JP2004360756A - Sealant for flange part - Google Patents

Sealant for flange part Download PDF

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Publication number
JP2004360756A
JP2004360756A JP2003158086A JP2003158086A JP2004360756A JP 2004360756 A JP2004360756 A JP 2004360756A JP 2003158086 A JP2003158086 A JP 2003158086A JP 2003158086 A JP2003158086 A JP 2003158086A JP 2004360756 A JP2004360756 A JP 2004360756A
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JP
Japan
Prior art keywords
layer
sealing
flange
resin
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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JP2003158086A
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Japanese (ja)
Inventor
Yasuhiro Mino
泰弘 蓑
Original Assignee
Three M Innovative Properties Co
スリーエム イノベイティブ プロパティズ カンパニー
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Priority to JP2003158086A priority Critical patent/JP2004360756A/en
Publication of JP2004360756A publication Critical patent/JP2004360756A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/06Sealing strips
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00Unspecified macromolecular compounds
    • B32B2398/10Thermosetting resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2581/00Seals; Sealing equipment; Gaskets

Abstract

An object of the present invention is to provide a flange sealing material capable of satisfactorily and easily sealing a flange portion of a vehicle or the like.
A flange portion sealing material for sealing a flange portion of a metal panel of a vehicle, comprising at least two layers, an inner layer and an outer layer, formed into a predetermined shape so as to fit and wrap the flange portion. Wherein said inner layer comprises a thermosetting resin that is heat-melt-flowable and has a curing temperature of 80 ° C to 200 ° C, and said outer layer does not show a significant morphological change due to flow at a temperature of 80 ° C to 200 ° C, The sealing material for a flange portion, wherein the inner layer contains foam beads.
[Selection] Figure 2

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flange sealing material for sealing a metal panel overlapping flange portion of a vehicle.
[0002]
[Prior art]
A metal panel joint formed by stacking metal panels (steel plates) of a vehicle, that is, a flange portion, is sealed to improve the appearance and prevent rust due to moisture or the like that can enter the flange portion. Sealed by material. Conventionally, sealing at the flange portion is generally performed by applying a paste-like sealer and then heating and solidifying it. In this case, as shown in FIG. 1, in order to prevent the sealer 2 from dripping from the flange portion 1, one side of the metal panel 3 is elongated to form a glue margin portion 4, and the glue margin portion 4 is attached to the glue margin portion 4. 2 is applied. However, in such a method, since a glue margin must be formed, an extra metal panel is required, which hinders a reduction in the weight of the vehicle. Further, the panel forming the glue margin must be designed to be arranged on the lower side, and in order to perform sufficient sealing, the glue margin is widened to secure a sufficient area for attaching the sealing material. It is necessary to design like this. Paste sealers that have been used in the past require a great deal of skill in handling them to keep the amount and width of application constant and to make the appearance uniform after application, and the application takes a considerable amount of time. In addition, the glue margin is less likely to be horizontal, and is often an inclined portion or a vertical portion. Therefore, in order to prevent dripping of the paste, it is necessary to adjust the viscosity of the paste to be high enough to maintain its own weight. Further, many of such paste-like sealing materials are mainly composed of a sol of vinyl chloride, and have recently become one of environmental problems.
[0003]
Techniques for improving the above-mentioned problem of the paste sealing material have also been developed. For example, Patent Document 1 discloses a sealing material in which a pressure-sensitive adhesive layer is provided on at least one surface of a molded product of a material containing a thermoplastic resin. However, since this molded product is adhered by the pressure-sensitive adhesive layer, it is necessary to take care that air bubbles are not caught at the time of application, and it is difficult to reapply once attached. Further, since a release liner for protecting the pressure-sensitive adhesive layer is also required, the release liner becomes a waste at the time of construction.
[0004]
Patent Literature 2 discloses a sealing method in which metal panels are spot-welded to each other via a foamed sealer, and a paste-like sealer is applied to the tips of both panels. However, in this method, it is necessary to bond the foamed spot sealer before joining the panels, apply the spot weld, and then apply the sealer to the end portion, and thus the process is time-consuming.
[0005]
Patent Literature 3 discloses a seal material in which a material mainly composed of a synthetic resin material is molded into a predetermined shape, and the molded product is attached to a joint and welded. However, since this sealing material is a thermoplastic material, it softens and flows each time heat is applied, so that it melt-flows in a heating cycle in a coating process and generates cracks and wrinkles in the coating film.
[0006]
[Patent Document 1]
JP-A-3-35076 (pages 1-2)
[Patent Document 2]
JP-A-4-192280 (pages 1-2)
[Patent Document 3]
JP-A-64-16479 (pages 1 to 3)
[0007]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION It is an object of the present invention to provide a flange sealing material capable of sealing a flange portion of a vehicle satisfactorily and easily.
[0008]
[Means for Solving the Problems]
According to the present invention, there is provided a flange sealing material for sealing a flange portion of a metal panel of a vehicle, comprising at least two layers of an interior and an outer layer, which are formed into a predetermined shape so as to be fitted and wrapped with the flange. Wherein the inner layer comprises a thermosetting resin that is heat-melt-flowable and has a curing temperature of 80 ° C to 200 ° C, and the outer layer shows a significant morphological change due to flow at a temperature of 80 ° C to 200 ° C. And the inner layer further includes foam beads.
[0009]
In such a sealing material, when heated after being attached to the flange portion, the thermosetting resin in the inner layer melts and flows, but the outer layer retains the molten resin without changing its form, so that the liquid is dripped. Good sealing can be performed without causing poor sealing performance and appearance. Furthermore, the foamed beads contained in the inner layer are foamed by heating, so that the space surrounded by the outer layer can be filled with the resin in the inner layer without forming a gap, and completely sealed.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described with reference to the drawings. FIG. 2 is a cross-sectional view of one embodiment of the flange sealing material of the present invention. The flange portion sealing material 10 has a U-shaped cross-sectional shape, is a molded product fitted to the flange portion and molded so as to wrap the flange portion, and includes at least two layers including an inner layer 12 and an outer layer 11. It is configured.
[0011]
The inner layer 12 includes a thermosetting resin that can be melted and flowed and has a curing temperature of 80C to 200C. The inner layer is made of a thermosetting composition capable of being melted and flowable containing such a thermosetting resin. The heat-meltable-flowable thermosetting composition usually contains an epoxy-containing material and a curing agent for the epoxy-containing material, and is capable of flowing when heated. The epoxy-containing material comprises an epoxidized thermoplastic, and preferably comprises a low hygroscopic epoxidized thermoplastic. This is because, if a resin having a low hygroscopicity is used, the sealing material does not expand due to foaming of water during heat curing and does not hinder the sealing of the flange portion.
[0012]
The epoxy-containing material in the thermosetting composition constituting the inner layer 12 preferably contains a low-hygroscopic epoxidized thermoplastic resin as described above. In addition, this "low hygroscopicity" means that the epoxidized thermoplastic resin has a saturated water absorption of 0.2 wt% or less at 35 ° C. and a relative humidity of 80% RH. Such epoxidized thermoplastic resins typically have a solubility parameter (SP) of about 9 or less. In the present specification, this solubility parameter is defined by Small's equation (described in the literature PA Small, J. Appl. Chem., 3, 71 (1953)). Epoxidized thermoplastic resin is a thermoplastic resin having an epoxy group. Generally, a thermoplastic resin can impart a certain shape to a thermosetting composition. Further, the epoxidized thermoplastic resin contributes to the thermosetting reaction due to the presence of the epoxy group. As a result, when the thermosetting composition is cured, the cured product has heat resistance and durability.
[0013]
Usually, such an epoxidized thermoplastic resin has a molecular weight of 1,000 to 10,000 in consideration of flowability during molding and hot melting. The epoxidized thermoplastic resin generally has an epoxy equivalent of 200 to 15,000 in consideration of heat resistance, durability, and water absorption.
[0014]
A typical example of the epoxidized thermoplastic resin described above is an epoxidized ethylene-based thermoplastic resin. This resin exhibits low hygroscopicity due to the presence of the ethylene moiety. As the epoxidized ethylene-based thermoplastic resin, an ethylene-glycidyl (meth) acrylate copolymer is preferable. This ethylene-glycidyl (meth) acrylate copolymer is obtained by converting polyethylene into an epoxy as disclosed in JP-A-9-137028 and JP-A-10-316955 as one component of an adhesive and a hot melt composition. And usually obtained by copolymerization of ethylene and glycidyl methacrylate. As a result, the ethylene-glycidyl (meth) acrylate copolymer is composed of an ethylene portion and a glycidyl (meth) acrylate portion. In such a case, the ethylene portion contributes to the low hygroscopicity of the thermosetting composition, and the glycidyl (meth) acrylate portion serves as an outer layer of a cation electrodeposition-coated automobile steel plate (metal panel) and a flange sealing material. Contributes to the adhesion.
[0015]
It is desirable that the ethylene-glycidyl (meth) acrylate copolymer is configured so that the monomer weight ratio of ethylene to glycidyl (meth) acrylate is in the range of 50:50 to 99: 1. Ethylene-glycidyl (meth) acrylate copolymers containing ethylene exceeding the upper limit tend not to impart desired mechanical strength and durability to the cured product. Conversely, ethylene-glycidyl (meth) acrylate copolymers containing ethylene below the lower limit tend to be unable to obtain the desired low hygroscopicity.
[0016]
In addition, a typical ethylene-glycidyl (meth) acrylate copolymer is easily melted even at a relatively low temperature of about 80 ° C. or less, and has a high fluidity when a thermosetting composition containing the same is heated and fluidized for sealing. Is obtained, resulting in high uniformity and smoothness. In addition, since it is possible to knead at a relatively low temperature in the heating and mixing process at the time of producing the inner layer material, there is little possibility that a reaction between the thermosetting component and the curing agent occurs during kneading, and furthermore, a curing agent having higher reactivity is used. You can also choose.
[0017]
As long as the effects of the present invention are not impaired, a ternary ethylene-glycidyl (meth) acrylate copolymer obtained by copolymerizing or graft-polymerizing a third component other than ethylene and glycidyl (meth) acrylate is used as the epoxidized thermoplastic resin. May be used. Examples of such a terpolymer include copolymers of alkyl (meth) acrylate and vinyl acetate, and examples of the graft polymer include polystyrene, polyalkyl (meth) acrylate, and acrylonitrile-styrene copolymer. It is obtained by grafting coalescence.
[0018]
Another typical example of an epoxidized thermoplastic resin is an epoxidized styrenic thermoplastic resin, which exhibits low hygroscopicity due to the presence of a conjugated diene. The epoxidized styrene-based thermoplastic resin is, for example, a block copolymer having a hard segment made of polystyrene and a soft segment made of epoxidized polybutadiene and imparting rubber elasticity to the elastomer. Alternatively, epoxidized polyisoprene can be used instead of, or in conjunction with, epoxidized polybutadiene.
[0019]
Usually, the glass transition temperature (Tg) of an epoxidized styrene-based thermoplastic resin is very low, such as −70 to −50 ° C., and at this time, the cured product of the thermosetting composition has a durability at a low temperature of about −30 ° C. (Particularly vibration durability) can be enhanced.
[0020]
Examples of such an epoxidized styrene-based thermoplastic resin are a styrene-epoxidized butadiene-styrene copolymer and a styrene-epoxidized isoprene-styrene copolymer. In either case, the epoxidation is performed by epoxidizing the unsaturated bonds of the conjugated diene.
[0021]
The epoxidized thermoplastic resin as described above is preferably contained in the thermosetting composition in an amount of 10 to 90% by weight. If the amount is less than about 10 wt%, the heat resistance is reduced. If the amount is more than about 90 wt%, the amount in which a filler described later can be added is relatively reduced, and a low coefficient of linear expansion may not be obtained.
[0022]
As the epoxy-containing material, in addition to the epoxidized thermoplastic resin described above, for example, a liquid or solid epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin, and a glycidylamine type epoxy resin may be used. It may be included, whereby the heat resistance and durability of the cured product of the thermosetting composition and the adhesion to the electrodeposition coated steel sheet can be further enhanced. Desirable epoxy resins, for example, hydrogenated bisphenol A type epoxy resin, alicyclic epoxy resin, linear aliphatic epoxy resin such as butadiene skeleton epoxy resin, or glycidyl ester type epoxy resin such as dimer acid modified epoxy resin, Epoxy resin with relatively low polarity. This is because the epoxidized thermoplastic resin has excellent compatibility with low water absorption components, for example, an ethylene portion and a butadiene portion. Further, the absorption of moisture into the cured product is prevented, which is advantageous during heating such as a coating process for automobiles. The amount of the epoxy resin is usually from 0 to 500 parts by mass, preferably from 5 to 400 parts by mass based on 100 parts by mass of the component (1), that is, 100 parts by mass of the low-hygroscopic epoxidized thermoplastic resin.
[0023]
If desired, the epoxy-containing material may further include a compatibilizer. More specifically, the compatibilizer is usually contained in an amount of 0 to 300 parts by mass, preferably 1 to 100 parts by mass, based on 100 parts by mass of the epoxidized thermoplastic resin. Compatibility with the resin can be increased. In the present invention, the compatibilizer is not particularly limited as long as the above-mentioned compatibility can be achieved, but preferably includes a polyester resin or an ethylene-vinyl acetate copolymer (EVA). In particular, when the polyester resin is blended with the epoxidized thermoplastic resin in a predetermined ratio, not only does the separation of the epoxidized thermoplastic resin and the epoxy resin be prevented, but also the curing temperature of the thermosetting composition ( This is because the fluidity at 80 to 200 ° C.) can also be significantly improved.
[0024]
The curing agent can cure the epoxy group contained in the epoxy-containing material to provide a crosslinked structure in the thermosetting composition, and obtain a cured product. According to the present invention, the curing agent is not limited as long as a cured product can be obtained. Accordingly, the curing agent may be, for example, an amine compound such as dicyandiamide, an acrylic compound having a carboxyl group (including an acid anhydride) in the molecule, rosin, an imidazole derivative, BF 3 Complexes, organic acid hydrazides, diaminomaleonitrile or melamines or mixtures thereof may be included. Further, the polarity of the curing agent is not limited. However, the curing of the glycidyl group of the ethylene-glycidyl (meth) acrylate copolymer involves the inclusion of a carboxyl group in the molecule, as disclosed in JP-A-9-137028 and JP-A-10-316955. It is required to use a curing agent containing an acrylic compound or rosin. Compared to a highly polar curing agent that is not compatible with the ethylene-glycidyl (meth) acrylate copolymer and cannot react substantially, such a curing agent is easily compatible with the ethylene-glycidyl (meth) acrylate copolymer. This is because the glycidyl group of the ethylene-glycidyl (meth) acrylate copolymer is cured.
[0025]
The curing agent may be used in combination with a curing accelerator. In particular, for the reaction between the curing agent having a carboxyl group and the epoxy, a curing accelerator containing a phenol-containing substance, an imidazole derivative or a tertiary amine can be advantageously used.
[0026]
The thermosetting composition preferably further comprises a filler containing, for example, calcium carbonate or silica or a mixture thereof. The filler can reduce the coefficient of linear expansion of the cured product. As a result, such a cured product has a reduced linear expansion coefficient, especially at a low temperature change, a reduced amount of shrinkage at a low temperature, and a coating film formed by applying an automotive paint on a sealing material. To stress. Thus, the formed coating film is hard to crack even at a low temperature.
[0027]
When the filler is added as described above, the thermosetting composition generally has an undesirable fluidity when heated and melted. Therefore, the thermosetting composition of the present invention can also contain a plasticizer. By including a plasticizer, the thermosetting composition maintains desired fluidity. This is because the plasticizer generally has a low viscosity and can contribute to improving the fluidity of the composition.
[0028]
Plasticizers that may be included in the thermosetting composition include, for example, phthalates such as di-2-ethylhexyl phthalate or diisononyl phthalate, adipic esters, epoxidized fatty acid esters, epoxidized soybean oil, Includes plasticizers containing epoxidized linseed oil, liquid terpene resin, liquid terpene phenol copolymer or liquid terpene styrene copolymer, azelaic esters, sebacic esters, epoxy hexaphthalic esters or mixtures thereof It is. Such a plasticizer can impart flexibility to a cured product of the thermosetting composition. Further, the cured product can lower the glass transition temperature and lower the elastic modulus even at a low temperature of −20 to −40 ° C. As a result, the cured product can greatly expand at such a low temperature, and dynamic durability such as vibration durability can be improved.
[0029]
The outer layer 11 is characterized in that it does not show a significant morphological change due to flow at a temperature of 80C to 200C. The material constituting the outer layer 11 is not particularly limited as long as it can maintain its shape in the above-mentioned temperature range. Such materials include polyamide resins, polyacetals, polybutylene terephthalates, modified engineering plastics such as modified polyphenylene oxide, polyimides, polyetherimides, special engineering plastics synthetic resins such as polyethersulfone, polystyrenes, polyurethanes, and polyolefins. A thermoplastic resin that does not show melt-flowability at the above temperature such as a thermoplastic elastomer, butadiene rubber, isoprene rubber, styrene butadiene rubber, vulcanized synthetic rubber represented by ethylene propylene rubber, and the like, and a metal material itself. A material that can maintain its shape at the above temperature, phenolic resin having suppressed fluidity when heated to the above temperature, melamine resin, epoxy resin, urethane resin, thermosetting resin such as unsaturated polyester resin and the like. Can be
[0030]
Also, polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer Even if the resin melts and flows at the above-mentioned temperature, the storage elastic modulus at the above-mentioned temperature is 5.0 × 10 by cross-linking the surface with an electron beam (Electron Beam). 5 When it is set to Pa or more, the shape can be maintained and it can be used as an outer layer. In this case, it is preferable to irradiate with an acceleration voltage of 200 KeV or more and a dose (Dose) of 10 Mrad or more.
[0031]
The material constituting the outer layer 11 has sufficient adhesiveness to an adjacent layer such as the inner layer 12 and is usually applied on the outer layer 11 with an automotive paint (for example, an organic solvent-based acrylic paint or an organic solvent-based paint). Alkyd paint). In addition, since the end of the flange portion may have a curved shape, it is preferable that the flange portion be made of a material having flexibility so as to follow such a curved shape. From such a viewpoint, the material forming the outer layer 11 is similar to the material forming the inner layer 12, but desirably has low fluidity during heating. Specifically, such a material preferably has a storage elastic modulus at 80 to 200 ° C. of 5.0 × 10 5. 5 Including a resin that is Pa or more. If the storage modulus is in this range, no significant fluidity is exhibited during heating. In order to have sufficient flexibility, the storage elastic modulus at room temperature is 1.0 × 10 6 ~ 1.0 × 10 8 Pa is preferred.
[0032]
When the thermosetting composition containing the thermosetting resin as described above is used as the outer layer 11, the thermosetting composition contains the same curing agent, curing accelerator and filler as the thermosetting composition constituting the inner layer 12. Good. Further, the outer layer 11 may be crosslinked by EB irradiation treatment to enhance the shape retention.
[0033]
The flange sealing material of the present invention is characterized in that the inner layer 12 contains foam beads (not shown). The foam beads are particulate material that expands when heated, and are preferably heat-expandable microcapsules in which a volatile liquid foaming agent is wrapped around a polymeric capsule outer shell that softens when heated.
[0034]
Examples of the volatile liquid include isobutane, isopentane, normal butane, normal pentane, neopentane, and hexane that are liquid at room temperature and vaporized by heating when the interior is melted, but hydrocarbons containing mainly isobutane and isopentane are preferred. Can be used for Other volatile liquids include certain freons such as trichlorofluoromethane, dichlorofluoromethane, dichlorofluoroethane, dichlorotrifluoroethane, trichlorotrifluoroethane, dichloropentafluoropropane, and alternative freons and petroleum ethers. Hydrocarbons, chlorinated hydrocarbons such as methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloroethylene are used, but are not limited thereto. The proportion of the volatile liquid foaming agent in the thermally expandable capsule is, for example, preferably 5 to 30% by weight.
[0035]
The outer shell of the polymer constituting the expanded beads is made of a thermoplastic material which softens when heated to 100 to 200 ° C., preferably 120 to 140 ° C. and expands due to the volatile expansion of the volatile liquid sealed therein. Constitute. The polymer constituting the outer shell needs to have a sufficiently large viscosity even at the heating temperature so as to maintain the capsule state without bursting even when thermally expanded. Polymers satisfying such conditions include vinylidene chloride, acrylonitrile, methacrylonitrile, and one or more copolymers of methyl methacrylate, for example, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylonitrile-methyl methacrylate copolymer. And acrylonitrile-methacrylonitrile copolymers, and copolymers of one or more of these with various monomers such as vinyl halides, styrene monomers, vinyl acetate, butadiene, vinylpyridine, and chloroprene can be used. This thermoplastic resin includes divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, It may be crosslinked or made crosslinkable with a crosslinking agent such as triacrylformal, triallyl isocyanate. Among these thermoplastic resins, a homopolymer of (meth) acrylonitrile having a high expansion start temperature and a high maximum expansion temperature or a copolymer having a high (meth) acrylonitrile content is particularly preferably used.
[0036]
Examples of the unexpanded expandable microcapsules having such a configuration include those commercially available from Nippon Philite Co., Ltd. under the trade name of EXPANCEL, and those manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. from Microsphere-F. Some are sold under the trade name. This uses the above vinylidene chloride-acrylonitrile copolymer, acrylonitrile-methacrylonitrile copolymer, etc. as the polymer for the capsule-shaped outer shell, and uses isobutane, isopentane, etc. as the volatile liquid contained therein. For example, Expancel product No. 642 (vinylidene chloride-acrylonitrile copolymer + isobutane) is about 90 ° C. or more, 551 (the same) is 100 ° C. or more, and 461 (the same) is about 110 ° C. or more, 091 and 092. (Acrylonitrile-methacrylonitrile copolymer + isopentane) expands at about 130 ° C. or more and expands up to about 4 times, and therefore expands about 60 times by volume. The particle diameter is about several μm to several tens μm in the case of unexpanded, so that for example about 15 μm becomes about 50 μm after expansion. The time required for the expansion is about 30 seconds to 1 minute, depending on the temperature. When quenched after expansion, the dimensions at the time of expansion are fixed. For example, when 1% by mass of unexpanded Expancel microcapsules is added to a thermoplastic resin constituting a substrate of a film packaging material, if the degree of foaming is adjusted to 10 to 50 times, the volume of the film after foaming becomes Increase by about 10% to 50%. Addition of 3% by mass results in about 30% to 50%.
[0037]
The amount of the foam beads is preferably 0.1 to 20 parts with respect to 100 parts by mass of the material constituting the inner layer. If the amount exceeds 20 parts, the melt flow property of the resin in the inner layer may be reduced, and if the amount is less than 0.1 part, a sufficient foaming effect cannot be obtained. Further, the foaming temperature of the foam beads, that is, the softening temperature of the outer shell is preferably lower than the melting temperature and the curing temperature of the resin in the inner layer. This is because the desired effect cannot be obtained unless the resin is foamed during melting and curing.
[0038]
When the flange portion is sealed with the flange portion sealing material, the resin in the inner layer melted as described above fills the space between the outer layer and the panel and is cured by curing. However, if the resin in the inner layer is not enough to fill the space between the outer layer and the panel, the molten resin will flow to the lower part of the space between the outer layer and the panel, creating a gap in the upper part of this space. I will. On the other hand, if foamed beads are mixed in the inner layer as in the present invention, the resin is melted by heating and the foamed beads are foamed, so that the molten resin expands in volume, and the outer layer and the panel do not leave a gap. Can be filled sufficiently. Furthermore, compared to a case where foam beads are not used, sealing can be achieved using a small amount of resin.
[0039]
In order to completely seal the flange portion, the cells in the resin filling between the outer layer and the panel need to be closed cells. When foaming is performed using foamed beads as in the present invention, the outer shell of the beads is not ruptured at the time of foaming, so that the cells obtained are all closed cells. Chemical blowing agents commonly used in the production of foams can be used in the present invention as long as closed cells can be obtained, but it is necessary to control the foaming conditions so that open cells are not formed.
[0040]
Another layer may be included between the inner layer 12 and the outer layer 11 of the flange sealing material of the present invention. Examples of such a layer include at least one barrier layer made of a nonwoven fabric, a resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or a metal. Such a barrier layer prevents air bubbles from appearing on the surface even if air bubbles enter during sealing.
[0041]
The flange sealing material of the present invention has a sufficient flow due to the shearing of a screw of a screw extruder such as an extruder (single-screw, twin-screw) in which the material constituting the outer layer is widely used for molding a plastic material. When the property is imparted, using such an extruder, the thermosetting composition (including foamed beads) constituting the inner layer and the material constituting the outer layer are sheared and melted, and the desired composition is obtained. It can be manufactured by coextrusion into a form. When the material of the outer layer does not have sufficient plasticity and fluidity even by such shearing of the screw extruder, a melt of the material constituting the inner layer is applied on the outer layer formed into a desired shape. Can be manufactured. In addition to the method for extruding a shaped material, it is also possible to extrude each layer into a sheet and then press it in a mold to form it into a desired shape.
[0042]
The flange portion sealing material of the present invention is attached to the flange portion, and heated to a temperature of 80 ° C to 200 ° C to flow the thermosetting resin that can be melted and flowable in the inner layer to foam the foam beads, Next, sealing is performed by curing the resin. At this time, since the outer layer does not show a large change in shape, dripping can be prevented when the resin of the inner layer is flowing. Furthermore, by foaming the foam beads in the fluid resin, the space surrounded by the outer layer can be filled with the resin without leaving a gap. The above sealing step can also be performed in a baking step (for example, a heating temperature of 80 to 200 ° C.) of an intermediate coating or a top coating, which is performed subsequently in an automobile coating line.
[0043]
【Example】
Example 1
As the inner layer, a composition having the following composition,
(I) an ethylene-glycidyl methacrylate copolymer containing 18 parts by mass of glycidyl methacrylate (60 parts by mass, CG5001 (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Ii) 6 parts by mass of a carboxyl group-containing rosin having an acid value of 240 mgKOH / g (curing agent, Arakawa Chemical's KE604 (trade name)),
(Iii) 1.5 parts by mass of an imidazole derivative (curing accelerator, 2MOAK (trade name) manufactured by Shikoku Chemicals),
(Iv) 3 parts by mass of calcium carbonate (filler, Shiroishi calcium whiten SB (trade name)),
And 2 parts by weight of Microsphere-F-82D (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) was added thereto, and as the outer layer, a composition having the following composition,
(I) an ethylene-glycidyl methacrylate copolymer containing 48 parts by mass of 12% by mass of glycidyl methacrylate (Bond First E (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Ii) an ethylene-glycidyl methacrylate copolymer containing 18 parts by mass of glycidyl methacrylate of 12 parts by mass (CG5001 (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Iii) 6 parts by mass of a carboxyl group-containing rosin having an acid value of 240 mgKOH / g (curing agent, Arakawa Chemical KE604 (trade name)),
(V) 1.5 parts by mass of an imidazole derivative (curing accelerator, 2MOAK (trade name) manufactured by Shikoku Chemicals),
(Iv) 3 parts by mass of calcium carbonate (filler, Shiroishi calcium whiten SB (trade name)),
These were kneaded with a twin-screw extruder (TSE) and co-extruded to obtain a laminate having a sectional shape as shown in FIG. The outer layer of this laminate was subjected to electron beam (EB) treatment (250 KeV, 30 Mrad) to crosslink the surface of the outer layer, thereby obtaining a flange sealing material of the present invention.
[0044]
Example 2
A flange portion sealing material was obtained in the same manner as in Example 1, except that the addition amount of Microsphere-F-82D was 4 parts by mass.
[0045]
Example 3
A flange portion sealing material was obtained in the same manner as in Example 1 except that the addition amount of Microsphere-F-82D was changed to 6 parts by mass.
[0046]
Example 4
A flange portion sealing material was obtained in the same manner as in Example 1, except that the addition amount of Microsphere-F-82D was changed to 8 parts by mass.
[0047]
Example 5
A flange portion sealing material was obtained in the same manner as in Example 1 except that the addition amount of Microsphere-F-82D was changed to 20 parts by mass.
[0048]
Comparative Example 1
In Example 1, a flange portion sealing material consisting of only the inner layer without forming the outer layer was obtained. That is, the composition of the following formulation,
(I) an ethylene-glycidyl methacrylate copolymer containing 18 parts by mass of glycidyl methacrylate (60 parts by mass, CG5001 (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Ii) 6 parts by mass of a carboxyl group-containing rosin having an acid value of 240 mgKOH / g (curing agent, Arakawa Chemical's KE604 (trade name)),
(Iii) 1.5 parts by mass of an imidazole derivative (curing accelerator, 2MOAK (trade name) manufactured by Shikoku Chemicals),
(Iv) 3 parts by mass of calcium carbonate (filler, Shiroishi calcium whiten SB (trade name)),
Was kneaded with a twin-screw extruder (TSE) and extruded in a different shape to obtain a single-layer sealing material as shown in FIG.
[0049]
Comparative Example 2
A paste-like PVC (polyvinyl chloride) sealer (Sandain 1361-5 (trade name) manufactured by Asahi Corporation) is used as a sample. In the evaluation test described below, the brush and the spatula are applied to a metal panel which is superimposed as shown in FIG. Please see).
[0050]
Comparative Example 3
100 parts by mass of an ethylene-vinyl acetate copolymer resin (H2031 (trade name) manufactured by Sumitomo Chemical Co., Ltd.) and 100 parts by mass of calcium carbonate (Whiteton SB (trade name) manufactured by Shiraishi Calcium Co., Ltd.) and a tackifier (Piccolite manufactured by Hercules) A135 (trade name)) 20 parts by mass and a polyester plasticizer (Polysizer W230-S (trade name) manufactured by Dai Nippon Ink Co., Ltd.) 15 parts by mass are heated and kneaded with a twin-screw extruder (TSE), and the extruder tip portion Then, a U-shaped base was fitted to the shape of the panel joint, extruded, cooled, and formed into a shape as shown in FIG.
[0051]
Comparative Example 4
A flange portion sealing material was obtained in the same manner as in Example 1 except that no foam beads were used. That is, as the inner layer, a composition having the following composition:
(I) an ethylene-glycidyl methacrylate copolymer containing 18 parts by mass of glycidyl methacrylate (60 parts by mass, CG5001 (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Ii) 6 parts by mass of a carboxyl group-containing rosin having an acid value of 240 mgKOH / g (curing agent, Arakawa Chemical's KE604 (trade name)),
(Iii) 1.5 parts by mass of an imidazole derivative (curing accelerator, 2MOAK (trade name) manufactured by Shikoku Chemicals),
(Iv) 3 parts by mass of calcium carbonate (filler, Shiroishi calcium whiten SB (trade name)),
Using, as the outer layer, a composition of the following formulation,
(I) an ethylene-glycidyl methacrylate copolymer containing 48 parts by mass of 12% by mass of glycidyl methacrylate (Bond First E (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Ii) an ethylene-glycidyl methacrylate copolymer containing 18 parts by mass of glycidyl methacrylate of 12 parts by mass (CG5001 (trade name) manufactured by Sumitomo Chemical Co., Ltd.);
(Iii) 6 parts by mass of a carboxyl group-containing rosin having an acid value of 240 mgKOH / g (curing agent, Arakawa Chemical KE604 (trade name)),
(V) 1.5 parts by mass of an imidazole derivative (curing accelerator, 2MOAK (trade name) manufactured by Shikoku Chemicals),
(Iv) 3 parts by mass of calcium carbonate (filler, Shiroishi calcium whiten SB (trade name)),
These were kneaded with a twin-screw extruder (TSE) and co-extruded to obtain a laminate having a sectional shape as shown in FIG. The outer layer of this laminate was subjected to an electron beam (EB) treatment (250 KeV, 30 Mrad) to crosslink the surface of the outer layer to obtain a flange sealing material.
[0052]
Comparative Example 5
A flange sealing material was obtained in the same manner as in Example 1 except that the amount of the foamed beads was changed to 30 parts by mass.
[0053]
The samples obtained in the above Examples and Comparative Examples were evaluated by the following methods.
Evaluation method
1. Panel mounting workability
4 (a) and 4 (b): Work for mounting to cover the end portions of the cationic electrodeposition coated plates ((a): Comparative Example 3, (b): other than Comparative Example 3) which are superimposed as shown in FIGS. Ease was evaluated.
A: Can be mounted in a short time without the need for a jig
B: Requires a jig and takes a little time
C: Requires jigs, requires time and skill
[0054]
2. Step absorption (sealability)
Two 25 mm × 150 mm × 0.8 mm cold-rolled steel sheets that have been subjected to cationic electrodeposition coating (E-Coating U-600 Black, manufactured by Nippon Paint Co., Ltd.) are attached with a double-sided tape as thin as possible. A sample was attached or applied along this seam, held at 120 ° C. for 10 minutes, and then left in a constant temperature oven at 140 ° C. for 30 minutes to simulate a process in which a flange portion to be sealed was subjected to a normal coating process. . Thereafter, the sample is taken out of the oven, and the step sealability with the steel plate is visually checked.
A: The step is completely sealed
B: There is a gap in the step
[0055]
3. Painted appearance
As shown in FIGS. 4 (a) and 4 (b), the sample is mounted on a cationic electrodeposition coated plate ((a): Comparative Example 3, (b): other than Comparative Example 3) or applied with a brush and a spatula. Next, it is left for 10 minutes in an oven adjusted to 120 ° C. A paint used for coating the body of an automobile (that is, an aminoalkyd paint obtained by crosslinking polyester with melamine) is applied by a bell spray, left at room temperature for about 5 minutes, and then left in an oven at 140 ° C. for 30 minutes. After taking out of the oven and leaving at room temperature for about 5 minutes, apply the paint used for car body coating (ie, an aminoalkyd type solid paint obtained by crosslinking polyester with melamine) by bell spraying and leave it at room temperature for about 5 minutes After that, it is left in an oven at 140 ° C. for 30 minutes. The thickness of each coating was about 40 μm for both the middle coat and the top coat after curing. The surface appearance of the sample coated as described above was visually evaluated.
A: Good
B: Surface is good, but seal line is not uniform
C: Wrinkles and coating film cracks occurred (large)
[0056]
4. Shape retention after heat treatment (horizontal direction and vertical downward direction)
As shown in FIGS. 4 (a) and 4 (b), a sample is mounted on a cation electrodeposition coated plate ((a): Comparative Example 3, (b): other than Comparative Example 3) or coated with a brush and a spatula. .
As shown in FIGS. 5A and 5B (only Example 1 is shown as an example), the sample on which the sample is mounted or applied is (a) horizontal and (b) vertically downward (as the seal is suspended). In an oven adjusted to 120 ° C. for 15 minutes. Thereafter, it is visually confirmed whether or not the sample taken out of the oven retains its original shape.
A: Good
B: Deformation and dripping due to its own weight
C: Drop out
[0057]
5. Panel gap seal test
As shown in FIG. 6, a sample was placed or painted on a panel having a gap of 1 mm, and left at 120 ° C. for 10 minutes and then at 140 ° C. for 30 minutes, and it was confirmed whether or not the sample sealed this gap.
A: Good sealability
B: Some gaps remain
D: No seal
[0058]
6. Anti-gravity sealing
As shown in FIG. 7, the sample was placed or painted on a panel with the sealing surface facing downward, and left at 120 ° C. for 10 minutes and then at 140 ° C. for 30 minutes to confirm the sealing property.
A: Good sealability
B: Some gaps remain
D: No seal
[0059]
7. Indentation concealment evaluation
A dent having a diameter of 6 mm and a depth of 0.3 mm was formed on the above-mentioned cationic electrodeposition coated plate, and the dent 5 was coated with each sample as shown in FIG. It was left for a few minutes, and the concealment of the dent was evaluated.
A: Almost concealed dents
B: Slight sink marks occurred
C: Obvious sink marks
[0060]
The results of the above evaluation tests are summarized in the following table.
[Table 1]
[0061]
In Examples 1 to 5, the mounting workability is good, and the surface in contact with the adherend (metal panel) has high fluidity by heating, so that the sealing performance is excellent. Since it does not exhibit properties, it has good shape retention properties, is also excellent in coating adhesion, and is excellent in heat resistance because the resin constituting the sealing material is thermosetting. Further, as shown in FIG. 9, since the inner seal layer 12 flows and expands by the foam beads, it seals without leaving a gap between the panel 3 and the outer layer 11, and further to a portion against gravity. Also sealing is possible.
[0062]
Comparative Example 1 is a single-layer sealing material made of a resin constituting the inner layer of the sealing material of the present invention. The sealing material has a good fit, a step absorption property, and a good paint appearance. Since there is no sufficient storage elastic modulus in the above, it is deformed by its own weight, is inferior in shape retention and cap sealability, and it is naturally impossible to seal a portion against gravity.
[0063]
Comparative Example 2 is a general PVC (polyvinyl chloride) sealer, which is a liquid material, and therefore, it is difficult to apply a predetermined amount of the liquid material and requires skill of an operator. In addition, it is deformed by its own weight, and the shape retention is not sufficient.
[0064]
Comparative Example 3 is made of a thermoplastic resin having a high fluidity, so that the sealing property is good. However, because of the thermoplasticity, wrinkles are generated in a repeated heating process encountered in the coating process, and the shape is maintained. Can not.
[0065]
Comparative Example 4 is a multilayer sealing material having a shape-maintaining layer in the outer layer and a high-flowable thermosetting resin in the inner layer, and has good mountability, sealability, shape retention, and coating adhesion. However, since the foamed beads are not contained in the inner layer, there is no change in the volume of the resin, and it is difficult to seal in a gap of 1 mm. Further, as shown in FIG. 10, the molten resin 12 flows downward according to the gravity, and a gap 13 is generated between the outer layer 11 and the panel 3, making it difficult to seal a portion against the gravity.
[0066]
In Comparative Example 5, since the amount of the foamed beads was too large, the fluidity of the molten resin was hindered. As a result, the sealing property was reduced, and the unevenness of the appearance became large, so that the coating appearance was inferior.
[0067]
【The invention's effect】
ADVANTAGE OF THE INVENTION With the sealing material of this invention, mounting | wearing workability | operativity is good, it is excellent in sealing property and shape retention becomes favorable.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a flange portion sealed with a conventional paste sealer.
FIG. 2 shows a cross-sectional view of one embodiment of the sealing material of the present invention.
FIG. 3 shows a cross-sectional view of a single-layer sealing material for comparison.
FIG. 4 shows a cross-sectional view of a flange portion formed by a metal panel (cation electrodeposition coated plate).
FIG. 5 is a schematic view showing a direction of a metal panel in a shape retention test.
FIG. 6 is a schematic diagram showing a configuration in a panel gap seal test.
FIG. 7 is a schematic view showing a configuration in an antigravity seal test.
FIG. 8 is a schematic view showing a configuration in a spot dent concealment test.
FIG. 9 is a cross-sectional view showing a configuration of a flange portion sealed using the sealing material of the present invention.
FIG. 10 is a cross-sectional view illustrating a configuration of a flange portion sealed using a sealing material that does not include expanded beads.
[Explanation of symbols]
10 ... Seal material
11 ... outer layer
12 ... Inner layer

Claims (5)

  1. A flange portion sealing material for sealing a flange portion of a metal panel of a vehicle, comprising at least two layers of an inner layer and an outer layer formed into a predetermined shape so as to be fitted and wrapped with the flange portion, wherein the inner layer is A hot-melt-flowable thermosetting resin having a curing temperature of 80 ° C to 200 ° C, wherein the outer layer does not show significant morphological change due to flow at a temperature of 80 ° C to 200 ° C; A sealing material for a flange portion comprising foam beads.
  2. The flange sealing material according to claim 1, wherein the outer layer contains a resin having a storage elastic modulus at 80 to 200 ° C. of 5.0 × 10 5 Pa or more.
  3. The flange sealing material according to claim 1, wherein the heat-meltable and flowable thermosetting resin includes an epoxidized thermoplastic resin.
  4. The flange sealing material according to claim 1, wherein the foam beads are heat-expandable microcapsules containing a foaming agent.
  5. The flange sealing material according to claim 1, wherein the content of the foam beads is 0.1 to 20 parts by mass with respect to 100 parts by mass of the material constituting the inner layer.
JP2003158086A 2003-06-03 2003-06-03 Sealant for flange part Pending JP2004360756A (en)

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JP2003158086A JP2004360756A (en) 2003-06-03 2003-06-03 Sealant for flange part
PCT/US2004/016329 WO2004108401A2 (en) 2003-06-03 2004-05-25 Flange section seal material

Publications (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009046618A (en) * 2007-08-21 2009-03-05 Iida Sangyo Kk Sealer and sealing method
JP2010232330A (en) * 2009-03-26 2010-10-14 Autech Japan Inc Case structure of strong electric body

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2908777A1 (en) * 2006-11-16 2008-05-23 Arkema France Use of composition based on polyolefins for preparing reticulated soft foams.
JP6022144B2 (en) * 2010-04-01 2016-11-09 東海興業株式会社 Glass run channel, its assembly and manufacturing method
DE102016220237A1 (en) 2016-10-17 2018-04-19 Tesa Se Method for producing a sealed seam connection
DE102018213824A1 (en) 2018-08-16 2020-02-20 Tesa Se Process for making a sealed seam connection
FR3087751A1 (en) * 2018-10-25 2020-05-01 Safran Nacelles Aerodynamic smoothing part for an aircraft propulsive assembly platform and associated assembly method

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1115247A (en) * 1965-06-15 1968-05-29 Atomic Energy Authority Uk Improvements in or relating to encapsulation resinous materials
FR2703689B1 (en) * 1993-04-09 1995-06-16 Minnesota Mining & Mfg Flame retardant epoxide composition conveniently free of halogen.
US5423147A (en) * 1994-02-17 1995-06-13 Gencorp Inc. Wireless carrier weatherstrip seal
FR2732974B1 (en) * 1995-04-11 1997-05-16 Atochem Elf Sa Strip comprising a polymeric material loaded with hollow microspheres (foam)
DE19531167C2 (en) * 1995-08-24 1998-10-22 Baedje K H Meteor Gummiwerke Motor vehicle sealing profile
JP2003170537A (en) * 2001-12-04 2003-06-17 Three M Innovative Properties Co Flange sealing material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009046618A (en) * 2007-08-21 2009-03-05 Iida Sangyo Kk Sealer and sealing method
JP4575940B2 (en) * 2007-08-21 2010-11-04 イイダ産業株式会社 Sealer and sealing method
US8398086B2 (en) 2007-08-21 2013-03-19 Toyota Jidosha Kabushiki Kaisha Sealing element and sealing method including fusing the element
JP2010232330A (en) * 2009-03-26 2010-10-14 Autech Japan Inc Case structure of strong electric body

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