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WO2018221898A1 - Two-component adhesive composition - Google Patents

Two-component adhesive composition Download PDF

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Publication number
WO2018221898A1
WO2018221898A1 PCT/KR2018/005987 KR2018005987W WO2018221898A1 WO 2018221898 A1 WO2018221898 A1 WO 2018221898A1 KR 2018005987 W KR2018005987 W KR 2018005987W WO 2018221898 A1 WO2018221898 A1 WO 2018221898A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
adhesive composition
group
weight
Prior art date
Application number
PCT/KR2018/005987
Other languages
French (fr)
Korean (ko)
Inventor
오완규
최경신
박승영
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180058409A external-priority patent/KR102136705B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/345,286 priority Critical patent/US10988640B2/en
Priority to EP18809891.7A priority patent/EP3508541B1/en
Priority to CN201880004169.0A priority patent/CN109890920B/en
Publication of WO2018221898A1 publication Critical patent/WO2018221898A1/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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a two-part adhesive composition, which can realize excellent lap shear strength and adhesion.
  • Two-component acrylic adhesives are used in fields such as automotive, construction, marine, wind power, etc. due to the advantages of being able to be cured at room temperature, large-area adhesive, fast curing, and adhesive to various plastics.
  • the two-component acrylic adhesive has a disadvantage in that the adhesive strength is lower than that of the one-component epoxy adhesive, and the elongation is lower than that of the urethane adhesive. As a result, more strong adhesive force, such as structural adhesive of the vehicle. And use in areas where high elongation is required, such as adhesion outside the vehicle.
  • the present invention is to provide a two-component adhesive composition, which can realize excellent lap shear strength and adhesion.
  • the present invention is a.
  • the two-part adhesive composition according to the present invention may include a (meth) acrylate-based compound having a specific composition, thereby achieving high adhesion according to excellent tensile overlapping shear strength, and exhibiting excellent adhesion to metal and plastic substrates. It can be used as an adhesive in various fields such as for vehicles, construction, ships, wind power.
  • each layer or element when each layer or element is referred to as being formed “on” or “on” of each layer or element, it means that each layer or element is directly formed on each layer or element, or It means that a layer or element can be additionally formed between each layer, the object, the substrate.
  • (meth) acrylate is used in the concept including both acrylate and methacrylate.
  • the adhesive composition includes a (meth) acrylate-based compound having a functional group of a specific structure in addition to the (meth) acrylate-based compound that is generally used, thereby improving tensile overlapping shear strength at the time of adhesion, It is possible to provide a two-part adhesive composition, which can exhibit high adhesion.
  • the effect of the invention can be further improved by controlling the type or physical property of each component.
  • the components will be described in detail.
  • one portion of the crab is a main portion and includes the following configuration.
  • the alkyl (meth) acrylate includes both alkyl acrylate monomers and alkyl methacrylate monomers.
  • the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms. If the alkyl group contains more than 20 carbon atoms, the glass transition temperature (Tg) of the adhesive composition may be high or the adhesion control may be difficult.
  • alkyl (meth) acrylate examples include methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylnuclear (meth) acrylate n-octyl (meth) acrylate, isooctyl (meth) acrylate, As isononyl (meth) acrylate, lauryl (meth) acrylate or tetradecyl (meth) acrylate, etc. are mentioned, 1 type, or 2 or more types of these can be used.
  • the alkyl group may be more specifically a linear or branched alkyl group having 1 to 4 carbon atoms, More specifically, it may be a methyl group or an ethyl group.
  • alkyl (meth) acrylates the total (meth) acrylate-based monomers common compound total, based on the weight of the can be included as about 40 to about 70 parts by weight 0/0, when included in such a content range, wet with and good adhesion Wetting properties can be improved.
  • the content of the alkyl (meth) acrylate is small, there is a fear that the wettability between the adhesive and the adherend is lowered.
  • the content is too high, there is a fear that the adhesive property is lowered.
  • the alkyl (meth) acrylates wherein the alkyl (meth) acrylate may be included to more specifically about 50 to about 60 Increased 0/0.
  • the (meth) acrylate compound which has an alkoxysilyl group contains all the monomers of the form in which the alkoxysilyl group substituted the alkyl group of the alkyl (meth) acrylate mentioned above.
  • the alkoxy group connected to the silicon source may be an alkoxy group having a linear or branched alkyl structure having 1 to 5 carbon atoms, and such alkoxy group is a monoalkoxysilyl group or dialkoxysilyl group having 1 to 3 carbon atoms connected to the silicon atom. It may be in the form of a trialkoxy silyl group. And, these alkoxysilyl groups may be in the form of being connected to the (meth) acryloyl group through an alkylene linking group having 1 to 5 carbon atoms. have.
  • Specific examples include mono, di, trimethoxysilylmethyl (meth) acrylate, methyl methacrylate, mono, di, trimethoxysilylethyl (meth) acrylate, mono, di, trimethoxysilylpropyl (meth) Acrylate and the like, and one or two or more of these may be used.
  • the alkyl group in the alkyl (meth) acrylate is more specifically a linear or branched alkyl group having 1 to 4 carbon atoms. It may be, and more specifically, may be an ethyl group or a propyl group.
  • (Meth) acrylate-based monomers common compound gun may be included as about 1 to about 10 parts by weight 0/0 by weight of contrast, when included in such a content range, metal, synthetic plastic, and excellent for a variety of bonding target substrate of glass or the like Adhesive properties can be implemented.
  • the alkoxysilyl group may react chemically with the silica-based layering agents such as silica and hollow silica of the sugar adhesive, thereby forming a secondary crosslink between the silica-based filler and the monomer, Better adhesion properties can be achieved.
  • the (meth) acrylate compound having an unsaturated functional group in the acryloyl group is a form in which an ethylenically unsaturated functional group other than the acryloyl group is substituted in the alkyl group of the alkyl (meth) acrylate described above. It includes all monomers of.
  • the ethylenically unsaturated functional group may be connected in the form of vinyl or allyl group, and in addition, the vinyl group may have a form connected by an alkylene linking group having 1 to 5 carbon atoms.
  • Such compounds include allyl (meth) acrylate, vinyl (meth) acrylate, propenyl (meth) acrylate, butenyl (meth) acrylate, and the like.
  • Compounds can be used, considering the effect of improving the adhesion of the alkylene by controlling the carbon number, vinyl (Meth) acrylate and allyl (meth) acrylate may be more preferred.
  • the urethane acrylate oligomer may improve the wetting properties between the adhesive and the adherend, increase the formation of hydrogen bonds with the filler ' or the alkyl (meth) acrylate, and improve the adhesion properties of the adhesive composition by increasing the dispersion of the adhesion enhancer. Can be.
  • the urethane acrylate oligomer is a concept including an aliphatic urethane (meth) acrylate oligomer, aromatic urethane (meth) acrylate oligomer, it may be preferable to use a molecular weight of the urethane is about 200 to about 40,000 g / m , The equivalent of acrylate, may be from about 1 to about 20 per oligomer.
  • oligomers having a molecular weight of about 1,000 to about 20,000 and containing 2 to 10 acrylate functional groups can be used.
  • urethane acrylate oligomer examples include Miramer PU2030i, PU2050, PU2300C, PU3000, PU3450, MU9500, SC2152, Enexryl 230, 244, 284, 4883, 8254, 8411, 8413, 8807, Arkema Corporation CN929, CN964, CN965, CN980, CN981, CN986, CN996, CN9005, CN9013, CN9026, etc. are mentioned, One or two or more combinations of these can be used.
  • the urethane acrylate oligomer, the entire (meth) acrylate-based monomers common compound total from about 10 to about 40 parts by weight 0/0, preferably, based on the weight from about 15 to about It may be included in an amount of 30% by weight. If the content is too small, the wettability between the adhesive and the adherend is lowered, the problem that the lamination strength is lowered at the joint surface after curing is known, and if the content is too high, the dispersion of the adhesive strengthening agent is lowered, Problems that the hardness of the surface is too low may occur.
  • the adhesion strengthening agent serves to improve mechanical properties in the adhesive composition, and may include rubber, rubber copolymers or rubber derivatives.
  • terminally terminated butadiene rubber chlorinated butadiene rubber, chlorosulfonated butadiene rubber, nitrile butadiene rubber (NBR), Butadiene-based rubbers such as styrene butadiene rubber (SBR); Silicone rubber; Styrene-butadiene-polymethylmethacrylate triblock copolymer, acrylonitrile-butadiene-styrene copolymer (poly (acrylonitrile-butadiene-styrene)), styrene-butadiene-styrene copolymer rubber copolymers such as (poly (styrene-butadiene styrene)); Or rubber derivatives and the like, and any one or two or more of these may be used.
  • the adhesion enhancer may comprise a core-shell rubber, or may comprise a non-core shell rubber.
  • the core shell rubber is a graft copolymer of the "core shell” type or "shell-free” crosslinked rubbery particulates such as acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS) and Methacrylate-acrylonitrile-butadiene-styrene (MABS).
  • the terminal vinylated butadiene rubber may be a liquid at room temperature, and It may have a glass transition temperature of less than o ° c.
  • the terminal vinylation is
  • (Meth) acrylate-terminated forms such as (meth) acrylate-terminated polybutadiene-acrylonitrile copolymers (such as HYCAR VTBN, etc.) or (meth) acrylate-terminated polybutadiene (such as HYCAR VTB (Emerald Performance) polymer's may be (Emerald Performance polymers)).
  • the adhesion enhancing agent, terminal binilhwa of about 20 for the butadiene rubber in the adhesive strength agents total weight 0 /. or less, and more specifically, in an amount from about 5 to about 15% by weight It may include.
  • the adhesive strengthening agent as described above may be included in an amount of 50 to 100 parts by weight, and preferably about 50 to about 70 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer mixture.
  • the content of the adhesive strengthening agent is too small, there is a fear that the mechanical properties of the adhesive composition are lowered, and when the content is too high, the adhesion with the substrate may be lowered.
  • the layering agent serves to improve the mechanical properties of the adhesive composition together with the adhesion enhancing agent.
  • the layering agent may include silica, article silica, nanoclay, and the like, and any one or two or more of these may be used.
  • the filler may include a silica-based layering agent, such as silica, fused silica, and the like, in consideration of the effect of improving the fluidity and small particle reinforcing properties of the adhesive composition, and may include an effect of controlling the depression of the applied adhesive beads. At this time, it may include a fused silica.
  • a silica-based layering agent such as silica, fused silica, and the like
  • the filler is included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer mixture, and preferably, about 2 to about 8 parts by weight.
  • the content of the layering agent is too small, the effect of improving mechanical properties may be lowered.
  • the content of the layering agent is too large, there is a fear of deterioration of adhesion and adhesion to the substrate.
  • the second portion is based on (bl) 100 parts by weight of the epoxy resin; (b2) containing saccharin and a leuridine-based compound 50 to 200 parts by weight of initiator. (Epoxy resin)
  • the epoxy resin affects the dielectric constant and dielectric loss coefficient of the adhesive composition and the adhesive film prepared therefrom, and serves to improve heat resistance and mechanical properties.
  • the type of the epoxy resin is not particularly limited, but having an epoxy equivalent of 200 g / eq to 500 g / eq may lower the dielectric constant and dielectric loss factor while increasing the heat resistance of the adhesive composition.
  • epoxy resins include cycloaliphatic epoxides, epoxy novolac resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, bisphenol-A epichlorohydrin-based epoxy resins, alkyl epoxides, and dicyclopentadiene phenol additions.
  • Reactive epoxy resins, limonene dioxide or polyepoxide, and the like, and any one or two or more of these may be used.
  • the said epoxy resin is contained in the said 1st liquid, when it mixes with a 1st liquid
  • About 100 parts by weight of the (meth) acrylate monomer may be used in an amount of about 1 to about 10 parts by weight, preferably about 2 to about 8 parts by weight.
  • the content of the epoxy resin is too small, the effect of improving heat resistance and mechanical properties may be lowered, and in too many cases, the fluidity of the composition may be excessively increased.
  • the initiator serves to initiate the polymerization reaction through the provision of free radicals, and the curing rate and adhesion may be improved depending on the combination of the initiator type and the curing accelerator.
  • the initiator is diisopropyl benzene hydroperoxide, t-nucleic acid hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclonuxanone Peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide 1,1-di ( ⁇ -butyl peroxy) cyclonucleic acid, 1,1-di (t -Butyl peroxy) 3,3,5-trimethylcyclonucleic acid : hydrogen peroxide, t-butyl peroxybenzoate, t-butyl peroxy 2-ethyl nucleosanate, bis (4-t-butylcyclonucleus
  • Such an initiator when mixed with the first liquid, is used in an amount of about 0.1 to about 10 parts by weight, or about 1 to about 5 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer included in the first solution. Can be.
  • the second portion may further include carbon nanotubes having an aspect ratio of 1 ⁇ 10 2 to 1 ⁇ 10 5 .
  • the carbon nanotube is a carbon structure in which a hexagonal honeycomb pattern in which six carbons are connected is combined to form a tube.
  • the carbon nanotube has a very high aspect ratio, and has a high polymer composite material with excellent mechanical properties, heat resistance, and chemical resistance. It has been used a lot as a layered material.
  • the carbon nanotubes may exhibit the effect of the nanocomposite together with the polymer resin used as the adhesion enhancing agent, and as a result, the mechanical properties, chemical resistance, and adhesiveness of the adhesive composition And heat resistance can be improved.
  • the carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, and the plurality of carbon nanotubes may be arranged side by side with the carbon nanotubes as a unit.
  • Bundled bundles of carbon nanotubes in the form of bundles or ropes, or non-bundle Ehsms entangled type carbon nanotubes in which the carbon nanotube units do not have a uniform shape such as bundles or ropes Can be. Any of these One or more combinations may be used.
  • the carbon nanotubes may be multi-walled carbon nanotubes in consideration of the improvement effect of improving the adhesiveness and heat resistance of the adhesive composition, and may be bundled carbon nanoleubes in view of excellent dispersibility in the adhesive composition.
  • the carbon nanotubes may have a large aspect ratio ranging from about 1 nm to about 50 nm in diameter and several tens / m in length.
  • the carbon nanotubes may be used for dispersing carbon nanotubes and forming a nanocomposite with an adhesive strengthening agent.
  • the carbon nanotubes can be of aspect ratio (length / diameter ratio) of about 2 to about 1X10 1X10 5, more specifically about 2 to about 5X10 5X10 4.
  • the carbon nanotubes may have a BET specific surface area of about 150 m 2 / g or more, or about 200 m 2 / g to about 500 m 2 / g, more specifically about 220 to about 300 m 2 / g.
  • the strand diameter of the carbon nanotubes may be about 2 nm to about 30 nm, and black is about 5 nm to about 20 nm, and more specifically about 5 nm to about 15 nm.
  • the most important factor to secure excellent properties in the composite of carbon nanotubes is the uniform dispersion of carbon nanotubes. Even in the case of adhesives containing carbon nanotubes, excellent dispersion can be achieved in mechanical properties such as strength and elasticity. Dispersibility can be improved by covalent attachment of species at the sidewalls and ends or at the defect sites of the carbon nanotubes, which are sandwiched between the bundles of carbon nanotubes to facilitate dispersion of the carbon nanotubes in the adhesive composition. Let's do it. In addition, it is possible to increase the dispersibility of the carbon nanotubes in the adhesive composition through surface modification through non-covalent bonds. Accordingly, in order to improve adhesion, it is important to find the modification of the optimum conditions, thereby improving the structure between the carbon nanotubes and the adhesive.
  • the carbon nano-leave may be used in the form of a dispersion solution dispersed in a dispersion medium.
  • the dispersion medium may include n-vinylpyridone, butyl acrylate, acrylic acid, benzoate ester oil or methyl methacrylate, and among these, excellent compatibility with carbon nanotubes and storage stability may be considered.
  • the dispersion medium for dispersing the carbon nanotubes is a constituent of the adhesive composition according to the present invention, the carbon nanotubes are first mixed with the above-mentioned compounds and dispersed in the preparation of the adhesive composition, and then used as a method of mixing by adding the remaining components. Can be.
  • Such carbon nanotubes may be included at about 0.01 to about 1 parts by weight 0/0 with respect to the total weight of the adhesive composition.
  • the content of the carbon nanotubes is too small, the effect of improving the adhesion force by using the carbon nanotubes is insignificant, and when too much, there is a fear of a decrease in the degree of dispersion and adhesion to the substrate.
  • Adhesive composition according to an embodiment of the present invention, at least one of the above (i) and (ii), within the range that does not inhibit the effect of the present invention in addition to the above components, additives commonly known, Specifically, it may further include one or more additives such as adhesion promoters, inhibitors, accelerators, antioxidants, lubricants, initiators, oils, curing agents, or curing accelerators.
  • the adhesion promoter is a material that forms a crosslink for metallic interaction with the metal surface and for strengthening the polymer network.
  • the mono-ester, phosphonic acid of phosphinic acid having 1 unit of vinyl or allyl unsaturated group Or phosphorus-containing compounds such as mono- and diesters of phosphoric acid.
  • More specific examples include phosphoric acid; 2-methacryloyloxyethyl phosphate, bis- (2-methacryloyloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, bis- (2-acryloyloxyethyl) phosphate, methyl-(2 -Methacryloyloxyethyl) phosphate, ethyl methacryloyloxyethyl phosphate, methyl acryloyloxyethyl phosphate, ethyl acryloyloxyethyl phosphate, propyl acryloyloxyethyl phosphate, Such as isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloylethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate or
  • adhesion promoter is (meth) acrylic acid or metal
  • Such an adhesion promoter may be included in the first portion of the adhesive composition, and may be included in about 0.5 to about 10 weight 0 /. More specifically, about 1 to about 5 weight% based on the total weight of the polymer.
  • the inhibitor also serves to stabilize the adhesive composition and inhibit the early free radical polymerization of alkyl (meth) acrylates to provide suitable initiation times. Specific examples include naphthoquinone, anthroquinone, methyl hydroquinone, benzoquinone or methylether hydroquinone, and the like, and any one or two or more of these may be used.
  • the inhibitor may comprise from about 0.01 to 1 parts by weight 0 /., More specifically from 0.01 to 0.5 0/0, based on the total adhesive, it may be included in the first section among the adhesive composition by weight of the composition.
  • the accelerator serves as a catalyst for accelerating or accelerating the curing of the adhesive composition, and specifically, may include an amine compound.
  • the amine compound is a secondary amine (HN (Ra) 2, Ra is each independently C4 to C10 alkyl, etc.), tertiary amine (N (Rb) 3, wherein Rb are each independently, C1 to C20 alkyl , C6 to C20 aryl, C7 to C20 alkylaryl or C7 to C20 arylalkyl), aromatic amine or heterocycle amine, more specifically 1,8-diazabicyclo (5.4.0) -7-ene (DBU), 1,4-diazabicyclo (2.2.2) octane (DABCO), triethylamine, guanidine-based compounds (such as tetramethylguanidine (TMG), etc.), rurudine-based compounds (such as dimethyl -P-lluidine (DMPT), diethyl -P-lluidine (DEPT), dihydroxy ethyl P-toluidine, dimethyl-P-lluidine (DMPT) or dimethyl
  • the promoter may be included in the first portion to among the adhesive composition, more specifically from about 0.1 to 5 parts by weight 0/0, with respect to the total weight of the adhesive composition may comprise from about 1 to about 3 parts by weight 0 /.
  • the antioxidant exhibits an antioxidant effect, such as improving the thermal stability of the adhesive composition, phosphorus-based, phenol-based, amine-based, or sulfur-based antioxidants may be used.
  • the phosphorus antioxidant may include phosphate esters such as (Triphenylphosphate; TPP) and (Triethyl Phosphate; TEP); Diethyl ( 3 , S-di-t-butyl 4-hydroxybenzyl) phosphonate (Diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate), bis (2,6-dit- butyl-4-methylphenyl) penta-erythro Li the diphosphite (bis (2,6-di-tert -butyl-4- methylphenyl) pentaerythritol diphosphate), bis (2, 4-di-t- butylphenyl) penta depot for re-erythro Spite (bis (2,4-di-tert-butylphenyl) pentaerytryltol diphosphate), bis (2,4-dicumylphenyl) pentaerythritol diphosphi
  • phenolic antioxidant 2,6-di-tert-butyl-P-cresol (2,6, -do-tert- butyl-p-cresol), tetrakis [methylene-3- (3,5] -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, Hindered phenol type compounds, such as ⁇ '-nucleic-acid 1, 6- diyl bis [3- (3, 5- di-tert- butyl- 4-hydroxyphenyl propionamide], are mentioned, These Either one or two or more combinations thereof may be used.
  • the antioxidant may be included as may be included in the first section among the adhesive composition, from about 0.1 to about 1% by weight based on the total adhesive composition increase, more specifically from about 0.1 to about 5 parts by weight lead 0/0.
  • the lubricant is to increase the moldability, and serves to provide a release property when desorption with the substrate, specifically, waxes such as olefin wax, montan wax, montanic acid ester wax may be used.
  • the lubricant may be included in to the first portion, among the adhesive composition, it is because there is a risk of moldability decreases if included in excess, more specifically from about 0.1 to about 1 parts by weight 0/0, with respect to the adhesive composition total weight is about 0.1 to about 0.5 can be included in a weight 0/0.
  • the adhesive composition may be an oil (eg, a benzoate ester oil such as alkyl benzoate, etc.); Curing agents (eg, ethylene diamine trianhydride, etc.); Curing accelerators (e.g., containing at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin, such as Cu naphtalenate, cobalt naphthenate) Additives such as organometallic salts or organometallic complexes).
  • the first and second parts having the configuration as described above may exhibit an appropriate viscosity through the kind and control of the components.
  • the second portion may have a higher viscosity than the first portion, more specifically, the viscosity of the crab portion is about 5,000 to about 60,000 cps, and the second portion has a viscosity of about 50,000 to about 150,000 cps. It may be higher than the viscosity of the first portion in the range of.
  • the adhesive composition according to the present invention can be used by preparing 1 part and 8 parts respectively of a mixture of the above-mentioned components, and then mixing 1 part and 2 parts of a crab when used to start semi-acupoint curing.
  • the first portion: two crabs may be mixed in a weight ratio of about 1: 1 to about 20: 1, preferably, about 5: 1 to about 15: 1, more preferably about 7: 1 To about 12: 1.
  • the ratio of 12 parts is too small, the curing of the adhesive may be uneven, and the problem of deterioration of adhesive strength, heat resistance and durability of the adhesive surface may occur, and when the ratio of the second part is too large, Problems may arise in the compatibility and solubility between the materials.
  • the adhesive composition having the composition as described above includes an initiator of a specific component, and proceeds with a stable polymerization initiation reaction, and thus shows excellent adhesion, such as zinc, copper, cadmium, iron, tin, aluminum, silver, chromium, and these metals.
  • an initiator of a specific component proceeds with a stable polymerization initiation reaction, and thus shows excellent adhesion, such as zinc, copper, cadmium, iron, tin, aluminum, silver, chromium, and these metals.
  • substrates including metals, polymers, reinforced plastics, fibers, glass, ceramics, wood, etc., such as alloys, and galvanized steels including hot dip galvanized and galvanealed steels. It can be used as an adhesive, a primer or a coating for, and can be used for heterojunction such as metal or plastic.
  • Carbon nanotubes aspect ratio: 1 ⁇ 10 4 , diameter: 5-20 nm, BET specific surface area: 220-300 m 2 / g; Vinyl terminated butadiene rubber: Emerald VTBN 1300X43;
  • Chlorosulphonated polyethylene CSM3570 from Santi Chemical
  • Nano titania Ti02 nanoparticles from US-Nano;
  • Lap shear strenth was measured by ASTM D 3163, and then summarized in a table.
  • Dongbu Steel Co., Ltd. general rolled / bright steel sheet (Cold Rolled Steel, CRS) substrate was used as the base material to be bonded.
  • the tensile overlapping shear strength value of about 20 MPa or more can be seen, and it can be confirmed that the adhesive strength is generally excellent.
  • Example 1 shows a value of about 28.6MPa, when homogeneous bonding of the CRS cold-rolled steel sheet, which is a metal material, it can be clearly seen that it is possible to implement a very excellent adhesive strength compared to the conventional.
  • the two-part adhesive composition of the present invention is considered to be applicable to various applications in industrial fields in which metals, polymer resin substrates, and the like are used.

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

Abstract

The present invention relates to an acryl-based adhesive composition that comprises acrylate-based compounds of particular ingredients and can realize excellent lap shear strength and adhesive strength.

Description

【발명의 명칭】  [Name of invention]
이액형 접착제 조성물  Two-part adhesive composition
【기술분야】 Technical Field
관련 출원 (들ᅵ과의 상호 인용  Cross citation with related application (s)
본 출원은 2017년 6월 2일자 한국 특허 출원 제 10-2017-0069237호 및 2018년 5월 23일자 한국 특허 출원 제 10-2018-0058409호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. 본 발명은 우수한 인장증첩 전단강도 (lap shear strength) 및 접착력을 구현할 수 있는, 이액형 접착제 조성물에 관한 것이다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0069237 dated June 2, 2017 and Korean Patent Application No. 10-2018-0058409 dated May 23, 2018. All content disclosed in the literature is included as part of this specification. The present invention relates to a two-part adhesive composition, which can realize excellent lap shear strength and adhesion.
【배경기술】 Background Art
이액형 아크릴 접착제는 상온 경화가 가능하고， 대면적 접착이 가능하며, 속경화되고, 다양한 플라스틱에 대해 접착성을 나타낸다는 장점으로 인해 차량용， 건축용， 선박용, 풍력용 등의 분야에 사용되고 있다.  Two-component acrylic adhesives are used in fields such as automotive, construction, marine, wind power, etc. due to the advantages of being able to be cured at room temperature, large-area adhesive, fast curing, and adhesive to various plastics.
그러나, 이액형 아크릴 접착제는 일액형 에폭시 접착제 비해서는 접착력이 떨어지고, 우레탄 접착제에 비해서는 연신율이 떨어지는 단점이 있다. 이에 따라 차량의 구조용 접착제 등 보다 강력한 접착력. 및 차량 외부의 접착 등 높은 연신율이 요구되는 분야에는 사용이 제한되었다.  However, the two-component acrylic adhesive has a disadvantage in that the adhesive strength is lower than that of the one-component epoxy adhesive, and the elongation is lower than that of the urethane adhesive. As a result, more strong adhesive force, such as structural adhesive of the vehicle. And use in areas where high elongation is required, such as adhesion outside the vehicle.
또, 다양한 접착체 조성물에서 유연성 /인성 및 강도 사이에는 트레이드 오프 관계가 존재한다. 통상 접착제 조성물내 유연성 및 인성을 증가시키기 위하여, 고무상 폴리머가 첨가되나, 이와 같은 고무상 폴리머의 첨가는 상기 접착제의 모들러스 및 최종적으로 강도에 악영향을 미치게 된다. 따라서 강도의 희생 없이 우수한 접착력을 나타내는 접착제 조성물의 개발이 요구된다.  In addition, there is a trade off relationship between flexibility / toughness and strength in various adhesive compositions. Rubbery polymers are usually added to increase flexibility and toughness in the adhesive composition, but the addition of such rubbery polymers adversely affects the modulus and finally strength of the adhesive. Therefore, there is a need for the development of adhesive compositions that exhibit good adhesion without sacrificing strength.
【발명의 상세한 설명】 [Detailed Description of the Invention]
【기술적 과제】 본 발명은 우수한 인장중첩 전단강도 (lap shear strength) 및 접착력을 구현할 수 있는， 이액형 접착제 조성물을 제공하는 것이다. [Technical problem] The present invention is to provide a two-component adhesive composition, which can realize excellent lap shear strength and adhesion.
【기술적 해결방법】 Technical Solution
본 발명은  The present invention
(i) 하기 (al) 내지 (a3)의 성분을 포함하는 제 1부분; 및 (ii) 하기 (bl) 및 (b2) 성분을 포함하는 제 2부분을, 1 : 1 내지 20: 1의 중량비로 포함하는 이액형 접착제 조성물을 제공한다.  (i) a first portion comprising the components of (al) to (a3) below; And (ii) a second portion comprising the following (bl) and (b2) components in a weight ratio of 1: 1 to 20: 1.
0)  0)
(al) (al l) 알킬 (메트)아크릴레이트 화합물; 및  (al) (al l) alkyl (meth) acrylate compounds; And
(a 12) (al21) 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물 및 (a 122) 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물 중 어느 하나 이상을; 포함하는，  (a 12) any one or more of a (meth) acrylate compound having an (al21) alkoxysilyl group and a (meth) acrylate compound having an unsaturated functional group in addition to the (a 122) acryloyl group; Including
(메트)아크릴레이트계 단량체 흔합물 100중량부;  100 parts by weight of the (meth) acrylate monomer mixture;
(a2) 접착강화제 50 내지 100중량부; 및  (a2) 50 to 100 parts by weight of an adhesive strengthening agent; And
(a3) 충진제 1 내지 10중량부;  (a3) 1 to 10 parts by weight of the filler;
(")  (")
(bl) 에폭시 수지 100 중량부에 대하여;  (bl) 100 parts by weight of an epoxy resin;
(b2) 개시제 50 내지 150중량부.  (b2) 50 to 150 parts by weight of initiator.
[발명의 효과】 [Effects of the Invention】
본 발명에 따른 이액형 접착제 조성물은, 특정 조성의 (메트)아크릴레아트계 화합물을 포함하여 우수한 인장중첩 전단강도에 따른 고접착력을 구현할 수 있고， 금속 및 플라스틱 기재에 대해 우수한 접착 특성을 나타낼 수 있어， 차량용， 건축용, 선박용, 풍력용 등의 다양한 분야에 접착제로서 사용될 수 있다.  The two-part adhesive composition according to the present invention may include a (meth) acrylate-based compound having a specific composition, thereby achieving high adhesion according to excellent tensile overlapping shear strength, and exhibiting excellent adhesion to metal and plastic substrates. It can be used as an adhesive in various fields such as for vehicles, construction, ships, wind power.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다"， "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 숫자， 단계， 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지 , 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. The terminology used herein is for the purpose of describing exemplary embodiments only. As used, it is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
또한 본 발명에 있어서， 각 층 또는 요소가 각 층들 또는 요소들의 "상에" 또는 "위에" 형성되는 것으로 언급되는 경우에는 각 층 또는 요소가 직접 각 층들 또는 요소들의 위에 형성되는 것을 의미하거나, 다른 층 또는 요소가 각 층 사이, 대상체， 기재 상에 추가적으로 형성될 수 있음을 의미한다.  Also, in the present invention, when each layer or element is referred to as being formed "on" or "on" of each layer or element, it means that each layer or element is directly formed on each layer or element, or It means that a layer or element can be additionally formed between each layer, the object, the substrate.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바， 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.  As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
본 명세서에서, (메트)아크릴레이트라고 함은, 아크릴레이트 및 메타크릴레이트를 모두 포함하는 개념으로 사용된다.  In the present specification, (meth) acrylate is used in the concept including both acrylate and methacrylate.
이하 발명의 구체적인 구현예에 따른 이액형 아크릴 접착제에 대해 설명하기로 한다.  Hereinafter, a two-component acrylic adhesive according to a specific embodiment of the present invention will be described.
본 발명의 일 측면에 따른 이액형 접착제 조성물은， (i) 하기 (al) 내지 Two-part adhesive composition according to an aspect of the present invention, (i) to (al) to
(a3)의 성분을 포함하는 제 1부분; 및 (ii) 하기 (bl) 및 (b2) 성분을 포함하는 게 2부분을 포함한다. a first portion comprising the component of (a3); And (ii) two parts comprising the following (bl) and (b2) components.
(i)  (i)
(al) (al l) 알킬 (메트)아크릴레이트 화합물; 및  (al) (al l) alkyl (meth) acrylate compounds; And
(al2) (al21) 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물 및 (al2¾ 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물 중 어느 하나 이상을; 포함하는，  (al2) (al21) any one or more of (meth) acrylate compounds having an alkoxysilyl group and (meth) acrylate compounds having an unsaturated functional group in addition to (al2¾ acryloyl group);
(메트)아크릴레이트계 단량체 흔합물 100중량부;  100 parts by weight of the (meth) acrylate monomer mixture;
(a2) 접착강화제 50 내지 100중량부; 및 (a3) 충진제 1 내지 10중량부; (a2) 50 to 100 parts by weight of an adhesive strengthening agent; And (a3) 1 to 10 parts by weight of the filler;
(ϋ)  (ϋ)
(bl) 에폭시 수지 100 중량부에 대하여;  (bl) 100 parts by weight of an epoxy resin;
(b2) 개시제 50 내지 150중량부. 상기한 접착제 조성물은 일반적으로 사용되는 (메트)아크릴레이트계 화합물 외에， 특정 구조의 작용기를 가지는 (메트)아크릴레이트계 화합물을 포함함으로써， 접착 시, 인장중첩 전단강도가 향상되고, 그 접착 결과물에서 고접착력을 나타낼 수 있는, 이액형 접착제 조성물을 제공할 수 있다.  (b2) 50 to 150 parts by weight of initiator. The adhesive composition includes a (meth) acrylate-based compound having a functional group of a specific structure in addition to the (meth) acrylate-based compound that is generally used, thereby improving tensile overlapping shear strength at the time of adhesion, It is possible to provide a two-part adhesive composition, which can exhibit high adhesion.
본 발명의 일 구현예에 따른 접착제 조성물에 있어서， 각 성분의 종류 또는 물성의 제어를 통해 발명의 효과를 더욱 향상시킬 수 있다. 이하 구성 성분 별로 상세하게 살펴보면 다음과 같다.  In the adhesive composition according to an embodiment of the present invention, the effect of the invention can be further improved by controlling the type or physical property of each component. Hereinafter, the components will be described in detail.
(제 1 부분) (First part)
본 발명의 일 구현예에 따른 접착제 조성물에 있어서, 게 1부분은 주제부로서, 하기 구성을 포함한다.  In the adhesive composition according to an embodiment of the present invention, one portion of the crab is a main portion and includes the following configuration.
(al) (al l) 알킬 (메트)아크릴레이트 화합물; 및  (al) (al l) alkyl (meth) acrylate compounds; And
(al 2) (al21) 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물 및 (al22) 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물 증 어느 하나 이상을; 포함하는，  (al 2) any one or more of the (meth) acrylate compound having an (al21) alkoxysilyl group and the (meth) acrylate compound having an unsaturated functional group in addition to the (al22) acryloyl group; Including
(메트)아크릴레이트계 단량체 흔합물 100중량부;  100 parts by weight of the (meth) acrylate monomer mixture;
(a2) 접착강화제 50 내지 100중량부; 및  (a2) 50 to 100 parts by weight of an adhesive strengthening agent; And
(a3) 충진제 1 내지 10증량부; 본 발명에 있어서， 알킬 (메트)아크릴레이트는 알킬아크릴레이트계 단량체 및 알킬메타크릴레이트계 단량체를 모두 포함한다. 상기 알킬 (메트)아크릴레이트에 있어서, 상기 알킬기는 탄소수 1 내지 20의 직쇄 또는 분지형 알킬기일 수 있다. 알킬기의 탄소수가 20개를 초과할 경우, 접착제 조성물의 유리 전이 온도 (Tg)가 높아지거나 또는 접착성 제어가어려울 수 있다ᅳ 상기 알킬 (메트)아크릴레이트의 구체적인 예로는 메틸메타크릴레이트, 에틸 (메트)아크릴레이트, n-프로필 (메트)아크릴레이트, 이소프로필 (메트)아크릴레이트, n-부틸 (메트)아크릴레이트， t-부틸 (메트)아크릴레이트, sec-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 2-에틸핵실 (메트)아크릴레이트 n-옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 이소노닐 (메트)아크릴레이트로, 라우릴 (메트)아크릴레이트 또는 테트라데실 (메트) 아크릴레이트 등을 들 수 있으며, 이들 중 1종 또는 2종 이상의 흔합물이 사용될 수 있다. (a3) 1 to 10 parts by weight of the filler; In the present invention, the alkyl (meth) acrylate includes both alkyl acrylate monomers and alkyl methacrylate monomers. In the alkyl (meth) acrylate, the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms. If the alkyl group contains more than 20 carbon atoms, the glass transition temperature (Tg) of the adhesive composition may be high or the adhesion control may be difficult. Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylnuclear (meth) acrylate n-octyl (meth) acrylate, isooctyl (meth) acrylate, As isononyl (meth) acrylate, lauryl (meth) acrylate or tetradecyl (meth) acrylate, etc. are mentioned, 1 type, or 2 or more types of these can be used.
알킬 (메트)아크릴레이트 내 알킬기의 탄소수 제어에 따른 접착성 개선 효과를 고려할 때, 상기 알킬 (메트)아크릴레이트에 있어서, 상기 알킬기는 보다 구체적으로 탄소수 1 내지 4의 직쇄 또는 분지형 알킬기일 수 있으며, 보다 더 구체적으로는 메틸기 또는 에틸기일 수 있다.  When considering the effect of improving the adhesion of the alkyl group in the alkyl (meth) acrylate by the carbon number, in the alkyl (meth) acrylate, the alkyl group may be more specifically a linear or branched alkyl group having 1 to 4 carbon atoms, More specifically, it may be a methyl group or an ethyl group.
이와 같은 알킬 (메트)아크릴레이트는, 전체 (메트)아크릴레이트계 단량체 흔합물 총 중량 대비 약 40 내지 약 70중량0 /0로 포함될 수 있으며, 이와 같은 함량 범위로 포함될 때, 우수한 접착성과 함께 습윤 (wetting) 특성이 개선될 수 있다. 알킬 (메트)아크릴레이트의 함량이 적을 경우, 접착제와 피착재 간의 습윤 특성이 저하될 우려가 있고, 함량이 지나치게 많을 경우, 접착 특성 저하의 우려가 있다. 이와 같은 접착제 조성물 내 알킬 (메트)아크릴레이트의 함량 제어에 따른 개선 효과의 우수함을 고려할 때 상기 알킬 (메트)아크릴레이트는 보다 구체적으로는 약 50 내지 약 60증량0 /0로 포함될 수 있다. 그리고, 본 발명에 있어서, 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물은, 상술한 알킬 (메트)아크릴레이트의 알킬기에, 알콕시실릴기가 치환된 형태의 단량체를 모두 포함한다. These alkyl (meth) acrylates, the total (meth) acrylate-based monomers common compound total, based on the weight of the can be included as about 40 to about 70 parts by weight 0/0, when included in such a content range, wet with and good adhesion Wetting properties can be improved. When the content of the alkyl (meth) acrylate is small, there is a fear that the wettability between the adhesive and the adherend is lowered. When the content is too high, there is a fear that the adhesive property is lowered. Thus when considering the same adhesive composition excellent in the improvement of the contents of control in the alkyl (meth) acrylates wherein the alkyl (meth) acrylate may be included to more specifically about 50 to about 60 Increased 0/0. In addition, in this invention, the (meth) acrylate compound which has an alkoxysilyl group contains all the monomers of the form in which the alkoxysilyl group substituted the alkyl group of the alkyl (meth) acrylate mentioned above.
이 때, 규소 원 에 연결된 알콕시 기는， 탄소수 1 내지 5의 직쇄 또는 분지형 알킬 구조를 가지는 알콕시기일 수 있으며， 이러한 알콕시 기는, 규소 원자에 1 내지 3개가 연결된, 모노알콕시실릴기， 디알콕시실릴기， 트리알콕시실릴기의 형태일 수 있다. 그리고， 이러한 알콕시실릴기들은, 탄소수 1 내지 5의 알킬렌 연결 그룹을 통해 (메트)아크릴로일기와 연결되는 형태일 수 있다. At this time, the alkoxy group connected to the silicon source may be an alkoxy group having a linear or branched alkyl structure having 1 to 5 carbon atoms, and such alkoxy group is a monoalkoxysilyl group or dialkoxysilyl group having 1 to 3 carbon atoms connected to the silicon atom. It may be in the form of a trialkoxy silyl group. And, these alkoxysilyl groups may be in the form of being connected to the (meth) acryloyl group through an alkylene linking group having 1 to 5 carbon atoms. have.
구체적인 예로는 모노, 디, 트리 메록시실릴메틸 (메트)아크릴레이트， 메틸메타크릴레이트, 모노, 디， 트리 메록시실릴에틸 (메트)아크릴레이트, 모노, 디, 트리 메록시실릴프로필 (메트)아크릴레이트 등을 들 수 있으며, 이들 중 1종 또는 2종 이상의 흔합물이 사용될 수 있다.  Specific examples include mono, di, trimethoxysilylmethyl (meth) acrylate, methyl methacrylate, mono, di, trimethoxysilylethyl (meth) acrylate, mono, di, trimethoxysilylpropyl (meth) Acrylate and the like, and one or two or more of these may be used.
알콕시실릴기를 가지는 (메트)아크릴레이트 내 알킬기의 탄소수 제어에 따른 접착성 개선 효과를 고려할 때, 상기 알킬 (메트)아크릴레이트에 있어서, 상기 알킬기는 보다 구체적으로 탄소수 1 내지 4의 직쇄 또는 분지형 알킬기일 수 있으며, 보다 더 구체적으로는 에틸기 또는 프로필기일 수 있다.  In consideration of the effect of improving the adhesion of the alkyl group in the (meth) acrylate having an alkoxysilyl group, the alkyl group in the alkyl (meth) acrylate is more specifically a linear or branched alkyl group having 1 to 4 carbon atoms. It may be, and more specifically, may be an ethyl group or a propyl group.
이와 같은 알콕시실릴기를 가지는 (메트)아크릴레이트는, 전체 (Meth) acrylate which has such an alkoxysilyl group is a whole
(메트)아크릴레이트계 단량체 흔합물 총 중량 대비 약 1 내지 약 10중량0 /0로 포함될 수 있으며, 이와 같은 함량 범위로 포함될 때, 금속, 합성 플라스틱, 및 유리 등의 다양한 접착 대상 기재에 대하여 우수한 접착 특성이 구현될 수 있다. 특히， 알콕시실릴기는 당 접착제의 실리카， 중공 실리카 등의 실리카계 층진제와 반응하여 화학적으로 상호작용 할 수 있으며, 이에 따라, 실리카계 충진제와 단량체 사이에 2차 가교 결합을 형성할 수 있기 때문에， 더욱 우수한 점착 특성을 구현할 수 있다. 그리고, 본 발명에 있어서, 아크릴로일기 꾀에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물은， 상술한 알킬 (메트)아크릴레이트의 알킬기에， 아크릴로일기가 아닌, 에틸렌성 불포화 작용기가 치환된 형태의 단량체를 모두 포함한다. (Meth) acrylate-based monomers common compound gun may be included as about 1 to about 10 parts by weight 0/0 by weight of contrast, when included in such a content range, metal, synthetic plastic, and excellent for a variety of bonding target substrate of glass or the like Adhesive properties can be implemented. In particular, the alkoxysilyl group may react chemically with the silica-based layering agents such as silica and hollow silica of the sugar adhesive, thereby forming a secondary crosslink between the silica-based filler and the monomer, Better adhesion properties can be achieved. In the present invention, the (meth) acrylate compound having an unsaturated functional group in the acryloyl group is a form in which an ethylenically unsaturated functional group other than the acryloyl group is substituted in the alkyl group of the alkyl (meth) acrylate described above. It includes all monomers of.
구체적으로 상기 에틸렌성 불포화 작용기는， 비닐, 또는 알릴 그룹의 형태로 연결될 수 있으며, 이 외에도， 비닐 그룹이 탄소수 1 내지 5의 알킬렌 연결 그룹에 의해 연결된 형태를 가질 수도 있다.  Specifically, the ethylenically unsaturated functional group may be connected in the form of vinyl or allyl group, and in addition, the vinyl group may have a form connected by an alkylene linking group having 1 to 5 carbon atoms.
이러한 화합물의 구체적인 예로는 알릴 (메트)아크릴레이트， 비닐 (메트)아크릴레이트， 프로페닐 (메트)아크릴레이트, 부테닐 (메트)아크릴레이트 등을 들 수 있으며, 이들 중 1종 또는 2종 이상의 흔합물이 사용될 수 있으며， 알킬렌의 탄소수 제어에 따른 접착성 개선 효과를 고려할 때, 비닐 (메트)아크릴레이트 및 알릴 (메트)아크릴레이트가 더욱 바람직할 수 있다. Specific examples of such compounds include allyl (meth) acrylate, vinyl (meth) acrylate, propenyl (meth) acrylate, butenyl (meth) acrylate, and the like. Compounds can be used, considering the effect of improving the adhesion of the alkylene by controlling the carbon number, vinyl (Meth) acrylate and allyl (meth) acrylate may be more preferred.
이와 같은 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물은 전체 (메트)아크릴레이트계 단량체 흔합물 총 중량 대비 약 1 내지 약 10중량%로 포함될 수 있으며, 이와 같은 함량 범위로 포함될 때, 아크릴로일기 상호 간의 가교 결합 외에 더욱 복잡한 형태의 2차 가교 결합을 형성하여, 우수한 접착 특성을 구현할 수 있다. 또한， 상기 (메트)아크릴레이트계 단량체 흔합물은, 우레탄 아크릴레이트 올리고머를 더 포함할 수도 있다.  (Meth) acrylate compound having an unsaturated functional group in addition to such acryloyl group may be included in about 1 to about 10% by weight relative to the total weight of the total (meth) acrylate-based monomer mixture, when included in such a content range, In addition to the crosslinking between the acryloyl groups, by forming a more complex form of secondary crosslinking, it is possible to implement excellent adhesive properties. In addition, the (meth) acrylate monomer mixture may further include a urethane acrylate oligomer.
상기 우레탄 아크릴레이트 올리고머는 접착제와 피착재 간의 습윤 특성을 개선시키고， 충진재' 또는 알킬 (메트)아크릴레이트와의 수소 결합 생성을 증가시키며， 접착강화제의 분산도를 높여 접착제 조성물의 접착 특성을 향상시킬 수 있다. 또한, 접착면 경화 후, 접착면에 유연성을 높여, 외부 층격에도, 깨짐 등의 현상이 발생하지 않도록 하여, 접착 안정성을 높여줄 수 있다. The urethane acrylate oligomer may improve the wetting properties between the adhesive and the adherend, increase the formation of hydrogen bonds with the filler ' or the alkyl (meth) acrylate, and improve the adhesion properties of the adhesive composition by increasing the dispersion of the adhesion enhancer. Can be. In addition, after curing the adhesive surface, it is possible to increase the flexibility on the adhesive surface, so that the phenomenon such as cracking does not occur even in the outer layer space, and the adhesion stability can be improved.
상기 우레탄 아크릴레이트 올리고머는 지방족 우레탄 (메트)아크릴레이트 올리고머, 방향족 우레탄 (메트)아크릴레이트 올리고머를 포함하는 개념으로, 우레탄의 분자량이 약 200 내지 약 40,000g/m이인 것을 사용하는 것이 바람직할 수 있으며, 아크릴레이트의 당량은, 을리고머 당 약 1 내지 약 20개인 것일 수 있다. 바람직하게는 지방족 우레탄 아크릴레이트로, .분자량이 약 1,000 내지 약 20,000이고, 2 내지 10개의 아크릴레이트 관능기를 포함하는 올리고머를 사용할 수 있다.  The urethane acrylate oligomer is a concept including an aliphatic urethane (meth) acrylate oligomer, aromatic urethane (meth) acrylate oligomer, it may be preferable to use a molecular weight of the urethane is about 200 to about 40,000 g / m , The equivalent of acrylate, may be from about 1 to about 20 per oligomer. Preferably, as the aliphatic urethane acrylate, oligomers having a molecular weight of about 1,000 to about 20,000 and containing 2 to 10 acrylate functional groups can be used.
상기 우레탄 아크릴레이트 올리고머의 구체적인 예로는 미원 스페셜티 케미칼사의 Miramer PU2030i, PU2050, PU2300C, PU3000, PU3450, MU9500, SC2152, Allnex사의 Ebecryl 230, 244, 284, 4883, 8254, 8411, 8413, 8807, Arkema사의 Sartomer CN929, CN964, CN965, CN980, CN981, CN986, CN996, CN9005, CN9013, CN9026 등을 들 수 있으며, 이들 중 1종 또는 2종 이상의 흔합물을 사용할 수 있다. 상기 우레탄 아크릴레이트 올리고머는, 전체 (메트)아크릴레이트계 단량체 흔합물 총 중량에 대하여 약 10 내지 약 40중량0 /0， 바람직하게는 약 15 내지 약 30중량%의 함량으로 포함될 수 있다. 함량이 너무 적은 경우， 접착제와 피착재 간의 습윤 특성이 저하되고, 경화 후 접합면에서 층격 강도가 저하되는 문제가 발새알 수 있으며, 함량이 지나치게 많은 경우, 접착강화제의 분산도가 저하되고, 접합면의 경도가 너무 낮아지는 문제점이 발생할 수 있다. Specific examples of the urethane acrylate oligomer include Miramer PU2030i, PU2050, PU2300C, PU3000, PU3450, MU9500, SC2152, Enexryl 230, 244, 284, 4883, 8254, 8411, 8413, 8807, Arkema Corporation CN929, CN964, CN965, CN980, CN981, CN986, CN996, CN9005, CN9013, CN9026, etc. are mentioned, One or two or more combinations of these can be used. The urethane acrylate oligomer, the entire (meth) acrylate-based monomers common compound total from about 10 to about 40 parts by weight 0/0, preferably, based on the weight from about 15 to about It may be included in an amount of 30% by weight. If the content is too small, the wettability between the adhesive and the adherend is lowered, the problem that the lamination strength is lowered at the joint surface after curing is known, and if the content is too high, the dispersion of the adhesive strengthening agent is lowered, Problems that the hardness of the surface is too low may occur.
이 외에도， 접착 강도 측면에서, 비스페놀 A 폴리에틸렌 글리콜 디에테르디메타크릴레이트 또는 PPG 메탈크릴레이트의 인산 에스테르 등을 사용할 수 있으며, 또한, 접착면의 내구성 및 유연성을 위하여, 우레탄 아크릴레이트 올리고머 등을 사용할 수도 있다. (접착강화제 )  In addition, in terms of adhesive strength, bisphenol A polyethylene glycol dietherdimethacrylate or phosphate ester of PPG metal acrylate can be used, and for the durability and flexibility of the adhesive surface, urethane acrylate oligomer or the like can be used. It may be. (Adhesive enhancer)
상기 접착강화제는 접착제 조성물내 기계적 물성을 향상시키는 역할을 하는 것으로, 고무, 고무 공중합체 또는 고무 유도체 등을 포함할 수 있다.  The adhesion strengthening agent serves to improve mechanical properties in the adhesive composition, and may include rubber, rubber copolymers or rubber derivatives.
구체적인 예로는 말단 비닐화된 부타디엔 고무 (vinyl terminated butadiene rubber),염소화된 부타디엔 고무 (chlorinated butadiene rubber), 클로로설포네이티드화된 부타디엔 고무 (chlorosulfonated butadiene rubber), 니트릴 부타디엔 고무 (nitrile butadiene rubber, NBR), 스타이렌 부타다이엔 고무 (styrene butadiene rubber, SBR) 등의 부타디엔계 고무; 실리콘 고무; 스티렌-부타디엔- 폴리메틸메타크릴레이트 트리블록 공중합체 (styrene-butadiene-polymethylmethacrylate triblock copolymer), 아크릴로니트릴 -부타디엔-스티렌 공증합체 (poly(acrylonitrile- butadiene-styrene)), 스티렌 -부타디엔-스티렌 공중합체 (poly(styrene-butadiene styrene)) 등의 고무 공중합체; 또는 고무 유도체 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다.  Specific examples include terminally terminated butadiene rubber, chlorinated butadiene rubber, chlorosulfonated butadiene rubber, nitrile butadiene rubber (NBR), Butadiene-based rubbers such as styrene butadiene rubber (SBR); Silicone rubber; Styrene-butadiene-polymethylmethacrylate triblock copolymer, acrylonitrile-butadiene-styrene copolymer (poly (acrylonitrile-butadiene-styrene)), styrene-butadiene-styrene copolymer rubber copolymers such as (poly (styrene-butadiene styrene)); Or rubber derivatives and the like, and any one or two or more of these may be used.
또, 상기 접착강화제는 코어-쉘 고무를 포함할 수도 있고, 또는 비 -코어 쉘 고무를 포함할 수도 있다. 상기 코어 쉘 고무는 "코어 쉘" 유형의 그라프트 공중합체이거나, 또는 "쉘-없는" 가교 고무질 미립자， 예컨대 아크릴로니트릴- 부타디엔-스티렌 (ABS), 메타크릴레이트 -부타디엔-스티렌 (MBS) 및 메타크릴레이트-아크릴로니트릴 -부타디엔-스티렌 (MABS)일 수 있다. 상기 말단 비닐화된 부타디엔 고무는 실온에서 액체인 것일 수 있으며, 또 o°c 미만의 유리 전이 온도를 갖는 것일 수 있다. 상기 말단 비닐화는In addition, the adhesion enhancer may comprise a core-shell rubber, or may comprise a non-core shell rubber. The core shell rubber is a graft copolymer of the "core shell" type or "shell-free" crosslinked rubbery particulates such as acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS) and Methacrylate-acrylonitrile-butadiene-styrene (MABS). The terminal vinylated butadiene rubber may be a liquid at room temperature, and It may have a glass transition temperature of less than o ° c. The terminal vinylation is
(메트)아크릴레이트 -종결 형태, 예를 들어 (메트)아크릴레이트 -종결 폴리부타디엔- 아크릴로니트릴 공중합체 (예컨대 HYCAR VTBN 등) 또는 (메트)아크릴레이트 -종결 폴리부타디엔 (예컨대 HYCAR VTB (에메랄드 퍼포먼스 폴리머스 (Emerald Performance Polymers)) 일 수 있다. 상기 접착강화제는, 말단 비닐화된 부타디엔 고무를 접착강화제 총 중량에 대하여 약 20중량 0/。 이하, 보다 구체적으로는 약 5 내지 약 15중량%의 함량으로 포함할 수 있다. (Meth) acrylate-terminated forms, such as (meth) acrylate-terminated polybutadiene-acrylonitrile copolymers (such as HYCAR VTBN, etc.) or (meth) acrylate-terminated polybutadiene (such as HYCAR VTB (Emerald Performance) polymer's may be (Emerald Performance polymers)). the adhesion enhancing agent, terminal binilhwa of about 20 for the butadiene rubber in the adhesive strength agents total weight 0 /. or less, and more specifically, in an amount from about 5 to about 15% by weight It may include.
상기한 바와 같은 접착강화제는 (메트)아크릴레이트계 단량체 흔합물 100중량부에 대하여 50 내지 100중량부， 바람직하게는, 약 50 내지 약 70중량부로 포함될 수 있다. 접착강화제의 함량이 너무 적은 경우， 접착제 조성물의 기계적 특성이 저하될 우려가 있고, 함량이 너무 많은 경우, 기재와의 밀착성이 저하될 우려가 있다.  The adhesive strengthening agent as described above may be included in an amount of 50 to 100 parts by weight, and preferably about 50 to about 70 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer mixture. When the content of the adhesive strengthening agent is too small, there is a fear that the mechanical properties of the adhesive composition are lowered, and when the content is too high, the adhesion with the substrate may be lowered.
(층진제) (Straightener)
상기 층진제는 접착강화제와 함께 접착제 조성물의 기계적 특성을 향상시키는 역할을 한다.  The layering agent serves to improve the mechanical properties of the adhesive composition together with the adhesion enhancing agent.
상기 층진제로는 실리카, 품드 실리카, 나노클레이 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다.  The layering agent may include silica, article silica, nanoclay, and the like, and any one or two or more of these may be used.
이중에서도 접착제 조성물의 유동성 개질 및 소 입자 강화 특성의 개선 효과를 고려할 때, 상기 충진제는 실리카, 품드 실리카 등의 실리카계 층진제를 포함할 수 있으며, 적용된 접착제 비드의 함몰을 제어하는 효과를 포함할 때, 품드 실리카를 포함할 수 있다.  In particular, the filler may include a silica-based layering agent, such as silica, fused silica, and the like, in consideration of the effect of improving the fluidity and small particle reinforcing properties of the adhesive composition, and may include an effect of controlling the depression of the applied adhesive beads. At this time, it may include a fused silica.
상기 충진제는 (메트)아크릴레이트계 단량체 흔합물 100중량부에 대하여 1 내지 10중량부로 포함되며, 바람직하게는， 약 2 내지 약 8중량부로 포함될 수 있다. 층진제의 함량이 너무 적은 경우， 기계적 특성 개선 효과가 저하될 수 있고， 함량이 너무 많은 경우, 접착력 및 기재에 대한 밀착력 저하의 우려가 있다. 본 발명의 일 구현예에 따른 접착제 조성물에 있어서, (ii) 제 2부분은 (bl) 에폭시 수지 100 증량부에 대하여; (b2) 사카린 및 를루이딘계 화합물을 포함하는 개시제 50 내지 200중량부를 포함한다. (에폭시 수지) The filler is included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer mixture, and preferably, about 2 to about 8 parts by weight. When the content of the layering agent is too small, the effect of improving mechanical properties may be lowered. When the content of the layering agent is too large, there is a fear of deterioration of adhesion and adhesion to the substrate. In the adhesive composition according to an embodiment of the present invention, (ii) the second portion is based on (bl) 100 parts by weight of the epoxy resin; (b2) containing saccharin and a leuridine-based compound 50 to 200 parts by weight of initiator. (Epoxy resin)
에폭시 수지는 접착용 조성물 및 이로부터 제조되는 접착 필름의 유전율 및 유전 손실 계수에 영향을 미치며, 내열성 및 기계적 물성을 개선시키는 역할을 한다.  The epoxy resin affects the dielectric constant and dielectric loss coefficient of the adhesive composition and the adhesive film prepared therefrom, and serves to improve heat resistance and mechanical properties.
이에 따라 상기 에폭시 수지의 종류는 특별히 한정되지 않으나， 200g/eq 내지 500 g/eq의 에폭시 당량을 갖는 것이 접착제 조성물의 내열성을 높이면서 유전율 및 유전 손실 계수를 낮출 수 있다.  Accordingly, the type of the epoxy resin is not particularly limited, but having an epoxy equivalent of 200 g / eq to 500 g / eq may lower the dielectric constant and dielectric loss factor while increasing the heat resistance of the adhesive composition.
상기 에폭시 수지의 구체적인 예로는 시클로지방족 에폭시드, 에폭시 노볼락 수지, 비스페놀ᅳ A 에폭시 수지, 비스페놀 -F 에폭시 수지, 비스페놀 -A 에피클로로히드린계 에폭시 수지, 알킬 에폭시드， 디시클로펜타디엔 페놀 부가반응형 에폭시 수지, 리모넨 디옥시드 또는 폴리에폭시드 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다.  Specific examples of the epoxy resins include cycloaliphatic epoxides, epoxy novolac resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, bisphenol-A epichlorohydrin-based epoxy resins, alkyl epoxides, and dicyclopentadiene phenol additions. Reactive epoxy resins, limonene dioxide or polyepoxide, and the like, and any one or two or more of these may be used.
상기 에폭시 수지는, 제 1액과 흔합하는 경우, 상기 제 1액에 포함되는 상기 The said epoxy resin is contained in the said 1st liquid, when it mixes with a 1st liquid
(메트)아크릴레이트 단량체 100 중량부에 대하여, 약 1 내지 약 10중량부, 바람직하게는, 약 2 내지 약 8중량부로 사용될 수 있다. 에폭시 수지의 함량이 너무 적은 경우, 내열성 및 기계적 물성의 개선 효과가 저하될 수 있고, 너무 많은 경우， 조성물의 유동성이 과도하게 증가할 수 있다. About 100 parts by weight of the (meth) acrylate monomer may be used in an amount of about 1 to about 10 parts by weight, preferably about 2 to about 8 parts by weight. When the content of the epoxy resin is too small, the effect of improving heat resistance and mechanical properties may be lowered, and in too many cases, the fluidity of the composition may be excessively increased.
(개시제) (Initiator)
상기 개시게 (initiator)는 자유 라디칼 제공을 통해 중합 반웅을 개시시키는 역할을 하며, 개시제 종류와 경화촉진제의 조합에 따라 경화 속도 및 접착력 향상을 기대할 수 있다.  The initiator serves to initiate the polymerization reaction through the provision of free radicals, and the curing rate and adhesion may be improved depending on the combination of the initiator type and the curing accelerator.
이러한 기타 개시제의 구체적인 예로는 하이드로겐 퍼옥사이드, 알킬퍼옥사이드， 알킬 하이드로퍼옥사이드, 아릴알킬 퍼옥사이드 또는 퍼옥시 에스테르 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다.  Specific examples of such other initiators include hydrogen peroxide, alkyl peroxide, alkyl hydroperoxide, arylalkyl peroxide or peroxy ester, and the like, and any one or two or more of these may be used.
보다 구체적으로는, 상기 개시제는 디이소프로필벤젠 하이드로 퍼옥사이드， t-핵실 하이드로 퍼옥사이드, 1,1,3,3-테트라메틸부틸 하이드로 퍼옥사이드, 디큐밀 퍼옥사이드, t-부틸 큐밀 퍼옥사이드, 메틸 에틸 케톤 퍼옥사이드, 메틸 이소부틸 케톤 퍼옥사이드, 사이클로핵사논 퍼옥사이드， 큐멘 하이드로퍼옥사이드, t-부틸 하이드로퍼옥사이드, 벤조일 퍼옥사이드, 아세틸 퍼옥사이드, 라우로일 퍼옥사이드 1,1-디({-부틸 퍼옥시)사이클로핵산, 1,1-디 (t-부틸 퍼옥시 )3,3,5-트리메틸사이클로핵산: 하이드로겐 퍼옥사이드, t-부틸 퍼옥시벤조에이트, t-부틸 퍼옥시 2-에틸 핵사노에이트, 비스 (4-t-부틸사이클로핵실)퍼옥시디카보네이트 또는 이들의 흔합물을 포함할 수 있으며， 이들 중에서도 벤조일 퍼옥사이드를 포함할 수 있다. 이와 같은 개시제는， 제 1액과 흔합하는 경우， 상기 제 1액에 포함되는 상기 (메트)아크릴레이트 단량체 100 중량부에 대하여， 약 0.1 내지 약 10중량부, 또는 약 1 내지 약 5중량부로 사용될 수 있다. More specifically, the initiator is diisopropyl benzene hydroperoxide, t-nucleic acid hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclonuxanone Peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide 1,1-di ({-butyl peroxy) cyclonucleic acid, 1,1-di (t -Butyl peroxy) 3,3,5-trimethylcyclonucleic acid : hydrogen peroxide, t-butyl peroxybenzoate, t-butyl peroxy 2-ethyl nucleosanate, bis (4-t-butylcyclonucleus) Peroxydicarbonate or combinations thereof, and among these, benzoyl peroxide. Such an initiator, when mixed with the first liquid, is used in an amount of about 0.1 to about 10 parts by weight, or about 1 to about 5 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer included in the first solution. Can be.
(탄소나노튜브) (Carbon nanotube)
발명의 일 실시예에 따르면， 상기 제 2부분은, 종횡비가 1X102 내지 1X105인 탄소나노튜브를 더 포함할 수 있다. According to an embodiment of the present invention, the second portion may further include carbon nanotubes having an aspect ratio of 1 × 10 2 to 1 × 10 5 .
상기 탄소나노튜브는 탄소 6개가 연결된 육각형의 벌집무늬가 결합되어 튜브 형태를 이루고 있는 탄소 구조체로서, 종횡비 (aspect ratio)가 매우 큰 특징을 가지며， 우수한 기계적 특성， 내열성 및 내화학성 등으로 고분자 복합 재료의 층진재로 많이 사용되어 왔다.  The carbon nanotube is a carbon structure in which a hexagonal honeycomb pattern in which six carbons are connected is combined to form a tube. The carbon nanotube has a very high aspect ratio, and has a high polymer composite material with excellent mechanical properties, heat resistance, and chemical resistance. It has been used a lot as a layered material.
본 발명의 일 구현예에 따른 접착제 조성물에 있어서 상기 탄소나노튜브는 상기 접착강화제로 사용되는 고분자 수지와 함께 나노복합재의 효과를 나타낼 수 있으며, 그 결과로서 접착제 조성물의 기계적 물성， 내화학성, 접착성 및 내열성을 향상시킬 수 있다.  In the adhesive composition according to the embodiment of the present invention, the carbon nanotubes may exhibit the effect of the nanocomposite together with the polymer resin used as the adhesion enhancing agent, and as a result, the mechanical properties, chemical resistance, and adhesiveness of the adhesive composition And heat resistance can be improved.
상기 탄소나노튜브는 구체적으로, 단일벽 탄소나노튜브, 이중벽 탄소나노튜브, 또는 다중벽 탄소나노튜브 일 수 있으며, 또 상기한 탄소나노튜브를 단위체로 하여 복수개의 탄소나노튜브가 나란하게 배열 또는 뒤영켜 있는 다발 (bundle) 또는 로프 (rope) 형태의 번들형 탄소나노튜브， 또는 다발 또는 로프 형태와 같은 일정한 형상이 없이 탄소나노튜브 단위체가 뒤엉킨 비번들형 (non-bundle Ehsms entangled type) 탄소나노튜브일 수 있다. 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 이중에서도 접착제 조성물의 접착성 및 내열성 향상의 개선 효과를 고려할 때 상기 탄소나노튜브는 다중벽 탄소나노튜브일 수 있으며, 접착제 조성물내 우수한 분산성을 고려할 때 번들형 탄소나노류브일 수 있다. Specifically, the carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, and the plurality of carbon nanotubes may be arranged side by side with the carbon nanotubes as a unit. Bundled bundles of carbon nanotubes in the form of bundles or ropes, or non-bundle Ehsms entangled type carbon nanotubes in which the carbon nanotube units do not have a uniform shape such as bundles or ropes Can be. Any of these One or more combinations may be used. In particular, the carbon nanotubes may be multi-walled carbon nanotubes in consideration of the improvement effect of improving the adhesiveness and heat resistance of the adhesive composition, and may be bundled carbon nanoleubes in view of excellent dispersibility in the adhesive composition.
또, 상기 탄소나노튜브는 직경 약 1 내지 약 50nm, 길이 수십 / m에 이르는 큰 종횡비 (aspect ratio)를 갖는 것일 수 있으며, 구체적으로는 탄소나노튜브의 분산성 및 접착강화제와의 나노복합재 형성에 따른 개선 효과의 우수함을 고려할때, 상기 탄소나노튜브는 종횡비 (길이 /직경의 비)가 약 1X102 내지 약 1X105, 보다 구체적으로는 약 5X102 내지 약 5X104 인 것일 수 있다. In addition, the carbon nanotubes may have a large aspect ratio ranging from about 1 nm to about 50 nm in diameter and several tens / m in length. Specifically, the carbon nanotubes may be used for dispersing carbon nanotubes and forming a nanocomposite with an adhesive strengthening agent. considering the excellent improvement effect, the carbon nanotubes can be of aspect ratio (length / diameter ratio) of about 2 to about 1X10 1X10 5, more specifically about 2 to about 5X10 5X10 4.
또, 상기 탄소나노튜브는 BET 비표면적이 약 150 m2/g 이상, 혹은 약 200 m2/g 내지 약 500 m2/g, 보다 구체적으로는 약 220 내지 약 300 m2/g일 수 있으며, 탄소나노튜브의 가닥 직경이 약 2nm 내지 약 30nm, 흑은 약 5nm 내지 약 20nm, 보다 구체적으로는 약 5nm 내지 약 15nm일 수 있다. 이와 같이 높은 비표면적과 함께 작은 직경을 가짐으로써, 고분자 기재와의 흔합성이 우수하고 또 접착제 조성물내 분산성이 우수하다. In addition, the carbon nanotubes may have a BET specific surface area of about 150 m 2 / g or more, or about 200 m 2 / g to about 500 m 2 / g, more specifically about 220 to about 300 m 2 / g. The strand diameter of the carbon nanotubes may be about 2 nm to about 30 nm, and black is about 5 nm to about 20 nm, and more specifically about 5 nm to about 15 nm. By having a small diameter with such a high specific surface area, it is excellent in compatibility with a polymeric base material, and excellent in dispersibility in an adhesive composition.
한편， 탄소나노튜브의 복합재에서 우수한 특성을 확보하기 위해 가장 중요한 요소는 탄소나노튜브의 균일한 분산이다. 탄소나노튜브가 포함된 접착제의 경우에도 우수한 분산을 이를 경우, 강도, 탄성 등 기계적 물성에서 현저히 개선된 효과를 얻을 수 있다. 탄소나노튜브의 측벽과 말단, 또는 결함 위치들에서 화학종들의 공유 부착에 의해 분산도가 향상될 수 있는데, 이들은 탄소나노튜브의 다발 사이에 끼어들어 접착제 조성물 내에서의 탄소나노튜브의 분산을 용이하게 한다. 또, 비공유 결합을 통한 표면개질을 통해서도 접착제 조성물 내에서의 탄소나노튜브의 분산성을 증가시킬 수 있다. 이에 따라, 접착력 향상을 위해서는 최적 조건의 개질을 찾는 것이 중요하며, 이를 통해 탄소나노튜브와 접착제 간의 구조물성을 향상시킬 수 있다.  On the other hand, the most important factor to secure excellent properties in the composite of carbon nanotubes is the uniform dispersion of carbon nanotubes. Even in the case of adhesives containing carbon nanotubes, excellent dispersion can be achieved in mechanical properties such as strength and elasticity. Dispersibility can be improved by covalent attachment of species at the sidewalls and ends or at the defect sites of the carbon nanotubes, which are sandwiched between the bundles of carbon nanotubes to facilitate dispersion of the carbon nanotubes in the adhesive composition. Let's do it. In addition, it is possible to increase the dispersibility of the carbon nanotubes in the adhesive composition through surface modification through non-covalent bonds. Accordingly, in order to improve adhesion, it is important to find the modification of the optimum conditions, thereby improving the structure between the carbon nanotubes and the adhesive.
일반적으로 탄소나노튜브는 큰 표면적으로 인하여 탄소나노튜브끼리 뭉침 현상이 잘 발생하고, 탄소나노튜브의 파이 전자 구름의 높은 분극은 탄소나노튜브 사이의 강한 반데르발스 힘을 발생시켜 균일한 분산을 방해한다. 이를 방지하기 위하여 상기 탄소나노류브는 분산매 중에 분산시킨 분산 용액의 형태로 사용될 수 있다. 이때, 상기 분산매로는 n-비닐피를리돈, 부틸아크릴레이트, 아크릴산, 벤조에이트 에스테르계 오일 또는 메틸메타크릴레이트 등을 들 수 있으며, 이중에서도 탄소나노튜브와의 우수한 상용성 및 저장안정성을 고려할 때， 벤조에이트 에스테르계 오일 및 메틸메타크릴레이트 중 어느 하나 또는 둘의 흔합물이 사용될 수 있다. 상기한 탄소나노튜브 분산용 분산매는 본 발명에 따른 접착제 조성물의 구성 성분이므로, 접착제 조성물의 제조 시 탄소나노튜브를 상기한 화합물과 먼저 흔합하여 분산시킨 후, 나머지 성분들을 첨가하여 흔합하는 방법으로 사용될 수 있다. In general, carbon nanotubes are agglomerated with carbon nanotubes due to their large surface area, and the high polarization of the pi electron cloud of carbon nanotubes generates strong van der Waals forces between carbon nanotubes, thus preventing uniform dispersion. do. In order to prevent this, the carbon nano-leave may be used in the form of a dispersion solution dispersed in a dispersion medium. Can be. In this case, the dispersion medium may include n-vinylpyridone, butyl acrylate, acrylic acid, benzoate ester oil or methyl methacrylate, and among these, excellent compatibility with carbon nanotubes and storage stability may be considered. At this time, a mixture of any one or both of benzoate ester oil and methyl methacrylate may be used. Since the dispersion medium for dispersing the carbon nanotubes is a constituent of the adhesive composition according to the present invention, the carbon nanotubes are first mixed with the above-mentioned compounds and dispersed in the preparation of the adhesive composition, and then used as a method of mixing by adding the remaining components. Can be.
이와 같은 탄소나노튜브는 접착제 조성물 총 중량에 대하여 약 0.01 내지 약 1중량0 /0로 포함될 수 있다. 탄소나노튜브의 함량이 너무 적은 경우, 탄소나노튜브 사용에 따른 접착력 개선 효과가 미미하고, 너무 많은 경우, 분산도 저하와 기재에 대한 밀착력 저하의 우려가 있다. Such carbon nanotubes may be included at about 0.01 to about 1 parts by weight 0/0 with respect to the total weight of the adhesive composition. When the content of the carbon nanotubes is too small, the effect of improving the adhesion force by using the carbon nanotubes is insignificant, and when too much, there is a fear of a decrease in the degree of dispersion and adhesion to the substrate.
(기타 첨가제 ) (Other additives)
본 발명의 일 구현예에 따른 접착제 조성물은， 상기 (i) 및 (ii) 부분 중 적어도 하나의 부분에, 상기한 성분들 외에 본 발명의 효과를 저해하지 않는 범위 내에서, 통상적으로 알려진 첨가제， 구체적으로는 접착증진제, 억제제, 촉진제, 산화방지제, 활제, 개시제, 오일, 경화제, 또는 경화촉진제 등의 첨가제를 1종 이상 더 포함할 수 있다. 상기 접착증진제 (adhesion promotor)는 금속 표면과의 금속성 상호작용 및 폴리머 네트워크 강화를 위한 가교를 형성하는 물질로, 구체적으로는 1 유닛의 비닐 또는 알릴계 불포화기를 갖는 포스핀산의 모노 -에스테르， 포스폰산 또는 인산의 모노- 및 디에스테르와 같은 인 -함유 화합물을 들 수 있다. 보다 구체적인 예로는 인산; 2-메타크릴로일옥시에틸 포스페이트， 비스 -(2- 메타크릴로일옥시에틸)포스페이트, 2-아크릴로일옥시에틸 포스페이트, 비스 -(2- 아크릴로일옥시에틸)포스페이트, 메틸 -(2-메타크릴로일옥시에틸)포스페이트, 에틸 메타크릴로일옥시에틸 포스페이트, 메틸 아크릴로일옥시에틸 포스페이트, 에틸 아크릴로일옥시에틸 포스페이트, 프로필 아크릴로일옥시에틸 포스페이트, 이소부틸 아크릴로일옥시에틸 포스페이트， 에틸핵실 아크릴로일에틸 포스페이트, 할로프로필 아크릴로일옥시에틸 포스페이트, 할로이소부틸 아크릴로일옥시에틸 포스페이트 또는 할로에틸핵실 아크릴로일옥시에틸 포스페이트 등과 같은Adhesive composition according to an embodiment of the present invention, at least one of the above (i) and (ii), within the range that does not inhibit the effect of the present invention in addition to the above components, additives commonly known, Specifically, it may further include one or more additives such as adhesion promoters, inhibitors, accelerators, antioxidants, lubricants, initiators, oils, curing agents, or curing accelerators. The adhesion promoter is a material that forms a crosslink for metallic interaction with the metal surface and for strengthening the polymer network. Specifically, the mono-ester, phosphonic acid of phosphinic acid having 1 unit of vinyl or allyl unsaturated group Or phosphorus-containing compounds such as mono- and diesters of phosphoric acid. More specific examples include phosphoric acid; 2-methacryloyloxyethyl phosphate, bis- (2-methacryloyloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, bis- (2-acryloyloxyethyl) phosphate, methyl-(2 -Methacryloyloxyethyl) phosphate, ethyl methacryloyloxyethyl phosphate, methyl acryloyloxyethyl phosphate, ethyl acryloyloxyethyl phosphate, propyl acryloyloxyethyl phosphate, Such as isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloylethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate or haloethylnuclear acryloyloxyethyl phosphate
(메트)아크릴레이티드 포스페이트; 비닐 포스폰산; 시클로핵센 -3-포스폰산; (α- 히드록시부텐 -2-포스폰산; 1 -히드록시 -1 -페닐메탄 -1,1-디포스폰산; 1 -히드록시 -1-메틸- 1-디포스폰산; 1-아미노 -1 -페닐 -1 ,1-디포스폰산; 3-아미노 -3-히드록시프로판 -1 ,1- 디포스폰산; 아미노-트리스 (메틸렌포스폰산); 감마-아미노 -프로필포스폰산; 감마- 글리시독시프로필포스폰산; 인산 -모노 -2-아미노에틸 에스테르; 알릴 포스폰산; 알릴 포스핀산; β-메타크릴로일옥시에틸 포스핀산; 디알릴포스핀산; β- 메타크릴로일옥시에틸포스핀산 또는 알릴 메타크릴로일옥시에틸 포스핀산 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. (Meth) acrylated phosphate; Vinyl phosphonic acid; Cyclonuxene-3-phosphonic acid; (α-hydroxybutene-2-phosphonic acid; 1-hydroxy-1 -phenylmethane-1,1-diphosphonic acid; 1-hydroxy-1-methyl-1-diphosphonic acid; 1-amino-1 -Phenyl-1,1-diphosphonic acid; 3-amino-3-hydroxypropane-1,1-diphosphonic acid; amino-tris (methylenephosphonic acid); gamma-amino-propylphosphonic acid; gamma- glycy Doxypropylphosphonic acid; phosphoric acid-mono-2-aminoethyl ester; allyl phosphonic acid; allyl phosphinic acid; β-methacryloyloxyethyl phosphinic acid; diallylphosphinic acid; β-methacryloyloxyethylphosphinic acid or Allyl methacryloyloxyethyl phosphinic acid, and the like, and any one or two or more of these may be used.
또 상기 접착증진제로는 (메트)아크릴산 또는 금속 In addition, the adhesion promoter is (meth) acrylic acid or metal
(메트)아크릴레이트 (예컨대 아디메타크릴산 아연 등) 등을 들 수 있다. (Meth) acrylate (for example, zinc dimethacrylate) etc. are mentioned.
이 같은 접착증진제는 접착제 조성물 중에서도 제 1부분에 포함될 수 있으며, 또 중합체 총 중량에 대하여 약 0.5 내지 약 10중량0 /。， 보다 구체적으로는 약 1 내지 약 5중량%로 포함될 수 있다. 또 상기 억제제 (inhibitor)는 접착제 조성물을 안정화하고, 알킬 (메트)아크릴레이트의 이른 자유 라디칼 중합을 억제하여 적합한 개시 시간을 제공하는 역할을 한다. 구체적인 예로는 나프토퀴논, 안트로퀴논, 메틸 히드로퀴논, 벤조퀴논 또는 메틸에테르 히드로퀴논 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. Such an adhesion promoter may be included in the first portion of the adhesive composition, and may be included in about 0.5 to about 10 weight 0 /. More specifically, about 1 to about 5 weight% based on the total weight of the polymer. The inhibitor also serves to stabilize the adhesive composition and inhibit the early free radical polymerization of alkyl (meth) acrylates to provide suitable initiation times. Specific examples include naphthoquinone, anthroquinone, methyl hydroquinone, benzoquinone or methylether hydroquinone, and the like, and any one or two or more of these may be used.
상기 억제제는 접착제 조성물 중에서도 제 1부분에 포함될 수 있으며， 접착제 조성물 총 중량에 대하여 약 0.01 내지 1중량0 /。， 보다 구체적으로는 0.01 내지 0.5중량0 /0로 포함될 수 있다. 상기 촉진게 (accelerator)는 접착제 조성물의 경화를 가속화 또는 촉진시키는 촉매로서 작용하는 것으로, 구체적으로는 아민계 화합물을 포함하는 것일 수 있다. 상기 아민계 화합물은 2급 아민 (HN(Ra)2, Ra은 각각 독립적으로 등 C4 내지 C10의 알킬)， 3급 아민 (N(Rb)3, 이때 Rb는 각각 독립적으로, C1 내지 C20의 알킬, C6 내지 C20 아릴, C7 내지 C20의 알킬아릴 또는 C7 내지 C20 아릴알킬로부터 선택됨), 방향족 아민 또는 헤테로사이클 아민일 수 있으며, 보다 구체적으로는 1,8-디아자비시클로 (5.4.0)운데스 -7-엔 (DBU), 1,4- 디아자비시클로 (2.2.2)옥탄 (DABCO), 트리에틸아민, 구아니딘계 화합물 (예컨대 테트라메틸구아니딘 (TMG) 등), 를루이딘계 화합물 (예컨대 디메틸 -P- 를루이딘 (DMPT), 디에틸 -P-를루이딘 (DEPT), 디히드록시 에틸 P-톨루이딘， 디메틸- P-를루이딘 (DMPT) 또는 디메틸 -0-를루이딘 (DMOT) 등), 아닐린계 화합물 (예컨대, 디메틸 아닐린, 디히드록시에틸 아닐린 등), 티오우레아계 화합물 (예컨대, 아실 티오우레아, 벤조일 -티오우레아 또는 아릴 -티오우레아 등) 또는 피리딘계 화합물 (예컨대, 디하이드로페닐 피리딘 등)을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. The inhibitor may comprise from about 0.01 to 1 parts by weight 0 /., More specifically from 0.01 to 0.5 0/0, based on the total adhesive, it may be included in the first section among the adhesive composition by weight of the composition. The accelerator serves as a catalyst for accelerating or accelerating the curing of the adhesive composition, and specifically, may include an amine compound. The amine compound is a secondary amine (HN (Ra) 2, Ra is each independently C4 to C10 alkyl, etc.), tertiary amine (N (Rb) 3, wherein Rb are each independently, C1 to C20 alkyl , C6 to C20 aryl, C7 to C20 alkylaryl or C7 to C20 arylalkyl), aromatic amine or heterocycle amine, more specifically 1,8-diazabicyclo (5.4.0) -7-ene (DBU), 1,4-diazabicyclo (2.2.2) octane (DABCO), triethylamine, guanidine-based compounds (such as tetramethylguanidine (TMG), etc.), rurudine-based compounds (such as dimethyl -P-lluidine (DMPT), diethyl -P-lluidine (DEPT), dihydroxy ethyl P-toluidine, dimethyl-P-lluidine (DMPT) or dimethyl -0-lluidine (DMOT ), Aniline compounds (e.g., dimethyl aniline, dihydroxyethyl aniline, etc.), thiourea compounds (e.g., acyl thiourea, benzoyl-ti Urea or aryl-thiourea and the like) or pyridine-based compounds (eg, dihydrophenyl pyridine and the like), and any one or two or more of these may be used.
상기 촉진제는 접착제 조성물 중에서도 게 1부분에 포함될 수 있으며， 접착제 조성물 총 중량에 대하여 약 0.1 내지 5중량0 /0, 보다 구체적으로는 약 1 내지 약 3중량0 /。로 포함될 수 있다. 또, 상기 산화방지제 (antioxident)는 접착제 조성물의 열안정성 향상 등 산화 방지 효과를 나타내는 것으로， 인계, 폐놀계, 아민계, 또는 유황계 산화방지제 등이 사용될 수 있다. 일례로， 상기 인계 산화방지제로는 (Triphenylphosphate; TPP), (Triethyl Phosphate; TEP)와 같은 인산에스테르 (phosphate); 디에틸 (3,S-디 -t-부틸 4- 히드록시벤질)포스포네이트 (Diethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate), 비스 (2,6-디 t-부틸 -4-메틸페닐) 펜타에리스리를디포스파이트 (Bis(2,6-di-tert-butyl-4- methylphenyl)pentaerythritol diphosphate), 비스 (2，4-디 t-부틸페닐) 펜타에리스리를 디포스파이트 (bis(2,4-di-tert-butylphenyl)pentaerytryltol diphosphate), 비스 (2，4- 디쿠밀페닐) 펜타에리스리를디포스파이트 (bis(2,4-dicumylphenyl)pentaerythritol- diphosphite), 또는 디스테아릴 펜타에리스리를 디포스파이트 (distearyl penta erythritol diphosphate)와 같은 포스포네이트 (phosphonate); 포스피네이트 (phosphinate); 포스핀옥사이드 (phosphine oxide); 포스파젠 (phosphazene); 또는 이들의 금속염 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 또， 상기 페놀계 산화 방지제로서는, 2,6-디 -tert-부틸 -P-크레졸 (2,6,-do-tert- butyl-p-cresol), 테트라키스 [메틸렌 -3-(3,5-디-터트-부틸 -4- 히드록시페닐)프로피오네이트]메탄， 티오디에틸렌 비스 [3-(3,5-디 - 터트 -부틸 -4-히드록시페닐)프로피오네이트], Ν,Ν'-핵산 -1,6-디일비스 [3-(3，5- 디 -터트 -부틸 -4- 히드록시페닐프로피온아미드] 등의 힌다드 페놀 (hindered phenol)계 화합물을 들 수 있으며， 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. The promoter may be included in the first portion to among the adhesive composition, more specifically from about 0.1 to 5 parts by weight 0/0, with respect to the total weight of the adhesive composition may comprise from about 1 to about 3 parts by weight 0 /. In addition, the antioxidant (antioxident) exhibits an antioxidant effect, such as improving the thermal stability of the adhesive composition, phosphorus-based, phenol-based, amine-based, or sulfur-based antioxidants may be used. For example, the phosphorus antioxidant may include phosphate esters such as (Triphenylphosphate; TPP) and (Triethyl Phosphate; TEP); Diethyl ( 3 , S-di-t-butyl 4-hydroxybenzyl) phosphonate (Diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate), bis (2,6-dit- butyl-4-methylphenyl) penta-erythro Li the diphosphite (bis (2,6-di-tert -butyl-4- methylphenyl) pentaerythritol diphosphate), bis (2, 4-di-t- butylphenyl) penta depot for re-erythro Spite (bis (2,4-di-tert-butylphenyl) pentaerytryltol diphosphate), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (bis (2,4-dicumylphenyl) pentaerythritol-diphosphite), or dis Phosphonates, such as tearyl pentaerythritol diphosphate; Phosphinate; Phosphine oxide; Phosphazene; Or metal salts thereof And the like, and any one or two or more of these may be used. Moreover, as said phenolic antioxidant, 2,6-di-tert-butyl-P-cresol (2,6, -do-tert- butyl-p-cresol), tetrakis [methylene-3- (3,5] -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, Hindered phenol type compounds, such as Ν'-nucleic-acid 1, 6- diyl bis [3- (3, 5- di-tert- butyl- 4-hydroxyphenyl propionamide], are mentioned, These Either one or two or more combinations thereof may be used.
상기 산화방지제는 접착제 조성물 중에서도 제 1부분에 포함될 수 있으며， 접착제 조성물 총 증량에 대하여 약 0.1 내지 약 1중량%, 보다 구체적으로는 약 0.1 내지 약 으5중량0 /0로 포함될 수 있다. 또, 상기 활제는 성형성을 높여, 기재와의 탈착시 이형성을 제공하는 역할을 하는 것으로, 구체적으로는 올레핀계 왁스, 몬탄계 왁스, 몬탄산 에스테르 왁스 등의 왁스가사용될 수 있다. The antioxidant may be included as may be included in the first section among the adhesive composition, from about 0.1 to about 1% by weight based on the total adhesive composition increase, more specifically from about 0.1 to about 5 parts by weight lead 0/0. In addition, the lubricant is to increase the moldability, and serves to provide a release property when desorption with the substrate, specifically, waxes such as olefin wax, montan wax, montanic acid ester wax may be used.
상기 활제는 접착제 조성물 중에서도 게 1부분에 포함될 수 있으며, 가 과량으로 포함될 경우 성형성 저하의 우려가 있으므로， 접착제 조성물 총 중량에 대하여 약 0.1 내지 약 1중량0 /0, 보다 구체적으로는 약 0.1 내지 약 0.5중량0 /0로 포함될 수 있다. 이외에도， 상기 접착제 조성물은 오일 (예를 들면, 알킬 벤조에이트와 같은 벤조에이트 에스테르계 오일 등); 경화제 (예를 들면, 에틸렌 디아민 트리언하이드라이드 등); 경화촉진제 (예를 들면, 나프탈네이트 구리 (Cu naphtalenate), 코발트 나프테네이트와 같은, 철, 구리, 아연, 코발트, 납, 니켈, 망간 및 주석으로 이루어진 군에서 선택된 1종 이상의 금속을 포함하는 유기 금속 염 또는 유기 금속 착물) 등의 첨가제를 더 포함할 수 있다. 상기한 바와 같은 구성을 갖는 제 1 및 제 2 부분은 그 구성성분의 종류 및 조절을 통해 적절한 점도를 나타낼 수 있다. 구체적으로 본 발명에 따른 접착제 조성물에 있어서 제 2부분은 제 1부분에 비해 높은 점도를 가질 수 있으며， 보다 구체적으로는 게 1 부분의 점도는 약 5,000 내지 약 60,000cp이고, 제 2부분은 점도가 약 50,000 내지 약 150,000cp의 범위에서 제 1 부분의 점도 보다 높은 것일 수 있다. 본 발명에 따른 접착제 조성물은 상기한 성분들의 흔합으로 게 1 및 거 12 부분을 각각 준비하고， 이후 반웅성 경화를 개시하기 위하여 사용시 게 1 부분과 게 2부분을 흔합함으로써 사용될 수 있다. 이때 상기 제 1부분: 게 2부분은 약 1 : 1 내지 약 20: 1의 중량비로 흔합될 수 있으며， 바람직하게는， 약 5: 1 내지 약 15: 1 , 더욱 바람직하게는, 약 7: 1 내지 약 12: 1의 비율로 흔합될 수 있다. 상기 거 12부분의 비율이 지나치게 적은 경우, 접착제의 경화가 불층분하게 이루어져， 접착력 및 접착면의 내열성, 내구성 등이 저하되는 문제점이 발생할 수 있으며, 상기 제 2부분의 비율이 지나치게 많은 경우, 흔합된 물질 간의 상용성 및 용해성에 문제가 발생할 수 있다. 상기와 같은 조성을 갖는 접착제 조성물은 특정 성분의 개시제를 포함하여, 안정적인 중합 개시 반웅을 진행시키고, 이에 따라 우수한 접착력을 나타냄으로써, 아연, 구리, 카드뮴， 철, 주석， 알루미늄, 은， 크롬, 이들 금속의 합금, 및 용융 전기아연도금강 및 합금화 아연도금강 (galvanealed steel)을 포함하는 아연도금강등과 같은 금속, 폴리머, 강화 플라스틱, 파이버, 유리， 세라믹, 목재 등을 포함하는 다양한 기재의 접착을 위한 접착제, 프라이머 또는 코팅제 등으로 사용될 수 있고, 금속 또는 플라스틱 같은 이종 접합에 사용될 수 있다. 또 상기 접착제 조성물은 우수한 인장중첩 전단강도을 나타내고, 상은 접착이 가능하여 대형 차량의 대면적 고접착 및 높은 연신율이 요구되는 분야, 구체적으로는 버스의 천장 및 사이드 패널 (side panel), 트럭의 트레일러 접착, 열차의 천장, 바닥， 창문, 헤드라이트 커버 등의 접착에 특히 유용할 수 있다. 이하, 발명의 구체적인 실시예를 통해, 발명의 작용 및 효과를 보다 상술하기로 한다. 다만， 이러한 실시예는 발명의 예시로 제시된 것에 불과하며， 이에 의해 발명의 권리범위가 정해지는 것은 아니다. The lubricant may be included in to the first portion, among the adhesive composition, it is because there is a risk of moldability decreases if included in excess, more specifically from about 0.1 to about 1 parts by weight 0/0, with respect to the adhesive composition total weight is about 0.1 to about 0.5 can be included in a weight 0/0. In addition, the adhesive composition may be an oil (eg, a benzoate ester oil such as alkyl benzoate, etc.); Curing agents (eg, ethylene diamine trianhydride, etc.); Curing accelerators (e.g., containing at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin, such as Cu naphtalenate, cobalt naphthenate) Additives such as organometallic salts or organometallic complexes). The first and second parts having the configuration as described above may exhibit an appropriate viscosity through the kind and control of the components. Specifically according to the present invention In the adhesive composition, the second portion may have a higher viscosity than the first portion, more specifically, the viscosity of the crab portion is about 5,000 to about 60,000 cps, and the second portion has a viscosity of about 50,000 to about 150,000 cps. It may be higher than the viscosity of the first portion in the range of. The adhesive composition according to the present invention can be used by preparing 1 part and 8 parts respectively of a mixture of the above-mentioned components, and then mixing 1 part and 2 parts of a crab when used to start semi-acupoint curing. In this case, the first portion: two crabs may be mixed in a weight ratio of about 1: 1 to about 20: 1, preferably, about 5: 1 to about 15: 1, more preferably about 7: 1 To about 12: 1. When the ratio of 12 parts is too small, the curing of the adhesive may be uneven, and the problem of deterioration of adhesive strength, heat resistance and durability of the adhesive surface may occur, and when the ratio of the second part is too large, Problems may arise in the compatibility and solubility between the materials. The adhesive composition having the composition as described above includes an initiator of a specific component, and proceeds with a stable polymerization initiation reaction, and thus shows excellent adhesion, such as zinc, copper, cadmium, iron, tin, aluminum, silver, chromium, and these metals. Of various substrates, including metals, polymers, reinforced plastics, fibers, glass, ceramics, wood, etc., such as alloys, and galvanized steels including hot dip galvanized and galvanealed steels. It can be used as an adhesive, a primer or a coating for, and can be used for heterojunction such as metal or plastic. In addition, the adhesive composition exhibits excellent tensile overlapping shear strength, and the phase can be bonded to a large area requiring high adhesion and high elongation of a large vehicle, specifically, a bus ceiling and side panels, and a truck trailer. It can be especially useful for bonding ceilings, floors, windows, headlight covers, etc. of trains. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, This does not determine the scope of the invention.
<실시예〉 EXAMPLE
실시예  Example
하기 표 1 및 2에 의한 조성으로, 이액형 아크릴레이트 접착제를 제조하였다. 사용한 시약은 다음과 같다.  To the composition according to Tables 1 and 2 below, a two-part acrylate adhesive was prepared. The reagents used are as follows.
(우레탄 아크릴레이트 올리고머: 미원 스페셜티 케미칼 사， Miramer MU9500;  (Urethane acrylate oligomer: Miramer MU9500 from Miwon Specialty Chemical Co., Ltd .;
탄소 나노튜브: 종횡비 : 1 X104, 직경: 5~20nm, BET 비표면적: 220~300 m2/g; Vinyl terminated butadiene rubber: Emerald사 VTBN 1300X43； Carbon nanotubes: aspect ratio: 1 × 10 4 , diameter: 5-20 nm, BET specific surface area: 220-300 m 2 / g; Vinyl terminated butadiene rubber: Emerald VTBN 1300X43;
Chlorosulphonated polyethylene: Santi Chemical사 CSM3570;  Chlorosulphonated polyethylene: CSM3570 from Santi Chemical;
Poly (styrene— butadiene-styrene): LG화학 LG41 1；  Poly (styrene— butadiene-styrene): LG Chem LG41 1;
Poly (acrylonitrile-butadiene-styrene): LG화학 HT700;  Poly (acrylonitrile-butadiene-styrene): LG Chem HT700;
Fumed Silica: Cabot사 M5;  Fumed Silica: Cabot M5;
Nano titania: US-Nano사 Ti02 nanoparticle;  Nano titania: Ti02 nanoparticles from US-Nano;
Wax: IGI사 IGI 1250A) 접착력 평가  Wax: IGI IGI 1250A) Adhesion Evaluation
상기 실시예의 2액형 접착제를 이용하여 , ASTM D 3163 방법에 의해 Lap shear strenth를 측정한 후， 표에 정리하였다.  Using the two-component adhesive of the above example, Lap shear strenth was measured by ASTM D 3163, and then summarized in a table.
접착 대상 기재는 동부제철 사 일반 넁연 /브라이트 강판 제품 (Cold Rolled Steel, CRS) 기재를 사용하였다.  As the base material to be bonded, Dongbu Steel Co., Ltd. general rolled / bright steel sheet (Cold Rolled Steel, CRS) substrate was used.
【표 1】 Table 1
Figure imgf000019_0001
단량체 methacrylate
Figure imgf000019_0001
Monomer methacrylate
흔합물 Allyl methacrylate 2  Complex Allyl methacrylate 2
Vinyl methacrylate 2 Vinyl methacrylate 2
Vinyl terminated butadiene Vinyl terminated butadiene
4.3 4.3 4.3 4.3 rubber  4.3 4.3 4.3 4.3 rubber
Chlorosulphonated  Chlororosulphonated
3 3 3 3 접착강화 polyethylene  3 3 3 3 Adhesive Strengthened Polyethylene
제 Poly (styrene-butadiene- Poly (styrene-butadiene-
2 2 2 2 styrene) 2 2 2 2 styrene)
Poly (acrylonitrile-butadiene- Poly (acrylonitrile-butadiene-
15.5 15.5 15.5 15.5 styrene) 15.5 15.5 15.5 15.5 styrene)
접착증진 Adhesion promotion
Methacrylated phosphate 2 2 2 2 제  Methacrylated phosphate 2 2 2 2 agent
Methylether Hydroquinone  Methylether Hydroquinone
억제제 0.02 0.02 0.02 0.02  Inhibitor 0.02 0.02 0.02 0.02
(억제제)  (Inhibitor)
산화방지 2,6-di-tert-butyl-p-cresol Antioxidant 2,6-di-tert-butyl-p-cresol
0.12 0.12 0.12 0.12 제 (산화방지제)  0.12 0.12 0.12 0.12 Agent (Antioxidant)
충진제 Fumed silica 3 2 2 2 충진제 Nano titania 1  Fillers Fumed silica 3 2 2 2 Fillers Nano titania 1
Carbon nanotube 0.05 0.05 0.05 0.05 Carbon nanotube 0.05 0.05 0.05 0.05
Wax (활제) 0.3 0.3 0.3 0.3Wax 0.3 0.3 0.3 0.3
Ethylenedi amine Ethylenedi amine
0.06 0.06 0.06 0.06 tri anhydride (7]타)  0.06 0.06 0.06 0.06 tri anhydride (7)
첨가제 Cu naphthenate (기타) 0.001 0.001 0.001 0.001  Additive Cu naphthenate (others) 0.001 0.001 0.001 0.001
Dimethyl-p-toluidine  Dimethyl-p-toluidine
1 1 1 1 1 1 1 1
(촉진제) (accelerant)
Saccharin (촉진게) 1 1 1 1 에폭시 Epoxy resin 2.6 2.6 2.6 2.6 첨가제 Polyether benzoate (오일 ) 2.6 2.6 2.6 2.6
Figure imgf000021_0001
οSaccharin 1 1 1 1 Epoxy Epoxy resin 2.6 2.6 2.6 2.6 Additive Polyether benzoate (oil) 2.6 2.6 2.6 2.6
Figure imgf000021_0001
ο
Figure imgf000021_0003
Figure imgf000021_0002
Figure imgf000021_0003
Figure imgf000021_0002
층진제 Nano titania Layered Nano titania
Carbon nanotube 0.05 0.05 0.05 0.05 Carbon nanotube 0.05 0.05 0.05 0.05
Wax (활제) 0.3 0.3 0.3 0.3Wax 0.3 0.3 0.3 0.3
Ethylenediamine Ethylenediamine
0.06 0.06 0.06 0.06 tri anhydride (7]타)  0.06 0.06 0.06 0.06 tri anhydride (7)
첨가제 Cu naphthenate (기타) 0.001 0.001 0.001 0.001  Additive Cu naphthenate (others) 0.001 0.001 0.001 0.001
Dimethyl-p-toluidine  Dimethyl-p-toluidine
1 1 1 1 1 1 1 1
(촉진제) (accelerant)
Saccharin (촉잔제) 1 1 1 1 에폭시 Epoxy resin 2.6 2.6 2.6 2.6 첨가제 Polyether benzoate (오일 ) 2.6 2.6 2.6 2.6 Saccharin 1 1 1 1 Epoxy Epoxy resin 2.6 2.6 2.6 2.6 Additive Polyether benzoate (oil) 2.6 2.6 2.6 2.6
2액 개시제 Benzoyl peroxide 2.6 2.6 2.6 2.6 접착강화 Poly(methacrylate-Two-liquid initiator Benzoyl peroxide 2.6 2.6 2.6 2.6 Adhesion reinforcement Poly (methacrylate-
2.1 2.1 2.1 2.1 제 butadiene- styrene) 2.1 2.1 2.1 2.1 Butadiene-styrene)
CRS/CRS Lap shear strength (MPa) 25.3 28.9 27.4 25.7  CRS / CRS Lap Shear Strength (MPa) 25.3 28.9 27.4 25.7
【표 3】 Table 3
Figure imgf000022_0001
상기 표 1 내지 3을 참조하면, 본원 실시예에 따른, 이액형 접착제 조성물의 경우, 약 20MPa 이상의 인장중첩 전단강도 값을 보여, 대체적으로 우수한 접착력을 가지는 것을 확인할 수 있다.
Figure imgf000022_0001
Referring to Tables 1 to 3, in the case of the two-component adhesive composition according to the present embodiment, the tensile overlapping shear strength value of about 20 MPa or more can be seen, and it can be confirmed that the adhesive strength is generally excellent.
특히, 실시예 1의 경우 약 28.6MPa 값을 보이는데, 금속 재질인 CRS 냉연 강판의 동종 접합 시, 기존에 비해 매우 우수한 접착력을 구현할 수 있는 것을 명확히 확인할 수 있다.  In particular, in the case of Example 1 shows a value of about 28.6MPa, when homogeneous bonding of the CRS cold-rolled steel sheet, which is a metal material, it can be clearly seen that it is possible to implement a very excellent adhesive strength compared to the conventional.
이는 상술한 바와 같이, 특정 성분와 아크릴레이트 단량체 혹은 을리고머 등을 동시에 사용하고, 이러한 단량체 혹은 올리고머의 아크릴레이트 중합 반응 외에도 아크릴레이트계 화합물 및 기타 첨가제 간 다양한 형태의 2차 가교 결합이 형성될 수 있는 것으로부터 기인하는 것으로 생각된다. This is described above, with certain components and acrylate monomers or oligomers And the like, and in addition to the acrylate polymerization of such monomers or oligomers, it is thought to be due to the fact that various types of secondary crosslinks can be formed between acrylate-based compounds and other additives.
이에 따라, 본원발명의 이액형 접착제 조성물은, 금속이나 고분자 수지 기재 등이 사용되는 산업 분야에서 다양한 용도로 활용이 가능할 것으로 생각된다.  Accordingly, the two-part adhesive composition of the present invention is considered to be applicable to various applications in industrial fields in which metals, polymer resin substrates, and the like are used.

Claims

【청구의 범위】 [Range of request]
【청구항 1】  [Claim 1]
(i) 하기 (al) 내지 (a3)의 성분을 포함하는 제 1부분; 및  (i) a first portion comprising the components of (al) to (a3) below; And
(ii) 하기 (bl) 및 (b2) 성분을 포함하는 게 2부분을, 1 : 1 내지 20:1의 중량비로 포함하는, 이액형 접착제 조성물:  (ii) a two-part adhesive composition comprising the following (bl) and (b2) components in a weight ratio of 1: 1 to 20: 1;
(i)  (i)
(al) (al l) 알킬 (메트)아크릴레이트 화합물; 및  (al) (al l) alkyl (meth) acrylate compounds; And
(al2) (al21) 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물 및 (al22) 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물 중 어느 하나 이상을; 포함하는,  (al2) any one or more of the (meth) acrylate compound having an (al21) alkoxysilyl group and the (meth) acrylate compound having an unsaturated functional group in addition to the (al22) acryloyl group; Included,
(메트)아크릴레이트계 단량체 흔합물 100중량부;  100 parts by weight of the (meth) acrylate monomer mixture;
(a2) 접착강화제 50 내지 100중량부; 및  (a2) 50 to 100 parts by weight of an adhesive strengthening agent; And
(a3) 층진제 1 내지 10중량부;  (a3) 1 to 10 parts by weight of the layering agent;
(ϋ)  (ϋ)
(bl) 에폭시 수지 100 중량부에 대하여;  (bl) 100 parts by weight of an epoxy resin;
(b2) 개시제 50 내지 150충량부.  (b2) 50 to 150 parts by weight of initiator.
【청구항 2】 [Claim 2]
제 1항에 있어서，  The method of claim 1,
상기 (메트)아크릴레이트계 단량체 흔합물은， . 우레탄 아크릴레이트 올리고머를 더 포함하는， 이액형 접착제 조성물. The (meth) acrylate-based monomer compound is common. A two-part adhesive composition further comprising a urethane acrylate oligomer.
[청구항 3】 [Claim 3]
제 1항에 있어서，  The method of claim 1,
상기 알킬 (메트)아크릴레이트는 메틸메타크릴레이트， 에틸 The alkyl (meth) acrylate is methyl methacrylate, ethyl
(메트)아크릴레이트, n-프로필 (메트)아크릴레이트, 이소프로필 (메트)아크릴레이트, n-부틸 (메트)아크릴레이트， t-부틸 (메트)아크릴레이트， sec-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 2-에틸핵실 (메트)아크릴레이트, n-옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 이소노닐 (메트)아크릴레이트로, 라우릴 (메트)아크릴레이트 및 테트라데실 (메트)아크릴레이트로 이루어진 군에서 선택되는, 이액형 접착제 조성물. (Meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, With pentyl (meth) acrylate, 2 -ethylnuclear (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, A two-part adhesive composition selected from the group consisting of lauryl (meth) acrylate and tetradecyl (meth) acrylate.
【청구항 4】 [Claim 4]
게 1항에 있어서,  According to claim 1,
상기 (al 21) 알콕시실릴기를 가지는 (메트)아크릴레이트 화합물은, 모노, 디, 트리 메록시실릴메틸 (메트)아크릴레이트, 메틸메타크릴레이트, 모노, 디, 트리 메특시실릴에틸 (메트)아크릴레이트, 및 모노, 디, 트리 메록시실릴프로필 (메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상을 포함하는, 이액형 접착제 조성물.  The (meth) acrylate compound which has the said (al 21) alkoxysilyl group is mono, di, trimethoxysilylmethyl (meth) acrylate, methyl methacrylate, mono, di, trimethoxysilylethyl (meth) acryl A two-component adhesive composition comprising a rate and at least one selected from the group consisting of mono, di, trimethoxysilylpropyl (meth) acrylate.
[청구항 5】 [Claim 5]
제 1항에 있어서,  The method of claim 1,
상기 (al22) 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물은， 알릴 (메트)아크릴레이트, 비닐 (메트)아크릴레이트, 프로페닐 (메트)아크릴레이트, 및 부테닐 (메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상을 포함하는， 이액형 접착제 조성물.  (Meth) acrylate compounds which have an unsaturated functional group other than the said (al22) acryloyl group are allyl (meth) acrylate, vinyl (meth) acrylate, propenyl (meth) acrylate, and butenyl (meth) acrylate. Containing at least one member selected from the group consisting of, two-component adhesive composition.
【청구항 6】 [Claim 6]
게 1항에 있어서,  According to claim 1,
상기 (al22) 아크릴로일기 외에 불포화 작용기를 가지는 (메트)아크릴레이트 화합물은, 상기 (al) (메트)아크릴레이트계 단량체 흔합물 총 중량 대비 , Γ내지 10중량0 /。로 포함되는, 이액형 접착제 조성물. The (meth) acrylate compound having an unsaturated functional group in addition to the (al22) acryloyl group is contained in a Γ to 10 weight 0 /. Relative to the total weight of the (al) (meth) acrylate-based monomer mixture. Adhesive composition.
【청구항 7】 [Claim 7]
제 1항에 있어서,  The method of claim 1,
상기 접착강화제는 말단 비닐화된 부타디엔 고무, 염소화된 부타디엔 고무, 클로로설포네이티드화된 부타디엔 고무, 니트릴 부타디엔 고무, 스타이렌' 부타다이엔 고무, 실리콘 고무, 스티렌-부타디엔 -폴리메틸메타크릴레이트 트리블록 공중합체, 아크릴로니트릴 -부타디엔-스티렌 공중합체 및 스티렌 -부타디엔-스티렌 공중합체로 이루어진 군에서 선택된 1종 이상을 포함하는, 이액형 접착제 조성물. The adhesion enhancer is terminal vinylated butadiene rubber, chlorinated butadiene rubber, chlorosulfonated butadiene rubber, nitrile butadiene rubber, styrene ' butadiene rubber, silicone rubber, styrene-butadiene-polymethylmethacrylate triblock A two-part adhesive composition comprising at least one selected from the group consisting of a copolymer, an acrylonitrile-butadiene-styrene copolymer and a styrene-butadiene-styrene copolymer.
【청구항 8] [Claim 8]
게 1항에 있어서,  According to claim 1,
상기 충진제는 실리카， 품드 실리카 및 나노클레이로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 흔합물을 포함하는， 이액형 접착제 조성물.  The filler comprises any one or two or more mixtures selected from the group consisting of silica, article silica and nanoclay, two-part adhesive composition.
【청구항 9】 [Claim 9]
제 1항에 있어서，  The method of claim 1,
상기 제 2부분은， 종횡비가 1X102 내지 1X105인 탄소나노튜브를 더 포함하는， 이액형 접착제 조성물. The second portion further comprises a carbon nanotube having an aspect ratio of 1 × 10 2 to 1 × 10 5 , a two- part adhesive composition.
【청구항 10] [Claim 10]
제 1항에 있어서,  The method of claim 1,
상기 에폭시 수지는 시클로지방족 에폭시드, 에폭시 노볼락 수지, 비스페놀 -A 에폭시 수지， 비스페놀 -F 에폭시 수지， 비스페놀 -A 에피클로로하드린계 에폭시 수지， 알킬 에폭시드， 디시클로펜타디엔 페놀 부가반웅형 에폭시 수지, 리모넨 디옥시드 및 폴리에폭시드로 이루어진 군에서 선택되는, 이액형 접착제 조성물.  The epoxy resin is cycloaliphatic epoxide, epoxy novolac resin, bisphenol -A epoxy resin, bisphenol -F epoxy resin, bisphenol -A epichlorohydrin epoxy resin, alkyl epoxide, dicyclopentadiene phenol addition reaction type epoxy resin , Limonene dioxide and polyepoxide.
【청구항 1 1】 [Claim 1 11]
게 1항에 있어서,  According to claim 1,
상기 개시제는 하이드로젠 퍼옥사이드, 알킬 퍼옥사이드, 알킬 하이드로퍼옥사이드， 아릴알킬퍼옥사이드 및 퍼옥시 에스테르로 이루어진 군에서 선택되는 1종 이상을 더 포함하는, 이액형 접착제 조성물.  The initiator further comprises one or more selected from the group consisting of hydrogen peroxide, alkyl peroxide, alkyl hydroperoxide, arylalkyl peroxide and peroxy ester, two-part adhesive composition.
【청구항 12】 [Claim 12]
제 1항에 있어서, 접착증진제, 억제제， 촉진제， 산화방지제, 활제, 개시제, 오일, 경화제 및 경화촉진제로 이루어진 군에서 선택되는 1종 이상의 첨가제를 더 포함하는， 이액형 접착제 조성물. The method of claim 1, A two-part adhesive composition further comprising at least one additive selected from the group consisting of adhesion promoters, inhibitors, accelerators, antioxidants, lubricants, initiators, oils, curing agents and curing accelerators.
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