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WO2019080045A1 - (meth)acrylate copolymer for thermally curable composition - Google Patents

(meth)acrylate copolymer for thermally curable composition

Info

Publication number
WO2019080045A1
WO2019080045A1 PCT/CN2017/107807 CN2017107807W WO2019080045A1 WO 2019080045 A1 WO2019080045 A1 WO 2019080045A1 CN 2017107807 W CN2017107807 W CN 2017107807W WO 2019080045 A1 WO2019080045 A1 WO 2019080045A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
resins
thermally curable
acrylate copolymer
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/CN2017/107807
Other languages
French (fr)
Inventor
Zhuming SHI
Cheng Lu
JinQian CHEN
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.)
Henkel China Co Ltd
Henkel AG and Co KGaA
Original Assignee
Henkel China Co Ltd
Henkel AG and Co KGaA
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 Henkel China Co Ltd, Henkel AG and Co KGaA filed Critical Henkel China Co Ltd
Priority to PCT/CN2017/107807 priority Critical patent/WO2019080045A1/en
Publication of WO2019080045A1 publication Critical patent/WO2019080045A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer, (b) a hydrophilic monomer, and optionally a vinyl monomer other than monomers (a) and (b) .
  • the (meth) acrylate copolymer is suitable to be used as filler in thermally curable composition, and prevents the viscosity slump of the thermally curable composition at elevated temperature before curing.
  • LCD liquid crystal display
  • ODF one-drop-filling
  • LC liquid crystal
  • thermally curable sealant compositions are used in the ODF process
  • heating is performed to cure the sealant composition after the substrates are attached, and afterwards the assembly will be heated in an oven from room temperature to an elevated temperature such as 100°C to 110°C in a time period sufficient for fully curing the sealant.
  • the viscosity of thermally curable sealant composition applied onto the substrate significantly decreases due to the Brown effect in the temperature range in which the curing has not initiated, such as from 50°C to 70°C.
  • the viscosity slump of the sealant composition may cause the sealant to spread out of the application position for example within only several millimetres in “slim border” or “narrow bezel” design, and penetrate into the liquid crystal, which results in a contamination of liquid crystal by the sealant.
  • WO 2016074187 A1 discloses a thermally curable sealant composition
  • a thermally curable sealant composition comprising a cyanate ester resin, an epoxy resin, a latent curing agent, and a gelling agent which comprises one or more core particles consisting of a resin having a glass transition temperature of lower than -10°C, and one or more shell layers consisting of a resin having a glass transition temperature of 50-150°C formed on the surface of the core particle.
  • the addition of a gelling agent can compensate the viscosity s of the sealant composition under an elevated temperature. By using the gelling agent the distortion or breaking of sealant can be prevented.
  • US 20120258314 A1 discloses a thermally epoxy resin composition for hermetic sealing of an electronic component or an electrical component, containing a liquid epoxy resin, dicyandiamide, and a filler including a thermal expansion filler particles which expand when heated and increase the viscosity of the epoxy resin composition, thereby suppressing an uncured epoxy resin flowing out of a gap.
  • an object of the present invention is to provide a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer, (b) a hydrophilic monomer, and optionally a vinyl monomer other than monomers (a) and (b) , which prevents a viscosity slump effect and is suitable to be used as such as filler in thermally curable composition of adhesives or sealants.
  • thermally curable composition comprising a thermally curable resin and the (meth) acrylate copolymer according to the present invention.
  • the present invention is directed to a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer of C 1 -C 22 alkyl mono (meth) acrylate, (b) a hydrophilic monomer selected from (b1) a hydroxyl-C 1 -C 10 alkyl mono (meth) acrylate, (b2) a carboxy-C 1 -C 10 alkyl mono (meth) acrylate, (b3) an optionally C 1 -C 10 alkyl terminated poly (C 2 -C 6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof, and (c) optionally a vinyl monomer other than monomers (a) and (b) .
  • a hydrophobic monomer of C 1 -C 22 alkyl mono (meth) acrylate a hydrophilic monomer selected from (b1) a hydroxyl-C 1 -C 10 alkyl
  • the inventors have surprisingly found that, by selecting the monomers, the (meth) acrylate copolymer exhibited an improved thermal expansion property, and avoided the viscosity slump effect for thermally curable compositions containing the (meth) acrylate copolymer when heated at elevated temperature before curing.
  • the hydrophobic monomer of the (meth) acrylate copolymer consists of C 1 -C 22 alkyl mono (meth) acrylate, and more preferably is C 1 -C 18 alkyl mono (meth) acrylate, and in particular is selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecy
  • the hydrophobic monomer is the combination of methyl methacrylate and n-butyl acrylate. In another embodiment, the hydrophobic monomer is the combination of methyl methacrylate and n-heptadecyl acrylate.
  • the hydrophobic monomer is present in an amount of 35%to 75%, preferably 50%to 70%by weight based on the total weight of all components of the (meth) acrylate copolymer.
  • the hydrophilic monomer of the (meth) acrylate copolymer is selected from (b1) a hydroxyl-C 1 -C 10 alkyl mono (meth) acrylate, (b2) a carboxy-C 1 -C 10 alkyl mono (meth) acrylate, (b3) an optionally C 1 -C 10 alkyl terminated poly (C 2 -C 6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof.
  • the hydroxy-C 1 -C 10 alkyl mono (meth) acrylate is hydroxy-C 1 -C 6 alkyl mono (meth) acrylate.
  • Suitable examples of hydroxy-C 1 -C 6 alkyl mono (meth) acrylate are hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and combination thereof.
  • the carboxy-C 1 -C 10 alkyl mono (meth) acrylate is carboxy-C 1 -C 6 alkyl mono (meth) acrylate.
  • Suitable examples of carboxy-C 1 -C 6 alkyl mono (meth) acrylate are carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxylpropyl (meth) acrylate, carboxylbutyl (meth) acrylate, carboxylpentyl (meth) acrylate, carboxylhexyl (meth) acrylate or carboxylcyclohexyl (meth) acrylate.
  • the optionally C 1 -C 10 alkyl terminated poly (C 2 -C 6 alkylene glycol) (meth) acrylate is selected from C 1 -C 6 alkyl terminated poly (C 2 -C 4 alkylene glycol) (meth) acrylate, poly (C 2 -C 4 alkylene glycol) (meth) acrylate, and combination thereof, and preferably is selected from methyl terminated poly (ethylene glycol) (meth) acrylate, poly (ethylene glycol) (meth) acrylate, and combination thereof.
  • the optionally C 1 -C 10 alkyl terminated poly (C 2 -C 6 alkylene glycol) (meth) acrylate has a number average molecular weight of 250 to 1000 Da, and preferably 300 to 800 Da, measured by gel penetration chromatography method.
  • the hydrophilic monomer may also contain methacrylic acid or acrylic acid singly or in combination with other hydrophilic monomers.
  • the hydrophilic monomer is methacrylic acid. In another embodiment, the hydrophilic monomer is the combination of 4-hydroxybutyl acrylate and methacrylic acid. In yet another embodiment, the hydrophilic monomer is the combination of 4-hydroxybutyl acrylate, methacrylic acid and methyl terminated poly (ethylene glycol) monomethacrylate. In yet another embodiment, the hydrophilic monomer is the combination of hydroxyethyl methacrylate and carboxyethyl acrylate.
  • the hydrophilic monomer is present in an amount of 1%to 45%, preferably 5%to 40%by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  • the (meth) acrylate copolymer may comprise, in polymerized form, an optionally substituted (meth) acrylamide in an amount of less than 20%, preferably less than 10%, more preferably less than 5%by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  • the (meth) acrylate copolymer contains, in polymerized form, essentially no optionally substituted (meth) acrylamide, and preferably no optionally substituted (meth) acrylamide.
  • Suitable examples of the optionally substituted (meth) acrylamide are (meth) acrylamide, hydroxyl (meth) acrylamide, and C 1 -C 10 alkyl (meth) acrylamide. It is believed that the larger amount of optionally substituted (meth) acrylamide used for the (meth) acrylate copolymer of the present invention possess unsatisfactory thermal expansion effect, and in turn may give negative influence on the viscosity stability of the sealant containing the (meth) acrylate copolymer particles at elevated temperature before curing.
  • the (meth) acrylate copolymer may also comprise in polymerized form, (c) a vinyl monomer other than monomers (a) and (b) .
  • vinyl monomers there is no limitation to such vinyl monomers as long as they are suitable to be used in the present invention and do not deteriorate the thermal expansion of the (meth) acrylate copolymer particles.
  • Suitable examples are styrene, vinyl naphthalene, 2, 4-dichlorostyrene, divinylbenzene, acrylonitrile, vinyl acetate, vinyl chloride used singly or in combination.
  • the vinyl monomers are selected from styrene, acrylonitrile and combination thereof, and more preferably is styrene.
  • the vinyl monomer other than monomers (a) and (b) is present in an amount of 0%to 30%, preferably 10%to 30%by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  • the present invention is directed to a (meth) acrylate copolymer comprising, in polymerized form, (a) 35%to 75%, preferably 50%to 70%by weight of a hydrophobic monomer of C 1 -C 22 alkyl mono (meth) acrylate, (b) 1%to 45%, preferably 5%to 40%by weight of a hydrophilic monomer selected from (b1) a hydroxyl-C 1 -C 10 alkyl mono (meth) acrylate, (b2) a carboxy-C 1 -C 10 alkyl mono (meth) acrylate, (b3) an optionally C 1 -C 10 alkyl terminated poly (C 2 -C 6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof, and (c) 0%to 30%, preferably 10%to 30%by weight of a vinyl monomer other than monomers (a) and (b) , in which the weight percentages are based on the
  • the (meth) acrylate copolymer has a number average molecular weight of 1,000 to 100,000 Da, and preferably 5,000 to 50,000 Da, measured by gel penetration chromatography method.
  • the (meth) acrylate copolymer is in the form of solid particles when used as filler in a thermal curable adhesive or sealant composition.
  • the particle size D 90 of the copolymer is no larger than 1000 nm, preferably 10 to 800 nm, more preferably 20 to 500 nm, and most preferably 50 to 300 nm.
  • the particle size D 90 means that 90%of the particles satisfy the given requirement, i.e. their diameter in the biggest dimension is no larger than 1000 nm, preferably 10 to 800 nm, more preferably 20 to 500 nm, and most preferably 50 to 300 nm.
  • the particle diameters can be determined by any suitable method.
  • Exemplary methods include sieving methods, sedimentation methods and methods that are based on the diffraction of electromagnetic waves, in particular light. Also suited are electron microscopic techniques, such scanning electron microscopy and transmission electron microscopy, and laser diffraction spectroscopy. Preferably, the particle sizes are determined by laser diffraction spectroscopy using a laser diffraction particle size analyzer, such as the Beckman Coulter LS 13 320.
  • the (meth) acrylate copolymer having such small particle size are also referred as microsphere or nanosphere herein.
  • the sphere structure ensures that when the copolymer is used as filler, it can be easily added to the sealant system without greatly increasing the initiate viscosity.
  • the (meth) acrylate copolymer in the present invention is temperature sensitive due to the selection of monomers. Not binding to any theory, it is believed that when thermally curable sealant compositions containing the (meth) acrylate copolymer are heated to an elevated temperature such as 40°C to 70°C, the copolymers will be dissolved into the resin matrix of the sealant, and help reduce the viscosity drop.
  • the (meth) acrylate copolymer is a copolymer which is obtained by polymerizing a mixture of monomers including the hydrophobic monomer (a) , the hydrophilic monomer (b) , and optionally the vinyl monomer other than monomers (a) and (b) with one or more initiators and one or more additives.
  • the (meth) acrylate copolymer can be prepared by a known polymerization method such as a solution polymerization method, a suspension polymerization method and an emulsification polymerization method, and suspension polymerization method is preferred.
  • Suitable initiators for preparing the (meth) acrylate copolymer according to the present invention are free radical water-soluble substances, in particular water-soluble peroxides or persulfates, for example hydrogen peroxide, potassium, sodium and ammonium persulfates, t-butyl hydroperoxide, and peracetic acid.
  • Redox catalysts may also be used which consist of peroxides or persulfates of the above types and reducing agents normally used for this purpose, such as ascorbic acid, sodium bisulfide, and sodium sulfoxylate. It is possible for two or more initiators to be used in the emulsion polymerization.
  • the initiator (s) may be used in an amount of 0.1%to 3%by weight based on the total weight of all monomers, preferably 0.1%to 2%by weight.
  • the initiator (s) can be introduced as initial charge to the polymerization vessel before the polymerization is initiated. It is also possible to introduce a portion of the initiator (s) as an initial charge to the polymerization vessel before the polymerization is initiated, and add the remaining amount continuously under polymerization conditions.
  • the additives for the preparation of the (meth) acrylate copolymer including but not limited to emulsifier, solvent (such as water) , stabilizer, pH adjustment and chelating agent.
  • emulsifier are sodium lauryl sulfate, sodium lauryl benzene sulfonate, sodium dodecyl sulfate, nonyl aryl polyether alcohol, lauryl ammonium nonylphenol ether or octyl phenol ethoxylates.
  • the (meth) acrylate copolymer in the form of microsphere or nanosphere can be formulated to provide the thermally curable composition by any method known in the art.
  • thermally curable composition comprising a thermally curable resin and the (meth) acrylate copolymer according to the present invention, and cured product of the thermally curable composition.
  • the (meth) acrylate copolymer according to the present invention may be present in an amount of 0.5%to 10%by weight, preferably 1%to 7%by weight based on the total amount of all components of the thermally curable composition.
  • the thermally curable resin may be selected from epoxy resins, cyanurate resins, bismaleimide resins, polyimide resins, phenolic resins, furan resins, xylene formaldehyde resins, ketone formaldehyde resins, urea resins, melamine resins, aniline resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, triallyl cyanurate resins, triazine resins, polyurethane resins, silicone resins and mixture thereof. Due to the excellent performance such as heat resistance for sealant used in ODF process, bismaleimide resins are preferred as the thermally curable resin.
  • the thermally curable resin is present in an amount of 20%to 80%by weight, preferably 30%to 70%by weight based on the total weight of all components of the thermally curable composition.
  • the thermally curable composition may also contain additives conventionally used in the art of thermally curable adhesives or sealant to satisfy different properties and meet specific application requirements. Such additives can optionally be included from 0%by weight to about 50%by weight, preferably 5%by weight to about 45%by weight in the thermally curable composition of the present invention.
  • additives include, for example, reactive diluent, curing agent, crosslinking agent, silane coupling agent, thermoplastic polymers, plasticizers, fillers other than the (meth) acrylate copolymer, pigments, curing catalysts, dissociation catalysts, anti-oxidants, flow modifiers, dyestuffs, flame retardants, inhibitors, UV absorbers, adhesion promoters, stabilizers, tackifiers and waxes which may be incorporated in minor or larger amounts into the composition, singly or in combination, depending on the purpose.
  • Suitable examples of the reactive diluents are monoglycidyl ethers, such as phenyl glycidyl ether, alkyl phenol monoglycidyl ether, aliphatic monoglycidyl ether, alkylphenol mono glycidyl ether, alkylphenol monoglycidyl ether, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 1- (3-glycidoxypropyl) 1, 1, 3, 3, 3-pentamethyl disiloxane; diglycidyl ethers, such as 1, 4-butanediol diglycidyl ether; 1, 4-cyclohexane-dimethanol; the diglycidyl ether of resorcinol; diglycidyl ether of cyclohexane dimethanol; diglycidyl ether of neopen
  • Suitable curing agents for use in the present invention can be selected from latent curing agents commonly used in the art. Particularly, amine-based latent curing agents are preferred. Examples of the amine-based latent curing agents include but are not limited to well-known amine compounds having a latent property, and modified amines such as amine adducts.
  • the modified amines include a core-shell type curing agent in which the surface of a core of an amine compound (or amine adducts) is surrounded with a shell of a modified product (the surface converted to adduct) of amine, and a master batch type curing agent in which the core-shell type curing agent is in a state of being mixed with an epoxy resin.
  • amine compounds having a latent property examples include aromatic primary amines such as diaminodiphenylmethane and diaminodiphenylsulfone; imidazoles such as 2-heptadecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2, 4-diamino-6- [2-methylimidazolyl- (1) ] -ethyl-S-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-phenylimidazolium isocyanurate and 2-phenyl-4-methyl-5-hydroxymethylimidazole; boron trifluoride-amine complex; dicyandiamide and derivatives thereof such as dicyandiamide, o-tolylbiguanide and a-2, 5-methylbiguanide; organic acid hydrazides such as succinic acid dihydrazide and adipic acid dihydra
  • Amine adducts are the reaction products of an amine compound with an epoxy compound, an isocyanate compound and/or a urea compound.
  • the amine compound used for producing amine adducts may be a compound which has one or more active hydrogens in a molecule, capable of addition reaction with an epoxy group, an isocyanate group or a urea compound, and has at least one substituent selected from a primary amino group, a secondary amino group or a tertiary amino group in a molecule.
  • amine compounds include but are not limited to diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, dimethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine and N-methyl piperazine; primary or secondary amines comprising a tertiary amino group in a molecule, including imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole; alcohols, phenols, thiols, carboxylic acids and hydrazides, which comprise a tertiary amino group in a molecule, such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-die
  • examples of the epoxy compounds which are used as a raw material for producing amine adducts include polyglycidyl ethers obtained by the reaction of polyhydric phenol such as bisphenol A, bisphenol F, catechol and resorcinol, or polyhydric alcohol such as glycerin and polyethylene glycol, with epichlorohydrin; glycidyl ether esters obtained by the reaction of hydroxycarboxylic acid such as p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by the reaction of polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; glycidyl amine compounds obtained from 4, 4’-diaminodiphenylmethane and m-aminophenol; polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin and epoxidized poly
  • isocyanate compounds which are used as a raw material for producing amine adducts monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4’-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1, 3, 6-hexamethylene triisocyanate and bicycloheptane triisocyanate; and compounds containing an isocyanate group at their ends, which are obtained by the reaction of the above polyfunctional isocyanate compounds with active hydrogen compounds, can be used, and examples of such compounds include addition reaction products having an isocyanate group at their ends which are obtained by the reaction
  • urea compounds which are used as a raw material for producing amine adducts, include urea, urea phosphate, urea oxalate, urea acetate, diacetyl urea, dibenzoylurea, and trimethylurea.
  • the core-shell type curing agent is obtained by further treating the surface of an amine compound (or amine adducts) with acid compounds such as a carboxylic acid compound and a sulfonic acid compound, isocyanate compounds or epoxy compounds to form a shell of a modified product (adducts, etc. ) onto the surface.
  • the master batch type curing agent is the core-shell type curing agent in a state of being mixed with an epoxy resin.
  • Examples of commercially available latent curing agents include, but are not limited to Adeka Hardener EH-5011 S (imidazole type) , Adeka Hardener EH-4357S (modified amine type) , Adeka Hardener EH-4357PK (modified amine type) , Adeka Hardener EH-4380S (special hybrid type) , Adeka Hardener EH-5001 P (special modified type) , Ancamine 2014FG/2014AS (modified polyamine) , Ancamine 2441 (modified polyamine) , Ancamine2337s (modified amine type) , Fujicure FXR-1081 (modified amine type) , Fujicure FXR-1020 (modified amine type) , Sunmide LH-210 (modified imidazole type) , Sunmide LH-2102 (modified imidazole type) , Sunmide LH-2100 (modified imidazole type) , Ajicure PN-
  • the curing agent may be present in an amount of 5%to 40%by weight, preferably 10%to 30%by weight based on the total weight of all components of the thermally curable composition.
  • crosslinking agents are N, N’-methylene-bis-acrylamide, N, N’-methylene-bis-methacrylamide, diallyl amine, diallyl acrylamide, diallyl methacrylamide, diallyl ether, diallyl methyl ether, divinyl benzene, diethylene glycol divinyl ether, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 6-hexanediol diacrylate, pentacrythritol triacrylate, glyceryl/propoxy triacrylate and the like.
  • a preferred crosslinking agent is N, N’-methylene-bis-acrylamide or 1, 6-hexanediol diacrylate.
  • the (meth) acrylate copolymer comprises in polymerized form essentially no, and preferably no crosslinking agent.
  • Suitable thixotropic agent which can be optionally used in the present invention includes, but is not limited to, talc, fume silica, superfine surface-treated calcium carbonate, fine particle alumina, plate-like alumina; layered compound such as montmorillonite, spicular compound such as aluminium borate whisker, and the like.
  • Suitable silane coupling agent which can be optionally used in the present invention include, but is not limited to, ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxylsilane, phenyltrimethoxysilane, and the like.
  • Suitable filler other than the (meth) acrylate copolymers according to the present invention includes, but is not limited to silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, magnesium carbonate, barium sulphate, gypsum, calcium silicate, talc, glass bead, sericite activated white earth, bentonite, aluminum nitride, silicon nitride, and the like.
  • the present invention discloses a thermally curable composition, comprising a thermally curable resin, the (meth) acrylate copolymer according to the present invention, a diluent and a curing agent.
  • the present invention discloses a thermally curable composition, comprising 20%to 80%by weight, preferably 30%to 70%by weight of a thermally curable resin, 0.5%to 10%by weight, preferably 1%to 7%by weight of the (meth) acrylate copolymer according to the present invention, 2%to 20%by weight, preferably 5%to 15%by weight of a reactive diluent and 5%to 40%by weight, preferably 10%to 30%by weight of a curing agent.
  • the adhesive or sealant composition according to the present invention can be prepared by conventional methods in the art.
  • the adhesive or sealant composition according to the present invention may be obtained by mixing the aforementioned each component by means of, for example, a mixer such as a stirrer having stirring blades and a three-roll mill.
  • the thermally curable composition according to the present invention exhibited an excellent viscosity stability when the composition such as adhesive or sealant formulations was heated to elevated temperature such as from 50°C to 70°C before the curing initiates.
  • the thermally curable composition possesses a complex viscosity of no less than 10 Pa ⁇ s at 50°C.
  • the thermally curable composition possesses a complex viscosity of no less than 10 Pa ⁇ s at 70°C.
  • the largest drop of complex viscosity of the thermally curable composition in the range of 50°C to 70°C is no larger than 55%, preferably is no larger than 50%, and more preferably is no larger than 45%.
  • Methyl methacrylate is commercially from Aldrich.
  • n-Butyl acrylate (BA) is commercially available from Aldrich.
  • Heptadecyl acrylate (C17A) is commercially available from BASF.
  • HEMA Hydroxyethyl methacrylate
  • 4-hydroxybutyl acrylate (4-HBA) is commercially available from BASF.
  • Poly (ethylene glycol) methacrylate (PEGMA) is commercially available from Aldrich.
  • Carboxyethyl acrylate (CEA) is commercially available under the trade name of HOA-MS from Kyoeisha Chemical.
  • Hydroxyacryamide (HO-AM) is commercially available from Sinopharm Chemical.
  • t-Butylacryamide (t-Bu-AM) is commercially available from Sinopharm Chemical.
  • Styrene (ST) is commercially available from Sinopharm Chemical.
  • Sodium dodecyl sulfate (SDS) is commercially available from Sinopharm Chemical.
  • Ammonium persulfate (APS) is commercially available from Sinopharm Chemical.
  • HDDA 1, 6-hexandioldiacrylate
  • Star polymer is a star grafted poly (meth) acrylate commercially available under the trade name of 88708 from Lubrizol.
  • Comb polymer is a comb grafted poly (meth) acrylate commercially available under the trade name of Viscoplex 12-209 from Evonik.
  • F351 is a core-shell type mixture of (meth) acrylate copolymer commercially available under the trade name of F351 from Ganz Chemical Co., Ltd.
  • Bismaleimide resin is commercially available under the trade name of 88708 from Lubrizol.
  • Epoxy diluent is commercially available under the trade name of Epon 828 from Dow Chemical Co., Ltd.
  • Curing agent is commercially available under the trade name of HX-3088 from Asahi KASEI.
  • (Meth) acrylate copolymers of inventive examples (Copolymers 1 to 6) and comparative examples (Copolymers 7 to 9) were prepared according to the formulation as shown in Table 1 in the following procedure: to a 250 mL round glass bottle, 120 mL water was added. Then the monomers except PEGMA (if present) were added to the water with 400 mg SDS as emulsifier. The mixture was purged with N 2 for 30 min with vigorous stirring. The emulsion was heated to about 50°C within 20 min. Then 400 mg APS dissolved in 20 mL water was added to the mixture. The temperature gradually reached to 60°C and the polymerization reaction was initiated. If used, PEGMA was added to the mixture at 1 hour after the reaction began.
  • the reaction lasted for another 5 hours at 70°C.
  • the crosslinking agent is added 10 minutes after the reaction temperature reaches 80°C, and then the reaction was maintained at 80°C for 5 hours.
  • the nanospheres were obtained by the freeze-drying method.
  • thermally curable sealants of inventive examples (Examples 1 to 6) and comparative examples (Examples 7 to 9) were prepared by adding a bismaleimide resin, an epoxy diluent, a curing agent, and the Copolymers in an amount according to Table 2 into a 250 mL round glass bottle, and stirring until homogenous.
  • a star grafted poly (meth) acrylate, a comb grafted poly (meth) acrylate and a core-shell type mixture of (meth) acrylate copolymer were used instead of the Copolymer.
  • the D90 particle sizes of the nanosphere of (meth) acrylate copolymer were measured by dynamic laser scattering (Beckman Coulter, LS 13-320) . The test results are shown in Table 1.
  • the complex viscosity of the thermally curable compositions was measured by an Anton Paar MCR 301 rheometer (manufactured by Anton Paar) , at a shear rate of 15 s -1 , using a plate/plate measuring system with a disc plate diameter of 25 mm and a gap of 0.2 mm, in temperature range of 50°C to 70°C.
  • the complex viscosity at 50°C, 70°C, and lowest complex viscosity from 50°C to 70°C were recorded.
  • the test results are listed in Table 2, in which the largest viscosity drop was calculated as: (complex viscosity at 50°C –lowest complex viscosity from 50°C to 70°C) /complex viscosity at 50°C.
  • the (meth) acrylate copolymers according to the present invention all possessed a physical appearance of nanospheres having D90 particle size less than 1,000 nm.
  • the thermally curable sealant containing the (meth) acrylate copolymers according to the present invention exhibited an excellent viscosity stability at elevated temperature before curing.
  • the largest viscosity drop achieved by Examples 1 to 6 were much smaller than Examples 7 to 9 having significantly amount of (meth) acrylamide or its derivatives in the (meth) acrylate copolymers, and were also much smaller than Examples 10 to 12 having conventional star or comb (meth) acrylate polymers and core-shell type (meth) acrylate polymers mixture as filler.
  • inventive thermally curable sealants having such improved viscosity stability are suitable to be used in ODF process in which the sealants do not flow or spread to the liquid crystal, and thus liquid crystal penetration failure can be avoided.

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Abstract

The present invention relates to a (meth)acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer, (b) a hydrophilic monomer, and optionally a vinyl monomer other than monomers (a) and (b). In particular, the (meth)acrylate copolymer is suitable to be used as filler in thermally curable composition, and prevents the viscosity slump of the composition at elevated temperature before curing.

Description

(Meth) acrylate copolymer for thermally curable composition Technical Field
The present invention relates to a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer, (b) a hydrophilic monomer, and optionally a vinyl monomer other than monomers (a) and (b) . In particular, the (meth) acrylate copolymer is suitable to be used as filler in thermally curable composition, and prevents the viscosity slump of the thermally curable composition at elevated temperature before curing.
Background
Liquid crystal display (LCD) panels having the characteristics of being light-weight and high-definition have been widely used as display panels for a variety of apparatuses including cell phones and TVs. Conventionally, the process for producing a LCD cell is called a one-drop-filling (ODF) process which comprises applying a sealant on a substrate having an electrode pattern and an alignment film under vacuum condition, dropping liquid crystal (LC) on the substrate having the sealant applied thereon, joining opposite facing substrates to each other under vacuum, then releasing the vacuum and performing pure ultraviolet (UV) radiation, pure heating, or the combination of UV radiation and heating to cure the sealant and thereby producing a LCD cell.
In the case that thermally curable sealant compositions are used in the ODF process, heating is performed to cure the sealant composition after the substrates are attached, and afterwards the assembly will be heated in an oven from room temperature to an elevated temperature such as 100℃ to 110℃ in a time period sufficient for fully curing the sealant. During the heating, the viscosity of thermally curable sealant composition applied onto the substrate significantly decreases due to the Brown effect in the temperature range in which the curing has not initiated, such as from 50℃ to 70℃. The viscosity slump of the sealant composition may cause the sealant to spread out of the application position for example within only several millimetres in “slim border” or “narrow bezel” design, and penetrate into the liquid crystal, which results in a contamination of liquid crystal by the sealant.
Attempts have been made to control the viscosity slump of thermally curable sealant compositions at elevated temperature.
For example, WO 2016074187 A1 discloses a thermally curable sealant composition comprising a cyanate ester resin, an epoxy resin, a latent curing agent, and a gelling agent  which comprises one or more core particles consisting of a resin having a glass transition temperature of lower than -10℃, and one or more shell layers consisting of a resin having a glass transition temperature of 50-150℃ formed on the surface of the core particle. The addition of a gelling agent can compensate the viscosity s of the sealant composition under an elevated temperature. By using the gelling agent the distortion or breaking of sealant can be prevented.
US 20120258314 A1 discloses a thermally epoxy resin composition for hermetic sealing of an electronic component or an electrical component, containing a liquid epoxy resin, dicyandiamide, and a filler including a thermal expansion filler particles which expand when heated and increase the viscosity of the epoxy resin composition, thereby suppressing an uncured epoxy resin flowing out of a gap.
Summary of the Invention
Based on the foregoing discussion, an object of the present invention is to provide a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer, (b) a hydrophilic monomer, and optionally a vinyl monomer other than monomers (a) and (b) , which prevents a viscosity slump effect and is suitable to be used as such as filler in thermally curable composition of adhesives or sealants.
Also provided is a thermally curable composition, comprising a thermally curable resin and the (meth) acrylate copolymer according to the present invention.
These and other objects, features and advantages of the present invention will become better understood upon having reference to the following description of the invention.
Detailed Description
It is to be understood by one of ordinary skill in the art that the present application is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
All percentages listed in this specification are percentages of components by weight, unless otherwise specifically mentioned.
In one aspect, the present invention is directed to a (meth) acrylate copolymer comprising, in polymerized form, (a) a hydrophobic monomer of C1-C22 alkyl mono (meth) acrylate, (b) a  hydrophilic monomer selected from (b1) a hydroxyl-C1-C10 alkyl mono (meth) acrylate, (b2) a carboxy-C1-C10 alkyl mono (meth) acrylate, (b3) an optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof, and (c) optionally a vinyl monomer other than monomers (a) and (b) .
The inventors have surprisingly found that, by selecting the monomers, the (meth) acrylate copolymer exhibited an improved thermal expansion property, and avoided the viscosity slump effect for thermally curable compositions containing the (meth) acrylate copolymer when heated at elevated temperature before curing.
(a) Hydrophobic monomer
According to the present invention, the hydrophobic monomer of the (meth) acrylate copolymer consists of C1-C22 alkyl mono (meth) acrylate, and more preferably is C1-C18 alkyl mono (meth) acrylate, and in particular is selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, isomers thereof, and combination thereof, and is more preferably selected from methyl methacrylate, n-butyl acrylate, heptadecyl acrylate, isomers thereof, and combination thereof. In one embodiment, the hydrophobic monomer is the combination of methyl methacrylate and n-butyl acrylate. In another embodiment, the hydrophobic monomer is the combination of methyl methacrylate and n-heptadecyl acrylate.
The hydrophobic monomer is present in an amount of 35％to 75％, preferably 50％to 70％by weight based on the total weight of all components of the (meth) acrylate copolymer.
(b) Hydrophilic monomer
According to the present invention, the hydrophilic monomer of the (meth) acrylate copolymer is selected from (b1) a hydroxyl-C1-C10 alkyl mono (meth) acrylate, (b2) a carboxy-C1-C10 alkyl mono (meth) acrylate, (b3) an optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof.
Preferably, the hydroxy-C1-C10 alkyl mono (meth) acrylate is hydroxy-C1-C6 alkyl mono (meth) acrylate. Suitable examples of hydroxy-C1-C6 alkyl mono (meth) acrylate are hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and combination thereof.
Preferably, the carboxy-C1-C10 alkyl mono (meth) acrylate is carboxy-C1-C6 alkyl mono (meth) acrylate. Suitable examples of carboxy-C1-C6 alkyl mono (meth) acrylate are carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxylpropyl (meth) acrylate, carboxylbutyl (meth) acrylate, carboxylpentyl (meth) acrylate, carboxylhexyl (meth) acrylate or carboxylcyclohexyl (meth) acrylate.
The optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) (meth) acrylate is selected from C1-C6 alkyl terminated poly (C2-C4 alkylene glycol) (meth) acrylate, poly (C2-C4 alkylene glycol) (meth) acrylate, and combination thereof, and preferably is selected from methyl terminated poly (ethylene glycol) (meth) acrylate, poly (ethylene glycol) (meth) acrylate, and combination thereof. In some embodiments, the optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) (meth) acrylate has a number average molecular weight of 250 to 1000 Da, and preferably 300 to 800 Da, measured by gel penetration chromatography method.
The hydrophilic monomer may also contain methacrylic acid or acrylic acid singly or in combination with other hydrophilic monomers.
In one embodiment, the hydrophilic monomer is methacrylic acid. In another embodiment, the hydrophilic monomer is the combination of 4-hydroxybutyl acrylate and methacrylic acid. In yet another embodiment, the hydrophilic monomer is the combination of 4-hydroxybutyl acrylate, methacrylic acid and methyl terminated poly (ethylene glycol) monomethacrylate. In yet another embodiment, the hydrophilic monomer is the combination of hydroxyethyl methacrylate and carboxyethyl acrylate.
According to the present invention, the hydrophilic monomer is present in an amount of 1％to 45％, preferably 5％to 40％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
According to the present invention, the (meth) acrylate copolymer may comprise, in polymerized form, an optionally substituted (meth) acrylamide in an amount of less than  20％, preferably less than 10％, more preferably less than 5％by weight based on the total weight of all monomers of the (meth) acrylate copolymer. In particular, the (meth) acrylate copolymer contains, in polymerized form, essentially no optionally substituted (meth) acrylamide, and preferably no optionally substituted (meth) acrylamide. Suitable examples of the optionally substituted (meth) acrylamide are (meth) acrylamide, hydroxyl (meth) acrylamide, and C1-C10 alkyl (meth) acrylamide. It is believed that the larger amount of optionally substituted (meth) acrylamide used for the (meth) acrylate copolymer of the present invention possess unsatisfactory thermal expansion effect, and in turn may give negative influence on the viscosity stability of the sealant containing the (meth) acrylate copolymer particles at elevated temperature before curing.
According to the present invention, the (meth) acrylate copolymer may also comprise in polymerized form, (c) a vinyl monomer other than monomers (a) and (b) .
There is no limitation to such vinyl monomers as long as they are suitable to be used in the present invention and do not deteriorate the thermal expansion of the (meth) acrylate copolymer particles. Suitable examples are styrene, vinyl naphthalene, 2, 4-dichlorostyrene, divinylbenzene, acrylonitrile, vinyl acetate, vinyl chloride used singly or in combination. Preferably, the vinyl monomers are selected from styrene, acrylonitrile and combination thereof, and more preferably is styrene.
The vinyl monomer other than monomers (a) and (b) is present in an amount of 0％to 30％, preferably 10％to 30％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
In one embodiment, the present invention is directed to a (meth) acrylate copolymer comprising, in polymerized form, (a) 35％to 75％, preferably 50％to 70％by weight of a hydrophobic monomer of C1-C22 alkyl mono (meth) acrylate, (b) 1％to 45％, preferably 5％to 40％by weight of a hydrophilic monomer selected from (b1) a hydroxyl-C1-C10 alkyl mono (meth) acrylate, (b2) a carboxy-C1-C10 alkyl mono (meth) acrylate, (b3) an optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) mono (meth) acrylate, (b4) (meth) acrylic acid, and combination thereof, and (c) 0％to 30％, preferably 10％to 30％by weight of a vinyl monomer other than monomers (a) and (b) , in which the weight percentages are based on the total weight of all monomers of the (meth) acrylate copolymer.
In the present invention, the (meth) acrylate copolymer has a number average molecular weight of 1,000 to 100,000 Da, and preferably 5,000 to 50,000 Da, measured by gel  penetration chromatography method.
In the present invention, the (meth) acrylate copolymer is in the form of solid particles when used as filler in a thermal curable adhesive or sealant composition. The particle size D90 of the copolymer is no larger than 1000 nm, preferably 10 to 800 nm, more preferably 20 to 500 nm, and most preferably 50 to 300 nm. The particle size D90 means that 90％of the particles satisfy the given requirement, i.e. their diameter in the biggest dimension is no larger than 1000 nm, preferably 10 to 800 nm, more preferably 20 to 500 nm, and most preferably 50 to 300 nm. The particle diameters can be determined by any suitable method. Exemplary methods include sieving methods, sedimentation methods and methods that are based on the diffraction of electromagnetic waves, in particular light. Also suited are electron microscopic techniques, such scanning electron microscopy and transmission electron microscopy, and laser diffraction spectroscopy. Preferably, the particle sizes are determined by laser diffraction spectroscopy using a laser diffraction particle size analyzer, such as the Beckman Coulter LS 13 320.
The (meth) acrylate copolymer having such small particle size are also referred as microsphere or nanosphere herein. The sphere structure ensures that when the copolymer is used as filler, it can be easily added to the sealant system without greatly increasing the initiate viscosity.
The (meth) acrylate copolymer in the present invention is temperature sensitive due to the selection of monomers. Not binding to any theory, it is believed that when thermally curable sealant compositions containing the (meth) acrylate copolymer are heated to an elevated temperature such as 40℃ to 70℃, the copolymers will be dissolved into the resin matrix of the sealant, and help reduce the viscosity drop.
Preparation of the (meth) acrylate copolymer
The (meth) acrylate copolymer is a copolymer which is obtained by polymerizing a mixture of monomers including the hydrophobic monomer (a) , the hydrophilic monomer (b) , and optionally the vinyl monomer other than monomers (a) and (b) with one or more initiators and one or more additives. As for the preparing method, the (meth) acrylate copolymer can be prepared by a known polymerization method such as a solution polymerization method, a suspension polymerization method and an emulsification polymerization method, and suspension polymerization method is preferred.
Suitable initiators for preparing the (meth) acrylate copolymer according to the present invention are free radical water-soluble substances, in particular water-soluble peroxides or persulfates, for example hydrogen peroxide, potassium, sodium and ammonium persulfates, t-butyl hydroperoxide, and peracetic acid. Redox catalysts may also be used which consist of peroxides or persulfates of the above types and reducing agents normally used for this purpose, such as ascorbic acid, sodium bisulfide, and sodium sulfoxylate. It is possible for two or more initiators to be used in the emulsion polymerization. In general, the initiator (s) may be used in an amount of 0.1％to 3％by weight based on the total weight of all monomers, preferably 0.1％to 2％by weight. The initiator (s) can be introduced as initial charge to the polymerization vessel before the polymerization is initiated. It is also possible to introduce a portion of the initiator (s) as an initial charge to the polymerization vessel before the polymerization is initiated, and add the remaining amount continuously under polymerization conditions.
The additives for the preparation of the (meth) acrylate copolymer including but not limited to emulsifier, solvent (such as water) , stabilizer, pH adjustment and chelating agent. Examples of emulsifier are sodium lauryl sulfate, sodium lauryl benzene sulfonate, sodium dodecyl sulfate, nonyl aryl polyether alcohol, lauryl ammonium nonylphenol ether or octyl phenol ethoxylates.
Thermally curable composition
The (meth) acrylate copolymer in the form of microsphere or nanosphere can be formulated to provide the thermally curable composition by any method known in the art.
Therefore, also provided in the present invention are a thermally curable composition comprising a thermally curable resin and the (meth) acrylate copolymer according to the present invention, and cured product of the thermally curable composition. The (meth) acrylate copolymer according to the present invention may be present in an amount of 0.5％to 10％by weight, preferably 1％to 7％by weight based on the total amount of all components of the thermally curable composition.
The thermally curable resin may be selected from epoxy resins, cyanurate resins, bismaleimide resins, polyimide resins, phenolic resins, furan resins, xylene formaldehyde resins, ketone formaldehyde resins, urea resins, melamine resins, aniline resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, triallyl cyanurate resins, triazine resins, polyurethane resins, silicone resins and mixture thereof. Due to the  excellent performance such as heat resistance for sealant used in ODF process, bismaleimide resins are preferred as the thermally curable resin.
The thermally curable resin is present in an amount of 20％to 80％by weight, preferably 30％to 70％by weight based on the total weight of all components of the thermally curable composition.
The thermally curable composition may also contain additives conventionally used in the art of thermally curable adhesives or sealant to satisfy different properties and meet specific application requirements. Such additives can optionally be included from 0％by weight to about 50％by weight, preferably 5％by weight to about 45％by weight in the thermally curable composition of the present invention. Such additives include, for example, reactive diluent, curing agent, crosslinking agent, silane coupling agent, thermoplastic polymers, plasticizers, fillers other than the (meth) acrylate copolymer, pigments, curing catalysts, dissociation catalysts, anti-oxidants, flow modifiers, dyestuffs, flame retardants, inhibitors, UV absorbers, adhesion promoters, stabilizers, tackifiers and waxes which may be incorporated in minor or larger amounts into the composition, singly or in combination, depending on the purpose.
Suitable examples of the reactive diluents are monoglycidyl ethers, such as phenyl glycidyl ether, alkyl phenol monoglycidyl ether, aliphatic monoglycidyl ether, alkylphenol mono glycidyl ether, alkylphenol monoglycidyl ether, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 1- (3-glycidoxypropyl) 1, 1, 3, 3, 3-pentamethyl disiloxane； diglycidyl ethers, such as 1, 4-butanediol diglycidyl ether； 1, 4-cyclohexane-dimethanol； the diglycidyl ether of resorcinol； diglycidyl ether of cyclohexane dimethanol； diglycidyl ether of neopentyl glycol； triglycidyl ether of trimethylolpropane dipentene； and the divinyl ether of cyclohexanedimethanol； and tri-or tetra-glycidyl ethers, such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and pentaerythritol tetraglycidyl ether. If present, the reactive diluent may be present in an amount of 2％to 20％by weight, preferably 5％to 15％by weight based on the total weight of all components of the thermally curable composition.
Suitable curing agents for use in the present invention can be selected from latent curing agents commonly used in the art. Particularly, amine-based latent curing agents are preferred. Examples of the amine-based latent curing agents include but are not limited to well-known amine compounds having a latent property, and modified amines such as  amine adducts. The modified amines include a core-shell type curing agent in which the surface of a core of an amine compound (or amine adducts) is surrounded with a shell of a modified product (the surface converted to adduct) of amine, and a master batch type curing agent in which the core-shell type curing agent is in a state of being mixed with an epoxy resin.
Examples of the amine compounds having a latent property include aromatic primary amines such as diaminodiphenylmethane and diaminodiphenylsulfone； imidazoles such as 2-heptadecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2, 4-diamino-6- [2-methylimidazolyl- (1) ] -ethyl-S-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-phenylimidazolium isocyanurate and 2-phenyl-4-methyl-5-hydroxymethylimidazole； boron trifluoride-amine complex； dicyandiamide and derivatives thereof such as dicyandiamide, o-tolylbiguanide and a-2, 5-methylbiguanide； organic acid hydrazides such as succinic acid dihydrazide and adipic acid dihydrazide； diaminomaleonitrile and derivatives thereof； and melamine derivatives such as melamine and diallylmelamine.
Amine adducts are the reaction products of an amine compound with an epoxy compound, an isocyanate compound and/or a urea compound.
The amine compound used for producing amine adducts may be a compound which has one or more active hydrogens in a molecule, capable of addition reaction with an epoxy group, an isocyanate group or a urea compound, and has at least one substituent selected from a primary amino group, a secondary amino group or a tertiary amino group in a molecule.
Examples of such amine compounds include but are not limited to diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, dimethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine and N-methyl piperazine； primary or secondary amines comprising a tertiary amino group in a molecule, including imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole； alcohols, phenols, thiols, carboxylic acids and hydrazides, which comprise a tertiary amino group in a molecule, such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole,  1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hdroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-botoxypropyl) -2-phenylimidazoline, 2- (dimethylaminomethyl) phenol, 2, 4, 6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.
Further, examples of the epoxy compounds which are used as a raw material for producing amine adducts include polyglycidyl ethers obtained by the reaction of polyhydric phenol such as bisphenol A, bisphenol F, catechol and resorcinol, or polyhydric alcohol such as glycerin and polyethylene glycol, with epichlorohydrin； glycidyl ether esters obtained by the reaction of hydroxycarboxylic acid such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin； polyglycidyl esters obtained by the reaction of polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin； glycidyl amine compounds obtained from 4, 4’-diaminodiphenylmethane and m-aminophenol； polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin and epoxidized polyolefin； and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether and glycidyl methacrylate.
As the isocyanate compounds which are used as a raw material for producing amine adducts, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate and benzyl isocyanate； polyfunctional isocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4’-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1, 3, 6-hexamethylene triisocyanate and bicycloheptane triisocyanate； and compounds containing an isocyanate group at their ends, which are obtained by the reaction of the above polyfunctional isocyanate compounds with active hydrogen compounds, can be used, and examples of such compounds include addition reaction products having an isocyanate group at their ends which are obtained by the reaction of tolylene diisocyanate with trimethylolpropane.
Examples of the urea compounds, which are used as a raw material for producing amine adducts, include urea, urea phosphate, urea oxalate, urea acetate, diacetyl urea, dibenzoylurea, and trimethylurea.
Further, the core-shell type curing agent is obtained by further treating the surface of an amine compound (or amine adducts) with acid compounds such as a carboxylic acid compound and a sulfonic acid compound, isocyanate compounds or epoxy compounds to form a shell of a modified product (adducts, etc. ) onto the surface. Further, the master batch type curing agent is the core-shell type curing agent in a state of being mixed with an epoxy resin.
Examples of commercially available latent curing agents include, but are not limited to Adeka Hardener EH-5011 S (imidazole type) , Adeka Hardener EH-4357S (modified amine type) , Adeka Hardener EH-4357PK (modified amine type) , Adeka Hardener EH-4380S (special hybrid type) , Adeka Hardener EH-5001 P (special modified type) , Ancamine 2014FG/2014AS (modified polyamine) , Ancamine 2441 (modified polyamine) , Ancamine2337s (modified amine type) , Fujicure FXR-1081 (modified amine type) , Fujicure FXR-1020 (modified amine type) , Sunmide LH-210 (modified imidazole type) , Sunmide LH-2102 (modified imidazole type) , Sunmide LH-2100 (modified imidazole type) , Ajicure PN-23 (modified imidazole type) , Ajicure PN-23J (modified imidazole type) , Ajicure PN-31 (modified imidazole type) , Ajicure PN-31J (modified imidazole type) , Novacure HX-3722 (master batch type) , Novacure HX-3742 (master batch type) , Novacure HX-3613 (masterbatch type) , and the like.
If present, the curing agent may be present in an amount of 5％to 40％by weight, preferably 10％to 30％by weight based on the total weight of all components of the thermally curable composition.
Suitable examples of crosslinking agents are N, N’-methylene-bis-acrylamide, N, N’-methylene-bis-methacrylamide, diallyl amine, diallyl acrylamide, diallyl methacrylamide, diallyl ether, diallyl methyl ether, divinyl benzene, diethylene glycol divinyl ether, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 6-hexanediol diacrylate, pentacrythritol triacrylate, glyceryl/propoxy triacrylate and the like. A preferred crosslinking agent is N, N’-methylene-bis-acrylamide or  1, 6-hexanediol diacrylate. In another embodiment, the (meth) acrylate copolymer comprises in polymerized form essentially no, and preferably no crosslinking agent.
Suitable thixotropic agent, which can be optionally used in the present invention includes, but is not limited to, talc, fume silica, superfine surface-treated calcium carbonate, fine particle alumina, plate-like alumina； layered compound such as montmorillonite, spicular compound such as aluminium borate whisker, and the like.
Suitable silane coupling agent, which can be optionally used in the present invention include, but is not limited to, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxylsilane, phenyltrimethoxysilane, and the like.
Suitable filler other than the (meth) acrylate copolymers according to the present invention, which can be optionally used in the present invention, includes, but is not limited to silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, magnesium carbonate, barium sulphate, gypsum, calcium silicate, talc, glass bead, sericite activated white earth, bentonite, aluminum nitride, silicon nitride, and the like.
In a preferred embodiment, the present invention discloses a thermally curable composition, comprising a thermally curable resin, the (meth) acrylate copolymer according to the present invention, a diluent and a curing agent.
In a more preferred embodiment, the present invention discloses a thermally curable composition, comprising 20％to 80％by weight, preferably 30％to 70％by weight of a thermally curable resin, 0.5％to 10％by weight, preferably 1％to 7％by weight of the (meth) acrylate copolymer according to the present invention, 2％to 20％by weight, preferably 5％to 15％by weight of a reactive diluent and 5％to 40％by weight, preferably 10％to 30％by weight of a curing agent.
The adhesive or sealant composition according to the present invention can be prepared by conventional methods in the art. For example, the adhesive or sealant composition according to the present invention may be obtained by mixing the aforementioned each component by means of, for example, a mixer such as a stirrer having stirring blades and a three-roll mill.
Due to the incorporation of the (meth) acrylate copolymer, preferably in nanosphere form, the thermally curable composition according to the present invention exhibited an excellent viscosity stability when the composition such as adhesive or sealant formulations was heated to elevated temperature such as from 50℃ to 70℃ before the curing initiates. In one embodiment, the thermally curable composition possesses a complex viscosity of no less than 10 Pa·s at 50℃. In another embodiment, the thermally curable composition possesses a complex viscosity of no less than 10 Pa·s at 70℃. In yet another embodiment, the largest drop of complex viscosity of the thermally curable composition in the range of 50℃ to 70℃ is no larger than 55％, preferably is no larger than 50％, and more preferably is no larger than 45％.
The present invention may be better understood with reference to the following examples.
Examples
Materials
Methyl methacrylate (MMA) is commercially from Aldrich.
n-Butyl acrylate (BA) is commercially available from Aldrich.
Heptadecyl acrylate (C17A) is commercially available from BASF.
Hydroxyethyl methacrylate (HEMA) is commercially available from Aldrich.
4-hydroxybutyl acrylate (4-HBA) is commercially available from BASF.
Poly (ethylene glycol) methacrylate (PEGMA) is commercially available from Aldrich.
Carboxyethyl acrylate (CEA) is commercially available under the trade name of HOA-MS from Kyoeisha Chemical.
Acryamide (AM) is commercially available from Sinopharm Chemical.
Hydroxyacryamide (HO-AM) is commercially available from Sinopharm Chemical.
t-Butylacryamide (t-Bu-AM) is commercially available from Sinopharm Chemical.
Styrene (ST) is commercially available from Sinopharm Chemical.
Sodium dodecyl sulfate (SDS) is commercially available from Sinopharm Chemical.
Ammonium persulfate (APS) is commercially available from Sinopharm Chemical.
1, 6-hexandioldiacrylate (HDDA) is commercially available from Sinopharm Chemical.
Star polymer is a star grafted poly (meth) acrylate commercially available under the trade name of 88708 from Lubrizol.
Comb polymer is a comb grafted poly (meth) acrylate commercially available under the trade name of Viscoplex 12-209 from Evonik.
F351 is a core-shell type mixture of (meth) acrylate copolymer commercially available under the trade name of F351 from Ganz Chemical Co., Ltd.
Bismaleimide resin is commercially available under the trade name of 88708 from Lubrizol.
Epoxy diluent is commercially available under the trade name of Epon 828 from Dow Chemical Co., Ltd.
Curing agent is commercially available under the trade name of HX-3088 from Asahi KASEI.
Preparation of (meth) acrylate copolymers
(Meth) acrylate copolymers of inventive examples (Copolymers 1 to 6) and comparative examples (Copolymers 7 to 9) were prepared according to the formulation as shown in Table 1 in the following procedure: to a 250 mL round glass bottle, 120 mL water was added. Then the monomers except PEGMA (if present) were added to the water with 400 mg SDS as emulsifier. The mixture was purged with N2 for 30 min with vigorous stirring. The emulsion was heated to about 50℃ within 20 min. Then 400 mg APS dissolved in 20 mL water was added to the mixture. The temperature gradually reached to 60℃ and the polymerization reaction was initiated. If used, PEGMA was added to the mixture at 1 hour after the reaction began. Then the reaction lasted for another 5 hours at 70℃. In the case that crosslinking agent is used, the crosslinking agent is added 10 minutes after the  reaction temperature reaches 80℃, and then the reaction was maintained at 80℃ for 5 hours. The nanospheres were obtained by the freeze-drying method.
Preparation of thermally curable sealants
The thermally curable sealants of inventive examples (Examples 1 to 6) and comparative examples (Examples 7 to 9) were prepared by adding a bismaleimide resin, an epoxy diluent, a curing agent, and the Copolymers in an amount according to Table 2 into a 250 mL round glass bottle, and stirring until homogenous. In Examples 10 to 12, a star grafted poly (meth) acrylate, a comb grafted poly (meth) acrylate and a core-shell type mixture of (meth) acrylate copolymer were used instead of the Copolymer.
Test methods
D90 particle size
The D90 particle sizes of the nanosphere of (meth) acrylate copolymer were measured by dynamic laser scattering (Beckman Coulter, LS 13-320) . The test results are shown in Table 1.
Complex viscosity
The complex viscosity of the thermally curable compositions was measured by an Anton Paar MCR 301 rheometer (manufactured by Anton Paar) , at a shear rate of 15 s-1, using a plate/plate measuring system with a disc plate diameter of 25 mm and a gap of 0.2 mm, in temperature range of 50℃ to 70℃. The complex viscosity at 50℃, 70℃, and lowest complex viscosity from 50℃ to 70℃ were recorded. The test results are listed in Table 2, in which the largest viscosity drop was calculated as: (complex viscosity at 50℃ –lowest complex viscosity from 50℃ to 70℃) /complex viscosity at 50℃.
Figure PCTCN2017107807-appb-000001
Figure PCTCN2017107807-appb-000002
As shown in Table 1, the (meth) acrylate copolymers according to the present invention all possessed a physical appearance of nanospheres having D90 particle size less than 1,000 nm.
As evident in Table 2, the thermally curable sealant containing the (meth) acrylate copolymers according to the present invention exhibited an excellent viscosity stability at elevated temperature before curing. The largest viscosity drop achieved by Examples 1 to 6 were much smaller than Examples 7 to 9 having significantly amount of (meth) acrylamide or its derivatives in the (meth) acrylate copolymers, and were also much smaller than Examples 10 to 12 having conventional star or comb (meth) acrylate polymers and core-shell type (meth) acrylate polymers mixture as filler.
The inventive thermally curable sealants having such improved viscosity stability are suitable to be used in ODF process in which the sealants do not flow or spread to the liquid crystal, and thus liquid crystal penetration failure can be avoided.
These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in component. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims (23)

  1. A (meth) acrylate copolymer comprising, in polymerized form,
    (a) a hydrophobic monomer of C1-C22 alkyl mono (meth) acrylate,
    (b) a hydrophilic monomer selected from,
    (b1) a hydroxyl-C1-C10 alkyl mono (meth) acrylate,
    (b2) a carboxy-C1-C10 alkyl mono (meth) acrylate,
    (b3) an optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) mono (meth) acrylate,
    (b4) (meth) acrylic acid, and combination thereof, and
    (c) optionally a vinyl monomer other than monomers (a) and (b) .
  2. The (meth) acrylate copolymer according to claim 1, wherein the hydrophobic monomer of C1-C22 alkyl mono (meth) acrylate is C1-C18 alkyl mono (meth) acrylate, and preferably is selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, isomers thereof, and combination thereof, and is more preferably selected from methyl methacrylate, n-butyl acrylate, heptadecyl acrylate, isomers thereof, and combination thereof.
  3. The (meth) acrylate copolymer according to claim 1 or 2, wherein the hydroxy-C1-C10 alkyl mono (meth) acrylate is hydroxy-C1-C6 alkyl mono (meth) acrylate, and preferably is selected from hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and combination thereof, and more preferably is selected from hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and combination thereof.
  4. The (meth) acrylate copolymer according to any one of claims 1 to 3, wherein the carboxy-C1-C10 alkyl mono (meth) acrylate is carboxy-C1-C6 alkyl mono (meth) acrylate, and preferably is selected from carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxylpropyl (meth) acrylate, carboxylbutyl (meth) acrylate,  carboxylpentyl (meth) acrylate, carboxylhexyl (meth) acrylate, carboxylcyclohexyl (meth) acrylate, and combination thereof, and more preferably is carboxymethyl methacrylate or carboxyethyl methacrylate.
  5. The (meth) acrylate copolymer according to any one of claims 1 to 4, wherein the optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) (meth) acrylate is selected from C1-C6 alkyl terminated poly (C2-C4 alkylene glycol) (meth) acrylate, poly (C2-C4 alkylene glycol) (meth) acrylate, and combination thereof, and preferably is selected from methyl terminated poly (ethylene glycol) (meth) acrylate, poly (ethylene glycol) (meth) acrylate, and combination thereof.
  6. The (meth) acrylate copolymer according to any one of claims 1 to 5, wherein the optionally C1-C10 alkyl terminated poly (C2-C6 alkylene glycol) (meth) acrylate has a number average molecular weight of 250 to 1000 Da, preferably 300 to 600 Da.
  7. The (meth) acrylate copolymer according to any one of claims 1 to 6, wherein the vinyl monomer other than monomers (a) and (b) is selected from styrene, vinyl naphthalene, 2, 4-dichlorostyrene, divinylbenzene, acrylonitrile, vinyl acetate, vinyl chloride, and combination thereof, preferably is selected from styrene, acrylonitrile and combination thereof.
  8. The (meth) acrylate copolymer according to any one of claims 1 to 7, wherein the (meth) acrylate copolymer has a particle size D90 of no larger than 1000 nm, preferably 10 to 800 nm, more preferably 20 to 500 nm, and most preferably 50 to 300 nm.
  9. The (meth) acrylate copolymer according to any one of claims 1 to 8, wherein the monomer (a) is present in an amount of 35％to 75％, preferably 50％to 70％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  10. The (meth) acrylate copolymer according to any one of claims 1 to 9, wherein the monomer (b) is present in an amount of 1％to 45％, preferably 5％to 40％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  11. The (meth) acrylate copolymer according to any one of claims 1 to 10, wherein the monomer (c) is present in an amount of 0％to 30％, preferably 10％to 30％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  12. The (meth) acrylate copolymer according to any one of claims 1 to 11, comprising, in polymerized form, an optionally substituted (meth) acrylamide in an amount of less than 20％, preferably less than 10％, more preferably less than 5％by weight based on the total weight of all monomers of the (meth) acrylate copolymer.
  13. The (meth) acrylate copolymer according to claim 12, comprising, in polymerized form, essentially no optionally substituted (meth) acrylamide, and preferably no optionally substituted (meth) acrylamide.
  14. The (meth) acrylate copolymer according to claim 12 or 13, wherein the optionally substituted (meth) acrylamide is selected from (meth) acrylamide, hydroxyl (meth) acrylamide, and C1-C10 alkyl (meth) acrylamide.
  15. A thermally curable composition, comprising a thermally curable resin and the (meth) acrylate copolymer according to any of claims 1 to 14.
  16. The thermally curable composition according to claim 15, wherein the thermally curable resin is selected from epoxy resins, cyanurate resins, bismaleimide resins, polyimide resins, phenolic resins, furan resins, xylene formaldehyde resins, ketone formaldehyde resins, urea resins, melamine resins, aniline resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, triallyl cyanurate resins, triazine resins, polyurethane resins, silicone resins and mixture thereof.
  17. The thermally curable composition according to claim 15 to 16, further comprising a reactive diluent.
  18. The thermally curable composition according to any of claims 15 to 17, further comprising a curing agent.
  19. The thermally curable composition according to claim 18, having a complex viscosity of no less than 10 Pa·sat 50℃.
  20. The thermally curable composition according to claim 18 or 19, having a complex viscosity of no less than 10 Pa·sat 70℃.
  21. The thermally curable composition according to any of claims 19 to 21, wherein the largest drop of complex viscosity of the thermally curable composition in the range of  50℃ to 70℃ is no larger than 55％, and preferably is no larger than 50％.
  22. Cured product of the thermally curable composition according to any of claims 16 to 22.
  23. Use of the (meth) acrylate copolymer according to any one of claims 1 to 15 in thermally curable adhesive or sealant.
PCT/CN2017/107807 2017-10-26 2017-10-26 (meth)acrylate copolymer for thermally curable composition Ceased WO2019080045A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107807 WO2019080045A1 (en) 2017-10-26 2017-10-26 (meth)acrylate copolymer for thermally curable composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107807 WO2019080045A1 (en) 2017-10-26 2017-10-26 (meth)acrylate copolymer for thermally curable composition

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WO2019080045A1 true WO2019080045A1 (en) 2019-05-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115667418A (en) * 2020-05-19 2023-01-31 毕克化学有限公司 Thermosetting polymer powder

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02145669A (en) * 1988-11-25 1990-06-05 Kansai Paint Co Ltd Pasting film and film-forming process
JP2013001847A (en) * 2011-06-17 2013-01-07 Hitachi Chemical Co Ltd Laminated sheet for semiconductor, method for manufacturing semiconductor chip with adhesive layer, and method for manufacturing semiconductor device
CN106674394A (en) * 2016-12-30 2017-05-17 北京化工大学 Initiation system for photo-polymerization of active free radicals of methacrylate monomers
CN106883794A (en) * 2017-02-24 2017-06-23 上海昭和高分子有限公司 A kind of one-component peelable type aqueous adhesive and its bonding sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02145669A (en) * 1988-11-25 1990-06-05 Kansai Paint Co Ltd Pasting film and film-forming process
JP2013001847A (en) * 2011-06-17 2013-01-07 Hitachi Chemical Co Ltd Laminated sheet for semiconductor, method for manufacturing semiconductor chip with adhesive layer, and method for manufacturing semiconductor device
CN106674394A (en) * 2016-12-30 2017-05-17 北京化工大学 Initiation system for photo-polymerization of active free radicals of methacrylate monomers
CN106883794A (en) * 2017-02-24 2017-06-23 上海昭和高分子有限公司 A kind of one-component peelable type aqueous adhesive and its bonding sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115667418A (en) * 2020-05-19 2023-01-31 毕克化学有限公司 Thermosetting polymer powder
CN115667418B (en) * 2020-05-19 2024-07-12 毕克化学有限公司 Thermosetting polymer powder

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