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WO2016002865A1 - Agent adhésif de type mélange en deux parties - Google Patents

Agent adhésif de type mélange en deux parties Download PDF

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Publication number
WO2016002865A1
WO2016002865A1 PCT/JP2015/069079 JP2015069079W WO2016002865A1 WO 2016002865 A1 WO2016002865 A1 WO 2016002865A1 JP 2015069079 W JP2015069079 W JP 2015069079W WO 2016002865 A1 WO2016002865 A1 WO 2016002865A1
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Prior art keywords
group
composition
compound
component mixed
meth
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English (en)
Japanese (ja)
Inventor
正樹 森次
匡彦 太田
清水　学
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Emulsion Technology Co Ltd
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Emulsion Technology Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives

Definitions

  • the present invention relates to a two-component mixed adhesive.
  • an adhesive using an organoborane complex has been studied as a material capable of adhering such a difficult-to-adhere material (see Japanese Patent Publication No. 11-512123 and International Publication No. 2012/160452).
  • this adhesive one composition contains a group derived from an organoborane and a complex having the protecting group, and the other composition contains a compound that acts on the protecting group to liberate the organoborane. It is.
  • the organoborane having radical polymerization initiating ability is liberated, and the adhesive component can be cured and bonded.
  • radicals generated from the liberated organoborane and oxygen molecules can modify the surface of difficult-to-adhere materials such as polypropylene, so that excellent adhesion can be achieved without plasma treatment or the like.
  • the present invention has been made based on the circumstances as described above, and an object thereof is to provide a two-component mixed adhesive that is excellent in adhesive strength, curing rate, hot strength, and dripping suppression.
  • composition (I) a first composition
  • composition (II) a second composition
  • a two-component mixed adhesive wherein the composition (I) contains a complex having a group derived from an organoborane and a protecting group thereof (hereinafter also referred to as “[A] complex”), and the composition (II) Contains a compound that undergoes a deprotection reaction with the protecting group (hereinafter also referred to as “[D] compound”), and the deprotection reaction product produced by the deprotection reaction between the protecting group and the [D] compound has a polymerizable property. It is characterized by having.
  • the two-component mixed adhesive includes the composition (I) containing the [A] complex and the composition (II) containing the [D] compound, so that the adhesive strength, the curing rate, the hot strength, Excellent sag control.
  • the reason why the two-component mixed adhesive has the above-described configuration and thus achieves the above effect is not necessarily clear, but can be inferred as follows, for example. That is, when the protecting group of the [A] complex and the [D] compound undergo a deprotection reaction, the released organoborane and the polymerization site in the deprotection reaction product are located closer to each other, resulting in more effective polymerization. It is considered that the curing rate is improved.
  • the adhesive layer formed by polymerization contains a group generated by the deprotection reaction, so that the strength is further improved and the interaction with the adherend is increased. It is considered that the hot strength is improved. Furthermore, it is considered that thixotropy is increased and liquid dripping suppression is improved due to the fact that moderate interaction is exerted between groups generated by the deprotection reaction.
  • the protecting group of the complex is preferably derived from a compound having two or more functional groups.
  • the deprotection reaction product formed from the protective group of [A] complex and the [D] compound by making the compound derived from the protective group of [A] complex have two or more functional groups.
  • the curing rate is further improved, and since the resulting polymer has a three-dimensional cross-linked structure, the adhesive strength and the hot strength can be further improved.
  • Diamine is preferable as the compound derived from the protecting group.
  • the speed of the deprotection reaction is increased and the curing rate is further improved, and the group formed by the deprotection reaction exhibits a hydrogen bond.
  • the strength of the adhesive layer and the interaction with the adherend can be further increased, and the adhesive strength and the hot strength are further improved.
  • a hydrogen bond can be appropriately formed between groups generated by the deprotection reaction, the dripping suppression property can be further improved.
  • the [D] compound is preferably a (meth) acrylate having an isocyanate group.
  • the deprotection reaction rate and the polymerization rate are further increased, the curing rate is further improved, and the groups formed by the deprotection reaction are increased.
  • the adhesive strength, the hot strength, and the dripping suppression property can be further improved.
  • the molar ratio of the isocyanate group to the diamine is preferably 1 or more and 3 or less.
  • the composition (I), the composition (II) or both further contain a (meth) acrylate or polymer component having no isocyanate group.
  • the composition (I) and / or the composition (II) contains a (meth) acrylate or polymer component having no isocyanate group, the two-component mixed adhesive has the strength of the adhesive layer. Further, the adhesive strength and the hot strength are further improved, and the initial adhesive strength can be improved and the curing shrinkage can be suppressed.
  • the (meth) acrylate having no isocyanate group preferably has an alicyclic ring. As described above, the (meth) acrylate having no isocyanate group has an alicyclic ring, whereby the two-component mixed adhesive can further improve the hot strength.
  • polymer particles are contained as the polymer component.
  • the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
  • the content of the polymer particles in the polymer component is preferably 10% by mass or more and 50% by mass or less.
  • the two-component mixed adhesive can increase both the flexibility and the adhesive strength of the adhesive layer.
  • the polymer particles preferably have a core-shell structure.
  • the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
  • the “core-shell structure” refers to a structure having a core part serving as a nucleus and a shell part covering the core part. However, it is not necessary that the core part is entirely covered with the shell part.
  • the molar ratio of the protecting group to the group derived from organoborane in the complex is preferably 1 or more and 8 or less.
  • the storage stability of the two-component mixed adhesive can be improved by setting the molar ratio of the protecting group to the group derived from the organoborane within the specific range.
  • the thixotropy index is preferably 3 or more.
  • the said 2 liquid mixture type adhesive can exhibit high dripping suppression property by making the value of TI into the said range.
  • the “thixotropic index (TI)” refers to the ratio of the viscosity ( ⁇ 5 ) measured at 5 rpm to the viscosity ( ⁇ 50 ) measured at 50 rpm.
  • the two-component mixed adhesive of the present invention high adhesive strength and hot strength can be obtained at a high curing rate while suppressing dripping. Therefore, the two-component mixed adhesive can be suitably used for bonding various materials including difficult-to-adhere materials such as automobile outer plates.
  • the two-component mixed adhesive includes a composition (I) and a composition (II).
  • the two-component mixed adhesive includes the composition (I) containing the [A] complex and the composition (II) containing the [D] compound, so that the adhesive strength, the curing rate, the hot strength, Excellent sag control.
  • the composition (I) and the composition (II) are mixed so that the [D] compound in the composition (II) is converted into the [A] in the composition (I).
  • a reaction occurs with the protecting group constituting the complex, and as a result, a reaction product of organoborane and the protecting group with the [D] compound (hereinafter also referred to as “deprotection reaction product (p)”).
  • This deprotection reaction product (p) has polymerizability, for example, it is polymerized using the produced organoborane as a polymerization initiator, and in addition, for example, a radical formed from the organoborane and the adherend. Bonding or the like is also formed, and adhesion proceeds.
  • the two-component mixed adhesive can exhibit the above effects without requiring the inclusion of a curing accelerator such as an acid halide compound.
  • a curing accelerator such as an acid halide compound.
  • the reason why the two-component mixed adhesive has the above-described configuration provides the above-mentioned effect is not necessarily clear, but can be inferred as follows, for example. That is, when the protective group of the [A] complex and the [D] compound undergo a deprotection reaction, the liberated organoborane and the polymerization site in the deprotection reaction product become closer to each other, resulting in more effective polymerization. It is believed that the cure rate is improved.
  • the adhesive layer formed by polymerization contains a group generated by the above deprotection reaction, so that the strength is further improved and the interaction with the adherend is increased, so the adhesive strength is improved.
  • the hot strength is improved.
  • thixotropy is increased and liquid dripping suppression is improved due to the fact that moderate interaction is exerted between groups generated by the deprotection reaction.
  • the deprotection reaction product (p) is bonded to the adhesive layer by polymerization and taken in by adopting the above configuration, so that the bleed out from the adhesive layer is prevented. It is thought to be reduced.
  • the two-component mixed adhesive further includes another composition that does not contain the [A] complex and the [D] compound, and is a mixture of three or more components.
  • a mold adhesive may be used.
  • composition (I) and the composition (II) will be described.
  • Composition (I) contains a [A] complex.
  • the composition (I) preferably contains a compound having one polymerizable group (hereinafter also referred to as “[B] polymerizable compound”) and / or a [C] polymer component.
  • [B] polymerizable compound a compound having one polymerizable group
  • [C] polymer component a compound having one polymerizable group
  • other components other than the above-mentioned components [A] to [C] may be contained.
  • each component will be described.
  • the complex is a complex having a group derived from organoborane and a protecting group thereof.
  • the complex is usually formed from an organoborane and a compound (a) capable of forming a protective group by coordination bonding to the organoborane and suppressing the polymerization initiation ability of the organoborane.
  • Organoborane can form an [A] complex by interacting with one or more compounds (a).
  • organoborane is a compound in which the hydrogen atom of borane is substituted with an organic group.
  • An organic group refers to a group containing at least one carbon atom.
  • Examples of the organoborane include compounds represented by the following formula (1).
  • R 1 , R 2 and R 3 are monovalent organic groups having 1 to 20 carbon atoms.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 1 , R 2 and R 3 include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the carbon-carbon gap of the hydrocarbon group. And a group ( ⁇ ) having a divalent heteroatom-containing group, a group in which part or all of the hydrogen atoms of the hydrocarbon group and the group ( ⁇ ) are substituted with a monovalent heteroatom-containing group, and the like.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include, for example, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Examples thereof include 6-20 monovalent aromatic hydrocarbon groups.
  • Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group; Examples thereof include alkynyl groups such as ethynyl group, propynyl group and butynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, and tricyclodecyl group; And cycloalkenyl groups such as a cyclopentenyl group, a cyclohexenyl group, a norbornenyl group, and a tricyclodecenyl group.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, and naphthylmethyl group.
  • hetero atom contained in the monovalent and divalent heteroatom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.
  • Examples of the divalent heteroatom-containing group include —O—, —CO—, —NR′—, —S—, —CS—, —SO—, —SO 2 —, —POR ′ 2 —, and —SiR. ' 2- , a group combining these and the like.
  • R ′ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the monovalent heteroatom-containing group include —OH, —COOH, —NH 2 , —CN, —NO 2 , —SH and the like.
  • the organoborane is preferably a compound in which R 1 to R 3 in the above formula (1) are hydrocarbon groups from the viewpoint of high polymerization initiating ability, stability, and availability, more preferably trialkylborane, Borane, triethylborane, tripropylborane and tributylborane are more preferred, and triethylborane is particularly preferred.
  • Compound (a) is a compound that serves as a protective group for organoborane and can undergo a deprotection reaction with the [D] compound described below.
  • Examples of the compound (a) include compounds having a functional group (hereinafter also referred to as “functional group (x)”).
  • the functional group (x) is preferably a functional group containing a hetero atom from the viewpoint of both the ability to form a complex with an organoborane and the ease of deprotection reaction with the [D] compound.
  • a functional group a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom etc. are mentioned, for example.
  • the hetero atom is preferably an atom having an unshared electron pair from the viewpoint of further enhancing the ability to form a complex with an organoborane and the ease of the deprotection reaction with the [D] compound.
  • Examples of the functional group containing the hetero atom include an amino group, a substituted amino group (a hydrogen atom of —NH 2 substituted with a hydrocarbon group), an imino group (—CH ⁇ N—), and the like.
  • Examples of the functional group containing an oxygen atom include a hydroxy group and an ether group.
  • Examples of the functional group containing a sulfur atom include a sulfanyl group and a thioether group.
  • Examples of the functional group containing a phosphorus atom include a phosphino group, a substituted phosphino group (a hydrogen atom of —PH 2 substituted with a hydrocarbon group), and the like.
  • Examples of compounds having an amino group include monoamines such as methylamine, ethylamine, propylamine, butylamine, aniline, and ethanolamine; 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4
  • Examples of the compound having a substituted amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclopentylamine, cyclohexylamine, dicyclopentylamine, dicyclohexylamine, N, N′-dimethyl-1,3-diaminopropane, N , N, N ′, N′-tetramethyl-1,3-diaminopropane, diethanolamine and the like.
  • Examples of the compound having an imino group include N-methylbutylaldimine.
  • Examples of the compound having a hydroxy group include monoalcohols such as methanol and ethanol; Diols such as ethylene glycol, 1,4-butanediol, 1,2-cyclohexanediol; Examples include triols such as glycerin and trimethylolpropane.
  • Examples of the compound having an ether group include diethyl ether, dibutyl ether, tetrahydrofuran and the like.
  • Examples of the compound having a sulfanyl group include monothiols such as mercaptan and ethanethiol; And dithiols such as ethanedithiol and butanedithiol.
  • Examples of the compound having a thioether group include diethyl thioether, dibutyl thioether, tetrahydrothiophene and the like.
  • Examples of the compound having a phosphino group include monophosphines such as ethylphosphine and butylphosphine; Examples include diphosphinoethane and diphosphinobutane.
  • Examples of the compound having a substituted phosphino group include diethyl phosphine and dibutyl phosphine.
  • the number of functional groups (x) possessed by the compound (a) may be 1 or 2 or more, preferably 2 or more, more preferably 2 to 4 and even more preferably 2 or 3 Two are particularly preferred.
  • a deprotection reaction product having a plurality of polymerization sites (A) and a protective group of the [A] complex formed from the compound (a) and a compound [D] As a result of the formation of p), the curing rate is further improved, and the resulting polymer has a three-dimensional crosslinked structure, so that the adhesive strength and the hot strength can be further improved.
  • the functional group (x) those having a hetero atom to which at least one hydrogen atom is bonded are preferred from the viewpoint of facilitating the deprotection reaction between the protective group and the [D] compound.
  • Examples of such a functional group (x) include an amino group, —NHR, hydroxy group, sulfanyl group, phosphino group, —PHR and the like.
  • R is a monovalent hydrocarbon group.
  • an amino group and —NHR are preferable, and an amino group is more preferable.
  • the compound (a) is preferably an active hydrogen-containing compound having a hetero atom to which at least one hydrogen atom is bonded, from the viewpoint of facilitating the deprotection reaction between the protecting group and the [D] compound.
  • the compound (a) is preferably a compound containing an amino group, more preferably a diamine and a triamine, from the viewpoint of further facilitating the deprotection reaction and further increasing the adhesive strength and hot strength.
  • diamines having diaminoalkanes and ether bonds More preferred are diamines having diaminoalkanes and ether bonds, particularly preferred are diaminoalkanes having 2 to 4 carbon atoms and diamines having ether bonds having 6 to 12 carbon atoms, and 1,3-aminopropane and 4,7 , 10-trioxatridecane-1,13-diamine is most preferred.
  • the lower limit of the molar ratio of the group derived from the compound (a) in the [A] complex to the group derived from the organoborane is preferably 0.5, more preferably 0.7, still more preferably 0.9, Is particularly preferred, 1.8 is more particularly preferred, 2.5 is even more particularly preferred, and 3.5 is most preferred.
  • the upper limit of the molar ratio is preferably 8, more preferably 7, still more preferably 6, and particularly preferably 5.5.
  • the lower limit of the molar ratio of the compound (a) to the organoborane used in the preparation of the composition (I) is preferably 0.5, more preferably 0.7, still more preferably 0.9, and particularly preferably 1. 1.8 is more particularly preferable, 2.5 is further particularly preferable, and 3.5 is most preferable.
  • the upper limit of the molar ratio is preferably 8, more preferably 7, still more preferably 6, and particularly preferably 5.5.
  • the lower limit of the content of the [A] complex in the composition (I) is 0.1 mass from the viewpoint of further improving the adhesive strength, curing rate, hot strength, and sag suppression of the two-component mixed adhesive.
  • % Is preferable 0.5% by mass is more preferable, 1% by mass is further preferable, and 2% by mass is particularly preferable.
  • the upper limit of the content is preferably 20% by mass, more preferably 10% by mass, further preferably 6% by mass, and particularly preferably 4% by mass from the viewpoint of easy handling of the two-component mixed adhesive.
  • the polymerizable compound is a compound having one polymerizable group (provided that the compounds corresponding to the [C] polymer component and the [D] compound are excluded).
  • the two-component mixed adhesive can improve the strength of the adhesive layer, and as a result, the adhesive strength and the hot strength can be further improved.
  • Examples of the polymerizable group include carbon-carbon double bond-containing groups such as a vinyl group, allyl group, styryl group, and (meth) acryloyl group; carbon-carbon triple bond-containing groups such as ethynyl group and propargyl group. .
  • a carbon-carbon double bond-containing group is preferable and a (meth) acrylolyl group is more preferable from the viewpoint of superior polymerizability.
  • Examples of the polymerizable compound include olefins such as butene, pentene, hexene, octene, decene, and dodecene; Styrene compounds such as styrene, ⁇ -methylstyrene and methylstyrene; Vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl laurate; Halogenated olefins such as vinyl chloride and vinylidene chloride; Vinyl compounds such as methyl vinyl ketone and methyl vinyl ether; Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate,
  • (meth) acrylate is preferred from the viewpoint of superior polymerizability, and (meth) acrylate having no isocyanate group is more preferred.
  • a heteroatom-containing (meth) acrylate is preferable, and tetrahydrofurfuryl (meth) acrylate is more preferable.
  • alkyl (meth) acrylate is preferable, and 2-ethylhexyl (meth) acrylate is more preferable.
  • (meth) acrylate having an alicyclic ring is preferable, cycloalkyl (meth) acrylate is more preferable, and tricyclodecyl (meth) acrylate is further preferable.
  • One or two or more polymerizable compounds may be used.
  • the lower limit of the content of the [B] polymerizable compound in the composition (I) is preferably 10% by mass, more preferably 30% by mass, 50 mass% is further more preferable, and 60 mass% is especially preferable.
  • the upper limit of the said content 99 mass% is preferable, 95 mass% is more preferable, 90 mass% is further more preferable, 85 mass% is especially preferable.
  • composition (I) preferably contains a [C] polymer component from the viewpoint of improving the initial adhesive strength and adjusting the viscosity of the two-component mixed adhesive, and suppressing the curing shrinkage of the adhesive layer.
  • the polymer component is not particularly limited as long as it is a polymer, and examples thereof include polyolefin, polystyrene, styrene copolymer, poly (meth) acrylate, polydiene, acrylic copolymer, and thermoplastic elastomer. Further, ethylene-vinyl acetate copolymer, epoxy resin, phenol resin, silicone resin, polyester resin, urethane resin, and the like can be used. Furthermore, as a [C] polymer component, the copolymer containing the structure of these polymers can also be used suitably.
  • polystyrene resin examples include polyethylene, polypropylene, and ethylene- ⁇ -olefin copolymers.
  • polystyrene examples include polystyrene and poly ( ⁇ -methylstyrene).
  • styrene copolymer examples include styrene-methyl methacrylate copolymer, styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, ABS (acrylonitrile-butadiene-styrene copolymer). Polymer) and the like.
  • poly (meth) acrylate include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate and the like.
  • polydiene examples include polybutadiene and polyisoprene.
  • acrylic copolymer examples include polymers having plural types of (meth) acrylic acid ester units, butyl (meth) acrylate-acrylonitrile copolymers, and the like.
  • thermoplastic elastomer examples include SBS (styrene-butadiene-styrene block copolymer), SEBS (styrene-ethylene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), and SEPS.
  • conjugated diene copolymers such as (styrene-ethylene-propylene-styrene block copolymer), and hydrogenated products thereof.
  • thermoplastic elastomers and poly (meth) acrylates are preferable, and thermoplastic elastomers are more preferable.
  • the polymer component preferably has a polymerization site.
  • the [C] polymer component and the deprotection reaction product (p), etc. are copolymerized.
  • the polymerization site include a carbon-carbon double bond in the polymer main chain, a polymerizable group in the side chain or terminal of the polymer, and the like.
  • the [C] polymer component having a polymerization site include an unhydrogenated product of a conjugated diene copolymer. Among these, SBS is preferable from the viewpoint of having a more appropriate viscosity.
  • the polymer component may be a polymer particle or a polymer that does not form a particle.
  • the composition (I) preferably contains polymer particles as the [C] polymer component. When the composition (I) contains polymer particles, the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
  • the composition (I) more preferably contains polymer particles and a polymer not forming particles as the [C] polymer component. When the composition (I) contains both the polymer particles and the polymer not forming the particles, the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
  • the polymer component forming the polymer particles is preferably a polyolefin, polystyrene, styrene copolymer, poly (meth) acrylate, polydiene acrylic copolymer, or a copolymer containing the structure of these polymers, and polystyrene.
  • Poly (meth) acrylates, polydienes and copolymers comprising the structures of these polymers are more preferred.
  • the lower limit of the average particle diameter of the polymer particles is preferably 0.005 ⁇ m, more preferably 0.01 ⁇ m, further preferably 0.05 ⁇ m, and particularly preferably 0.1 ⁇ m.
  • the upper limit of the average particle diameter is preferably 1 ⁇ m, more preferably 0.8 ⁇ m, further preferably 0.6 ⁇ m, and particularly preferably 0.4 ⁇ m.
  • polymer particles examples include single particles and particles having a core-shell structure (core-shell particles). Of these, core-shell particles are preferred.
  • core-shell particles are preferred.
  • the two-component mixed adhesive can further improve the flexibility of the adhesive layer. Examples of such commercially available core-shell particles include “Kane Ace M-511”, “M-521”, “M-570”, “M-711” of Kaneka Corporation, “FX602P” of JSR Corporation. ”,“ FX501 ”,“ Zeon F351 ”manufactured by Nippon Zeon Co., Ltd., and the like.
  • the lower limit of the content of the polymer particles in the [C] polymer component is preferably 10% by mass, more preferably 15% by mass, and 20% by mass. Further preferred is 25% by mass.
  • 70 mass% is preferable, 50 mass% is more preferable, 45 mass% is further more preferable, 40 mass% is especially preferable.
  • the [C] polymer component not forming the particles styrene copolymer, poly (meth) acrylate, polydiene, thermoplastic elastomer, silicone resin, polyester resin and urethane resin are preferable, and thermoplastic elastomer is more preferable. SBS is more preferred.
  • the lower limit of the content of the [C] polymer component in the composition (I) is preferably 1% by mass, more preferably 5% by mass, and 8% by mass. % Is more preferable, and 10% by mass is particularly preferable.
  • As an upper limit of the said content 60 mass% is preferable, 45 mass% is more preferable, 35 mass% is further more preferable, 30 mass% is especially preferable.
  • composition (I) may contain, for example, a crosslinkable compound, a plasticizer, an inorganic filler, a colorant, a polymerization inhibitor and the like as other components other than the above-described components [A] to [C]. These other components may contain 1 type (s) or 2 or more types, respectively.
  • the crosslinkable compound is a compound having two or more polymerizable groups.
  • a crosslinkable compound in the composition (I) By including a crosslinkable compound in the composition (I), the hot strength and the elongation percentage of the adhesive layer can be further increased.
  • Examples of the polymerizable group possessed by the crosslinkable compound include those exemplified as the polymerizable group possessed by the above-mentioned [B] polymerizable compound.
  • a (meth) acryloyl group is preferable from the viewpoint that the polymerization rate can be increased and the hot strength can be further increased.
  • the number of polymerizable groups possessed by the crosslinkable compound is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2 from the viewpoint of improving the hot strength.
  • crosslinkable compounds examples include chain glycol crosslinkable compounds such as ethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate; Alicyclic glycol-based crosslinkable compounds such as tricyclodecanediyl di (meth) acrylate; Trimethylolpropane-based crosslinkable compounds such as trimethylolpropane tri (meth) acrylate; Bisphenol crosslinkable compounds such as bisphenol A bis (polyethylene glycol (meth) acrylate); Imido isocyanurate crosslinkable compounds such as tri (N-hydroxyethyl) isocyanurate di (meth) acrylate; Urethane-based crosslinkable compounds such as compounds represented by the following formula (2); Examples thereof include terminal bismaleimide-modified polyimide crosslinkable compounds such as a compound represented by the following formula (3).
  • chain glycol crosslinkable compounds such as ethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate
  • n is an integer of 1-20.
  • R 4 and R 5 are each independently an alkylene group having 1 to 20 carbon atoms.
  • Ar 1 is an arylene group having 6 to 20 carbon atoms.
  • n is 2 or more, the plurality of R 4 may be the same or different, and the plurality of Ar 1 may be the same or different.
  • crosslinkable compound an alicyclic glycol-based crosslinkable compound is preferable, and tricyclodecanediyl di (meth) acrylate is more preferable.
  • the content of the crosslinkable compound in the composition (I) is 0.1% by mass from the viewpoint of further increasing the hot strength and the elongation rate of the adhesive layer.
  • 0.5 mass% is more preferable, and 2 mass% is further more preferable.
  • 20 mass% is preferable, 15 mass% is more preferable, 12 mass% is further more preferable, and 10 mass% is especially preferable.
  • plasticizer examples include phthalic acid esters such as dibutyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; dipropylene glycol dibenzoate, tri Examples thereof include benzoic acid esters such as ethylene glycol dibenzoate.
  • examples of the inorganic filler include alumina, silica, titanium dioxide and the like.
  • Examples of the colorant include carbon black.
  • the metal salt can be contained for adjusting the pot life of the two-component mixed adhesive.
  • the metal salt include copper (II) bromide, copper (II) chloride, copper (II) 2-ethylhexanoate and the like.
  • polymerization inhibitor examples include hydroquinone and hydroquinone monomethyl ether.
  • Composition (II) contains a [D] compound.
  • the composition (II) preferably contains the [B] polymerizable compound ”and / or the [C] polymer component, and may contain other components, like the composition (I). .
  • each component will be described.
  • the compound [D] is a compound that forms a deprotection reaction product (p) by deprotection reaction with the protecting group of the above-mentioned [A] complex, and the deprotection reaction product (p) has polymerizability.
  • the two-component mixed adhesive by mixing the composition (I) and the composition (II), the [D] compound undergoes a deprotection reaction with the protecting group of the [A] complex.
  • a deprotection reaction product (p) and an organoborane are produced, and the deprotection reaction product (p) is polymerized due to the polymerization initiation ability of the organoborane, whereby the adhesion proceeds.
  • Examples of the [D] compound include a compound having a group capable of deprotecting with the above protecting group (hereinafter also referred to as “group (a)”) and a polymerizable group.
  • the group (a) is not particularly limited as long as it can react with the protecting group.
  • a cyclic group containing a hetero atom such as an epoxy group or a cyclic carbonate group; Examples include an acid halide group, an ester group, an amide group, an acid anhydride group, and a leaving group-containing group such as a carboxy group.
  • the group (a) includes a vinyl group corresponding to a polymerizable group described later.
  • a group having a heteroatom-containing multiple bond is preferable from the viewpoint of easier deprotection reaction and higher curing rate, and higher interaction between groups formed by the deprotection reaction, and adhesion.
  • an isocyanate group and an isothiocyanate group are more preferable, and an isocyanate group is further preferable.
  • polymeric group the group similar to what was illustrated as a polymeric group which the said [B] polymeric compound has, for example is mentioned.
  • a (meth) acryloyl group is preferable from the viewpoints of high polymerizability and a higher curing rate.
  • the number of groups (a) possessed by the [D] compound is preferably 1 to 3, more preferably 1 and 2, and even more preferably 1 from the viewpoint of facilitating the deprotection reaction.
  • the number of polymerizable groups possessed by the compound is preferably 1 to 3, more preferably 1 and 2, more preferably 1 from the viewpoint of further increasing the polymerization rate of the deprotection reaction product (p) to be formed. preferable.
  • the number of groups (a) is preferably 1 and 2, and the number of polymerizable groups is preferably 1 and 2, and the group (a) And the number of polymerizable groups is preferably 1.
  • Isocyanatoalkyl (meth) acrylates such as isocyanatoethyl (meth) acrylate and isocyanatopropyl (meth) acrylate;
  • (meth) acrylates having an isocyanate group such as an adduct of diisocyanate and hydroxyalkyl (meth) acrylate;
  • alkenes having an isocyanate group such as isocyanatobutene, isocyanatopentene, and isocyanatohexene.
  • Isothiocyanatoalkyl (meth) acrylates such as isothiocyanatoethyl (meth) acrylate and isothiocyanatopropyl (meth) acrylate; having an isothiocyanate group such as an adduct of diisothiocyanate and hydroxyalkyl (meth) acrylate ( (Meth) acrylate;
  • Examples include alkene having an isothiocyanate group such as isothiocyanatobutene, isothiocyanatopentene, isothiocyanatohexene and the like.
  • (meth) acrylate having an isocyanate group and (meth) acrylate having an isothiocyanate group are preferable, (meth) acrylate having an isocyanate group is more preferable, isocyanatoalkyl (meth) acrylate is further preferable, and isocyanate. Natoethyl (meth) acrylate is particularly preferred.
  • the lower limit of the content of the [D] compound in the composition (II) is preferably 0.2% by mass, more preferably 1% by mass, further preferably 2% by mass, and particularly preferably 2.5% by mass.
  • As an upper limit of the said content 40 mass% is preferable, 20 mass% is more preferable, 10 mass% is further more preferable, 7 mass% is especially preferable.
  • the group (a) is an isocyanate group or an isothiocyanate group
  • the group (x) is It is preferably an amino group, more preferably the group (a) is an isocyanate group and the group (x) is an amino group.
  • the lower limit of the molar ratio of the group (a) to the protecting group is preferably 0.5, more preferably 0.7, still more preferably 1, and particularly preferably 1.5.
  • the upper limit of the molar ratio is preferably 6, more preferably 4, more preferably 3, and particularly preferably 2.5.
  • the lower limit of the molar ratio of the isocyanate group to the diamine is preferably 1, more preferably 1.3, and even more preferably 1.5 1.7 is particularly preferable.
  • the upper limit of the molar ratio is preferably 3, more preferably 2.7, even more preferably 2.5, and particularly preferably 2.3.
  • the lower limit of the thixotropy index (TI) of the two-component mixed adhesive is preferably 3 as a value immediately after mixing the composition (I) and the composition (II), more preferably 5, and further 6 preferable.
  • the upper limit of the TI is preferably 10, more preferably 9, and even more preferably 8.
  • the said 2 liquid mixture type adhesive can exhibit high dripping suppression property by making TI value between the said minimum and the said upper limit.
  • the said TI value can be calculated
  • composition (II) preferably contains [B] a polymerizable compound.
  • the explanation about the polymerizable compound, the preferred one and the content thereof are the same as in the case of the composition (I).
  • composition (II) preferably contains a [C] polymer component.
  • [C] The explanation, preferred and content of the polymer component are the same as in the case of the composition (I).
  • composition (II) may contain other components. About description, preferable thing, and content about another component, it is the same as that of the case of composition (I).
  • the crosslinkable compound is preferably contained in the composition (II).
  • the two-component mixed adhesive is prepared by, for example, preparing the composition (I) by mixing the [A] complex and, if necessary, the [B] polymerizable compound, the [C] polymer component, and other components, Separately, it can be obtained by preparing the composition (II) by mixing the [D] compound and, if necessary, the [B] polymerizable compound, the [C] polymer component and other components.
  • the two-component mixed adhesive can be used by a known method. For example, during the bonding operation, the composition (I) and the composition (II) are mixed, and after the obtained mixture is applied to one of the adherends, the other adherend is brought into close contact with the applied mixture. Thus, it can be carried out by overlapping. Moreover, after apply
  • the thickness of the adhesive layer formed between the two adherends is usually 0.01 mm to 5 mm, preferably 0.05 mm to 3 mm, more preferably 0.1 mm to 1 mm.
  • composition (I) 97.5 g of the mixed solution (a) prepared above and 2.5 g of triethylborane-diaminopropane complex (TEB-DAP) as a complex [A] were placed in a plastic container and mixed to obtain a composition (I- 1) was prepared.
  • TEB-DAP triethylborane-diaminopropane complex
  • composition (II) 95.5 g of the prepared mixed solution (a) and 4.5 g of 2-isocyanatoethyl methacrylate (MOI) as the [D] compound were placed in a plastic container and mixed to obtain a composition (II-1) Was prepared.
  • compositions (I) to (II-4) Preparation of two-component mixed adhesives (J-2) to (J-4)
  • the composition (I) prepared in Example 1 was directly used as the compositions (I-2) to (I-4).
  • the mass of MOI used / the mass of the mixed solution (a) used in the preparation of the composition (II-1) of Example 1 was 6.75 g / 93.25 g, 5.
  • Compositions (II-2) to (II-4) were prepared in the same manner as in Example 1, except that the amount was 4 g / 94.6 g, 3.6 g / 96.4 g.
  • Composition (II) was prepared as follows. A 300 mL separable flask equipped with a stirrer was charged with 20.0 g of SBS and 54.75 g of THFMA and stirred in an oil bath at 40 ° C. for 3 hours to completely dissolve SBS in THFMA. Next, 15.0 g of 2EHMA, 10.0 g of mono-2- (methacryloyloxy) ethyl maleate and 0.25 g of p-toluenesulfonyl chloride were added, and the mixture was further stirred for 1 hour and then degassed under reduced pressure for 2 hours. A composition (II-C) was obtained.
  • [Measurement of shear strength] (Test piece preparation method) Prepare two adherends (each 2.5 cm long ⁇ 10 cm wide) and immediately before applying the adhesive, clean the surface with a paper wiper containing acetone (“Kimwipe” from Nippon Paper Crecia). Removed. Next, the composition (I) and the composition (II) were mixed by a bag mixing method. That is, in a polyethylene bag, the composition (I) and the composition (II) are respectively weighed so as to have a mass ratio of 1: 1, sealed, and mixed uniformly. Mix for 1 minute by rolling. Next, the corners of the bag were cut with scissors, and the mixed adhesive was uniformly applied to one 1.25 cm square portion of the adherend. In order to make the thickness of the adhesive constant, glass beads having a diameter of 0.25 mm were sandwiched, and the other adherend was stacked on top to prepare a test piece.
  • T-peel strength (Test piece preparation method) Prepare two pieces of adherend processed by bending an adherend (ED steel plate) 2.5 cm long ⁇ 20 cm wide at 90 ° at 5 cm from one side, and applying an adhesive to each. Immediately before, surface dirt was removed with a paper wiper containing acetone (“Kimwipe” manufactured by Nippon Paper Crecia Co., Ltd.). Adhesives were mixed in the same manner as in the above-described shear test piece preparation method, and the mixed adhesive was uniformly applied to one long side portion of the adherend. In order to make the thickness of the adhesive constant, glass beads having a diameter of 0.25 mm were sandwiched, and the other adherend was stacked on top to prepare a test piece.
  • T-type peel test method With respect to the prepared test piece, the T-shaped peel strength of the bonded portion was measured according to JIS-K6854-3 using a tensile tester (“Autograph AG5000B” manufactured by Shimadzu Corporation). The measurement conditions were as follows: temperature: 23 ° C., distance between chucks: 50 mm, test speed: 200 mm / min.
  • the elongation at break of the cured product was measured using a tensile tester (“Autograph AG5000B” manufactured by Shimadzu Corporation). The measurement conditions were as follows: temperature: 23 ° C., distance between chucks: 30 mm, test speed: 100 mm / min. The elongation percentage of the adhesive layer was calculated from the moving distance of the chuck when the test piece broke.
  • Table 1 (in the case of glass fiber reinforced polypropylene / glass fiber reinforced polypropylene (GFPP / GFPP)) and Table 2 show the relationship between curing time and adhesive strength for the two-component mixed adhesives of Example 1 and Comparative Example 1. (In the case of electrodeposited steel / electrodeposited steel (ED / ED)).
  • the fracture modes indicate A: interface fracture, B: material fracture, B ′: material stretching, and C: cohesive fracture, respectively. “C> A” indicates that the fracture mode is complex, mainly cohesive fracture, and partially interfacial fracture).
  • the subscripts A and B in the failure mode indicate the material in which the failure occurred.
  • composition (I ′) Using a composition to which diaminopropane is added (composition (I ′)), the composition (I ′) and each composition (II) (compositions (II-1) and (II-C) are in a mass ratio)
  • the measured values and calculated TI values are shown in Table 6 below.
  • composition (I) [A] 2.5 g of TEB-DAP as a complex, 6B of THFMA and 17.5 g of 2EHMA as a [B] polymerizable compound, and 20.0 g of SBS as a [C] polymer component are mixed in a plastic container. To prepare a composition (I-5).
  • composition (II) [B] 55.7 g of THFMA and 16.2 g of 2EHMA as polymerizable compounds, 18.6 g of SBS as a polymer component and 5.0 g of “Kaneace M-521” of Kaneka Corporation as core-shell particles, [D] A 4.5 g MOI compound was placed in a plastic container and mixed to prepare a composition (II-5).
  • Example 6 to 11 Preparation of two-component mixed adhesives (J-6) to (J-11)
  • a composition (I) and a composition (II) were prepared in the same manner as in Example 5 except that the components of the types and blending amounts shown in Table 7 below were used. “-” In Table 7 indicates that the corresponding component was not used.
  • Table 7 shows the types and blending amounts of the components in the compositions (I) and (II) of the two-component mixed adhesive prepared in Examples 1 to 4 and Comparative Example 1.
  • “* 1” in Comparative Example 1 indicates that 10.0 g of mono 2- (methacryloyloxy) ethyl maleate and 0.25 g of p-toluenesulfonyl chloride were blended.
  • [C] the polymer component can be used in combination with the matrix component and the particle component to improve the T-shaped peel strength and the adhesive layer. It was shown that the flexibility of can be increased. Moreover, from the result of Table 8, according to the two-component mixed adhesive of the example, it was also shown that the shear strength and the T-shaped peel strength can be further improved by optimizing the blending amount of the [A] complex. .
  • composition (I) [A] 2.5 g of TEB-DAP as a complex, 60.0 g of THFMA as a polymerizable compound and 17.5 g of tricyclodecyl methacrylate (TCDMA: “FA-513M” from Hitachi Chemical Co., Ltd.), [C] A composition (I-12) was prepared by placing 20.0 g of SBS as a polymer component in a plastic container and mixing them.
  • composition (II) [B] THFMA 58.0 g and TCDMA 17.5 g as a polymerizable compound, [C] SBS 20.0 g as a polymer component, and MOD 4.5 g as a [D] compound were placed in a plastic container and mixed. Composition (II-12) was prepared.
  • Example 13 to 16 A composition (I) and a composition (II) were prepared in the same manner as in Example 12 except that the components of the types and blending amounts shown in Table 9 below were used.
  • TCDDMA tricyclodecane dimethacrylate
  • - Light Ester DCP-M
  • Table 9 indicates that the corresponding component was not used.
  • composition (I) [A] A mixture of 2.5 g of TEB-DAP as a complex and 1.0 g of 4,7,10-trioxatridecane-1,13-diamine (TTD), and [B] 53.8 g of THFMA as a polymerizable compound; 15.6 g of 2EHMA, 17.7 g of SBS as a [C] polymer component, and 9.9 g of core-shell particles were placed in a plastic container and mixed to prepare composition (I-17).
  • TTD 4,7,10-trioxatridecane-1,13-diamine
  • composition (II) [B] THFMA 52.0 g and 2EHMA 15.2 g as a polymerizable compound, [C] SBS 17.3 g and core-shell particles 9.6 g as a polymer component, and [D] MOI 5.9 g as a compound A composition (II-17) was prepared by mixing in a container.
  • Example 18 and 19 A composition (I) and a composition (II) were prepared in the same manner as in Example 17 except that the components of the types and blending amounts shown in Table 11 below were used. “-” In Table 11 indicates that the corresponding component was not used.
  • the two-component mixed adhesive of the present invention high adhesive strength and hot strength can be obtained at a high curing rate while suppressing liquid dripping. Therefore, the two-component mixed adhesive can be suitably used for bonding various materials including difficult-to-adhere materials such as automobile outer plates.

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

Abstract

La présente invention concerne un agent adhésif de type mélange en deux parties comprenant une première composition et une deuxième composition, ledit agent adhésif étant caractérisé en ce que la première composition contient un complexe ayant à la fois un groupe dérivé d'un organoborane et un groupe protecteur pour le groupe mentionné ci-dessus, la deuxième composition contient un composé apte à réaliser une réaction de déprotection avec le groupe protecteur ; un produit de réaction de déprotection produit par la réaction de déprotection entre le groupe protecteur et le composé présente une aptitude à la polymérisation. Il est préférable que le groupe protecteur dans le complexe soit dérivé d'un composé ayant au moins deux groupes fonctionnels. Le composé duquel est dérivé le groupe protecteur est, de préférence, une diamine.
PCT/JP2015/069079 2014-07-03 2015-07-01 Agent adhésif de type mélange en deux parties Ceased WO2016002865A1 (fr)

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