MXPA99007195A - Unsaturated polymer polyurethane structural adhesive - Google Patents

Abstract

This invention is a structural adhesive and a laminate of untreated substrates adhered together with a structural adhesive which combines a two part polyurethane adhesive with a two part free radical curing adhesive. The adhesive is especially useful in the manufacture of personal watercraft built to withstand rough waves and made of fiberglass reinforced plastic.

Description

STRUCTURAL POLYURETHANE POLYURETHANE ADHESIVE INSATURED DESCRIPTION OF THE INVENTION This invention relates to useful adhesives glass fiber reinforced polyester substrates (FR used to make personal aquatic vehicles that must withstand the rough handling of waves) Background of the Invention Polyurethane commercially available has been used to adhere FRP structural adhesives on personal aquatic vehicle substrates, but only if the surface to be adhered has been previously treated, for example by polishing or sealing with a solvent before applying adhesive to the substrate. As aquatic vehicle manufacturers have become aware of the intensity of work and the environmental problems caused by these treatments, they require new adhesives to glue these structures together without any surface treatment Detailed Description of the Invention Personal watercraft are constructed colo manually cutting glass mats or glass fibers onto a mold or shape. The glass is then adhered to one another with a resin, generally unsaturated polyesters vulcanized at room temperature by means of libr radical chemistry initiated by peroxides. Typically those parts are vulcanized open air, although sometimes they are briefly compressed to control thickness uniformity. In either process, the air surrounding the atmosphere inhibits the crosslinking reaction which results in a superi partially unvulcanized surface. It is well known that an improperly vulcanized surface is difficult to adhere to any surface treatment such as cleaning with polished solvent. It has been found that if the adhesive contains unsaturation functionality, hereafter called "unsaturated polymer" can be vulcanized by chemical free radicals initiated by means of peroxide and used to adhere parts of aquatic vehicles without any surface treatment. However, the unsaturated polymer / adhesive cured with peroxide is very brittle, since there are no reinforcements in adhesive such as the glass fibers used to form the aquatic vehicle itself. It was discovered that such adhesives vulcanized with peroxide can be reinforced or rendered flexible by co-vulcanizing a polyurethane adhesive. In addition to the adhesion, this unsaturated polyuret / polyuret adhesive, not very flexible for aquatic vehicles, showed excellent resistance to setting, rapid development of raw initial strength and adhesion free surface. Adhesion retention was also demonstrated by exposing the l joints to an environment with a relative humidity of 100% at 38 ° for 8 weeks. Tests of the resistance between joints after such exposure typically showed to be at 230 psi. Examples of unsaturated polymers for these adhesives include the same type of unsaturated polyesters used to build aquatic vehicles as well as unsaturated polyurethanes. Typical unsaturated polyesters are the reaction product of a glycol and an unsaturated carboxylic acid or dicyclopentadiene or styrene anhydride. The unsaturated polyurethane is typically prepared by mixing a polymeric polyolefin with a polyisocyanate at the ends to prepare a prepolymer. Then the final isocyanate groups are converted to the unsaturation by reaction of the isocyanate with the hydroxyl group of an unsaturated alcohol, such such as hydroxyethyl acrylate or hydroxyethyl methacrylate (HEMA). U.S. Patent 4,480,079, 5,126,396, 5,250,608 describe the preparation of unsaturated polyurethane. To reduce the viscosity of the unsaturated polyurethane product, more isocyanate is commonly added to the polymer to prepare a low molecular weight polyisocyanate adduct coated with HEMA simultaneously with the prepolymer preparation step. Also very effective for viscosity reduction is the addition of reactive low molecular weight diluents such as styrene, acrylates or methacrylates. These diluents are also covulcanized with the unsaturated polymer when exposed to a free radical initiator such as peroxide. Alternatively the prepolymer stage is polyurethane can be deviated by simply making HEMA reaction, polyol and polyisocyanate in one step to form unsaturated polyurethane. A vulcanizable adhesive at ambient temperature for bonding personal aquatic vehicles without surface preparation is formed by combining the unsaturated polymer with polyurethane. Exemplary polyurethane adhesives are disclosed in U.S. Patents 4,923,756, 5,002.80 and 5,548,056. Examples of such combination include 1) having polyisocyanate and peroxide as part A and polyol / unsaturated polymer amine as part B or 2) having polyol and peroxy as part A and polyisocyanate and unsaturated polymer as part B. Structural adhesives of interpenetrating networks It is prepared by mixing all the ingredients in a single mixture instead of part A and part B. When the adhesive is ready to vulcanize, heat is applied to initiate the formation of free radicals as well as to crosslink. Among glass fiber reinforced polyester substrates useful in the practice of the present invention, are those cold-applied manually applied substrates provided by Artic Cat, Inc. Thief Rive Fallas, MN (formerly known as Arctco) or Mercury Marine Hartford , Wl.

The unsaturated polymeric polyurethane adhesive of this invention is prepared by combining a polyisocyanate, or reactive component against the polyisocyanate, an unsaturated polymer and free radical initiator. Although the polyisocyanates useful in this invention are: diphenylmethane diisocyanate, toluene diisocyanate, 1,4-phenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl, 3,3-dimethyl-4,4'-diisocyanatobiphenyl diisocyanate, diphenyl methane of 3, 3 '-dimethyl-4, 4 • -diisocyanate, or its polymerized versions or mixtures thereof. The isocyanates ma preferred in the practice of this invention is polymeric Rubinate 931 distributed by ICI, Sterling Heights, Michigan polyisocyanate Isonate 143 L from Dow Chemical, Midla Michigan. Alternatively, the polyisocyanate useful in this invention can also be derived from the reaction product of a polyisocyanate and a polyol with a functionality of 1.8-6. The polyols useful for the preparation of these prepolymers can be a diol of polypropylene oxide ether of a molecular weight of 700 to 10,000, ether diol of propylene oxide, polyethylene oxide, polyethylene glycol ether polyether diol glycol, polyester diol, polyepsiles caprolactone diol polycarbonate diol, polybutadiene diol or mixtures of those diols The preferred polyol is polyol ether diol of polypropylene with a molecular weight of 1000 to 2000 distributed by Ol Chemical, New Haven, Connecticut as poly G 20-112 or poly G 2 56, respectively. The component selected to cure polyisocyanate in the polymerized polyurethane unsaturated adhesive of this invention includes the polyols used to make prepolymers and polyamines. Other polyols include polyester and polyether polyols having a functionality of 1.8 to 6.0 and a hydroxyl number of 100 to 1200. Hydroxyl numbers of 100 to 1200 are preferred. A hydroxy number range of 200 to 700 and a functionality in the range of 3 to 5. Suitable materials containing suitable active hydrogen include diols, triols and tetroles, having primary, secondary and / or tertiary alcohol groups. Among the preferred polyether polyols are: polyol Plurac PeP 550, a propoxylated pentaerythritol derivative having four secondary hydroxyl groups, a hydroxyl number of 450 and a molecular weight of 500 distributed by BASF Wyandot Corporation, Parsippany, N.J .; Arcol F 3220, an ethoxylated / propoxylated glycerin derivative having three secondary hydroxyl groups, a hydroxyl number of 52 and a molecular weight of 3200 distributed by ARCO Chemical Company, Newto Square, PA; Fomrez ET3500, a propoxylated derivative of glyceri having three secondary hydroxyl groups, a hydroxyl number of 48 and a molecular weight of approximately 350 distributed by Witco Corporation, Organic Division, Houst Texas, polyol Pluracol P-355 an ethoxylated derivative / ethylene propoxylate diamine having approximately 80% hydroxyl group as primary and having a hydroxyl number 4 also distributed by BASF Wyandotte Corporation; Thanol R470X poly, distributed by Texaco Chemical CO., Bellair Tex., a propoxylated derivative of diethanolamine with a functionality of about 4 and a hydroxy number of 50 polyol Thanol SF-265, also distributed by Texaco Chemic Co., a propoxylated derivative of triethanolamine with functionality of about 3 and a hydroxyl number of 60 Voranol 230-660 polyol, a polyether triol with a pe equivalent of 85.4 based on the propoxylation of glycerin distributed by Dow Chemical Co., Midland, Mich .; and Dianol 22 polyol, an ethoxylated derivative of biphenol A with a functionality of 2 and a hydroxyl number of 280, distributed by Akzo Chem America, Chicago 111. Among the numerous diamines useful for vulcanizing polymeric polyurethane adhesive of this invention are the following diamines aromatics: toluene diamine l-methyl-3, 5-diethyl-2,4-diaminobenzene 1-methyl-3,5-diethyl-2,6-diaminobenzene (also known as DETDA or diethyl toluene diamine) di (methyltrio) toluene diamine l3,5-triethyl-2,6-diaminobenzene derivatives of toluene diamine containing halogen groups cyano, alkoxy, alkylthio, alkenyl or carbonyl groups m-phenylene diamine p-phenylene diamine 4,4'-methylenedianiline 4,4 '- diaminophenyl sulfone 2,6-diamino-pyridine 4,4 '-methylene bis (3-chloroaniline) 4,4'-methylene bis (3-chloro-2,6-diethylaniline) 4,4' -methylene bis (3-chloro) -2,5-diethylaniline) 3,3 '-di-isopropyl-4,4'-diaminodiphenylmethane 3,5,3', 5'-tetraethyl-4,4'-diaminophenylmethane popylene-di-4-aminobenzoate 4-chloro -3,5-diaminobenzoate isobutyl disulfide bis (2-aminophenyl) disulfide secondary bis (4-aminophenyl) diamine of di (amino alkylated) benzene secondary diamine of bis (aminophenyl alkylated) methane 3,3'-carbomethoxy -4, 4 '-diamino diphenylmethane and its mixtures. The most preferred diamine for the adhesive of this invention is diethyl toluene diamine (Ethacure 100, from Albermarl Corporation, Orangeburg, SC), which also contributes to the resistance to the bonding of the adhesive due to its reactivity. Another ingredient in the adhesive formulation of this invention is an optional catalyst for facilitating the crosslinking reaction of the adhesive between isocyanate amines, and between polyols and isocyanates. Suitable tertiary amine catalysts include N, N ', Np-dimethylaminopropyl hexahydrothiazine (Polycat 41) and 1,4-diazabicyclooctane, suitable organometallic catalysts such as those derived from zinc, potassium, bismuth and tin include dibutyltin dilaurate, dibitules tin diacetate, acetyl ferric acetone, nickel acetyl acetone, dibutyltin dialkyl acid, tin octato, dibutyl-di-octyl mercapto acetate, butyl tin diisocotyl maleate, and mixtures of these catalysts. The preferred organometallic catalysts are dibutyltin diacetate known as DAB TI distributed by Air Products, Allentown, PA. The preferred tertiary amine catalyst is dimethyl aniline. Other optional ingredients in the adhesive formulation of this invention include coloring thickeners, odor control and siccatives. Preferred optional thickening agents are: carbon black aluminum silicates (magnesium silicates), calcium carbonate, calcium silicates, barium sulfates, graphite, filler or filler mixtures. The preferred filled ingredient is Aerosil 200 or Aerosil R972 smoked silica Degussa Inc., New York, N.Y., and Cabosil TS 7 smoked silica from Cabot Corporation, Cab-O-Sil Division, Tuscola, IL. Small amounts of other optional materials can also be added to the adhesive formulation. Est include coloring agents, for example Stantone HCCC. 67 green coloring agent from Harwick Chemical Company, Akron, Ohi which is a mixture of green pigment C. I. # 7 and the pigment neg C.l. # 7 dispersed in a polyoxypropylene polyol at a ratio of 17.8 parts of pigment to 82.2 parts of polyol It may also be desirable to use 0.5 to 15.0 percent of a drying agent such as molecular sieve powder with a size of 5A distributed by Union Carbide or anhydrous aluminum sulfate powder from Geo Specialty Chemicals, In Little Rock, Arkansas. The customer combines Part A and Part B in desired proportion, generally i part by weight of Part A mixed with 1-10 parts by weight of part B. The structural adhesives of polymeric polyurethane are prepared by mixing part A and B typically using a model 200 mixed machine from EMC2, Sterling Heights, Michigan. The adhesive applies to the first substrate by conventional means. The second substrate is then laminated onto the first substrate coated with adhesive. The adhesive typically vulcanizes at room temperature although other energy sources such as microwave, radio frequency or dielectric energy or electromagnetic energy may be used to accelerate the vulcanization of the adhesive. Crosslinking adhesion samples were prepared using polyester plates reinforced with manually applied glass fibers vulcanized at ambient temperature prepared from dicyclopentadiene, vinyl esters or reaction product of unsaturated dicarboxylic acid and glycol. Representative types of those substrates are the construction Arctco FRP or Arctco Cold Press or Mercury Marine FRP used to manufacture personal watercraft. A fiberglass reinforced polystyrene plate is cut into 1 x inch strips. The adhesive was applied in the center with an area of x i inches without previous surface treatment. Some glass beads of 30 mils in diameter are sprayed onto the adhesive to control the thickness of the bond line when the cent of a second polyester plate reinforced with 1 x 3-inch glass fiber is attached onto the first strip with adhesive. After curing the adhesive at room temperature. The detached samples were tensioned on a Monsanto tensometer provided with clamps to hold the four adhered ends of the detached samples. The upper strip detached is pulled until it is pulled until it separates from the lower strip. Adhesion strength values greater than 600 psi were observed with failure to tear vulcanized polyester resin from the glass fiber used to reinforce the substrate. This is called in the industry with fiber tearing "or" FT "and is a very desirable result. The performance of an adhesive is graded depending on the amount of fiber tearing based on the percentage of one square inch adhered. as pound per square inch (psi) followed by a parenthesis that contains a first percentage of fiber tearing and a second of cohesive failure When the sum of the percentage values in the parentheses is not equal to 100 the residue is understood to be an error adhesive The cohesive error is designed as an error that leaves the adhesive on both pieces of plac forming an adhesion sample with shared separation.The adhesive failure is said to be the failure with separation of adhesive from the substrate without exposure of the fiberglass What reinforces the substrate The initial resistance development of the adhesive is evaluated by testing the adhesion samples after the separation. They vulcanize at different time intervals at room temperature, typically 20 and 30 minutes. An adhesion strength of approximately 50 psi is considered adequate to handle the weight of the personal watercraft part in the production line. The tearing of fibers that apanies the failure of the shared separation sample is considered a superior performance of the adhesive. The nature and advantages of this invention can be easily observed and appreciated with reference to the following representative examples, wherein all the components are expressed in parts by weight (ppp). All The patents mentioned herein are expressly incorporated by reference. EXAMPLE 1 This example describes the preparation of polyisocyanate / peroxide as part A to be vulcanized by means of a polyol / polyamine / unsaturated polymer as part B Formulation: Polyisocyanate 4495 Polydiphenylmethane diisocyanate Rubinate 9310 11.92 ppi Moisture absorbing powder Molecular Sieve 5A 0.18 Smoked silica treated Cabosil TS720 0.88 Benzoyl peroxide 50% Luperco ATC 5.29 18.27 Procedure The Rubinate 9310 was loaded in a 22 liter flask With an efficient high tear agitator and under a nitrogen blanket. The molecular sieve powder 5A was added followed by the Cabosil TS720. Then Luperco ATC was added to the resulting very viscous mixture. The peroxide mixture was started manually with a paddle. Fine deep mixing was achieved with low tearing with a mechanical mixer for 15 minutes. The degassing of the final mixture started by slowly opening the steam line. When a total vacuum was reached the product degassed for 30 min before discharge. The product was stored under a nitrogen blanket. EXAMPLE 2 This example 2 describes the preparation of another polyisocyanate / peroxide as part A, polyol is reacted with the polyisocyanate before the addition of peroxide.

Formulation: Polyisocyanate 4627 Ethylene oxide polyG 20-112 covered with polypropylene ether glycol (molecular weight 1000) 50.00 ppp Moisture absorbing powder Molecular sieve 5A 3.86 Polydiphenylmethane diisocyanate Rubinate 9310 158.40 Miscon RCS 46.31 Hydrophobic smoked silica Aerosil R972 11.58 50% Benzoyl peroxide Luperco ATC 115.78 385.93 Procedure Polypropylene ether glycol (PPG) (molecular weight 1000) PolyF 20-112 hydrate in a container at 100-105 ° C and a vac less than 1 mm Hg, or until the moisture content is 0.05%. The dried PPG was cooled to 85 ° C before adding 5A molecular sieve and Rubinate 9310. Degassing was stopped and polyol and the polyisocyanate reacted at 85-95 ° C for one hour or until the isocyanate content reached the theoretical value. 19.79%. The mixture was cooled to 50 ° C and vacuum cracked. A nitrogen blanket was introduced before the addition of Mistron RCS and then Aerosil R972. When the addition of the filler was completed, Luperco ATC was added. The mixing of the resulting viscous mixture was manually started with a pallet. The final deep mixing was achieved with low tear and a mechanical mixer for 15 minutes. The degassing the final mixture started. When it came to a total vacuum product was degassed for 30 minutes before the discharge The product was stored under a nitrogen blanket. EXAMPLE 3 This example 3 describes the preparation of an unsaturated polyurethane (UPU) to be mixed with a polio and / or a polyamine to form part B. Formulation: Unsaturated polyurethane (UPU) Methyl methacrylate, MMA 48.0 ppi Hydroquinone, HQ 0.008 p-benzoquinone, BQ 0.008 Hydroxyethyl methacrylate, HEMA 9.6 Triol coated with ethylene oxide Rubinol F428 (hydroxyl number 28) 29.3 Polydi enylmethane diisocyanate Rubinate M 11.5 Dibutyltin dilaurate 0.68 MMA _ 0.86 99.96 Procedure MMA was loaded and HEMA. Hydroquinone (HQ and p-benzoquinone (BQ) was added and stirred until homogeneity, with Rubinol F428, an ethylene oxide covered with ethylene oxide with a hydroxyl number of 28. The moisture content was less than 600 ppm Rubinate M was charged and continuous stirring Dibutyl tin dilaurate previously dissolved in MMA was added The reaction was stirred and continued for 90 minutes EXAMPLE 4 This example 4 describes the preparation of another unsaturated polymer similar to polyester chemistry unsaturated used to adhere glass fibers for the manufacture of aquatic vehicles Unsaturated polyester UPE Diethylene glycol 467.2 ppp Dipropylene glycol 31.1 Maleic anhydride 99.3 Isophthalic acid 536.3 Styrene 538.0 Monothecial butyl hydroquinone 0.193 Methanol 0.772 Procedure Diethylene glycol and propylene glycol were charged and heated 140 ° C under an inert cover.The maleic anhydride and the isophthalic acid were added and heated to 210 ° The continuous reaction to a viscosity of 13-15 stoke with 2 styrene. Styrene and hydroquinone from monoteriary buti were added dissolved in methanol. The product cooled to 170 ° C and was discharged. EXAMPLE 5 This Example 5 describes the preparation of the polyol / polyamine / unsaturated polymer portion to vulcanize a polyisocyanate such as polyisocyanate 4495 d Example 1. Vulcanizer 4600 Propoxylated pentaerythritol PeP 550 2.67 ppi (No. Hydroxyl 450, molecular weight 500) Propoxylated glycerin ET 3500 (OH # 48, weight 10.98 molecular 3500) Diethyltoluene diamine Ethacure 100 2.72 Unsaturated polyurethane of example 3 43.59 Methacrylate methyl (MMA) 8.38 Diallyl phthalate (DAP) 6.70 Smoked silica treated Cabosil TS720 7.54 Powder absorbs moisture from molecular sieve 5A 0.42 Green pigment StanTone 6783 0.17 Dimethyl aniline (DMA) 0.59 Dibutyl tin diacetate Dabco Ti 0.059 83.819 Procedure PeP550, ET3500, Ethacure 100, Modar 839 and DAP loaded and agitated to mix them deeply. Cabosil TS720 half required. When the mixture was still in a fairly fluid state, the 5A molecular sieve, StanTone 6783, DMA and Dabco TI were added. Under a nitrogen blanket, ending with the addition of the Cabosil TS72 When the filter was wetted and completely dispersed the mixture degassed. When the total vacuum was obtained continuous degassing for 20 minutes before discharge. The product is stored under an air atmosphere. EXAMPLE 6 This example 6 illustrates the performance of unsaturated polyurethane adhesion plus polyurethane 46 hybrid adhesive by mixing polyisicianate 4495 of example 1 with vulcanizate 4600 of example 5. After vulcanizing at room temperature over fiberglass reinforced polyester substrate Arctic Cat, Inc., Thief River Falls, MN 56701, or cold-pressed F Arctic Cat, Inc. or FRP Mercury Marine, observed an adhesive strength of up to 610 psi with 98% fiber tear . The adhesive also exhibited excellent resistance to settlement by not showing lumps when applied on a vertical surface. It has an adhesion time of 5.75 minutes and developed a force of 127 psi after 3 minutes at room temperature (table 1). Table 1. Adhesion performance of hybrid acrylic / polyurethane polyurethane adhesive EXAMPLE 7 This example 7 illustrates the adhesion performance of a hybrid adhesive of unsaturated polyurethane and polyurethane prepolymer on FRP. Table 2 Performance of a prepolymer hybrid adhesive (acrylated polyurethane / polyurethane EXAMPLE 8 This example 8 illustrates the adhesion performance of unsaturated polyester hybrid adhesive, polyurethane unsaturated and polyurethane on FR.

Table 3. Performance of a hybrid adhesive of unsaturated polyether / acrylated polyurethane / polyurethane EXAMPLE 9 This example 9 illustrates the formulation of polyols c peroxide to form part A and polyisocyanate unsaturated polymer to form part B. Table 4. Performance of polyol peroxide / acrylated polyurethane / polyisocyanate hybrid adhesives to * Vulcanizer 4002 is prepared by reacting polyols PolyTHF250 (275.00 ppp) and TMP (36.76 ppm) with Mondur MRS polyisocyanate (133.0) before the addition of Luperc ATC (443.76 ppm). EXAMPLE 10 This example 10 illustrates the use of benzoyl peroxide (BPO) / dimethylaniline (DMA) or methyl ethyl ketone peroxide (DDM9) / cobalt naphtenlate to vulcanize the unsaturated polymer and polyurethane hybrid adhesives. Table 5. Vulcanization with peroxide of hybrid adhesives ARCTCO FRP plate 7 days at RT 7 days at RT 8 days at RT 360 (100/0) 337 (60/40) 299 (95/5) 181 (100/0) 250 (40/60) 266 (95/5 ) 326 (100/0) 19 da RT 291 (100/0) 397/100/0) 310 (100/0) 313 (95/5) 316 (100/0) 273 (75/25) 292 (96 / 4) * OM Group, Inc., Outokumpu Chemicals. Mooney Chemicals Ine Vasset S.A. Cleveland, Ohio. EXAMPLE 11 This example 11 illustrates the use of diallyl phthalate (DAP) to achieve flexibility in hybrid polymers of unsaturated polyurethane / polyurethane. Final elongation values of up to 85% measured in the elongation stress test of the pure adhesives were observed. Table 6. Diallyl phthalate (DAP) as an effective promoter for flexibility for hybrid polymers of unsaturated polyurethane / polyurethane * Pol tetramethylene ether glycol, molecular weight 250. In reviewing the data in table 6, it is shown that diallyl phthalate is very effective in promoting high final elongation values of 59 to 85% for both unsaturated polyurethane / polyurethane prepolymer adhesives. and d unsaturated polyurethane / polyisocyanate.

EXAMPLE HA This example illustrates the use of an epoxy resin t as Epon 826 to achieve flexibility in unsaturated polymer / polyurethane adhesives. Final elongation values of 63% measured in the tensio elongation test of the pure adhesive were observed. Table 6a. Epoxide resin as an effective promoter flexibility of hybrid polyurethane unsaturated polymer adhesives Table 6a. Epoxide resin as an effective promoter flexibility for hybrid polymers unsaturated / polyurethane adhesives * Res ep ep x da EPON 826 is the product of epichlorhydrin biphenol A distributed by Shell. EXAMPLE 12 This example 12 illustrates the moisture resistance of unsaturated polymer / polyurethane hybrid adhesives. Tables 7, 8 and 9 show adhesives that retain up to 100% d adhesion to FRP after exposure to a relative humidity of 100% at a relative humidity at 38 ° C for 4 to weeks. Table 7. Formulations of polyurethane-unsaturated polyurethane / polyurethane hybrid adhesives Table 8. Moisture resistance of unsaturated polyurethane / polyurethane hybrid adhesive of table 7 Table 9. Moisture resistance of adhesive 4606 in table 1, example 6 The review of tables 7, 8 and 9 reveals that some adhesives of this invention provide laminates that have moisture resistance whether the adhesives are polyisocyanate part A plus unsaturated polyurethane. Polyol part B plus peroxy or polyisocyanate part A plus peroxide, psiol part B plus unsaturated polyurethane.

Claims (28)

1. CLAIMS 1.- A structural adhesive composition of d components for substrates that do not require previous surface treatment and that vulcanize at ambient temperature that consist of any of: a) a first component of polyisocyanate and peroxy mixture and a second component of polyol mixture or polyamines or combinations thereof, and a saturated polymer thereof, b) a first component of a mixture of polyisocyanate and unsaturated polymer and a second component of a mixture of polyol and peroxide.
2. 2. The adhesive according to claim 1, wherein the peroxide in benzoyl peroxide.
3. 3. The adhesive according to claim 1 which further contains diallyl phthalate.
4. 4. The adhesive according to claim 1 wherein the polyisocyanate is polyethylene diphenyl-polymeric polyisocyanate, the polyol is a mixture of propoxylated pentaerythritol and propoxylated glycerin, the polyamine is diethyl toluene diamine, and the unsaturated polymer consists of unsaturated polyurethane or polyester unsaturated combinations.
5. 5. The adhesive according to claim 1 wherein the substrates are selected from the group of plastic reinforced with glass fiber, metal and wood.
6. 6. - The adhesive according to claim 1 in which the substrates are made of plastic reinforced with glass fibers.
7. 7.- A laminate of two substrates that do not have previous surface treatment adhered to each other by means of the vulcanized residue of a two-component adhesive mixture before application to one of the substrates, the adhesive consists of polyisocyanate, polyol or polyamine or mixtures they, unsaturated polyurethane or unsaturated polyester, mixtures and peroxide.
8. 8. - The laminate according to claim 7 in which the polyisocyanate and the peroxide are supplied in a first component mixture and the polyol or polyamine and the unsaturated polyme are provided in a second component mixture.
9. 9. The laminate according to claim 7 in which the polyol and the peroxide are supplied in a mixture of the first component and the polyisocyanate and the unsaturated polyurethane or unsaturated polyester are provided with a mixture of the second component.
10. 10. The laminate according to claim 7 shows, when it is separated, tearing of the plastic substrate reinforced with glass fibers and the remaining integrity of the vulcanized adhesive residue.
11. 11. - The laminate according to claim 7 wherein the polyisocyanate is polymeric methylene difeni polyisocyanate, the polyol is a mixture of propoxylated pentaerythritol and propoxylated glycerin, the polyamine is diethylene toluene diamine, and the unsaturated polymer consists of unsaturated polyurethane or polyester unsaturated combinations.
12. 12. - The laminate according to claim 7 wherein the substrates are selected from the group of plasti reinforced with fiberglass, metal and wood.
13. 13. - The laminate according to claim 7 in which the substrates are plastic reinforced with glass fibers.
14. 14. The method for preparing a laminate of an untreated first substrate or a second substrate adhered between with a structural adhesive consisting of an unsaturated polymer vulcanizable with peroxide in combination with polyurethane or polyurethane urethane, such adhesive has vulcanizing properties at room temperature , time open resistance to the vertical surface, compression ridge without adhesion along the bonding line, cut-off flange along the bonding line, rapid development of the initial raw strength, final elongation of at least 20% , resistance to humidity and resistance to low temperatures, comprising the steps of applying to the first substrate an adhesive composition consisting of a mixture a first component a) polyisocyanate and peroxide and a second component b) unsaturated polymer and polyol or polyamine or its mixtures.
15. 15. - The method according to claim 14 in which the equivalent ratio of polyisocyanate: polyol to polyamine is 0.8 to 1.8: 1.
16. 16. The method according to claim 14 which consists of 15 to 50 parts by weight of the first component and 50 parts by weight of the second component.
17. 17. - The method according to claim 14 in which the first component consists of polyisocyanate and unsaturated polymer and the second component consists of peroxide polyol.
18. 18. - The method according to claim 17 in which the equivalent ratio of polyisocyanate: polyol is 0. to 1.8: 1.
19. 19. The method according to claim 17 in which the polyisocyanate is polyethylene diphenyl-polyisocyanate, the polyol is a mixture of propoxylated pentaerythritol and propoxylated glycerin, the polyamine is diethyl toluene diamine, and the unsaturated polymer consists of unsaturated polyurethane or unsaturated polyester or combinations thereof.
20. 20. The laminate according to claim 17 wherein the substrates are selected from the group of plastic reinforced with glass fiber, metal and wood.
21. 21. - The laminate according to claim 17 in which the substrates are made of plastic reinforced with glass fibers.
22. 22. - An adhesive composition for substrates that do not require previous surface treatment consisting of polyisocyanate, peroxide, polyol, optionally unsaturated polyamine polymer.
23. 23. The adhesive according to claim 22 in which the tertiary butyl perbenzoate peroxide.
24. 24. The adhesive according to claim 22 in the lime substrates are selected from the group of plastic reinforced with fiberglass, metal and wood.
25. 25. The laminate according to claim 22 in which the substrates are made of plastic reinforced with glass fibers.
26. 26. The adhesive according to claim 1 which also contains an epoxy resin.
27. 27. - The laminate according to claim 7 wherein the adhesive further contains an epoxy resin. * »
28. 28. The method according to claim 14 in which the adhesive also contains an epoxide resin.