CA2186638C - Curable, sprayable compositions for reinforcing thin rigid plates - Google Patents
Curable, sprayable compositions for reinforcing thin rigid plates Download PDFInfo
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- CA2186638C CA2186638C CA002186638A CA2186638A CA2186638C CA 2186638 C CA2186638 C CA 2186638C CA 002186638 A CA002186638 A CA 002186638A CA 2186638 A CA2186638 A CA 2186638A CA 2186638 C CA2186638 C CA 2186638C
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/236—Forming foamed products using binding agents
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
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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
- 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
Abstract
A curable, sprayable composition suitable for reinforcing thin rigid plates or sheets such as are used in the assembly of automobiles is provided. The composition comprises a thermosetting resin, expandable microspheres and a particulate reinforcing material selected from the group consisting of milled glass fibers, milled carbon fibers and mixtures thereof.
Description
~1 ~n6~8 CURABLE, SPRAYABLE COMPOSITIONS
FOR REINFORCING THIN RIGID PLATES
FIELD OF THE INVENTION
The present invention relates to sprayable, curable compositions and their use for rssinforcing thin rigid plates or sheets, and to the reinforced plate or sheet itself.
BACKGROUND OF THE INVENTION
The use of thin gauge rigid plates or sheets in automobile manufacture has been greatly acceslerated due to improved corrosion protection, lighter weight, easy formability and lower cost. This practice has left certain parts of a car more vulnerable to easy denting and damage. Historically, either a reinforcing plate is welded or bonded to these areas, or a precut patch of epoxy impregnated glass fibers is attached.
Reinforcing compositions prepared from thermosetting resins, particularly epoxy resins, used to reinforce thin rigid sheets used in automobiles exhibit a number of advantages including strength, adhesion, and corrosion resistance. One distinct disadvantage is that many thermosetting resins, particularly epoxy based compositions, deform the substrates to which they bond due to shrinkage during curing.
In the automobile industry this deformation is of particular concern where the appearance of the substrate is critical. This substrate deformation necessitates additional costs in labor and materials in order to restore the intended appearance of the substrate.
U. S. Patent 5,151,327 discloses an adhesive sheet for reinforcing thin rigid plates. :>uch adhesive sheets comprise several resinous layers and need to undergo a sizing treatment before application to the thin rugid plates. The adhesive .. 2186638 sheets contain foaming agents to prevent shrinkage during cure. ' Application is by lamination.
U. S. Patent 4,739,019 discloses an adhesive composition for use in automotive applications. This composition contains an epoxide and a thermoplastic polyester. Such a composition loses its strength when heated to curing temperatures because the viscosity of the thermoplastic polyester decreases, and when applied to the underside of a substrate, the composition tends to sag or fall off the substrate during heating.
U. S. Patent 5,155,138 disc: loses the use of expandable thermoplastic microspheres in polymers and paints. It is also known to use expandable microspheres in car underbody coatings .
and sealants. (See Nobel Industries Technical Bulletin no. 21).' There is no teaching of the use of such microspheres in thin panel reinforcing compositions.
It is desirable to develop a sprayable curable thermosetting composition, for convenient application, which when used to reinforce thin rigid plates used in automobile manufacture exhibits excellent physical properties and reduced shrinkage.
SUI~lARY OF 7.'>:IE INVENTION
In accordance with the present invention there is provided a curable, sprayable composition comprising: (i) a thermosetting resinous composition; (ii) expandable microspheres; and (iii) a particulate reinforcing material. selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof.
The present invention also provides a method of reinforcing thin rigid plates comprising applying the composition described above to one side of a rigid plate, followed by curing the composition, and to the reinforced rigid plate itself comprising a rigid plate and the cured composition AMENDED SHEET
IPEAIEP
WO 95/27000 218 6 6 3 8 pCT~S95/03474 described above primarily adhered to one side of the rigid plate.
DETAILED DESCRIPTION
Examples of the thermosetting resin used in the composition of the present invention include various kinds of epoxy resins, such as glycidyl ethers, glycidyl esters, glycidyl amines, linear-aliphatic epoxide~~ and alicyclic epoxides, and modified epoxy resins derived the:refrom..
The preferred epoxy-based materials in the composition of the present invention contain at least two 1,2-epoxide groups per molecule. These materials are also referred to as polyepoxides. In general, the eF~oxy equivalent weight can range from about 140 to about 750. These polyepoxides may be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic, or heterocyclic. They may contain substituents such as halogens, hydroxyl groups, and ether groups.
Suitable classes of polyepoaides include epoxy ethers obtained by reacting an epihalohydrin such as epichlorohydrin with a polyphenol in the presence of an alkali. Suitable polyphenols include resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)-2,2-propane (i. e.; Bisphenol A), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyphenyl)-1,1-ethane, bis(2-hydroxyphenyl)-methane, 4,4-dihydroxybenzophenone, and 1,5-dihydroxynaphthalene. The polyglycidyl ether, particularly the diglycidyl ether, of Bisphenol A is preferred.
Other suitable polyepoxides include polyglycidyl ethers of polyhydric alcohols. These compounds may be derived from polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane, and pentaerythritol. These compounds may also be derived from 23 ~3~~38 polymeric polyols such as polypropylene glycol and hydroxyl functional polyesters.
Examples of other suitable polyepoxides include polyglycidyl esters of polycarboxylic acids. These compounds may be formed by reacting epichlorohydrin or another epoxy material with an aliphatic or aromatic polycarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, malefic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or trimellitic acid. Dimerized unsaturated fatty acids containing about 36 carbon atoms (Dimer Acid) may also be used in the formation of these polyglycidyl esters of polycarboxylic.
acids. Preferred are epoxy-terminated adducts of dimer fatty acids and epoxy-terminated adducts of polyesters including those IS containing sebacic, azelaic, and/or dodecanedioic acids.
Other suitable polyepoxide.c include epoxy novolac resins.
These resins are obtained by reacting an epihalohydrin with the condensation product of aldehyde and monohydric or polyhydric phenols. A typical example is the reaction product of epichlorohydrin with a phenol-formaldehyde condensate.
The polyepoxides can be partially defunctionalized by carboxylic acids, alcohol, water, phenols, mercaptans, or other active hydrogen-containing compounds to yield hydroxyl-containing polyepoxides if desired.
Although the curable compo:cition usually comprises a mixture of two or more epoxide group-containing materials selected from the group consisting of diglycidyl ether of Bisphenol A, diglycidyl ether of polypropylene glycol, and glycidyl ether-terminated adducts of diepoxides and diacid-containing moieties, monoepoxides can be used to modify the viscosity of the composition and modulate the rate of cure.
Typically, the curable composition of the present invention contains from about 40 to about 80 percent of epoxide group-containing material(s), preferably from about 50 to 65 percent, based upon total weight of the composition.
AM~NDED SHEET
I~EA/EP
_a,_ The expandable microspheres in the composition of the present invention usually comprise a thermoplastic polymeric shell containing a volatile liquid propellant. Upon heating to a temperature above the softening point of the polymer and the boiling point of the propellant, the spheres expand to as much as five times their original diameter. The polymeric shell may be a polymer or copolymer of, for example, vinyl chloride, vinylidene chloride, acrylonitri.le, methyl methacrylate, styrene, or mixtures thereof. ~~uitable propellants include freons, such as trichlorofluoromethane, hydrocarbons, such as n pentane, isopentane, neopentane, butane, isobutane, or other conventional propellants.
The expandable microspheres prevent shrinkage of the composition during cure, allowing the substrate to which the IS composition is applied to retain its surface shape and appearance. When the curable composition is applied to the under surface of a substrate and cured, the expandable microspheres are advantageous in that they do not cause the composition to fall or blow off the substrate, unlike foaming agents. The foaming action of foaming agents is often forceful enough to blow a reinforcing composition off the underside of a substrate during cure.
Expandable microspheres su~~h as those described in U. S.
Patent numbers 4,005,033 and 5,1.55,138 are suitable for use in the composition of the present invention. Particularly preferred expandable microspheres are available from Casco Nobel AB under the name EXPANCELT'''.
The expandable microspheres are present in an amount ranging from 1 to 7 percent by weight, preferably 2 to 5 percent by weight, based upon total weight of the composition.
The particulate reinforcing agent in the composition of the present invention are millec! glass fibers, milled carbon fibers, or mixtures thereof. Tree milled fibers are typically about 1/16 inch (1.59 mm) in length. The reinforcing agent is present in an amount ranging from 8 to 40 percent by weight, WO 95/27000 21 ~3 6 6 ~ 8 PCT/US95103474 preferably 15 to 30 percent by weight, based upon total weight of the composition.
The composition of the present invention may also contain a latent crosslinking agent such as boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride triethylamine complex, boron trifluoride pyridine complex, boron trifluori.de benzyldimethylamine complex, boron trifluoride benzylamine, and boron trifluoride etherate.
By latent is meant that these materials are inactive until the application of heat. Mixtures of crosslinking agents may also be used.
The crosslinking agent is typically present in an amount ranging from about 1 to about 13 percent by weight, preferably from about 3 to about 8 percent t>y weight, based upon total weight of the curable composition.
The curable composition of 'the present invention may also contain one or more catalysts that are capable of initiating epoxy cure at moderate temperatures. Typically these are dihydrazides of dibasic acids such as adipic and sebacic acids.
Sebacic dihydrazide is the preferred catalyst. Other suitable catalysts include dicyandiamide a.nd the reaction product of (i) an organic polyisocyanate, preferably a diisocyanate, with a diamine containing a primary or secondary amine group and a tertiary amine group, and (ii) an. acid functional compound, preferably a polyphenol. The equivalent ratio of polyisocyanate to diamine to acid functional compound is generally about 1:1:3 to 1:1:4. The adduct of isophorone diisocyanate and dimethylaminopropyl amine and Bisphenol A is preferred.
The catalysts, when present, are typically present in an amount ranging from about 0.5 to about 5 percent by weight, preferably from about 1 to about 2.5 percent by weight, based upon total weight of the curable composition.
The curable composition of l~he present invention may also contain a variety of optional additives including pigments such as carbon black, fillers such as calcium oxide, aluminum powder, _.,_ and wollastonite, and thixotropes such as bentonite clay. The composition may be prepared as a one-package composition.
The optional additives, when present, are typically present in an amount ranging from about 5 to about 30 percent by weight, preferably from about 10 to about 20 percent by weight, based upon total weight of the curable composition.
The substrates to which the curable compositions of the present invention are generally applied may be thin rigid sheets or plates such as thin metal plates including steel plates, aluminum plates, copper plates, and stainless steel plates, and thin plastic plates such as fiberglass reinforced polyester plates, and other plastic plate:.. Steel plates are preferred. .
The thin metal rigid plates or sheets generally have a thickness of about 0.3 to 2 mm.
The curable composition of the present.invention may be applied to the substrate in a number of ways including spraying, extrusion, or by hand with a blade. Spraying is the preferred method of application because of ease of application and consistent thickness of the applied layer. The applied layer generally has a thickness of about 40 to 240 mils (1 to 6 mm) before curing and 80 to 360 mils (2 to 9 mm) after curing.
The composition is typical7.y cured by heating to a temperature of about 300°F (149°C) to about 375°F
(191°C), preferably about 325°F (163°C) for a period ranging from about 20 minutes to 1 hour.
The curable composition of the present invention is preferably used in a method for :reinforcing thin rigid plates or sheets. Such a method would comprise applying the composition to the thin rigid plate or sheet as described above and curing the composition while it is in contact with only the rigid plate or sheet. When used to reinforce. a thin rigid plate or sheet, the composition is applied to once side of the plate or sheet and is adhered to no other surface; t=hat is, it is not serving as an adhesive composition. In hemmed fixtures, upon expansion during AMENDED SH~-t PEACE r' - Et -cure the composition may touch and adhere to another surface.
This is incidental, however.
The invention will further be described by reference to the following examples. Unless otherwise indicated, all parts are by weight.
The following examples (1 'to 3) illustrate the effect of fiber reinforcement and expandable microspheres on flexural strength and readthrough.
Reinforcing compositions were prepared from the following mixture of ingredients:
Ex~lp 1 a : 1 2.
I
di ncrre ent 39.4 39.4 39.4 EPON*8281 Epoxy ester2 8.12 8.12 8.12 EPON Dimer acid3 4.06 4.06 4.06 CARDOLITE*, NC-51344.06 4.06 4.06 BENTONE*275 4.87 4.87 4.87 CABOSIL* TS-7206 0.61 0.61 0.61 Dicyandiamide 3.05 3.05 3.05 Sebacic.dihydrazide0.81 0.81 0.81 Milled glass fiber?16.25 - 8.125 Milled carbon fiber- 16.25 8.125 Calcium oxide ~ 2.44 2.44 2.44 VANSIL*W-109 11.78 11.78 11.78 EXPANCEL 051 DU10 2.84 2.84 2.84 EXPANCEL 091 DU11 0.81 0.81 0.81 Carbon black 0.08 0.08 0.08 Catalystl2 0.81 0.81 0.81 lPolyglycidyl ether of Bisphenol A, available from Shell Oil and Chemical Co.
2Diglycidyl ether polyester formed from reacting a carboxylic acid terminated polyester (Diethylene sebacate dodecanedioate) with an excess of EPON 828.
* Trade-mark _ g _ 3Adduct of Dimer Fatty acid and EPON 828 in a 1 to 5 mole ratio.
4Cashew oil-derived monoepoxide available from Cardolite Corporation SThixotropic clay, available from NL Industries 6Hydrophobic fumed silica, available from Cabot Corporation 7Available as 739DD from Owens-Corning Fiberglas Corp.
BAvailable as PANEXTMMF33 from Zoltek Corp., Carbon and Graphite Div.
9Wollastonite clay available from R. T. Vanderbilt Co., Inc.
10,11Expandable microspheres, available from Nobel Industries l2Adduct of dimethylaminopropyl amine and isophorone diisocyanate and Bisphenol A in an equivalent ratio of about 1:1:3.75.
BENTONE 27 was premixed with EPON 828 and heated to about 100°C.
Under shear mixing, the epoxy ester, EPON-dimer acid adduct and the CARDOLITE NC-513 were added. With the exception of the dicyandiamide, sebacic dihydrazide, and catalyst (12), the other ingredients were then added in order under a high rate of shear.
The mixture was cooled to less than 35°C and the catalysts were added under a moderate amount. of shear. The mixture was degassed under reduced pressure using gentle mixing.
The compositions of Examplsa 1 to 3 were evaluated for deflection, readthrough, and flexural strength as follows:
1) Deflection: A film of about 50 mils (1.27 mm)in thickness and 1 inch (2.54 cm) in width of the composition was drawn onto a flat, oiled 1x6 inch (2.54x15.24 cm) strip of metal. The strip was placed in an oven at 325 to 350°F (163 to 177°C) for 20 to 30 minutes. The strip was cooled to ambient temperature and placed on a flat surface. Then one end of the strip was pressed down and the distance that the other- end lifted from the horizontal was measured.
2) Readthrough: A film of about.50 mils (1.27 mm) of the composition about 2 inches (5.08 cm) in length and 1 inch (2.54 cm)in width was drawn onto a 4x7.2 inch (10.16x30.48 cm) strip of metal. The strip was placed in an oven at 325 to 350°F (163 to 177°C) for 20 to 30 minutes. The strip was cooled to ambient temperature and observed at eye level to assess the occurrence of wrinkling above the cured coe.ting. The strip was further coated with glossy black paint if necessary to aid visibility of any wrinkling. A rating was assigned from 0 ("perfect") to 5 ("worst").
3) Flexural strength: A lxEi inch (2.54x15.24 cm) strip was prepared as for the Deflection test above and then placed in a jig on an Instron machine so that the edges were supported on each end while a blunt wedge was positioned in the middle, -nearly touching the metal. On activation, the wedge flexed the reinforced metal until failure of the coating. The maximum load needed to induce failure was recorded.
The results are reported in. Table I below:
E pEp SHEd''~
M IP~~Ep 21 ~~6638 - 1.1 -Table I
E 3.
Pronertv:
Viscosity 0.5 rpml762,808 1,113,542 1,066,358 Viscosity 1.0 rpm 472,626 747,080 676,304 Thixotropic ratio21.61 1.5 1.58 Deflection, inches0.098 0.048 0.20 (mm) (2.49) (1.22) (5.04) Flexural strength,13 24 15.5 pounds, (kg) (28.6) (52.8) (34.1) room temperature Flexural strength,14.5 22.5 17.5 180 F (82.8 C) (31.9) (49.5) ~ (38.5) Readthrough rating1-1.5 2-2.5 1 Metal thickness, 32 32 32 mils (mm) (0.81) (0.81) (0.81) Cured coating 148 148 163 thickness, mils (3.76) (3.76) (4.14) (mm lMeasured with a Brookfield cone and plate viscometer, expressed in centipoise.
2Ratio of viscosity at 0.5 rpm to viscosity at 1.0 rpm.
ANfENDED SHEE' I p E~:/E P
FOR REINFORCING THIN RIGID PLATES
FIELD OF THE INVENTION
The present invention relates to sprayable, curable compositions and their use for rssinforcing thin rigid plates or sheets, and to the reinforced plate or sheet itself.
BACKGROUND OF THE INVENTION
The use of thin gauge rigid plates or sheets in automobile manufacture has been greatly acceslerated due to improved corrosion protection, lighter weight, easy formability and lower cost. This practice has left certain parts of a car more vulnerable to easy denting and damage. Historically, either a reinforcing plate is welded or bonded to these areas, or a precut patch of epoxy impregnated glass fibers is attached.
Reinforcing compositions prepared from thermosetting resins, particularly epoxy resins, used to reinforce thin rigid sheets used in automobiles exhibit a number of advantages including strength, adhesion, and corrosion resistance. One distinct disadvantage is that many thermosetting resins, particularly epoxy based compositions, deform the substrates to which they bond due to shrinkage during curing.
In the automobile industry this deformation is of particular concern where the appearance of the substrate is critical. This substrate deformation necessitates additional costs in labor and materials in order to restore the intended appearance of the substrate.
U. S. Patent 5,151,327 discloses an adhesive sheet for reinforcing thin rigid plates. :>uch adhesive sheets comprise several resinous layers and need to undergo a sizing treatment before application to the thin rugid plates. The adhesive .. 2186638 sheets contain foaming agents to prevent shrinkage during cure. ' Application is by lamination.
U. S. Patent 4,739,019 discloses an adhesive composition for use in automotive applications. This composition contains an epoxide and a thermoplastic polyester. Such a composition loses its strength when heated to curing temperatures because the viscosity of the thermoplastic polyester decreases, and when applied to the underside of a substrate, the composition tends to sag or fall off the substrate during heating.
U. S. Patent 5,155,138 disc: loses the use of expandable thermoplastic microspheres in polymers and paints. It is also known to use expandable microspheres in car underbody coatings .
and sealants. (See Nobel Industries Technical Bulletin no. 21).' There is no teaching of the use of such microspheres in thin panel reinforcing compositions.
It is desirable to develop a sprayable curable thermosetting composition, for convenient application, which when used to reinforce thin rigid plates used in automobile manufacture exhibits excellent physical properties and reduced shrinkage.
SUI~lARY OF 7.'>:IE INVENTION
In accordance with the present invention there is provided a curable, sprayable composition comprising: (i) a thermosetting resinous composition; (ii) expandable microspheres; and (iii) a particulate reinforcing material. selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof.
The present invention also provides a method of reinforcing thin rigid plates comprising applying the composition described above to one side of a rigid plate, followed by curing the composition, and to the reinforced rigid plate itself comprising a rigid plate and the cured composition AMENDED SHEET
IPEAIEP
WO 95/27000 218 6 6 3 8 pCT~S95/03474 described above primarily adhered to one side of the rigid plate.
DETAILED DESCRIPTION
Examples of the thermosetting resin used in the composition of the present invention include various kinds of epoxy resins, such as glycidyl ethers, glycidyl esters, glycidyl amines, linear-aliphatic epoxide~~ and alicyclic epoxides, and modified epoxy resins derived the:refrom..
The preferred epoxy-based materials in the composition of the present invention contain at least two 1,2-epoxide groups per molecule. These materials are also referred to as polyepoxides. In general, the eF~oxy equivalent weight can range from about 140 to about 750. These polyepoxides may be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic, or heterocyclic. They may contain substituents such as halogens, hydroxyl groups, and ether groups.
Suitable classes of polyepoaides include epoxy ethers obtained by reacting an epihalohydrin such as epichlorohydrin with a polyphenol in the presence of an alkali. Suitable polyphenols include resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)-2,2-propane (i. e.; Bisphenol A), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyphenyl)-1,1-ethane, bis(2-hydroxyphenyl)-methane, 4,4-dihydroxybenzophenone, and 1,5-dihydroxynaphthalene. The polyglycidyl ether, particularly the diglycidyl ether, of Bisphenol A is preferred.
Other suitable polyepoxides include polyglycidyl ethers of polyhydric alcohols. These compounds may be derived from polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane, and pentaerythritol. These compounds may also be derived from 23 ~3~~38 polymeric polyols such as polypropylene glycol and hydroxyl functional polyesters.
Examples of other suitable polyepoxides include polyglycidyl esters of polycarboxylic acids. These compounds may be formed by reacting epichlorohydrin or another epoxy material with an aliphatic or aromatic polycarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, malefic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or trimellitic acid. Dimerized unsaturated fatty acids containing about 36 carbon atoms (Dimer Acid) may also be used in the formation of these polyglycidyl esters of polycarboxylic.
acids. Preferred are epoxy-terminated adducts of dimer fatty acids and epoxy-terminated adducts of polyesters including those IS containing sebacic, azelaic, and/or dodecanedioic acids.
Other suitable polyepoxide.c include epoxy novolac resins.
These resins are obtained by reacting an epihalohydrin with the condensation product of aldehyde and monohydric or polyhydric phenols. A typical example is the reaction product of epichlorohydrin with a phenol-formaldehyde condensate.
The polyepoxides can be partially defunctionalized by carboxylic acids, alcohol, water, phenols, mercaptans, or other active hydrogen-containing compounds to yield hydroxyl-containing polyepoxides if desired.
Although the curable compo:cition usually comprises a mixture of two or more epoxide group-containing materials selected from the group consisting of diglycidyl ether of Bisphenol A, diglycidyl ether of polypropylene glycol, and glycidyl ether-terminated adducts of diepoxides and diacid-containing moieties, monoepoxides can be used to modify the viscosity of the composition and modulate the rate of cure.
Typically, the curable composition of the present invention contains from about 40 to about 80 percent of epoxide group-containing material(s), preferably from about 50 to 65 percent, based upon total weight of the composition.
AM~NDED SHEET
I~EA/EP
_a,_ The expandable microspheres in the composition of the present invention usually comprise a thermoplastic polymeric shell containing a volatile liquid propellant. Upon heating to a temperature above the softening point of the polymer and the boiling point of the propellant, the spheres expand to as much as five times their original diameter. The polymeric shell may be a polymer or copolymer of, for example, vinyl chloride, vinylidene chloride, acrylonitri.le, methyl methacrylate, styrene, or mixtures thereof. ~~uitable propellants include freons, such as trichlorofluoromethane, hydrocarbons, such as n pentane, isopentane, neopentane, butane, isobutane, or other conventional propellants.
The expandable microspheres prevent shrinkage of the composition during cure, allowing the substrate to which the IS composition is applied to retain its surface shape and appearance. When the curable composition is applied to the under surface of a substrate and cured, the expandable microspheres are advantageous in that they do not cause the composition to fall or blow off the substrate, unlike foaming agents. The foaming action of foaming agents is often forceful enough to blow a reinforcing composition off the underside of a substrate during cure.
Expandable microspheres su~~h as those described in U. S.
Patent numbers 4,005,033 and 5,1.55,138 are suitable for use in the composition of the present invention. Particularly preferred expandable microspheres are available from Casco Nobel AB under the name EXPANCELT'''.
The expandable microspheres are present in an amount ranging from 1 to 7 percent by weight, preferably 2 to 5 percent by weight, based upon total weight of the composition.
The particulate reinforcing agent in the composition of the present invention are millec! glass fibers, milled carbon fibers, or mixtures thereof. Tree milled fibers are typically about 1/16 inch (1.59 mm) in length. The reinforcing agent is present in an amount ranging from 8 to 40 percent by weight, WO 95/27000 21 ~3 6 6 ~ 8 PCT/US95103474 preferably 15 to 30 percent by weight, based upon total weight of the composition.
The composition of the present invention may also contain a latent crosslinking agent such as boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride triethylamine complex, boron trifluoride pyridine complex, boron trifluori.de benzyldimethylamine complex, boron trifluoride benzylamine, and boron trifluoride etherate.
By latent is meant that these materials are inactive until the application of heat. Mixtures of crosslinking agents may also be used.
The crosslinking agent is typically present in an amount ranging from about 1 to about 13 percent by weight, preferably from about 3 to about 8 percent t>y weight, based upon total weight of the curable composition.
The curable composition of 'the present invention may also contain one or more catalysts that are capable of initiating epoxy cure at moderate temperatures. Typically these are dihydrazides of dibasic acids such as adipic and sebacic acids.
Sebacic dihydrazide is the preferred catalyst. Other suitable catalysts include dicyandiamide a.nd the reaction product of (i) an organic polyisocyanate, preferably a diisocyanate, with a diamine containing a primary or secondary amine group and a tertiary amine group, and (ii) an. acid functional compound, preferably a polyphenol. The equivalent ratio of polyisocyanate to diamine to acid functional compound is generally about 1:1:3 to 1:1:4. The adduct of isophorone diisocyanate and dimethylaminopropyl amine and Bisphenol A is preferred.
The catalysts, when present, are typically present in an amount ranging from about 0.5 to about 5 percent by weight, preferably from about 1 to about 2.5 percent by weight, based upon total weight of the curable composition.
The curable composition of l~he present invention may also contain a variety of optional additives including pigments such as carbon black, fillers such as calcium oxide, aluminum powder, _.,_ and wollastonite, and thixotropes such as bentonite clay. The composition may be prepared as a one-package composition.
The optional additives, when present, are typically present in an amount ranging from about 5 to about 30 percent by weight, preferably from about 10 to about 20 percent by weight, based upon total weight of the curable composition.
The substrates to which the curable compositions of the present invention are generally applied may be thin rigid sheets or plates such as thin metal plates including steel plates, aluminum plates, copper plates, and stainless steel plates, and thin plastic plates such as fiberglass reinforced polyester plates, and other plastic plate:.. Steel plates are preferred. .
The thin metal rigid plates or sheets generally have a thickness of about 0.3 to 2 mm.
The curable composition of the present.invention may be applied to the substrate in a number of ways including spraying, extrusion, or by hand with a blade. Spraying is the preferred method of application because of ease of application and consistent thickness of the applied layer. The applied layer generally has a thickness of about 40 to 240 mils (1 to 6 mm) before curing and 80 to 360 mils (2 to 9 mm) after curing.
The composition is typical7.y cured by heating to a temperature of about 300°F (149°C) to about 375°F
(191°C), preferably about 325°F (163°C) for a period ranging from about 20 minutes to 1 hour.
The curable composition of the present invention is preferably used in a method for :reinforcing thin rigid plates or sheets. Such a method would comprise applying the composition to the thin rigid plate or sheet as described above and curing the composition while it is in contact with only the rigid plate or sheet. When used to reinforce. a thin rigid plate or sheet, the composition is applied to once side of the plate or sheet and is adhered to no other surface; t=hat is, it is not serving as an adhesive composition. In hemmed fixtures, upon expansion during AMENDED SH~-t PEACE r' - Et -cure the composition may touch and adhere to another surface.
This is incidental, however.
The invention will further be described by reference to the following examples. Unless otherwise indicated, all parts are by weight.
The following examples (1 'to 3) illustrate the effect of fiber reinforcement and expandable microspheres on flexural strength and readthrough.
Reinforcing compositions were prepared from the following mixture of ingredients:
Ex~lp 1 a : 1 2.
I
di ncrre ent 39.4 39.4 39.4 EPON*8281 Epoxy ester2 8.12 8.12 8.12 EPON Dimer acid3 4.06 4.06 4.06 CARDOLITE*, NC-51344.06 4.06 4.06 BENTONE*275 4.87 4.87 4.87 CABOSIL* TS-7206 0.61 0.61 0.61 Dicyandiamide 3.05 3.05 3.05 Sebacic.dihydrazide0.81 0.81 0.81 Milled glass fiber?16.25 - 8.125 Milled carbon fiber- 16.25 8.125 Calcium oxide ~ 2.44 2.44 2.44 VANSIL*W-109 11.78 11.78 11.78 EXPANCEL 051 DU10 2.84 2.84 2.84 EXPANCEL 091 DU11 0.81 0.81 0.81 Carbon black 0.08 0.08 0.08 Catalystl2 0.81 0.81 0.81 lPolyglycidyl ether of Bisphenol A, available from Shell Oil and Chemical Co.
2Diglycidyl ether polyester formed from reacting a carboxylic acid terminated polyester (Diethylene sebacate dodecanedioate) with an excess of EPON 828.
* Trade-mark _ g _ 3Adduct of Dimer Fatty acid and EPON 828 in a 1 to 5 mole ratio.
4Cashew oil-derived monoepoxide available from Cardolite Corporation SThixotropic clay, available from NL Industries 6Hydrophobic fumed silica, available from Cabot Corporation 7Available as 739DD from Owens-Corning Fiberglas Corp.
BAvailable as PANEXTMMF33 from Zoltek Corp., Carbon and Graphite Div.
9Wollastonite clay available from R. T. Vanderbilt Co., Inc.
10,11Expandable microspheres, available from Nobel Industries l2Adduct of dimethylaminopropyl amine and isophorone diisocyanate and Bisphenol A in an equivalent ratio of about 1:1:3.75.
BENTONE 27 was premixed with EPON 828 and heated to about 100°C.
Under shear mixing, the epoxy ester, EPON-dimer acid adduct and the CARDOLITE NC-513 were added. With the exception of the dicyandiamide, sebacic dihydrazide, and catalyst (12), the other ingredients were then added in order under a high rate of shear.
The mixture was cooled to less than 35°C and the catalysts were added under a moderate amount. of shear. The mixture was degassed under reduced pressure using gentle mixing.
The compositions of Examplsa 1 to 3 were evaluated for deflection, readthrough, and flexural strength as follows:
1) Deflection: A film of about 50 mils (1.27 mm)in thickness and 1 inch (2.54 cm) in width of the composition was drawn onto a flat, oiled 1x6 inch (2.54x15.24 cm) strip of metal. The strip was placed in an oven at 325 to 350°F (163 to 177°C) for 20 to 30 minutes. The strip was cooled to ambient temperature and placed on a flat surface. Then one end of the strip was pressed down and the distance that the other- end lifted from the horizontal was measured.
2) Readthrough: A film of about.50 mils (1.27 mm) of the composition about 2 inches (5.08 cm) in length and 1 inch (2.54 cm)in width was drawn onto a 4x7.2 inch (10.16x30.48 cm) strip of metal. The strip was placed in an oven at 325 to 350°F (163 to 177°C) for 20 to 30 minutes. The strip was cooled to ambient temperature and observed at eye level to assess the occurrence of wrinkling above the cured coe.ting. The strip was further coated with glossy black paint if necessary to aid visibility of any wrinkling. A rating was assigned from 0 ("perfect") to 5 ("worst").
3) Flexural strength: A lxEi inch (2.54x15.24 cm) strip was prepared as for the Deflection test above and then placed in a jig on an Instron machine so that the edges were supported on each end while a blunt wedge was positioned in the middle, -nearly touching the metal. On activation, the wedge flexed the reinforced metal until failure of the coating. The maximum load needed to induce failure was recorded.
The results are reported in. Table I below:
E pEp SHEd''~
M IP~~Ep 21 ~~6638 - 1.1 -Table I
E 3.
Pronertv:
Viscosity 0.5 rpml762,808 1,113,542 1,066,358 Viscosity 1.0 rpm 472,626 747,080 676,304 Thixotropic ratio21.61 1.5 1.58 Deflection, inches0.098 0.048 0.20 (mm) (2.49) (1.22) (5.04) Flexural strength,13 24 15.5 pounds, (kg) (28.6) (52.8) (34.1) room temperature Flexural strength,14.5 22.5 17.5 180 F (82.8 C) (31.9) (49.5) ~ (38.5) Readthrough rating1-1.5 2-2.5 1 Metal thickness, 32 32 32 mils (mm) (0.81) (0.81) (0.81) Cured coating 148 148 163 thickness, mils (3.76) (3.76) (4.14) (mm lMeasured with a Brookfield cone and plate viscometer, expressed in centipoise.
2Ratio of viscosity at 0.5 rpm to viscosity at 1.0 rpm.
ANfENDED SHEE' I p E~:/E P
Claims (19)
1. A curable, sprayable composition comprising:
(i) a thermosetting resinous composition comprising an epoxy-based material containing at least two 1,2-epoxide groups per molecule and a catalyst to initiate cure of the epoxy-based material;
(ii) from about 1 to about 7 percent by weight based upon total weight of the composition of expandable microspheres which expand during curing of the composition so that the composition with expanded microspheres overcomes deformation of the substrate to which the composition is applied, wherein said deformation is due to shrinkage, and wherein the composition does not fall or blow of the substrate during curing; and (iii) about 8 to about 40 percent by weight based upon total weight of the composition of a particulate reinforcing material selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof.
(i) a thermosetting resinous composition comprising an epoxy-based material containing at least two 1,2-epoxide groups per molecule and a catalyst to initiate cure of the epoxy-based material;
(ii) from about 1 to about 7 percent by weight based upon total weight of the composition of expandable microspheres which expand during curing of the composition so that the composition with expanded microspheres overcomes deformation of the substrate to which the composition is applied, wherein said deformation is due to shrinkage, and wherein the composition does not fall or blow of the substrate during curing; and (iii) about 8 to about 40 percent by weight based upon total weight of the composition of a particulate reinforcing material selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof.
2. The curable composition of claim 1 wherein the epoxy-based material comprises a polyglycidyl ether of Bisphenol A.
3. The curable composition of claim 1 wherein the epoxy-based material comprises a mixture of two or more epoxy-based materials selected from the group consisting of epoxy-terminated dimer acids and epoxy-terminated polyesters.
4. The curable composition of claim 1 wherein the catalyst is selected from the group consisting of dihydrazides of dibasic acids and dicyandiamide and the reaction product of (i) an organic polyisocyanate with a diamine containing a primary or secondary amine group and a tertiary amine group and (ii) an acid functional compound.
5. The curable composition of claim 1 wherein the epoxy-based material is present in an amount ranging from 50 to 65 percent by weight based upon total weight of the, composition.
6. The curable composition of claim 1 wherein the catalyst is present in an amount ranging from 0.5 to 5 percent by weight based upon total weight of the composition.
7. The curable composition of claim 1 wherein the expandable microspheres comprise thermoplastic polymeric shells containing a volatile liquid propellant.
8. The curable composition of claim 1 wherein the expandable microspheres are present in an amount ranging from 2 to 5 percent by weight based upon total weight of the composition.
9. The curable composition of claim 1 wherein the particulate reinforcing material is about 1/16 inch (1.59 mm) in length.
10. The curable composition of claim 1 wherein the particulate reinforcing material is present in an amount ranging from 15 to 30 percent by weight based upon total weight of the composition.
11. A method for reinforcing thin rigid plates comprising:
(A) spraying the composition having:
(i) a thermosetting resinous composition comprising an epoxy-based material containing at least two 1,2-epoxide groups per molecule and a catalyst to initiate cure of the epoxy-based material;
(ii) expandable microspheres; and (iii) a particulate reinforcing material selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof to one side of the rigid plate, and (B) curing said composition while only in contact with said rigid plate.
(A) spraying the composition having:
(i) a thermosetting resinous composition comprising an epoxy-based material containing at least two 1,2-epoxide groups per molecule and a catalyst to initiate cure of the epoxy-based material;
(ii) expandable microspheres; and (iii) a particulate reinforcing material selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof to one side of the rigid plate, and (B) curing said composition while only in contact with said rigid plate.
12. The method of claim 11 wherein the thin rigid plate is selected from the group consisting of steel plates, aluminum plates, copper plates, stainless steel plates, and plastic plates.
13. The method of claim 11 wherein the composition, before curing, has a thickness of about 1 to 6 mm.
14. A reinforced thin rigid plate comprising the rigid plate and the cured composition of claim 1 adhered primarily to one side of the rigid plate.
15. The reinforced thin rigid plate of claim 14 wherein the thin rigid plate is selected from the group consisting of steel plates, aluminum plates, copper plates, stainless steel plates, and plastic plates.
16. The reinforced thin rigid plate of claim 14 wherein the cured composition has a thickness of about 2 to 9 mm.
17. A curable, sprayable composition of claim 1, wherein (i) the thermosetting resinous composition is comprised of an epoxy-based material containing at least two 1,2-epoxide groups per molecule wherein the epoxy-based material is present in an amount ranging from 40 to about 80 percent by weight based upon total weight of the curable composition, and a catalyst to initiate cure of the epoxy-based material;
(ii) the expandable microspheres are comprised of thermoplastic polymeric shells containing a volatile liquid propellant, wherein the expandable microspheres are present in an amount ranging from 1 to 7 percent by weight based upon total weight of the curable composition and which expand during curing of the composition to as much as five times their diameter; and (iii) the particulate reinforcing material is selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof, wherein the particulate reinforcing material is present in an amount ranging from 8 to about 40 percent by weight based upon total weight of the curable composition.
(ii) the expandable microspheres are comprised of thermoplastic polymeric shells containing a volatile liquid propellant, wherein the expandable microspheres are present in an amount ranging from 1 to 7 percent by weight based upon total weight of the curable composition and which expand during curing of the composition to as much as five times their diameter; and (iii) the particulate reinforcing material is selected from the group consisting of milled glass fibers, milled carbon fibers, and mixtures thereof, wherein the particulate reinforcing material is present in an amount ranging from 8 to about 40 percent by weight based upon total weight of the curable composition.
18. The curable composition of claim 17 wherein the epoxy-based material comprises a mixture of two or more epoxy-based materials selected from the group consisting of polyglycidyl ethers of polyhydric alcohols and polyglycidyl esters of polycarboxylic acids.
19. The curable composition of claim 17 wherein the epoxy-based material is present from about 50 to 65 percent by weight based upon total weight of the composition, the expandable microspheres are present in an amount ranging from about 2 to about 5 percent by weight, and the particulate reinforcing material is present in an amount ranging from about 15 to 30 percent by weight where all percents by weight are based upon the total weight of the composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/220,656 US5470886A (en) | 1994-03-31 | 1994-03-31 | Curable, sprayable compositions for reinforced thin rigid plates |
| US08/220,656 | 1994-03-31 | ||
| PCT/US1995/003474 WO1995027000A1 (en) | 1994-03-31 | 1995-03-21 | Curable, sprayable compositions for reinforcing thin rigid plates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2186638A1 CA2186638A1 (en) | 1995-10-12 |
| CA2186638C true CA2186638C (en) | 2000-05-16 |
Family
ID=22824417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002186638A Expired - Fee Related CA2186638C (en) | 1994-03-31 | 1995-03-21 | Curable, sprayable compositions for reinforcing thin rigid plates |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US5470886A (en) |
| EP (1) | EP0753023B1 (en) |
| JP (1) | JP2912019B2 (en) |
| KR (1) | KR100186923B1 (en) |
| AT (1) | ATE183532T1 (en) |
| CA (1) | CA2186638C (en) |
| DE (1) | DE69511538T2 (en) |
| ES (1) | ES2138196T3 (en) |
| MX (1) | MX9604432A (en) |
| WO (1) | WO1995027000A1 (en) |
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| SE9003600L (en) * | 1990-11-12 | 1992-05-13 | Casco Nobel Ab | EXPANDABLE THERMOPLASTIC MICROSPHERES AND PROCEDURES FOR PRODUCING THEREOF |
| JP3124301B2 (en) * | 1991-01-11 | 2001-01-15 | 帝人株式会社 | Manufacturing method of composite molded products |
| IT1263866B (en) * | 1993-03-31 | 1996-09-04 | Giancarlo Ferrari | COMPOSITION OF PROTECTIVE COVERING FOR UNDERBODY OF VEHICLES |
-
1994
- 1994-03-31 US US08/220,656 patent/US5470886A/en not_active Expired - Fee Related
-
1995
- 1995-03-21 CA CA002186638A patent/CA2186638C/en not_active Expired - Fee Related
- 1995-03-21 MX MX9604432A patent/MX9604432A/en not_active IP Right Cessation
- 1995-03-21 JP JP7525730A patent/JP2912019B2/en not_active Expired - Lifetime
- 1995-03-21 AT AT95914129T patent/ATE183532T1/en not_active IP Right Cessation
- 1995-03-21 EP EP95914129A patent/EP0753023B1/en not_active Revoked
- 1995-03-21 DE DE69511538T patent/DE69511538T2/en not_active Expired - Fee Related
- 1995-03-21 ES ES95914129T patent/ES2138196T3/en not_active Expired - Lifetime
- 1995-03-21 WO PCT/US1995/003474 patent/WO1995027000A1/en not_active Application Discontinuation
- 1995-03-21 KR KR1019960705442A patent/KR100186923B1/en not_active IP Right Cessation
- 1995-06-07 US US08/475,475 patent/US5712317A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5470886A (en) | 1995-11-28 |
| EP0753023A1 (en) | 1997-01-15 |
| MX9604432A (en) | 1997-12-31 |
| ATE183532T1 (en) | 1999-09-15 |
| DE69511538T2 (en) | 2000-05-04 |
| KR100186923B1 (en) | 1999-05-15 |
| DE69511538D1 (en) | 1999-09-23 |
| CA2186638A1 (en) | 1995-10-12 |
| WO1995027000A1 (en) | 1995-10-12 |
| JP2912019B2 (en) | 1999-06-28 |
| EP0753023B1 (en) | 1999-08-18 |
| ES2138196T3 (en) | 2000-01-01 |
| KR970702319A (en) | 1997-05-13 |
| US5712317A (en) | 1998-01-27 |
| JPH09505109A (en) | 1997-05-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |