WO2019124712A1 - Composition d'adhésif à base d'époxy à un seul composant et article utilisant celle-ci - Google Patents

Composition d'adhésif à base d'époxy à un seul composant et article utilisant celle-ci Download PDF

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Publication number
WO2019124712A1
WO2019124712A1 PCT/KR2018/012593 KR2018012593W WO2019124712A1 WO 2019124712 A1 WO2019124712 A1 WO 2019124712A1 KR 2018012593 W KR2018012593 W KR 2018012593W WO 2019124712 A1 WO2019124712 A1 WO 2019124712A1
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Prior art keywords
epoxy
weight
adhesive composition
resin
parts
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PCT/KR2018/012593
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English (en)
Korean (ko)
Inventor
박주경
김정택
장성일
신동우
박상언
배민관
Original Assignee
주식회사 동성화학
주식회사 성우하이텍
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Priority claimed from KR1020180040191A external-priority patent/KR102122762B1/ko
Application filed by 주식회사 동성화학, 주식회사 성우하이텍 filed Critical 주식회사 동성화학
Publication of WO2019124712A1 publication Critical patent/WO2019124712A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • 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

Definitions

  • the present invention relates to an adhesive composition
  • an adhesive composition comprising a phenoxy resin, an epoxy amphipathic block copolymer and at least three toughening agents including a urethane resin to improve the brittleness of the epoxy adhesive to provide excellent impact properties at a low temperature and a high temperature Based epoxy adhesive composition and an article using the same.
  • Epoxy-based adhesives specifically epoxy-based structural adhesives for adhesion of automotive structures, are used for multiple bonds, including metal-to-metal bonds in frames and other structures of automobiles.
  • This type of adhesive is referred to as "impact resisting adhesive” or “CDA” since these adhesives must resist strongly against breakage in the event of a vehicle collision.
  • epoxy adhesives are generally combined with a variety of rubbers and / or "toughening agents ".
  • These toughening agents have blocking functional groups that can be released from the blocking under cure reaction conditions to react with the epoxy resin.
  • Such toughening agents are described in U.S. Patent Nos. 5,202,390, 5,278,257, WO 2005/118734, U.S. Patent Publication No. 2005/0070634, U.S. Patent Application Publication No. 2005/0209401, U.S. Patent Application Publication No. 2006/0276601, EP-A-0 308664, EP-A 1728825, EP-A 1896517, EP-A 1916269, EP-A 1916270, EP-A 1916272 and EP-A-1916285.
  • the groups showing excellent physical properties are those in which a blocked urethane resin containing phenol, polyphenol, and aminophenol is used as a toughening agent.
  • a blocked urethane resin containing phenol, polyphenol, and aminophenol is used as a toughening agent.
  • Such an adhesive containing a urethane-based toughening agent exhibits excellent impact peel strength at a low temperature, but has a problem that the impact peel strength remarkably deteriorates at a high temperature due to the inherent characteristics of the urethane.
  • the present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide a thermoplastic resin composition which is excellent in impact resistance at low temperature as well as at low temperature by mixing at least three toughening agents comprising a phenoxy resin, an epoxy amphiphilic block copolymer and a urethane resin. Which can exhibit peel strength and at the same time provide physical properties (shear strength, T peel strength, and impact peel strength) required as a structural adhesive.
  • the present invention also provides an adhesive composition for one-
  • the present invention provides an epoxy resin composition comprising an epoxy resin, at least three toughening agents, and a curing agent, wherein the at least three toughening agents are phenoxy resin; An epoxy amphiphilic block copolymer containing an epoxy affinity block and an epoxy non-affinity block; And a urethane resin having an isocyanate group capped at least at one terminal end thereof.
  • the content ratio of the phenoxy resin, the epoxy amphiphilic block copolymer and the urethane resin may be 1: 0.7 to 2: 1 to 5 by weight.
  • the phenoxy resin may be a resin formed by reacting bisphenol A with epichlorohydrin.
  • the phenoxy resin has a weight average molecular weight (Mw) of 30,000 to 70,000 g / mol, a glass transition temperature (Tg) of 80 to 100 ° C, 200 to 400 g / eq.
  • the epoxy amphiphilic block copolymer includes an epoxy affinity block (A) containing at least one selected from the group consisting of an acrylonitrile-based polymer, an ethylene oxide polymer and a propylene oxide polymer; And an epoxy non-affinity block (B) containing an alkylene polymer, and can form a micelle in the epoxy resin.
  • A an epoxy affinity block
  • B an epoxy non-affinity block
  • the epoxy amphiphilic block copolymer has a weight average molecular weight (Mw) of 3,000 to 10,000 g / mol, and may be a multi-block copolymer of two or more.
  • the urethane resin comprises at least one segment selected from the group consisting of polyether, polybutadiene and polyester, and a prepolymer having an isocyanate group capped with either phenol or polyphenol or a prepolymer.
  • the urethane resin may have a weight average molecular weight (Mw) of 8,000 to 40,000 g / mol and a viscosity of 440 to 1280 Pa ⁇ s (40 ° C).
  • the curing agent may have a curing initiation temperature of 80 ° C or higher.
  • the one-pack type epoxy adhesive composition may further include at least one of a curing accelerator, a moisture removing agent and a filler.
  • the adhesive composition comprises, based on 100 parts by weight of the adhesive composition, 40 to 70 parts by weight of an epoxy resin; 3 to 15 parts by weight of a phenoxy resin; 3 to 13 parts by weight of an epoxy amphiphilic block copolymer; 5 to 30 parts by weight of a urethane resin; 1.5 to 15 parts by weight of a curing agent; 0.1 to 4 parts by weight of a curing accelerator; 0.5 to 10 parts by weight of a moisture removing agent; And 2 to 25 parts by weight of a filler.
  • the present invention also relates to a semiconductor device comprising: a first member; A second member adhered to the first member; And an adhesive layer disposed between the first member and the second member and having the above-mentioned one-pack type epoxy adhesive composition cured.
  • the first member and the second member may be the same or different from each other, and each of the first member and the second member may be a metal, a steel plate, a wood, a film, a tile, a plastic, a glass, a resin, a ceramic, , Fibers, and composites thereof.
  • one of the first member and the second member is an aluminum (Al) or aluminum alloy based member, and the other is a metal member which is the same as or different from the first base member have.
  • the article may satisfy the following properties (i) to (iii) when measured according to ISO 11343: (i) -40 ° C impact peel strength of 20 N / mm or more (Ii) the impact peel strength at 20 ° C is 30 N / mm or more, and (iii) the impact peel strength at 80 ° C is 30 N / mm or more.
  • the one-part epoxy-based structural adhesive composition according to the present invention can maintain good physical properties such as impact peel strength, workability, adhesive strength, shear strength and T peel strength in a wide temperature range of -40 ° C to 80 ° C .
  • the epoxy adhesive of the present invention can be usefully applied to fasten component materials of the same kind or dissimilar in a wide range of industrial fields including automobile, aircraft, ship, space, civil engineering, and architectural fields.
  • Structural adhesives are materials used for adhesive boding at least two structural components making up a structure. Such a structural adhesive has superior power distribution, high working speed, and high economy as compared with conventional mechanical fastening techniques such as riveting or welding. Particularly, in the transportation industry such as automobile, airplane or ship, it is advantageous to use a structural adhesive rather than a mechanical fastening technique to reduce weight.
  • structural adhesives applied to the automotive field require performance that is resistant to impact and cracking in the event of an accident such as a vehicle collision.
  • properties such as workability, adhesive strength, impact peel strength and the like should be kept excellent even in a temperature range (-40 ° C to 80 ° C) which is wider than the temperature that can be commonly experienced.
  • Conventional epoxy based automotive structural adhesives have relatively high static strength (i.e., high tensile strength and high adhesive shear strength), while they exhibit poor dynamic strength (i.e., low impact peel strength) It is added as an essential component of the adhesive.
  • the toughening agent is included, it is difficult to continuously realize excellent impact characteristics in a wide temperature range (-40 to 80 ° C) only at a specific temperature, which can show local impact properties.
  • an object of the present invention to provide an epoxy-based structural adhesive capable of continuously realizing excellent impact properties not only at a low temperature but also at a high temperature.
  • the present invention at least three kinds of toughening agents including a phenoxy resin and an epoxy amphipathic block copolymer are mixed and controlled at an optimum ratio, together with a urethane resin that realizes excellent impact properties at a low temperature. It has been found that when the above-mentioned three kinds of toughening agents are used in combination, superior shock characteristics can be realized in a wider temperature range than when they are used singly.
  • the present invention can compensate for the brittleness of the epoxy-based structural adhesive by adjusting the mixing ratio of the three kinds of toughening agents and the other components to optimize the content thereof. As a result, The physical properties (shear strength, T peel strength and impact peel strength) can be continuously expressed. Accordingly, the epoxy adhesive composition of the present invention can be usefully applied as a structural adhesive in a process of fastening parts of the same or different materials in a wide range of industrial fields including aircraft, ship, space, civil engineering, have.
  • the one-pack type epoxy adhesive composition of the present invention is a structural adhesive capable of forming a structure, specifically containing an epoxy resin, at least three toughening agents and a curing agent in an optimum ratio, An epoxy amphiphilic block copolymer and a urethane resin. If necessary, it may further contain an inorganic filler, a moisture removing agent, a curing accelerator, and at least one additive commonly used in the art.
  • composition of the one-part epoxy-based adhesive composition will be specifically described.
  • the one-pack epoxy-based adhesive composition according to the present invention uses an epoxy resin which is usually used in the field of structural adhesives as a main resin.
  • an epoxy resin is an epoxy compound (monomer), an oligomer or a polymer containing at least one epoxy group in the molecule, preferably at least two epoxy groups, and an epoxy group formed by a ring-opening reaction of the epoxy group Polymers or oligomers, and the like.
  • Examples of usable epoxy resins include, but are not limited to, bisphenol epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, phenol novolac epoxy resin, cresol epoxy resin, aliphatic epoxy resin, Family epoxy resins, polyaromatic epoxy resins, and epoxidized oil-based epoxy resins.
  • the epoxy resin examples include bisphenol A type epoxy resin, alicyclic epoxy resin, cresol novolak type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, Bisphenol A novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol novolak type epoxy resin, (C) an aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, a triphenyl methane type epoxy resin, a tetraphenyl ethane type epoxy resin, a dicyclopentadiene type epoxy resin, a dicyclopentadiene type epoxy resin, Diene type epoxy resin, dicyclopentadiene phenol addition reaction type epoxy resin, Aralkyl type epoxy resin, there are, a polyfunctional phenol resin, naphthol aralkyl type
  • the content of the epoxy resin is not particularly limited and may be, for example, 40 to 70 parts by weight, preferably 45 to 65 parts by weight, based on 100 parts by weight of the total weight of the epoxy adhesive composition, More preferably 45 to 60 parts by weight.
  • the content of the epoxy resin falls within the above range, it can exhibit excellent shear adhesive strength and static strength such as tensile strength.
  • the one-pack type epoxy adhesive composition according to the present invention is a mixture of at least three toughening agents, one of which is a phenoxy resin.
  • a phenoxy resin is a thermoplastic polymer having a phenolic functional group at its terminal.
  • the inclusion of a phenoxy resin can solve the problem of tackiness and brittleness at room temperature.
  • phenoxy resin those known in the art can be used without limitation.
  • examples of the skeleton of the phenoxy resin include bisphenol A type, bisphenol A / F type, bisphenol F type, bisphenol S type, bisphenol A / S type, cardo-skeleton type and the like .
  • the phenoxy resin may be a bisphenol A phenoxy resin obtained by reacting bisphenol A with epichlorohydrin.
  • a bisphenol A type phenoxy resin has a structure similar to that of an epoxy resin, and thus has high compatibility, low melt viscosity, and excellent adhesion.
  • the phenoxy resin is a polyether series polymer not containing an epoxide and can be modified by a crosslinking reaction with a compound such as an isocyanate and an amine including a hydroxyl group as a functional group.
  • the phenoxy resin may have a weight average molecular weight (Mw) of 30,000 to 70,000 g / mol, and preferably 40,000 to 70,000 g / mol.
  • Mw weight average molecular weight
  • the phenoxy resin preferably has a glass transition temperature (Tg) of 80 to 100 DEG C and a hydroxyl group (OH) equivalent of 200 to 400 g / eq. Lt; / RTI > When the glass transition temperature (Tg) of the phenoxy resin is 80 to 100 ° C, it can exhibit an effect of enhancing the adhesive strength, the softening agent and the chemical resistance.
  • the content of the phenoxy resin is not particularly limited and may be, for example, 3 to 15 parts by weight, preferably 5 to 10 parts by weight per 100 parts by weight of the total weight (for example, 100 parts by weight) . If the content of the phenoxy resin is less than 3 parts by weight, the toughening effect may be significantly deteriorated. If the content of the phenoxy resin exceeds 15 parts by weight, the viscosity may become very high.
  • an epoxy amphiphilic block copolymer is applied as a toughening agent.
  • the epoxy amphiphilic block copolymer is a surfactant material comprising an epoxyphilic block and an epoxy non-epoxyphobic block.
  • the epoxy-amphiphilic block copolymer spontaneously forms a micelle in the epoxy resin by an epoxy affinity block and an epoxy non-affinity block.
  • the epoxy non-affinity block composed of a flexible chain forms a core ) Is formed so that shock absorption is possible without lowering the glass transition temperature (Tg).
  • the epoxy amphiphilic block copolymer includes an epoxy affinity block (A) containing at least one selected from the group consisting of an acrylonitrile-based polymer, an ethylene oxide polymer, and a propylene oxide polymer; And an epoxy-incompatible block (B) containing an alkylene polymer.
  • the epoxy noncurable block may include polyethylene propylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polyalkylmethylmethacrylate, polyethylhexylmethacrylate, or combinations thereof.
  • the form of the epoxy-amphiphilic block copolymer is not particularly limited, and may be, for example, a multi-block copolymer of two or more.
  • the size and shape of the micelle formed by the epoxy-amphiphilic block copolymer are not particularly limited, and may be, for example, nanoscale spherical or worm-like.
  • the epoxy-amphiphilic block copolymer may have a weight average molecular weight (Mw) of 3,000 to 10,000 g / mol, and preferably 5,000 to 9,000 g / mol.
  • the content of the epoxy amphiphilic block copolymer is not particularly limited and may be, for example, 3 to 13 parts by weight based on the total weight (for example, 100 parts by weight) of the epoxy adhesive composition, 10 parts by weight. If the amount of the epoxy-amphiphilic block copolymer is less than 3 parts by weight, micelle formation is insignificant and the toughening effect is hardly obtained. If the amount is more than 13 parts by weight, the toughening effect may be reduced.
  • the urethane resin is a toughening agent used for realizing excellent impact properties at a low temperature.
  • the urethane resin is a urethane resin well known in the art and can be used without limitation as long as it has an isocyanate group capping at one end.
  • capped or blocked means that the blocking agent is bound to the end of the polymer chain such that the coupled end is no longer reactive group, ie, the capping compound is monofunctional.
  • the urethane resin may be a liquid type having a capped isocyanate group or a polymer having a low melting point.
  • the capped isocyanate group is reacted with a compound (e.g., a blocking agent) having at least one functional group capable of reversibly reacting with an isocyanate group to form a blocking moiety.
  • a compound e.g., a blocking agent
  • the compound capable of forming the blocking group is not particularly limited, and may be, for example, any one of phenol and polyphenol.
  • the urethane resin according to the present invention may be a prepolymer comprising an isocyanate reactive segment and an epoxy group non-reactive blocking segment.
  • the isocyanate-reactive segment may include at least one selected from the group consisting of polyether, polybutadiene and polyester having a weight average molecular weight (Mw) of 300 to 3,000.
  • the epoxy-non-reactive segments may also include an isocyanate group capped with at least one of phenol and polyphenol as a blocking agent that is not reactive with the epoxy group. These epoxy-non-reactive segments are located at least at one end of the urethane resin.
  • the urethane resin may have a weight average molecular weight (Mw) of 8,000 to 40,000 g / mol and a viscosity of 440 to 1280 Pa ⁇ s at 40 ° C.
  • the content of the urethane resin is not particularly limited and may be, for example, 5 to 30 parts by weight, preferably 10 to 25 parts by weight per 100 parts by weight of the total weight of the epoxy adhesive composition have. If the content of the urethane resin is less than 5 parts by weight, the effect of low temperature impact strength is insignificant and the effect of toughening is little. If the content of the urethane resin is more than 30 parts by weight, the toughening effect may be reduced.
  • the content ratio of the phenoxy resin, the epoxy amphiphilic block copolymer and the urethane resin mixed together as a toughening agent may be 1: 0.7 to 2: 1 to 5: 1, preferably 1: 0.8 to 1.5: 2 To 4 weight ratio.
  • the total content of the toughening agent comprising a phenoxy resin, an epoxy amphiphilic block copolymer and a urethane resin may be 20 to 50 parts by weight based on the total weight (for example, 100 parts by weight) of the epoxy adhesive composition, 20 to 45 parts by weight, more preferably 25 to 40 parts by weight.
  • the curing agent is a component which reacts with the epoxy resin as the main resin and proceeds the curing of the composition.
  • the curing agent a conventional curing agent known in the art can be used without limitation.
  • the curing agent is reactive with an epoxy resin and has a curing initiation temperature of 80 ° C or higher.
  • a curing initiating temperature Preferably a curing initiating temperature of 120 ° C or higher, more preferably 140 ° C or higher.
  • the curing agent rapidly cures upon heating above the cure initiation temperature, but it is appropriate to use, alone or in combination, any catalyst (s) that allow the cure to occur very slowly at room temperature (about 22 ° C) and at temperatures up to at least 50 ° C.
  • the curing agent is a nitrogen-containing compound (e.g., an amine and a derivative thereof); Oxygen-containing compounds (e.g., carboxylic acid-terminated polyesters), anhydrides, phenol-formaldehyde resins, amino-formaldehyde resins, phenol, bisphenol A and cresol novolak, phenol-terminated epoxy resins; Sulfur-containing compounds (e.g., polysulfides, polymercaptans); (E.g., tertiary amine, Lewis acid, Lewis base) or a combination thereof may be used.
  • Oxygen-containing compounds e.g., carboxylic acid-terminated polyesters
  • anhydrides phenol-formaldehyde resins, amino-formaldehyde resins, phenol, bisphenol A and cresol novolak, phenol-terminated epoxy resins
  • Sulfur-containing compounds e.g., polysulfides, polymercaptans
  • Lewis acid Lewis base
  • Non-limiting examples of usable curing agents include boron trichloride / amine and boron trifluoride / amine complexes, dicyanamide, melamine, diallyl melamine; Guanylamines such as acetoguanamine and benzoguanamine; Aminotriazole such as 3-amino-1,2,4-triazole; Hydrazides such as adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide, cyanoacetamide and the like; And aromatic polyamines such as diaminodiphenylsulfone.
  • the above-mentioned components may be used alone, or two or more of them may be used in combination.
  • the curing agent may be used in an amount sufficient to cure the epoxy-based adhesive composition. Generally, the amount that can dissipate at least 80% of the epoxy groups present in the adhesive composition is controlled and used, and an excess amount than the amount required to consume all the epoxy groups is unnecessary.
  • the content of the curing agent may be, for example, from 1.5 to 15 parts by weight, preferably from 2.5 to 10 parts by weight, more preferably from 3 to 10 parts by weight, based on 100 parts by weight of the epoxy- To 8 parts by weight.
  • the one-pack type epoxy adhesive composition according to the present invention may further contain a curing accelerator known in the art as needed.
  • the curing accelerator is a thermally activatable catalyst, and solid or liquid tertiary amine compounds having a boiling point of 130 ° C or higher can be used without limitation.
  • a urea-based compound for example, a urea-based compound; Aminophenol; And various aliphatic urea compounds such as C 1 -C 12 alkylene imidazole or N-arylimidazole.
  • Non-limiting examples of available curing accelerators include p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3,4-dichlorophenyl- Methyl urea, N- (3-chloro-4-methylphenyl) -N ', N'-dimethylurea, benzyldimethylamine; 2,4,6-tris (dimethylaminomethyl) phenol, piperidine, 2-ethyl-2-methylimidazole, N-butylimidazole, and 6-caprolactam.
  • it may be an aminophenol compound such as 2,4,6-tris (dimethylaminomethyl) phenol.
  • the above-mentioned components may be used alone or in combination of two or more.
  • the curing accelerator may be mixed with at least one or more other catalysts, preferably a heat-activatable catalyst.
  • Such miscible catalysts may include the various amine compounds described above, which are blocked with a blocking group different from the novolak resin, and specific examples include blocked 1- (2- (2-hydroxylbenzamino) ethyl) - 2- (2-hydroxylphenyl-2-imidazoline).
  • the content of the curing accelerator (for example, a thermally activatable catalyst) is not particularly limited and may be, for example, 0.1 to 4 parts by weight based on the total weight (for example, 100 parts by weight) of the epoxy- Preferably 0.5 to 1.5 parts by weight, more preferably 0.5 to 1.0 part by weight.
  • the one-part epoxy-based adhesive composition according to the present invention may further contain fillers known in the art as needed.
  • the filler is not particularly limited as long as it does not react with other components contained in the epoxy-based adhesive composition.
  • Examples of the filler include inorganic fillers, organic fillers, and complex forms thereof.
  • the filler may be selected from the group consisting of a function of preferably improving the rheology of the adhesive, a function of reducing the total cost per unit weight, a function of absorbing moisture or oil from the adhesive or from the substrate to which it is applied, and / And the like, and the like.
  • Non-limiting examples of fillers that can be used include calcium carbonate, talc, carbon black, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, inorganic silicates, mica, powdered quartz, hydrated aluminum oxide, Silica, alumina, aluminum nitride, boron nitride, talc, carbon, polyurea compounds, polyamide compounds or metal powders, and the like.
  • the above-mentioned components may be used alone or in combination of two or more.
  • the metal powder may include at least one of, for example, aluminum powder or iron powder.
  • the average particle diameter of the filler is not particularly limited and may be appropriately adjusted within a range known in the art. In one example, the average particle size of the inorganic filler may range from 1 to 100 mu m.
  • the shape of the inorganic filler is not particularly limited, and may be, for example, spherical, angular, plate-like, acicular or amorphous.
  • the content of the filler is not particularly limited and may be, for example, 2 to 25 parts by weight, specifically 5 to 20 parts by weight, based on 100 parts by weight of the epoxy adhesive composition.
  • the one-pack type epoxy adhesive composition according to the present invention may further comprise a moisture removing agent known in the art as needed.
  • the moisture removing agent is a substance that physically or chemically bonds with free water present in the thermosetting structural adhesive composition, and specifically does not release binding water until it is heated to a temperature of 160 ⁇ or higher, preferably 200 ⁇ or higher
  • the water content can be reduced.
  • the presence of the moisture removing agent can be confirmed by significantly extending the opening time of the epoxy-based structural adhesive at a temperature lower than 80 ⁇ .
  • Non-limiting examples of usable moisture scavengers include calcium oxide, magnesium oxide, phosphorus pentoxide, various molecular sieves, or mixtures thereof.
  • calcium oxide, and such calcium oxide may be provided in the form of fine particles, specifically, less than 100 mu m in diameter.
  • the content of the moisture removing agent is not particularly limited and may be, for example, 0.5 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the total weight of the epoxy adhesive composition have.
  • the one-part epoxy-based adhesive composition of the present invention may optionally further contain additives conventionally used in the art within the range not detracting from the inherent characteristics of the composition.
  • Non-limiting examples of usable additives include rheology modifiers, rheology modifiers, pigments, dyes, diluents, plasticizers, extenders, flame retardants, thixotropic agents, swelling agents, flow control agents, adhesion promoters, thermoplastic powders, core- Rubber, dimerized fatty acids, antioxidants, or combinations thereof.
  • the content of each of the additives may be appropriately added within a range of contents known in the art, and may be 0.1 to 5 parts by weight based on the total weight (for example, 100 parts by weight) of the epoxy adhesive composition .
  • the total content of the additive may be 0.1 to 25 parts by weight based on the total weight of the epoxy adhesive composition, but is not particularly limited thereto.
  • a conventional flame retardant may be included in the art to further improve the flame retardancy.
  • usable flame retardants include metal hydroxides (e.g., alumina trihydrate), phosphorus and nitrogen containing organic compounds (such as resorcinol diphosphate, phosphate, phenoxyphosphazene, Melamine or melamine derivatives [e.g., melamine cyanurate, phenolic melamine resin], zinc borate, or mixtures thereof.
  • metal hydroxides include hydroxides of metals selected from magnesium, calcium, strontium, barium, boron, aluminum and gallium.
  • the rate and selectivity of curing can be controlled by incorporating a monomeric or oligomeric addition-polymerizable ethylenically unsaturated material into the structural adhesive.
  • the ethylenically unsaturated material preferably has a molecular weight of less than about 1500.
  • examples of such ethylenically unsaturated materials may be acrylate or methacrylate compounds, unsaturated polyesters, vinyl ester resins, or epoxy adducts of unsaturated polyester resins, and the like.
  • the structural adhesive composition of the present invention comprises a free radical initiator which is a free radical initiator to polymerize the ethylenically unsaturated material.
  • the incorporation of such an ethylenically unsaturated material can be achieved by the selective polymerization of ethylenically unsaturated groups, Thereby providing the possibility of performing partial curing.
  • the swelling agent includes both physical and chemical type materials known in the art.
  • the adhesive may also contain a thermoplastic powder, for example polyvinyl butyral or polyester polyol.
  • the diluting agent may be a miscible solvent used in the adhesive composition of the present invention.
  • examples thereof include ketones, ethers, acetates, aromatic hydrocarbons, cyclohexanone, dimethylformamide, glycol ethers, or combinations thereof.
  • the one-pack type epoxy adhesive composition of the present invention constituted as described above can be applied to all applications in which an epoxy adhesive is used.
  • the one-component epoxy adhesive composition can be used for a structural adhesive to form a structure by adhering and bonding at least two components to be fastened .
  • it is preferably used to manufacture structures for the electronics, construction, aircraft and automotive industries, and is made of various materials including wood, metal, coated metal, aluminum, various plastics and filled plastic substrates, For example.
  • the one-part epoxy adhesive composition of the present invention can continuously maintain the overall requirement of the structural adhesive for automobiles in the temperature range of -40 DEG C to 80 DEG C, so that the adhesion of the automobile parts to each other, And can be usefully applied as structural adhesives in the automotive field.
  • the present invention also provides articles, preferably articles in the automotive field, having a cured adhesive layer using the one-part epoxy-based adhesive composition described above.
  • the article comprises: a first member; A second member adhered to the first member; And an adhesive layer disposed between the first member and the second member, the adhesive layer being formed from the one-part epoxy-based adhesive composition described above.
  • the first member and the second member are not particularly limited as long as they are joined by the adhesive layer and can be fastened, and they may be the same or different from each other.
  • the first member and the second member may be selected from the group consisting of a metal, a steel sheet, a wood, a film, a tile, a plastic, a glass, a resin, a ceramic, a concrete, a carbonaceous material, .
  • it may be a component material of the automobile field, and may specifically be steel, coated steel, galvanized steel, aluminum, coated aluminum, plastic, filled plastic material, or composite material.
  • the one-part epoxy adhesive according to the present invention is preferably used as a structural adhesive for bonding the same or different automotive frame components.
  • the first member and the second member may each be a general metal material, plastic material, and / or composite frame material used in the automotive field.
  • metal materials may be conventional metals used for automobile materials, household appliances, building materials, and industrial applications, and examples thereof include cold rolled steel (CR), zinc hot dip steel (GI), electro- ), Alloy-plate steel (GA), copper sheet or tin-plate steel, hot-dip galvanized steel sheet, galvannealed galvanized steel sheet, electrogalvanized steel sheet, molten aluminum- Plated metal or aluminum plate. More specifically, it may be cold-rolled steel, galvanized metal or aluminum.
  • one of the first member and the second member is an aluminum (Al) or aluminum alloy-based member, and the other is a metal member which is the same as or different from the first member have.
  • both the first member and the second member may be aluminum (Al) or an aluminum alloy based material.
  • aluminum means pure aluminum metal or any alloy containing 80 wt% or more of aluminum.
  • the article according to the present invention can be produced by a conventional method known in the art, except that the above-mentioned one-pack type epoxy adhesive composition is used.
  • the epoxy-based adhesive composition may be applied to at least one of the first member and the second member, and then the adhesive may be cured to form and bond the adhesive layer.
  • the method of applying the epoxy adhesive composition is not particularly limited as long as it is a method known in the art.
  • powder-coating or spray-coating may be applied.
  • the epoxy adhesive composition of the present invention can be applied according to any technique known in the art, and can be applied cold or warm as required.
  • it can be applied by extruding from a robot in the form of a bead onto a substrate, and mechanical application means such as a caulking gun or any other application means can be applied. It may also be applied by using a jet injection method, for example a streaming method or a swirl method.
  • the epoxy-based adhesive composition may be applied to one or both of the first member and the second member, and the adhesive is disposed between the first member and the second member.
  • the epoxy-based adhesive composition can be cured by heating to a temperature not lower than the curing initiation temperature of the curing agent.
  • the heating conditions are not particularly limited and may be appropriately changed depending on conditions such as the width and thickness of the first and second members to be used, the process line speed, and the like.
  • the curing initiation temperature may be about 80 ° C to 220 ° C, preferably about 140 ° C to 180 ° C, more preferably 150 to 170 ° C.
  • the curing process described above can use a heat source, a radiation source, or a combination of energy sources known in the art.
  • the adhesive layer (for example, structural bonding portion) is formed between the first member and the second member in a state of being in contact with them.
  • the first member and the second member may constitute at least part of the automobile frame assembly.
  • the first and second members may be coated by a coating that requires calcination curing, and the structural adhesive may be cured simultaneously with the calcination cure of the coating described above. Further, the first member (aluminum member) and the second member (metal member) may be welded before the epoxy-based structural adhesive is cured.
  • the article can satisfy the following properties (i) to (iii) when measured according to ISO 11343 standard.
  • the impact peel strength at -40 ⁇ ⁇ is 20 N / mm or more
  • the impact peel strength at 20 ⁇ ⁇ is 30 N / mm or more
  • the impact peel strength at 80 ⁇ ⁇ is 30 N / mm or more. It can also exhibit excellent shear strength and T-peel strength.
  • Example 1 a one part epoxy adhesive composition of Example 1 was prepared by adding 4.8 wt% of a curing agent and 0.7 wt% of a heat-activatable catalyst and stirring in vacuum for 30 minutes.
  • Table 2 the usage unit of each composition is% by weight.
  • a one-pack type epoxy adhesive composition of Example 2 was prepared in the same manner as in Example 1, except that each component was blended according to the composition shown in Table 2 below.
  • a one-pack type epoxy adhesive composition of Comparative Examples 1 to 3 was prepared in the same manner as in Example 1, except that each component was blended according to the composition shown in Table 2 above.
  • the shear strength test was carried out after decontamination of cold rolled steel sheet (CR) of 100 mm ⁇ 25 mm ⁇ 1.6 T size with ethanol. A 12.5 mm adhesive was applied to one side of the steel sheet and a small amount of microbeads was used to maintain a constant adhesive thickness thereon. The other specimens were covered and fixed, and then cured at 180 ° C for 20 minutes. After curing, the specimens cooled to 23 ° C were measured for shear strength using a universal material tester. At this time, the test conditions were such that a load was applied in the direction of 180 ° at a pulling rate of 5 mm / min.
  • the impact peel strength test was conducted according to ISO 11343 standard.
  • the size of the test piece was 90 mm ⁇ 20 mm ⁇ 1.6 T, and the size of one side to which the adhesive was applied was 30 ⁇ 20 mm.
  • One side of the test piece was coated with an adhesive after removing contaminants using ethanol.
  • the thickness of the adhesive was kept constant by using microbeads, other specimens were placed on top of it, fixed, and cured at 180 ° C for 20 minutes. After curing, the specimens were stabilized at each test temperature for more than 1 hour, and then the shear strength was measured using an impact strength tester conforming to ISO 11343. At this time, the load was applied at a speed of 2 m / sec.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition d'adhésif à base d'époxy à un seul composant qui permet la compensation de la fragilité d'un adhésif à base d'époxy au moyen de l'utilisation conjointe d'au moins trois agents de renforcement comprenant une résine phénoxy, un copolymère séquencé amphiphile époxy et une résine d'uréthane. La présente invention permet d'obtenir d'excellentes propriétés au choc à une température élevée ainsi qu'à une basse température au moyen de l'application de l'adhésif à base d'époxy susmentionné en tant qu'adhésif structural et, plus particulièrement, en tant qu'adhésif structural pour un véhicule.
PCT/KR2018/012593 2017-12-21 2018-10-24 Composition d'adhésif à base d'époxy à un seul composant et article utilisant celle-ci WO2019124712A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170177235 2017-12-21
KR10-2017-0177235 2017-12-21
KR1020180040191A KR102122762B1 (ko) 2017-12-21 2018-04-06 1액형 에폭시계 접착제 조성물 및 이를 이용한 물품
KR10-2018-0040191 2018-04-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113667436A (zh) * 2021-08-03 2021-11-19 海程新材料科技有限公司 一种单组分高韧性耐冲击环氧树脂结构胶及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873637A (en) * 1973-02-23 1975-03-25 Sony Corp Adhesive composition containing phenoxy and epoxy resins and a cross-linking agent therefor
KR20100048943A (ko) * 2008-10-31 2010-05-11 시카 테크놀러지 아게 차체 접착제 또는 구조 발포체로서 사용할 수 있는 열경화형 에폭시 수지 조성물
KR101226342B1 (ko) * 2004-11-10 2013-01-24 리전츠 오브 더 유니버시티 오브 미네소타 양친매성 블록 공중합체-강인화된 에폭시 수지
KR20130070609A (ko) * 2010-05-10 2013-06-27 제피로스, 인크. 구조 접착제에서의 개선 또는 구조 접착제와 관련된 개선
KR20140138760A (ko) * 2012-03-23 2014-12-04 다우 글로벌 테크놀로지스 엘엘씨 향상된 응력 내구성을 가진 내충돌성 접착제

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873637A (en) * 1973-02-23 1975-03-25 Sony Corp Adhesive composition containing phenoxy and epoxy resins and a cross-linking agent therefor
KR101226342B1 (ko) * 2004-11-10 2013-01-24 리전츠 오브 더 유니버시티 오브 미네소타 양친매성 블록 공중합체-강인화된 에폭시 수지
KR20100048943A (ko) * 2008-10-31 2010-05-11 시카 테크놀러지 아게 차체 접착제 또는 구조 발포체로서 사용할 수 있는 열경화형 에폭시 수지 조성물
KR20130070609A (ko) * 2010-05-10 2013-06-27 제피로스, 인크. 구조 접착제에서의 개선 또는 구조 접착제와 관련된 개선
KR20140138760A (ko) * 2012-03-23 2014-12-04 다우 글로벌 테크놀로지스 엘엘씨 향상된 응력 내구성을 가진 내충돌성 접착제

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113667436A (zh) * 2021-08-03 2021-11-19 海程新材料科技有限公司 一种单组分高韧性耐冲击环氧树脂结构胶及其制备方法

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