KR20010101322A - Sealant Compositions and Sealant Articles Using the Same - Google Patents

Abstract

A sealant composition comprising a curable epoxy containing material, a thermoplastic polyamide component having a melting point lower than the curing temperature of the epoxy containing material, and a formulation for the epoxy containing material. After curing the epoxy containing material, the sealant composition exhibits at least 2% elongation at -20 ^° C. The sealant composition can effectively seal the gap while maintaining sufficient flexibility to absorb the applied stress, thereby preventing the formation of defects in the sealant that allow the ingress of dust, moisture and other undesirable materials.

Description

Sealant Compositions and Sealant Articles Using the Same

For example, automobiles such as passenger cars and trucks have metal joints and seams to be sealed. Welding two panels of a vehicle (for example, a loop and a side panel) together, such as those commonly used in automobiles to create a U-shaped trough or channel called a roof ditch. An example is a generally non-planar overlap joint formed by. One purpose of the roof ditch is to collect and discharge water from the side of the car.

In order to prevent water from seeping through the overlap joint formed by the U-shaped trough, it is necessary to seal the joint. Since the joints overlap and are not planar, it is often difficult to obtain a good seal. In addition, since the width of the loop deodorant generally varies with its length, it complicates the ability to provide good sealing. Various materials have been used to seal loop deodorant joints, fill voids in automobiles, and block passages of dust, moisture and other undesirable materials.

The sealant was supplied as a liquid or solid material according to the requirements for that specific use. In the automotive industry, for example, loop deodorant joints have been sealed using paste-like plastisol that is painted, baked and cooled to room temperature. Hot melt sealants have also been used and are generally solid thermoplastics which melt quickly when heated and then form solid bonds upon cooling. In use, the molten liquid sealant beads are generally applied to the joint or seam in such a way that caulking is applied. The operator then paints or evens the material. Proper application of such sealants requires skill, and human error can often lead to poorly sealed joints or seams. Such hot melt sealants are undesirable for visual use because of their uneven appearance. Typical hot melt sealant compositions utilize polyolefins that can be difficult to paint and have poor adhesion to nonporous metal surfaces, such as steel and aluminum.

Recently, polyvinyl chloride base sealants, which are supplied in the form of ropes or tapes, are more user friendly. Sealants of this type are disclosed in Japanese Laid-Open Publication No. 9-505335. Manipulation of these sealant materials allows for faster installation and eliminates the need for finesing the material after application.

Once the sealant is applied, its exposed surface may be covered with a plastic or rubber article (eg, molding, cap, etc.) having a flexible top surface, which may be, for example, outside of an automobile. It can be painted to match or complement the color. In addition, the exposed surface of the sealant may be covered with a metal article. The article is generally attached to the sealant surface using a mechanical fastener or pressure sensitive adhesive.

During the service life, in particular when the car is to be used in an extremely northern climate, the car can be exposed to very cold temperatures of -20 ^o C or less, for example -30 to -40 ^o C. Prior art sealants used in these severely cold conditions, in particular those which can be used for roof deodorant applications, result from stresses that can be generated, for example, by conventional automotive use, resulting in cracking, breaking, It is known to exhibit drawbacks such as delaminating or lifting up from the surface to which it can be applied. Such defects in sealants can allow the penetration of dust, moisture and other undesirable materials as well as loosen sequentially applied articles (eg, castings, caps, etc.).

Therefore, there is a need for an answer to the problem described above. In particular, sealants that can withstand the stresses generated during use, for example, can effectively seal gaps while remaining sufficiently flexible at low temperatures to prevent dust, moisture, and other undesirable substances through sealing. There is a need for compositions and sealant articles.

The present invention relates to sealant compositions and sealant articles and more particularly to compositions for sealing gaps found in, for example, automobiles, and articles used to seal the gaps, and to methods of sealing the gaps.

Summary of the Invention

According to one aspect of the invention, a curable epoxy containing material; A thermoplastic polyamide component having a melting point lower than the curing temperature of the epoxy containing material; And a curing agent for the epoxy containing material, wherein an elongation at -20 ^° C. is at least 2% as a result of curing of the epoxy containing material.

In one preferred embodiment of the invention, the sealant composition according to the invention comprises 10-60% by weight epoxy containing material and 30-70% by weight thermoplastic polyamide component.

According to another aspect of the invention, there is provided a sealant composition comprising a formed sealant layer of the sealant composition of the invention (hereinafter also referred to as "first layer").

In another preferred embodiment of the invention, the sealant article according to the invention is provided with an adhesion layer (hereinafter also referred to as "second layer") on one surface of the sealant layer (first insect). The second layer (ie, adhesion layer) preferably comprises a plurality of adhesion microspheres.

In another embodiment of the present invention, the surface of the second layer having adhesion properties is provided with a release layer in which a plurality of protrusions are formed, the protrusions being at least in contact with the second layer.

In a further embodiment of the invention, the flexible layer (hereinafter also referred to as "third layer") is further provided over the sealant layer. As flexible, the third layer can be at any location, for example located at the sealant layer. It may also be attached to another surface of the sealant layer (ie, opposite surface of the second layer).

Brief description of the drawings

1 is a cross sectional view showing one preferred embodiment of a sealant article according to the invention.

2 is a cross sectional view showing another preferred embodiment of a sealant article according to the invention.

3 is a perspective view showing a release layer used in the sealant article shown in FIG. 2.

4 is a cross sectional view of another preferred embodiment of a sealant article according to the invention.

5 is a cross sectional view showing a further preferred embodiment of a sealant article according to the invention.

6 is a cross sectional view showing a further embodiment of a sealant article according to the invention placed in an automobile roof deodorant before heating.

FIG. 7 is a cross sectional view showing the sealant article and automotive roof deodorant of FIG. 6 after heating. FIG.

Embodiments for Carrying Out the Invention

The invention will be described in detail by the following embodiments. Those skilled in the art will readily understand that the present invention is not limited to the following embodiments.

In the cross sectional view of FIG. 1, a sealant article 10 using the sealant composition of the present invention is shown illustratively. This sealant article 10 comprises a sealant layer or first layer 1 of a sealant composition and is present in the form of a rope, tape, strip or other such structure. This first layer 1 is placed in a predetermined position above the gap (for example overlap joint or seam, butt joint or seam, recess or indentation, or manufacturing defect), The sealant composition constituting layer 1 forms a protective seal to coat the gap, thereby preventing moisture, dust, snow, and other undesirable substances from entering the gap and causing corrosion. do.

The sealant composition may be considered to be melt flowable. That is, when placed on a joint and heated, the sealant composition first becomes flexible and fits to the surface of the gap, thereby repelling the trapped air. In addition to the heating cycle, as the composition gets hotter, it becomes tacky and binds to the surface. The sealant composition is cured by heating and thermoset to inhibit the flow following cooling and reheating.

The sealant compositions of the present invention, once cured, exhibit excellent flexibility at low temperatures and can be easily bent around the mandrel without cracking or breaking, as described in more detail below. Preferably, each cured sealant composition has, but is not limited to, an elongation of at least 10% when tested at -20 ^° C. Basically, when tested at -20 ^° C, the cured sealant composition has an elongation of at least 2%. In such cases, paints used in automobiles, in particular automotive paints, will exhibit substantially the same or lower elongation as cured sealant compositions when tested at -20 ^° C. As a result, even if the cured sealant composition is applied and the paint is coated over the exposed sealant composition, it is possible to prevent the cracking or breaking of the sealant composition before the cracking or breaking of the coated paint. Thus, the sealant composition can maintain its integrity above the gap, thereby avoiding the ingress of dust, moisture, snow and other undesirable materials therein.

The sealant composition of the invention in the first layer 1 may more preferably consist essentially of an epoxy containing material, a thermoplastic polyamide component, and a curing agent for the epoxy containing material. Epoxy containing materials contribute to the ultimate strength and heat resistance of the sealant composition, and the thermoplastic polyamide component provides compliance, adaptability, flexibility, especially at low temperatures. The curing agent cures the composition. Preferably, the curing agent is thermally activated such that the composition is cured by exposure to a suitable heat source for a suitable time.

Useful epoxy containing materials are epoxy resins having at least one oxirane ring that can be polymerized by ring cleavage reactions. Such materials, widely called epoxides, include both monomeric and polymeric epoxides and may be aliphatic, cycloaliphatic, or aromatic. Generally these materials have at least two epoxy groups per average molecule and preferably have more than two epoxy groups per molecule. Such materials may be referred to as polyepoxides and include epoxy containing materials having an epoxy functionality of 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 an epoxy containing material divided by the total number of epoxy molecules present. Polymer epoxides have straight chain polymers having terminal epoxy groups (eg, diglycidyl ethers of polyoxyalkylene glycols), polymers having skeletal oxirane units (eg, polybutadiene polyepoxides), and epoxy groups Polymers (eg, glycidyl methacrylate polymers or copolymers). The molecular weight of the epoxy containing material may be from 58 to about 100,000 or more. Mixtures of various epoxy containing materials can also be used.

Useful epoxy containing materials include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarbox Carboxylates, and those containing cyclohexene oxide groups such as epoxycyclohexanecarboxylate, represented by bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. Further particularly useful epoxy containing materials are glycidyl ether monomers such as glycidyl ethers of polyhydric phenols obtained by reacting an excess of chlorohydrin such as epichlorohydrin with polyhydric phenols (e.g., 2 Diglycidyl ether of, 2-bis- (2,3-epoxypropoxyphenol) propane).

There are a number of commercially available epoxy containing materials that can be used in the practice of the present invention. That is, they are commercially available from Yuka Shell Chemical Co. under the trade names EPIKOTE 1001, Epicorte 1002, Epicorte 1003, Epicorte 1004, Epicorte 8028 and Epicorte 154.

The sealant composition of the present invention also includes a thermoplastic polyamide component. By thermoplastic polyamide component is meant a polymeric material containing an amide moiety (-HNCO-), which has thermoplastic processing properties. That is, the thermoplastic polyamide material is softened and heated to become fluid and then molded and subsequently cooled and cured. Upon reheating, the material becomes soft again. The thermoplastic polyamide component adds desirable miscibility with the epoxy containing material and other sealant composition components that do not promote curing of the epoxy containing material. The thermoplastic polyamide component also contributes to the good low temperature properties of the sealant composition, in particular its flexibility.

Preferred thermoplastic polyamide components are mixed with the epoxy containing material in the molten phase (ie the molten mixture) and preferably form a homogeneous single phase mixture when the epoxy containing material is not cured. The formation of a uniform single phase is evident when this mixture (melt mixture) becomes transparent. Preferably, about 90 to about 350 parts by weight of the polyamide component is contained in about 100 parts by weight of the epoxy containing material. When the polyamide component is contained in an amount of about 90 parts by weight or less, the cured sealant composition becomes brittle. On the other hand, when the polyamide component is contained in an amount of about 350 parts by weight or more, the cured sealant composition is not sufficiently cured and easily flows by reheating. When the epoxy containing material is cured, a composition of two separate phases or many 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. When the two phases are formed from a homogeneous single phase comprising an epoxy containing material and a thermoplastic polyamide component, the two phases are uniformly distributed even if the epoxy containing material is cured as described above. Thus, the properties of the sealant composition are provided by the epoxy containing material and the thermoplastic polyamide component. Some non-uniformity of the mixed thermoplastic polyamide components may be acceptable as long as the desired properties are provided in the sealant composition.

In addition, the preferred thermoplastic polyamide component has a melting point not higher than the curing temperature of the epoxy containing material in order to inhibit the epoxy containing material from curing by heating and sealing of the sealant composition on the desired surface. In addition, the sealant composition is melted by heating, which makes it easier to penetrate the composition into the gap. When sealant compositions are used in the automotive industry, thermoplastic polyamide components typically have a melting point no greater than about 180 ^° C.

The sealant composition comprises a curing agent for curing the epoxy containing material. Preferably, the curing agent is thermally activated to affect the curing or curing of the epoxy containing material under the influence of heating. For example, useful thermally activated curing agents include amide groups containing amines and imidazoles. Preferably, the curing agent with amide groups is generally dicyandiamide. Preferably, the curing agent with imidazole is largely a triazine derivative. Dicyamide amide curing agent is commercially available from ACR Co. under the trade name "EH3636". Triazine derivative curing agents are commercially available from Shigoku Chemical Co. under the trade name "2MZA".

The sealant compositions may also contain additives, for example fillers such as calcium and silica powder, an antioxidant commercially available from Ciba Geigy Corp. under the trade name "IGRANOX 1010", "TINUVIN". UV absorber commercially available from Ciba-Geigy Corp. under the trade name of P ", and surfactant marketed from 3M under the trade name of" FC36 ".

The sealant composition of the first layer (sealant layer) 1 is a solid at room temperature. Small amounts of thickness at room temperature or slightly below room temperature are desirable to assist in the initial placement of sealant containing articles on joints or seams, such as in sealant compositions or automotive loop deodorants 12. However, when the sealant composition is in ropes, tapes, strips or similar structures, it eliminates the need for technology and labor to quickly adhere and use the sealant composition (eg, forming an applied sealant material with an acceptable appearance). The sealant compositions of the invention are expected to be substantially viscous at room temperature. In the case of a substantially viscous sealant composition, as shown in FIG. 1, any second layer 2 with adhesive properties is preferably on one surface of the first layer 1 containing the sealant composition. Is provided. This is one way in which a substantially viscous sealant composition can still be positioned as described above.

The adhering second layer 2 may be formed by a plurality of adhering microspheres 3, preferably arranged at even intervals from each other, as shown in FIGS. 6 and 7. The microspheres 3 can provide a surface that is sufficiently adherent to themselves to form the adherent second layer 2. Whether they form all the adhesion layers 2 or only a part of the adhesion layers 2, the microspheres 3, such as the overlap joint of the loop deodorant 12, to exit under the sealant article 10. One or more channels may be formed that provide air bubble passages that are trapped in the gap. These channels or channels can act to draw air bubbles trapped in the gap so that as much of the sealant composition as possible is not separated from the gap by the trapped air. As a result, when the sealant composition becomes pliable by heating, more sealant composition may contact and seal the surface of the gap, such as a joint formed at the bottom of the loop deodorant shown in FIG. By trapping fewer air bubbles, the formation of recesses or recesses on the exposed surface of the sealant composition is suppressed. Such recesses or recesses may form on the exposed surface of the sealant composition as a result of trapped air bubble expansion by heating and subsequent shrinkage by cooling. Therefore, for the use of these microspheres 3, excellent appearance can be obtained. Preferred attached microspheres 3 are made of acrylic polymer material. To form good channels, the attached microspheres preferably have a particle diameter of 30 to 500 μm. When the article 10 is heated such that the sealant composition is flexible and sealed to the surface of the gap (eg, inside the loop deodorant 12), the microspheres 3 enter the sealant composition (eg, FIG. 7). ).

A release layer can also be provided on the surface of the second layer 2, thereby allowing it to adhere quickly. 2 shows an embodiment in which the projecting surface of the release layer 4 with the projecting portion on one surface is in contact with the surface of the second layer 2 of the sealant article 10. An example of the protruding pattern of the release layer 4 as used herein will be readily understood from the perspective view of the release layer of FIG. 3.

In the practice of the present invention, a particularly preferred release layer 4 is provided with a plurality of protrusions spaced on one or more of their surfaces. In this case, when the protrusion on the surface of the leaving layer 4 is at least in contact with the second layer 2, it is possible to partially remove the attachment surface of the second layer 2 to form a channel therein. . Thus, if this protrusion has a sharp tip portion, the channel can be manufactured more efficiently. In addition, the second layer 2 can also be provided with the attached microspheres spaced apart from one another or evenly. More preferably, a plurality of consecutive sharp protrusions, intersecting with each other or vertically as shown in FIG. 3, are provided at intervals to form a channel in the second layer 2, through which the air bubbles are isotropic. Can be pulled out. This release layer 4 is commercially available from 3M, for example, as "EA Liner (trade name)." The protrusions on the release layer 4 can be formed by known microreplication techniques.

According to another preferred embodiment of the invention, the sealant article 10 of the invention is provided with a flexible third layer 5 on the surface of the first layer (the sealant layer) or on another surface. With this configuration, air bubbles trapped in the sealant article can be prevented from reaching the surface of the sealant article 10. 4 and 5 show two preferred arrangements of the third layer 5. The sealant article 10 of FIG. 4 comprises a third layer 5 on the surface of the first layer 1 facing the second layer 2. The sealant article 10 of FIG. 5 comprises a third layer 5 between two first layers 1 and 11. The preferred article 10 is flexible or compliant and does not trap visible air bubbles at the interface between the first layer 1 and the third layer 5. Preferably, this third layer 5 is made of polyethylene terephthalate (PET) or polyethylene (PE), for example.

A particularly preferred flexible third layer 5 is commercially available from Nippon Filte KK, for example under the name "Expancel", which has a porosity due to the contained plastic droplets (not shown). The third layer 5 can easily and uniformly disperse the air trapped in the gap by capillary action, in particular, this air dispersion can be promoted during the curing of the first layer 1 with heating. In the subsequent step of cooling the sealant composition to room temperature, the local shrinkage of the trapped air can be suppressed by causing the uniform shrinkage properties of the sealant composition, as a result, the formation of local depressions can be easily reduced. Regardless of the porosity of the flexible layer 5, fillers composed of uniformly dispersed whiskers or nonwoven fabrics fh may also be included in the flexible layer 5 to trap air bubbles. .

The adhesion layer 2 and the release layer 4 described above can be applied to the above-mentioned sealant composition and other suitable sealant compositions, respectively. For example, in view of the use of the adhesion layer 2 and the release layer 4, the sealant composition may be made of a thermoplastic polyurethane component or a polyester component instead of the thermoplastic polyamide component already mentioned in the specification of the present invention. . In particular, when the sealant composition contains 30-70% by weight of thermoplastic polyurethane components or polyester components, it exhibits excellent properties in the evaluation of mimicked seal sealing, temperature cycle aging and cold extension or wrap joint sealing evaluation. Indicates. This thermoplastic polyurethane component is commercially available from Takeda Bodischurethane Industries, Ltd. under the trade name "ET370" and has a melting point of 160 ^° C. and elongation of at least 100%. The thermoplastic polyester component is commercially available from Hughes America Inc. under the trade name "DINAPOL S1402" and has a melting point of 80 ^° C.

The following examples illustrate the invention but do not limit the scope of the invention.

Example 1

A thermoplastic polyamide component (trade name: MACROMOMELT 6238) manufactured by Henschel Co. was prepared, which has a melting point of 135 ^° C. and elongation of 130% at −20 ^° C. Yucca Shell Co An epoxy-containing material (trade name: Epicorte 1001) prepared by. Was also prepared.Dicyamide (trade name: EH3636) manufactured by ACR Co. and a triazine derivative produced by Shigoku Chemical Co. (2MZA) was mixed at a weight ratio of 2: 1 to prepare a formulation.

Thereafter, 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 curing agent were uniformly mixed to obtain a sealant composition. The sealant composition was placed in an extruder to form a sheet (sealant article) having a thickness of 2.0 mm.

Test substrates were prepared by the following method. First, a glass plate having a width of 25 mm, a length of 150 mm and a thickness of 0.8 mm is made of cold-rolled steel having a width of 25 mm, a length of 150 mm and a thickness of 0.8 mm, in overlapping conditions. The resulting strip was attached using double sided adhesive tape. The step of descending from steel to the glass surface was made by overlapping strips and plates, mimicking a seam at the bottom of the roof deodorant in automobiles. After the uncured sheet was cut into rectangular strips having a length of 100 mm and a width of 20 mm, the strip was placed on one edge of the steel strip and heated at 120 ^o C for 10 minutes and then 140 ^o C for 40 minutes. Heated at. After cooling the test substrate to room temperature, the mimetic seam (reproduced by descent from the steel strip to the glass plate surface) was visually inspected through glass to determine the seal formed. In this example, an acceptable seal was specified by the sealant composition that melted and flowed over the steel strip to fill the gap between the glass plate surface and the steel strip.

1 mm thick cold-rolled steel sheet coated with automotive grade electronic deposition coating (E-coating, Nippon Fate Co., Ltd. U-600 black) was 25 mm long, 8 mm wide and 3 mm It was bent into a square U-shaped channel with depth to mimic the car roof deodorant.

The uncured sheet was cut into rectangular strips having a length of 25 mm and a width of 8 mm, then the strip was placed at the bottom of the mimic loop deodorant channel and heated at 120 ^° C. for 10 minutes to cure the sealant composition. . After cooling to room temperature, a conventional automotive paint primer of polyester in high solid form 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 subjected to a temperature cycle aging test.

In the temperature cycle aging test, one cycle consisted of 2 hours at −30 ^° C., then 2 hours at room temperature (about 23 ^° C.) and then 2 hours at 70 ^° C. After 5 cycles, the state of the sealant composition in the simulated loop deodorant channel was visually examined. As a result, no difference was found in the visual appearance of the sealant composition before and after the test.

Cold elongation evaluation was performed by the following method. The portion of the uncured sealant composition was heated at 140 ^° C. for 30 minutes and then cooled to room temperature. Test specimens of the cured samples were then die cut into the shape of No. 1 dumbbell in accordance with Japan Industrial Standard (JIS) K-6251. Test specimens were then marked to show two parallel 40 mm parts to each other. Test specimens were then secured to a crosshead clamp (clamp distance of about 60-70 mm) in a Tensilon tester (manufactured by Oriental Corporation) with a controlled temperature holding chamber. The fixed specimens were adjusted for 20 minutes at −20 ^° C. in the chamber and then stretched at a crosshead speed of 50 mm / min until the specimens were destroyed. Elongation at break was calculated by the following equation:

Elongation [%] = [(A-40) / 40] x 100

Where A is the distance in mm between two parallel lines when the specimen breaks. The elongation of the sealant composition of this example was 10%. This elongation will make it possible to prevent cracks, fractures, talamina or lifting up from the applied surface, as a result of the defects formed in the sealant, for example, stresses caused by conventional automotive use at low temperatures. These sealant defects not only allow the ingress of dust, moisture and other undesirable materials through the sealant, but can also impede the stable fixation of sequentially applied articles (eg, molds, caps, etc.).

Immersion tests were performed in the following manner. Samples were prepared by placing the uncured sheet (25 mm × 40 mm) on a steel sheet (65 mm × 150 mm) coated with an electrical deposition coating and heating at 120 ^° C. for 10 minutes. After cooling to room temperature, the automotive paint primer was sprayed onto the uncured sheet. Samples were cured at 140 ^° C. for 20 minutes. After cooling for at least 10 minutes, the automotive primary paint was sprayed onto the primer coated sealant composition. Samples were cured at 140 ^° C. for 20 minutes and then cooled to room temperature. The electrical deposition coated steel sheets, paint primers, and primer paints used were all as described in the temperature cycle aging test. The samples were soaked in water at 40 ^° C. for 250 hours and then visually inspected before and after the test. As a result, there was no difference in visual appearance.

Wrap joint seal evaluation was performed by the following method. Two 0.8 mm thick electrical deposition steel sheets similar to those used in the temperature cycle aging test described above were welded together to form a wrap joint. The uncured sheet (20 mm × 100 mm) was applied over the lap joint and heated at 95 ^° C. for 10 minutes and then at 140 ^° C. for 36 minutes. After cooling, the sheet was visually inspected. As a result, the wrap joint was sealed and flowed into the wrap joint as indicated by the desirable properties of the sealant composition and attached to the steel sheet.

In addition, the surface appearance test was performed by the following method. A mimicked automotive loop deodorant was made by bending two electrically deposited coated steel sheets (similar to those mentioned above in the temperature cycle aging test) into a square U-shaped channel and spot welding together in an overlapping shape. This mimic loop deodorant has a width of 20 mm, a depth of 10 mm and a depth of 300 mm with seams or joints welded at the bottom of the deodorant. In addition, ten recesses or recesses, each having a diameter of about 5 mm and a depth of about 0.8 mm, were formed at the bottom of the deodorant. The uncured sheet was cut into strips having a width of 19 mm and a length of 300 mm, and the strip was placed at the bottom of the mimic loop deodorant. The test specimens were heated at 100 ^° C. for 10 minutes, then at 140 ^° C. for 20 minutes, and then cooled to room temperature. The simulated loop deodorant was then visually inspected, especially in the concave portion. As a result, the surface of the sealant composition formed a recess after the test. Thus, for the depression portion, the sealant compositions do not satisfy the desired properties and do not sufficiently fill the recess.

The results of the seam seal test, the temperature cycle aging test, the cold and hot elongation rate and the 250 hour immersion test imitated among the evaluation tests are described in Table 1 below with the results of Comparative Example 1 described below.

Example 2

The surface appearance test was carried out using one surface coated uniformly with adherent microspheres having a particle diameter of 35 μm made by 3M at a coating weight of 7 g / m ² instead of the uncured sheet used in the test. On the sheet having, the method described in Example 1 was repeated except that the method described in Example 1 was carried out, as described above. The sealant composition formed a surface with recesses after testing. Thus, with respect to the depression portion, the sealant composition can satisfy the desired properties and fill the recess.

Example 3

Instead of the uncured sheet with adhered microspheres used in the test, the surface appearance test of Example 2 was a 125 μm thick polyethylene terephthalate (PET) film made by ICI-Dupont Co. The method described in Example 2 was repeated except that it was carried out on a sheet supplied with phosphorus film (Melinanex, MELLINEX # 316). The sealant composition formed a surface with recesses after testing. Thus, with respect to the depression portion, the sealant composition can satisfy the desired properties and fill the recess.

Comparative Example 1

In Example 1, except that the thermoplastic polyamide component (trade name: Micromelt 6238) manufactured by Henschel Co. was used instead of the thermoplastic polyamide component (trade name: Micromelt 6217) manufactured by Henschel Co. In the same manner as described, sealant compositions were prepared and their sheets formed. This thermoplastic polyamide component has a softening point of 112-122 ^° C. and an elongation of 8% at −20 ^° C. In much the same manner as described in Example 1, evaluation tests of mimicked seam sealing, temperature cycle aging, cold extension and 250 hour immersion were performed. However, as shown in Table 1 below, the elongation of the sealant composition of this comparative example was 1% or less in the evaluation of the cold elongation. It has also been found that temperature cycle aging causes the comparative sealant composition to cause cracking, breaking or lifting up from the applied surface as a result of the stresses generated by conventional automotive use. Thus, when using such sealant compositions, this allows the penetration of dust, moisture and other undesirable materials and unstablely secures articles (e.g. castings, caps, etc.) to be applied sequentially.

Sealant composition Patterned seam seal test Temperature cycle aging Cold and hot growth rate 250 hours immersion Example 1 Good Good 10% immutability Comparative Example 1 Good Not good 1% less than immutability

As described above, according to the present invention, sealant compositions and sealant articles can be obtained that can effectively seal gaps while maintaining sufficient flexibility to withstand the stresses generated during use. In particular, the sealant compositions and sealant articles of the present invention can maintain excellent properties, such as flexibility, under severe conditions, so that they can prevent sealant defects such as, for example, cracking, fracture, talamina, and lifting up from the surface. Can be. Avoiding these sealant defects can prevent dust, moisture, and other undesirable substances from entering through the sealant through the sealant and in a manner suitable for the sealant to which the article (e.g., casting, cap, etc.) will be applied. It can be fixed.

Claims (14)

Curable epoxy containing materials; A thermoplastic polyamide component having a melting point lower than the curing temperature of the epoxy containing material; And Curing agent for the epoxy containing material And a sealant composition having an elongation of at least 2% at -20 ^° C. after curing the epoxy containing material. The sealant composition of claim 1 comprising 10-60 wt% epoxy containing material and 30-70 wt% thermoplastic polyamide component. Sealant article comprising a sealant layer of the sealant composition according to claim 1. The sealant article of claim 3, wherein the adhesion layer is provided on the bottom surface of the sealant layer. The sealant article of claim 4, wherein the adhesion layer contains a plurality of adhesion microspheres. 6. The sealant article of claim 4 or 5, wherein the surface of the attachment layer is provided with a plurality of protrusions formed with the release layer at least in contact with the attachment layer. The sealant article of claim 3, wherein the flexible layer is further provided on the top surface of the sealant layer. The sealant article according to any one of claims 3 to 6, wherein the flexible layer is further provided in the sealant layer. The sealant article of claim 3, wherein the sealant article is dimensioned to seal against the inner surface of the automotive roof deodorant. The combination of sealant article and gap of any one of claims 3 to 8, wherein the sealant article is positioned and processed to seal the gap. 10. The combination according to claim 9, wherein said gap forms part of a difference. 10. The combination of claim 9, wherein the gap forms part of a motor vehicle. 10. The combination of claim 9, wherein said gap is a loop deodorant. The combination of any one of claims 9 to 13, further comprising a layer of pate on the sealant article.