CA1051726A - Two-part primer system for frp bonding - Google Patents
Two-part primer system for frp bondingInfo
- Publication number
- CA1051726A CA1051726A CA232,041A CA232041A CA1051726A CA 1051726 A CA1051726 A CA 1051726A CA 232041 A CA232041 A CA 232041A CA 1051726 A CA1051726 A CA 1051726A
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- treating agent
- isocyanate
- polyester
- treating
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Abstract
TWO-PART PRIMER SYSTEM FOR FRP BONDING
Abstract of the Disclosure An improved adhesion between polyester compositions using the isocyanate-type adhesive is obtained by first treating the polyisocyanate composition with a first and a second treating agent without regard to sequence where the first treating agent is an organic polyisocyanate and the second treating agent is a tertiary amine.
Abstract of the Disclosure An improved adhesion between polyester compositions using the isocyanate-type adhesive is obtained by first treating the polyisocyanate composition with a first and a second treating agent without regard to sequence where the first treating agent is an organic polyisocyanate and the second treating agent is a tertiary amine.
Description
~ ~ 5~7J~ ~
This invention relates to a method of obtaining im-proved adhesion between polyester compositions per se and/or metals. More specifically~ this invention relates to a me-thod of treating the sur~ace of a polyester composition which may contain glass ~lber reinforcement to enh~nce the ef'fec-tiveness of an isocyanate adhesive~
Hereto~ore~ in making laminates between polyester compositions per se and/or me-tals, it has been customary to clean the sur~ace to be bonded with a suitable solvent to re-move greases and other contaminants. This treatment has fre-quently resulted in a sur~ace that would not give satisfac-tory bonds for some unknown reason. Therefore~ to insure that a satisfactory bond is obtained under all conditions the better practice has ~een to sandblast the surface of the polyester composition or otherwise abrade it away and then g~ve the surface a solvent wash. It should be readily evi-dent that the use o~ a sandblas-ting treatment increases the cos-t and also presents problems due to the contaminatlon of the surrounding area with the fines from the sandblasting treatmentO
The molders o~ polyester compositions in recent years have tended to add compounding agents such as waxes~
polyethylene, polypropylene or broadly unsaturated to satura-ted polymers or copolymers of ole~ins o~ 2 to 20 carbon atoms to give a finished molded polyester composition frequently referred to as a "low profile" molded part~ Also, the so-called "low profile" molded polyester composition responds to treatment wi-th the treating agents of this invention to give improved laminates.
~ ~ 5~
Therefore, it is an object of this invention to pro-vide a method for obtaining improved adhesion between poly-ester compositions per se and/or metals and a polyester com-position having a treated surface. This object and other advantages ~ay be obtained by the practice o~ this invention as will be evident from the ensuing discussion.
The method for improving the adhesion between an aahesive of the isocyanate class a~d a polyes-ter composition comprising treating the surface of the polyester composition with a first treating agent which is an organic polyisocya-nate and a second treating agent which is a tertiary amine without regard to sequence and then applying an adhesive Of the isocyanate class and curing said adhesive.
More specifically, the polyester compositions are those utilized for constructing panels or built-up objects of ~ubstanti~1 rigidity, for instance, the use of solid poly ester compositions containing glass fiber reinforcements such as those used in making automobile bodies or parts, boats and related objects are the ones to which this inve~tion has its primary bene~it. m ese polyester compositions ma~ be made by reacting suitable polycarboxylic acids or their anhydrides wlth suitable glycols such as ethylene, propylene~ butylene and higher. For these purposes the polycarboxylic acids of the aromatic type are particularly suitable as they tend to ; 25 ~ive a more rigid composition. Speci~ic examples o~ these aromatic pol~carboxylic acid~ are phthalic, isophthalic and terephthalic. Also unsaturated polycarbox~lic acids su¢h as maleic and fumeric are utiliæed where it is desired toint~Dduce a small to a relatively large amount of unsatura-
This invention relates to a method of obtaining im-proved adhesion between polyester compositions per se and/or metals. More specifically~ this invention relates to a me-thod of treating the sur~ace of a polyester composition which may contain glass ~lber reinforcement to enh~nce the ef'fec-tiveness of an isocyanate adhesive~
Hereto~ore~ in making laminates between polyester compositions per se and/or me-tals, it has been customary to clean the sur~ace to be bonded with a suitable solvent to re-move greases and other contaminants. This treatment has fre-quently resulted in a sur~ace that would not give satisfac-tory bonds for some unknown reason. Therefore~ to insure that a satisfactory bond is obtained under all conditions the better practice has ~een to sandblast the surface of the polyester composition or otherwise abrade it away and then g~ve the surface a solvent wash. It should be readily evi-dent that the use o~ a sandblas-ting treatment increases the cos-t and also presents problems due to the contaminatlon of the surrounding area with the fines from the sandblasting treatmentO
The molders o~ polyester compositions in recent years have tended to add compounding agents such as waxes~
polyethylene, polypropylene or broadly unsaturated to satura-ted polymers or copolymers of ole~ins o~ 2 to 20 carbon atoms to give a finished molded polyester composition frequently referred to as a "low profile" molded part~ Also, the so-called "low profile" molded polyester composition responds to treatment wi-th the treating agents of this invention to give improved laminates.
~ ~ 5~
Therefore, it is an object of this invention to pro-vide a method for obtaining improved adhesion between poly-ester compositions per se and/or metals and a polyester com-position having a treated surface. This object and other advantages ~ay be obtained by the practice o~ this invention as will be evident from the ensuing discussion.
The method for improving the adhesion between an aahesive of the isocyanate class a~d a polyes-ter composition comprising treating the surface of the polyester composition with a first treating agent which is an organic polyisocya-nate and a second treating agent which is a tertiary amine without regard to sequence and then applying an adhesive Of the isocyanate class and curing said adhesive.
More specifically, the polyester compositions are those utilized for constructing panels or built-up objects of ~ubstanti~1 rigidity, for instance, the use of solid poly ester compositions containing glass fiber reinforcements such as those used in making automobile bodies or parts, boats and related objects are the ones to which this inve~tion has its primary bene~it. m ese polyester compositions ma~ be made by reacting suitable polycarboxylic acids or their anhydrides wlth suitable glycols such as ethylene, propylene~ butylene and higher. For these purposes the polycarboxylic acids of the aromatic type are particularly suitable as they tend to ; 25 ~ive a more rigid composition. Speci~ic examples o~ these aromatic pol~carboxylic acid~ are phthalic, isophthalic and terephthalic. Also unsaturated polycarbox~lic acids su¢h as maleic and fumeric are utiliæed where it is desired toint~Dduce a small to a relatively large amount of unsatura-
-2-7~;
tion in the polyester composition~ especially where the com-position is to be cured or set by peroxide curing7 either alone or in conjunction with an unsaturated monomer or alpha olefirl such as styrene or acrylonitrile~ etc.
The glass fiber reinforced polyester compositions are well known and are in wide commercial use, but in general these compositions are prepared by forming a copolymer con-taining maleic anhydride or related unsaturated polycarbo~y-lic acids and one of the phthalic acids or lower aliphatic dicarboxylic acids with ethylene glycol or the ether glycols such as di or tri ethylene glycol.
As indicated heretofore~ the objects and advantages of this invention are obtained by applying in succession a trea-tment with two different treating agents to the clean sur~ce of the polyester composition and/or metal, followed by application of the polyurethane adhesive, bringing the polyester composition or metal into laminating contact with another polyester composition until the adhesive has set or cured. For convenience~ the different treating agents wlll be referred to as first and second treating agents~ respect~
vely, as this designated sequence of treatment gives pre-ferred results. It should be appreciated the order or se-quence of treatment can be reversedO Thus~ the treatment in some instances can be referred to as without sequence.
Hereinaf-ter~ the term "first treating agent" will be used to designate an organic polyisocyanate or a solution of an organic polyisocyanate~
Any of the organic polyisocyanates may be used as the first treating agent to pretreat the polyester surface -~. ', ' .
~ 3 ~ S~ 7~ 6 to enhance the adhesion. Represen-tative classes of these are the aromatic~ aliphatic~ and cycloaliphatic diisocyanates and the triisocyanates such as those listed in U.S.Patents 2~917 489 and 3,102 9 875.
Since the organic polyisocyanates of higher molecu-lar weight and higher isocyanate content are more viscous or even solids9 the use of a solvent as a vehicle to dissolve, dilute or lower the viscosity aids the control application during the pretreatment to the polyester or metal surface.
Suitable c,nd representative vehicles for the organic polyiso-cyanates are the ketones such as methyl ethyl ketone, aceto~, the hydrocarbon distlllatesg chlorinated solvents as hydro-carbons and other solvents boili~g below about 300F. and preferably below 2500F.
The polyester composition, preferably in the form of a sheet or thin film, is treated with the first treating agent by applying the treating agent preferably dispersed or dissolved in a solvent to the surface by brushing~ spraying9 rolling or other suitable techniques~ then allowing the sol~
vent to evaporate to leave the treating agent deposited on the surface of the polyester composition It has been discovered that the benefits of this invention are obtained if the second treatment immediately fo1lo~s the first treatment or if considerable time is al-lowed to eIapse. Usually an elapse of one to several days is desirable as it gives greater freedom in schedullng the work in the plant.
The~second treating agent is applied to the sur~ace of the polyester composition by brushing9 spraying~ rolling :
:: :
~ ~ -4-` ~ ~ , .....
- \
; ~ ~ S~ ~ ~6 or o-ther sul-table -techniques and allowed -to dry. Then -the polyester whose surface has been so prepared is treated with a polyure-thane adhesive and the two surfaces to be joined : are placed in contact and maintained in contact until the adhesive has had time to laminate or bond the two compo~ons together.
The second treating agent for treating the surface - of the polyester composition is a tertiary amine of the ali-phatic, cycloaliphatic~ or heteroaromat-lc hydrocarbon class.
. lO Representative tertiary amines are triethylene diamlne~ al-.kyl piperazines, alkyl morpholines, and dial.kylated lower amines such as triethylamine. The agent or treating agent is preferably dissolved in a suitable solvent such as the ketones or halogenated hydrocarbon solvents~ although any of the low boiling inert organic liquias in which the amine is soluble may be used. Usually about 0.5 to 5 or more parts of the agent is dissolved in a 100 parts o~ solvent, and de-. pending on the specific activity of the tertiaryamine about one to -three parts is preferred~ This concentratlon of the treating agent in the solvent allows adhesion to be obtained with the usual appllcation methods. Of course, it should be appreciated that higher concéntrations~ viz. 5 or lO parts to even lOO percent liquid tertiaryamine can be used~ but difficulty will be experienced in getting a uniform applicant of the tertiaryamine to the polyester surface at concentra-; tions abo~e lO percent~ and the cost of the treatment tends to:become too expensive~
In genaral~ washing of the polyester composition orthe metals~ for example~ steel~ copper~ aluminum~ magnesium - . . .- . . . . .. . . .
~ S17~j and rela-ted alloys, is not necessary since the solvent in the firs-t treating agent can function to loosen the grease and o-ther surface contaminants to permit the isocyanate to bond to the solid polyester composition, viz. an FRP panel.
5 Likewise, in some instances, i-t is preferred to treat metals with the amine treating agent before using the isocyanate treating agent. It should be no-ted that some o~ the chlo-rinated solvents tend to react with some tertiaryamines to form a precipitate. Consequently, the solvent solution sometimes has limited pot life and is made immediately be-fore its use.
An adhesive of the isocyana-te class can be prepared by reacting the reactive hydrogen containing materials of about 500 to 4000 molecular weight with an organic polyiso-15 - cyanate, a low molecular weight polyamine containing ma~ n ~
and pre~erably an inert filler. The adhesive o~ the isocya-nate class is prepared by forming a prepolymer~ then mixing the prepolymer with a curative9 the prepolymer being formed by the reaction of the reactive hydrogen containing material.
Pre~erred is a polypropylene ether polyol of 1000~3000 mole-cular weight and an organic polyisocyanate containing at least 2 and pre~erabl~ more than an average of 2 isocyanates per molecule. This prepolymer can contain about 5 to as much as 70% by weight o~ a ~iller based on the reactive ; ~ 25 hydrogen containing material. One o~ the prime functions o~
the inert filler such as clays, silica, e-tc. is to act as a viscosity increaser and to hasten the building of green strength or tack ln the adhesive. The curative may contain polyhydroxyl terminated materials of rela-tively low molecu-.
;~ :
~5~7Z6 ].ar w~ight~ us-ually less -than about Goo. ~epresen-ta.-t-lve Or -these materials are N,N~N',N'-(2-hydro~ylpropyl) e-thylene diamine or the adduct formed by reacting a material such as pentaerythritol, trimethylol~ propane, trimethylol ethane and the hydroxylated sugars with alkylene oxides such as propylene oxide. These curatives may also contain in addi-tion to the low molecular weight hydroxyl terminated or amine terminated materials, a small amount of catalysts such as the tertiary amines or the organic tin compounds. Usually the adhesives of the isocyanate class of a relatively high iso-- cyanate to reactive hydrogen material ratio is in excess of 2~5 and preferably about 5 to 7 moles per mole. The nature of the isocyanate adhesive and the first and second treating . agents is also described in U.SgPatents 3~647~513 and 3,703, 26.
;, : The nature of this invention may be more specifi~
cally exemplified by the following examples wherein all parts are by weight unless otherwise indicated:
EXAMPLE A
` 20 : A suitable adhesive of the isocyanate class was prepared by reacting the following ingredients:: 100 parts - ~of a polypropylene ether glycol o~ about 2000 molecular weight having dispersed therein 60 parts of talc coated with zinc stearate and an organic polyisocyanate mixture compris-~; ing 28 par-ts of a polyisocyanate A and 32 parts of toluene diisocyanate where polyisocyanate A is the pho~genated mix- -. ture obtained by phosgenation of the rearrangement product of the reaction of aniline and~formaldehyde as taught in U.S.
Patent 2,683~730~ :
` : :
- . .. . ~ . . . . ..
~ ~ S~ 6 This prepolymer was then mixed in a two-comp~rtmen-t pres~ure adhesive gun with a cllrative comprising 30.8 parts N,N~N'~N'-(2-hydroxylpropyl) ethylene diamine and 1302 parts of a propylene oxide adduct of pentaerythritol of about l~oo molecular weigh-t to form the adhesive.
EXAMPLE B
Another adhesive of the isocyanate class was pre-pared by reacting lO0 parts polypropylene ether glycol of 2000 molecular weight having dispersed therein 63 parts of zinc stearate coated talc with an isocyanate mi~ture com-prising 29.8 parts of a polyisocyanate A and 33.7 parts of toluene diisocyanate. This prepolymer was mixed with a cura-tive to foIm an adhesive. The cura-tive was formed by mix-ing 49.6 parts of a propylene oxide adduct of ethylene dia-1~ mine of about 500 molecular weight with 12.4 parts of a propylene oxide adduct of pentaerythritol of about 500 molecular weight.
EXAMPLE I
A ~ive percent by weight solution of polyphenyl me-thane polyisocyanate (available from the supplier under the name PAP~in a chlorinated naphtha having a boiling po1nt below 2500F. was spray applied to clean d~y automoblle grade polyester fiber glass test panels and allowed to dry at room ternperature for 30 minutesO
Then the test panels were spray coated with a one percent by weight solution of triethylene diamine in methyl ethyl ketone. The panels were allowed to dry at room tem-perature for 30 minutes before being coated wlth the iso-cyanate adhesive of Example ~. The panel containing the ~ . .
~ Z6 isocy~nate ~clh~siv~ was covered with a second panel in cross relationship and held in this relationship for 2 hours ~o develop the cross laminate bond.
The cross laminate specimens were subjected to a 5 pull ~st in an "Instron'~test machine at test temperatures indicated belowO
_~b~ Bond Failur~ S-i:
750F. 680*
180F. 390 10 2~0~. 237 -40F. 808~
* This cross laminate failed due to polyester delaminating.
These bond strengths represent approximately a 75 percent improvem~nt in bond strength over thos~ where no primer treatme~t was used.
The sequence of primer use above can be reversed~
but Example I exemplifies the preferred sequence. Also, the chlorinated hydrocarbon organic polyisocyanate solu-tions of 2 to 10 percen-t are normally used~
While certain representative embodiments and details have been shown for the purpose of illustrating the inven-tion9 it wi11 be apparent to those skilled in this art th~t various changes and modifications may be made ther~în with-out departing from the spirit or scope of the invention.
.
'~
_9_ . . . . . .
tion in the polyester composition~ especially where the com-position is to be cured or set by peroxide curing7 either alone or in conjunction with an unsaturated monomer or alpha olefirl such as styrene or acrylonitrile~ etc.
The glass fiber reinforced polyester compositions are well known and are in wide commercial use, but in general these compositions are prepared by forming a copolymer con-taining maleic anhydride or related unsaturated polycarbo~y-lic acids and one of the phthalic acids or lower aliphatic dicarboxylic acids with ethylene glycol or the ether glycols such as di or tri ethylene glycol.
As indicated heretofore~ the objects and advantages of this invention are obtained by applying in succession a trea-tment with two different treating agents to the clean sur~ce of the polyester composition and/or metal, followed by application of the polyurethane adhesive, bringing the polyester composition or metal into laminating contact with another polyester composition until the adhesive has set or cured. For convenience~ the different treating agents wlll be referred to as first and second treating agents~ respect~
vely, as this designated sequence of treatment gives pre-ferred results. It should be appreciated the order or se-quence of treatment can be reversedO Thus~ the treatment in some instances can be referred to as without sequence.
Hereinaf-ter~ the term "first treating agent" will be used to designate an organic polyisocyanate or a solution of an organic polyisocyanate~
Any of the organic polyisocyanates may be used as the first treating agent to pretreat the polyester surface -~. ', ' .
~ 3 ~ S~ 7~ 6 to enhance the adhesion. Represen-tative classes of these are the aromatic~ aliphatic~ and cycloaliphatic diisocyanates and the triisocyanates such as those listed in U.S.Patents 2~917 489 and 3,102 9 875.
Since the organic polyisocyanates of higher molecu-lar weight and higher isocyanate content are more viscous or even solids9 the use of a solvent as a vehicle to dissolve, dilute or lower the viscosity aids the control application during the pretreatment to the polyester or metal surface.
Suitable c,nd representative vehicles for the organic polyiso-cyanates are the ketones such as methyl ethyl ketone, aceto~, the hydrocarbon distlllatesg chlorinated solvents as hydro-carbons and other solvents boili~g below about 300F. and preferably below 2500F.
The polyester composition, preferably in the form of a sheet or thin film, is treated with the first treating agent by applying the treating agent preferably dispersed or dissolved in a solvent to the surface by brushing~ spraying9 rolling or other suitable techniques~ then allowing the sol~
vent to evaporate to leave the treating agent deposited on the surface of the polyester composition It has been discovered that the benefits of this invention are obtained if the second treatment immediately fo1lo~s the first treatment or if considerable time is al-lowed to eIapse. Usually an elapse of one to several days is desirable as it gives greater freedom in schedullng the work in the plant.
The~second treating agent is applied to the sur~ace of the polyester composition by brushing9 spraying~ rolling :
:: :
~ ~ -4-` ~ ~ , .....
- \
; ~ ~ S~ ~ ~6 or o-ther sul-table -techniques and allowed -to dry. Then -the polyester whose surface has been so prepared is treated with a polyure-thane adhesive and the two surfaces to be joined : are placed in contact and maintained in contact until the adhesive has had time to laminate or bond the two compo~ons together.
The second treating agent for treating the surface - of the polyester composition is a tertiary amine of the ali-phatic, cycloaliphatic~ or heteroaromat-lc hydrocarbon class.
. lO Representative tertiary amines are triethylene diamlne~ al-.kyl piperazines, alkyl morpholines, and dial.kylated lower amines such as triethylamine. The agent or treating agent is preferably dissolved in a suitable solvent such as the ketones or halogenated hydrocarbon solvents~ although any of the low boiling inert organic liquias in which the amine is soluble may be used. Usually about 0.5 to 5 or more parts of the agent is dissolved in a 100 parts o~ solvent, and de-. pending on the specific activity of the tertiaryamine about one to -three parts is preferred~ This concentratlon of the treating agent in the solvent allows adhesion to be obtained with the usual appllcation methods. Of course, it should be appreciated that higher concéntrations~ viz. 5 or lO parts to even lOO percent liquid tertiaryamine can be used~ but difficulty will be experienced in getting a uniform applicant of the tertiaryamine to the polyester surface at concentra-; tions abo~e lO percent~ and the cost of the treatment tends to:become too expensive~
In genaral~ washing of the polyester composition orthe metals~ for example~ steel~ copper~ aluminum~ magnesium - . . .- . . . . .. . . .
~ S17~j and rela-ted alloys, is not necessary since the solvent in the firs-t treating agent can function to loosen the grease and o-ther surface contaminants to permit the isocyanate to bond to the solid polyester composition, viz. an FRP panel.
5 Likewise, in some instances, i-t is preferred to treat metals with the amine treating agent before using the isocyanate treating agent. It should be no-ted that some o~ the chlo-rinated solvents tend to react with some tertiaryamines to form a precipitate. Consequently, the solvent solution sometimes has limited pot life and is made immediately be-fore its use.
An adhesive of the isocyana-te class can be prepared by reacting the reactive hydrogen containing materials of about 500 to 4000 molecular weight with an organic polyiso-15 - cyanate, a low molecular weight polyamine containing ma~ n ~
and pre~erably an inert filler. The adhesive o~ the isocya-nate class is prepared by forming a prepolymer~ then mixing the prepolymer with a curative9 the prepolymer being formed by the reaction of the reactive hydrogen containing material.
Pre~erred is a polypropylene ether polyol of 1000~3000 mole-cular weight and an organic polyisocyanate containing at least 2 and pre~erabl~ more than an average of 2 isocyanates per molecule. This prepolymer can contain about 5 to as much as 70% by weight o~ a ~iller based on the reactive ; ~ 25 hydrogen containing material. One o~ the prime functions o~
the inert filler such as clays, silica, e-tc. is to act as a viscosity increaser and to hasten the building of green strength or tack ln the adhesive. The curative may contain polyhydroxyl terminated materials of rela-tively low molecu-.
;~ :
~5~7Z6 ].ar w~ight~ us-ually less -than about Goo. ~epresen-ta.-t-lve Or -these materials are N,N~N',N'-(2-hydro~ylpropyl) e-thylene diamine or the adduct formed by reacting a material such as pentaerythritol, trimethylol~ propane, trimethylol ethane and the hydroxylated sugars with alkylene oxides such as propylene oxide. These curatives may also contain in addi-tion to the low molecular weight hydroxyl terminated or amine terminated materials, a small amount of catalysts such as the tertiary amines or the organic tin compounds. Usually the adhesives of the isocyanate class of a relatively high iso-- cyanate to reactive hydrogen material ratio is in excess of 2~5 and preferably about 5 to 7 moles per mole. The nature of the isocyanate adhesive and the first and second treating . agents is also described in U.SgPatents 3~647~513 and 3,703, 26.
;, : The nature of this invention may be more specifi~
cally exemplified by the following examples wherein all parts are by weight unless otherwise indicated:
EXAMPLE A
` 20 : A suitable adhesive of the isocyanate class was prepared by reacting the following ingredients:: 100 parts - ~of a polypropylene ether glycol o~ about 2000 molecular weight having dispersed therein 60 parts of talc coated with zinc stearate and an organic polyisocyanate mixture compris-~; ing 28 par-ts of a polyisocyanate A and 32 parts of toluene diisocyanate where polyisocyanate A is the pho~genated mix- -. ture obtained by phosgenation of the rearrangement product of the reaction of aniline and~formaldehyde as taught in U.S.
Patent 2,683~730~ :
` : :
- . .. . ~ . . . . ..
~ ~ S~ 6 This prepolymer was then mixed in a two-comp~rtmen-t pres~ure adhesive gun with a cllrative comprising 30.8 parts N,N~N'~N'-(2-hydroxylpropyl) ethylene diamine and 1302 parts of a propylene oxide adduct of pentaerythritol of about l~oo molecular weigh-t to form the adhesive.
EXAMPLE B
Another adhesive of the isocyanate class was pre-pared by reacting lO0 parts polypropylene ether glycol of 2000 molecular weight having dispersed therein 63 parts of zinc stearate coated talc with an isocyanate mi~ture com-prising 29.8 parts of a polyisocyanate A and 33.7 parts of toluene diisocyanate. This prepolymer was mixed with a cura-tive to foIm an adhesive. The cura-tive was formed by mix-ing 49.6 parts of a propylene oxide adduct of ethylene dia-1~ mine of about 500 molecular weight with 12.4 parts of a propylene oxide adduct of pentaerythritol of about 500 molecular weight.
EXAMPLE I
A ~ive percent by weight solution of polyphenyl me-thane polyisocyanate (available from the supplier under the name PAP~in a chlorinated naphtha having a boiling po1nt below 2500F. was spray applied to clean d~y automoblle grade polyester fiber glass test panels and allowed to dry at room ternperature for 30 minutesO
Then the test panels were spray coated with a one percent by weight solution of triethylene diamine in methyl ethyl ketone. The panels were allowed to dry at room tem-perature for 30 minutes before being coated wlth the iso-cyanate adhesive of Example ~. The panel containing the ~ . .
~ Z6 isocy~nate ~clh~siv~ was covered with a second panel in cross relationship and held in this relationship for 2 hours ~o develop the cross laminate bond.
The cross laminate specimens were subjected to a 5 pull ~st in an "Instron'~test machine at test temperatures indicated belowO
_~b~ Bond Failur~ S-i:
750F. 680*
180F. 390 10 2~0~. 237 -40F. 808~
* This cross laminate failed due to polyester delaminating.
These bond strengths represent approximately a 75 percent improvem~nt in bond strength over thos~ where no primer treatme~t was used.
The sequence of primer use above can be reversed~
but Example I exemplifies the preferred sequence. Also, the chlorinated hydrocarbon organic polyisocyanate solu-tions of 2 to 10 percen-t are normally used~
While certain representative embodiments and details have been shown for the purpose of illustrating the inven-tion9 it wi11 be apparent to those skilled in this art th~t various changes and modifications may be made ther~în with-out departing from the spirit or scope of the invention.
.
'~
_9_ . . . . . .
Claims (4)
1. A method for improving the adhesion between an adhesive of the isocyanate class and a polyester composi-tion comprising treating the surface of the polyester com-position with a first and second treating agent without regard to sequence and then applying an adhesive of the isocyanate class and curing said adhesive, said first treating agent being an organic polyisocyanate and the second treating agent being a tertiary amine.
2. The method of claim 1 wherein the organic poly-isocyanate is a phosgenation product of the rearranged product of the reaction of aniline and formaldehyde.
3. The method of claim 1 wherein the tertiary amine is triethylene diamine.
4. The method of claim 1 wherein the adhesive is of the isocyanate class, obtained by reacting organic poly-isocyanate with polypropylene ether glycol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/500,220 US4004050A (en) | 1974-08-26 | 1974-08-26 | Two-part primer system for FRP bonding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051726A true CA1051726A (en) | 1979-04-03 |
Family
ID=23988535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,041A Expired CA1051726A (en) | 1974-08-26 | 1975-07-22 | Two-part primer system for frp bonding |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4004050A (en) |
| JP (1) | JPS5844461B2 (en) |
| BR (1) | BR7505157A (en) |
| CA (1) | CA1051726A (en) |
| DE (1) | DE2534741C2 (en) |
| FR (1) | FR2283197A1 (en) |
| GB (1) | GB1479065A (en) |
| IT (1) | IT1041191B (en) |
| ZA (1) | ZA754763B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2633764C2 (en) * | 1976-07-28 | 1978-09-07 | Bayer Ag, 5090 Leverkusen | Process for the production of plastic-metal composites |
| CA1140815A (en) * | 1978-11-15 | 1983-02-08 | Richard L. Cline | Primer system for frp bonding |
| US4335187A (en) * | 1981-03-02 | 1982-06-15 | Ppg Industries, Inc. | Method for bonding polycarbonate to metal |
| US4340682A (en) * | 1981-05-07 | 1982-07-20 | Synthetic Surfaces, Inc. | Adhesive consisting essentially of an isocyanate terminated ricinoleate prepolymer and a chlorinated polyvinyl chloride |
| US4968383A (en) * | 1985-06-18 | 1990-11-06 | The Dow Chemical Company | Method for molding over a preform |
| US4861407A (en) * | 1985-06-18 | 1989-08-29 | The Dow Chemical Company | Method for adhesive bonding articles via pretreatment with energy beams |
| US4755251A (en) * | 1987-02-09 | 1988-07-05 | Ashland Oil, Inc. | Bonding method employing primer for fiberglass reinforced polyester |
| US4923756A (en) * | 1987-08-20 | 1990-05-08 | Ashland Oil, Inc. | Primerless adhesive for fiberglass reinforced polyester substrates |
| JPH01279987A (en) * | 1987-12-02 | 1989-11-10 | Mitsui Toatsu Chem Inc | Bonding method |
| US4876308A (en) * | 1988-02-18 | 1989-10-24 | Gencorp Inc. | Polyurethane adhesive for a surface treatment-free fiber reinforced plastic |
| US5002806A (en) * | 1990-01-11 | 1991-03-26 | Ashland Oil, Inc. | Curative for structural urethane adhesive |
| DE4108877A1 (en) * | 1991-03-19 | 1992-09-24 | Bayer Ag | METHOD FOR GLUING SUBSTRATES MADE OF GLASS FIBER REINFORCED POLYESTER RESIN |
| US5551197A (en) * | 1993-09-30 | 1996-09-03 | Donnelly Corporation | Flush-mounted articulated/hinged window assembly |
| US7838115B2 (en) * | 1995-04-11 | 2010-11-23 | Magna Mirrors Of America, Inc. | Method for manufacturing an articulatable vehicular window assembly |
| US5853895A (en) * | 1995-04-11 | 1998-12-29 | Donnelly Corporation | Bonded vehicular glass assemblies utilizing two-component urethanes, and related methods of bonding |
| CA2279737C (en) | 1998-08-06 | 2004-04-27 | Naoya Haruta | Decorative film for use in platics molding, process for preparing the same and injection-molded part by use of the same |
| CN113429893A (en) * | 2021-07-22 | 2021-09-24 | 南京海配新材料有限公司 | Nonpolar rubber and plastic material surface treatment agent and surface treatment method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2905582A (en) * | 1955-04-29 | 1959-09-22 | Lord Mfg Co | Method of bonding polyurethanes to rubbers |
| US2921828A (en) * | 1956-12-03 | 1960-01-19 | Eastman Kodak Co | Surface treating polyester films and fibers with primary amino compounds |
| US3326742A (en) * | 1963-03-25 | 1967-06-20 | Princeton Chemical Res Inc | Surface treatment and bonding of organic high polymers |
| DE2114749C3 (en) * | 1970-04-21 | 1975-11-20 | Kuraray Co., Ltd., Kurashiki, Okayama (Japan) | Process for improving the rubber adhesion of fibrous polyester materials |
| US3647513A (en) * | 1970-10-26 | 1972-03-07 | Goodyear Tire & Rubber | Method for improving the adhesion of polyester compositions |
| US3703426A (en) * | 1970-11-18 | 1972-11-21 | Goodyear Tire & Rubber | Method of making polyester laminates |
| GB1401296A (en) * | 1972-05-08 | 1975-07-16 | Yarsley Res Lab | Polyester film treatment process |
-
1974
- 1974-08-26 US US05/500,220 patent/US4004050A/en not_active Expired - Lifetime
-
1975
- 1975-04-25 GB GB1729075A patent/GB1479065A/en not_active Expired
- 1975-07-22 CA CA232,041A patent/CA1051726A/en not_active Expired
- 1975-07-23 ZA ZA00754763A patent/ZA754763B/en unknown
- 1975-08-04 DE DE2534741A patent/DE2534741C2/en not_active Expired
- 1975-08-08 IT IT5088775A patent/IT1041191B/en active
- 1975-08-13 BR BR7505157A patent/BR7505157A/en unknown
- 1975-08-21 FR FR7525881A patent/FR2283197A1/en active Granted
- 1975-08-22 JP JP50102003A patent/JPS5844461B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2534741C2 (en) | 1984-03-01 |
| AU8357275A (en) | 1977-02-03 |
| GB1479065A (en) | 1977-07-06 |
| US4004050A (en) | 1977-01-18 |
| JPS5844461B2 (en) | 1983-10-03 |
| BR7505157A (en) | 1976-08-03 |
| FR2283197B1 (en) | 1978-05-19 |
| IT1041191B (en) | 1980-01-10 |
| DE2534741A1 (en) | 1976-03-11 |
| FR2283197A1 (en) | 1976-03-26 |
| JPS5149273A (en) | 1976-04-28 |
| ZA754763B (en) | 1976-07-28 |
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