WO2022176887A1 - Matériau de liaison facile à désassembler, corps lié et procédé de désassemblage - Google Patents

Matériau de liaison facile à désassembler, corps lié et procédé de désassemblage Download PDF

Info

Publication number
WO2022176887A1
WO2022176887A1 PCT/JP2022/006093 JP2022006093W WO2022176887A1 WO 2022176887 A1 WO2022176887 A1 WO 2022176887A1 JP 2022006093 W JP2022006093 W JP 2022006093W WO 2022176887 A1 WO2022176887 A1 WO 2022176887A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive material
dismantling
meth
acrylate
structural member
Prior art date
Application number
PCT/JP2022/006093
Other languages
English (en)
Japanese (ja)
Inventor
絵理子 佐藤
耕三 伊藤
翔太 安藤
皓一 眞弓
Original Assignee
国立大学法人九州大学
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
Application filed by 国立大学法人九州大学 filed Critical 国立大学法人九州大学
Publication of WO2022176887A1 publication Critical patent/WO2022176887A1/fr

Links

Images

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
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C09J105/16—Cyclodextrin; Derivatives thereof
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to an easy-to-dismantle adhesive technology.
  • the easily dismantling adhesive material is an adhesive material that has sufficient adhesive strength according to the purpose of use and a property that the adhesive strength can be lowered at an arbitrary timing and easily peeled (dismantled).
  • Demands for easily dismantled adhesive materials are increasing for purposes such as separating and collecting dissimilar materials, repairing or replacing defective parts, and improving productivity by temporary bonding in the manufacturing process.
  • the "dismantling mechanism" of the easily dismantling adhesive material the mechanical strength decrease due to the decomposition of the polymer used as the adhesive, the physical property change due to the polymer reaction, the solid-liquid conversion due to photoisomerization, and the formation of thermally expandable microcapsules.
  • Various studies and proposals have been made on the expansion and deformation of the adhesive layer due to thermal expansion.
  • Patent Document 1 is cited as a prior art document relating to adhesives containing thermally expandable microcapsules. Further, Patent Document 2 discloses a copolymer (X) having an alkoxycarbonyloxystyrene structural unit (a) and a glycidyl group-containing (meth)acrylate structural unit (b), and an acid generator (Y). An adhesive composition is described.
  • Non-Patent Document 1 describes an easily dismantleable adhesive material using a polymer having a tertiary-butoxycarbonyl group in its side chain and using a mechanism whereby the adhesive strength is reduced by decomposition of this functional group.
  • design points are that the mechanism for dismantling does not hinder the adhesiveness, and that the adhesive strength decreases at any timing. It is often not easy to achieve both of these contradictory properties.
  • an object of the present invention is to provide an easily dismantleable adhesive material that has both excellent adhesive strength and easy dismantleability.
  • An easily dismantleable adhesive material used for bonding a first structural member and a second structural member to obtain a joined body, and then dismantling the joined body by applying heat or active energy rays.
  • a polyrotaxane comprising a cyclic molecule forming an opening, a linear molecular chain passing through the opening of the cyclic molecule, and blocking groups attached to both ends of the linear molecular chain,
  • An easily dismantling adhesive material is provided in which the cyclic molecule has a polymerizable group.
  • a first structural member a second structural member;
  • a joined body is provided, which joins the first structural member and the second structural member, and includes the hardened body of the easily dismantleable adhesive material.
  • a dismantling method which includes a dismantling step of dismantling the bonded body by applying heat or active energy rays to the bonded body.
  • an easy-to-dismantle adhesive material having both excellent adhesive strength and easy-to-dismantle property is provided.
  • FIG. 2 is a diagram for explaining polyrotaxane; It is a figure which shows the TG curve obtained by the thermogravimetric analysis.
  • X to Y in the explanation of the numerical range means X or more and Y or less unless otherwise specified.
  • “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
  • a description without indicating whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent.
  • alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
  • the notation "(meth)acryl” used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate”.
  • organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified.
  • a "monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
  • the easily dismantling adhesive material of the present embodiment adheres a first structural member and a second structural member to obtain a joined body, and then disassembles the joined body by applying heat or active energy rays. used for purposes.
  • the easily dismantling adhesive material of the present embodiment comprises a cyclic molecule forming an opening, a linear molecular chain penetrating the opening of the cyclic molecule, and blocking groups bonded to both ends of the linear molecular chain. including polyrotaxanes. And the cyclic molecule in this polyrotaxane has a polymerizable group.
  • the easily dismantleable adhesive material of the present embodiment contains polyrotaxane.
  • a polyrotaxane usually comprises a cyclic molecule forming an opening, a linear molecular chain passing through the opening of the cyclic molecule, and blocking groups attached to both ends of the linear molecular chain. Blocking groups prevent the cyclic molecule from leaving the linear chain.
  • a single linear molecular chain can pass through an opening in one or more cyclic molecules.
  • FIG. 1 is a diagram schematically showing an example of polyrotaxane.
  • the polyrotaxane in FIG. 1 is a cyclic molecule cyclodextrin, a polyether chain (polyoxyethylene chain) which is a linear molecular chain penetrating the opening of the cyclodextrin, and both ends of the polyether chain. and an adamantyl group, which is a blocking group. The bulky adamantyl group prevents the cyclodextrin from leaving the polyether chain.
  • a cyclic molecule such as cyclodextrin has a polymerizable group.
  • a polymerizable group such as a (meth)acryloyl group is bonded directly or via a linking group to a cyclic molecule such as cyclodextrin.
  • a polyether chain passes through only one cyclodextrin opening in FIG. 1, one polyether chain may pass through two or more cyclodextrin openings.
  • m and n are each independently an integer of 0 or more, preferably 0 or 1 or more, more preferably 1-30, still more preferably 5-15.
  • x represents the number of repeating ether units constituting the linear molecular chain, and x is, for example, 100 to 5,000, preferably 100 to 3,000, more preferably 100 to 1,000.
  • the cyclic molecule in the polyrotaxane is not particularly limited as long as it forms an opening through which a linear molecular chain can pass.
  • a cyclic molecule does not have to be completely closed by a covalent bond, as long as the linear molecular chain passing through the opening does not break off.
  • Cyclic molecules include, for example, cyclodextrins, crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns, and derivatives or modifications thereof. From the viewpoint of inclusion ability of linear molecular chains, the cyclic molecule is preferably cyclodextrin or a derivative or modified form thereof.
  • the cyclodextrins may be of ⁇ -type, ⁇ -type, or ⁇ -type.
  • the cyclic molecule is cyclodextrin or a derivative or modification thereof, some or all of the hydroxy groups in the cyclodextrin may be substituted with any group.
  • the relative amount of the cyclic molecule to be included is, for example, 0.001 or more, preferably 0.01 or more, more preferably 0.1 or more, and the upper limit is, for example, 0.7 or less, preferably 0.6 or less, more preferably 0 .5 or less.
  • the inclusion amount of the cyclic molecule is within the above range, the mobility of the cyclic molecule on the linear molecular chain is likely to be maintained.
  • the linear molecular chain in the polyrotaxane is not particularly limited as long as it is a molecular chain that can penetrate the cyclic molecule and the cyclic molecule can move on the linear molecular chain.
  • the straight-chain molecular chain only needs to contain a substantially straight-chain portion, and may have a branched chain or a cyclic substituent or the like.
  • the length and molecular weight of the linear portion are not particularly limited.
  • Linear molecular chains include, for example, alkylene chains, polyester chains, polyether chains, polyamide chains, and polyacrylate chains. Among these, a polyester chain or a polyether chain is preferred, and a polyether chain is more preferred, from the viewpoint of the flexibility of the linear molecular chain itself.
  • Polyether chains are preferably polyethylene glycol chains (polyoxyethylene chains).
  • the blocking groups in the polyrotaxane are not particularly limited as long as they are groups arranged at both ends of the linear molecular chain and capable of maintaining the state in which the linear molecular chain penetrates the cyclic molecule.
  • the blocking group includes a group having a structure larger than the opening of the cyclic molecule, a group that cannot pass through the opening of the cyclic molecule due to ionic interaction, and the like.
  • Specific examples of blocking groups include adamantyl groups, groups containing cyclodextrin, anthracene groups, triphenylene groups, pyrene groups, trityl groups, and isomers and derivatives thereof.
  • the combination of a cyclic molecule and a linear molecular chain is preferably a combination of ⁇ -cyclodextrin or a derivative thereof as the cyclic molecule and a polyethylene glycol chain or derivative thereof as the linear molecular chain. .
  • This combination facilitates movement of the cyclic molecule on the linear molecular chain.
  • This combination also has the advantage of being relatively easy to synthesize.
  • the cyclic molecule in the polyrotaxane has a polymerizable group.
  • the easily dismantleable adhesive material is cured and develops adhesiveness.
  • the cyclic molecule since the cyclic molecule has a polymerizable group, the cyclic molecule can be kept slidable along the linear molecular chain even after heat curing. This contributes to high toughness of the cured product of the easily dismantleable adhesive material.
  • the polymerizable group may be directly bonded to a cyclic molecule such as cyclodextrin, or may be bonded to a cyclic molecule such as cyclodextrin via some linking group.
  • the type of the polymerizable group is not particularly limited as long as it exhibits adhesiveness and easy dismantling properties, but from the viewpoint of good adhesiveness, easy dismantling property, stability at room temperature, etc., a preferred polymerizable group is polymerizable carbon.
  • - groups containing carbon double bonds can be mentioned.
  • the group containing a polymerizable carbon-carbon double bond is preferably a (meth)acryloyl group or a vinyl group, more preferably a (meth)acryloyl group.
  • cationic polymerizable groups such as an epoxy group and an oxetanyl group can also be mentioned as the polymerizable group.
  • a preferred embodiment is an embodiment in which the cyclic molecule is cyclodextrin and the polymerizable group is bonded to the cyclodextrin directly or via a linking group.
  • a particularly preferred embodiment is one in which the cyclic molecule is cyclodextrin, and at least part of the hydrogen atoms of the hydroxy groups of the cyclodextrin are substituted with groups represented by general formula (I) below. .
  • R is a hydrogen atom or a methyl group
  • A is a single bond, -COO- or -CONH-
  • B is a single bond or a linear or branched alkylene group
  • L is a single bond or a carbonyl group
  • p is an integer from 0 to 10
  • q is an integer of 0 or more.
  • A is preferably -CONH-.
  • B is preferably a linear alkylene group.
  • the carbon number of B is preferably 1-6, more preferably 1-4.
  • L is preferably a carbonyl group.
  • p is preferably an integer of 1 to 8, more preferably 4 to 6, still more preferably 5 to 6, and particularly preferably 5. However, when L is a single bond, p is preferably 2-4, more preferably 2-3.
  • q is preferably an integer of 0 or 1 or more, more preferably 1-30, still more preferably 5-15.
  • the cyclic molecule may have only one polymerizable group, or may have a plurality of polymerizable groups. When the cyclic molecule has multiple polymerizable groups, the chemical structures of the multiple polymerizable groups may be the same or different.
  • the weight-average molecular weight of the polyrotaxane is, for example, from 10,000 to 1,000,000, preferably from 100,000 to 1,000,000, from the viewpoint of appropriate applicability (viscosity), strength as an adhesive material, and durability. , more preferably 200,000 to 800,000.
  • the polyrotaxane may be synthesized with reference to a known method, or may be a commercially available product.
  • Commercially available products include the "Serum” (registered trademark, SeRM in the alphabet) series sold by Advanced Soft Materials Co., Ltd.
  • SeRM registered trademark, SeRM in the alphabet
  • the easily dismantleable adhesive material of the present embodiment may contain only one type of polyrotaxane, or may contain two or more types.
  • the easily dismantleable adhesive material of the present embodiment contains polyrotaxane, the stress in the cured product of the easily dismantleable adhesive material is relaxed, the cured product can be self-repaired even if it is deformed by an external force, and the adhesive material is resistant to stress. There is a tendency to easily obtain at least one of the effects of increasing the impact resistance.
  • the easily dismantleable adhesive material of the present embodiment may contain a compound having a polymerizable carbon-carbon double bond, which is different from polyrotaxane.
  • the use of such compounds tends to increase the bond strength, especially before the dismantling process.
  • Examples of compounds having a polymerizable carbon-carbon double bond include monofunctional (meth)acrylates and/or polyfunctional (meth)acrylates.
  • the number of (meth)acryloyl groups per molecule of polyfunctional (meth)acrylate is, for example, 2-8, preferably 2-6, more preferably 2-4.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ) alkyl (meth)acrylates such as acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate; hydroxy group-containing acrylates such as hydroxyethyl acrylate and 4-hydroxybutyl acrylate; benzyl acrylates such as benzyl (meth)acrylate; Phenoxy group-containing acrylates such as phenoxyethyl acrylate and phenoxymethyl acrylate; polyalkylene glycol mono(
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate.
  • acrylate dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) ) acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethylene oxide modified Diacrylate, propylene oxide-modified diacrylate, EO adduct di(meth)acrylate of bisphenol A, EO adduct di(meth)acrylate of hydrogenated bisphenol A, PO adduct di(meth)acrylate of bisphenol A, 1,2 , 3-propanetriol 1,3-dimethacrylate, n
  • polyfunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin ethoxy tri (Meth)acrylate, glycerin propoxy tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol ethoxyte
  • (meth)acrylate oligomers such as urethane (meth)acrylate oligomers and polyester (meth)acrylates can be used in addition to the above-described monomers.
  • the amount thereof is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass with respect to 100% by mass of the polyrotaxane. Above, most preferably 5% by mass or more.
  • the upper limit of the amount is, for example, 900% by mass or less, preferably 600% by mass or less, more preferably 300% by mass or less, and most preferably 100% by mass or less with respect to 100% by mass of the polyrotaxane.
  • the easily dismantleable adhesive material of this embodiment may or may not contain a polymerization initiator.
  • the polymerization initiator is not particularly limited as long as it can polymerize the polymerizable group possessed by the cyclic molecule of the polyrotaxane.
  • Polymerization initiators typically generate active chemical species that polymerize the polymerizable groups with heat and/or light (preferably heat). When using a polymerization initiator, only one polymerization initiator may be used, or two or more polymerization initiators may be used.
  • Preferred polymerization initiators include azo thermal polymerization initiators and organic peroxide thermal polymerization initiators. Among these, an organic peroxide thermal polymerization initiator is preferable in terms of excellent low-temperature curability.
  • organic peroxide thermal polymerization initiators include dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxyketals. More specifically, dialkyl peroxides include t-butyl cumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide and the like.
  • Diacyl peroxides include diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, and di(4-methylbenzoyl) peroxide. etc.
  • peroxydicarbonates examples include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4- t-butylcyclohexyl)peroxydicarbonate and the like.
  • Peroxyesters include t-hexylperoxybenzoate, t-hexylperoxypivalate, 2,5-dimethyl-2,5di(2-ethylhexanoylperoxy)hexane and the like.
  • Peroxyketals include 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di(t-hexaperoxy)cyclohexane, 1,1-di(t- butylperoxy)cyclohexane, n-butyl 4,4-(di-butylperoxy)pentanoate, 2,2-di(t-butylperoxy)butane and the like.
  • azo thermal polymerization initiator for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1 -carbonitrile), 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide ⁇ , 2,2′-azobis[2-methyl-N-(2- hydroxyethyl)propionamide], 2,2′-azobis[2-(hydroxymethyl)propionitrile], 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy -2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis[2-(2-imidazolin-2-yl ) propane], 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)
  • the easily dismantling adhesive material of the present embodiment preferably contains 1% by mass or more, more preferably 1 to 10% by mass, and still more preferably 1 to 5% by mass of a polymerization initiator in all nonvolatile components. is preferred. Since the easily dismantleable adhesive material of the present embodiment contains an appropriate amount of polymerization initiator, the polymerizable groups in the polyrotaxane and/or the compound having a polymerizable carbon-carbon double bond are polymerized even at a relatively low temperature. can be made That is, the article can be adhered even by heating at a relatively low temperature.
  • the easily dismantleable adhesive material of the present embodiment does not contain a polymerization initiator, or even if it contains a polymerization initiator, less than 1% by mass (more preferably less than 0.5% by mass) of the total nonvolatile components It preferably contains an initiator.
  • the easily dismantleable adhesive material of the present embodiment does not contain a polymerization initiator or contains a small amount of polymerization initiator, it is possible to suppress release of decomposition products of the polymerization initiator as gas. By suppressing gas release, for example, contamination and corrosion of structural members can be suppressed, and a decrease in adhesive strength can be suppressed.
  • the easily dismantleable adhesive material of the present embodiment does not contain a polymerization initiator, the polymerizable group in the polyrotaxane and/or the compound having a polymerizable carbon-carbon double bond is formed by heating at a sufficiently high temperature. Polymerization causes the easily dismantleable adhesive material to harden.
  • the easily dismantleable adhesive material of the present embodiment may contain a polymer other than polyrotaxane.
  • a polymer other than polyrotaxane for example, an epoxy resin may be used in combination to increase adhesive strength.
  • the easily dismantling adhesive material of the present embodiment may contain a volatile organic solvent.
  • a volatile organic solvent those capable of dissolving or dispersing the polyrotaxane and sufficiently volatilizing by a normal adhesion process (coating, heating, etc.) can be mentioned without particular limitation.
  • acetone methyl ethyl ketone (MEK)
  • ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other acetic acid esters, cellosolve, butyl carbitol and other carbines.
  • aromatic hydrocarbons such as toluene and xylene, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and the like can be mentioned.
  • acetone, MEK, ethyl acetate, DMF, etc. are preferable because they have a high solubility for polyrotaxane and tend to volatilize easily during use.
  • a volatile organic solvent may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount thereof is preferably such that the nonvolatile component concentration of the easily dismantleable adhesive material is 10 to 50% by mass.
  • the nonvolatile component concentration is more preferably 10 to 40% by mass, more preferably 10 to 30% by mass.
  • a moderately large amount of the volatile organic solvent can provide better coatability.
  • the amount of the organic solvent is not too large, the easily dismantling adhesive material will be prevented from "wetting and spreading too much" and the drying time will be shortened.
  • the easily dismantleable adhesive material of this embodiment does not need to contain an organic solvent as long as it is possible to bond structural members.
  • the easily dismantleable adhesive material of this embodiment may or may not contain various optional components.
  • optional components include inorganic particles such as silica and alumina, fiber fillers such as glass fiber and carbon fiber, thermoplastic elastomers, flame retardants, antifoaming agents, and silane coupling agents.
  • the ratio of F2 to F1 (F2/F1) measured under the following conditions is preferably 0.9 or less, more preferably 0.8 or less.
  • the lower limit is not particularly limited and may be 0. For example, 0.01 or more, or 0.1 or more is sufficient. By doing so, it is possible to achieve both high adhesive strength at the time of use and dismantling properties such as easy peeling with a weak force at a high level.
  • (i) A sample obtained by bonding two stainless steel plates (SUS304) together with an easily dismantling adhesive material is measured for shear bond strength in accordance with JIS K 6850:1999.
  • F1 is the shear bond strength of Sample 1 obtained by heat-treating the easily dismantleable adhesive material under the first heat treatment conditions of 150° C. for 7 hours, and after the easily dismantleable adhesive material is heat-treated under the first heat treatment conditions. , and 200° C. for 2 hours.
  • the technical significance of the F2/F1 value is as follows.
  • the value of F2/F1 indicates ease of dismantling by heating.
  • F2/F1 being less than 1 means that the heat treatment under the second heat treatment conditions reduces the tensile shear bond strength.
  • heat treatment at a high temperature generally promotes cross-linking of the thermosetting resin and improves the shear adhesive strength of the cured product.
  • the easily dismantleable adhesive material of the present embodiment has a reduced tensile shear bond strength due to the heat treatment under the second heat treatment conditions.
  • the value of F2/F1 indicates the degree of this decrease, and this value is an index showing the ease of dismantling by heating.
  • Drying conditions can be, for example, about overnight (about 8 to 16 hours) under reduced pressure conditions of 50° C. and 10 to 100 Pa.
  • the sample may also be dried after the heat treatment under the first heat treatment conditions (after curing).
  • the drying conditions here can be, for example, room temperature under reduced pressure conditions of 10 to 100 Pa for about 15 to 20 hours (17.5 hours as a specific example).
  • the sample is allowed to stand at room temperature and normal pressure for about 15 to 20 hours (17.5 hours as a specific example) to allow the sample to settle. good too.
  • the cured product of the easily dismantleable adhesive material of the present embodiment tends to be less likely to decrease in adhesive strength when placed at a low temperature or high temperature and then returned to room temperature.
  • the easily dismantleable adhesive material of this embodiment can be preferably applied, for example, in the manufacture of automobiles.
  • the ratio of F2′ and F1′ (F2′/F1′, index of cold resistance) measured under the following conditions is preferably 0.6 or more, more preferably 0.7 or more, and even more preferably is greater than or equal to 0.8.
  • F1′ is the shear bond strength of Sample 1′ obtained by heat-treating the easily dismantleable adhesive material under the first heat treatment conditions of 150° C. for 7 hours, and the easily dismantleable adhesive material is heat-treated under the first heat treatment conditions. After cooling at -30°C for 2 hours, the shear adhesive strength of sample 2' obtained is defined as F2'.
  • F1' is basically synonymous with F1.
  • the ratio of F2'' and F1'' measured under the following conditions is preferably 0.6 or more, more preferably 0.7 or more, and Preferably it is 0.8 or more.
  • F1'' is the shear bond strength of the sample 1'' obtained by heat-treating the easily dismantleable adhesive material under the first heat treatment conditions of 150°C for 7 hours, and the easily dismantleable adhesive material is treated under the first heat treatment conditions. After the heat treatment, the shear bond strength of sample 2'' obtained by heating at 150° C. for 2 hours is defined as F2''.
  • F1'' is basically synonymous with F1.
  • the easily dismantleable adhesive material or its cured product have good "thermal stability". Quantitatively, it is as follows.
  • the 0.5% decomposition temperature of the easily detachable adhesive material (uncured) in thermogravimetric analysis is, for example, 200 to 220°C, preferably 210 to 220°C.
  • the 1% decomposition temperature of the easily dismantling adhesive material (uncured) is, for example, 230 to 260.degree. C., preferably 240 to 260.degree.
  • the 0.5% decomposition temperature is, for example, 230 to 260.degree. C., preferably 230 to 250.degree.
  • the 1% decomposition temperature of the cured product obtained by thermogravimetric analysis is, for example, 250 to 280°C, preferably 250 to 270°C.
  • the conditions for thermogravimetric analysis refer to the examples given later.
  • the easily dismantleable adhesive material of the present embodiment can preferably be used in the following processes (1) and (2).
  • a dismantling adhesive material is sandwiched between a first structural member and a second structural member, and the dismantling adhesive material is heat cured by a first heat treatment.
  • an article is obtained that includes the first structural member, the second structural member, and the cured adhesive material that bonds the first structural member and the second structural member.
  • the article obtained in (1) above is subjected to a second heat treatment to dismantle the first structural member and the second structural member.
  • the second temperature condition is the first temperature condition.
  • a higher temperature is preferable.
  • first structural member and the second structural member are not particularly limited. Examples of materials include metals such as aluminum, aluminum alloys, and SUS, plastics such as polypropylene, polyethylene, and nylon, and ceramics.
  • both the first structural member and the second structural member are preferably metallic structural members.
  • the structural member may be subjected to various surface treatments, or may not be subjected to surface treatment. In terms of adhesive strength and ease of dismantling, it is preferable to remove foreign matter/contamination by cleaning the surface of the structural member before applying the easy-to-dismantle adhesive to the surface of the structural member. .
  • the easily dismantleable adhesive material of the present embodiment is used for bonding a first structural member and a second structural member. Therefore, normally, the cured body of the easily dismantleable adhesive material is sandwiched between the first structural member and the second structural member and is not exposed.
  • the method of adhering the easily dismantling adhesive material to the surface of the first structural member and/or the second structural member is not particularly limited. If the easily dismantling adhesive material has a viscosity that allows it to be applied, the easily dismantling adhesive material may be applied to the surface of the structural member by a known coating method.
  • drying treatment is preferably performed.
  • the drying treatment may be performed at room temperature (without heating), or may be performed with heating at about 30 to 100°C.
  • the drying time here is, for example, about 3 to 24 hours.
  • drying treatment under reduced pressure may be performed even after heat curing of the easily dismantleable adhesive material.
  • the drying treatment here may be performed with heating at, for example, 30 to 100° C., specifically about 30 to 50° C., but is preferably performed at room temperature (without heating).
  • the drying time here is, for example, about 1 to 24 hours.
  • drying treatment under reduced pressure may not be performed, and even if some treatment is performed, it is specific. conditions are not particularly limited. In some cases, it is sufficient to simply leave the heat-cured easily dismantleable adhesive material at room temperature for about 1 to 24 hours.
  • the value of (T2-T1) is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. . By doing so, sufficient hardened body strength and dismantling easiness can be achieved.
  • the upper limit of the value of (T2-T1) is preferably 130.degree. Practically preferred temperature conditions are T1 of 20 to 160°C and T2 of 170 to 250°C.
  • the time for the first heat treatment is not particularly limited as long as the easily dismantleable adhesive material is sufficiently hardened.
  • the duration of the first heat treatment is 1 to 24 hours.
  • the time for the second heat treatment is not particularly limited as long as the easy dismantling property is exhibited.
  • the duration of the second heat treatment is 5 minutes to 6 hours.
  • active energy rays may be applied to the hardened body instead of/along with the second heat treatment as long as the dismantling property is exhibited.
  • the easily dismantleable adhesive material can be configured to include, for example, the following (A) and (B).
  • Polyrotaxane provided
  • the polymerizable group in (A) above is preferably a group containing a polymerizable carbon-carbon double bond, and can be, for example, a (meth)acryloyl group.
  • the cyclic molecule in the above (A) is a cyclodextrin, and it is preferable that the polymerizable group is bonded to the cyclodextrin directly or via a linking group.
  • a preferred embodiment of the cyclic molecule is cyclodextrin, and more preferably, at least part of the hydrogen atoms of the hydroxy groups of this cyclodextrin are substituted with groups represented by general formula (I) below.
  • R is a hydrogen atom or a methyl group
  • A is a single bond, -COO- or -CONH-
  • B is a single bond, or a linear or branched alkylene group
  • L is a single bond or a carbonyl group
  • p is an integer of 0 to 10
  • q is an integer of 0 or more.
  • Embodiments of the easily dismantleable adhesive material including the above (A) and (B) include the following.
  • Examples of aspect 1 include the following.
  • Examples of aspect 2 include the following.
  • Example 2-2 An easily dismantleable adhesive material containing the following (A) and one or both of (B1) and (B2).
  • acrylate oligomers and other oligomers may be blended. Moreover, you may mix
  • Example 3-1 Formulation example containing a polymerization initiator
  • Example 3-2 Formulation example containing a polymerization initiator
  • the hyperbranched polymer is synthesized by the method described in Japanese Patent No. 6516319, for example.
  • Example 1 [Preparation of easily dismantled adhesive material]
  • a polyrotaxane having a total molecular weight of 400,000 g/mol and a linear molecular chain portion molecular weight of 20,000 g/mol was synthesized.
  • This polyrotaxane, as shown in FIG. 1, comprises a polyether chain passing through openings in a cyclic molecule, cyclodextrin, and adamantyl groups bonded to both ends of the polyether chain.
  • thermogravimetric analysis The easily dismantleable adhesive material itself and the cured product obtained by heating and curing the easily dismantleable adhesive material at 150° C. for 7 hours, 10 hours or 16 hours are each subjected to thermogravimetric analysis to obtain a TG curve. Painted.
  • the conditions for thermogravimetric analysis are as follows. ⁇ Measurement start temperature: room temperature ⁇ Temperature increase rate: 10°C/min ⁇ Atmosphere: nitrogen gas
  • the 0.5% decomposition temperature and the 1% decomposition temperature were obtained from the TG curve of the cured product obtained by curing the easily dismantling adhesive material at 150° C. for 7 hours. Table 1 shows the results. For reference, the TG curve itself is shown in FIG.
  • a conjugate for evaluation was produced in the following manner.
  • (1) Application of Easily Dismantled Adhesive Material to First Structural Member A stainless steel plate (SUS304) was prepared as the first structural member. 25 ⁇ L of the prepared easily dismantling adhesive material was applied to a 1 cm ⁇ 1 cm area on the surface of this stainless steel plate and dried overnight under reduced pressure conditions of 50° C. and 10 to 100 Pa.
  • the shear bond strength of the bonded body obtained in the above [Production of bonded body] was measured in accordance with JIS K 6850:1999 at room temperature (23° C.) and a test speed of 1 mm/min. The measurement was performed 3 times and the average value was taken as F1.
  • the adhesive strength did not decrease even with heating (heating at a temperature lower than the dismantling temperature).
  • TTMA trimethylolpropane trimethacrylate
  • the cured product of the adhesive material of Example 2 in which the specific polyrotaxane and the compound having a polymerizable carbon-carbon double bond were used in combination also showed easy disassembly.
  • F1 that is, the shear bond strength before dismantling treatment was significantly higher than in Example 1, while the magnitude of F2 was about the same as in Example 1. That is, the adhesive material of Example 2 can bond the structural members together more strongly than the adhesive material of Example 1, but the force required for dismantling is the same for the adhesive material of Example 1 and the adhesive material of Example 2. It was about From the viewpoint of increasing the bonding strength before dismantling treatment, it can be said that it is preferable to use a specific polyrotaxane and a compound having a polymerizable carbon-carbon double bond in combination.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un matériau de liaison facile à désassembler qui peut être utilisé dans une application d'utilisation de sorte qu'un premier élément structural est lié à un second élément structural pour obtenir un corps lié, puis chauffer ou permettre à un rayon d'énergie active d'agir sur le corps lié afin de le désassembler, le matériau de liaison facile à désassembler comprenant un polyrotaxane qui possède une molécule en forme d'anneau présentant une ouverture, une chaîne de molécules linéaires pénétrant par l'ouverture dans la molécule en forme d'anneau, et des groupes de coiffage liés respectivement aux deux extrémités de la chaîne de molécules linéaires, dans laquelle la molécule en forme d'anneau possède un groupe polymérisable.
PCT/JP2022/006093 2021-02-18 2022-02-16 Matériau de liaison facile à désassembler, corps lié et procédé de désassemblage WO2022176887A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-024069 2021-02-18
JP2021024069A JP7248328B2 (ja) 2021-02-18 2021-02-18 易解体性接着材料、接合体および解体方法

Publications (1)

Publication Number Publication Date
WO2022176887A1 true WO2022176887A1 (fr) 2022-08-25

Family

ID=82930502

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/006093 WO2022176887A1 (fr) 2021-02-18 2022-02-16 Matériau de liaison facile à désassembler, corps lié et procédé de désassemblage

Country Status (2)

Country Link
JP (1) JP7248328B2 (fr)
WO (1) WO2022176887A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート
WO2017191827A1 (fr) * 2016-05-02 2017-11-09 国立大学法人 東京医科歯科大学 Polyrotaxane dégradable intérieurement et son procédé de synthèse
JP2019189819A (ja) * 2018-04-27 2019-10-31 リンテック株式会社 感温性粘着シートおよび積層体
JP2020176183A (ja) * 2019-04-16 2020-10-29 信越化学工業株式会社 活性エネルギー線硬化性組成物
JP2021001276A (ja) * 2019-06-21 2021-01-07 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート及び積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート
WO2017191827A1 (fr) * 2016-05-02 2017-11-09 国立大学法人 東京医科歯科大学 Polyrotaxane dégradable intérieurement et son procédé de synthèse
JP2019189819A (ja) * 2018-04-27 2019-10-31 リンテック株式会社 感温性粘着シートおよび積層体
JP2020176183A (ja) * 2019-04-16 2020-10-29 信越化学工業株式会社 活性エネルギー線硬化性組成物
JP2021001276A (ja) * 2019-06-21 2021-01-07 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート及び積層体

Also Published As

Publication number Publication date
JP2022126154A (ja) 2022-08-30
JP7248328B2 (ja) 2023-03-29

Similar Documents

Publication Publication Date Title
JP6564695B2 (ja) 粘着剤組成物、その製造方法、粘着シートおよび画像表示装置
US9637596B2 (en) Polyhemiaminal and polyhexahydrotriazine materials from 1,4 conjugate addition reactions
US8242185B2 (en) Adhesive compositions for easy application and improved durability
JP5591543B2 (ja) 反応性希釈剤
US8686060B2 (en) Adhesive compositions for easy application and improved durability
TW201217478A (en) Pressure-sensitive adhesive compound, pressure-sensitive adhesive tape, and wafer treatment method
JP5671500B2 (ja) 樹脂組成物、粘着剤および重合体の製造方法
JP7450545B2 (ja) 外部刺激に基づき変化可能な特性を有する接着剤として使用される硬化性組成物並びにその作製方法及び使用方法
KR20220110736A (ko) 점착재, 점착 시트 및 굴곡성 적층 부재
WO2022176887A1 (fr) Matériau de liaison facile à désassembler, corps lié et procédé de désassemblage
KR20120101099A (ko) 광경화형 점접착제 조성물, 광경화형 점접착제층 및 광경화형 점접착 시트
CN116194541A (zh) (甲基)丙烯酸酯结构粘合剂和方法
JP6461927B2 (ja) 粘着フィルム用光硬化性樹脂組成物および粘着フィルム
TWI725645B (zh) 用於接合聚合物之可固化熱封黏著劑
JP7043120B2 (ja) 粘着剤組成物
JP6516319B2 (ja) 熱硬化性多分岐型高分子とその製造方法および硬化多分岐型高分子
JP6525619B2 (ja) 光硬化する組成物ならびにその組成物から得られる光硬化物および粘接着剤
KR101795116B1 (ko) 점착 필름용 광경화성 수지 조성물 및 점착 필름
WO2021225167A1 (fr) Matériau adhésif pouvant se désintégrer facilement
WO2022130340A1 (fr) Composition comprenant un monomère avec un groupe acide carboxylique, un monomère avec un groupe hydroxyle, un monomère cycloalkyle, et agent de réticulation ainsi qu'articles et procédés associés
EP4263640A1 (fr) Composition comprenant un monomère acrylique ayant un groupe acide carboxylique, monomère acrylique ayant un groupe hydroxyle, monomère (méth)acrylate d'alkyle et agent de réticulation, articles et procédés associés
WO2019182155A1 (fr) Composition durcissable, produit durci, procédé de production d'un produit durci, et procédé de réparation d'un endommagement d'un produit durci
KR102545923B1 (ko) 이중 경화형 점착제 조성물, 그 제조방법 및 이를 이용한 점착 보호 테이프, 피착재 표면 보호방법
JP7248716B2 (ja) 離型フィルム用コーティング剤、離型フィルム、物品及び離型フィルムの製造方法
JP7380185B2 (ja) ブロック共重合体、樹脂組成物および粘着フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22756205

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22756205

Country of ref document: EP

Kind code of ref document: A1