldable devices, can be preferably provided.
• Isophorone diisocyanate “Desmodur (registered trademark) I”, manufactured by Sumika Covestro Urethane Co., Ltd. ⁇ 2- Hydroxyethyl acrylate; manufactured by Tokyo Chemical Industry Co., Ltd.
• Detector Differential refractive index (RI) detector
• RI Differential refractive index
• Eluent tetrahydrofuran
• Flow rate 0.8 mL/min
• Sample concentration 0.5% by mass
• Sample injection volume 100 ⁇ L
• Sample injection volume 100 ⁇ L
• Sample injection volume 100 ⁇ L
• sample sample polystyrene
• the isocyanate group (NCO) content was quantified by back titration using an indicator titration method in accordance with JIS K 1603-1:2007 Method A.
• curable composition and its cured product [Production of curable composition and its cured product] (Examples 1-4) Using each of the urethane acrylates (1) to (4) obtained in Production Examples 1 to 4, curable compositions and cured products thereof were produced, and the following items were measured and evaluated.
• a curable composition was prepared by mixing 100 parts by mass of urethane acrylate with 0.3 parts by mass of a photopolymerization initiator. Table 1 shows the measurement evaluation results.
• Example 1 is an example, and Examples 2-4 are comparative examples.
• the curable composition was applied using an applicator to the release surface of a PET film that had been subjected to silicone release treatment so as to have a thickness of about 100 ⁇ m. Then, in a nitrogen gas atmosphere, it was cured with a conveyor-type UV irradiation machine (manufactured by Oak Manufacturing Co., Ltd.; mercury xenon lamp, illuminance 100 mW/cm 2 , integrated light intensity 3 J/cm 2 ) to prepare a specimen for a tensile test. .
• a conveyor-type UV irradiation machine manufactured by Oak Manufacturing Co., Ltd.; mercury xenon lamp, illuminance 100 mW/cm 2 , integrated light intensity 3 J/cm 2
• a tensile tester (Tensilon universal testing machine "RTG-1310", manufactured by A&D Co., Ltd.; tensile speed 300 mm / min) is used to perform a tensile test on the specimen, and tensile elongation was measured.
• the evaluation is shown in Table 1, with "A” when the tensile elongation is 250% or more and "B" when the tensile elongation is less than 250%.
• the curable composition was sandwiched between a soda-lime glass stage and a measurement spindle (“Disposable plate D-PP20/AL/S07”, manufactured by Anton Paar) with a width of 0.2 mm.
• a mercury-xenon lamp (“Spot Cure (registered trademark) SP-9”, manufactured by Ushio Inc.; illuminance 100 mW/cm 2 ) installed at the bottom of the stage. Then, a cured product sample of the curable composition was obtained.
• the position of the spindle was automatically adjusted so as not to generate stress in the normal direction of the spindle.
• the storage shear modulus of the cured product sample was measured with a rheometer ("Physica MCR301", manufactured by Anton Paar; dynamic shear strain of 1% was applied) while irradiating with ultraviolet rays. It can be said that the smaller the storage shear modulus, the more flexible the cured product and the better the bendability.
• the evaluation is shown in Table 1, with "A” when the storage shear modulus of the cured product is 700 kPa or less, and "B" when the storage shear modulus is over 700 kPa.
• the urethane acrylate of the present invention had a low viscosity and good workability during handling.
• the cured product of the curable composition containing the urethane acrylate (Example 1) of the present invention has a large tensile elongation and a small storage shear modulus and residual strain, so that it has excellent elongation, flexibility and bendability, and , it can be said that the shape recovery property at the time of bending is excellent.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyurethanes Or Polyureas (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=86730232

Family Applications (1)

Country Status (6)

Citations (6)

Family Cites Families (1)

• 2022
  • 2022-11-28 CN CN202280076288.3A patent/CN118265736A/zh active Pending
  • 2022-11-28 WO PCT/JP2022/043687 patent/WO2023106144A1/ja not_active Ceased
  • 2022-11-28 JP JP2023566243A patent/JPWO2023106144A1/ja active Pending
  • 2022-11-28 KR KR1020247016308A patent/KR20240113767A/ko active Pending
  • 2022-12-01 TW TW111146176A patent/TW202334076A/zh unknown
• 2024
  • 2024-06-06 US US18/735,267 patent/US20240317680A1/en active Pending

Patent Citations (6)

Also Published As

Similar Documents

Legal Events