WO2019124713A1 - Single-component epoxy-based adhesive composition and article using same - Google Patents

Abstract

The present invention relates to a single-component epoxy-based adhesive composition for adhering a component comprising heterogeneous material, and an article using same. The present invention enables both excellent elongation properties and impact strength by resolving the differential in the thermal expansion properties between a non-metallic member introduced for weight reduction and a metallic member.

Description

One-pack epoxy-based adhesive composition and articles using the same

More particularly, the present invention relates to a one-component epoxy adhesive composition for bonding components made of different materials, and more particularly to a composition for overcoming the difference in thermal expansion characteristics between a non-metal member and a metal member introduced for weight reduction, Type epoxy adhesive composition and an article using the same.

In recent years, there has been a growing demand for lighter weight automobiles in accordance with environmental issues. Accordingly, there is an increasing tendency to utilize lightweight materials, especially carbon fiber reinforced plastic (CFRP) materials, in automobile structures.

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. Conventional structural adhesives used for bonding between metals are relatively important in ensuring durability against impact. Recently, adhesives for dissimilar materials for automobile lightweight have not only improved durability against impact but also overcome the difference in thermal expansion between different materials such as steel sheet and CFRP A stretching property is also required.

In order to overcome the thermal expansion characteristics between different materials, structural adhesives composed of polyurethane having excellent elasticity have been reported. Examples of the prior art for the structural adhesive include U.S. Pat. Nos. 2016/0053147, 5,548,056, 5,468,831 and 4,002,142 B9. Among the above-mentioned prior arts, the group showing excellent physical properties is a flexible resin such as polytrimethylene glycol and polytetramethylene glycol. However, the above-mentioned urethane-based adhesive has a problem that it can not satisfy the collision characteristics required in the automobile field.

Therefore, it is urgently required to develop a structural adhesive capable of stretching over thermal expansion characteristics between different kinds of materials introduced for the purpose of lightening automobile weight, and securing the required shear strength and impact properties as structural adhesives.

Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide an epoxy-based adhesive composition which is excellent in elongation and shock resistance by using glycidyl ether or glycidyl ester compound having at least two epoxy groups as one component of the epoxy- And to provide an adhesive composition for one-pack type epoxy structure which is capable of securing properties simultaneously.

In order to achieve the above object, A second epoxy compound containing at least two glycidyl ether groups or glycidyl ester groups; Toughness agents; And a curing agent, wherein the content ratio of the first epoxy compound and the second epoxy compound is 1: 0.05 to 2: 1.

According to an embodiment of the present invention, the second epoxy compound may be 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, castor oil polyglycidyl Ether, sorbitol polyglycidyl ether, hexahydrophthalic anhydride diglycidyl ester, and tetrahydrophthalic anhydride diglycidyl ester.

According to one embodiment of the present invention, the toughening agent may be a urethane resin having an isocyanate group capped at least at one end.

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.

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).

According to an embodiment of the present invention, the curing agent may have a curing initiation temperature of 80 ° C or higher.

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.

According to one embodiment of the present invention, the adhesive composition comprises, based on 100 parts by weight of the adhesive composition, 10 to 60 parts by weight of the first epoxy compound; 5 to 35 parts by weight of a second epoxy compound; 5 to 40 parts by weight of a toughening agent; 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.

According to one embodiment of the present invention, the adhesive composition may be selected from the group consisting of a rheology control agent, a rheology improver, a pigment, a dye, a diluent, a plasticizer, an extender, a flame retardant, a thixotropic agent, a swelling agent, a flow control agent, - at least one additive selected from the group consisting of a shell rubber, and an antioxidant.

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.

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.

According to an embodiment of the present invention, one of the first member and the second member may be a metal member, and the other may be a metal member different from the first base member, or a carbon fiber-reinforced plastic member.

The one-part epoxy-based structural adhesive composition according to the present invention can exhibit excellent stretching properties even when adhering different kinds of materials, and at the same time, physical properties such as impact peel strength, workability, adhesive force and shear strength are kept excellent .

Accordingly, the epoxy adhesive of the present invention is useful for fastening parts made of different materials in a wide range of industrial fields including automobile, aircraft, ship, space, civil engineering, and architectural fields.

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.

As used herein, the term " epoxy compound " means a compound having at least one epoxy group in a molecule, preferably a compound having at least two epoxy groups in a molecule, and includes a monomer, an oligomer, A compound in the form of a resin, and a resin, a polymer or an oligomer produced by a ring-opening reaction of an epoxy group, and the like. Preferably, the first epoxy compound of the present invention is in the form of a resin and the second epoxy compound may be in the form of a monomer, oligomer, polymer or resin.

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. Especially, in the transportation industry such as automobile, aircraft or ship, it is advantageous to use a structural adhesive rather than a mechanical fastening technique such as welding, thereby achieving weight reduction.

Currently, non-metallic parts such as CFRP are applied to lighten the automobile. Such a non-metallic material has a poor drawing characteristic due to a difference in thermal expansion from a metal part. Even if the additive is used to overcome the difference in thermal expansion, the impact property is lowered, and it becomes impossible to secure the physical properties as a structural adhesive.

Accordingly, in the present invention, an epoxy-based structural adhesive capable of overcoming the difference in thermal expansion between a non-metallic composite member (for example, a composite material such as CFRP) and a metal member (for example, aluminum and steel steel plate) .

Specifically, in the present invention, a specific epoxy compound (for example, a second epoxy compound) having at least two glycidyl ether groups or glycidyl ester groups as one component of the epoxy-based structural adhesive composition is used in an optimum ratio. It has been found that when the above-mentioned specific glycidyl ether or glycidyl ester compound is included as an epoxy adhesive component, excellent stretching property and impact property can be simultaneously realized. In addition, through the optimized combination of the second epoxy compound and other components, the present invention can exhibit the required properties required for the epoxy-based structural adhesive, for example, the shear strength, the stretching property and the impact peel strength as an overall excellent . Accordingly, the epoxy-based adhesive composition of the present invention can be usefully applied as a structural adhesive in a process of fastening parts of different materials in a wide range of industries including aircraft, ship, space, civil engineering, and architectural as well as automotive applications.

≪ One-component epoxy-based adhesive composition &

The one-pack type epoxy adhesive composition of the present invention is a structural adhesive agent capable of forming a structure, and is preferably a structural adhesive agent for the automotive field which adhesively bonds at least two members made of heterogeneous materials.

Specifically, the adhesive composition contains two kinds of epoxy compounds, toughening agents and hardening agents which are different from each other in an optimum ratio, and at least two glycidyl ether groups or glycidyl esters as one of the two types of epoxy compounds described above Group is used. 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.

Hereinafter, the composition of the one-part epoxy-based adhesive composition will be specifically described.

The first epoxy compound

In the one-pack epoxy-based adhesive composition according to the present invention, the first epoxy compound is an epoxy resin which is commonly used in the field of structural adhesives, and is used as a main resin.

The first epoxy compound may be any conventional epoxy resin known in the art without limitation, and includes a glycidyl ether group or a glycidyl ester group in the molecule as compared with the second epoxy compound described later.

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. Preferable examples of the first epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a structure of bisphenol A and bisphenol F, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Containing phenoxy resin, and the like.

In the present invention, the content of the first epoxy compound is not particularly limited and may be, for example, 10 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the epoxy- And more preferably 20 to 45 parts by weight. When the content of the first epoxy compound falls within the above-mentioned content range, excellent adhesion characteristics can be exhibited.

The second epoxy compound

In the one-part epoxy-based adhesive composition according to the present invention, the second epoxy compound may be any known compound having no less than two glycidyl ether groups or glycidyl ester groups in one molecule.

The second epoxy compound plays an advantageous role in terms of the adhesive strength and the viscosity, and the stretching property can be improved by mixing with the first epoxy compound.

Nonlimiting examples of the second epoxy compound that can be used include 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, Cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylol propane triglycidyl ether, glycerol polyglycidyl ether, castor oil polyglycidyl ether, Sorbitol polyglycidyl ether, hexahydrophthalic anhydride diglycidyl ester, and tetrahydrophthalic anhydride diglycidyl ester. In the present invention, it is also possible to use at least one selected from the group consisting of sorbitol polyglycidyl ether, hexahydrophthalic anhydride diglycidyl ester, and tetrahydrophthalic anhydride diglycidyl ester. Preferred are 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether , Castor oil polyglycidyl ether, sorbitol polyglycidyl ether, or combinations thereof.

In the present invention, the content of the second epoxy compound is not particularly limited and may be, for example, 5 to 35 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the epoxy- And more preferably 10 to 25 parts by weight. If the content of the second epoxy compound is less than 5 parts by weight, there is no effect of stretching. If the content of the second epoxy compound exceeds 35 parts by weight, the shear strength and impact peel strength may be lowered.

In one embodiment of the present invention, the content ratio between the first epoxy compound and the second epoxy compound may be 1: 0.05 to 2, preferably 1: 0.1 to 1.5, more preferably 1: 1 < / RTI > When the content ratio is satisfied, excellent adhesion properties and stretching properties can be realized at the same time. The total content of the epoxy compound containing the first epoxy compound and the second epoxy compound may be 40 to 70 parts by weight, preferably 50 to 100 parts by weight, relative to the total weight (for example, 100 parts by weight) of the epoxy- 68 parts by weight.

Urethane resin

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.

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.

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.

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.

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.

In the present invention, the content of the urethane resin is not particularly limited and may be, for example, 5 to 40 parts by weight, preferably 10 to 30 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 toughening effect is insignificant and the impact resistance is low. If the content of the urethane resin is more than 40 parts by weight, the toughening effect may be reduced due to low modulus.

Hardener

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.

The curing agent may be any conventional curing agent known in the art. 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.

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.

The curing agent may be used in an amount sufficient to cure the epoxy-based adhesive composition. It is generally used in a controlled amount so as to consume at least 60% of the epoxy groups present in the adhesive composition, and an excess amount more than that 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.

Hardening accelerator

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. 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. 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.

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).

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.

Filler

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.

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.

Moisture remover

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 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.

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.

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.

additive

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.

Examples of usable additives include, but are not limited to, rheology control agents, rheology improvers, pigments, dyes, diluents, plasticizers, extenders, flame retardants, thixotropic agents, swelling agents, flow control agents, adhesion promoters, thermoplastic powders, 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.

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.

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.

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. 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.

Particularly, the one-part epoxy adhesive composition of the present invention can be advantageously applied as a structural adhesive for automobiles, which is mainly used for weight reduction because it can secure excellent stretching property and impact property even when adhering different kinds of materials. The automotive structural adhesive may be used for bonding parts of different materials provided in a vehicle or for bonding such automobile parts to automobiles.

<Article>

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.

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.

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.

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. Here, aluminum means pure aluminum metal or any alloy containing 80 wt% or more of aluminum.

In one embodiment of the present invention, one of the first member and the second member may be a metal member and the other may be a metal member different from the first member, or may be a nonmetal composite member. In a preferred example, one of the first member and the second member may be a steel sheet of iron, aluminum, or an alloy thereof, and the other may be a carbon fiber-reinforced plastic (CFRP) member.

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.

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.

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.

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. The first member (e.g., a metal member) and the second member (e.g., a nonmetal member) may be welded before the epoxy-based structural adhesive is cured.

According to one embodiment of the present invention, the article may satisfy the following properties (i) and (ii). Specifically, (i) the elongation measured according to the ISO 527 standard is 3.0 N / 25 mm or more, and (ii) the impact peel strength measured according to the MS 715-60 standard may be 4.0 N / mm or more. And (iii) the shear strength measured in accordance with ISO 4587 may be greater than 15.0 MPa.

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.

[Examples 1 to 3] 1-part epoxy-based structural adhesive]

Example 1. Production of one-pack type epoxy structural adhesive

The components and composition ratios shown in Tables 1 and 2 below were combined to prepare a one-pack type epoxy adhesive composition.

Specifically, 59.6% by weight of bisphenol A type epoxy resin, 5.4% by weight of polypropylene glycol diglycidyl ester (PPGDGE, Kukdo Chemical Co., Ltd.) and 21.6% by weight of a urethane hardening agent were weighed into the reactor, Min. Then, 2.2 weight% of aluminum hydroxide, 3.2 weight% of calcium oxide and 3 weight% of hydrophobic fumed silica were added to the reactor and kneaded under vacuum for 30 minutes. Thereafter, 4.2% by weight of a curing agent and 0.5% by weight of a curing accelerator were added and vacuum kneaded for 30 minutes to prepare an adhesive composition of Example 1.

Examples 2 to 3

The one-part epoxy adhesive compositions of Examples 2 to 3 were prepared in the same manner as in Example 1, except that each component was blended according to the composition shown in Table 2 below.

Component	Detailed specification
The first epoxy compound	Bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd. / YD-128) - epoxy equivalent: 184 g / eq, viscosity: 11500 to 13500 cps
The second epoxy compound	Polypropylene glycol diglycidyl ester (PPGDGE, Kukdo Chemical / PG-207P) - Epoxy equivalent: 320 g / eq, viscosity = 70 cps
A tough topic	Urethane resin (HUNTSMAN / Flexibilizer DY-965) -Hydroxyl group equivalent: 612.5, viscosity: 440-1280 Pa s (40 캜)
Hardener	Evonik / Dicyanex ®® 1400
Hardening accelerator	Evonik / Amicure ®® UR-D
Moisture remover	Calcium oxide (swimming material / UNI-OX)
Filler 1	Aluminum hydroxide (Oriental material industry / H-WF-1)
Filler 2	Fumed silica (Evonik / Aerosil ® R202)

Constituent	Example 1	Example 2	Example 3	Comparative Example 1
The first epoxy compound	59.6	48.9	32.8	65.4
The second epoxy compound	5.4	16.3	32.6	0.0
A tough topic	21.6	21.7	21.8	21.3
Hardener	4.2	4.0	3.6	4.4
Hardening accelerator	0.5	0.5	0.5	0.5
Moisture remover	3.2	3.3	3.3	3.2
Filler 1	2.2	2.2	2.2	2.1
Filler 2	3.2	3.3	3.3	3.2
Total (wt%)	100	100	100	100

[Comparative Example 1]

A one-part epoxy-based structural adhesive composition of Comparative Example 1 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.

[Experimental Example. Property evaluation]

Test pieces were prepared using the one-part epoxy adhesive compositions prepared in Examples 1 to 3 and Comparative Example 1, and physical properties of the test pieces were measured by the following methods. The results are shown in Table 3 below.

In this case, cold-rolled steel sheet CR-440 and carbon fiber reinforced plastic (CFRP) were used as the first and second members for the following shear strength and impact peel strength measurement, respectively.

(1) Evaluation of single lap shear strength (Mpa)

Shear strength tests were carried out at 20 ° C and atmospheric pressure in accordance with ISO 4587.

(2) Elongation (%) Evaluation

The elongation test was carried out at 20 ° C and atmospheric pressure in accordance with the ISO 527 standard.

(3) Evaluation of Impact Peel Strength (N / 25 mm)

The impact peel strength test was carried out at 20 ° C and atmospheric pressure according to the MS 715-60 standard.

	Shear strength (MPa)	Elongation (%)	Impact Peel Strength (N / mm)
Example 1	26.9	3.0	21.2
Example 2	21.7	21.2	10.5
Example 3	15.1	35.3	4.3
Comparative Example 1	26.3	1.6	29.8

From the results of Table 3, Comparative Example 1 in which the essential constituents of the present invention were not included showed excellent shear strength and impact properties, but exhibited poor elongation properties. In contrast, Examples 1 to 3, in which the essential constituents of the present invention were all included, exhibited excellent shear strength, elongation, and excellent impact peel strength. Particularly, as the content of the glycidyl ether or glycidyl ester second epoxy compound increases, the elongation percentage increases, but the shear strength and impact peel strength tend to decrease.

From the above results, it can be confirmed that the one-part type epoxy adhesive composition according to the present invention can be effectively applied as a structural adhesive for adhesion between different materials in the automobile field.

Claims (12)

1. A first epoxy compound;

   A second epoxy compound containing at least two glycidyl ether groups or glycidyl ester groups;

   Toughness agents; And

   A curing agent,

   Wherein the content ratio of the first epoxy compound to the second epoxy compound is 1: 0.05 to 2 by weight.
2. The method according to claim 1,

   Wherein the second epoxy compound is selected from the group consisting of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4 -Cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, castor oil polyglycidyl ether, sorbitol polyglycidyl ether, Hexahydrophthalic anhydride diglycidyl ester, and tetrahydrophthalic anhydride diglycidyl ester. The one-pack type epoxy adhesive composition according to claim 1,
3. The method according to claim 1,

   Wherein the toughening agent is a urethane resin having an isocyanate group capped at least at one end thereof.
4. The method of claim 3,

   The urethane resin,

   At least one segment selected from the group consisting of polyether, polybutadiene and polyester,

   Wherein the prepolymer has an isocyanate group capped with any one of phenol and polyphenol.
5. The method of claim 3,

   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).
6. The method according to claim 1,

   Wherein the curing agent has a curing initiation temperature of 80 ° C or higher.
7. The method according to claim 1,

   A curing accelerator, a moisture removing agent and a filler.
8. 8. The method of claim 7,

   The adhesive composition may contain, based on 100 parts by weight of the adhesive composition,

   10 to 60 parts by weight of the first epoxy compound;

   5 to 35 parts by weight of a second epoxy compound;

   5 to 40 parts by weight of a toughening agent;

   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

   Based epoxy adhesive composition.
9. The method according to claim 1,

   The present invention relates to a process for the preparation of a composition for the preparation of a pharmaceutical composition comprising an effective amount of at least one compound selected from the group consisting of a rheology modifier, a rheology improver, a pigment, a dye, a diluent, a plasticizer, an extender, a flame retardant, a thixotropic agent, Wherein the adhesive composition further comprises at least one additive selected from the group consisting of the epoxy-based adhesive composition.
10. A first member;

    A second member adhered to the first member; And

    Wherein the one-component epoxy adhesive composition according to any one of claims 1 to 9, which is disposed between the first member and the second member,

    &Lt; / RTI &gt;
11. 11. The method of claim 10,

    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.
12. 11. The method of claim 10,

    Wherein one of the first member and the second member is a metal member and the other is a metal member or a carbon fiber-reinforced plastic member different from the first base member.