WO2018221564A1 - Adhésif et structure - Google Patents

Adhésif et structure Download PDF

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Publication number
WO2018221564A1
WO2018221564A1 PCT/JP2018/020704 JP2018020704W WO2018221564A1 WO 2018221564 A1 WO2018221564 A1 WO 2018221564A1 JP 2018020704 W JP2018020704 W JP 2018020704W WO 2018221564 A1 WO2018221564 A1 WO 2018221564A1
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Prior art keywords
group
adhesive
polymer
structural unit
aromatic ring
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PCT/JP2018/020704
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English (en)
Japanese (ja)
Inventor
公二 西口
耀平 大古田
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日立化成株式会社
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Priority to JP2019521256A priority Critical patent/JPWO2018221564A1/ja
Priority to CN201880024167.8A priority patent/CN110546223B/zh
Publication of WO2018221564A1 publication Critical patent/WO2018221564A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene

Definitions

  • the present disclosure relates to an adhesive and a structure.
  • resins used as adhesives such as acrylic resins, urethane resins, and epoxy resins (see, for example, Patent Documents 1 and 2).
  • acrylic resin is excellent in transparency and weather resistance, and demand is steadily increasing as an adhesive.
  • the adhesive strength to metal, glass, polyimide, etc. was insufficient.
  • the present disclosure provides an adhesive having excellent adhesive force.
  • the present disclosure also provides a structure having excellent strength.
  • the present invention includes various embodiments. Examples of embodiments are listed below. The present invention is not limited to the following embodiments.
  • One embodiment is a polymer comprising an ethylene structural unit (A) having an aromatic ring group having two adjacent hydroxyl groups and an ethylene structural unit (B) not having an aromatic ring group having two adjacent hydroxyl groups
  • the present invention relates to an adhesive containing
  • the proportion of the ethylene structural unit (A) contained in the polymer is 0.05 to 55 mol% based on the total of structural units other than the ethylene structural unit (A). preferable.
  • the polymer preferably has a weight average molecular weight of 70,000 or more.
  • the aromatic ring group having two adjacent hydroxyl groups preferably includes a group represented by the following formula (a1).
  • Ar represents an aromatic ring
  • R represents a substituent
  • l represents an integer of 0 or more
  • R represents the number of R.
  • * Represents a bonding position with another atom.
  • the ethylene structural unit (A) preferably includes a structural unit represented by the following formula (A1).
  • A represents an aromatic ring group having two adjacent hydroxyl groups
  • X represents a divalent linking group
  • m represents an integer of 0 or 1
  • R a1 to R a3 each independently represents hydrogen. Represents an atom or a substituent, and “*” represents a bonding position with another atom.
  • the ethylene structural unit (B) preferably includes a structural unit represented by the following formula (B1).
  • R b1 to R b4 each independently represent a hydrogen atom or a substituent. “*” Represents a bonding position with another atom.
  • the polymer is preferably a polymer represented by the following formula (P1).
  • P1 represents an aromatic ring group having two adjacent hydroxyl groups
  • X represents a divalent linking group
  • m represents an integer of 0 or 1
  • R a1 to R a3 each independently represent a hydrogen atom or a substituent.
  • R b1 to R b4 each independently represents a hydrogen atom or a substituent.
  • “*” Represents a bonding position with another atom.
  • a and b satisfy 0.05 ⁇ [a / b (mol / mol)] ⁇ 100 ⁇ 55. )
  • the polymer includes an aromatic ring group having two adjacent hydroxyl groups and a monomer (A) having an ethylenically unsaturated group, and an aromatic ring group having two adjacent hydroxyl groups. It is preferable that it is a copolymer of the monomer containing the monomer (B) which has no ethylenically unsaturated group.
  • the adhesive may further contain a solvent.
  • Another embodiment includes an adherend (1), an adhesive layer, and an adherend (2), and the adherend (1) and the adherend (2) form the adhesive layer.
  • the adhesive layer contains any one of the adhesives.
  • the adherend (1) preferably includes at least one selected from the group consisting of stainless steel, copper, aluminum, magnesium, glass, and polyimide.
  • the adherend (2) preferably includes at least one selected from the group consisting of stainless steel, copper, aluminum, magnesium, glass, and polyimide.
  • an adhesive having an excellent adhesive force is provided. Moreover, according to this indication, the structure which has the outstanding intensity
  • FIG. 1 is a 1 H-NMR spectrum of an adhesive polymer contained in the adhesive of Example 3.
  • the adhesive comprises an ethylene structural unit (A) having an aromatic ring group having two adjacent hydroxyl groups and an ethylene structural unit (B) having no aromatic ring group having two adjacent hydroxyl groups.
  • A ethylene structural unit having an aromatic ring group having two adjacent hydroxyl groups
  • B ethylene structural unit having no aromatic ring group having two adjacent hydroxyl groups.
  • this polymer may be referred to as “adhesive polymer”.
  • the adhesive may contain arbitrary components such as a solvent and an additive.
  • the adhesive polymer includes an ethylene structural unit (A) and an ethylene structural unit (B).
  • the adhesive polymer may have any structural unit other than the ethylene structural unit (A) and the ethylene structural unit (B).
  • the ethylene structural unit (A) is a structural unit having at least one aromatic ring group having an ethylene structure serving as a polymer skeleton and having two adjacent hydroxyl groups in the structural unit.
  • An aromatic ring group is a substituent derived from an aromatic ring, and is bonded to the ethylene structure directly or via a divalent linking group.
  • Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the aromatic ring is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.
  • Aromaatic ring group having two adjacent hydroxyl groups refers to an aromatic ring group in which hydrogen atoms bonded to two adjacent atoms constituting the aromatic ring are each substituted by a hydroxyl group (hereinafter, the aromatic group).
  • the ring group may be referred to as a “dihydroxyaryl group”.
  • the aromatic ring group is a phenyl group, it means a phenyl group in which each hydrogen atom bonded to two adjacent carbon atoms constituting the benzene ring is substituted with a hydroxyl group (hereinafter, the phenyl group). May be referred to as a “catechol group”). Examples include 2,3-dihydroxyphenyl group and 3,4-dihydroxyphenyl group. From the viewpoint of obtaining excellent adhesive strength, 3,4-dihydroxyphenyl group is preferred.
  • dihydroxyaryl group examples include a group represented by the following formula (a1).
  • Ar represents an aromatic ring
  • R represents a substituent
  • l is an integer of 0 or more, and represents the number of R.
  • the upper limit of l is determined according to the structure of Ar.
  • “*” represents a bonding position with another atom. The same applies hereinafter.
  • R is preferably a substituent other than a hydroxyl group, and examples thereof include an alkyl group having 1 to 4 carbon atoms.
  • examples of the dihydroxyaryl group include a group represented by the following formula (a2).
  • R represents a substituent
  • l is an integer of 0 to 3 and represents the number of R.
  • l is preferably 0.
  • R is preferably a substituent other than a hydroxyl group, and examples thereof include an alkyl group having 1 to 4 carbon atoms.
  • examples of the dihydroxyaryl group include a group represented by the following formula (a3).
  • the dihydroxyaryl group is bonded to the ethylene structure directly or via a divalent linking group.
  • the divalent linking group include a divalent group containing an amide bond (—NH—CO—) and a divalent group containing an ester bond (—O—CO—).
  • Examples of the divalent group include a group represented by the following formula (x1) and a group represented by the following formula (x2).
  • n represents an integer of 0 to 10. From the viewpoint of improving adhesive strength, n is preferably 1 or more. Moreover, 6 or less is preferable from a viewpoint of suppressing adhesiveness, 4 or less is more preferable, and 3 or less is still more preferable.
  • Examples of the ethylene structural unit (A) include a structural unit represented by the following formula (A1).
  • A represents a dihydroxyaryl group
  • X represents a divalent linking group
  • m represents an integer of 0 or 1
  • R a1 to R a3 each independently represent a hydrogen atom or a substituent.
  • the substituent is preferably a group other than a dihydroxyaryl group, and examples thereof include an alkyl group having 1 to 4 carbon atoms.
  • A is preferably a group represented by the formula (a1), more preferably a group represented by the formula (a2), and still more preferably a group represented by the formula (a3).
  • X is preferably a group represented by the formula (x1) or a group represented by the formula (x2), and more preferably a group represented by the formula (x1).
  • m is preferably 1.
  • R a1 and R a2 are preferably hydrogen atoms.
  • R a3 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • An ethylene structural unit (B) is a structural unit which has an ethylene structure used as a polymer skeleton in a structural unit, and does not have a dihydroxyaryl group.
  • Examples of the ethylene structural unit (B) include a structural unit represented by the following formula (B1).
  • each represent R b1 ⁇ R b4 are independently a hydrogen atom or a substituent.
  • the substituent is a group other than a dihydroxyaryl group. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a monovalent group containing an ester bond, and a monovalent group containing an amide bond.
  • R b1 and R b2 are preferably a hydrogen atom.
  • R b3 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • R b4 is preferably a monovalent group containing an ester bond or a monovalent group containing an amide bond, an alkyloxycarbonyl group (R—O—CO— group (R is alkyl)), monoalkylaminocarbonyl Group (R—NH—CO— group (R is alkyl)) or dialkylaminocarbonyl group (R—NR′—CO— group (R and R ′ are alkyl)), preferably an alkyloxycarbonyl group or A dialkylaminocarbonyl group is more preferable, and an alkyloxycarbonyl group is still more preferable.
  • the number of carbon atoms in the alkyl here is preferably 1 to 4.
  • the ratio of the structural unit (A) is preferably 0.05 mol% or more based on the total of other structural units in the adhesive polymer. More preferably, it is 1 mol% or more, more preferably 1 mol% or more, and particularly preferably 1.5 mol% or more.
  • the ratio of the structural unit (A) is preferably 55 mol% or less with respect to the total of other structural units in the adhesive polymer, and is preferably 10 mol% or less. More preferably, it is more preferably 7.5 mol% or less, and particularly preferably 3 mol% or less.
  • the ratio of the structural unit (A) is within the above range, the adhesive force is easily improved.
  • the ratio of the structural unit (A) is 55 mol% or less, the structural unit (which contributes to the improvement of the adhesive strength with the adherend due to the interaction in the polymer) It is mentioned that the substantial amount of A) increases.
  • the ratio of the structural unit (A) can be determined by nuclear magnetic resonance spectroscopy (NMR spectroscopy).
  • the “other structural unit” is a structural unit other than the structural unit (A).
  • the weight average molecular weight is preferably 70,000 or more, more preferably 80,000 or more, and further preferably 100,000 or more. 120,000 or more is particularly preferable.
  • the weight average molecular weight is preferably 200,000 or less, more preferably 180,000 or less, and still more preferably 160,000 or less.
  • the number average molecular weight is preferably 18,000 or more, more preferably 20,000 or more, and further preferably 25,000 or more. Similarly, from the viewpoint of improving adhesive strength, the number average molecular weight is preferably 40,000 or less, more preferably 35,000 or less, and further preferably 33,000 or less.
  • PDI Mw / Mn
  • PDI is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Although a minimum is not specifically limited, Usually, it is 1 or more.
  • the weight average molecular weight and the number average molecular weight can be measured by size exclusion chromatography. Specifically, it can obtain
  • GPC gel permeation chromatography
  • the adhesive polymer can be represented by the following formula (P1).
  • A represents a dihydroxyaryl group
  • X represents a divalent linking group
  • m represents an integer of 0 or 1
  • R 1a to R 3a each independently represents a hydrogen atom or a substituent
  • R 1b ⁇ R 4b each independently represents a hydrogen atom or a substituent.
  • a and b satisfy 0.05 ⁇ [a / b (mol / mol)] ⁇ 100 ⁇ 55.
  • the molar ratio [a / b] of the two structural units can be determined by nuclear magnetic resonance spectroscopy (NMR spectroscopy).
  • NMR spectroscopy nuclear magnetic resonance spectroscopy
  • the terminal of an adhesive polymer is not specifically limited, Usually, the structure derived from a monomer, a polymerization initiator, etc. is contained.
  • 0.1 ⁇ [a / b] is preferable, 1 ⁇ [a / b] is more preferable, and 1.5 ⁇ [a / b] is satisfied. Further preferred.
  • [a / b] ⁇ 10 is preferable, [a / b] ⁇ 7.5 is more preferable, and [a / b] ⁇ 3. More preferably it is.
  • the adhesive polymer includes a monomer (A) having a dihydroxyaryl group and an ethylenically unsaturated group, and a monomer (B) having no dihydroxyaryl group and having an ethylenically unsaturated group. ) -Containing monomer copolymer.
  • a monomer (A), a monomer (B), etc. are mentioned later.
  • the adhesive polymer may be a monomer copolymer composed of the monomer (A) and the monomer (B).
  • the adhesive polymer is obtained by polymerizing at least two types of monomers having an ethylenically unsaturated group.
  • the two types of monomers are a monomer (A) having a dihydroxyaryl group and an ethylenically unsaturated group, and a monomer (B) having no dihydroxyaryl group and having an ethylenically unsaturated group. Therefore, one embodiment of the method for producing an adhesive polymer includes copolymerizing a monomer containing the monomer (A) and the monomer (B).
  • the method for copolymerizing at least two types of monomers is not particularly limited. Methods such as radical polymerization, anionic polymerization, and cationic polymerization can be used.
  • the polymerization method may be any of solution polymerization, suspension polymerization, emulsion polymerization and the like.
  • the monomer (A) has at least one dihydroxyaryl group and at least one ethylenically unsaturated group in the molecule.
  • the dihydroxyaryl group is as described above.
  • the monomer (A) may have an ethylenically unsaturated group as a “group containing an ethylenically unsaturated group”.
  • groups of the group containing an ethylenically unsaturated group include a vinyl group, an allyl group, and an acryloyl group.
  • Methacryloyl group, acryloyloxy group, methacryloyloxy group, acrylamino group, and methacryloylamino group, and methacryloylamino group is preferable.
  • Examples of the monomer (A) include a vinyl compound having a catechol group, a (meth) acrylic acid ester compound having a catechol group, and a (meth) acrylamide compound having a catechol group.
  • monomer (A) examples include compounds represented by the following formula (A2).
  • examples of the monomer (A) include a compound (1) represented by the following formula.
  • the monomer (B) does not have a dihydroxyaryl group and has at least one ethylenically unsaturated group in the molecule.
  • the dihydroxyaryl group and the ethylenically unsaturated group are as described above.
  • monomer (B) examples include compounds represented by the following formula (B2).
  • Monomer (B) is, for example, styrene (vinyl benzene); acrylamide, methacrylamide; alkyl-substituted acrylamide or alkyl-substituted methacrylamide such as dimethylacrylamide and dimethylmethacrylamide; methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid Ethyl, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid Acrylic acid alkyl esters such as 2-ethylhexyl, n-octyl acrylate, n-octyl methacrylate, lauryl acrylate
  • a monomer containing a reactive functional group in the molecule can be used as the monomer (B).
  • the reactive functional group include a hydroxyl group, a carboxyl group, an epoxy group, and a halogen group.
  • a monomer containing a reactive functional group a compound in which a reactive functional group is substituted on the alkyl group of the above-mentioned alkyl-substituted acrylamide, alkyl-substituted methacrylamide, alkyl acrylate ester, or alkyl methacrylate ester can be given.
  • Specific examples include (meth) acrylic acid esters having a hydroxyl group such as (meth) acrylic acid-2-hydroxyethyl and (meth) acrylic acid-4-hydroxybutyl.
  • Urethane (meth) such as a reaction product of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate, a reaction product of trimethylhexamethylene diisocyanate, cyclohexanedimethanol and 2-hydroxyethyl (meth) acrylate, etc. Acrylate may be used.
  • the monomer (B) is composed of alkyl-substituted acrylamide, alkyl-substituted methacrylamide, alkyl acrylate ester, and alkyl methacrylate ester. It is preferable to include one or more selected, and more preferable to include one or more selected from alkyl-substituted methacrylamide and alkyl methacrylate.
  • alkyl-substituted methacrylamide dimethylacrylamide is preferable, and as the methacrylic acid alkyl ester, methyl methacrylate, n-butyl methacrylate and the like are preferable.
  • the ratio of the monomer (A) used when synthesizing the adhesive polymer is 0.05 mol% or more with respect to the total of the monomers other than the monomer (A) in the monomer. preferable. Moreover, it is preferable that the ratio of a monomer (A) is 55 mol% or less with respect to the sum total of monomers other than the monomer (A) in a monomer.
  • the adhesive polymer obtained by polymerizing the monomer composition containing the monomer (A) in the above range expresses higher adhesive strength to various adherends. From the viewpoint of adhesive strength, the ratio of the monomer (A) is more preferably 0.1 mol% or more, further preferably 1 mol% or more, and particularly preferably 1.5 mol% or more. . Similarly, the ratio of the monomer (A) is more preferably 10 mol% or less, further preferably 7.5 mol% or less, and particularly preferably 3 mol% or less.
  • the total ratio of one or more selected from alkyl-substituted acrylamide, alkyl-substituted methacrylamide, alkyl acrylate, and alkyl methacrylate in monomer (B) is the total monomer (B), It is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.
  • filled the outstanding adhesive strength and storage stability are obtained.
  • the upper limit can be 100 mol%.
  • radical polymerization initiator In obtaining the adhesive polymer, it is preferable to use a radical polymerization initiator in order to polymerize the monomer.
  • the radical polymerization initiator is not particularly limited, and a normal radical polymerization initiator can be used.
  • azo compounds and peroxides are preferred.
  • azo radical initiators and organic peroxides that generate free radicals by heat are preferred.
  • azo radical initiator examples include azobisisobutyronitrile (AIBN, trade name V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylisobutyronitrile).
  • AIBN trade name V-60, manufactured by Wako Pure Chemical Industries, Ltd.
  • 2,2′-azobis (2-methylisobutyronitrile) trade name V-59, manufactured by Wako Pure Chemical Industries, Ltd.
  • 2,2′-azobis (2,4-dimethylvaleronitrile) trade name V-65, manufactured by Wako Pure Chemical Industries, Ltd.
  • dimethyl -2,2'-azobis (isobutyrate) trade name V-601, manufactured by Wako Pure Chemical Industries, Ltd.
  • 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) trade name V -70, manufactured by Wako Pure Chemical Industries, Ltd.
  • organic peroxides examples include isobutyl peroxide, ⁇ , ⁇ '-bis (neodecanoyl peroxyisopropyl) benzene, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, lauroyl peroxide.
  • the amount of radical polymerization initiator used can be appropriately selected according to the type of monomer, and is used in a general amount. Specifically, the content is preferably 0.01 to 2% by mass and more preferably 0.1 to 1% by mass with respect to the total amount of monomers.
  • reaction solvent When obtaining an adhesive polymer, it is preferably synthesized by solution polymerization using a reaction solvent.
  • the reaction solvent is preferably an organic solvent, and the organic solvent is not particularly limited as long as the monomer dissolves. From the viewpoint of solubility of the monomer (A), it is preferable to use ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, or N, N-dimethylformamide (DMF).
  • the amount of the reaction solvent is not particularly limited, and may be determined from the viewpoint of polymerization rate, polymer molecular weight after polymerization, and the like.
  • the polymer molecular weight (Mw) after polymerization is about 100,000
  • the total amount of monomers is preferably 15 to 60% by mass with respect to the solvent.
  • the temperature at which the adhesive polymer is synthesized is not particularly limited and may be determined in consideration of the type of monomer used, the boiling point of the solvent, the half-life temperature of the polymerization initiator, and the like.
  • the reaction temperature is preferably 60 to 70 ° C.
  • the adhesive polymer When the adhesive polymer is obtained by solution polymerization, the adhesive polymer can be taken out as it is as a polymer solution after the reaction, but may be purified by precipitation.
  • the unreacted monomer remaining in the polymer solution can be removed by dropping the polymer solution after the reaction into a poor solvent for the adhesive polymer to obtain the adhesive polymer as a precipitate.
  • two types of monomers, compound (1) and methyl methacrylate are polymerized using N, N-dimethylformamide (DMF)
  • the polymer solution is placed in water that becomes a poor solvent for the adhesive polymer after the reaction. It is possible to remove the unreacted monomer component by dropping and obtaining a precipitate.
  • the method for producing the adhesive polymer is not limited to the method described above. It is also possible to produce an adhesive polymer by a method of introducing a dihydroxyaryl group into a polymer containing an ethylene structural unit.
  • the adhesive may contain any component such as a solvent, an additive, another polymer, and other adhesive components.
  • the solvent is preferably an organic solvent, and specifically, the solvents mentioned as the reaction solvent can be used.
  • the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, and a surfactant.
  • the content of the adhesive polymer is based on the total amount of the adhesive (however, when the adhesive includes a solvent, the total mass of the solid content excluding the mass of the solvent), for example, 80 to 100% by mass.
  • the adhesive preferably contains a solvent because the adhesive can be easily applied to the adherend by a coating method.
  • the content of the adhesive polymer is, for example, 5 to 30% by mass based on the total amount of the adhesive (the total mass including the mass of the solvent).
  • Adhesion method There is no restriction
  • the adhesive may be used for repair use, reinforcement use, or the like.
  • objects used for repairing and reinforcing purposes include building floors, building materials such as walls, and concrete.
  • materials to be used include metal, glass, plastic, and concrete.
  • the structure includes an adherend (1), an adhesive layer, and an adherend (2), and the adherend (1) and the adherend (2) are interposed via the adhesive layer.
  • the adhesive layer contains the adhesive of the above embodiment. Since the adherend (1) and the adherend (2) are bonded to each other with an adhesive having high adhesive strength, the structure has excellent strength.
  • adherend (1) and adherend (2) include metal, glass, plastic, and concrete, and the types of metal, glass, plastic, and concrete are not particularly limited.
  • the plastic include engineering plastics such as polyimide, polyamideimide, and polyamide.
  • Either or both of the adherend (1) and the adherend (2) may be at least one selected from the group consisting of stainless steel, copper, aluminum, magnesium, glass, and polyimide. .
  • the structure can be obtained using, for example, an adhesive containing a solvent.
  • the structure is formed by applying an adhesive to both the adherend (1) and the adherend (2), or one of the adherend (A) and the adherend ( It can be produced by bonding B) and removing the solvent.
  • the coating method include a potting method, a dipping method, a spray method, and a roll coating method.
  • the solvent removal include a method of drying by heating, reduced pressure, a combination thereof or the like.
  • Examples of structures include automobile parts, household appliance parts, display devices, portable terminals, electronic parts, building materials, concrete, and the like.
  • Adhesives containing an adhesive polymer were prepared and evaluated for adhesive strength and storage stability.
  • the adhesive polymer was synthesized by changing the ratio of the monomer (A) and the monomer (B), and the molecular weight and composition ratio were determined.
  • Example 1 In a 50 mL two-necked eggplant type flask, 100 mg of compound (1) ((N- (3,4-dihydroxyphenylethyl) methacrylamide)), 75 mg of azobisisobutyronitrile (AIBN), and a rotor were placed. A reflux tube and a nitrogen inlet tube were attached.
  • MMA methyl methacrylate
  • DMF N, N-dimethylformamide
  • composition analysis of adhesive polymer 10 mg of adhesive polymer is dissolved in 0.8 mL of deuterated dimethyl sulfoxide, nuclear magnetic resonance apparatus (“AV400M” manufactured by Bruker BioSpin Co., Ltd., frequency: 400 MHz, integration frequency: 16, temperature: 25 ° C., reference substance : Tetramethylsilane (TMS)) was used for 1 H-NMR measurement. From the proton ratio of the obtained spectrum, the ratio of structural units contained in the adhesive polymer was calculated. The results are shown in Table 1.
  • Example 2 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 200 mg, AIBN 75 mg, MMA 9.1 g, and DMF 17.2 g, and the molecular weight and composition ratio were determined. The yield was 86% by mass.
  • Example 3 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 400 mg, AIBN 76 mg, MMA 9.1 g, and DMF 17.6 g, and the molecular weight and composition ratio were determined. The yield was 89% by mass.
  • FIG. 1 shows the 1 H-NMR spectrum.
  • Example 4 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 900 mg, AIBN 70 mg, MMA 8.1 g, and DMF 16.8 g, and the molecular weight and composition ratio were determined. The yield was 83% by mass.
  • Example 5 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 1.7 g, AIBN 69 mg, MMA 7.7 g, and DMF 17.4 g, and the molecular weight and composition ratio were determined. It was. The yield was 83% by mass.
  • Example 6 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 5.0 g, AIBN 56 mg, MMA 4.5 g, and DMF 17.7 g, and the molecular weight and composition ratio were obtained. It was. The yield was 93% by mass.
  • Example 1 In the synthesis of the adhesive polymer, an adhesive polymer was synthesized in the same manner as in Example 1 except that 62 mg of AIBN, 7.5 g of MMA, and 14.5 g of DMF were used, and the molecular weight and the composition ratio were determined. The yield was 84% by mass.
  • Example 2 In the synthesis of the adhesive polymer, an adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 6.0 g, AIBN 22 mg, and DMF 11.1 g. The yield was 84% by mass. Since the adhesive polymer was not dissolved in tetrahydrofuran, the molecular weight could not be measured.
  • Example 3 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that AIBN was 115 mg, MMA 13.9 g, acrylic acid (AA) 100 mg, and DMF 26.0 g, and the molecular weight and composition ratio were determined. . The yield was 84% by mass.
  • Two base materials coated with the polymer solution for each type of base material were prepared, and after leaving for 10 minutes in a dryer at 80 ° C. to remove the solvent, the two base materials were coated with the polymer solution. They were superposed so that they were bonded together, fixed with clips, and allowed to stand in a dryer at 180 ° C. for 2 hours to obtain test pieces for evaluation of shear bond strength.
  • the adhesion width of the metal substrate was 10 mm, and the adhesion width of the glass substrate was 5 mm. In all the substrates, the thickness of the adhesive layer was about 60 ⁇ m.
  • the adhesive polymer containing the structural unit (A) and the structural unit (B) greatly improved the adhesion strength to various metals and glasses.
  • the adhesive polymer having the structural unit (A) ratio of 2 mol% has the highest adhesive strength.
  • the compositions of the adhesive polymers of Examples 2, 3 and 5 did not change after standing. According to the adhesive polymer containing the structural unit (A) and the structural unit (B), both high adhesive strength and excellent storage stability can be achieved.
  • Example 8 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that the compound (1) was 400 mg, AIBN 15 mg, MMA 9.1 g, and DMF 17.6 g, and the molecular weight and composition ratio were determined. The yield was 84% by mass.
  • the adhesive polymers of Examples 7 and 8 also showed high adhesive strength. In particular, the highest adhesive strength was obtained in the adhesive polymer of Example 7.
  • Adhesive 3 An adhesive containing an adhesive polymer was prepared, and the adhesive strength was evaluated.
  • Example 4 In the synthesis of the adhesive polymer, the adhesive polymer was synthesized in the same manner as in Example 1 except that AIBN was 75 mg, BMA 10.0 g, and DMF 18.6 g, and the molecular weight and composition ratio were determined. The yield was 88% by mass.
  • the adhesive polymer of Example 9 also showed high adhesive strength.
  • the adhesive polymer containing the structural unit (A) and the structural unit (B) greatly improved the adhesive strength to polyimide.
  • the adhesive polymer containing the structural unit (A) and the structural unit (B) exhibits excellent adhesive strength.

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

Abstract

Un mode de réalisation de la présente invention concerne un adhésif comprenant un polymère qui comprend une unité éthylène structurale (A) ayant un groupe cyclique aromatique ayant deux groupes hydroxyles adjacents et une unité éthylène structurale (B) n'ayant pas de groupe cyclique aromatique ayant deux groupes hydroxyles adjacents.
PCT/JP2018/020704 2017-05-31 2018-05-30 Adhésif et structure WO2018221564A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019214718A (ja) * 2018-06-12 2019-12-19 日本化薬株式会社 重合性組成物及びその硬化物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010501027A (ja) * 2006-08-04 2010-01-14 ネリテス コーポレイション バイオミメティック化合物およびその合成方法
JP2012233059A (ja) * 2011-04-28 2012-11-29 Japan Science & Technology Agency 新規ポリマー
WO2015152176A1 (fr) * 2014-03-31 2015-10-08 独立行政法人物質・材料研究機構 Nanomatériau de revêtement, procédé de fabrication de ce dernier, agent de revêtement, matériau fonctionnel et procédé de fabrication de ce dernier
WO2016190400A1 (fr) * 2015-05-26 2016-12-01 国立研究開発法人科学技術振興機構 Hydrogel adhésif contenant du catéchol, composition pour préparer cet hydrogel adhésif, et compositions comprenant chacune ledit hydrogel adhésif

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755870B (zh) * 2014-01-06 2016-10-26 苏州大学 一种含多巴胺无规共聚物及其精细制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010501027A (ja) * 2006-08-04 2010-01-14 ネリテス コーポレイション バイオミメティック化合物およびその合成方法
JP2012233059A (ja) * 2011-04-28 2012-11-29 Japan Science & Technology Agency 新規ポリマー
WO2015152176A1 (fr) * 2014-03-31 2015-10-08 独立行政法人物質・材料研究機構 Nanomatériau de revêtement, procédé de fabrication de ce dernier, agent de revêtement, matériau fonctionnel et procédé de fabrication de ce dernier
WO2016190400A1 (fr) * 2015-05-26 2016-12-01 国立研究開発法人科学技術振興機構 Hydrogel adhésif contenant du catéchol, composition pour préparer cet hydrogel adhésif, et compositions comprenant chacune ledit hydrogel adhésif

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019214718A (ja) * 2018-06-12 2019-12-19 日本化薬株式会社 重合性組成物及びその硬化物
JP7294586B2 (ja) 2018-06-12 2023-06-20 日本化薬株式会社 重合性組成物及びその硬化物

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