WO2019124712A1 - Single-component epoxy-based adhesive composition and article using same - Google Patents

Single-component epoxy-based adhesive composition and article using same 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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WO
WIPO (PCT)
Prior art keywords
epoxy
weight
adhesive composition
resin
parts
Prior art date
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PCT/KR2018/012593
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French (fr)
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/en
Application filed by 주식회사 동성화학, 주식회사 성우하이텍 filed Critical 주식회사 동성화학
Publication of WO2019124712A1 publication Critical patent/WO2019124712A1/en

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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.

Abstract

The present invention relates to a single-component epoxy-based adhesive composition which enables compensation of brittleness of an epoxy-based adhesive by means of using together at least three toughening agents comprising phenoxy resin, epoxy amphiphilic block copolymer and urethane resin. The present invention enables excellent impact properties at a high temperature as well as a low temperature by applying the aforementioned epoxy-based adhesive as a structural adhesive and, more particularly, as a structural adhesive for a vehicle.

Description

1액형 에폭시계 접착제 조성물 및 이를 이용한 물품One-pack epoxy-based adhesive composition and articles using the same
본 발명은 페녹시 수지, 에폭시 양친성 블록공중합체 및 우레탄 수지를 포함하는 적어도 3종의 강인화제를 혼용(混用)함으로써, 에폭시계 접착제의 취성(脆性)을 보완하여 저온 및 고온에서 우수한 충격 특성을 구현할 수 있는 1액형 에폭시계 구조용 접착제 조성물 및 이를 이용한 물품에 관한 것이다. The present invention relates to 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.
에폭시계 접착제, 구체적으로 자동차 구조체의 접착을 위한 에폭시계 구조용 접착제는 프레임 및 자동차의 다른 구조체에서의 금속-금속 결합을 비롯한 다수의 결합을 위해 사용된다. 이들 접착제는 차량 충돌시 파손에 강력하게 저항해야 하므로, 이러한 유형의 접착제는 "충돌 내구성 접착제" 또는 "CDA"로 불린다.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.
자동차 성능 조건을 충족시키는데 필요한 요구물성들 간의 균형을 달성하기 위하여, 에폭시 접착제는 일반적으로 다양한 고무 및/또는 "강인화제"와 함께 배합된다. 이러한 강인화제는 경화 반응 조건하에서 차단이 해제되어 에폭시 수지와 반응할 수 있는 차단된(blocking) 작용기를 갖는다. 상기 강인화제는, 미국 특허 제 5,202,390 호, 미국 특허 제 5,278,257 호, WO 2005/118734 호, 미국 특허 공개 제 2005/0070634 호, 미국 특허 공개 제 2005/0209401 호, 미국 특허 공개 제 2006/0276601 호, EP-A-0 308664 호, EP-A 1728825 호, EP-A 1896517 호, EP-A 1916269호, EP-A 1916270 호, EP-A 1916272 호 및 EP-A-1916285 호 등에 기재되어 있다.In order to achieve a balance between the required properties required to meet automotive performance conditions, 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.
전술한 선행기술 중에서 우수한 물성을 나타내는 군은 페놀, 폴리페놀, 및 아미노페놀을 포함하는 블록화된 우레탄 수지를 강인화제로 사용한 경우이다. 이러한 우레탄계 강인화제를 함유하는 접착제는 저온에서 매우 우수한 충격 박리강도를 나타내는 반면, 우레탄 고유의 특성으로 인하여 고온에서 충격 박리강도가 현저히 저하되는 문제가 초래된다. Among the above-mentioned prior arts, 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. 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.
이에 따라, 저온 뿐만 아니라 고온에서도 우수한 충격특성을 지속적으로 유지할 수 있는 에폭시계 구조용 접착제의 개발이 절실히 요구되고 있다. Accordingly, it is urgently required to develop an epoxy-based structural adhesive capable of continuously maintaining excellent impact properties not only at a low temperature but also at a high temperature.
본 발명은 전술한 문제점을 해결하기 위해서 안출된 것으로서, 페녹시 수지, 에폭시 양친성 블록공중합체 및 우레탄 수지를 포함하는 적어도 3종의 강인화제를 혼용(混用)함으로써, 저온 뿐만 아니라 고온에서 우수한 충격박리강도를 나타내고, 이와 동시에 구조용 접착제로서 요구되는 물성(전단강도, T 박리강도 및 충격박리강도)을 제공할 수 있는 1액형 에폭시계 구조용 접착제 조성물을 제공하는 것을 목적으로 한다. SUMMARY OF THE INVENTION 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-
상기한 기술적 과제를 달성하고자, 본 발명은 에폭시 수지, 적어도 3종의 강인화제, 및 경화제를 포함하며, 상기 적어도 3종의 강인화제는, 페녹시 수지; 에폭시 친화성 블록과 에폭시 비(非)친화성 블록을 함유하는 에폭시 양친성 블록공중합체; 및 적어도 일측 말단부에 캡핑된 이소시아네이트기를 갖는 우레탄 수지를 포함하는 구조용 접착제 조성물을 제공한다. In order to achieve the above object, 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.
본 발명의 일 구현예에 따르면, 상기 페녹시 수지와 에폭시 양친성 블록 공중합체와 우레탄 수지의 함량비는 1 : 0.7~2 : 1~5 중량비일 수 있다. According to one embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 페녹시 수지는 비스페놀 A와 에피클로로히드린을 반응시켜 형성된 수지일 수 있다. According to one embodiment of the present invention, the phenoxy resin may be a resin formed by reacting bisphenol A with epichlorohydrin.
본 발명의 일 구현예에 따르면, 상기 페녹시 수지는, 중량평균 분자량(Mw)이 30,000 내지 70,000 g/mol이며, 유리전이온도(Tg)가 80 내지 100℃이고, 수산기(OH)가 당량이 200 내지 400 g/eq.일 수 있다. According to an embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 에폭시 양친성 블록공중합체는, 아크릴로니트릴계 고분자, 에틸렌옥사이드 고분자 및 프로필렌 옥사이드 고분자로 구성된 군에서 선택된 적어도 하나를 함유하는 에폭시 친화성 블록(A); 및 알킬렌 고분자를 함유하는 에폭시 비친화성 블록(B)을 포함하며, 에폭시 수지 내에서 마이셀(micelle)을 형성할 수 있다. According to one embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 에폭시 양친성 블록공중합체는 중량평균 분자량(Mw)이 3,000 내지 10,000 g/mol이며, 2중 이상의 다중 블록 공중합체일 수 있다. According to one embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 우레탄 수지는, 폴리에테르, 폴리부타디엔 및 폴리에스테르로 구성된 군에서 선택되는 적어도 하나의 분절(segment)과, 페놀 및 폴리페놀 중 어느 하나로 캡핑된 이소시아네이트기를 갖는 프리폴리머(prepolymer)일 수 있다. According to one embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 우레탄 수지는 중량평균 분자량(Mw)이 8,000 내지 40,000 g/mol이며, 점도가 440 내지 1280 Pa·s (40℃ 기준)일 수 있다. According to an embodiment of the present invention, 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).
본 발명의 일 구현예에 따르면, 상기 경화제는 경화 개시 온도가 80℃ 이상일 수 있다. According to an embodiment of the present invention, the curing agent may have a curing initiation temperature of 80 ° C or higher.
본 발명의 일 구현예에 따르면, 상기 1액형 에폭시계 접착제 조성물은 경화촉진제, 수분 제거제 및 충전제 중 적어도 하나를 더 포함할 수 있다. According to one embodiment of the present invention, the one-pack type epoxy adhesive composition may further include at least one of a curing accelerator, a moisture removing agent and a filler.
본 발명의 일 구현예에 따르면, 상기 접착제 조성물은 당해 접착제 조성물 100 중량부를 기준으로, 에폭시 수지 40 내지 70 중량부; 페녹시 수지 3 내지 15 중량부; 에폭시 양친성 블록공중합체 3 내지 13 중량부; 우레탄 수지 5 내지 30 중량부; 경화제 1.5 내지 15 중량부; 경화촉진제 0.1 내지 4 중량부; 수분제거제 0.5 내지 10 중량부; 및 충전제 2 내지 25 중량부를 포함할 수 있다. According to one embodiment of the present invention, 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.
또한 본 발명은 제1부재; 상기 제1부재와 접착 결합되는 제2부재; 및 상기 제1부재와 제2부재 사이에 배치되고, 전술한 1액형 에폭시계 접착제 조성물을 경화시킨 접착제층을 포함하는 물품을 제공한다. 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.
본 발명의 일 구현예에 따르면, 상기 제1부재와 제2부재는 서로 동일하거나 또는 상이하며, 각각 독립적으로 금속, 강판, 목재, 필름, 타일, 플라스틱, 유리, 수지, 세라믹, 콘크리트, 탄소재, 섬유 및 이들의 복합 소재로 이루어진 군으로부터 선택될 수 있다. According to an embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 제1부재와 제2부재 중 하나는 알루미늄(Al) 또는 알루미늄 합금(alloy)계 부재이며, 다른 하나는 상기 제1기재와 동일하거나 또는 상이한 금속 부재일 수 있다. According to an embodiment of the present invention, 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.
본 발명의 일 구현예에 따르면, 상기 물품은 ISO 11343 규격에 따라 측정시, 하기 (i) 내지 (iii)의 물성을 만족할 수 있다: (i) -40℃ 충격박리강도가 20 N/mm 이상이며, (ii) 20℃ 충격박리강도가 30 N/mm 이상이며, (iii) 80℃ 충격박리강도가 30 N/mm 이상일 수 있다.According to one embodiment of the present invention, 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.
본 발명에 따른 1액형 에폭시계 구조용 접착제 조성물은, -40℃ 내지 80℃의 광범한 온도 범위에서 충격박리강도, 작업성, 접착력, 전단강도, T박리강도 등의 물성이 우수하게 유지될 수 있다. 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 .
이에 따라, 본 발명의 에폭시 접착제는 자동차, 항공기, 선박, 우주, 토목, 건축분야를 비롯한 광범위한 산업 분야에서 동종(同種) 또는 이종(異種)의 부품 소재들을 체결시키는데 유용하게 적용될 수 있다. Accordingly, 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.
이하, 본 발명에 대하여 상세히 설명한다. 그러나 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성요소가 다양하게 변형되거나 또는 선택적으로 혼용될 수 있다. 따라서 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. Hereinafter, the present invention will be described in detail. However, it should be understood that the present invention is not limited to the following embodiments, and that various elements may be variously modified or selectively mixed according to need. Accordingly, it is to be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
구조용 접착제(Structural adhesives)는, 구조물을 구성하는 적어도 2개의 구조적 부품을 서로 접착결합(adhesive boding) 시키는데 사용되는 재료이다. 이러한 구조용 접착제는, 종래 리벳팅 또는 용접 등의 기계적 체결기법에 비해 힘 분배가 우수하고 작업 속도가 빠르며 경제성이 높다. 특히 자동차, 항공기 또는 선박 등의 운송 산업 분야의 경우는 기계적 체결 기법을 이용하는 것보다 구조용 접착제를 사용함으로써 경량화를 기대할 수 있는 장점이 있다.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.
일례로, 자동차 분야에 적용되는 구조용 접착제는, 차량 충돌과 같은 사고 시에 충격에 견디고 균열되지 않는 성능이 요구된다. 또한 통상적으로 경험할 수 있는 온도보다 광범위한 온도 범위(-40℃ 내지 80℃)에서도 작업성, 접착력, 충격박리강도 등의 물성이 우수하게 유지되어야 한다. 종래 에폭시계 자동차 구조용 접착제는 비교적 높은 정적 강도 (즉, 높은 인장 강도 및 높은 접착 전단 강도)를 가지는 반면, 불량한 동적 강도 (즉, 낮은 충격박리강도)를 나타내므로, 이를 보완하기 위한 강인화제가 구조용 접착제의 필수 성분으로 첨가된다. 그러나 강인화제가 포함되더라도 특정 온도에서만 국부적인 충격특성을 나타낼 수 있을 뿐, 광범위한 온도(-40~80℃) 영역에서 우수한 충격특성을 지속적으로 구현하기가 어려웠다. For example, 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. Also, 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. However, even if 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.
이에, 본 발명에서는 저온 뿐만 아니라 고온에서도 우수한 충격 특성을 지속적으로 구현할 수 있는 에폭시계 구조용 접착제를 제공하고자 한다. Accordingly, it is 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.
구체적으로, 본 발명에서는 저온에서 우수한 충격특성을 구현하는 우레탄 수지와 더불어, 페녹시 수지와 에폭시 양친성 블록공중합체를 포함하는 적어도 3종의 강인화제를 혼용하면서 이들을 최적의 비율로 조절한다. 상술한 3종의 강인화제를 혼용할 경우, 이들을 각각 단독으로 사용하는 경우보다 광범위한 온도 영역에서 우수한 충격 특성이 구현할 수 있음을 발견하였다. 또한 전술한 3종의 강인화제와 다른 구성성분의 함량이 최적화된 배합 조절을 통해, 본 발명에서는 에폭시계 구조용 접착제가 갖는 취성을 보완할 수 있으며, 이로 인해 에폭시계 구조용 접착제가 필요로 하는 전반적인 요구물성(전단강도, T 박리강도 및 충격박리강도)을 지속적으로 발현할 수 있다. 이에 따라, 본 발명의 에폭시계 접착제 조성물은 자동차 분야 뿐만 아니라, 항공기, 선박, 우주, 토목, 건축분야를 비롯한 광범위한 산업 분야에서 동종 또는 이종 소재의 부품들을 체결시키는 공정에 구조용 접착제로서 유용하게 적용될 수 있다.Specifically, in 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. In addition, 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.
<1액형 에폭시계 접착제 조성물>&Lt; One-component epoxy-based adhesive composition &
본 발명의 1액형 에폭시계 접착제 조성물은, 구조물을 형성할 수 있는 구조용 접착제로서, 구체적으로 에폭시 수지, 적어도 3종의 강인화제 및 경화제를 최적의 비율로 포함하되, 상기 강인화제로서 페녹시 수지, 에폭시 양친성 블록 공중합체 및 우레탄 수지를 혼용한다. 필요에 따라, 무기충전제, 수분제거제, 경화촉진제 및 당 분야에서 통상적으로 사용되는 적어도 1종의 첨가제를 더 포함할 수 있다. 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.
이하, 상기 1액형 에폭시계 접착제 조성물의 조성을 구체적으로 살펴보면 다음과 같다. Hereinafter, the composition of the one-part epoxy-based adhesive composition will be specifically described.
에폭시 수지Epoxy resin
본 발명에 따른 1액형 에폭시계 접착제 조성물은, 구조용 접착제 분야에 통상적으로 사용되는 에폭시 수지를 주(主) 수지로서 사용한다. 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.
에폭시 수지로는 당 분야에 공지된 통상적인 에폭시 수지를 사용할 수 있다. 본 발명에서, 에폭시 수지는 분자 내 적어도 1개의 에폭시기, 바람직하게는 적어도 2개의 에폭시기를 포함하는 에폭시 화합물(모노머), 올리고머(oligomer) 또는 폴리머(polymer), 및 그 에폭시기의 개환 반응에 의해 생성되는 폴리머 또는 올리고머 등을 모두 포함한다. As the epoxy resin, a conventional epoxy resin known in the art can be used. In the present invention, 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.
사용 가능한 에폭시 수지의 비제한적인 예를 들면, 비스페놀형 에폭시 수지, 글리시딜에스테르계 에폭시 수지, 글리시딜아민계 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸형 에폭시 수지, 지방족 에폭시 수지, 지환족 에폭시 수지, 다방향족 에폭시 수지, 에폭시화 유계 에폭시 수지 등이 있다. 상기 에폭시 수지의 구체적인 일례를 들면, 비스페놀 A형 에폭시 수지, 지환형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 나프탈렌형 에폭시 수지, 안트라센 에폭시 수지, 비페닐형 에폭시 수지, 테트라메틸 비페닐형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 비스페놀 A 노볼락형 에폭시 수지, 비스페놀 S 노볼락형 에폭시 수지, 비페닐 노블락형 에폭시 수지, 나프톨 노볼락형 에폭시 수지, 나프톨 페놀 공축 노볼락형 에폭시 수지, 나프톨 코레졸 공축 노볼락형 에폭시 수지, (다)방향족 탄화수소 포름알데히드 수지 변형 페놀 수지형 에폭시 수지, 트리페닐 메탄형 에폭시 수지, 테트라 페닐에탄형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 디시클로펜타디엔 페놀 부가반응형 에폭시 수지, 페놀 아랄킬형 에폭시 수지, 다관능성 페놀 수지, 나프톨 아랄킬형 에폭시 수지 또는 이들의 혼합형태 등이 있다. 바람직하게는, 비스페놀 A형 에폭시 수지, 지환형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 디시클로펜타디엔형 에폭시 및 비페닐형 에폭시 수지로 이루어진 군에서 선택되는 1종 이상을 사용할 수 있다.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. Specific examples of the epoxy resin 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 epoxy resin or a mixture of such. Preferably, at least one selected from the group consisting of bisphenol A type epoxy resin, alicyclic epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy and biphenyl type epoxy resin can be used.
본 발명에서, 에폭시 수지의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 40 내지 70 중량부일 수 있으며, 바람직하게는 45 내지 65 중량부, 보다 바람직하게는 45 내지 60 중량부일 수 있다. 상기 에폭시 수지의 함량이 전술한 함량 범위에 해당될 경우 우수한 전단 접착력과 인장강도 등의 정적 강도를 나타낼 수 있다. In the present invention, 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. When 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.
페녹시 수지Phenoxy resin
본 발명에 따른 1액형 에폭시계 접착제 조성물은 적어도 3종의 강인화제를 혼용하되, 이중 하나가 페녹시 수지이다. 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.
페녹시 수지는 열가소성 고분자로서, 말단에 페놀성 작용기를 갖춘 것을 일컫는다. 본 발명에서는 페녹시 수지를 포함함에 따라 실온에 있어서 태크성(tackiness)이나 취성(brittleness) 문제를 해소할 수 있다. A phenoxy resin is a thermoplastic polymer having a phenolic functional group at its terminal. In the present invention, the inclusion of a phenoxy resin can solve the problem of tackiness and brittleness at room temperature.
상기 페녹시 수지로는 당 분야에 공지된 것을 제한 없이 사용할 수 있다. 이러한 페녹시 수지가 갖는 골격의 일례를 들면, 비스페놀 A형, 비스페놀 A/F형, 비스페놀 F형, 비스페놀 S형, 비스페놀 A/S형, 카르도 골격(cardo-skeleton)형 등을 들 수 있다. As the 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 .
본 발명의 일 구현예를 들면, 상기 페녹시 수지는 비스페놀 A와 에피클로로히드린을 반응시켜 얻어지는 비스페놀 A형 페녹시 수지일 수 있다. 이러한 비스페놀 A형 페녹시 수지는, 에폭시 수지와 구조가 유사하여 상용성(相容性)이 높고, 용융 점도가 낮으며 접착성이 우수할 수 있다. 또한 상기 페녹시 수지는 에폭사이드를 포함하지 않는 폴리에테르계열의 고분자로서, 작용기로 수산기를 포함하여 이소시아네이트 및 아민 등의 화합물과 가교 반응을 통하여 개질될 수 있다.In one embodiment of the present invention, the phenoxy resin may be a bisphenol A phenoxy resin obtained by reacting bisphenol A with epichlorohydrin. Such 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.
본 발명의 다른 일 구현예를 들면, 상기 페녹시 수지는 중량평균 분자량(Mw)이 30,000 내지 70,000 g/mol이며, 바람직하게는 40,000 내지 70,000 g/mol일 수 있다. 페녹시 수지의 중량평균 분자량(Mw)이 전술한 하한 미만일 경우 지지성이 약해져 취약성이 강해지는 경향이 있고, 상기 상한을 초과하면 용융 점도가 높아지는 경향이 있다. 또한 상기 페녹시 수지는 유리전이온도(Tg)가 80 내지 100℃이며, 수산기(OH)가 당량이 200 내지 400 g/eq. 일 수 있다. 상기 페녹시 수지의 유리전이온도(Tg)가 80 내지 100℃일 경우 접착력, 유연화제 및 내화학성을 강화 효과를 나타낼 수 있다. In another embodiment of the present invention, 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. When the weight average molecular weight (Mw) of the phenoxy resin is less than the lower limit described above, the support tends to weaken and the fragility tends to become strong. When the upper limit is exceeded, the melt viscosity tends to increase. 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 &gt; 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.
본 발명에서, 페녹시 수지의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 3 내지 15 중량부일 수 있으며, 바람직하게는 5 내지 10 중량부일 수 있다. 상기 페녹시 수지의 함량이 3 중량부 미만이면 강인화 효과가 현저히 저하될 수 있으며, 15 중량부를 초과할 경우 점도가 매우 높아지는 문제가 발생될 수 있다. In the present invention, 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.
에폭시 양친성 블록 공중합체Epoxy amphiphilic block copolymer
본 발명에 따른 1액형 에폭시계 접착제 조성물에서, 에폭시 양친성 블록 공중합체(epoxy amphiphilic block copolymer)는 강인화제로서 적용된다.In the one-part epoxy-based adhesive composition according to the present invention, an epoxy amphiphilic block copolymer is applied as a toughening agent.
에폭시 양친성 블록공중합체는 에폭시 친화성(epoxyphilic) 블록과 에폭시 비(非)친화성(epoxyphobic) 블록을 포함하는 계면 활성 물질이다. 상기 에폭시 양친성 블록공중합체는 에폭시 친화성 블록과 에폭시 비친화성 블록에 의해 에폭시 수지 내에서 자발적으로 미셀(micelle)을 형성하게 되는데, 이때 유연한 사슬로 구성된 에폭시 비친화성 블록에 의해 미셀의 코어(core)가 형성됨으로써 유리전이온도(Tg)의 저하 없이 충격 흡수를 가능하게 된다.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. At this time, 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).
구체적으로, 상기 에폭시 양친성 블록공중합체는, 아크릴로니트릴계 고분자, 에틸렌옥사이드 고분자 및 프로필렌 옥사이드 고분자로 구성된 군에서 선택된 적어도 하나를 함유하는 에폭시 친화성 블록(A); 및 알킬렌 고분자를 함유하는 에폭시 비친화성 블록(B)을 포함한다. 상기 에폭시 비친화성 블록의 예를 들면, 폴리에틸렌 프로필렌(PEP), 폴리부타디엔, 폴리이소프렌, 폴리디메틸 실록산, 폴리알킬 메틸 메타크릴레이트, 폴리에틸 헥실 메타크릴레이트, 또는 이들의 조합을 포함할 수 있다. 이러한 에폭시 양친성 블록공중합체의 형태는 특별히 제한되지 않으며, 일례로 2중 이상의 다중 블록공중합체(multi-block copolymer)일 수 있다. 구체적으로 2중 블록공중합체(예, A-B) 또는 3중 블록공중합체(예, A-B-A, B-A-B 등)일 수 있다. 또한 상기 에폭시 양친성 블록공중합체가 형성하는 미셀의 크기와 형태는 특별히 제한되지 않으며, 일례로 나노 스케일의 구형(spherical)이거나 벌레형(worm-like)일 수 있다. Specifically, 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. Examples of 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. Specifically, it may be a double-block copolymer (e.g., A-B) or a triblock copolymer (e.g., A-B-A, B-A-B, etc.). 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.
본 발명의 일 구현예를 들면, 상기 에폭시 양친성 블록공중합체는 중량평균 분자량(Mw)이 3,000 내지 10,000 g/mol일 수 있으며, 바람직하게는 5,000 내지 9,000 g/mol일 수 있다. In one embodiment of the present invention, 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.
본 발명에서, 에폭시 양친성 블록공중합체의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 3 내지 13 중량부일 수 있으며, 바람직하게는 5 내지 10 중량부일 수 있다. 상기 에폭시 양친성 블록공중합체의 함량이 3 중량부 미만이면 미셀 형성이 미미하여 강인화 효과가 거의 없게 되며, 13 중량부를 초과할 경우 강인화 효과가 오히려 감소될 수 있다. In the present invention, 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.
우레탄 수지Urethane resin
본 발명에 따른 1액형 에폭시계 접착제 조성물에서, 우레탄 수지는 저온에서 우수한 충격특성을 구현하기 위해 사용되는 강인화제이다. In the one-pack type epoxy adhesive composition according to the present invention, the urethane resin is a toughening agent used for realizing excellent impact properties at a low temperature.
우레탄 수지는 당 분야에 공지된 우레탄 수지로서, 적어도 일측 말단부에 캡핑(capping, blocking)된 이소시아네이트기를 갖는 것을 제한 없이 사용할 수 있다. 여기서, "캡핑된 또는 블록킹된"은 결합되는 말단이 더 이상 반응성기를 갖지 않는 방식으로, 즉 캡핑 화합물이 일관능성이 되도록 중합체 쇄 말단에 블록킹제가 결합되는 것을 의미한다. 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. As used herein, "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.
구체적으로, 우레탄 수지는 캡핑된 이소시아네이트 기를 가진 액체형 또는 저융점을 가진 고분자일 수 있다. 상기 캡핑된 이소시아네이트기는, 이소시아네이트기와 가역적으로 반응하여 블록킹 기(blocking moiety)를 형성할 수 있는 하나 이상의 작용기를 가진 화합물(예, 블록킹제)과 반응된 것이다. 상기 블록킹기를 형성할 수 있는 화합물은 특별히 제한되지 않으며, 일례로 페놀 및 폴리페놀 중 어느 하나일 수 있다. Specifically, 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. The compound capable of forming the blocking group is not particularly limited, and may be, for example, any one of phenol and polyphenol.
본 발명에 따른 우레탄 수지는, 이소시아네이트 반응성 분절(segment)과, 에폭시기 비반응성 블록킹 분절을 포함하는 프리폴리머(prepolymer)일 수 있다. 여기서, 상기 이소시아네이트 반응성 분절은 중량평균 분자량(Mw)이 300 내지 3,000인 폴리에테르, 폴리부타디엔 및 폴리에스테르로 구성된 군에서 선택되는 적어도 하나를 포함할 수 있다. 또한 상기 에폭시기 비반응성 분절은 에폭시기에 대해 반응성이 없는 블록킹제로서, 페놀 및 폴리페놀 중 적어도 하나로 캡핑된 이소시아네이트기를 포함할 수 있다. 이러한 에폭시기 비반응성 분절은 우레탄 수지의 적어도 일측 말단부에 위치하게 된다. 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. Here, 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.
본 발명의 일 구현예를 들면, 상기 우레탄 수지는 중량평균 분자량(Mw)이 8,000 내지 40,000 g/mol 이며, 점도가 40℃에서 440 내지 1280 Pa·s 일 수 있다. In one embodiment of the present invention, 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.
본 발명에서, 우레탄 수지의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 5 내지 30 중량부일 수 있으며, 바람직하게는 10 내지 25 중량부일 수 있다. 상기 우레탄 수지의 함량이 5 중량부 미만이면 저온 충격강도 효과가 미미하여 강인화 효과가 거의 없게 되며, 30 중량부를 초과할 경우 강인화 효과가 오히려 감소되는 문제가 발생될 수 있다. In the present invention, 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.
한편 본 발명에서 강인화제로서 혼용되는 페녹시 수지와 에폭시 양친성 블록 공중합체와 우레탄 수지의 함량비는 1 : 0.7~2 : 1~5 중량비일 수 있으며, 바람직하게는 1 : 0.8~1.5 : 2~4 중량비일 수 있다. 또한 페녹시 수지, 에폭시 양친성 블록공중합체와 우레탄 수지를 포함하는 강인화제의 총 함량은, 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 20 내지 50 중량부일 수 있으며, 바람직하게는 20 내지 45 중량부, 보다 바람직하게는 25 내지 40 중량부일 수 있다.In the present invention, 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.
경화제Hardener
본 발명에 따른 1액형 에폭시계 접착제 조성물에서, 경화제는 주(主)수지인 에폭시 수지와 반응하고 조성물의 경화를 진행시키는 성분이다.In the one-component epoxy adhesive composition according to the present invention, the curing agent is a component which reacts with the epoxy resin as the main resin and proceeds the curing of the composition.
경화제는 당 분야에 공지된 통상적인 경화제를 제한없이 사용할 수 있다 구체적으로, 상기 경화제는 에폭시 수지와 반응성이 있으며, 경화 개시 온도가 80℃ 이상인 것을 사용할 수 있다. 바람직하게는 경화 개시 온도가 120℃ 이상, 보다 바람직하게는 140℃ 이상인 것을 사용할 수 있다. 상기 경화제는 경화 개시 온도 이상으로 가열시 급속히 경화되지만, 실온(약 22℃) 및 적어도 50℃ 까지의 온도에서 매우 느리게 경화되도록 하는 임의의 촉매(들)를 단독 또는 혼용하는 것이 적절하다. 일례로, 상기 경화제는 질소-함유 화합물(예컨대, 아민 및 이의 유도체); 산소-함유 화합물(예컨대, 카르복실산-종결된 폴리에스테르), 무수물, 페놀-포름알데히드 수지, 아미노-포름알데히드 수지, 페놀, 비스페놀 A 및 크레솔 노볼락, 페놀-종결된 에폭시 수지; 황-함유 화합물(예컨대, 폴리술파이드, 폴리메르캅탄); 촉매작용성 경화제(예컨대, 3급 아민, 루이스 산, 루이스 염기) 또는 이들의 조합 등을 사용할 수 있다. As the curing agent, a conventional curing agent known in the art can be used without limitation. Specifically, the curing agent is reactive with an epoxy resin and has a curing initiation temperature of 80 ° C or higher. 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. In one example, 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.
사용 가능한 경화제의 비제한적인 예로는, 붕소 트라이클로라이드/아민 및 붕소 트라이플루오라이드/아민 착체, 다이시안다이아미드, 멜라민, 다이알릴멜라민; 아세토구안아민, 벤조구안아민 등의 구안아민; 3-아미노-1,2,4-트라이아졸 등의 아미노트라이아졸; 아디프산 다이하이드라자이드, 스테아르산 다이하이드라자이드, 이소프탈산 다이하이드라자이드, 세미카바자이드, 시아노아세트아미드 등의 하이드라자이드; 다이아미노다이페닐설폰 등의 방향족 폴리아민이 있다. 전술한 성분을 단독 사용하거나 또는 이들을 2종 이상 혼용할 수 있다. 특히, 다이시안다이아미드, 이소프탈릭 다이하이드라자이드, 아디프산 다이하이드라자이드, 및 4,4'-다이아미노다이페닐설폰으로 구성된 군에서 선택된 1종 이상을 사용하는 것이 바람직하다. 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. In particular, it is preferable to use at least one selected from the group consisting of dicyanamide, isophthalic dihydrazide, adipic acid dihydrazide, and 4,4'-diaminodiphenylsulfone.
경화제는 에폭시계 접착제 조성물을 경화하기에 충분한 양으로 사용될 수 있다. 일반적으로 접착제 조성물 내 존재하는 에폭시기의 적어도 80% 이상을 소비시킬 수 있는 함량을 조절하여 사용하며, 모든 에폭시기를 소비하는데 필요한 양보다 과량의 양은 불필요하다. 본 발명에서, 상기 경화제의 함량은 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 1.5 내지 15 중량부일 수 있으며, 바람직하게는 2.5 내지 10 중량부, 보다 바람직하게는 3 내지 8 중량부일 수 있다.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. In the present invention, 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.
경화촉진제Hardening accelerator
본 발명에 따른 1액형 에폭시계 접착제 조성물은, 필요에 따라 당 분야에 공지된 경화촉진제를 더 포함할 수 있다. The one-pack type epoxy adhesive composition according to the present invention may further contain a curing accelerator known in the art as needed.
경화촉진제는 열 활성화 가능한 촉매로서, 130℃ 이상의 비점을 가진 고체 또는 액체 3급 아민 화합물을 제한 없이 사용할 수 있다. 일례로, 우레아계 화합물; 아미노페놀; C1-C12 알킬렌 이미다졸 또는 N-아릴이미다졸 등의 다양한 지방족 우레아 화합물 등이 있다. 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. For example, a urea-based compound; Aminophenol; And various aliphatic urea compounds such as C 1 -C 12 alkylene imidazole or N-arylimidazole.
사용 가능한 경화촉진제의 비제한적인 예를 들면, p-클로로페닐-N,N-다이메틸우레아, 3-페닐-1,1-다이메틸우레아, 3,4-다이클로로페닐-N,N-다이메틸우레아, N-(3-클로로-4-메틸페닐)-N',N'-다이메틸우레아, 벤질다이메틸아민; 2,4,6-트리스(다이메틸아미노메틸)페놀, 피페리딘, 2-에틸-2-메틸이미다졸, N-부틸이미다졸, 6-카프로락탐 등이 있다. 바람직하게는, 2,4,6-트리스(다이메틸아미노메틸)페놀 등의 아미노페놀 화합물일 수 있다. 전술한 성분을 단독 사용하거나 또는 2종 이상 혼용할 수 있다. 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. Preferably, 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.
상기 경화촉진제는, 적어도 하나 이상의 다른 촉매, 바람직하게는 열-활성화 가능한 촉매와 혼용될 수 있다. 이와 같이 혼용 가능한 촉매는 상술한 다양한 아민 화합물(이는 노볼락 수지와 다른 블록킹 기로 블록킹됨)을 포함할 수 있으며, 구체적인 예로는 블록킹된 1-(2-(2-하이드록실벤즈아미노)에틸)-2-(2-하이드록실페닐-2-이미다졸린)일 수 있다. 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).
본 발명에서, 경화촉진제(예, 열 활성화 가능한 촉매)의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대해 0.1 내지 4 중량부일 수 있으며, 바람직하게는 0.5 내지 1.5 중량부, 보다 바람직하게는 0.5 내지 1.0 중량부일 수 있다. In the present invention, 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.
충전제Filler
본 발명에 따른 1액형 에폭시계 접착제 조성물은, 필요에 따라 당 분야에 공지된 충전제를 더 포함할 수 있다. The one-part epoxy-based adhesive composition according to the present invention may further contain fillers known in the art as needed.
충전제는 전술한 에폭시계 접착제 조성물 중에 포함되는 다른 성분과 반응하지 않는 재료라면 특별한 제한 없이 사용될 수 있으며, 일례로 무기 충전제, 유기 충전제 또는 이들의 복합 형태 등이 있다. 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.
상기 충전제는 접착제의 레올로지를 바람직하게 개선하는 기능, 단위 중량당 총 비용을 감소시키는 기능, 상기 접착제로부터 또는 이것이 적용되는 기재로부터 수분 또는 오일을 흡수하는 기능, 및/또는 응집 실패(cohesive failure)를 촉진하는 기능 등을 적어도 하나 이상 복합적으로 수행할 수 있다.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.
사용 가능한 충전제의 비제한적인 예로는, 탄산 칼슘, 활석, 카본블랙, 텍스타일 섬유, 유리 입자 또는 섬유, 아라미드펄프, 붕소 섬유, 탄소 섬유, 무기 실리케이트, 운모, 분말 수정, 수화된 산화 알루미늄, 벤토타이트, 월라스토나이트, 카올린, 실리카, 흄드 실리카, 실리카 에어로겔, 실리카 나이트라이드, 알루미나, 알루미늄 나이트라이드, 보론 나이트라이드, 탈크, 카본, 폴리우레아 화합물, 폴리아미드 화합물 또는 금속 분말 등이 있다. 전술한 성분을 단독으로 사용하거나 또는 2종 이상 혼용할 수 있다. 상기 금속 분말의 예를 들면, 알루미늄 분말 또는 철 분말과 같은 물질 중 적어도 하나 이상을 포함할 수 있다. 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.
상기 충전제의 평균 입경은 특별히 제한되지 않으며, 당 분야에 공지된 범위 내에서 적절히 조절할 수 있다. 일례로, 무기 충전제의 평균 입경은 1 내지 100 ㎛일 수 있다. 또한 무기 충전재의 형상은 특별히 제한되지 않으며, 일례로 구형, 각형, 판상형, 침상형 또는 무정형일 수 있다. 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.
본 발명에서, 충전제의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대하여 2 내지 25 중량부일 수 있으며, 구체적으로 5 내지 20 중량부일 수 있다. In the present invention, 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.
수분제거제Moisture remover
본 발명에 따른 1액형 에폭시계 접착제 조성물은, 필요에 따라 당 분야에 공지된 수분 제거제를 더 포함할 수 있다. 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.
수분 제거제는 열경화성 구조용 접착제 조성물에 존재하는 유리 수(free water)와 물리적 또는 화학적으로 결합하는 물질로서, 구체적으로 160℃ 이상, 바람직하게는 200℃ 이상의 온도로 가열될 때까지 결합수를 방출하지 않음으로써 수분 함량을 저감시킬 수 있다. 상기 수분 제거제는 80℃ 미만의 온도에서 전술한 에폭시계 구조용 접착제의 개방 시간을 크게 연장하는 것에 의해 그 존재를 확인할 수 있다. 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 캜 or higher, preferably 200 캜 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 캜.
사용 가능한 수분 제거제의 비제한적인 예로는 산화칼슘, 산화마그네슘, 오산화인, 다양한 분자체, 또는 이들의 혼합물 등이 있다. 바람직하게는 산화칼슘이며, 이러한 산화칼슘은 미세 입자, 구체적으로 직경 100 ㎛ 미만의 형태로 제공될 수 있다. Non-limiting examples of usable moisture scavengers include calcium oxide, magnesium oxide, phosphorus pentoxide, various molecular sieves, or mixtures thereof. Preferably calcium oxide, and such calcium oxide may be provided in the form of fine particles, specifically, less than 100 mu m in diameter.
본 발명에서, 수분 제거제의 함량은 특별히 제한되지 않으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)에 대하여 0.5 내지 10 중량부일 수 있으며, 바람직하게는 2 내지 5 중량부일 수 있다.In the present invention, 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.
첨가제additive
본 발명의 1액형 에폭시계 접착제 조성물은, 상기 조성물의 고유 특성을 해하지 않는 범위 내에서, 당 분야에 통상적으로 사용되는 첨가제를 선택적으로 더 포함할 수 있다.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.
사용 가능한 첨가제의 비제한적인 예를 들면, 레올로지 개선제, 유변성 조절제, 안료, 염료, 희석제, 가소제, 증량제, 난연제, 틱소트로프제, 팽창제, 유동제어제, 접착 촉진제, 열가소성 분말, 코어-쉘 고무, 이량화된 지방산, 산화방지제 또는 이들의 조합 등이 있다. 상기 각 첨가제의 함량은 당 분야에 공지된 함량 범위 내에서 적절히 첨가될 수 있으며, 일례로 당해 에폭시계 접착제 조성물의 전체 중량(예, 100 중량부)을 기준으로 하여 각각 0.1 내지 5 중량부일 수 있다. 또한 상기 첨가제의 전체 함량은 당해 에폭시계 접착제 조성물의 전체 중량 대비 0.1 내지 25 중량부일 수 있으나, 이에 특별히 제한되지 않는다. 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.
본 발명에서는 난연성을 보다 향상시키기 위하여 당 분야의 통상적인 난연제를 포함할 수 있다. 사용 가능한 난연제의 비제한적인 예로는 금속 수산화물[예컨대, 알루미나 삼수화물], 인 및 질소 함유 유기화합물 [예컨대, 레조르시놀디포스페이트 (resorcinol diphosphate), 포스페이트 (phosphate), 페녹시포스파젠 (phenoxyphosphazene), 멜라민 또는 멜라민 유도체 [예컨대, 멜라민 시아누레이트 (melamine cyanurate), 페놀 멜라민 수지(phenolic melamine resin)], 붕산아연 또는 이들의 혼합물 등이 있다. 상기 금속 수산화물의 예로는 마그네슘, 칼슘, 스트론튬, 바륨, 보론, 알루미늄 및 갈륨 중에서 선택된 금속의 수산화물을 들 수 있다. In the present invention, a conventional flame retardant may be included in the art to further improve the flame retardancy. Non-limiting examples of 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. Examples of such metal hydroxides include hydroxides of metals selected from magnesium, calcium, strontium, barium, boron, aluminum and gallium.
또한 본 발명에서는 단량체성 또는 올리고머성의 부가중합 가능한 에틸렌형 불포화 물질을 상기 구조용 접착제에 혼입시킴으로써 경화의 속도 및 선택성을 조절할 수 있다. 상기 에틸렌형 불포화 물질은 대략 1500 미만의 분자량을 갖는 것이 바람직하다. 이러한 에틸렌형 불포화 물질의 예를 들면, 아크릴레이트 또는 메타크릴레이트 화합물, 불포화된 폴리에스터, 비닐 에스터 수지, 또는 불포화된 폴리에스터 수지의 에폭시 부가물 등일 수 있다. 본 발명의 구조용 접착제 조성물은 유리 라디칼 공급원인 유리 라디칼 개시제가 포함되어 상기 에틸렌형 불포화 물질을 중합할 수 있는데, 이러한 에틸렌형 불포화 물질의 혼입은, 에틸렌형 불포화기의 선택적인 중합을 통해 구조용 접착제의 부분적 경화를 수행할 가능성을 제공하게 된다.In the present invention, 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.
팽창제는 당 분야에 공지된 물리적 및 화학적 유형 물질 모두를 포함한다. 또한 접착제는 열가소성 분말, 예를 들면 폴리비닐부티랄 또는 폴리에스터 폴리올을 함유할 수 있다.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.
희석제는 당 분야의 접착제 조성물에 사용되는 혼화성 용매를 사용할 수 있으며, 일례로 케톤, 에테르, 아세테이트, 방향족 탄화수소, 시클로헥산온, 디메틸포름아미드, 글리콜 에테르, 또는 이들의 조합을 사용할 수 있다.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.
전술한 바와 같이 구성되는 본 발명의 1액형 에폭시 접착제 조성물은, 에폭시 접착제가 사용되는 모든 용도에 적용 가능하며, 일례로 체결하고자 하는 적어도 2개의 부품을 접착 접합하여 구조물을 형성하는 구조용 접착제 용도로 사용될 수 있다. 구체적으로 전자, 건축, 항공기 및 자동차 산업용 구조물을 제조하는 데 사용되는 것이 바람직하며, 예컨대 목재, 금속, 코팅된 금속, 알루미늄, 다양한 플라스틱 및 충전된 플라스틱 기재, 섬유유리 등을 비롯한 다양한 소재로 이루어진 부품들을 접착시키는데 사용될 수 있다.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. For example, 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 . Specifically, 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.
특히, 본 발명의 1액형 에폭시 접착제 조성물은 -40℃ 내지 80℃의 온도 영역에서 자동차 구조용 접착제의 전반적인 요구물성을 지속적으로 유지할 수 있으므로, 자동차 부품들을 서로 접착시키거나 또는 자동차 부품들을 자동차에 접착시키는 자동차 분야의 구조용 접착제로서 유용하게 적용될 수 있다.Particularly, 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.
<물품><Article>
또한 본 발명은 전술한 1액형 에폭시계 접착제 조성물을 이용하여 경화된 접착제층을 구비하는 물품(articles), 바람직하게는 자동차 분야의 물품을 제공한다.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.
구체적으로, 상기 물품은 제1부재; 상기 제1부재와 접착 결합되는 제2부재; 및 상기 제1부재와 제2부재 사이에 배치되며, 전술한 1액형 에폭시계 접착제 조성물로부터 형성된 접착제층을 포함한다. Specifically, 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.
제1부재와 제2부재는 접착제층에 의해 결합되어 체결 가능한 소재라면 특별히 제한되지 않으며, 서로 동일하거나 또는 상이할 수 있다. 일례로, 상기 제1부재와 제2부재는 각각 금속, 강판, 목재, 필름, 타일, 플라스틱, 유리, 수지, 세라믹, 콘크리트, 탄소재, 섬유 및 이들의 복합 소재로 이루어진 군으로부터 선택될 수 있다. 바람직하게는 자동차 분야의 부품소재일 수 있으며, 구체적으로 스틸(steel), 코팅된 스틸, 아연도금된 스틸, 알루미늄, 코팅된 알루미늄, 플라스틱, 충전된 플라스틱 소재, 복합 소재일 수 있다. 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. For example, 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, . Preferably, 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.
특히 본 발명에 따른 1액형 에폭시 접착제는, 동일하거나 또는 상이한 자동차 프레임 컴포넌트들을 접착시키는 구조용 접착제로 사용되는 것이 바람직하다. 이에 따라, 제1부재와 제2부재는 각각 자동차 분야에 사용되는 일반적인 금속 소재, 플라스틱 소재, 및/또는 복합 소재의 프레임 컴포넌트일 수 있다. 이중에서, 금속 소재는 자동차 재료, 가전제품, 건축재료, 산업 용도로 이용되는 통상의 금속일 수 있으며, 일례로 냉간압연강철(CR), 아연 핫디핑 강철(GI), 일렉트로-아연강철(EGI), 합금-플레이트강철(GA), 구리시트 또는 주석-플레이트 강철, 용융아연도금강판, 합금화용융아연도금강판, 전기아연도금강판, 용융알루미늄-아연합금도금강판, 아연과 알루미늄의 금속 재료, 아연도금된 금속 또는 알루미늄판 등이 있다. 보다 구체적으로, 냉간압연된 스틸, 아연도금된 금속 또는 알루미늄 등일 수 있다. In particular, 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. Accordingly, 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. Of these, 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.
본 발명의 일 구현예를 들면, 상기 제1부재와 제2부재 중 하나는 알루미늄(Al) 또는 알루미늄 합금(alloy)계 부재이며, 다른 하나는 상기 제1부재와 동일하거나 또는 상이한 금속 부재일 수 있다. 바람직하게는 제1부재와 제2부재 모두 알루미늄(Al) 또는 알루미늄 합금계 소재일 수 있다. 여기서, 알루미늄은 순수한 알루미늄 금속 또는 알루미늄을 80 중량% 이상 함유하는 임의의 합금(alloy)을 의미한다. In one embodiment of the present invention, 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. Preferably, both the first member and the second member may be aluminum (Al) or an aluminum alloy based material. Here, aluminum means pure aluminum metal or any alloy containing 80 wt% or more of aluminum.
본 발명에 따른 물품은, 전술한 1액형 에폭시계 접착제 조성물을 사용하는 것을 제외하고는, 당 분야에 알려진 통상의 방법에 의해 제조될 수 있다. 일례로, 제1부재와 제2부재 중 적어도 하나에 상기 에폭시계 접착제 조성물을 도포한 후, 경화시켜 접착제층을 형성하고 결합시킴으로써 제조될 수 있다.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. For example, 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.
상기 에폭시계 접착제 조성물을 도포하는 방법은 당 업계에 공지된 방법이라면 특별히 한정되지 않으며, 일례로 분말-코팅, 분무-코팅 등이 적용될 수 있다. 구체적으로, 본 발명의 에폭시계 접착제 조성물은 당 분야에 공지된 임의의 기법에 따라 적용될 수 있으며, 필요에 따라 차게 또는 따뜻하게 적용될 수 있다. 일례로, 로봇으로부터 비드(bead) 형태로 기재 상에 압출함으로써 적용할 수 있으며, 코킹 건(caulking gun) 또는 다른 임의의 적용 수단 등과 같은 기계적 적용 수단을 적용할 수 있다. 또한 제트 분사 방법, 일례로 스트리밍 방법 또는 와류(swirl) 기법을 사용함으로써 적용될 수도 있다. 상기 에폭시계 접착제 조성물은 제1부재와 제2부재 중 하나에 적용되거나 또는 이들 모두에 적용될 수 있으며, 제1부재와 제2부재 사이에 접착제가 위치되도록 배치한다.The method of applying the epoxy adhesive composition is not particularly limited as long as it is a method known in the art. For example, powder-coating or spray-coating may be applied. Specifically, 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. For example, 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.
이어서, 에폭시계 접착제 조성물을 경화제의 경화 개시 온도 이상으로 가열함으로써 경화될 수 있다. 이때 가열 조건은 특별히 한정되지 않으며, 사용하고자 하는 제1부재와 제2부재의 폭 및 두께, 공정 라인 스피드 등의 조건에 따라 적절히 변경 가능하다. 상기 경화 개시 온도는 대략 80℃ 내지 220℃, 바람직하게는 약 140℃ 내지 180℃, 보다 바람직하게는 150 내지 170℃일 수 있다. 특히, 본 발명에서는 약 170℃ 이하, 구체적으로 140 내지 170℃, 바람직하게는 150 내지 170℃의 온도로 경화시, 우수한 충격 박리 강도 및 응력 내구성을 발휘할 수 있다는 장점이 있다. 전술한 경화공정은 당 분야에 공지된 열원, 방사선원 또는 에너지원의 조합을 사용할 수 있다.Subsequently, the epoxy-based adhesive composition can be cured by heating to a temperature not lower than the curing initiation temperature of the curing agent. In this case, 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. Particularly, in the present invention, there is an advantage that excellent impact peel strength and stress durability can be exhibited when curing at a temperature of about 170 캜 or less, specifically 140 to 170 캜, preferably 150 to 170 캜. The curing process described above can use a heat source, a radiation source, or a combination of energy sources known in the art.
상술한 방법에 의해, 접착제층(예, 구조용 접착부)은 제1부재와 제2부재 사이에서 이들과 접촉한 상태로 형성된다. 이때, 제1부재와 제2부재는 자동차 프레임 어셈블리의 전체를 구성하거나 또는 적어도 일부를 형성할 수 있다. 제1부재와 제2부재는 하소 경화를 필요로 하는 코팅에 의해 코팅될 수 있으며, 상기 구조용 접착제는 전술한 코팅의 하소 경화와 동시에 경화될 수 있다. 또한 제1부재(알루미늄 부재)와 제2부재(금속 부재)는 상기 에폭시계 구조용 접착제가 경화되기 전에 용접될 수도 있다. By the above-described method, 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. At this time, 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.
본 발명의 일 구현예에 따르면, 상기 물품은 ISO 11343 규격에 따라 측정시, 하기 (i) 내지 (iii)의 물성을 만족할 수 있다. (i) -40℃ 충격박리강도가 20 N/mm 이상이며, (ii) 20℃ 충격박리강도가 30 N/mm 이상이며, (iii) 80℃ 충격박리강도가 30 N/mm 이상일 수 있다. 또한 우수한 전단 강도와 T-박리 강도를 나타낼 수 있다. According to one embodiment of the present invention, the article can satisfy the following properties (i) to (iii) when measured according to ISO 11343 standard. (i) the impact peel strength at -40 占 폚 is 20 N / mm or more, (ii) the impact peel strength at 20 占 폚 is 30 N / mm or more, and (iii) the impact peel strength at 80 占 폚 is 30 N / mm or more. It can also exhibit excellent shear strength and T-peel strength.
이하, 실시예를 통하여 본 발명을 보다 구체적 설명한다. 그러나 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to assist the understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.
<실시예 1~2. 1액형 에폭시계 접착제 조성물 제조>&Lt; Examples 1 to 2 > Preparation of one-pack epoxy-based adhesive composition>
[실시예 1][Example 1]
하기 표 1 및 표 2에 나타낸 성분과 조성비로 배합하여 에폭시 접착제 조성물을 제조하였다. The components and compositions shown in Tables 1 and 2 were blended to prepare an epoxy adhesive composition.
구체적으로, 비스페놀 A형 에폭시 수지 55 중량%에 페녹시 수지 6.1 중량%를 녹인 후 우레탄 강인화제 20 중량%를 반응기에 정량하여 10분 동안 교반시켰다. 이후, 상기 반응기에 블록공중합체 7.4 중량%, 산화칼슘 3 중량%, 소수성 흄드실리카 3 중량%를 첨가하고 30분 동안 진공 교반시켰다. 그 이후 경화제 4.8 중량%, 및 열-활성화 가능한 촉매 0.7 중량%를 첨가하고 30분 동안 진공 교반시켜 실시예 1의 1액형 에폭시 접착제 조성물을 제조하였다. 하기 표 2에서 각 조성물의 사용량 단위는 중량%이다. Specifically, 6.1% by weight of phenoxy resin was dissolved in 55% by weight of bisphenol A type epoxy resin, 20% by weight of a urethane injection molding agent was quantitatively measured in a reactor, and the mixture was stirred for 10 minutes. Then, 7.4 weight% of a block copolymer, 3 weight% of calcium oxide and 3 weight% of hydrophobic fumed silica were added to the reactor, followed by vacuum stirring for 30 minutes. Thereafter, 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. In Table 2, the usage unit of each composition is% by weight.
[실시예 2][Example 2]
하기 표 2에 기재된 조성에 따라 각 성분을 배합한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 수행하여 실시예 2의 1액형 에폭시 접착제 조성물을 제조하였다. 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.
구성요소Component 구분division 상세 스펙Detailed specification
에폭시 수지Epoxy resin AA 비스페놀A형 에폭시 수지(국도화학 / YD-128)- 에폭시 당량(EEW): 184-190Bisphenol A type epoxy resin (Kukdo Chemical / YD-128) - Epoxy equivalent (EEW): 184-190
강인화제A tough topic B-1B-1 페녹시 수지 (Gavriel/PKHH)- Mw: 52000, 수산기 당량: 280 g/eq, Tg: 92℃Phenoxy resin (Gavriel / PKHH) - Mw: 52000, hydroxyl equivalent: 280 g / eq, Tg: 92 ° C
B-2B-2 에폭시 양친성 블록 공중합체 (DOW / FORTEGRATM 100)- 점도: 3600 cPEpoxy amphiphilic block copolymer (DOW / FORTEGRA TM 100) viscosity: 3600 cP
B-3B-3 우레탄 수지 (HUNTSMAN / Flexibilizer DY 965)- 수산기 당량: 558-667 g/eq, 점도: 440-1280 Pa s(40℃) Urethane resin (HUNTSMAN / Flexibilizer DY 965) - hydroxyl equivalent: 558-667 g / eq, viscosity: 440-1280 Pa s (40 ° C)
경화제Hardener CC Evonik / Dicyanex®® 1400FEvonik / Dicyanex ®® 1400F
경화촉진제Hardening accelerator DD Evonik / Amicure®® UR-DEvonik / Amicure ®® UR-D
수분 제거제Moisture remover EE 산화칼슘 (유영소재 / UNI-OX)Calcium oxide (swimming material / UNI-OX)
충전제Filler FF 흄드 실리카 (Evonik / aerosil®® R202)Fumed silica (Evonik / aerosil ® R202)
구분division 실시예Example 비교예Comparative Example
1One 22 1One 22 33
에폭시 수지Epoxy resin AA 55.055.0 52.552.5 62.762.7 61.161.1 59.059.0
강인화제A tough topic B-1B-1 6.16.1 7.37.3 -- 6.76.7 --
B-2B-2 7.47.4 8.98.9 -- -- 9.09.0
B-3B-3 20.020.0 20.020.0 25.025.0 20.020.0 20.020.0
경화제Hardener CC 4.84.8 4.64.6 5.55.5 5.45.4 5.25.2
촉매catalyst DD 0.70.7 0.70.7 0.80.8 0.80.8 0.80.8
수분 제거제Moisture remover EE 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0
충전제Filler FF 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0
총 계 (중량%)Total weight (% by weight) 100100 100100 100100 100100 100100
[비교예 1~3][Comparative Examples 1 to 3]
상기 표 2에 기재된 조성에 따라 각 성분을 배합한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 수행하여 비교예 1 내지 3의 1액형 에폭시 접착제 조성물을 제조하였다. 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.
[실험예. 물성 평가][Experimental Example. Property evaluation]
실시예 1~2 및 비교예 1~3에서 제조된 에폭시 접착제 조성물을 이용하여 하기와 같은 방법으로 물성을 측정하고, 그 결과를 하기 표 3에 나타내었다. The properties of the epoxy adhesive compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were measured in the following manner, and the results are shown in Table 3 below.
(1) 전단강도(Single lap shear strength, Mpa) 평가(1) Evaluation of single lap shear strength (Mpa)
전단강도 시험은, 100 mm × 25 mm × 1.6T 크기의 냉간 압연 강판(CR)을 에탄올을 사용하여 오염을 제거한 후 사용하였다. 상기 강판의 일면에 12.5 mm 접착제를 도포한 후 그 위에 일정한 접착 두께를 유지하기 위해서 마이크로 비즈를 소량 사용하였다. 그리고 다른 시편을 덮고 고정시킨 후 180℃, 20분의 조건 하에서 경화시켰다. 경화 이후 23℃로 냉각된 시험편을 만능재료시험기를 이용하여 전단강도를 측정하였다. 이때 시험 조건은 5 mm/min의 인장속도로 180° 방향으로 하중을 가하였다. 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.
(2) T-박리강도(T-peel strength, N/25 mm) 평가(2) Evaluation of T-peel strength (N / 25 mm)
T-박리강도 시험은, 150 mm × 25 mm × 0.8T 크기의 강판을 직각으로 절곡하였으며, 구부린 후 각 면의 길이가 70mm, 80mm 되도록 하였다. 80mm 부분에 접착제를 도포하고 마이크로 비즈를 이용하여 일정한 접착 두께를 유지 시켰다. 그리고 다른 시편을 덮고 고정시킨 후 180℃, 20분의 조건 하에서 경화시켰다. 경화 이후 23℃로 냉각된 시험편을 만능재료시험기를 이용하여 전단강도를 측정하였다. 이때 시험 조건은 50 mm/min의 인장속도로 180° 방향으로 하중을 가하였다. In the T-peel strength test, a steel sheet having a size of 150 mm x 25 mm x 0.8 T was bent at right angles, and the length of each surface was 70 mm and 80 mm after bending. An adhesive was applied to the 80 mm portion and a uniform adhesive thickness was maintained using microbeads. 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 applied in the direction of 180 ° at a tensile speed of 50 mm / min.
(3) 충격박리강도(Impact peel strength, N/25 mm) 평가 (3) Evaluation of Impact Peel Strength (N / 25 mm)
충격박리강도 시험은, ISO 11343 규격에 따라 시행하였다. 시험편의 크기는 90mm × 20mm × 1.6T 이며, 접착제가 도포되는 일면의 크기는 30×20 mm이었다. 상기 시험편의 일면을 에탄올을 이용하여 오염물을 제거한 후 접착제를 도포하였다. 접착제 두께는 마이크로 비즈를 사용하여 일정하게 유지하고, 그 위에 다른 시편을 덮어 고정시킨 후 180℃, 20분의 조건 하에서 경화시켰다. 경화 이후 각 시험 온도 조건에서 1시간 이상 안정화시킨 후 ISO 11343 규격에 적합한 충격강도 시험기를 이용하여 전단강도를 측정하였다. 이때 시험 조건은 2m/초 속도로 하중을 가하였다. 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.
전단강도(MPa)Shear strength (MPa) T 박리강도(N/25mm)T peel strength (N / 25 mm) 충격 박리 강도 (N/mm)Impact Peel Strength (N / mm)
저온(-40℃)Low temperature (-40 ℃) 상온(20℃)At room temperature (20 ° C) 고온(80℃)High temperature (80 ℃)
실시예 1Example 1 36.536.5 390390 25.125.1 39.339.3 36.736.7
실시예 2Example 2 37.637.6 374374 21.721.7 35.335.3 38.338.3
비교예 1Comparative Example 1 31.331.3 387387 31.131.1 37.537.5 --
비교예 2Comparative Example 2 35.935.9 371371 22.422.4 32.532.5 26.926.9
비교예 3Comparative Example 3 32.832.8 401401 -- 29.029.0 14.514.5
상기 표 3에 나타난 바와 같이, 3종의 강인화제를 비포함하는 비교예 1~3에서는 특정 온도 영역에서만 우수한 충격 박리강도가 구현되는 것을 알 수 있었다. 이에 비해, 적어도 3종의 강인화제를 포함하는 실시예 1 및 2에서는, 우수한 전단강도와 T 박리강도를 나타낼 뿐만 아니라 -40℃ 내지 80℃의 전체 온도 영역에서 우수한 충격 박리강도를 발휘한다는 것을 알 수 있었다. 전술한 결과를 통해, 본 발명에 따른 1액형 에폭시계 접착제 조성물은 자동차 구조체의 접착을 위한 구조용 접착제로 유용하게 적용될 수 있음을 확인할 수 있었다. As shown in Table 3, in Comparative Examples 1 to 3 which did not include three kinds of toughening agents, excellent impact peel strength was realized only in a specific temperature range. On the other hand, in Examples 1 and 2 including at least three kinds of toughening agents, not only excellent shear strength and T peel strength were shown but also excellent impact peel strength was exhibited in the entire temperature range of -40 캜 to 80 캜 there was. From the above results, it can be confirmed that the one-pack type epoxy adhesive composition according to the present invention can be effectively applied as a structural adhesive for bonding an automobile structural body.

Claims (16)

  1. 에폭시 수지, 적어도 3종의 강인화제, 및 경화제를 포함하며, An epoxy resin, at least three toughening agents, and a curing agent,
    상기 적어도 3종의 강인화제는,The at least three toughening agents are selected from the group consisting of:
    페녹시 수지; Phenoxy resins;
    에폭시 친화성 블록과 에폭시 비(非)친화성 블록을 함유하는 에폭시 양친성 블록공중합체; 및 An epoxy amphiphilic block copolymer containing an epoxy affinity block and an epoxy non-affinity block; And
    적어도 일측 말단부에 캡핑된 이소시아네이트기를 갖는 우레탄 수지;A urethane resin having an isocyanate group capped at least at one end thereof;
    를 포함하는 1액형 에폭시계 접착제 조성물.Based epoxy adhesive composition.
  2. 제1항에 있어서,The method according to claim 1,
    상기 페녹시 수지와 에폭시 양친성 블록 공중합체와 우레탄 수지의 함량비는 1 : 0.7~2 : 1~5 중량비인 1액형 에폭시계 접착제 조성물.Wherein the content ratio of the phenoxy resin, the epoxy amphiphilic block copolymer and the urethane resin is 1: 0.7 to 2: 1 to 5: 1.
  3. 제1항에 있어서, The method according to claim 1,
    상기 페녹시 수지는 비스페놀 A와 에피클로로히드린을 반응시켜 형성되는 1액형 에폭시계 접착제 조성물.Wherein the phenoxy resin is formed by reacting bisphenol A with epichlorohydrin.
  4. 제1항에 있어서,The method according to claim 1,
    상기 페녹시 수지는, 중량평균 분자량(Mw)이 30,000 내지 70,000 g/mol이며, 유리전이온도(Tg)가 80 내지 100℃이고, 수산기(OH)가 당량이 200 내지 400 g/eq.인 1액형 에폭시계 접착제 조성물.Wherein 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 and a hydroxyl group (OH) equivalent of 200 to 400 g / Liquid type epoxy adhesive composition.
  5. 제1항에 있어서,The method according to claim 1,
    상기 에폭시 양친성 블록공중합체는, The epoxy-amphiphilic block copolymer can be obtained by, for example,
    아크릴로니트릴계 고분자, 에틸렌옥사이드 고분자 및 프로필렌 옥사이드 고분자로 구성된 군에서 선택된 적어도 하나를 함유하는 에폭시 친화성 블록(A); 및An 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
    알킬렌 고분자를 함유하는 에폭시 비친화성 블록(B)을 포함하며, An epoxy-incompatible block (B) containing an alkylene polymer,
    에폭시 수지 내에서 마이셀(micelle)을 형성하는 1액형 에폭시계 접착제 조성물. A one-part epoxy-based adhesive composition for forming a micelle in an epoxy resin.
  6. 제1항에 있어서,The method according to claim 1,
    상기 에폭시 양친성 블록공중합체는 중량평균 분자량(Mw)이 3,000 내지 10,000 g/mol이며, 2중 이상의 다중 블록 공중합체인 1액형 에폭시계 접착제 조성물.Wherein the epoxy-amphiphilic block copolymer has a weight average molecular weight (Mw) of 3,000 to 10,000 g / mol, and is a multi-block copolymer of two or more.
  7. 제1항에 있어서,The method according to claim 1,
    상기 우레탄 수지는, The urethane resin,
    폴리에테르, 폴리부타디엔 및 폴리에스테르로 구성된 군에서 선택되는 적어도 하나의 분절과, At least one segment selected from the group consisting of polyether, polybutadiene and polyester,
    페놀 및 폴리페놀 중 어느 하나로 캡핑된 이소시아네이트기를 갖는 프리폴리머인, 1액형 에폭시계 접착제 조성물. Wherein the prepolymer has an isocyanate group capped with any one of phenol and polyphenol.
  8. 제1항에 있어서,The method according to claim 1,
    상기 우레탄 수지는 중량평균 분자량(Mw)이 8,000 내지 40,000 g/mol이며, 점도가 440 내지 1280 Pa·s (40℃ 기준)인, 1액형 에폭시계 접착제 조성물. Wherein the urethane resin has a weight average molecular weight (Mw) of 8,000 to 40,000 g / mol and a viscosity of 440 to 1280 Pa 占 퐏 (based on 40 占 폚).
  9. 제1항에 있어서,The method according to claim 1,
    상기 경화제는 경화 개시 온도가 80℃ 이상인 1액형 에폭시계 접착제 조성물. Wherein the curing agent has a curing initiation temperature of 80 ° C or higher.
  10. 제1항에 있어서,The method according to claim 1,
    경화촉진제, 수분 제거제 및 충전제 중 적어도 하나를 더 포함하는 1액형 에폭시계 접착제 조성물. A curing accelerator, a moisture removing agent and a filler.
  11. 제10항에 있어서,11. The method of claim 10,
    상기 접착제 조성물은, 당해 접착제 조성물 100 중량부를 기준으로,The above-mentioned adhesive composition, based on 100 parts by weight of the adhesive composition,
    에폭시 수지 40 내지 70 중량부;40 to 70 parts by weight of an epoxy resin;
    페녹시 수지 3 내지 15 중량부; 3 to 15 parts by weight of a phenoxy resin;
    에폭시 양친성 블록공중합체 3 내지 13 중량부; 3 to 13 parts by weight of an epoxy amphiphilic block copolymer;
    우레탄 수지 5 내지 30 중량부; 5 to 30 parts by weight of a urethane resin;
    경화제 1.5 내지 15 중량부;1.5 to 15 parts by weight of a curing agent;
    경화촉진제 0.1 내지 4 중량부;0.1 to 4 parts by weight of a curing accelerator;
    수분제거제 0.5 내지 10 중량부; 및 0.5 to 10 parts by weight of a moisture removing agent; And
    충전제 2 내지 25 중량부2 to 25 parts by weight of a filler
    를 포함하는 1액형 에폭시계 접착제 조성물.Based epoxy adhesive composition.
  12. 제1항에 있어서, The method according to claim 1,
    레올로지 개선제, 유변성 조절제, 안료, 염료, 희석제, 가소제, 증량제, 난연제, 틱소트로프제, 팽창제, 유동제어제, 접착 촉진제, 열가소성 분말, 코어-쉘 고무, 이량화된 지방산, 및 산화방지제로 구성된 군에서 선택된 적어도 1종 이상의 첨가제를 더 포함하는 1액형 에폭시계 접착제 조성물. A rheology modifier, a rheology modifier, a pigment, a dye, a diluent, a plasticizer, an extender, a flame retardant, a thixotropic agent, an expander, a flow control agent, an adhesion promoter, a thermoplastic powder, a core- Wherein the adhesive composition further comprises at least one additive selected from the group consisting of the epoxy-based adhesive composition.
  13. 제1부재; A first member;
    상기 제1부재와 접착 결합되는 제2부재; 및 A second member adhered to the first member; And
    상기 제1부재와 제2부재 사이에 배치되고, 제1항 내지 제12항 중 어느 한 항에 따른 1액형 에폭시계 접착제 조성물을 경화시킨 접착제층The adhesive composition according to any one of claims 1 to 12, which is disposed between the first member and the second member,
    을 포함하는 물품. &Lt; / RTI &gt;
  14. 제13항에 있어서, 14. The method of claim 13,
    상기 제1부재와 제2부재는 서로 동일하거나 또는 상이하며, 각각 독립적으로 금속, 강판, 목재, 필름, 타일, 플라스틱, 유리, 수지, 세라믹, 콘크리트, 탄소재, 섬유 및 이들의 복합 소재로 이루어진 군으로부터 선택되는 물품.The first member and the second member may be the same or different from each other and each independently may be made of metal, steel, wood, film, tile, plastic, glass, resin, ceramic, concrete, carbon material, Goods selected from the Army.
  15. 제13항에 있어서, 14. The method of claim 13,
    상기 제1부재와 제2부재 중 하나는 알루미늄(Al) 또는 알루미늄 합금(alloy)계 부재이며, 다른 하나는 상기 제1부재와 동일하거나 또는 상이한 금속 부재인 물품. Wherein one of the first member and the second member is an aluminum (Al) or aluminum alloy member and the other is a metal member that is the same as or different from the first member.
  16. 제13항에 있어서, 14. The method of claim 13,
    ISO 11343 규격에 따라 측정시, 하기 (i) 내지 (iii)의 물성을 만족하는 물품: An article satisfying the following properties (i) to (iii) when measured according to ISO 11343:
    (i) -40℃ 충격박리강도가 20 N/mm 이상이며, (i) the impact peel strength at -40 캜 is 20 N / mm or more,
    (ii) 20℃ 충격박리강도가 30 N/mm 이상이며,(ii) the impact peel strength at 20 占 폚 is 30 N / mm or more,
    (iii) 80℃ 충격박리강도가 30 N/mm 이상임.(iii) Impact peel strength at 80 캜 is 30 N / mm or more.
PCT/KR2018/012593 2017-12-21 2018-10-24 Single-component epoxy-based adhesive composition and article using same WO2019124712A1 (en)

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