WO2020136538A1 - Composition pour la formation d'un matériau d'étanchéité, matériau d'étanchéité, article thermodurci à base du matériau d'étanchéité et procédé de fabrication d'une structure adhésive - Google Patents

Composition pour la formation d'un matériau d'étanchéité, matériau d'étanchéité, article thermodurci à base du matériau d'étanchéité et procédé de fabrication d'une structure adhésive Download PDF

Info

Publication number
WO2020136538A1
WO2020136538A1 PCT/IB2019/061235 IB2019061235W WO2020136538A1 WO 2020136538 A1 WO2020136538 A1 WO 2020136538A1 IB 2019061235 W IB2019061235 W IB 2019061235W WO 2020136538 A1 WO2020136538 A1 WO 2020136538A1
Authority
WO
WIPO (PCT)
Prior art keywords
sealing material
meth
mass
epoxy compound
polyvinyl chloride
Prior art date
Application number
PCT/IB2019/061235
Other languages
English (en)
Inventor
Kotaro Shinozaki
Original Assignee
3M Innovative Properties Company
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 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2020136538A1 publication Critical patent/WO2020136538A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present disclosure relates to a composition for forming a sealing material, a sealing material, a thermally cured product of a sealing material, and a method for manufacturing an adhesive structure.
  • Vehicles such as automobiles and the like have discontinuous joints capable of overlapping members such as metal panels.
  • An example of a general non-planar overlap joint includes a roof ditch.
  • the roof ditch is formed in a front-back direction of a vehicle by folding and overlapping a roof panel and a side edge of a side panel of the vehicle with each other.
  • a polyvinyl chloride sol is used particularly in the automobile industry (see, for example, Patent Documents 1 and 2).
  • the polyvinyl chloride sol is a sol-like paste containing polyvinyl chloride and a plasticizer, and when the polyvinyl chloride sol is heated, the polyvinyl chloride sol is solidified in the heated shape, so in the case of attempting to seal sites having a complicated shape with only the polyvinyl chloride sold, there may be a problem in that the polyvinyl chloride sol can be solidified without entering a gap between the sites, the gap remains unsealed, and the like. Therefore, the inventors of the present disclosure investigate a sealing material for sealing sites which are hardly sealed with the polyvinyl chloride sol.
  • the sealing material is preferably a thermosetting sealing material capable of expressing an adhesion by heating like the polyvinyl chloride sol from the viewpoint that production efficiency is not reduced when used in combination with the polyvinyl chloride sol.
  • a thermosetting sealing material for example, a sealing material made of an epoxy-based adhesive
  • sufficient adhesive strength may not be obtained at a contact portion between a thermally cured product of the sealing material and a cured body (cured body containing polyvinyl chloride) derived from the polyvinyl chloride sol.
  • an object of the present disclosure is to provide a sealing material capable of forming a cured body which exhibits good adhesive strength to a cured body derived from a polyvinyl chloride sol even when the sealing material is heated and cured together with the polyvinyl chloride sol in a state where the sealing material is in contact with the polyvinyl chloride sol.
  • An aspect of the present disclosure relates to a composition for forming a sealing material including: a (meth)acrylic compound; an epoxy compound; a photopolymerization initiator; and a thermal curing agent, in which the (meth)acrylic compound contains a tetrahydrofuryl (mete)acrylate, and a content of the tetrahydrofuryl (mete)acrylate is 70% by mass or more with respect to a total mass of (meth)acrylic compound.
  • a content of the epoxy compound in the composition for forming a sealing material may be from 70 to 200 parts by mass with respect to 100 parts by mass of the (meth)acrylic compound.
  • the epoxy compound may contain a flexible epoxy compound.
  • Another aspect of the present disclosure relates to a sealing material including a photocured product of the composition for forming a sealing material.
  • Still another aspect of the present disclosure relates to a sealing material including: a (meth)acrylic polymer; an epoxy compound; and a thermal curing agent, in which the (meth)acrylic polymer contains at least 70% by mass or greater of constituent unit represented by Formula (1) below with respect to a total mass of the (meth)acrylic polymer.
  • R represents a hydrogen atom or a methyl group.
  • a content of the epoxy compound in the sealing material may be from 70 to 200 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer.
  • the epoxy compound may contain a flexible epoxy compound.
  • the sealing material may be formed in a sheet shape.
  • Still another aspect of the present disclosure relates to a thermally cured product of the sealing material.
  • Still another aspect of the present disclosure is a method for manufacturing an adhesive structure having a structure in which a first cured body as a thermally cured product of the sealing material and a second cured body containing polyvinyl chloride adhere onto an adherend, the method including: arranging the sealing material and a polyvinyl chloride sol containing the polyvinyl chloride and a plasticizer on the adherend in a state where the sealing material is in contact with the polyvinyl chloride sol; and obtaining the adhesive structure by heating the sealing material and the polyvinyl chloride sol.
  • a sealing material capable of forming a cured body which exhibits good adhesive strength to a cured body derived from a polyvinyl chloride sol even when the sealing material is heated and cured together with the polyvinyl chloride sol in a state where the sealing material is in contact with the polyvinyl chloride sol.
  • FIG. l is a schematic cross-sectional view showing an embodiment of a method for manufacturing an adhesive structure.
  • FIG. 2 is a schematic cross-sectional view showing a test piece used for an adhesive strength evaluation of an example. DESCRIPTION OF EMBODIMENTS
  • “(meth)acrylic” means“acrylic” and“methacrylic” corresponding thereto.
  • a sealing material includes a composition containing a (meth)acrylic polymer, an epoxy compound, and a thermal curing agent, in which the (meth)acrylic polymer contains at least 70% by mass or greater of constituent unit represented by Formula (1) below with respect to a total mass of the (meth)acrylic polymer.
  • a composition of the sealing material serves as a thermosetting adhesive, and is cured by a reaction of the epoxy compound and the thermal curing agent by heating to express an adhesion.
  • R represents a hydrogen atom or a methyl group.
  • the sealing material is typically molded into a shape which can obtain shape followability to an adherend.
  • the shape of the sealing material is not particularly limited, and may be appropriately changed according to a shape of the adherend, flexibility of the sealing material, and the like.
  • the shape of the sealing material may be, for example, a sheet shape (for example, a tape shape).
  • a protective film (a release liner or the like) may be provided on one side or both sides of a main surface of the sheet-like sealing material. Since the sealing material typically has stickiness at room temperature, the protective film is provided, so for example, a plurality of sheets wound in a roll shape or cut into a desired size or shape can be stored in a stacked state.
  • a thickness of the sheet-like sealing material may be, for example, 0.05 mm or greater, 0.1 mm or greater, or 0.15 mm or greater, and may be 3 mm or less, 2.5 mm or less, or 2 mm or less.
  • the sealing material typically has property (heat melting property) which can melt and flow before being completely cured by heating.
  • the sealing material preferably has suitable fluidity at, for example, 100°C.
  • a viscosity (viscosity of the adhesive constituting the sealing material) of the sealing material at 100°C is preferably 50 Pa-s or greater and 400 Pa-s or greater.
  • the viscosity (viscosity of the adhesive constituting the sealing material) of the sealing material at 100°C is preferably 1500 Pa-s or less and 1000 Pa-s or less.
  • the viscosity is a value measured when temperature rises at a rate of 10 °C/minute to a target measurement temperature in air under normal pressure using a dynamic viscoelasticity measuring device. The viscosity can be adjusted by selecting the type and amount of each component contained in the sealing material.
  • the sealing material can be obtained by photocuring the composition for forming a sealing material described later. That is, the sealing material may contain a photocured product of the composition for forming a sealing material.
  • the sealing material preferably includes only the photocured product of the composition for forming a sealing material.
  • the composition for forming a sealing material is applied on a base material (for example, a protective film) to form a layer made of the composition for forming a sealing material, and then the layer is irradiated with light (active rays) to cure the composition for forming a sealing material.
  • the light is, for example, ultraviolet light (UV).
  • An irradiation amount of light may be, for example, 0.1 J/cm2 or greater and 100 J/cm2 or less with respect to a total energy amount.
  • the sealing material can be used, for example, to make a first member and a second member adhere to each other and to seal a gap formed by the two members.
  • the sealing material is suitably used for sealing a U-shaped groove called a roof ditch formed by a roof panel of a vehicle and a side panel of the vehicle.
  • the sealing material can be used together with a polyvinyl chloride sol. According to the sealing material, it is possible to form a sealing material capable of forming a cured body (thermally cured product of a sealing material) which exhibits good adhesive strength to a cured body derived from a polyvinyl chloride sol even when the sealing material is heated and cured together with the polyvinyl chloride sol in a state where the sealing material is in contact with the polyvinyl chloride sol. A cause of obtaining such an effect is not clear, but the inventors of the present disclosure estimate the cause as follows.
  • thermosetting sealing material for example, a sealing material made of an epoxy-based adhesive
  • the known thermosetting sealing material is heated and cured with the polyvinyl chloride sol in a state where the thermosetting sealing material is in contact with the polyvinyl chloride sol, as the cause that the sufficient adhesive strength cannot be obtained, it is considered that adhesiveness of the sealing material itself is insufficient, adhesiveness of a thermally cured product of the sealing material to polyvinyl chloride is reduced due to the intrusion of a plasticizer derived from the polyvinyl chloride sol into the sealing material during the heating and flow of the sealing material, and the like.
  • the sealing material it is possible to suppress the intrusion of the plasticizer during the heating and melting of the sealing material by appropriate polarity (for example, an SP value different from an SP value of the plasticizer) of the (meth)acrylic polymer containing a predetermined amount or more of a constituent unit represented by the Formula (1) and/or steric hindrance, and the like, so it is considered that a cured product having a high adhesion to the polyvinyl chloride is obtained after the sealing material is cured.
  • appropriate polarity for example, an SP value different from an SP value of the plasticizer
  • the specific (meth)acrylic polymer in particular, the constituent unit represented by the Formula (1)
  • an epoxy compound in particular, an aromatic epoxy compound
  • the (meth)acrylic polymer is a polymer (for example, a radical polymer) of a polymerizable monomer containing a compound containing a (meth)acryloyl group (hereinafter, also simply referred to as“(meth)acrylic compound”), and at least includes the constituent unit represented by the Formula (1) as the constituent unit derived from the (meth)acrylic compound.
  • the constituent unit represented by the Formula (1) can be paraphrased to a constituent unit derived from tetrahydrofurfuryl(meth)acrylate.
  • R in the constituent unit represented by the Formula (1) is preferably a hydrogen atom.
  • the (meth)acrylic polymer preferably contains more a constituent unit H in which R is a hydrogen atom than a constituent unit M in which R is a methyl group, and as a constituent unit represented by the Formula (1), it is more preferable to include only the constituent unit H in which R is a hydrogen atom.
  • a ratio of the constituent unit represented by the Formula (1) is 70% by mass or greater and preferably 75% by mass or greater with respect to the total mass of the (meth)acrylic polymer, from the viewpoint of further improving the adhesiveness to the polyvinyl chloride.
  • the (meth)acrylic polymer may contain only the constituent unit represented by the Formula (1) and a terminal group (for example, a functional group derived from a polymerization initiator, and a functional group derived from a chain transfer agent).
  • the ratio of the constituent unit represented by the Formula (1) may be 100% by mass or less, 95% by mass or less, or 90% by mass or less.
  • the (meth)acrylic polymer may further contain other constituent units other than the constituent unit represented by the Formula (1).
  • the other constituent units are, for example, a constituent unit derived from a compound having a polymerizable carbon- carbon double bond, and more preferably a constituent unit derived from a (meth)acrylic compound.
  • the (meth)acrylic compound include (meth)acrylates such as n- butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and isobornyl (meth)acrylate, (meth)acrylamide such as dimethyl (meth)acrylamide, and the like.
  • alkyl (meth)acrylate is preferable, and from the viewpoint of reducing an odor of the sealing material, alkyl (meth)acrylate (for example, 2-ethylhexyl (meth)acrylate) containing an alkyl group having 8 or more carbon atoms is more preferable.
  • the (meth)acrylic polymer may include, as other constituent units, a constituent unit containing a functional group (hereinafter, also referred to as a“crosslinkable functional group”) capable of forming a structure which is directly crosslinked with an epoxy compound or a structure which is indirectly crosslinked with the epoxy compound via a thermal curing agent.
  • a“crosslinkable functional group” capable of forming a structure which is directly crosslinked with an epoxy compound or a structure which is indirectly crosslinked with the epoxy compound via a thermal curing agent.
  • the (meth)acrylic polymer forms the structure which is crosslinked with the epoxy compound, so the strength of the cured body tends to be improved.
  • the functional group capable of forming the structure which is directly crosslinked with the epoxy compound is, for example, a functional group which reacts with an epoxy group (oxirane ring) and contains at least one nucleophilic or electrophilic moiety (for example, active hydrogen atom), and examples thereof include a phenolic hydroxyl group and the like.
  • the functional group capable of forming the structure which is indirectly crosslinked with the epoxy compound is a functional group capable of reacting with the thermal curing agent, and examples thereof include an epoxy group.
  • the constituent unit containing a crosslinkable functional group include a constituent unit derived from compounds such as glycidyl (meth)acrylate, hydroxypropyl acrylate, and oxetane.
  • the crosslinking between the (meth)acrylic polymers by a bifunctional or higher (meth)acrylate compound and the like such as hexanediol diacrylate is as small as possible.
  • the ratio of the constituent unit containing the crosslinkable functional group is preferably 10% by mass or less and more preferably 7% by mass or less with respect to the total mass of the (meth)acrylic polymer, from the viewpoint of improving the fluidity during heating.
  • the ratio of the constituent unit containing the crosslinkable functional group is preferably 0.001% by mass or greater and 3% by mass or greater with respect to the total mass of the (meth)acrylic polymer, from the viewpoint of improving the strength of the thermally cured product.
  • the (meth)acrylic polymer is a polymer (copolymer) of a plurality of types of compounds, the arrangement of each constituent unit is not particularly limited.
  • the (meth)acrylic polymer may be an alternating copolymer, a random copolymer, a block copolymer, a graft copolymer or the like.
  • a weight average molecular weight of the (meth)acrylic polymer may be 3000 or greater and 300000 or less.
  • a weight average molecular weight is a polystyrene conversion value which uses a calibration curve by standard polystyrene by a gel permeation chromatography method (GPC).
  • a melting point of the (meth)acrylic polymer is preferably lower than a curing initiation temperature of the epoxy compound, from the viewpoint of the heat melting property of the sealing material.
  • the melting point of the (meth)acrylic polymer may be, for example, 140°C or lower or 120°C or lower, and may be 80°C or higher or 90°C or higher.
  • the content of the (meth)acrylic polymer in the sealing material is preferably 20% by mass or greater, more preferably 30% by mass or greater, and still more preferably 35% by mass or greater with respect to the total mass of the sealing material, from the viewpoint of further improving the adhesiveness to the polyvinyl chloride.
  • the content of the (meth)acrylic polymer in the sealing material is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the sealing material, from the viewpoint of further improving the adhesiveness to the polyvinyl chloride.
  • the epoxy compound is a compound containing two or more epoxy groups in one molecule, and preferably a compound containing 2 to 4 epoxy groups.
  • the compounds containing the two or more epoxy groups in one molecule the compounds corresponding to the (meth)acrylic polymer and the (meth)acrylic compound do not correspond to the epoxy compound.
  • the epoxy compound includes a compound (for example, polymer compound) generally called an epoxy resin.
  • an epoxy equivalent of the epoxy compound may be 80 g/eq. or greater or 90 g/eq. or greater, and from the viewpoint of the compatibility with other components and the flexibility of the sealing material, the epoxy equivalent of the epoxy compound may be 1000 g/eq. or less or 600 g/eq. or less.
  • the epoxy equivalent is a value determined in accordance with JIS K 7236.
  • the epoxy compound is an aliphatic epoxy compound having an aliphatic structure, an alicyclic epoxy compound having an alicyclic structure, an aromatic epoxy compound having an aromatic structure, or a heterocyclic epoxy compound having a heterocyclic structure.
  • the aromatic epoxy compound is preferable.
  • Examples of the aromatic epoxy compound include a bisphenol type epoxy compound and a novolak type epoxy compound.
  • Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a dimer acid modified bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and the like.
  • Examples of the novolac type epoxy compound include a phenol novolac type epoxy compound, a cresol novolac type epoxy compound and the like.
  • epoxy compound in addition to the above, for example, aliphatic epoxy compounds such as hexanediol glycidyl ether, glycidyl amine type epoxy compounds such as p-aminophenol triglycidyl, brominated epoxy compounds, and alicyclic epoxy compounds can be used.
  • the epoxy compound is preferably a bisphenol type epoxy compound, a glycidyl amine type epoxy compound, or a novolac type epoxy compound, more preferably a bisphenol type epoxy compound, and still more preferably a bisphenol A type epoxy compound.
  • the epoxy compound may be a commercially available product.
  • the commercially available product include YDF-170, YD-128, YD-011, YDPN-638, and YDCN-700-3 (available from Nippon Steel & Sumikin Chemical Co., Ltd.), MY0510 (available from Huntsman Corporation), jERlOOl (available from Mitsubishi Chemical Corporation), and the like.
  • One type of the epoxy compound may be used alone, and may be used in combination of 2 or more types thereof. When two or more types of epoxy compounds are used in combination, from the viewpoint of shape stability and flexibility of the sealing material, an epoxy compound having an epoxy equivalent of 150 to 250 g/eq. and an epoxy compound having an epoxy equivalent of 400 to 600 g/eq. are preferably used in combination.
  • the content of the epoxy compound is preferably 70 parts by mass or more, and more preferably 80 parts by mass or greater, and still more preferably 90 parts by mass or greater with respect to 100 parts by mass of the (meth)acrylic polymer.
  • the content of the epoxy compound is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 110 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic polymer.
  • a flexible epoxy compound can be used as the epoxy compound.
  • the flexible epoxy compound is a compound in which a flexible skeleton (for example, a long chain alkyl skeleton, a polyalkylene oxide skeleton or the like) is introduced into the epoxy compound, and as the compound, for example, a compound having a bisphenol skeleton and a flexible skeleton and the like has been known.
  • a bisphenol A alkylene oxide modified epoxy compound is preferably used as the flexible epoxy compound.
  • the bisphenol A alkylene oxide modified epoxy compound include a compound having a partial structure represented by Formula (2) below.
  • R1 and R2 each independently represent an alkylene group, and nl and n2 are integers of 0 or greater (however, nl + n2 is 1 or greater).
  • the alkylene group of R1 and R2 may be linear for or branched.
  • the number of carbon atoms of the alkylene group is, for example, 1 to 5.
  • the alkylene group is preferably an ethylene group or an isopropylene group.
  • ADEKA Resin EP-4000 Commercially available products of the flexible epoxy compound include ADEKA Resin EP-4000, ADEKA Resin EP-4005, ADEKA Resin EP-70001, ADEKA Resin EPU- 1 IF, ADEKA Resin EPU-15F (available from ADEKA Corporation), and the like.
  • the present embodiment it is particularly preferable to use a combination of the flexible epoxy compound and the bisphenol A type epoxy compound.
  • the bisphenol A type epoxy compound in combination with a compound (flexible epoxy compound) which is more excellent in flexibility after the thermosetting than the bisphenol A type epoxy compound, it is possible to further increase the extensibility and adhesiveness after the thermosetting.
  • the content of the flexible epoxy compound is preferably 10% by mass or greater, more preferably 15% by mass or greater, and still more preferably 20% by mass or greater with respect to the total mass of the epoxy compound, from the viewpoint of further increasing the extensibility of the thermally cured product.
  • the content of the flexible epoxy compound is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the epoxy compound, from the viewpoint of giving a predetermined hardness to the thermally cured product.
  • thermal curing agent various thermal curing agents known in the art to be usable as a thermal curing agent for an epoxy compound can be used.
  • the thermal curing agent can include the compound which can react with the epoxy group (oxirane ring) of the epoxy compound and can form a crosslinked structure (crosslinked polymer network).
  • the compounds include a compound which reacts with the epoxy group and contains at least one nucleophilic or electrophilic moiety (for example, active hydrogen atom).
  • a latent curing agent which is inactive at around room temperature and activated by heat is preferably used.
  • latent curing agent examples include dicyandiamide and a derivative thereof, a hydrazide compound, a boron trifluoride-amine complex, a reaction product of an amine compound with an isocyanate compound or a urea compound (urea derivative), and the like.
  • the dicyandiamide is preferably used.
  • Commercially available products suitable as the thermal curing agent include EH-3636AS (available from ADEKA Corporation).
  • the thermal curing agent also includes a“curing accelerator” to increase a cure reaction rate of the epoxy compound.
  • the curing accelerator is a multifunctional compound.
  • the curing accelerator may be the latent curing accelerator which is inactive around room temperature and activated by heating.
  • Examples of the curing accelerator include an imidazole compound, a reaction product of an amine compound with an epoxy compound (amine-epoxy adduct), a urea derivative, and the like.
  • Commercially available products of the suitable latent curing accelerator include 2MZA- PW and 2PHZ-PW (available from Shikoku Kasei Kogyo Co., Ltd.).
  • thermal curing agent may be used alone, and two or more types of the thermal agents may be used in combination.
  • the latent curing agent and the latent curing accelerator may be used in combination as the thermal curing agent for the epoxy compound.
  • the content of the thermal curing agent may be 0.1 parts by mass or greater, 1 part by mass or greater, or 3 parts by mass or greater, and 80 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less with respect to 100 parts by mass of the epoxy compound, from the viewpoint of realizing the good crosslinking reaction of the epoxy compound.
  • the sealing material may further contain other components other than the components described above, as long as the effects of the present disclosure are not impaired.
  • the other components include a molding aid, a filler, an antioxidant, a colorant (pigment or the like), and the like.
  • the molding aid examples include polyvinyl butyral, a phenoxy resin and the like. By using the molding aid, it is possible to improve the strength of the sealing material and enhance the moldability.
  • the content of the molding aid may be from 5 to 50 parts by mass with respect to 100 parts by mass of the (meth)acrylic compound.
  • the filler it is possible to use an organic filler or an inorganic filler according to the purpose such as increasing a weight of an adhesive constituting the sealing material, reducing a weight, imparting flame resistance, imparting thermal conductivity, modifying, controlling a flow, and coloring.
  • the filler include calcium carbonate particles, mica particles, talc particles, hollow glass beads, aluminum hydroxide particles, magnesium hydroxide particles, silica particles (including fumed silica), and the like.
  • the content of the filler may be from 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth)acrylic compound.
  • antioxidant examples include Irganox 1010 (available from BASF Japan Ltd.) and the like.
  • the content of the antioxidant may be from 0.1 to 1.0 part by mass with respect to 100 parts by mass of the (meth)acrylic compound.
  • the known organic pigments and inorganic pigments can be used as the colorant.
  • the content of the pigment may be 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the (meth)acrylic compound.
  • the sealing material preferably does not contain a shock absorber.
  • the shock absorber has, for example, a core-shell structure, and a shock absorber in which a part of an epoxy resin is impregnated and dispersed is used. When the sealing material contains the shock absorber, it may be difficult to obtain sufficient heat melting property. Examples of the shock absorber include Paraloid BTA 731 (The Dow Chemical Company) and the like.
  • the sealing material of the present embodiment described above has various advantages as compared with the polyvinyl chloride sol.
  • the polyvinyl chloride sol may not provide sufficient sealability to a site having a complicated shape, but the sealing material of the present embodiment has the shape stability and can be not only processed and/or molded (for example, shape (for example, a sheet shape) according to the application site by punching) into a shape according to the application site, but also maintains its own shape at room temperature, and can be melted when heated to follow the complicated shape, such that the sealing material of the present embodiment can improve the sealability of the site having the complicated shape.
  • shape for example, a sheet shape
  • the polyvinyl chloride sol needs to be shaped by brushing or the like after application to an adherend, and since the polyvinyl chloride sol is cured as it is when heated, the sealability cannot be secured depending on a skill level of a worker. Also, in the polyvinyl chloride sol, even the control of the thickness or the uniform appearance is obtained depending on a skill level of a worker. Since the sealing material of the present embodiment has a predetermined shape, the sealing material can be performed at a preset thickness, and easily has a uniform appearance regardless of a skill level of a worker. As described above, the sealing material of the present embodiment can be suitably used as a substitute for the polyvinyl chloride sol. By using such a sealing material in combination with the polyvinyl chloride sol, the sealing property to a site (for example, a screw portion in a joint provided with a screw, and the like) having a complicated shape can be improved.
  • a site for example, a screw portion in a joint provided with a screw, and the
  • composition for forming a sealing material for forming the sealing material above will be described.
  • the composition for forming a sealing material contains a (meth)acrylic compound, an epoxy compound, a photopolymerization initiator, and a thermal curing agent.
  • the (meth)acrylic compound contains tetrahydrofurfuryl (meth)acrylate.
  • the content of the tetrahydrofurfuryl (meth)acrylate is 70% by mass or greater with respect to the total mass of the (meth)acrylic compound.
  • the composition for forming a sealing material is cured by polymerizing the (meth)acrylic compound by light irradiation to form the sealing material of the embodiment described above.
  • the composition for forming a sealing material may further contain a photopolymerizable compound (a compound which can be polymerized with the (meth)acrylic compound) other than the (meth)acrylic compound.
  • a (meth)acrylic compound is a compound containing a (meth)acryloyl group, and contains at least tetrahydrofurfuryl (meth)acrylate.
  • the (meth)acrylic polymer described above is obtained by polymerizing the (meth)acrylic compound and other photopolymerizable compounds optionally contained.
  • the content of tetrahydrofurfuryl (meth)acrylate is preferably adjusted so that the proportion of the constituent unit represented by the Formula (1) in the (meth)acrylic polymer obtained after photocuring is in the above range.
  • the content of the tetrahydrofurfuryl (meth)acrylate is, for example, 70% by mass or greater and preferably 75% by mass or greater with respect to the total mass of the (meth)acrylic compound.
  • the content of the tetrahydrofurfuryl (meth)acrylate is, for example, 100% by mass or less, 95% by mass or less, or 90% by mass or less with respect to the total mass of the (meth)acrylic compound.
  • the (meth)acrylic compound may further contain the above-described (meth)acrylic compound which can be a constituent unit of the (meth)acrylic polymer.
  • the (meth)acrylic compound may further contain an alkyl (meth)acrylate containing an alkyl group having 8 or more carbon atoms.
  • the (meth)acrylic compound may further contain a (meth)acrylic compound containing a crosslinkable functional group.
  • the content of the (meth)acrylic compound containing the crosslinkable functional group may be, for example, 10% by mass or less or 7% by mass or less and 0.001% by mass or more or 3 mass% or greater with respect to the total mass of the (meth)acrylic compound.
  • the content of the (meth)acrylic compound in the composition for forming a sealing material is preferably adjusted so that the content of the (meth)acrylic polymer in the sealing material obtained after photocuring is in the above-described range.
  • the content of the (meth)acrylic compound may be, for example, 20% by mass or greater, 30% by mass or greater, or 35% by mass or greater, and 70% by mass or less, 60% by mass or less, or 50% by mass or less with respect to the total mass of the composition for forming a sealing material.
  • the photopolymerization initiator is, for example, a photoradical polymerization initiator.
  • a cleavage type or a hydrogen withdrawing type is effective.
  • the cleavage type photopolymerization initiator include benzoethyl ether, diethoxyacetophenone, 2,2-dimethoxy-l,2-diphenylethane-l-one (2,2- dimethoxy-2-phenylacetophenone), 2-hydroxy -2-methyl- 1 -phenylpropan- 1 -one, 1 - hydroxycyclohexyl phenyl ketone, 2-hydroxy-l- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)- benzyl] -phenyl ⁇ -2-methyl-propan- 1 -one, 2-methyl- 1 -[4-(methylthio)phenyl]-2- morpholinopropan- 1 -one, 2-benzyl-2-dimethylamino- 1
  • Examples of the hydrogen withdrawing type photopolymerization initiator include benzophenone, 2,4-diethylthioxanthone and the like.
  • the content of the photopolymerization initiator may be 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic compound, from the viewpoint that the composition for forming a sealing material can be sufficiently photocured.
  • the composition for forming a sealing material further includes a photopolymerizable compound (a compound which can be polymerized with a (meth)acrylic compound) other than the (meth)acrylic compound, the content of the photopolymerization initiator with respect to 100 parts by mass of the photopolymerizable compound may be in the above range.
  • the epoxy compound and the thermal curing agent As the epoxy compound and the thermal curing agent, the epoxy compound and the thermal curing agent contained in the sealing material described above are used.
  • the content of the epoxy compound is preferably adjusted so that the content of the epoxy compound in the sealing material obtained after photocuring is in the above- described range.
  • the preferable range of the content of the epoxy compound in the composition for forming a sealing material with respect to 100 parts by mass of the (meth)acrylic compound is the same as the preferable range of the content of the epoxy compound in the sealing material with respect to 100 parts by mass of the (meth)acrylic polymer.
  • the content of the thermal curing agent is preferably adjusted so that the content of the thermal curing agent in the sealing material obtained after photocuring is in the above- described range.
  • the range of the content of the thermal curing agent in the composition for forming a sealing material with respect to 100 parts by mass of the epoxy compound may be the same as the range exemplified as the content of the thermal curing agent in the sealing material with respect to 100 parts by mass of the epoxy compound.
  • composition for forming a sealing material may contain other components which can be included in the above-described sealing material.
  • the composition for forming a sealing material preferably contains a chain transfer agent from the viewpoint of controlling a molecular weight of the (meth)acrylic polymer.
  • a chain transfer agent examples include carbon tetrabromide, a mercapto compound and the like.
  • Examples of the mercapto compound include ethanethiol, butanethiol, dodecanethiol, mercaptoethanol (thioglycol), 3-mercaptopropanol, thioglycerin (mercaptoglycerin), thioglycolic acid (mercaptoacetic acid), 2-mercaptopropionic acid (thiolactic acid), 3-mercaptopropionic acid, a-mercaptoisobutyric acid, methyl mercaptopropionate, ethyl mercaptopropionate, and the like.
  • the content of the chain transfer agent may be 0.1 parts by mass or greater and 1.0 part by mass or less with respect to 100 parts by mass of the (meth)acrylic compound.
  • the composition for forming a sealing material further includes a photopolymerizable compound (a compound which can be polymerized with a (meth)acrylic compound) other than the (meth)acrylic compound, the content of the chain transfer agent with respect to 100 parts by mass of the photopolymerizable compound may be in the above range.
  • FIG. l is a schematic cross-sectional view showing an embodiment of a method for manufacturing an adhesive structure.
  • An adhesive structure 10 illustrated in FIG. 1 has a structure in which a first cured body 11 as a thermally cured product of a sealing material and a second cured body 12 containing polyvinyl chloride adheres onto an adherend 3.
  • the method for manufacturing an adhesive structure 10 includes a step (a) of preparing an adherend 3 (see (a) of FIG. 1), a step (b) of arranging a sealing material 1 and a polyvinyl chloride sol 2 containing polyvinyl chloride and a plasticizer on the adherend 3 in a state where the sealing material 1 and the polyvinyl chloride are in contact with each other (see (b) of FIG. 1), and a step (c) of obtaining an adhesive structure 10 by heating the sealing material 1 and the polyvinyl chloride sol 2 (see (c) of FIG. 1).
  • the adherend 3 illustrated in FIG. 1 includes a first member 4, a second member 5, and a screw 6 which penetrates and fixes the first member 4 and the second member 5.
  • the adherend 3 is, for example, a U-shaped groove called a roof ditch formed by a roof panel (first member 4) of a vehicle and a side panel (second member 5) of the vehicle.
  • the adherend 3 is configured by a plurality of members, but the adherend may be configured by one member.
  • Examples of the materials of the adherend 3 may include glass, metal (for example, iron, aluminum, titanium, and an alloy (for example, stainless steel) containing at least one thereof), plastic, wood, ceramics, and the like.
  • the adherend 3 is constituted by a plurality of members, the plurality of members may be formed of the same material, or may be formed of different materials.
  • the sealing material 1 and the polyvinyl chloride sol 2 are preferably arranged on the adherend 3 so that a portion where the screw 6 of the adherend 3 is provided is sealed by the sealing material 1.
  • the sealing material 1 and the polyvinyl chloride sol 2 may be arranged so that one of the sealing material 1 and the polyvinyl chloride sol 2 overlaps the other thereof, and may be arranged adjacent to each other without overlapping.
  • the polyvinyl chloride sol the known polyvinyl chloride sol mainly made of the polyvinyl chloride (for example, polyvinyl chloride particles) and the plasticizer can be used.
  • the sealing material 1 and the polyvinyl chloride sol 2 are cured to form the first cured body 11 and the second cured body 12, respectively.
  • the sealing material 1 is melted by heating, and can fill a gap between the portion where the screw 6 of the adherend is provided and a stepped portion.
  • a heating temperature and a heating time in the step (c) are preferably temperature and time at which the sealing material 1 can be melted and can flow before being cured, and the sealing material 1 and the polyvinyl chloride sol 2 can be sufficiently cured.
  • the heating temperature may be, for example, 60°C or higher or 100°C or higher, and may be 200°C or lower or 180°C or lower.
  • the heating may be performed in two or more steps where the heating temperature is changed.
  • the heating temperature may be 60°C to 100°C
  • the heating temperature may be 80°C to 200°C.
  • the heating time may be, for example, 5 minutes or longer or 10 minutes or longer, and 60 minutes or less or 30 minutes or less through one or more steps.
  • the heating time of each step when heating is performed in two or more steps may be set appropriately.
  • Components (i) to (vii) shown in the following Table 1 below were prepared. Subsequently, components (i), (ii), (iii), and (v) were mixed in blending amounts (unit: part by mass) shown in the following Tables 2 to 4, and were stirred at a temperature of 60°C or lower until a homogeneous mixture is obtained. After the resulting mixture (a) was cooled to room temperature, the mixture (a) after cooling was added with components (iv), (vi) and (vii) in the blending amounts (unit: part by mass) shown in the following Tables 2 to 4 and stirred at room temperature. As a result, the composition for forming a sealing material was obtained.
  • Two transparent PET films whose surfaces are coated were prepared, and the composition for forming a sealing material obtained was applied onto one of the PET films. Thereafter, the other PET film was disposed on a layer made of the composition for forming a sealing material. A gap (thickness of the layer made of the composition for forming a sealing material) between the two PET films was 0.5 mm. Subsequently, a sheet-like sealing material (sealing material sheet) was obtained by irradiating UV light from above the obtained laminate. In addition, an irradiation amount (total energy amount) of the UV light was 1 J/cm2.
  • FIG. 2 is a schematic cross-sectional view showing a test piece for measuring shear adhesion.
  • the test piece of FIG. 2 was produced in the following procedure, and the adhesive strength was evaluated. In this evaluation, it was determined that the adhesive strength is good when the shear adhesion is greater than 1.50 MPa.
  • the results are shown in Table 5.
  • one in which the cured product (cured product containing polyvinyl chloride) derived from the polyvinyl chloride sol is cohesively fractured is defined as fracture mode A
  • fracture mode B one in which peeling occurs at an interface between the cured product derived from the polyvinyl chloride sol and the thermally cured product of the sealing material.
  • fracture mode the adhesive strength at the interface between the cured product derived from the polyvinyl chloride sol and the thermally cured product of the sealing material is estimated to be better than the measured value.
  • An aluminum wire 23 (diameter of 1.6 mm) was disposed as a spacer on both sides (positions adjacent to both ends in a width direction) of the polyvinyl chloride sol layer 22.
  • the sealing material sheet produced was cut out in a rectangular shape having 25 mm long x 12 mm wide, and disposed on the other substrate 21b.
  • the laminate after heating was cooled to room temperature, and this was used as the test piece 20 for measuring shear adhesion.
  • the shear adhesion between the two substrates of the test piece 20 was measured using a Tensilon universal tester manufactured by Orientec Co., Ltd. The measurement was performed at room temperature, and a test speed was 50 mm/min.
  • the elongation of the thermally cured product of the sealing material was evaluated in the following procedure. In the present evaluation, it was determined that the extensibility was good when the rupture elongation was greater than 50%. The results are shown in Table 5.
  • the sealing material sheet produced was cut out in a rectangular shape having 30 cm long c 12 cm wide, and disposed on the PET film whose surface is treated with silicone.
  • both ends of the laminate cut out in (3) were covered with a tape having a width of 25 mm so that an exposed portion of 50 mm remains at a central part. This was used as a test piece for elongation evaluation.
  • the gripping tool was operated at a displacement speed of 50 mm/min, and an operation distance until the test piece is ruptured was measured.
  • the odor of the sealing material was evaluated according to the following procedure. (1) The sealing material sheet produced was cut out in a rectangular shape having 100 mm long x 25 mm wide, and was put into a glass bottle (capacity of 900 ml).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un matériau d'étanchéité capable de former un corps durci qui présente un bon pouvoir adhésif à un corps durci issu d'un sol de polychlorure de vinyle même lorsque le matériau d'étanchéité est chauffé et durci conjointement avec le sol de polychlorure de vinyle tout en étant en contact avec ce dernier. L'invention concerne donc un matériau d'étanchéité contenant un polymère (méth)acrylique, un composé époxy et un agent de durcissement thermique, dans lequel le polymère (méth)acrylique contient au moins 70 % en masse d'un motif constitutif représenté par la formule (1) ci-dessous par rapport à la masse totale du polymère (méth)acrylique. Dans la formule (1), R représente un atome d'hydrogène ou un groupe méthyle.
PCT/IB2019/061235 2018-12-26 2019-12-20 Composition pour la formation d'un matériau d'étanchéité, matériau d'étanchéité, article thermodurci à base du matériau d'étanchéité et procédé de fabrication d'une structure adhésive WO2020136538A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018242491A JP2020105253A (ja) 2018-12-26 2018-12-26 シール材形成用組成物、シール材、シール材の熱硬化物及び接着構造体の製造方法
JP2018-242491 2018-12-26

Publications (1)

Publication Number Publication Date
WO2020136538A1 true WO2020136538A1 (fr) 2020-07-02

Family

ID=69411480

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2019/061235 WO2020136538A1 (fr) 2018-12-26 2019-12-20 Composition pour la formation d'un matériau d'étanchéité, matériau d'étanchéité, article thermodurci à base du matériau d'étanchéité et procédé de fabrication d'une structure adhésive

Country Status (2)

Country Link
JP (1) JP2020105253A (fr)
WO (1) WO2020136538A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0690896A1 (fr) * 1993-03-24 1996-01-10 Minnesota Mining And Manufacturing Company Materiau stratifie a relief et procede d'utilisation dudit materiau
JPH08113766A (ja) * 1994-10-17 1996-05-07 Sekisui Chem Co Ltd 粘着テープもしくはシート
US5670006A (en) * 1992-01-22 1997-09-23 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials
EP0881066A2 (fr) * 1993-11-10 1998-12-02 Minnesota Mining And Manufacturing Company Matériaux pouvant être rendus coulants par fusion et procédé de protection de surface.
US5861211A (en) * 1995-02-16 1999-01-19 Minnesota Mining & Manufacturing Company Articles incorporating pressure-sensitive adhesives having improved adhesion to plasticized polyvinyl chloride
JPH11302619A (ja) * 1998-04-21 1999-11-02 Murata Mfg Co Ltd 接着剤、接着剤の製造方法、および封止型電子部品
JP2002080811A (ja) * 2000-06-22 2002-03-22 Sony Chem Corp Ｉｐｎ型接着剤、ｉｐｎ型接着シート及び接着方法
WO2005056675A1 (fr) * 2003-11-21 2005-06-23 Lord Corporation Agents d'encapsulation appliques a une plaquette a deux etages
US20130102698A1 (en) * 2010-06-08 2013-04-25 Henkel Corporation Dual cure adhesives

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670006A (en) * 1992-01-22 1997-09-23 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials
EP0690896A1 (fr) * 1993-03-24 1996-01-10 Minnesota Mining And Manufacturing Company Materiau stratifie a relief et procede d'utilisation dudit materiau
EP0881066A2 (fr) * 1993-11-10 1998-12-02 Minnesota Mining And Manufacturing Company Matériaux pouvant être rendus coulants par fusion et procédé de protection de surface.
JPH08113766A (ja) * 1994-10-17 1996-05-07 Sekisui Chem Co Ltd 粘着テープもしくはシート
US5861211A (en) * 1995-02-16 1999-01-19 Minnesota Mining & Manufacturing Company Articles incorporating pressure-sensitive adhesives having improved adhesion to plasticized polyvinyl chloride
JPH11302619A (ja) * 1998-04-21 1999-11-02 Murata Mfg Co Ltd 接着剤、接着剤の製造方法、および封止型電子部品
JP2002080811A (ja) * 2000-06-22 2002-03-22 Sony Chem Corp Ｉｐｎ型接着剤、ｉｐｎ型接着シート及び接着方法
WO2005056675A1 (fr) * 2003-11-21 2005-06-23 Lord Corporation Agents d'encapsulation appliques a une plaquette a deux etages
US20130102698A1 (en) * 2010-06-08 2013-04-25 Henkel Corporation Dual cure adhesives

Also Published As

Publication number Publication date
JP2020105253A (ja) 2020-07-09

Similar Documents

Publication Publication Date Title
KR102295538B1 (ko) 접착제 물품 및 관련 방법
JP6226070B2 (ja) ポリオレフィン系接着剤組成物
EP3012284B1 (fr) Composition pour film de matériau d'encapsulation, film de matériau d'encapsulation et dispositif électronique le comprenant
TW201728651A (zh) 含烷氧基矽烷基之陽離子聚合型聚丙烯酸酯及其用途
CN110643286B (zh) Uv固化组合物及包含该组合物的胶膜、胶带和粘结构件
KR100730680B1 (ko) 접착제/밀봉제 조성물 및 이를 사용한 접착된 구조체
WO2012029960A1 (fr) Composition de résine et adhésif
WO2018030086A1 (fr) Composition d'adhésif à base de polyoléfine
WO2021132523A1 (fr) Composition adhésive durcissable à l'humidité
JPH1017780A (ja) 樹脂組成物、硬化型接着剤及び硬化型粘接着剤
JP2018030989A (ja) 光硬化性組成物、硬化組成物含有製品、貼り合せ方法、及び製品の製造方法
WO2020136538A1 (fr) Composition pour la formation d'un matériau d'étanchéité, matériau d'étanchéité, article thermodurci à base du matériau d'étanchéité et procédé de fabrication d'une structure adhésive
JP4215119B2 (ja) アクリル系のホットメルト型粘着剤樹脂組成物及びそれを用いる粘着シート
JPH11254608A (ja) 樹脂積層物及びその製造方法
JP3524181B2 (ja) フィルム状接着剤
JPH10120995A (ja) 硬化型粘接着シート、部材の接合方法及び粘接着部材
CN110079218B (zh) 胶黏剂和相关方法
JPH10120993A (ja) 硬化型粘接着シート及び部材の接合方法
JPH10120994A (ja) 硬化型粘接着シート及び部材の接合方法
JP2019094449A (ja) 接着剤、接着剤物品及びヘムフランジ接着方法
WO2021181316A1 (fr) Composition de résine pour adhérence de membrane électrolytique, film de résine pour adhérence de membrane électrolytique, et procédé de production de film de résine pour adhérence de membrane électrolytique
JP6264518B1 (ja) ポリオレフィン系接着剤組成物
JP4026096B2 (ja) ドライラミネート用一液型水性接着剤
US10633512B2 (en) Sheet adhesive and adhesion process using the same
JP2018030963A (ja) 粘接着シート、およびそれを用いた補強方法。

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: 19845831

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: 19845831

Country of ref document: EP

Kind code of ref document: A1