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WO2020026575A1 - Corps assemblé et procédé de production d'un corps assemblé - Google Patents

Corps assemblé et procédé de production d'un corps assemblé Download PDF

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Publication number
WO2020026575A1
WO2020026575A1 PCT/JP2019/021430 JP2019021430W WO2020026575A1 WO 2020026575 A1 WO2020026575 A1 WO 2020026575A1 JP 2019021430 W JP2019021430 W JP 2019021430W WO 2020026575 A1 WO2020026575 A1 WO 2020026575A1
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WO
WIPO (PCT)
Prior art keywords
adherend
intermediate layer
group
carbon atoms
bonding agent
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/021430
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English (en)
Japanese (ja)
Inventor
明寛 昆野
村山　利美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
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 Kureha Corp filed Critical Kureha Corp
Publication of WO2020026575A1 publication Critical patent/WO2020026575A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a bonded article and a method for producing the same, and more particularly, to a bonded article joined via a molecular bonding agent and a method for producing the same.
  • Patent Document 1 discloses a structural adhesive having excellent adhesive performance and flexibility in a wide temperature range.
  • Patent Document 2 discloses an adhesive having a high adhesive strength retention rate in a pressure cooker test, which is one of the moisture resistance tests.
  • Patent Literature 1 is studied with respect to strength in each of low temperature, room temperature, and high temperature ranges, data such as moisture resistance is not described, and weather resistance is not studied.
  • the technology described in Patent Document 2 is evaluated for moisture resistance, the bonding strength is as low as about 0.5 N / mm, which is insufficient. As described above, there is no adhesive that achieves both strength and weather resistance.
  • an object of the present invention is to provide a bonded article having both high adhesive strength and weather resistance, and a method for producing the same.
  • the present invention has been found in the study of the bonding method, and is a technique for joining two adherends using a vinylidene fluoride resin having excellent weather resistance, chemical resistance, and heat resistance.
  • vinylidene fluoride resin is a difficult-to-bond material, and there is no example of application as a material for joining vinylidene fluoride resin.
  • the present invention relates to a joined article obtained by joining a first adherend and a second adherend via an intermediate layer, wherein the intermediate layer contains vinylidene fluoride as a main component.
  • the bonding agent is a compound having —NX 1 X 2 (where X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and an alkoxysilyl group or a silanol group. .
  • the present invention is a method for manufacturing a joined article in which a first adherend and a second adherend are joined via an intermediate layer, wherein the intermediate layer and the first adherend are provided.
  • a compound having -NX 1 X 2 (X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and an alkoxysilyl group or a silanol group; It is.
  • the joint according to the present embodiment is a joint formed by joining a first adherend and a second adherend via an intermediate layer formed of a vinylidene fluoride polymer.
  • the intermediate layer and the first adherend, and the intermediate layer and the second adherend, are respectively bonded via a molecular bonding agent.
  • the molecular bonding agent in the present embodiment is a compound that bonds the intermediate layer formed of the vinylidene fluoride polymer to each of the first adherend and the second adherend.
  • the molecular bonding agent in the present embodiment has —NX 1 X 2 and an alkoxysilyl group or a silanol group.
  • X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • X 1 is preferably a hydrogen atom.
  • the number of carbon atoms in the alkoxy moiety of the alkoxysilyl group is not particularly limited, but preferably has 1 to 5 carbon atoms.
  • the molecular bonding agent in the present embodiment is preferably a compound represented by the following general formula (I).
  • R 1 is represented by a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aminoalkyl group having 1 to 5 carbon atoms or the following general formula (II), and R 2 is a group having 1 to 5 carbon atoms.
  • R 3 to R 5 are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and at least one of R 3 to R 5 One is a hydroxy group or an alkoxy group having 1 to 5 carbon atoms.
  • R 6 is an alkylene group having 1 to 10 carbon atoms
  • R 7 is —NH—R 8 —NH 2 or —NR 9 R 10
  • R 8 has 1 to 10 carbon atoms
  • R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms.
  • the symbol * represents a bonding site to the nitrogen atom to which R 1 in formula (I) is bonded.
  • R 1 is preferably a hydrogen atom, an aminoalkyl group having 1 to 3 carbon atoms or a group represented by the general formula (II), and is preferably a hydrogen atom or a group represented by the general formula (II). More preferably, it is more preferably a group represented by the general formula (II).
  • R 2 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 2 to 5 carbon atoms. .
  • R 3 to R 5 are preferably a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
  • R 6 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms. .
  • R 7 is preferably —NH—R 8 —NH 2 .
  • R 8 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. More preferred is an alkylene group having 1 to 2 carbon atoms.
  • R 1 is represented by the general formula (II)
  • R 2 is an alkylene group having 1 to 5 carbon atoms
  • R 3 to R 5 is an alkoxy group having 1 to 3 carbon atoms
  • R 7 is —NH—R 8 —NH 2
  • R 8 is an alkylene group having 1 to 3 carbon atoms.
  • Most preferred as a molecular conjugating agent is N, N'-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine (hereinafter, referred to as "the molecular bonding agent").
  • A-TES N, N'-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine
  • R 1 may be a hydrogen atom or an aminoalkyl group having 1 to 5 carbon atoms
  • R 2 may be an alkylene group having 1 to 10 carbon atoms
  • R 3 to R 5 May be an alkoxy group having 1 to 5 carbon atoms.
  • the intermediate layer in the present embodiment is formed from a vinylidene fluoride polymer.
  • the vinylidene fluoride polymer in the present embodiment has a structural unit derived from vinylidene fluoride as a main component.
  • “being the main component” means that the content is 50 mol% or more.
  • the vinylidene fluoride polymer may be a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride with a structural unit derived from a copolymerizable monomer.
  • monomers copolymerizable with vinylidene fluoride include fluorine-containing monomers, hydrocarbon monomers such as ethylene and propylene, acrylic monomers such as alkyl (meth) acrylate compounds and carboxy group-containing acrylate compounds, and maleic monomers.
  • fluorine-containing monomers include fluorine-containing monomers, hydrocarbon monomers such as ethylene and propylene, acrylic monomers such as alkyl (meth) acrylate compounds and carboxy group-containing acrylate compounds, and maleic monomers.
  • examples thereof include acids, unsaturated dibasic acid derivative monomers such as monomethyl maleate and dimethyl maleate, and carboxylic acid anhydride group-containing monomers, among which fluorine-containing monomers are preferred from the viewpoint of weather resistance and chemical resistance.
  • the other monomers may be used alone or in combination of two or more.
  • fluorine-containing monomer examples include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ethers represented by perfluoromethyl vinyl ether.
  • Examples of unsaturated dibasic acid derivative monomers include maleic acid, citraconic acid, monomethyl maleate, dimethyl maleate and monomethyl citraconic acid.
  • alkyl (meth) acrylate compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, 2- (hydroxy Methyl) methyl acrylate and 2- (hydroxyethyl) methyl acrylate.
  • carboxy group-containing acrylate compound examples include (meth) acrylic acid, 2-carboxyethyl acrylate, (meth) acryloyloxypropyl succinic acid, (meth) acryloyloxyethyl succinic acid, 2-hydroxyethyl acrylate and hydroxypropyl acrylate. Is mentioned.
  • the inherent viscosity of the vinylidene fluoride polymer according to the present embodiment is not particularly limited, but is preferably in a range of 0.5 to 7.0 dL / g, and is preferably 0.7 to 5.0 dL / g. The value is more preferably in the range of g, and even more preferably in the range of 1.0 to 4.0 dL / g.
  • the inherent viscosity of the vinylidene fluoride polymer can be determined as the logarithmic viscosity at 30 ° C. of a solution obtained by dissolving 4 g of the resin in 1 liter of N, N-dimethylformamide.
  • the vinylidene fluoride polymer according to the present embodiment can be manufactured by, for example, suspension polymerization, emulsion polymerization, or the like.
  • a molded article of the vinylidene fluoride polymer can be used as the intermediate layer formed from the vinylidene fluoride polymer according to the present embodiment.
  • the molded article of the vinylidene fluoride polymer can be produced by a known method such as injection molding, press molding, calendar molding, extrusion molding, and melt spinning, similarly to the production of a molded article of a normal vinylidene fluoride polymer. it can. Further, the manufacturing method can be selected according to the form of the molded body.
  • the shape of the molded body is not particularly limited, and examples thereof include a plate, a rod, a sphere, a hemisphere, a fiber, a powder, a cloth, a net, a film, a sheet, and a laminate. From the viewpoint of increasing the bonding strength, a plate-like, film-like or sheet-like material having a large contact area between the intermediate layer and the adherend is preferred. Further, a film-like or sheet-like material is preferable because the distance between the adherends can be shortened.
  • the surface of the intermediate layer is bonded to the adherend by covalently bonding a molecular bonding agent to the surface. Therefore, unlike conventional adhesives utilizing non-bonding force, strong adhesion is possible even on a smooth surface.
  • the surface of the intermediate layer is preferably a smooth surface from the viewpoint of the airtightness of the joint, but may be a rough surface.
  • adherend material The materials and forms of the first and second adherends to be joined (hereinafter, simply referred to as adherends when there is no need to distinguish between them) are not particularly limited.
  • the material for the adherend include metal materials (including alloys), various resins, ceramic materials, and composite materials thereof, and are preferably formed from resin or metal.
  • metal material examples include various metals and alloys thereof.
  • metals include Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Rh, Ir, and Ni.
  • Pd, Pt Cu, Ag, Au, Zn, Cd, Hg, Al, Ge, Sn, Pb, Sb, Bi and Nd.
  • the resin examples include a thermoplastic resin, a thermosetting resin, a fiber reinforced plastic, a photocurable resin, a vulcanized rubber, and an uncrosslinked rubber.
  • examples thereof include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, or poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride or chlorinated vinyl resin; Acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, or acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, poly Polyesters such as butylene terephthalate or polyethylene naphthalate; Polyamides such as Nylon 6, Nylon 66, or Nylon 610; Polyacetals; Polycarbonates; Polyphenylene oxides
  • the ceramic material for example, porcelain (such as kaolin, frog eye clay, pottery stone, feldspar, quartzite, quartz, or alumina), glass, cement, gypsum, and enamel are given. From the viewpoint of composition, oxides, zirconia, hydroxides, carbides, carbonates, nitrides, halides, and phosphates are exemplified.
  • the form of the adherend is not particularly limited, and examples thereof include a plate, a rod, a sphere, a hemisphere, a fiber, a powder, a cloth, a net, a film, a sheet, and a laminate.
  • the surface of the adherend is bonded to the intermediate layer by covalently bonding a molecular bonding agent to the surface. Therefore, unlike conventional adhesives utilizing non-bonding force, strong adhesion is possible even if the surface of the adherend is smooth, but even if the surface of the adherend is rough. Good.
  • first adherend and the second adherend may be of the same material and of the same form, may be of different materials, and of different forms.
  • first and second adherends can be manufactured by a method well known to those skilled in the art.
  • the bonded article according to the present embodiment has an intermediate layer made of a vinylidene fluoride polymer between the first adherend and the second adherend, and the first adherend and the intermediate layer are joined. Then, since the second adherend and the intermediate layer are joined, the first adherend and the second adherend are joined.
  • the bonding between the intermediate layer and each of the adherends is via a covalent bond by a molecular bonding agent.
  • the adherend and the intermediate layer are interposed with the molecular bonding agent, the distance between the adherend and the intermediate layer is extremely small and substantially directly in contact with each other. More specifically, the adherend is covalently bonded to the molecular bonding agent at molecules on its surface, and the intermediate layer is covalently bonded to the molecular bonding agent at molecules on its surface.
  • it may be simply referred to as “covalent bond with the adherend” or “covalent bond with the intermediate layer”.
  • the covalent bond between the adherend and the molecular bonding agent is different depending on whether the surface of the adherend is metal or ceramic or resin.
  • the molecular bonding agent covalently bonds to the metal or ceramic at the alkoxysilyl group or silanol group of the molecular bonding agent.
  • the adherend is covalently bonded to a molecular bonding agent that is (or is) covalently bonded to the intermediate layer. Thereby, the adherend and the intermediate layer are joined.
  • the surface of the adherend is, although not have a reactive alkoxysilyl group or silanol group of the molecule bonding agent, when the resin reactive with the -NX 1 X 2, adherends and molecular bonding agent Is a covalent bond at —NX 1 X 2 possessed by the molecular bonding agent. Then, the adherend and the molecular bonding agent are bonded by condensation of alkoxysilyl groups or silanol groups of the molecular bonding agent covalently bonded to both.
  • each molecular bonding agent there may be a plurality of alkoxy groups or hydroxy groups in the alkoxysilyl group or silanol group, and it is sufficient that at least one of these groups is condensed.
  • an example of the molecular bonding agent when one is condensed is shown in the following general formula (III).
  • R 1 to R 4 are the same as those described for the general formula (I) shown above.
  • the adherend may be covalently bonded to the intermediate bonding layer —NX 1 X 2 , which is covalently bonded to the intermediate layer.
  • the surface of the adherend is, when a resin having no reactivity with the -NX 1 X 2, by performing the pre-process for bonding described later, the molecular bonding agent to the adherend, the molecular The bonding agent and the adherend are covalently bonded at the alkoxysilyl group or silanol group of the molecular bonding agent.
  • the bonding between the adherend and the intermediate layer in the bonded article according to the present embodiment is a bonding via a molecular bonding agent, whereby the distance between the bonding material and the intermediate layer is reduced by one to several molecular bonding agents. It can fit within the size of a minute. Therefore, the distance between the adherend and the intermediate layer may be 0.1 ⁇ m or less, may be 0.05 ⁇ m or less, and may be 10 nm or less. As described above, in the joining between the adherend and the intermediate layer in the joint according to the present embodiment, since the distance between the adherend and the intermediate layer is extremely small, the joint between the adherend and the intermediate layer is not shared. Bonding occurs, and the bonding between the adherend and the intermediate layer is further strengthened.
  • the adherend and the intermediate layer are in a state of being strongly bonded. Since the first adherend and the intermediate layer and the second adherend and the intermediate layer are strongly bonded to each other, the bonded article in the present embodiment, that is, the first adherend and the second adherend Is firmly joined. Specifically, the first adherend and the second adherend in the present embodiment are connected via a middle layer, but are each bonded by a covalent bond via a molecular bonding agent. For this reason, stronger bonding is enabled as compared with bonding using a conventional adhesive using non-bonding force such as hydrogen bonding. Therefore, even if the contact area is small, for example, the contact surface is smooth, a strong connection is possible.
  • each joint in the present embodiment is based on a covalent bond, unlike an adhesive, the joint does not deteriorate even under a severe environment such as high temperature and high pressure. Therefore, high joining reliability can be obtained.
  • the intermediate layer is formed of a vinylidene fluoride polymer which is known to have excellent weather resistance. Therefore, the bonded article of the present embodiment is a bonded article having excellent weather resistance.
  • the bonded article according to the present embodiment can have a shear strength retention rate of 50% or more and 60% or more when subjected to a highly accelerated life test of 121 ° C., humidity RH 100%, pressure 2 atm, and 200 hours. And even more than 70%.
  • the shear strength is measured according to JIS K6850.
  • the shear strength retention rate is calculated as strength [MPa] after the high acceleration life test / initial strength [MPa].
  • the adherend in the present embodiment can be made of various materials as listed above.
  • the molecular bonding agent not only the molecular bonding agent but also the intermediate material can be used to interpose any material.
  • the adherends can be firmly joined together in the same manner.
  • the adherends can be used when the first adherend and the second adherend are directly joined to each other with a molecular bonding agent without using an intermediate layer. Since the surfaces of both adherends have no roughness and no distortion, both adherends can be used. Since the adherend can be joined at a shorter distance, it can be bonded. However, it is difficult to obtain an adherend having no roughness and no distortion, and particularly when the adherend is metal or ceramic, it requires appropriate equipment and processing such as polishing.
  • the intermediate layer and the adherend can be brought into contact with each other in the vicinity of the melting point or the softening point of the vinylidene fluoride polymer constituting the intermediate layer in the contact step described later. Therefore, even with an adherend having some distortion and roughness, the intermediate layer and the adherend can be easily bonded.
  • At least one of the intermediate layer and the first adherend and at least one of the intermediate layer and the second adherend are formed by using a solution containing a molecular bonding agent (hereinafter referred to as a molecule).
  • a solution containing a molecular bonding agent hereinafter referred to as a molecule.
  • Surface treatment using a bonding agent solution and a contact step of contacting the first adherend with the intermediate layer and the second adherend with the intermediate layer.
  • at least one of the intermediate layer and the first adherend and at least one of the intermediate layer and the second adherend are formed using a molecular bonding agent solution.
  • the intermediate layer and / or the first adherend is at least one of the first adherend and the second adherend” is used.
  • And at least one of the intermediate layer and the second adherend is used.
  • the intermediate layer and the adherend may be collectively referred to as a “joining material”.
  • the surface treatment step according to this embodiment includes an immersion treatment of immersing the bonding material in a molecular bonding agent solution.
  • the content of the molecular bonding agent in the solution is preferably at most 1 wt%, more preferably at most 0.5 wt%, even more preferably at most 0.1 wt%.
  • the solvent of the molecular bonding agent solution is preferably water, but may be, for example, an alcohol solvent such as ethanol, an ether solvent, a ketone solvent or a mixed solvent thereof.
  • 10 10 seconds is sufficient for the immersion time, but it is preferably 30 seconds or more, and more preferably 60 seconds or more.
  • the joining material may be applied directly to only the portion to be joined without being limited to the immersion treatment, since the portion to be joined may be treated with the solution of the molecular bonding agent, or a sprayer or the like. May be used to spray the solution.
  • the surface of the adherend is metal or ceramic, either the intermediate layer or the adherend may be surface-treated.
  • alkoxysilyl groups or silanol groups react more easily than amino groups. Therefore, from the viewpoint of covalently bonding more molecular bonding agents to the surface of the bonding material, the surface of the bonding surface of the adherend is first treated, that is, the reaction between the alkoxysilyl group or silanol group and the adherend is performed first. It is preferable to perform it.
  • the adherend is a resin having reactivity with —NX 1 X 2
  • the resin reactive with the -NX 1 X 2 in -NX 1 X 2 molecular bonding agent has covalently bound.
  • the intermediate layer and the adherend are bonded by condensing alkoxysilyl groups or silanol groups of a molecular bonding agent covalently bonded to both.
  • the surface treatment step may include other treatments in addition to the immersion treatment described above.
  • the adherend does not contain a COO bond but contains a CH bond
  • a compound having both a functional group that binds to the adherend and a functional group that binds to the molecular bonding agent is bonded to the surface where the adherend is bonded to the intermediate layer. More specifically, it is preferable to bond a compound having an azide group and an alkoxysilyl group or a silanol group. Examples of such a compound include those represented by the following general formula (IV).
  • R 11 is an alkylene group having 1 to 10 carbon atoms
  • R 12 to R 14 are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
  • An alkyl group, at least one of R 12 to R 14 is a hydroxy group or an alkoxy group having 1 to 5 carbon atoms
  • R 15 is an azide group or an alkyl group having 1 to 10 carbon atoms.
  • R 11 is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
  • R 12 to R 14 are preferably a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
  • R 15 is more preferably an azide group.
  • the most preferred compound is 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol (hereinafter, P-TES).
  • the method for bonding such a compound to the surface of the adherend is not particularly limited.
  • the adherend is immersed in a solution containing the compound and a radical generating reaction is performed by irradiation with ultraviolet rays.
  • the solution containing the compound of the formula (IV) may contain a molecular bonding agent in advance.
  • a step of immersing the compound of the formula (IV) in a molecular bonding agent solution after the treatment with the compound and the ultraviolet irradiation, or a molecular bonding The step of applying the agent solution can be omitted.
  • the contacting step in the method for manufacturing a bonded article according to the present embodiment is a step of contacting the first adherend with the intermediate layer and the second adherent with the intermediate layer at 80 ° C. or higher.
  • Examples of the contacting method include, but are not limited to, a pressing method, and a method of performing injection molding after inserting a processing substrate.
  • the temperature at the time of contact is 80 ° C. or higher, and a more preferable temperature is, when the surface of the adherend is metal or ceramic, the melting point of the vinylidene fluoride polymer constituting the intermediate layer is mp. Then, it is mp ⁇ 50 ° C. or more and mp + 50 ° C. or less, and more preferably mp ⁇ 30 ° C. or more and mp + 30 ° C. or less.
  • the more preferable temperature is mp (H) ⁇ 50 ° C. or more and mp (H) + 50 ° C. or less, where mp (H) is the higher melting point of the bonding material. , still more preferably mp (H) -30 °C higher mp (H) + 30 °C or less.
  • the more preferable contact temperature is sp-50 ° C or more and sp + 50 ° C or less, and further preferably sp-30 ° C or more and sp + 30 ° C or less.
  • the “softening point” in the present specification indicates a workable temperature at which the amorphous resin can flow and deform.
  • the adherend and the intermediate layer can be bonded at a shorter distance.
  • a vinylidene fluoride polymer can be partially substituted with an amino group by reacting with an amine. Therefore, some molecular bonding agents may bond to the intermediate layer without going through the contacting step.
  • a covalent bond with the intermediate layer is formed in many molecular bonding agents by applying heat of 80 ° C. or higher. As a result, it is possible to obtain a bonded body that is very strongly bonded.
  • the contact step is not limited to the case where the contact between the first adherend and the intermediate layer and the contact between the second adherend and the intermediate layer are performed simultaneously. That is, the contact between the first adherend and the intermediate layer and the contact between the second adherend and the intermediate layer may be independently performed as separate steps.
  • the contacting step is not limited to being performed after all the operations of the surface treatment step are completed, and a part of the contacting step may be performed during the surface treatment step.
  • the first adherend is brought into contact with the intermediate layer, and then the surface of the intermediate layer which comes into contact with the second adherend and At least one of the second adherends may be surface-treated to bring the second adherent into contact with the intermediate layer.
  • a bonded article according to the present invention is a bonded article obtained by bonding a first adherend and a second adherend via an intermediate layer, wherein the intermediate layer is mainly composed of vinylidene fluoride.
  • the first adherend and the intermediate layer, and the second adherend and the intermediate layer are joined via a molecular bonding agent.
  • the molecular bonding agent is a compound having —NX 1 X 2 (where X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and an alkoxysilyl group or a silanol group. is there.
  • the first adherend and the second adherend are each independently a resin or a metal.
  • X 1 is a hydrogen atom.
  • the molecular bonding agent is a compound represented by the following general formula (I).
  • R 1 is represented by a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aminoalkyl group having 1 to 5 carbon atoms or the following general formula (II), and R 2 is a group having 1 to 10 carbon atoms.
  • R 3 to R 5 are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and at least one of R 3 to R 5 is a hydroxy group;
  • a group or an alkoxy group having 1 to 5 carbon atoms R 6 is an alkylene group having 1 to 10 carbon atoms, R 7 is —NH—R 8 —NH 2 or —NR 9 R 10 ;
  • And 8 is an alkylene group having 1 to 10 carbon atoms, and R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms. Is a bonding site with the nitrogen atom to which R 1 is bonded.
  • R 1 is represented by the general formula (II).
  • the molecular bonding agent may be NN′-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine. preferable.
  • R 1 is a hydrogen atom.
  • the distance between the first adherend and the intermediate layer and the distance between the second adherend and the intermediate layer are each 0.1 ⁇ m or less.
  • the method for manufacturing a bonded article according to the present invention is a method for manufacturing a bonded article in which a first adherend and a second adherend are bonded via an intermediate layer, wherein the intermediate layer and the second A surface treatment step of performing surface treatment on at least one of the first adherend and at least one of the intermediate layer and the second adherend using a molecular bonding agent solution; And a contact step of contacting the second adherend with the intermediate layer at a temperature of 80 ° C. or more, wherein the intermediate layer is formed from a vinylidene fluoride polymer containing vinylidene fluoride as a main constituent.
  • the molecular bonding agent includes —NX 1 X 2 (X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and an alkoxysilyl group or a silanol group.
  • Example 1 A steel plate (SPCC, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, the sample was immersed in a 0.1 wt% aqueous solution of A-TES (manufactured by Io Chemical Laboratory Co., Ltd.) to modify the surface to obtain Sample A-1. Note that two samples A-1 were prepared.
  • SPCC manufactured by Testpiece Co., Ltd.
  • PVDF polyvinylidene fluoride
  • the tensile strength was evaluated using a tensile tester (AG-2000E, manufactured by Shimadzu Corporation). As a result, the shear tensile strength of the bonded article 1 was 22 MPa.
  • Example 2 An Al plate (A5052P, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, it was immersed in a 5 wt% aqueous solution of a degreaser SK-144 (manufactured by JCU) at 70 ° C. for 1 minute, and then ultrasonically washed with ion-exchanged water for 3 minutes. After drying, the sample was immersed in a 0.1 wt% A-TES aqueous solution to modify the surface to obtain a sample A-2. Note that two samples A-2 were prepared.
  • Example 2 the same processing as in Example 1 was performed to obtain a sample B-1.
  • the sample A-2 was placed on a SUS plate with the A-TES treated surface facing upward, the sample B-1 was placed at the end, and another sample A-2 was overlapped so that the overlap length was 12.5 mm. Placed. This was hot-pressed at 200 ° C., 2 MPa, for 5 minutes using a press molding machine to obtain a joint 2.
  • the shear tensile strength of the joint 2 was 20 MPa.
  • Example 3 The same treatment as in Example 2 was performed except that a 0.1% aqueous solution of 3-aminoprolyltriethoxysilane (hereinafter, APS, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the A-TES aqueous solution. Sample A-3 was obtained instead of sample A-2. Next, the same process as in Example 2 was performed except that Sample A-2 was changed to Sample A-3, to obtain a joined product 3.
  • APS 3-aminoprolyltriethoxysilane
  • the shear tensile strength of the joint 3 was 16 MPa.
  • Example 4 The same treatment as in Example 2 was performed except that a 1.0% aqueous solution of APS was used instead of the A-TES aqueous solution, to obtain a sample A-4 instead of the sample A-2. Next, the same process as in Example 2 was performed except that Sample A-2 was changed to Sample A-4, to thereby obtain a joined product 4.
  • the shear tensile strength of the joint 4 was 23 MPa.
  • Example 5 An Al plate (A5052P, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, the sample was immersed in a 5 wt% aqueous solution of a degreaser SK-144 (manufactured by JCU Corporation) at 70 ° C. for 1 minute, and then ultrasonically washed with ion-exchanged water for 3 minutes to obtain a sample A-5. In addition, two samples A-5 were prepared.
  • a degreaser SK-144 manufactured by JCU Corporation
  • a PVDF film (# 1000, manufactured by Kureha Corporation) having a width of 30 mm, a length of 20 mm and a thickness of 79 ⁇ m was ultrasonically washed with ethanol for 10 minutes.
  • a corona treatment was performed using a table type surface treatment apparatus (manufactured by Kasuga Electric Co., Ltd.) under the conditions of an output power of 150 W, a gap length of 2 mm, a moving speed of 4 m / min, and a number of movements of 4 times.
  • a 1.0 wt% APS aqueous solution was applied to modify the surface to obtain Sample B-2.
  • the surface modification of Sample B-2 was performed on both sides.
  • Sample A-5 was placed on a SUS plate, sample B-2 was placed at the end, and another sample A-5 was placed so that the overlap length was 12.5 mm. This was hot-pressed at 200 ° C., 2 MPa, for 5 minutes using a press molding machine to obtain a joint 5. As a result of evaluating the tensile strength using a tensile tester, the shear tensile strength of the joint 5 was 23 MPa.
  • Example 6 A sample A-6 was obtained in place of the sample A-1, except that the steel plate was a 1.0 mm-thick ceramic plate (alumina ceramics manufactured by Testpiece Co., Ltd.). . Then, the same processing as in Example 1 was performed except that Sample A-1 was changed to Sample A-6, to thereby obtain a joined product 6. The tensile strength of the joint 6 was evaluated using a tensile tester. As a result, when a shear stress of 7 MPa was applied to the joint of Sample B-1, Sample A-6 was broken. Although the sample A-6 was broken, it was shown that the shear tensile strength of the joint 6 was 7 MPa or more.
  • Example 1 The operation was performed in the same manner as in Example 1 except that the A-TES treatment of SPCC was not performed, but the PVDF film was peeled off during cooling after hot pressing, and a bonded product could not be obtained.
  • Example 2 The operation was performed in the same manner as in Example 2 except that the A-TES treatment of Al was not performed, but the PVDF film was peeled off during cooling after hot pressing, and a bonded product could not be obtained.
  • the shear tensile strength of the joint 7 was 24 MPa.
  • a durability test was performed by exposing the bonded article for 200 hours under the conditions of 121 ° C., RH 100%, and 2 atm using a high-acceleration life test apparatus, and then evaluating the tensile strength.
  • the strength retention rate in the durability test was calculated as strength [MPa] after high-acceleration life test / initial strength [MPa]. As a result, the strength retention of the joint 7 after the durability test was 22%.
  • Comparative Example 4 The same operation as in Comparative Example 3 was performed, except that the SPCC was changed to an Al plate, to obtain a joint 8.
  • the shear tensile strength of the joint 8 was 19 MPa.

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

Abstract

L'invention concerne un corps assemblé présentant aussi bien une résistance à l'adhérence élevée qu'une résistance aux intempéries élevée, et un procédé de production du corps assemblé. Le corps assemblé est obtenu en assemblant un premier élément à assembler et un second élément à assembler, une couche intermédiaire étant interposée entre ces derniers, la couche intermédiaire étant formée d'un polymère de fluorure de vinylidène contenant un fluorure de vinylidène en tant que constituant principal, le premier élément à assembler et la couche intermédiaire, et le second élément à assembler et la couche intermédiaire, étant assemblés l'un à l'autre par un agent de liaison moléculaire. L'agent de liaison moléculaire est un composé présentant -NX1X2 (où X1 et X2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle présentant 1 à 5 atomes de carbone), et un groupe alcoxysilyle ou un groupe silanol.
PCT/JP2019/021430 2018-08-02 2019-05-29 Corps assemblé et procédé de production d'un corps assemblé Ceased WO2020026575A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023080183A1 (fr) * 2021-11-05 2023-05-11 日東電工株式会社 Feuille de liaison moléculaire et procédé de liaison

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0796575A (ja) * 1993-09-29 1995-04-11 Tokai Rubber Ind Ltd 積層体およびその製法
JP2004536722A (ja) * 2001-05-21 2004-12-09 スリーエム イノベイティブ プロパティズ カンパニー フルオロポリマーの接着
WO2013186941A1 (fr) * 2012-06-11 2013-12-19 株式会社いおう化学研究所 Procédé de traitement de surface, agent de traitement de surface et nouveau composé
JP2015096326A (ja) * 2013-10-11 2015-05-21 住友電工プリントサーキット株式会社 フッ素樹脂基材の製造方法及びプリント配線板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0796575A (ja) * 1993-09-29 1995-04-11 Tokai Rubber Ind Ltd 積層体およびその製法
JP2004536722A (ja) * 2001-05-21 2004-12-09 スリーエム イノベイティブ プロパティズ カンパニー フルオロポリマーの接着
WO2013186941A1 (fr) * 2012-06-11 2013-12-19 株式会社いおう化学研究所 Procédé de traitement de surface, agent de traitement de surface et nouveau composé
JP2015096326A (ja) * 2013-10-11 2015-05-21 住友電工プリントサーキット株式会社 フッ素樹脂基材の製造方法及びプリント配線板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023080183A1 (fr) * 2021-11-05 2023-05-11 日東電工株式会社 Feuille de liaison moléculaire et procédé de liaison

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