WO2000039235A1 - Compositions de scellement et articles de scellement utilisant ces compositions - Google Patents

Compositions de scellement et articles de scellement utilisant ces compositions Download PDF

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Publication number
WO2000039235A1
WO2000039235A1 PCT/US1999/030325 US9930325W WO0039235A1 WO 2000039235 A1 WO2000039235 A1 WO 2000039235A1 US 9930325 W US9930325 W US 9930325W WO 0039235 A1 WO0039235 A1 WO 0039235A1
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WIPO (PCT)
Prior art keywords
sealant
layer
epoxy
sealant composition
containing material
Prior art date
Application number
PCT/US1999/030325
Other languages
English (en)
Inventor
Kotaro Shinozaki
Kazuyoshi Shiozaki
Original Assignee
Minnesota Mining And Manufacturing 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 Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to JP2000591136A priority Critical patent/JP4471500B2/ja
Priority to AU21989/00A priority patent/AU2198900A/en
Priority to KR1020017008211A priority patent/KR20010101322A/ko
Priority to EP99966458A priority patent/EP1157075A1/fr
Priority to CA002353882A priority patent/CA2353882A1/fr
Priority to US09/868,703 priority patent/US6489023B1/en
Publication of WO2000039235A1 publication Critical patent/WO2000039235A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2463/00—Presence of epoxy resin
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2477/00—Presence of polyamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/04—Non-macromolecular organic compounds
    • C09K2200/0429—Alcohols, phenols, ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0647—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0667—Polyamides, polyimides

Definitions

  • This invention relates to sealant compositions and sealant articles and, more particularly, to compositions for sealing discontinuities, for example of the type found in motor vehicles, and to articles used in sealing the discontinuities, as well as to methods of sealing the discontinuities.
  • roof ditch One purpose of the roof ditch is to collect and drain water away from the sides of the vehicle.
  • Hot melt sealants have been supplied as liquid or solid materials depending upon the requirements of the particular application. In the automotive industry, for instance, roof ditch joints have been sealed using a paste-like plastisol which is then painted, baked and cooled to room temperature. Hot melt sealants have also been used and are generally solid thermoplastic materials which quickly melt with heating and then form a firm bond upon cooling. In use, a bead of molten liquid sealant is applied on the joint or seam, much in the way caulking is applied. A worker then brushes or levels the material. Applying such a sealant properly takes skill and, because of human error, often results in a poorly sealed joint or seam. Such hot melt sealants are undesirable for visible applications due to their non-uniform appearance.
  • a typical hot melt sealant composition utilizes polyolefms that can be difficult to paint and which have poor adhesion to non-porous metallic surfaces, such as steel and aluminum.
  • the sealant Once the sealant has been applied, its exposed surface may be covered with a plastic or rubber article (for example, a molding, cap, etc.) having a flexible top surface, which article may be painted, for example to match or complement the color of the vehicle exterior.
  • a plastic or rubber article for example, a molding, cap, etc.
  • the exposed surface of the sealant may be covered with a metal article.
  • the article is typically attached to the sealant surface using a mechanical fastener or a pressure sensitive adhesive.
  • the motor vehicle may be exposed to very cold temperatures of -
  • a sealant composition and a sealant article capable of effectively sealing discontinuities while remaining flexible enough at lower temperatures to survive the stresses encountered while in use and, thereby, prevent the intrusion of dirt, moisture, and other undesirable substances through the seal.
  • a sealant composition comprising a curable epoxy-containing material; a thermoplastic polyamide component having a melting point lower than a curing temperature of the epoxy- containing material; and a curative for the epoxy-containing material; wherein elongation at -20°C becomes at least 2% as a result of curing of the epoxy-containing material.
  • the sealant composition according to the present invention comprises 10-60% by weight of the epoxy-containing material and 30-70% by weight of the thermoplastic polyamide component.
  • a sealant article comprising a formed sealant layer of a sealant composition of the present invention (hereinafter also referred to as a "first layer").
  • the sealant article according to the present invention is provided with an adhesive layer (hereinafter also referred to as a "second layer") on one surface of the sealant layer (first layer).
  • the second layer that is, the adhesive layer
  • the second layer preferably comprises a plurality of adhesive microspheres.
  • the surface of the second layer having an adhesive property is provided with a release layer on which a plurality of protrusions are formed, and the protrusions are at least in contact with the second layer.
  • a flexible layer (hereinafter also referred to as a "third layer”) is further provided on the sealant layer.
  • the third layer may be disposed at any position, for example, it may be disposed in the sealant layer. Alternatively, it may be attached to the other surface of the sealant layer (i.e. the surface opposite the second layer).
  • Fig. 1 is a cross-sectional view showing one preferred embodiment of a sealant article according to the present invention.
  • Fig. 2 is a cross-sectional view showing another preferred embodiment of a sealant article according to the present invention.
  • Fig. 3 is a perspective view showing a release layer used in the sealant article shown in Fig. 2.
  • Fig. 4 is a cross-sectional view showing still another preferred embodiment of a sealant article according to the present invention.
  • Fig. 5 is a cross-sectional view showing a further preferred embodiment of a sealant article according to the present invention.
  • Fig. 6 is a cross-sectional view showing an additional embodiment of a sealant article according to the present invention situated in an automobile roof ditch prior to heating.
  • Fig. 7 is a cross-sectional view showing the sealant article and automobile roof ditch of Fig. 6 after heating.
  • a sealant article 10 using a sealant composition of the present invention is schematically shown.
  • This sealant article 10 comprises a sealant layer or first layer 1 of the sealant composition, and is in the shape of a rope, tape, strip or other such structure.
  • this first layer 1 is disposed at a predetermined position over discontinuities (for example, overlap joint or seam, butt joint or seam, recess or indentation, or a manufacturing defect)
  • the sealant composition constituting the layer 1 forms a protective seal portion to coat the discontinuities, thereby making it possible to prevent moisture, dirt, snow, and other undesirable substances from intruding into the discontinuities and cause corrosion.
  • the sealant compositions may be regarded as melt-flowable. That is, when placed over the joint and heated, the sealant composition first softens and conforms to the surface of the discontinuity, thereby pushing out trapped air. Further into the heating cycle, as the composition becomes hotter, it becomes tacky, and bonds to the surface.
  • the sealant composition is thermosetting such that it cures (i.e., covalently crosslinks) upon heating and resists flowing following cooling and re-heating.
  • each of the cured sealant compositions possess at least 10% elongation when tested at -20°C, however, this is not intended to be restrictive.
  • the cured sealant compositions, when tested at -20°C possess at least 2% elongation.
  • the paints used in motor vehicles, especially automotive paints will exhibit a degree of elongation when tested at -20°C that is substantially identical to or lower than that of the cured sealant composition.
  • the sealant composition can retain its integrity over the discontinuities, thereby avoiding the intrusion of dirt, moisture, snow and other undesirable substances therein.
  • the sealant compositions of the invention in the first layer 1 can comprise, and more preferably consist essentially of, an epoxy-containing material, a thermoplastic polyamide component, and a curative for the epoxy-containing material.
  • the epoxy- containing material contributes to the ultimate strength and heat resistance of the sealant composition, while the thermoplastic polyamide component provides conformability, pliability and flexibility, especially at low temperatures.
  • the curative permits the composition to cure.
  • the curative is thermally-activated such that the composition cures upon exposure to an appropriate heat source for an appropriate period of time.
  • Useful epoxy-containing materials are epoxy resins that have at least one oxirane ring polymerizable by a ring opening reaction.
  • Such materials include both monomeric and polymeric epoxides and can be aliphatic, cycloaliphatic, or aromatic. These materials generally have, on the average, at least two epoxy groups per molecule and preferably more than two epoxy groups per molecule. Such materials may be referred to as polyepoxides and include epoxy-containing materials in which the epoxy functionality is slightly less than 2.0, for example, 1.8. The "average" number of epoxy groups per molecule is defined as the number of epoxy groups in the epoxy-containing material divided by the total number of epoxy molecules present.
  • the polymeric epoxides include linear polymers having terminal epoxy groups (e.g., a diglycidyl ether of a polyoxyalkylene glycol), polymers having skeletal oxirane units (e.g., polybutadiene polyepoxide), and polymers having pendent epoxy groups (e.g., a glycidyl methacrylate polymer or copolymer).
  • the molecular weight of the epoxy-containing material may vary from 58 to about 100,000 or more. Mixtures of various epoxy-containing materials can also be used.
  • Useful epoxy-containing materials include those which contain cyclohexene oxide groups such as the epoxy cyclohexanecarboxylates, typified by 3,4- epoxycyclohexylmethyl-3 ,4-epoxycyclohexanecarboxylate, 3 ,4-epoxy-2- methylcyclohexylmethyl-3 ,4-epoxy-2-methylcyclohexanecarboxylate, and bis(3 ,4-epoxy- 6-methylcyclohexylmethyl) adipate.
  • cyclohexene oxide groups such as the epoxy cyclohexanecarboxylates, typified by 3,4- epoxycyclohexylmethyl-3 ,4-epoxycyclohexanecarboxylate, 3 ,4-epoxy-2- methylcyclohexylmethyl-3 ,4-epoxy-2-methylcyclohexanecarboxylate, and bis(3 ,4-epoxy- 6-
  • epoxy-containing materials which are particularly useful are glycidyl ether monomers such as glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of chlorohydrin such as epichlorohydrin (e.g., the diglycidyl ether of 2,2-bis-(2,3-epoxypropoxyphenol) propane).
  • chlorohydrin e.g., epichlorohydrin (e.g., the diglycidyl ether of 2,2-bis-(2,3-epoxypropoxyphenol) propane).
  • EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 8028 and EPIKOTE 154 from Yuka Shell Chemical Co.
  • thermoplastic polyamide component refers to a polymeric material containing amide moieties
  • thermoplastic polyamide material softens and flows upon heating so that it can be shaped, and then hardened upon cooling. Upon reheating, the material becomes soft again.
  • the thermoplastic polyamide component achieves the desired miscibility with the epoxy- containing material as well as other sealant composition ingredients that do not promote curing of the epoxy-containing material.
  • the thermoplastic polyamide component also contributes to the excellent low temperature properties of the sealant composition, particularly flexibility thereof.
  • the desired thermoplastic polyamide component is blended with the epoxy- containing material in the melt phase (i.e. melt-blending) and, preferably, form a homogeneous single phase mixture when the epoxy-containing material is not cured. Formation of the homogeneous single phase becomes clear when such a mixture (melt- mixture) becomes transparent.
  • a polyamide component is contained in about 100 parts by weight of the epoxy-containing material.
  • the polyamide component is contained in the amount of about 90 parts by weight or less, the cured sealant composition is liable to become brittle.
  • the cured sealant composition is not sufficiently cured and is liable to flow by re-heating.
  • the epoxy-containing material is cured, a composition of two separate phases or a lot of phases is formed as a result.
  • One phase is derived from the cured epoxy-containing material, and another phase is derived from the thermoplastic polyamide component.
  • both phases are formed from the homogeneous single phase comprising the epoxy-containing material and thermoplastic polyamide component, both phases are distributed homogeneously, even if the epoxy-containing material is cured as described above. Accordingly, characteristics due to the epoxy-containing material and thermoplastic polyamide component are imparted to the sealant composition.
  • Some degree of non-homogeneity of the blended thermoplastic polyamide component may be acceptable as long as the desired characteristics are imparted to the sealant composition.
  • the desirable thermoplastic polyamide component has a melting point that is not more than the curing temperature of the epoxy-containing material, in order to inhibit the epoxy-containing material from curing upon the heating and sealing of the sealant composition on a desired surface. Furthermore, the sealant composition is molten by heating, thereby making it easier to intrude into the discontinuities.
  • the thermoplastic polyamide component usually has a melting point of not more than about 180°C.
  • the sealant composition includes a curative for curing the epoxy-containing material.
  • the curative is thermally activated so as to effect curing or hardening of the epoxy-containing material under the influence of heat.
  • useful thermally activated curatives include amide group containing amine, and imidazole.
  • the curative having an amide group is typically dicyanediamide.
  • the curative having an imidazole is typically a triazine derivative.
  • Dicyaneamide curatives are commercially available from ACR Co. under the trade name of "EH3636”.
  • Triazine derivative curatives are commercially available form Shikoku Chemical Co. under the trade name of "2MZA”.
  • the sealant composition may optionally contain additives, for example, fillers such as calcium and silica powders, antioxidants commercially available from Ciba-Geigy Corp. under the trade name of "IRGANOX 1010", ultraviolet absorbers commercially available from Ciba-Geigy Corp. under the trade name of "TINUVINTM P", and surfactants commercially available from Minnesota Mining and Manufacturing Company under the trade name of "FC36".
  • fillers such as calcium and silica powders, antioxidants commercially available from Ciba-Geigy Corp. under the trade name of "IRGANOX 1010", ultraviolet absorbers commercially available from Ciba-Geigy Corp. under the trade name of "TINUVINTM P", and surfactants commercially available from Minnesota Mining and Manufacturing Company under the trade name of "FC36".
  • the sealant composition in the first layer (sealant layer) 1 is solid at room temperature.
  • a slight amount of tackiness at or slightly below room temperature is desirable for helping to initially position the sealant composition or an article containing the sealant over a joint or a seam, such as in a motor vehicle roof ditch 12.
  • the sealant composition is in the shape of a rope, tape, strip or similar structure, it becomes possible to attach rapidly and to eliminate the need of skill and labor for treating the sealant composition after application (for example, forming the applied sealant material with an acceptable appearance).
  • the sealant composition of the present invention can be substantially tack- free at room temperature. In the case of the substantially tack-free sealant composition, as shown in Fig.
  • an optional second layer 2 having an adhesive property is preferably provided on one surface of the first layer 1, containing the sealant composition.
  • the adhesive second layer 2 may be formed, as shown in Figs. 6 and 7, by a plurality of adhesive microspheres 3 disposed, preferably homogeneously, at intervals from each other.
  • the microspheres 3 can provide a sufficiently adhesive surface, by themselves, to form the adhesive second layer 2. Whether they form all or only part of the adhesive layer 2, the microspheres 3 can form at least one channel that provides a path for air bubbles, trapped at the discontinuities such as the overlap joint of a roof ditch 12, to escape out from under the sealant article 10.
  • Such a channel or channels can act to pump out air bubbles trapped at the discontinuities so that as much of the sealant composition as possible is not separated from the discontinuities by trapped air.
  • the sealant composition when the sealant composition is softened by heating, more of the sealant composition can contact and seal to the surface of the discontinuities, such as the joint formed at the bottom of the roof ditch shown in Fig. 7.
  • By trapping fewer air bubbles the formation of a recess or indentation on the exposed surface of the sealant composition is inhibited.
  • Such recesses or indentations can be formed on the exposed surface of the sealant composition as a result of trapped air bubbles expanding by heating and then contracting by cooling. Therefore, with the use of these microspheres 3, excellent appearance can be obtained.
  • Preferable adhesive microspheres 3 are made of an acrylic polymer material. In order to form a good channel, the adhesive microspheres preferably have a particle diameter of 30 to 500 ⁇ m. When the article 10 is heated so that the sealant composition softens and seals to the surface of the discontinuities (for example, the inside surface of the roof ditch 12), the microspheres 3 go into the sealant composition (see, for example, Fig. 7).
  • a release layer may also be provided on the surface of the second layer 2, thereby making it possible to attach rapidly.
  • Fig. 2 shows an embodiment wherein the protrusion surface of the release layer 4 having protrusions on one surface is contacted with the surface of the second layer 2 of a sealant article 10.
  • the exemplary pattern of the protrusions of the release layer 4 used herein will be understood easily from a perspective view of the release layer of Fig. 3.
  • a particularly desirable release layer 4, in the practice of the present invention, is provided with a plurality of protrusions at intervals on at least one surface thereof.
  • the protrusions on the surface of the release layer 4 are at least contacted with the second layer 2, it is possible to partially eliminate the adhesive surface of the second layer 2 in order to form a channel therein. Accordingly, if such a protrusion has a sharp tip portion, the channel can be made more efficiently.
  • the second layer 2 may also be provided with the above adhesive microspheres at intervals from each other or homogeneously. More preferably, a plurality of continuous sharp protrusions, which intersect each other or intersect perpendicularly as shown in Fig.
  • the sealant article 10 of the present invention is provided with a flexible third layer 5 on the surface of the first layer (sealant layer) 1 or the other surface. With such a construction, it is possible to prevent the air bubbles trapped in the sealant article from reaching the surface of the sealant article 10.
  • Figs. 4 and 5 show two preferable dispositions of the third layer 5.
  • the sealant article 10 of Fig. 5 comprises the third layer 5 between two first layers 1 and 11. Desirable article 10 has flexibility or conformability, and does not trap significant air bubbles at the interface between the first layer 1 and third layer 5.
  • a third layer 5 is, for example, made of polyethylene terephthalate (PET) or polyethylene (PE).
  • the flexible third layer 5 which is particularly preferred is commercially available, for example, from Nihon Filite KK under the trade mark "Expancel", and this layer has a porosity due to the included plastic bubbles (not shown).
  • the flexible third layer 5 can easily and uniformly disperse the air trapped in the discontinuities by its capillary action and others. In particular, such air dispersion can be accelerated during curing of the first layer 1 with heating. In the subsequent step of cooling the sealant composition to a room temperature, local shrinkage of the trapped air can be inhibited to thereby cause a tendency of uniform shrinkage of the sealant composition. As a result, the formation of local depressions can be easily diminished.
  • the sealant composition may be made of a thermoplastic polyurethane component or polyester component in place of the thermoplastic polyamide component previously mentioned in the specification of the present application.
  • the sealant composition contains 30-70% by weight of the thermoplastic polyurethane component or polyester component, it displays excellent characteristics in the evaluation of simulated seal sealing, temperature cycle aging and cold temperature elongation or that of lap joint sealing.
  • a thermoplastic polyurethane component is commercially available from
  • thermoplastic polyester component is commercially available from Huels America Inc. under the trade name of "DINAPOL S1402", and has a melting point of 80°C.
  • thermoplastic polyamide component manufactured by Henschel Co. (trade name: MACROMELT 6238) was prepared. This thermoplastic has a melting point of 135°C and elongation of 130% at -20°C.
  • An epoxy-containing material (trade name: EPIKOTE 1001) manufactured by Yuka Shell Co. was also prepared. Furthermore, dicyanamide (trade name: EH3636) manufactured by ACR Co. and a triazine derivative
  • thermoplastic polyamide component 50 parts by weight of the thermoplastic polyamide component, 40 parts by weight of the epoxy-containing material and 10 parts by weight of the curative were homogeneously mixed to obtain a sealant composition.
  • the sealant composition was charged in an extrusion-forming machine to form into a sheet (sealant article) having a thickness of 2.0 mm.
  • a test substrate was made in the following manner. First, a glass plate having a width of 25 mm, a length of 150 mm and a thickness of 0.8 mm was attached, in an overlapping condition, onto a strip made of a cold-rolled steel having a width of 25 mm, a length of 150 mm and a thickness of 0.8 mm by using a double-sided adhesive tape. The step from the steel down to the glass surface, formed by the overlapping strip and plate, simulated a seam in the bottom of a roof ditch in a motor vehicle.
  • the strip was placed over one edge of the steel strip and heated at 120°C for 10 minutes and then at 140°C for 40 minutes.
  • the test substrate was cooled to room temperature, the simulated seam (represented by the step from the steel strip down to the surface of the glass plate) was examined visually through the glass to determine the seal that had formed.
  • an acceptable seal was evidenced by the sealant composition having melted and flowed over the steel strip and filled the gap between the surface of the glass plate and the steel strip.
  • a 1 mm thick cold-rolled steel plate coated with an automotive grade electron deposition coating (E-coating, U-600 Black from Nippon Paint Co., Ltd.) was bent into a square U-shaped channel having a length of 25 mm, a width of 8 mm and a depth of 3 mm to simulate a motor vehicle roof ditch.
  • the strip was placed in the bottom of the simulated roof ditch channel and heated at 120°C for 10 minutes to cure the sealant composition.
  • a standard automotive paint primer of a high-solid type polyester crosslinked with melamine alkyd was sprayed onto the sealant composition and then cured at 140°C for 30 minutes. After cooling to room temperature, the painted sealant composition was exposed to a temperature cycle aging test.
  • one cycle consisted of 2 hours at -30°C, followed by 2 hours at room temperature (about 23°C) , and then 2 hours at 70°C. After 5 cycles, the condition of the sealant composition in the simulated roof ditch channel was examined visually. As a result, no difference in the visual appearance of the sealant composition was recognized before and after the test.
  • the evaluation of cold temperature elongation was performed in the following manner. A section of uncured sealant composition was heated at 140°C for 30 minutes and then cooled to room temperature. A test specimen of the cured sample was then die cut into a No. 1 dumbbell shape according to Japan Industrial Standard (JIS) K-6251. The test specimen was then marked to show two parallel lines 40 mm parts from each other. The test specimen was then clamped into the crosshead clamps (clamp distance is about 60-70 mm) of a Tensilon tester (manufactured by Orientec Corporation) fitted with a controlled temperature conditioning chamber. The clamped specimen was conditioned at -20°C for
  • A is the distance between the two parallel lines in mm when the specimen broke.
  • the elongation of the sealant composition of this example was 10%. Such elongation will make it possible to prevent defects forming in the sealant, for example cracking, breaking, delaminating or lifting up from the surface to which it has been applied, as a result of stresses caused by ordinary vehicle use at low temperature. Such sealant defects not only permit the intrusion of dirt, moisture, and other undesirable substances through the sealant but can also prevent the stable fixation of a subsequently applied article (e.g., a molding, cap, etc.).
  • a water soak test was performed in the following manner.
  • a sample was prepared by placing the above uncured sheet (25 mm x 40 mm) on a steel plate (65 mm x 150 mm) coated with an electron deposition coating, and heating at 120°C for 10 minutes. After cooling to room temperature, an automotive paint primer was sprayed over the uncured sheet. The sample was cured at 140°C for 20 minutes. After cooling at least for 10 minutes, an automotive base paint was sprayed over the primer-coated sealant composition. The sample was cured at 140°C for 20 minutes, and then cooled to room temperature.
  • the electron deposition-coated steel plates, the paint primer, and the base paint that was used were all as described in the temperature cycle aging test. The sample was soaked in water at 40°C for 250 hours and then visually examined before and after the test. As a result, no difference in the visual appearance was recognized.
  • lap joint sealing was performed in the following manner. Two 0.8 mm thick electron deposition-coated steel plates like those used in the temperature cycle aging test described above were welded together to form a lap joint. The above uncured sheet (20 mm x 100 mm) was applied over the lap joint, heated at 95°C for 10 minutes, and then at 140°C for 36 minutes. After cooling, the sheet was examined visually. As a result, the lap joint was sealed as indicated by the desired tendency of the sealant composition to flow into the lap joint and adhere to the steel plate.
  • a simulated motor vehicle rood ditch was prepared by bending two electron deposition- coated steel plate (like those described previously in the temperature cycle aging test) into a square-U-shaped channel and spot welding them together in an overlapping configuration.
  • This simulated roof ditch has a width of 20 mm, a depth of 10 mm and a length of 300 mm with the welded seam or joint at the bottom of the ditch.
  • the above uncured sheet was cut into a strip having a width of 19 mm and a length of 300 mm, and the strip was placed in the bottom of the simulated roof ditch.
  • the test specimen was heated at 100°C for 10 minutes, followed by at 140°C for 20 minutes, and then cooled to room temperature.
  • the simulated roof ditch was then visually examined, especially in the area of the indentations.
  • the surface of the sealant composition formed recesses after the test. Accordingly, regarding the depression region, the sealant composition does not satisfy the desirable tendency and does not sufficiently fill the indentations.
  • Example 1 The procedure described in Example 1 was repeated, except that the above surface appearance test was performed on a sheet, as described above, having one surface homogeneously coated with adhesive microspheres having a particle diameter of 35 ⁇ m manufactured by Minnesota Mining and Manufacturing Company in a coating weight of 7 g/m2> in place of the uncured sheet used in the above tests.
  • the sealant composition formed the surface with recesses after the test. Accordingly, regarding the depression region, the sealant composition can satisfy the desirable tendency and sufficiently fills the indentations.
  • Example 2 The procedure described in Example 2 was repeated, except that the above surface appearance test of Example 2 was performed on the sheet whose other side is provided with a film (MELLINEX #316) of a 125 ⁇ m thick polyethylene terephthalate (PET) film manufactured by ICI-Du Pont Co., in place of the uncured sheet with adhesive microspheres used in the above tests.
  • the sealant composition formed the surface with recesses after the test. Accordingly, regarding the depression region, the sealant composition can satisfy the desirable tendency and sufficiently fills the indentations.
  • thermoplastic polyamide component manufactured by Henschel Co. (trade name: MICROMELT 6238) in place of a thermoplastic polyamide component manufactured by Henschel Co. (trade name: MICROMELT 6217)
  • a sealant composition was made and a sheet thereof was formed.
  • This thermoplastic polyamide component has a softening point of 112-122°C and elongation of 8% at -20°C.
  • tests for evaluation of the simulated seam sealing, temperature cycle aging, cold temperature elongation and 250 hours water soak were performed.
  • the elongation of the sealant composition of this comparative example was not more than 1% in the evaluation of the cold temperature elongation. It was also found that the temperature cycle aging caused the comparative sealant composition to crack, break, delaminate or lift up from the surface to which it has been applied as result of stress caused by ordinary vehicle use. Accordingly, when using such a sealant composition, this not only permits the intrusion of dirt, moisture, and other undesirable substances, but unstably fixes the article (e.g., a molding, cap, etc.) to be subsequently applied.
  • the article e.g., a molding, cap, etc.
  • the sealant composition and sealant article of the present invention can maintain excellent characteristics, e.g. flexibility, under severe cold conditions and, therefore, they can prevent sealant defects such as, for example, cracking, breaking, delaminating, and lifting up from the surface.
  • sealant defects such as, for example, cracking, breaking, delaminating, and lifting up from the surface.
  • the avoidance of such sealant defects prevents the intrusion of dirt, moisture, and other undesirable substances through the sealant and into the discontinuities being sealed, and also enables an article (e.g., a molding, cap, etc.) to be fixed in a stable manner onto the applied sealant.

Abstract

L'invention concerne une composition de scellement qui comprend une substance durcissable contenant de l'époxy, un composant de polyamide thermoplastique possédant un point de fusion inférieur à la température de durcissement de la substance contenant de l'époxy et un agent de durcissement pour la substance contenant de l'époxy. Après le durcissement de la substance contenant de l'époxy, la composition de scellement manifeste une élongation d'au moins 2 à20 °C. La composition de scellement permet de sceller efficacement les discontinuités de scellement tout en gardant suffisamment de souplesse pour absorber la contrainte appliquée et empêcher ainsi la formation dans l'agent de scellement de défauts susceptibles de permettre la pénétration de la boue, de l'humidité et d'autres substances indésirables.
PCT/US1999/030325 1998-12-28 1999-12-20 Compositions de scellement et articles de scellement utilisant ces compositions WO2000039235A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2000591136A JP4471500B2 (ja) 1998-12-28 1999-12-20 シーラント物品及びその組み合わせ
AU21989/00A AU2198900A (en) 1998-12-28 1999-12-20 Sealant compositions and sealant articles using the same
KR1020017008211A KR20010101322A (ko) 1998-12-28 1999-12-20 실란트 조성물 및 이를 사용한 실란트 물품
EP99966458A EP1157075A1 (fr) 1998-12-28 1999-12-20 Compositions de scellement et articles de scellement utilisant ces compositions
CA002353882A CA2353882A1 (fr) 1998-12-28 1999-12-20 Compositions de scellement et articles de scellement utilisant ces compositions
US09/868,703 US6489023B1 (en) 1998-12-28 1999-12-20 Sealant compositions and sealant articles using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10373892A JP2000192013A (ja) 1998-12-28 1998-12-28 シ―ラント組成物及びそれを用いたシ―ラント物品
JP10373892 1998-12-28

Publications (1)

Publication Number Publication Date
WO2000039235A1 true WO2000039235A1 (fr) 2000-07-06

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PCT/US1999/030325 WO2000039235A1 (fr) 1998-12-28 1999-12-20 Compositions de scellement et articles de scellement utilisant ces compositions

Country Status (7)

Country Link
EP (1) EP1157075A1 (fr)
JP (2) JP2000192013A (fr)
KR (1) KR20010101322A (fr)
CN (1) CN1198896C (fr)
AU (1) AU2198900A (fr)
CA (1) CA2353882A1 (fr)
WO (1) WO2000039235A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003072677A1 (fr) * 2002-02-27 2003-09-04 3M Innovative Properties Company Procede de scellement
WO2008104439A1 (fr) * 2007-02-28 2008-09-04 Tesa Se Élément plat collant sous l'effet de la chaleur
EP2183150B1 (fr) 2007-07-27 2016-11-23 Sika Technology AG Elément de renforcement destiné à renforcer des cavités de composants structurels

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2653486T3 (pl) * 2012-04-20 2015-04-30 3M Innovative Properties Co Kompozycja epoksydowa o niskiej gęstości i niskim wychwycie wody
DE102018102238B4 (de) * 2018-02-01 2022-06-23 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Verfahren zum Verkleben und Abdichten von Naht- und Fügestellen und Anwendung eines Verfahrens

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US4560579A (en) * 1981-11-02 1985-12-24 W. R. Grace & Co. Process for coating of substrates with heat curable coating
US4707388A (en) * 1981-09-14 1987-11-17 Raychem Limited Heat-recoverable article
US5034251A (en) * 1984-02-14 1991-07-23 Raychem Limited Adhesive composition
US5086088A (en) * 1989-03-09 1992-02-04 Minnesota Mining And Manufacturing Company Epoxy-acrylate blend pressure-sensitive thermosetting adhesives
US5296557A (en) * 1992-07-02 1994-03-22 Union Camp Corporation Two-component curable hot melt compositions
US5296556A (en) * 1990-10-30 1994-03-22 Union Camp Corporation Three-component curable resin compositions
US5612448A (en) * 1993-09-28 1997-03-18 Union Camp Corporation Curable adhesive compositions containing polyamide resins
EP0798354A1 (fr) * 1996-03-29 1997-10-01 Minnesota Mining And Manufacturing Company Adhésif thermodurcissable avec revêtabilité améliorée

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US4707388A (en) * 1981-09-14 1987-11-17 Raychem Limited Heat-recoverable article
US4560579A (en) * 1981-11-02 1985-12-24 W. R. Grace & Co. Process for coating of substrates with heat curable coating
US4517340A (en) * 1982-08-25 1985-05-14 Raychem Corporation Adhesive composition
US5034251A (en) * 1984-02-14 1991-07-23 Raychem Limited Adhesive composition
US5086088A (en) * 1989-03-09 1992-02-04 Minnesota Mining And Manufacturing Company Epoxy-acrylate blend pressure-sensitive thermosetting adhesives
US5296556A (en) * 1990-10-30 1994-03-22 Union Camp Corporation Three-component curable resin compositions
US5296557A (en) * 1992-07-02 1994-03-22 Union Camp Corporation Two-component curable hot melt compositions
US5612448A (en) * 1993-09-28 1997-03-18 Union Camp Corporation Curable adhesive compositions containing polyamide resins
EP0798354A1 (fr) * 1996-03-29 1997-10-01 Minnesota Mining And Manufacturing Company Adhésif thermodurcissable avec revêtabilité améliorée

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003072677A1 (fr) * 2002-02-27 2003-09-04 3M Innovative Properties Company Procede de scellement
WO2008104439A1 (fr) * 2007-02-28 2008-09-04 Tesa Se Élément plat collant sous l'effet de la chaleur
EP2183150B1 (fr) 2007-07-27 2016-11-23 Sika Technology AG Elément de renforcement destiné à renforcer des cavités de composants structurels

Also Published As

Publication number Publication date
CA2353882A1 (fr) 2000-07-06
JP4471500B2 (ja) 2010-06-02
EP1157075A1 (fr) 2001-11-28
CN1332778A (zh) 2002-01-23
KR20010101322A (ko) 2001-11-14
JP2000192013A (ja) 2000-07-11
JP2002533557A (ja) 2002-10-08
AU2198900A (en) 2000-07-31
CN1198896C (zh) 2005-04-27

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