MXPA97003688A

MXPA97003688A - Adhesives sensitive to pressure and constructions of amortiguamie

Info

Publication number: MXPA97003688A
Application number: MXPA/A/1997/003688A
Authority: MX
Inventors: S Bennett Greggory
Original assignee: Minnesota Mining And Manufacturing Company
Priority date: 1994-11-22
Filing date: 1997-05-20
Publication date: 1997-08-01

Abstract

The pressure sensitive adhesives, and the pressure adhesives expressed, and the viscoelastic materials which are the polymerization product of an acrylic acid ester of a monohydric alcohol, whose homopolymer has a Tg less than 0 ° C, a non-polar monomer ethylenically, are described. unsaturated whose homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C, and 0-5 parts by weight of a polar ethylenically unsaturated monomer, whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15

Description

PRESSURE SENSITIVE ADHESIVES AND CUSHION CONSTRUCTIONS BACKGROUND OF THE INVENTION Field of the Invention This invention relates to pressure sensitive adhesives and pressure sensitive adhesives, thickened.

Description of the Previous Technique Acrylate pressure sensitive adhesives are well known in the art. Many of these adhesives are copolymers of an alkyl ester of acrylic acid and a minor portion of a polar comonomer. Due to the presence of the polar comonomer, these adhesives in general do not adhere well to low energy surfaces and oily surfaces (for example, surfaces that have a critical surface tension of wetting no greater than about 35 dynes / cm). Although the adhesion can be improved through the addition of a thickener, the degree of improvement is limited to FBP: 2057 because most commercially available thickeners are immiscible in the polar adhesive containing the monomer.

BRIEF DESCRIPTION OF THE INVENTION In one aspect, the present invention features a pressure sensitive adhesive that includes the polymerization product of: a) 25-97 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a Tg less than 0 ° C; b) 3-75 parts by weight of an ethylenically unsaturated, non-polar monomer whose homopolymer has a solubility parameter of not greater than 10.50 and a Tq greater than 15 ° C; and c) 0-5 parts by weight of a polar ethylenically unsaturated monomer, which homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C. The relative amounts of the acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the ethylenically unsaturated polar monomer are chosen such that the adhesion to the 90 ° release or adhesion of the 90 ° film of the pressure sensitive adhesive to a polypropylene surface, is at least 0.7 kg / cm (2 pounds / 0.5 inch), after a residence time of 72 hours at room temperature, as measured according to Test Procedure BI, below. In the second aspect, the present invention features a pressure sensitive adhesive that includes the polymerization product of: a) 25-97 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a Tg less than 0 ° C; b) 3-75 parts by weight of a non-polar ethylenically unsaturated monomer, whose homopolymer has a solubility parameter of not more than 10.50 and .ia Tq greater than 15 ° C; and c) 0-5 parts by weight of a polar ethylenically unsaturated monomer, which homopolymer has a solubility parameter of 10.50 and a Tg greater than 15 ° C. The relative amounts of the acrylic acid ester, the ethylenically unsaturated non-polar monomer, and the ethylenically unsaturated polar monomer are chosen such that the adhesion of the 90 ° film of the pressure sensitive adhesive to a surface provided with 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 g / inch2) of oil is greater than zero after a residence time of 10 seconds at room temperature, as measured according to Test Procedure B-II, below. In a third aspect, the invention features a pressure sensitive adhesive including: a) the polymerization product of: i) 25-98 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a lower T9 of 0 ° C; ii) 2-75 parts by weight of a non-polar ethylenically unsaturated monomer, whose homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; iii) 0-5 parts by weight of a polar ethylenically unsaturated monomer, whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C; and b) at least one thickener that is miscible in the polymerization product at room temperature. By "misicible" it is meant that the final pressure sensitive adhesive does not exhibit macroscopic phase separation, as evidenced by optical clarity at room temperature.

In a preferred embodiment, the relative amounts of the acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the ethylenically unsaturated polar monomer, are chosen such that the adhesion of the 90 ° film of pressure sensitive adhesive to a surface of polypropylene is at least 0.7 kg / cm (2 pounds / 0.5 inches) after a residence time of 72 hours at room temperature, as measured according to Test Procedure Bl-III, below. In another preferred embodiment, the relative amounts of the acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the ethylenically unsaturated polar monomer are chosen such that the adhesion of the 90 ° film of the pressure sensitive adhesive to a surface provided with 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch2) of oil, is greater than zero, after a residence time of 10 seconds at room temperature, as measured according to Test Procedure B2-III, more ahead. The solubility parameter referred to herein is calculated according to the technique described in Fedors, Polym. Eng. And Sci., 14: 147 (1974). A monomer whose homopolymer has a solubility parameter greater than 10.50 when measured according to the Fedors technique, is referred to herein as a polar monomer, while a monomer whose homopolymer has a solubility parameter of 10.50 or less, when it is measured according to the Fedors technique, it is denominated in the present, as a non-polar monomer. The invention provides pressure sensitive adhesives and thickened pressure sensitive adhesives, which, by virtue of incorporating a non-polar ethylenically unsaturated monomer and limiting the content of the polar monomer to no more than 5 parts, show good adhesion to low energy surfaces (for example, plastics such as polyolefins) and oily surfaces. The adhesives show good adhesion to high energy surfaces such as stainless steel as well. Because the non-polar monomer reduces the polarity of the adhesive, commercially available thickeners (many of which have low polarity by themselves) are miscible in the adhesives, and thus can be used. Thus, rather than designing the thickener to make it miscible with the acrylate polymer, the invention moderates the properties of the acrylate polymer to make it miscible with the thickener. The adhesives are less toxic than, for example, adhesives containing polar heteroatom acrylates. The adhesives also show good cutting properties at both low and high temperatures, particularly when a small amount (not more than 5 parts) of a polar comonomer is included. The adhesives offer the additional advantage of reduced sensitivity to moisture, and reduced tendency to corrode metals such as copper, in relation to pressure sensitive adhesives containing higher amounts of polar comonomers. In addition, adhesives interact to a lesser degree with polar additives and, in some cases, increase the solubility of non-polar additives as compared to pressure sensitive adhesives containing higher amounts of polar comonomers. Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims.

DESCRIPTION OF THE PREFERRED MODALITIES A class of pressure sensitive adhesives according to this invention shows good adhesion to low energy surfaces such as polypropylene and to high energy surfaces such as stainless steel. In both cases, the peel strength at 90 ° after a residence time of 72 hours is at least 0.7 kg / cm2 (2 pounds / 0.5 inch), preferably at least 0.88 kg / cm (2.5 pounds / 0.5 inch), and more preferably at least 1.05 kg / cm (3 pounds / 0.5 inch) measured according to the BI Test Procedure, later. The adhesives also show good cohesive strength properties as measured by shear strength. Preferably, the cut resistance at room temperature and at 70 ° C is greater than 50 minutes, more preferably greater than 1,000 minutes, and even more preferably greater than 10,000 minutes measured according to Test Procedure C-I, below. A second class of pressure sensitive adhesives according to this invention shows good adhesion to oily surfaces (eg, oily metal surfaces). Examples of oily surfaces include surfaces provided with mineral oil, emulsion oils, peanut oil, motor oil (eg, 5 -30), WD40, and Ferricote 61 A US (Quaker Chemical Company) (a common protector for steel cold rolled). The adhesion of the pelíucla to 90 °, to a surface provided with 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch2) of oil after a residence time of 10 seconds at room temperature, is greater than zero, preferably at minus 44.6 g / cm (2 oz / 0.5 inch), and more preferably at least 89.2 g / cm (4 oz / 0.5 inch), measured according to Test Procedure B-II, below. After a residence time of 1 minute, the adhesion is preferably at least 111.5 g / cm (5 ounces / 0.5 inch), and more preferably at least 223 g / cm (10 ounces / 0.5 inch) measured in accordance to Test Procedure B-II, below. The adhesives also show good cohesive strength properties as measured by shear or shear strength. Preferably, the cut resistance at room temperature and at 70 ° C is greater than 50 minutes, more preferably greater than 300 minutes, and even more preferably 600 minutes.

The thickened pressure sensitive adhesives of this invention show good adhesion to low energy surfaces such as polypropylene, to high energy surfaces such as stainless steel, and to oily surfaces (eg, oily metal). Examples of oily surfaces include surfaces provided with mineral oil, emulsion oils, peanut oil, motor oil (eg, 5W-30), WD40, and Ferricote 61 A US (Quaker Chemical Company) (a common protector for steel cold rolled) . Adhesion of the 90 ° film to polypropylene or steel after a residence time of 72 hours at room temperature is at least 0.7 kg / cm (2 pounds / 0.5 inch), preferably at least 1.05 kg / cm ( 3 pounds / 0.5 inch), and even more preferably at least 1.4 kg / cm (4 pounds / 0.5 inch) measured according to Test Procedure Bl-III, below. The adhesion of the film at 90 °, to a surface provided with 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch squared) of oil after a residence time of 10 seconds at room temperature, is greater than zero, preferably at least 44.6 g / cm (2 oz / 0.5 inch), and more preferably at least 89.2 g / cm (4 oz / 0.5 inch) measured according to Test Procedure B2-III, below. After a residence time of 1 minute, the adhesion is preferably at least 111.5 g / cm (5 oz / 0.5 inch), and more preferably at least 223 g / cm (10 oz / 0.5 inch) measured according to Test Procedure B2-III, below. The thickened adhesives also show good cohesive strength properties as measured by the shear strength. Preferably, the cut resistance at room temperature and at 70 ° C is greater than 50 minutes, more preferably greater than 1,000 minutes, and even more preferably greater than 10,000 minutes, measured according to Test Procedures Cl-III and C2-III. , later. The properties of the pressure sensitive adhesives and of the pressure sensitive adhesives thickened, according to the invention, are achieved by controlling the monomeric composition to achieve the proper polarity (as measured by the solubility parameter of the homopolymers of the individual monomers, determined according to the Fedors technique) and the rheological properties (Tg as measured by the maximum temperature delta of 1 radian / second tangent of the adhesive polymer).

The ability to incorporate a thickener increases the value of the peel strength beyond what it could be in the absence of the thickener. The thickener also increases the "freedom of formulation", for example, the ability to adjust the properties of adhesives for particular applications by introducing another variable, namely the thickener. Table 1 shows a list of several common monomers and their respective Fedors solubility parameters. Table 1 is subdivided into four sections: low Tg acrylate monomers, high Tg acrylate monomers, high Tg methacrylate monomers and vinyl monomers.

TABLE 1: PAR FOLLOWING SOLUBILITY METERS TABLE 1: FEDORS SOLUBILITY PARAMETERS TABLE 1: FEDORS SOLUBILITY PARAMETERS The rheological character of the adhesive polymer may be partially but usefully described by the Tg as measured by the maximum temperature delta of 1 radian / second tangent. In the case of adhesives designed for adhesion to low energy surfaces, it is preferable that the Tg as measured by the maximum delta of 1 radian / second tangent of the polymer, have a value between -45 ° C and 15 ° C, more preferably between -25 ° C and 0 ° C, and even more preferably between -20 ° C and -5 ° C. In the case of adhesives designed for adhesion to oily surfaces, it is preferable for Tg, as measured by the maximum temperature delta of 1 radian / second tangent of the polymer, having a value between 45 ° C and 15 ° C, more preferably between -35 ° C and 0 ° C, and even more preferably between -30 ° C and -5 ° C. In both cases, the adhesives according to the invention having the required polarity and the rheological properties, contain 25-97 parts (more preferably 40-85 parts) of an ester of acrylic acid whose homopolymer has a Tg less than 0 ° C (more preferably less than -20 ° C), 3-75 parts (more preferably 15-60 parts) of a non-polar ethylenically unsaturated monomer, which homopolymer has a Tg greater than 15 ° C, and 0-5 parts (more preferably 0-3 parts) of an ethylenically unsaturated polar monomer, whose homopolymer has a Tg greater than 15 ° C. In the case of thickened pressure-sensitive adhesives, it is preferred that the delta of maximum temperature of 1 radian / second tangent of the polymer, have a value between -45 ° C and 15 ° C, more preferably between -25 ° C and 5 ° C, and even more preferably between -20 ° C and 0 ° C. The thickened adhesives according to the invention having the required polarity and the required rheological properties, contain 25-98 parts (more preferably 70-97 parts) of an ester of acrylic acid whose homopolymer has a Tg less than 0 ° C (more preferably less than -20 ° C), 2-75 parts (more preferably 3-30 parts) of a non-polar ethylenically unsaturated monomer whose homopolymer has a Ta greater than 15 ° C, 0-5 parts (more preferably 0-3 parts ) of an ethylenically unsaturated polar monomer, whose homopolymer has a Tg greater than 15 ° C, and one or more thickeners. In all cases, the acrylic acid ester is a monofunctional acrylic ester of a monohydric alcohol having from about 4 to about 18 carbon atoms in the alcohol portion, which homopolymer has a Tg less than 0 ° C. Included in this class of acrylic acid esters are isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, decyl acrylate, lauryl acrylate, hexyl acrylate, butyl acrylate, and octadecyl acrylate, or combinations thereof.

In the case of octadecyl acrylate, the amount is chosen such that the crystallization of the side chain does not occur at room temperature. The non-polar ethylenically unsaturated monomer is a monomer whose homopolymer has a solubility parameter as measured by the Fedors method of no more than 10.50, and a Tg greater than 15 ° C. In a preferred embodiment, the non-polar ethylenically unsaturated monomer is a monomer whose homopolymer has a solubility parameter, as measured by the Fedors method, of not more than 10.3, more preferably not greater than 9.9. The non-polar nature of this monomer improves adhesion to the low energy surfaces, and adhesion to oily surfaces, of the adhesive. It also improves the structural properties of the adhesive (for example, the cohesion resistance), relative to an homopolymer of the acrylic acid ester described above. . Examples of suitable non-polar monomers include 3, 3, 5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, N-octyl-acrylamide, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate. or combinations thereof. The adhesive may contain a limited amount (eg, no more than 5 parts) of a polar ethylenically unsaturated monomer, whose homopolymer has a solubility parameter as measured by the Fedors method, greater than 10.50 and a Tg greater than 15 °. C, to improve the structural properties (for example, the resistance to cohesion). It is not desirable to include more than 5 parts of the polar monomer, because the polar monomer deteriorates adhesion to low energy surfaces and adhesion to oily surfaces, and reduces the miscibility of the thickener. Examples of suitable polar monomers include acrylic acid, itaconic acid, certain substituted acrylamides such as N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, tetrahydrofurfuryl acrylate, glycidyl acrylate, acrylate 2-phenoxyethyl and benzyl acrylate, or combinations thereof. In the case of thickened compositions, the thickener must be miscible with the acrylate-containing polymer of the adhesive, such that macroscopic phase separation does not occur, in order to improve the properties of the adhesive. Preferably, the adhesive is also free from microscopic phase separation. The most commercially available thickeners are hydrocarbon based and thus are of low polarity. Such thickeners are ordinarily not miscible with conventional, polar, monomer containing adhesives. However, by incorporating a non-polar monomer within the adhesive (whereby the non-polar character of the adhesive is increased) the invention allows a variety of commercially available thickeners to be used. The total amount of thickener is preferably 5-60 parts per 100 parts of polymers containing acrylate, and more preferably about 15-30 parts. The particular amount of the thickener depends on the composition of the acrylate-containing polymer, and is generally selected to maximize the release or film properties without compromising the desired cut resistance. Because the adhesives are preferably prepared by the polymerization of monomers in the presence of the thickener, according to a free radical process, it is further desirable to select a thickener that does not substantially impede the polymerization process, for example, by acting as a free radical scavenger, chain terminator, or chain transfer agent. A measure of the ability of the thickener to inhibit free radical polymerization in a bulk polymerization process for a given process condition is defined herein as the "inhibition factor". The inhibition factor (IF) is determined from the monomer conversion test and is the ratio of 1) the percentage of volatile compounds in the thickened sample (C.) minus the percent of volatile compounds in an identically formulated sample and processed, without thickener (C.) and 2) the percentage of volatile compounds of an identically formulated and processed sample, without thickener (C0). The inhibition factor equation is shown below: IF - _ (.Ct-Co). Co Although a wide variety of thickeners can be used, in cases where polymerization with free radicals is involved, the class of thickeners known under the commercial name of Regalrez resins, commercially available from Hercules, are preferable. These thickeners are produced by polymerization and hydrogenation of pure monomeric hydrocarbon raw material. Suitable resins include Regalrez resins 1085, 1094, 6108, and 3102. The monomer mixture can be polymerized by various techniques, with the photoinitiated bulk polymerization, which is preferred. An initiator is preferably added to assist in the polymerization of the monomers. The type of initiator used depends on the polymerization process. Photoinitiators which are useful for the polymerization of the acrylate monomers include benzoin ethers such as benzoin methyl ether or benzoin isopropyl ether, substituted benzoin ethers such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl such as 2-naphthalenesulfonyl chloride, and photoactive oxides such as 1-pheny1,2, 2-propanedione-2- (o-ethoxycarbonyl) oxime. An example of a commercially available photoinitiator is Irgacure * 651 available from Ciba-Geigy Corporation, which has the formula 2, 2-d? .. ethoxy-l, 2-diphenyletan-1-one). In general, the photoinitiator is present in an amount of about 0.005 to 1 percent by weight based on the weight of the monomers. Examples of thermal initiators include AIBN and peroxides. The mixture of the polymerizable monomers may also contain a crosslinking agent, or a combination of crosslinking agents, to increase the cut resistance of the adhesive. Useful crosslinking agents include the substituted triazines such as 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (3, -dimethoxyphenyl) - s-triazine, and the chromophore-substituted halo-s-triazines described in U.S. Patent Nos. 4,329,384 and 4,330,590 (Vesley). Other useful crosslinking agents include the multifunctional alkyl acrylate monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,2-ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and dialkyl diacrylate. 1, 12-dodecanol.

Various other crosslinking agents with different molecular weights between the functional group (meth) acrylate could also be useful. In general, the crosslinker is present in an amount of about 0.005 to 1 percent by weight based on the combined weight of the monomers. Where a pressure-sensitive adhesive tape in the form of foam is desired, a monomer mixture containing microspheres can be used. Appropriate microspheres are commercially available from Kema Nord Plastics under the trade name "Expancel" and from Matsumoto Yushi Seiyaku under the trade name "Micropearl". When expanded, the microspheres have a specific density of approximately 0.02-0.036 g / cmJ. It is possible to include the unexpanded microspheres in the pressure sensitive adhesive composition, and subsequently to heat them to cause expansion when they are properly processed, but it is generally preferred to mix the expanded microspheres within the adhesive. This process makes it easier to ensure that the "hollow microspheres in the final adhesive are substantially surrounded by at least one thin layer of adhesive.The polymer microspheres having an average diameter of from 10 to 200 microns can be mixed in the polymerizable composition in amounts from about 15% to about 75% by volume before coating, glass microspheres having an average diameter of from 5 to 200 micrometers, preferably from about 20 to 80 micrometers are also useful.Such microspheres may comprise 5% to 65% by weight. Volume of Pressure Sensitive Adhesive Polymeric and glass microspheres are known in the art The pressure sensitive adhesive layer of the tape should be at least 3 times as thick as the diameter of the spheres, preferably at least 7. times.

Other tape constructions in which the pressure sensitive adhesives according to the invention are useful, include mechanical fasteners such as the Dual Lock5 brand fastener (Minnesota Mining and Manufacturing Co., Saint Paul, MN) and the fastener brand Scotchmate31 (Minnesota Mining and Manufacturing Co., Saint Paul, MN). Pressure sensitive adhesives are also useful in vibration damping applications. Other materials that can be mixed with the polymerizable monomers before coating include plasticizers, tackifiers, coloring agents, reinforcing agents, fire retardants, foaming agents, thermally conductive agents, electrically conductive agents, post curing agents, and curative agents. post cure and its accelerators, and the like. The pressure sensitive adhesives according to the invention are preferably prepared by photoinitiated bulk polymerization, according to the technique described in Martens et al., US Pat. No. 4,181,752. The polymerizable monomers and a photoinitiator are mixed together in the absence of solvent and partially polymerized at a viscosity in the range of about 500 cps to about 50,000 cps to achieve a coatable syrup. Alternatively, the monomers can be mixed with a thixotropic agent such as fumed hydrophilic silica to achieve a coatable thickness. The crosslinking agent and any other ingredients (including any thickeners) are then added to the prepolymerized syrup. Alternatively, these ingredients (including any thickeners but with the exception of the crosslinking agent) can be added directly to the monomer mixture before prepolymerization. The resulting composition is coated on a substrate (which may be transparent to ultraviolet radiation) and polymerized in an inert atmosphere (eg, free of oxygen), for example, a nitrogen atmosphere by exposure to ultraviolet radiation. Examples of suitable substrates include release liners (e.g., silicone release liners) and tape liners or reinforcements (which may be sized or unprepared paper or plastic). A sufficiently inert atmosphere can also be achieved by covering a layer of the polymerizable coating with a plastic film which is substantially transparent to ultraviolet radiation, and irradiating through that film the air, as described in the Martens patent and collaborators mentioned above, using ultraviolet light lamps. Alternatively, instead of covering the polymerizable coating, an oxidizable tin compound may be added to the polymerizable syrup, to increase the tolerance of the syrup to oxygen as described in U.S. Patent No. 4,303,485 (Levens). The ultraviolet light source preferably has 90% of the emissions between 280 and 400 nanometers (more preferably between 300 and 400 nanometers), with a maximum at 351 nanometers. The thickeners can be added after the polymerization of the acrylate monomers. Where multi-layer tape constructions are desirable, one method of construction is multi-layer coating using conventional techniques. For example, the coatings may be applied concurrently (for example, through a die coater), after which the entire multilayer structure is cured at one time. The coatings can also be applied sequentially, whereby each individual layer is partially or completely cured before the application of the next layer. The compositions of the invention are also useful for damping vibrations, when in contact with vibrating parts, especially when the vibrating parts are made of oily metals or polymeric materials. In addition to the adhesives described above, the vibration damping materials of the invention can not be pressure sensitive adhesives. The invention provides a damping construction comprising at least one layer of an adhesive applied to a solid vibrating article, and a damping construction comprising at least one layer of viscoelastic material applied to a solid vibrating article. The invention provides a damping construction comprising at least one layer of a viscoelastic material applied to a solid vibrating article, the viscoelastic material comprising the reaction product of starting materials comprises: a) 3-97 parts by weight of an ester of acrylic acid of a monohydric alcohol whose homopolymer has a T7 less than 0 ° C; b) 3-97 parts by weight of a non-polar ethylenically unsaturated monomer, the homopolymer of which has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; and c) 0-5 parts by weight of an ethylenically unsaturated polar monomer whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C, and substantially no epoxy component. In a preferred embodiment, the starting materials comprise from 25 to 97 parts by weight of component a), 3 to 75 parts by weight of component b), and 0 to 5 parts by weight of component c). The damping of vibration is measured in terms of the loss factor, which is a proportion of the energy dissipated to the stored energy. The greater the amount of energy dissipated, the greater the loss factor, and therefore the better the buffering properties of the material. The vibration dampers operate in a range of temperatures, and the compositions can be formulated to provide optimum damping at a desired temperature range. The compositions may provide materials for vibration dampers that are pressure sensitive at room temperature, or are substantially non-tacky at room temperature, for example, the sheet may not instantly adhere to a substrate at room temperature, under the pressure of the finger. Typically, compositions having larger amounts of the non-polar comonomer having a Tg of the homopolymer greater than 15 ° C, for example, greater than about 45-50 parts, depending on the comonomer, are not sensitive to pressure at room temperature. If desired, a non-tacky cushion can be adhered to a substrate, by heating the substrate while in contact with the sheet material for vibration damping, or the non-tacky cushion can be adhered to the substrate with known adhesives, preferably adhesives. rigid. The vibration dampers of the invention are not particularly sensitive to moisture, and may provide advantages in areas where the damper is exposed to the atmosphere, or where spontaneous gas shedding, usually caused by moisture absorbed by the damper, may be of interest In practice, the compositions are typically formed on a sheet or on a plate. The thickness of the sheet is determined to a greater degree by the application, and useful thicknesses may be in the range of about 0.015 mm to above 2.54 cm. The sheet can be applied to a constraint layer or forced layer that is stiffer than the sheet to form a composite called a forced layer cushion. Suitable materials for constraint layers or forced layers are metal sheets, such as aluminum and steel, and plastics, such as polyester. The forced layer is generally selected so that the stiffness of the panel is greater than the rigidity, for example, of the module, of the sheet material. Optimally, although not required, the rigides of the panel is approximately equal to that of the object to be damped. The sheet can also be applied directly to the object to be cushioned, as a free-layer cushion. The vibration damping compounds of the invention are particularly useful in automobile constructions, in which the compounds can be applied directly to a car panel, such as a door panel, during the stamping or die cutting step without requiring cleaning and removal of the laminate oils on the panel. During the stamping stage, the metal, usually cold-rolled steel or aluminum, is still coated with laminate oils, used to prevent mildew or oxidation. Sheet materials are also useful as vibration dampers, either as a shock absorber for a forced layer or as a shock absorber, for oily motor covers, to dampen vibrations and reduce the noise coming from the motor. The sheet materials of the invention are especially advantageous, since they can be applied to the cover without requiring tedious cleaning with solvents and / or detergents to remove the oil. In this application, the sheet materials do not need to be sensitive to pressure, and can be applied by heating the motor cover above the Tg of the damper. The vibration damping materials of the invention are also for use in damping applications where gas evolution is of interest. Such applications include computer components such as suspension dampers for the read / write head, free-wheel or forced-bed dampers for disc-port covers, or for joint sealing of the disc-port covers. The vibration dampers of the invention can be processed without acid; these can be advantageously used where corrosion is a potential problem, such as on bare copper surfaces.

Other useful applications of the invention include the damping of vibration for shock absorbers and seismic dampers for buildings. The sheet materials can be die cut to a desired shape, for example a donut or donut shape or a circular disk, or these can be formed into a mold in the desired configuration, such as a molded plate.

The invention will now be further described by means of the following examples.

EXAMPLES I. Adhesives for Low Energy Surfaces Test Procedures-Adhesion to Low Energy Surfaces The test procedures used in the examples for evaluating pressure sensitive adhesives, useful for adhesion to low energy surfaces, include the following.

Monomer Conversion Test (Test Procedure A-I) The monomer conversion was determined gravimetrically. A sample of the adhesive was weighed after it was coated and subsequently dried at 120 ° C for 3 hours and then weighed again. The percent of volatile materials was taken as an indicator of monomer conversion.

Release Adhesion Test at 90 ° C (Test Procedure B-I) Strips of 1.27 cm (half an inch) in width of the adhesive sample were carefully cut and placed on the substrate of interest. The thickness of the adhesive was 0.127 mm (5 mils). An anodized aluminum liner of 0.127 mm (5 mils) of 1.59 cm (0.625 inch wide) was then laminated to the adhesive, which is approximately 12.7 mm (5 inches) long. The test substrates of interest included low energy surfaces such as polypropylene (5.08 x 12.7 x 0.5 cm (2"x 5" x 3/16") natural polypropylene panels of Precision Punch and Plastic, Minneapolis, MN, with a mask on both sides that is removed before cleaning and testing) and polycarbonate (Lexan® by General Electric Company), and high-energy surfaces such as stainless steel (28-gauge 304-2BA stainless steel with a surface roughness of 5.08 x 10"d cm ± 2.54 x 10" ° (2.0 ± 1.0 icropulgadas) A free end of the liner or reinforcement to which the adhesive was laminated, extended beyond the test substrate, so that it could be attached to a load cell, to determine the peel strength, the sample was laminated back and forth twice with a 2 kg hard rubber roller, to ensure contact between the adhesive and the test substrate. removed after for a given residence time (usually 72 hours unless otherwise indicated) at 30.48 cm / minato (12"/ minute) in a 90 ° C release mode. The stainless steel substrates were washed once with acetone and three times with a 50/50 mixture of isopropanol / water before the test. The plastic substrates were washed 3 times with heptane before the test. The results are reported in 0.350 kg / cm (pounds / 0.5 inch) in width as the average of two tests. All tests were conducted at room temperature.

Cutting Test (Test Procedure C-I) A strip of 1.27 cm (0.5 inch) of tape was adhered to a piece of stainless steel (stainless steel 28 gauge 304-2BA with a superficial asperes of 5.08 x 10"6 ± 2.54 x 10" 6 cm (2.0 ± 1.0 micropulgadas ) which had been cleaned once with acetone and three times with a 50/50 mixture of isopropanol / water such that an overlap of 1.61 cm2 (one half square inch) was achieved.A piece of anodised aluminum 0.27 mm (5 mils) inch) of 1.59 cm (0.625 inch) width was then laminated to the entire area of the pressure sensitive adhesive, leaving an additional area to which a load could be applied.The thickness of the adhesive was 0.127 mm (5 mils) The sample was then licked back and forth twice with a 6.8 kg (15 lb.) roller and left for four hours.The samples at 70 ° C were left for an additional 10 minutes after a residence time. , the sample was tested either at room temperature or at 70 ° C. At room temperature, a load of 1 kg was applied to the adhesive and the time before the fall of the load was recorded. At 70 ° C, a 500 g load was applied to the adhesive, and the time before the fall of the load was recorded. The results are reported as the average of 2 tests.Comparative Examples-Adhesion to Low Energy Surfaces Comparative Example C-1 A premix was prepared using 90 parts of isooctyl acrylate (IOA), 10 parts of acrylic acid (AA) and 0.04 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator (Irgacure® 651, available from Ciba Geigy Corporation). This mixture was partially polymerized under a nitrogen-rich atmosphere by exposure to ultraviolet radiation, to provide a coatable syrup having a viscosity of about 3000 cps. 0.15 parts of 2,6-bis-trichloromethyl-6- (4-methoxyphenyl) -s-triazine and 0.16 additional parts of Irgacure8 651 were added to the syrup and this was then knife coated onto a paper release liner coated with polyethylene, treated with silicone, to a thickness of 0.127 mm (5 mils). The resulting compound was then exposed to ultraviolet radiation having a spectrum of 300 to 400 nm, with a maximum at 351 nanometers in a nitrogen-rich environment. An intensity of approximately 1.0 mW / cm2 was used for the first third of the exposure time, and an intensity of approximately 2.2 mW / cm2 was used for the second two thirds of the exposure time, resulting in a total energy of 250 mj / cm2. The adhesive was then tested to the test methods listed above, and the results are shown in Table 1-2. The designation "RT" means room temperature.

Comparative Examples C2 and C3 Comparative example C2 was prepared in the same manner as comparative example Cl, except that a premix of 94 parts of IOA and 6 parts of AA was used. Comparative example C3 was prepared in the same manner as comparative example Cl, except that a premix of 100 parts of IOA and 0 parts of AA was used. The comparative examples C2 and C3 were tested according to the test methods listed above, and the results are shown in Table 1-2.

TABLE Y-2 Examples-Adhesion to Low Energy Surfaces Examples 1-23 Example 1 was prepared in the same manner as comparative example Cl, except that the mixture consisted of 66 parts of IOA, 33.5 parts of isobornyl acrylate (IBA), and 0.5 parts of AA. In addition, 0.09 parts of 2,6-bis-trichloromethyl-6- (4-methoxyphenyl) -s-triazine were added and then the premix was partially polymerized. The compound was exposed to ultraviolet radiation having a spectrum of 300 to 400 nanometers, with a maximum at 351 nm in a nitrogen-rich environment, at an average intensity of approximately 2.05 mW / cm2. The total energy was 650 mJ / cm2. Example 2 was prepared in the same manner as Example 1, except that a pre-mix consisting of 69 parts of IOA, 30 parts of IBA and 1 part of AA was used. Example 3 was prepared in the same manner as Example 1, except that a premix was used which consisted of 65.5 parts of IOA, 34.25 parts of IBA and 0.25 parts of AA. Example 4 was prepared in the same manner as Example 1, except that a premix consisting of 65 parts of IOA and 35 parts of IBA, and 0.05 parts of 2,5-bis-trichloromethyl-6- (4-methoxyphenyl) was used. -s-triazine. Example 5 was prepared in the same manner as Example 4, except that a premix of 55 parts of IOA and 45 parts of 3,3,5-trimethylcyclohexyl acrylate (TMCA) was used. Example 6 was prepared in the same manner as Example 5, except that 0.10 parts of 2,6-bis-trichloromethyl-4- (p-methoxyphenyl) -s-triazine were used. Example 7 was prepared in the same manner as Example 1, except that a premix of 72 parts of IOA, 27 parts of IBA and 1 part of AA was used. Example 8 was prepared in the same manner as Example 1, except that a premix of 66 parts of IOA, 33 parts of IBA and 1 part of AA was used. Example 9 was prepared in the same manner as Example 1, except that a premix of 63 parts of IOA, 36 parts of IBA and 1 part of AA was used. Example 10 was prepared in the same manner as Example 1, except that a premix of 70.75 parts of IOA, 29 parts of TMCA and 0.25 parts of AA was used.

Example 11 was prepared in the same manner as Example 1, except that a premix of 64.5 parts of IOA, 35 parts of TMCA and 0.5 parts of AA was used. Example 12 was prepared in the same manner as Example 1, except that a premix of 49 parts of IOA, 51.5 parts of cyclohexyl acrylate (CHA), and 0.5 parts of AA was used. Example 13 was prepared in the same manner as Example 1, except that a premix of 80 parts of IOA, 19.5 parts of N-octylacrylamide (NOA), and 0.5 parts of AA was used. Example 14 was prepared in the same manner as Example 6, except that a premix of 90 parts of IOA, 10 parts of IBA and 0.5 parts of AA was used. Example 15 was prepared in the same manner as Example 6, except that a premix of 80 parts of IOA, 20 parts of IBA and 0.5 parts of AA was used. Example 16 was prepared in the same manner as Example 6, except that a premix of 70 parts of IOA, 30 parts of IBA and 0.5 parts of AA was used.

Example 17 was prepared in the same manner as Example 6, except that a premix of 90 parts of IOA, 10 parts of TMCA, and 0.5 parts of AA was used. Example 18 was prepared in the same manner as Example 6, except that a premix of 80 parts of IOA, 20 parts of TMCA, and 0.5 parts of AA was used. Example 19 was prepared in the same manner as Example 6, except that a premix of 70 parts of IOA, 30 parts of TMCA, and 0.5 parts of AA was used. Example 20 was prepared in the same manner as Example 6, except that a premix of 60 parts of IOA, 40 parts of TMCA, and 0.5 parts of AA was used. Example 21 was prepared in the same manner as Example 6, except that a premix of 55 parts of IOA, 45 parts of TMCA, and 0.5 parts of AA was used. Example 22 was prepared in the same manner as Example 6, except that a premix of 50 parts of IOA, 50 parts of CHA, and 0.5 parts of AA was used.

Example 23 was prepared in the same manner as Example 6, except that a premix of 45 parts of IOA, 55 parts of CHA, and 0.5 parts of AA was used. The data of Examples 1-23 are shown in Table 1-3. In the table "St.St" refers to stainless steel. The designation "n.t." it means not tested. The designation "RT" means room temperature. The designation "(1/2)" means that 1 of the 2 samples tested passed the test. The samples for the adhesion test in Examples 4 and 5 were prepared using a 6.8 kg (15 lb.) roller. A residence period of 24 hours was used. Because Examples 13, 14, 17, 18, 22, and 23 do not meet the minimum requirement for adhesion to detachment, these were included here as additional comparative examples.

TABLE 1-3 TABLE 1-3 TABLE 1-3 The data in Table 1-3 show that adhesion to low energy surfaces such as polypropylene can be increased without decreasing adhesion to the high energy surface, such as stainless steel, as observed in the comparative examples of the Table 1-2. In addition, the data in Table 1-3 show that desirable cohesive strength properties can also be achieved in the pressure sensitive adhesives of this invention.

II. Adhesives for Adhesion to Oily Surfaces Test Procedures-Adhesion to Oily Surfaces The test procedures used in the examples for evaluating pressure sensitive adhesives, useful for adhesion to oily surfaces, include the following.

Monomer Conversion Test (Test Procedure A-II) The conversion of monomers was determined gravimetrically. They were laminated 7.62 cm x 7.62 cm (3 inches x 3 inches) to a piece of aluminum foil, weighed, and placed in a forced air oven at 121 ° C (250 ° F) for 90 minutes. The samples were then equilibrated at room temperature and reweighed for weight loss. The percentage of volatiles was taken as an indicator of monomer conversion. 90 ° Release Adhesion Test (Test Procedure B-II) Pieces of 1.27 cm (half an inch) in width of the samples were cut and rolled up to anodized aluminum of 0.127 mm (5 mils) which had a width of 1.58 cm (0.625 inch). The thickness of the adhesive was 0.127 mm (5 mils). The release liner was then removed from the adhesive and the samples were placed on either a stainless steel substrate (304 stainless steel with a # 7 finish) or a cold rolled steel substrate (20-gauge cold plate, CRS 1018 with finish). by laminate). The stainless steel substrate was cleaned before application of the adhesive by rubbing, once with acetone, and 3 times with heptane. The cold rolled steel substrate was cleaned before application of the adhesive by rubbing once with acetone. Before application of the adhesive, an excess of general oil was applied to each substrate of cold rolled steel, with a small piece of gauze fabric and then removed to leave an oil coating that was 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch2). A free end of the liner to which the adhesive was laminated was extended beyond the test substrate, so that it could be attached to a load cell to determine the peel strength. The sample was rolled back and forth twice with a 2.04 kg (4.5 lb.) roller to ensure contact between the adhesive and the test substrate. The adhesive was then removed after a given residence time (10 seconds, 1 minute, or 24 hours) at 30.48 cm / minute (12 inches / minute) in a 90 ° release mode. The reported values are in (ounces / 0.5 inches) and represent the average release values (based on two tests) obtained between 2.54 and 10.16 cm (1 and 4 inches) on a detachment sample of 12.7 cm (5 inches) . All tests were performed at room temperature. Cutting Test (Test Procedure C-II) Pieces of 1.27 cm (half an inch) in width, of samples, were cut and laminated to anodized aluminum of 0.127 mm (5 mils) in thickness which was 1.58 cm (0.625 in) wide. This construction was placed on stainless steel panels (304 stainless steel with a # 7 finish) that had been cleaned by rubbing once with acetone and 3 times with heptane. The placement was such that a 2.54 cm x 1.27 cm (1.0 inch x 0.5 inch) adhesive sample (adhesive thickness = 0.127 mm (5 mils) was in contact with the panel.) The adhesive sample was laminated back and forward twice with a 2.04 kg (4.5 lb.) roller, with some excess material protruding from the sample for weight attachment.The samples were then left for 24 hours after the weight was hung on the samples. The samples at 70 ° C were also left for an additional 10 minutes in the oven, before the weight was applied, for the samples at room temperature, a weight of 1000 g was used, while for the samples at 70 ° C a weight of 500 g was used.The cut data are reported in minutes until the weight falls, and represent the average of two tests.

Phase Separation (Test Procedure D-II) The presence or absence of phase separation was judged by the optical clarity of the resulting polyacrylate / thickener mixture. The visual observation of the opacity was taken as an indicator of phase separation.

Comparative Examples-Adhesion to Oily Surfaces Comparative Example Cl 94 parts of isooctyl acrylate (IOA) and 6 parts of acrylic acid (AA) were mixed together in a vessel under a constant nitrogen purge together with 0.4 parts of the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (Irgacure9 651, available from Ciba Geigy Corp.). This mixture was partially polymerized under a nitrogen-rich atmosphere, to provide a coatable syrup having a viscosity of about 3000 cps. 0.16 parts of 2, -bis (trichloromethyl) -6- (3, 4-dimethoxyphenyl) -s-triazine and 0.16 additional parts of Irgacure9 651 were added to the syrup and this was then coated by blades on a coated paper backing, release, at a thickness of 0.127 mm (5 mils). The resulting coating was then exposed to ultraviolet radiation having a spectral yield of 300-400 nm with a maximum at 351 nm in a nitrogen-rich environment. An intensity of approximately 2.05 mW / cm2 was used for a total dose of 650 mj / cm2. The resulting adhesive was then tested according to the test methods listed.

Comparative Examples C2 and C3 Comparative example C2 was prepared in the same manner as comparative example Cl, except that a premix of 10 parts of AA and 90 parts of IOA was used. In addition, 0.12 parts of triazine were used. Comparative example C3 was prepared in the same manner as comparative example Cl, except that a premix of 14 parts of AA and 86 parts of IOA was used.

Examples-Adhesion to Oily Surfaces Examples 1-20 Example 1 was prepared in the same manner as comparative example Cl, except that the premix consisted of 25 parts of N-octyl-acrylamide (NOA) and 75 parts of lauryl acrylate (LA). The NOA was heated to about 40 ° C before the syrup and coating formation. In addition, 0.08 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized.

Example 2 was prepared in the same manner as example 1, except that the premix consisted of 35 parts of NOA and 65 parts of LA. The NOA was heated to about 40 ° C before the syrup and coating formation. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 3 was prepared in the same manner as example 1, except that the premix consisted of 45 parts of NOA and 55 parts of LA. The NOA was heated to about 40 &C before the syrup and coating formation. Example 4 was prepared in the same manner as example 1, except that the premix consisted of 25 parts of isobornyl acrylate (IBA) and 75 parts of IOA. Example 5 was prepared in the same manner as example 1, except that the premix consisted of 30 parts of IBA and 70 parts of LA. Example 6 was prepared in the same manner as example 1, except that the premix consisted of 40 parts of IBA and 60 parts of LA. In addition, 0.12 parts of 2,6-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 7 was prepared in the same manner as example 1, except that the premix consisted of 30 parts of IBA and 70 parts of isodecyl acrylate (IDA). Example 8 was prepared in the same manner as Example 1, except that the premix consisted of 40 parts of IBA and 60 parts of IDA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 9 was prepared in the same manner as Example 1, except that the premix consisted of 40 parts of IBA, 15 parts of IOA, and 45 parts of LA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 10 was prepared in the same manner as example 1, except that the premix consisted of 35 parts of NOA, 15 parts of IOA, and 50 parts of LA. The NOA was heated to about 40 ° C before the formation of syrup and coating. In addition, 0.12 parts of 2,4-biS-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 11 was prepared in the same manner as example 1, except that the premix consisted of 35 parts of NOA, 35 parts of IOA, and 30 parts of LA. The NOA was heated to about 40 ° C before the formation of syrup and coating. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 12 was prepared in the same manner as Example 1, except that the premix consisted of 35 parts of NOA, 45 parts of IOA, and 20 parts of LA. The NOA was heated to about 40 ° C before the formation of syrup and coating. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 13 was prepared in the same manner as Example 1, except that the premix consisted of 35 parts of IBA, 15 parts of IOA, and 50 parts of octadecyl acrylate (ODA). In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized.

Example 14 was prepared in the same manner as example 1, except that the premix consisted of 35 parts of IBA, 35 parts of IOA, and 30 parts of ODA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 15 was prepared in the same manner as example 1, except that the premix consisted of 35 parts of IBA, 45 parts of IOA, and 20 parts of ODA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 16 was prepared in the same manner as example 1, except that the premix consisted of 30 parts of NOA, 40 parts of IOA, and 30 parts of ODA. The NOA was heated to about 40 ° C before the formation of the syrup and the coating. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 17 was prepared in the same manner as example 1, except that the premix consisted of 67 parts of IOA, 32.5 parts of IBA, and 0.5 parts of AA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine was added after the premix was partially polymerized. Example 18 was prepared in the same manner as example 1, except that the premix consisted of 69 parts of IOA, 30 parts of IBA, and 1 part of AA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 19 was prepared in the same manner as Example 1, except that the premix consisted of 71 parts of IOA, 27 parts of IBA, and 2 parts of AA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. Example 20 was prepared in the same manner as example 1, except that the premix consisted of 76 parts of IOA, 21 parts of IRA, and 3 parts of AA. In addition, 0.12 parts of 2,4-bis-trichloromethyl-6- (3,4-dimethoxyphenyl) -s-triazine were added after the premix was partially polymerized. The data of Examples 1-20, as well as the comparative examples Cl, C2, and C3, are shown in Table II-2. The designation "DNS" means that the adhesive did not stick to the substrate. The designation "nt" means not proven.

TABLE I I -2 TABLE I I -2 III. Thickened Pressure Sensitive Adhesives Test Procedures - Sensitive Adhesives Pressure The test procedures used in the examples for evaluating thickened pressure sensitive adhesives include the following.

Monomer Conversion Test (Test Procedure Al-III The monomer conversion was determined gravimetrically. A sample of the adhesive was weighed after it was coated and subsequently dried at 120 ° C for 3 hours, and then reweighed. The percentage of volatile materials was taken as an indicator of monomer conversion.

Monomer Conversion Test (Test Procedure A2-III) The conversion of monomers was determined gravimetrically. They were laminated 7.62 cm x 7.62 cm (3 inches x 3 inches) to a piece of aluminum foil, weighed, and placed in a forced air oven at 121 ° C (250 ° F) for 90 minutes. The samples were then equilibrated at room temperature and reweighed for weight loss. The percentage of volatiles was taken as an indicator of monomer conversion.

Adhesion to Release Test at 90 ° C (Test Procedure Bl-III) 1.27 cm (half inch) wide strips of a 0.127 mm (5 mils) adhesive sample was carefully cut and placed on the substrate of interest. An anodized aluminum reinforcement of 0.127 mm (5 mils), 1.58 cm (0.625 in) wide, was then rolled, to the adhesive, which was approximately 12.7 cm (5 inches) long. The test substrates of interest included low energy surfaces, such as polypropylene (2"x 5" x 3/16"natural polypropylene panels available from Precision Punch and Plastic, Minneapolis, MN, which have a mask on both sides that is removed before cleaning and testing) and polycarbonate (Lexan3 'available from General Electric Co.), and high energy surfaces such as stainless steel (28 gauge, 304 stainless steel -2BA with a superficial asperes of 5.08 x 10"° ± 2.54 x 10" "cm (2.0 ± 1.0 microinches)). A free end of the reinforcement to which the adhesive was laminated was extended beyond the test substrate, so that it could be fastened to a load cell to determine the peel strength. The sample was laminated back and forth twice with a 2 kg hard rubber roller to ensure contact between the adhesive and the test substrate. The adhesive was then removed after a given residence time (usually 72 hours unless otherwise indicated) at 30.58 cm / minute (12 inches / minute), in a 90 ° release mode. Detachment data are reported in kg / 1.27 cm (pounds / 0.5 inch) in width and represent the average of two tests. The stainless steel substrates were washed once with acetone and 3 times with 50/50 isopropanol / water mixture before the test. The plastic substrates were washed 3 times with heptane before the test. 90 ° Peel Adhesion Test (Test Procedure B2-III) 1.27 cm (half inch) pieces of width samples were cut and laminated to 0.127 mm (5 mil) thick anodized aluminum which was 1.58 cm (0.625 inches) wide. The thickness of the adhesive was 0.127 mm (5 mils). The release liner was then removed from the adhesive and the samples were placed either on a stainless steel substrate (304 stainless steel with a # 7 finish) or a cold rolled steel substrate (20-gauge cold-rolled plate, CRS 1018 with laminate finish). The stainless steel substrate was cleaned before application of the adhesive by rubbing once with acetone and 3 times with heptane. The cold rolled steel substrate was cleaned before application of the adhesive by rubbing once with acetone. Before application of the adhesive, an excess of mineral oil was applied to each substrate of cold rolled steel with a small piece of gauze and then removed to leave an oil coating that was 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch squared). A free end of the liner to which the adhesive was laminated, extended beyond the test substrate, so that it could be attached to a load cell to determine the resistance of the release film. The sample was laminated back and forth twice with a 2 kg (4.5 lb.) roller to ensure contact between the adhesive and the test substrate. The adhesive was then removed after a given residence time (10 seconds, 1 minute, or 24 hours) at 30.48 cm / minute (12 inch / minute) in a 90 ° release mode. The reported values are in /l.27 cm (ounce / 0.5 inch), and represent average release values (based on two tests) obtained between 2.54 and 10.16 cm (1 and 4 inches) on a sample for peeling 12.7 cm (5 inches) . All tests were performed at room temperature.

Cutting Test (Test Procedure Cl-III) A strip of 1.27 cm tape was adhered. (0.5 inch) to a piece of stainless steel (304 stainless steel with a # 1 finish) which had been cleaned once with acetone and three times with 50/50 isopropanol / water such that an overlap of 1.6 cm2 was achieved (1 / 2 inch2). An anodized aluminum piece of 0.127 mm (5 mil in) was then laminated to the entire area of the pressure sensitive adhesive, leaving an additional area to which a load could have been applied. The thickness of the adhesive was 0.127 mm (5 mils of an inch). The sample was rolled back and forth twice with a 6.8 kg (15 lb.) roller and left for four hours. The samples at 70 ° C were then left for 10 minutes at 70 ° C. After the residence time the sample was tested either at room temperature or at 70 ° C. At room temperature, a 1 kg load was applied to the adhesive and the time was recorded before the load fell. At 70 ° C, a 500 g load was applied to the adhesive and the time was recorded before the load fell.

Cutting data are reported in minutes and represent the average of two tests.

Cutting Test (Test Procedure C2-III) Pieces of 1.27 cm (1/2 inch) in width were cut and laminated to anodized aluminum of 0.127 mm (5 mil in) thick, which was 1.58 cm (0.625 in) wide. This construction 63-2 It was placed on stainless steel panels (304 stainless steel with a # 7 finish) that had been cleaned by rubbing with acetone and 3 times with heptane. The placement was such that a sample of adhesive of 2.54 cm x 1.27 cm (1.0 inch x 0.5 inch) (adhesive thickness = 0.127 mm (5 mil in)) was in contact with the panel. The adhesive sample was laminated twice back and forth with a 2 kg (4.5 lb.) roller with some excess material protruding from the sample for weight coupling. The samples were then allowed to recur for 24 hours before the weight was hung on the samples. The samples at 70 ° C were then left for an additional 10 minutes in the oven, before the weight was applied. For the samples at room temperature, a weight of 1000 g was used, while a weight of 500 g was used for the samples at 70 ° C.

Cutting data are reported in minutes, until the weight falls, and represent the average of two tests.

Phase Separation (Test Procedure D-III) 63-3 The presence or absence of phase separation was judged by the optical clarity of the resultant polyacrylate / thickener mixture. The visual observation of the opacity was taken as an indicator of phase separation. 64 Examples - Pressure Sensitive Adhesive, Thickened Examples 1-56 Example 1: 100 parts isooctyl acrylate (IOA), isobornyl acrylate (IBA), and acrylic acid (AA) with a monomer ratio of 80 / 19.5 / 0.5 (IOA / IBA / AA) was mixed with 0.04 parts of benzyldi ethylketal ( KB-1, SARTOMER Company) as a photoinitiator, and was photopolymerized with an ultraviolet light source under a constant nitrogen purge at a viscosity of approximately 2000 cps. 0.16 parts of additional benzyldimethyl ketal photoinitiator, 0.15 parts of 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl), and 20 parts of Regalrez 1085 thickener resin (Hercules Company) were added to the acrylate syrup and mixed until that all the components had been completely dissolved.

After mixing, the mixture was knife-coated to a thickness of 0.127 mm (5 mils) on a silicone-treated polyethylene coated paper release liner. The compound was then exposed to radiation 65 ultraviolet having a spectral performance of 300-400 with a maximum at 351 nanometers in a nitrogen-rich environment. The average intensity was approximately 2.05 mW / cm2, resulting in a total energy of 650 mJ / cm2. Example 2 was prepared in the same manner as Example 1, except that 40 parts of Regalrez 1085 thickener was used. Example 3 was prepared in the same manner as Example 1, except that the Regalrez 1085 thickener was used (Hercules Company ). Example 4 was prepared in the same manner as Example 1, except that 40 parts of Regalrez 1094 thickener was used. Example 5 was prepared in the same manner as Example 1, except that the Regalrez 1128 thickener was used (Hercules Company ). Example 6 was prepared in the same manner as Example 1, except that 40 parts of the Regalrez 1128 thickener was used. Example 7 was prepared in the same manner as Example 1, except that the Regalrez 6108 thickener was used (Hercules Company ). 66 Example 8 was prepared in the same manner as Example 1, except that 40 parts of the Regalrez 6108 thickener was used. Example 9 was prepared in the same manner as Example 1, except that the Regalrez 3102 thickener was used (Hercules Company ). Example 10 was prepared in the same manner as Example 1, except that 40 parts of Regalrez 3102 thickener were used. Example 11 was prepared in the same manner as Example 1, except that Regalrez 5095 thickener was used (Hercules Company ). Example 12 was prepared in the same manner as Example 1, except that 40 parts of the Regalrez 5095 thickener were used. Example 13 was prepared in the same manner as Example 1, except that the Escorez 5340 thickener was used (Exxon Company ). Example 14 was prepared in the same manner as Example 1, except that 40 parts of the Escorez 5340 thickener was used. Example 15 was prepared in the same manner as Example 1, except that the Araka thickener was used at KE-311 (Araka a). 67 Example 16 was prepared in the same manner as Example 1, except that 40 parts of the Arakawa KE-311 thickener was used. Example 17 was prepared in the same manner as Example 1, except that the Escorez 5300 thickener (Exxon Company) was used. Example 18 was prepared in the same manner as Example 1, except that 40 parts of the Escorez 5300 thickener was used. Example 19 was prepared in the same manner as Example 1, except that the Arkon E90 thickener (Arakawa) was used. . Example 20 was prepared in the same manner as Example 1, except that 40 parts of the Arkon E90 thickener were used. Example 21 was prepared in the same manner as Example 1, except that the Arkon P115 thickener (Arakawa) was used. Example 22 was prepared in the same manner as Example 1, except that 40 parts of the Arkon P115 thickener were used. Example 23 was prepared in the same manner as Example 1, except that the Regalite 90 thickener (Hercules Company) was used. 68 Example 24 was prepared in the same manner as Example 1, except that 40 parts of Regalite 90 thickener were used. Example 25 was prepared in the same manner as Example 1, except that the Exxon ECR 165B thickener was used. Example 26 was prepared in the same manner as Example 1, except that 40 parts of the Exxon ECR 165B thickener was used. Example 27 was prepared in the same manner as Example 1, except that the Exxon ECR 177 thickener was used. Example 28 was prepared in the same manner as Example 1, except that 40 parts of the Exxon ECR 177 thickener was used. Example 29 was prepared in the same manner as Example 1, except that the Arkon M100 thickener (Arakawa) was used. Example 30 was prepared in the same manner as Example 1, except that 40 parts of the Arkon M100 thickener was used. Example 31 was prepared in the same manner as Example 1, except that the Arkon M90 thickener (Arakawa) was used. 69 Example 32 was prepared in the same manner as Example 1, except that 40 parts of the Arkon M90 thickener was used. Example 33 was prepared in the same manner as Example 1, except that the Hercotac RT110 thickener (Hercules Company) was used. Example 34 was prepared in the same manner as Example 1, except that 40 parts of the Hercotac RT110 thickener was used. Example 35 was prepared in the same manner as Example 1, except that Escorez 5380 thickener (Exxon Company) was used. Example 36 was prepared in the same manner as Example 1, except that 40 parts of the Escorez 5380 thickener were used. Example 37 was prepared in the same manner as Example 1, except that the Foral 85 thickener was used (Hercules Company ). Example 28 was prepared in the same manner as Example 1, except that 40 parts of Foral 85 thickener were used. Example 39 was prepared in the same manner as Example 1, except that the Kristalex 5140 thickener was used (Hercules Company ). 70 Example 40 was prepared in the same manner as Example 2, except that 40 parts of the Kristalex 5140 thickener was used. Example 41 was prepared in the same manner as Example 1, except that the Hercotac 100S thickener was used (Hercules Company ). Example 42 was prepared in the same manner as Example 1, except that 40 parts of the Hercotac 100S thickener were used. Example 43 was prepared in the same manner as Example 1, except that the Regalite 355 thickener (Hercules Company) was used. Example 44 was prepared in the same manner as Example 1, except that 40 parts of the Regalite 355 thickener was used. Example 45 was prepared in the same manner as Example 1, except that the Wingtack Plus thickener was used (Goodyear Company ). Example 46 was prepared in the same manner as Example 1, except that 40 parts of the Wingtack Plus thickener were used. Example 47 was prepared in the same manner as Example 1, except that the Hercotac RT 400 (Hercules Company) thickener was used. 71 Example 48 was prepared in the same manner as Example 1, except that 40 parts of the Hercotac RT 400 thickener was used. Example 49 was prepared in the same manner as Example 1, except that the Piccotac thickener HM2162 (Hercules) was used. Company). Example 50 was prepared in the same manner as Example 1, except that 40 parts of the Piccotac thickener HM2162 were used. Example 51 was prepared in the same manner as Example 1, except that the Kristalex 3100 thickener (Hercules Company) was used. Example 52 was prepared in the same manner as Example 1, except that 40 parts of the Kristalex 3100 thickener was used. Example 53 was prepared in the same manner as Example 1, except that the Kristalex 1120 thickener was used (Hercules Company ). Example 54 was prepared in the same manner as Example 1, except that 40 parts of the Kristalex 1120 thickener was used. Example 55 was prepared in the same manner as Example 1, except that the Piccolyte A135 thickener was used (Hercules Company ). 72 Example 56 was prepared in the same manner as Example 1, except that 40 parts of the Piccolyte A135 thickener was used. The characteristics of the inhibition factor and phase separation of the previous examples are shown in Table III-2. The peel strength on polypropylene of various samples was determined according to Test Procedure Bl-III and reported in Table III-2. If the samples had an inhibition factor greater than 1.0, the sample was dried in an oven at 120 ° C to reduce the inhibition factor below 1, before the test. The designation "nt" means not proven. The designation "na" means not applicable. The designation "nc" means not conclusive.

TABLE III-2 73 74 75 4. 76 The data in Table III-2 show that various commercial thickeners are soluble in the non-polar acrylate pressure-sensitive adhesive matrix, but that only Regalrez thickener resins also have low inhibition factors.

Example 57-115 Example 57 was prepared in the same manner as Example 1, except that an 85/15/0 solution of IOA / IBA / AA monomers was used. Example 58 was prepared in the same manner as Example 57, except that 40 parts of the Regalrez 1085 thickener were used. Example 59 was prepared in the same manner as Example 1, except that an 85/14/1 ratio was used. of IOA / IBA / AA monomers. Example 60 was prepared in the same manner as Example 1, except that an 85/13/2 ratio of IOA / IBA / AA monomers was used. Example 61 was prepared in the same manner as Example 1, except that a ratio 85/11/4 of IOA / IBA / AA monomers was used. 77 Example 62 was prepared in the same manner as Example 57, except that 20 parts of the Regalrez 6108 thickener was used. Example 63 was prepared in the same manner as Example 62, except that 40 parts of the Regalrez 6108 thickener were used. Example 64 was prepared in the same manner as Example 62, except that an IOA / IBA / AA ratio of 85/14/1 was used. Example 65 was prepared in the same manner as Example 64, except that 40 parts of the Regalrez 6108 thickener were used. Example 66 was prepared in the same manner as Example 64, except that an IOA / IBA / ratio was used. AA of 85/13/2. Example 67 was prepared in the same manner as Example 66, except that an IOA / IBA / AA ratio of 85/12/3 was used. Example 68 was prepared in the same manner as Example 57, except that 20 parts of Regalrez 3102 thickener were used. Example 69 was prepared in the same manner as Example 68, except that 40 parts of Regalrez 3102 thickener were used. 78 Example 70 was prepared in the same manner as Example 68, except that an IOA / IBA / AA ratio of 85/14/1 was used. Example 71 was prepared in the same manner as Example 70, except that 40 parts of Regalrez 3102 thickener was used. Example 72 was prepared in the same manner as Example 70, except that an IOA / IBA / ratio was used. AA of 85/13/2. Example 73 was prepared in the same manner as Example 72, except that an IOA / IBA / AA ratio of 85/12/3 was used. Example 74 was prepared in the same manner as Example 57, except that 20 parts of the Regalrez 1094 thickener were used. Example 75 was prepared in the same manner as Example 74, except that 40 parts of the Regal94 1094 thickener were used. Example 76 was prepared in the same manner as Example 74, except that an IOA / IBA / AA ratio of 85/14/1 was used. Example 77 was prepared in the same manner as Example 74, except that an IOA / IBA / AA ratio of 85/13/2 was used. 79 Example 78 was prepared in the same manner as Example 57, except that an IOA / IBA / AA ratio of 90/9/1 was used. Example 79 was prepared in the same manner as Example 78, except that an IOA / IBA / AA ratio of 81/13/11 was used. Example 80 was prepared in the same manner as Example 79, except that 30 parts of the Regalrez 1085 thickener were used. Example 81 was prepared in the same manner as Example 79, except that an IOA / IBA / AA ratio of 76/23/1 was used. Example 82 was prepared in the same manner as Example 81, except that 40 parts of the Regalrez 1085 thickener were used. Example 83 was prepared in the same manner as Example 81, except that an IOA / IBA / ratio was used. AA of 81/17/2. Example 84 was prepared in the same manner as Example 81, except that an IOA / IBA / AA ratio of 76/22/2 was used. Example 85 was prepared in the same manner as Example 62, except that an IOA / IBA / AA ratio of 90/9/1 was used. 80 Example 86 was prepared in the same manner as Example 85, except that 30 parts of the Regalrez 6108 thickener was used. Example 87 was prepared in the same manner as Example 85, except that an IOA / IBA / ratio was used. AA of 81/18/1. Example 88 was prepared in the same manner as in Example 87, except that 40 parts of the Regalrez 5108 thickener were used. Example 89 was prepared in the same manner as Example 85, except that an IOA / IBA ratio was used. / AA of 76/23/1. Example 90 was prepared in the same manner as Example 89, except that 40 parts of the Regalrez 5108 thickener were used. Example 91 was prepared in the same manner as Example 85, except that an IOA / IBA / ratio was used. AA of 90/8/2. Example 92 was prepared in the same manner as Example 91, except that an IOA / IBA / AA ratio of 85/13/2 was used. Example 93 was prepared in the same manner as Example 92, except that an IOA / IBA / AA ratio of 81/17/2 was used.

Example 94 was prepared in the same manner as Example 93, except that 30 parts of the Regalrez 6108 thickener was used. Example 95 was prepared in the same manner as Example 94, except that 40 parts of the Regalrez 6108 thickener was used. Example 96 was prepared in the same manner as Example 92, except that an IOA / IBA / AA ratio of 76/22/2 was used. Example 97 was prepared in the same manner as Example 96, except that 30 parts of the Regalrez 6108 thickener was used. Example 98 was prepared in the same manner as Example 97, except that 40 parts of the Regalrez 6108 thickener were used. Example 99 was prepared in the same manner as Example 68, except that an IOA / IBA / AA ratio of 90/9/1 was used. Example 100 was prepared in the same manner as Example 99, except that 30 parts of Regalrez 3102 thickener was used. Example 101 was prepared in the same manner as Example 68, except that an IOA / IBA / ratio was used. AA of 81/18/1. 82 Example 102 was prepared in the same manner as Example 101, except that 30 parts of the Regalrez 3102 thickener was used. Example 103 was prepared in the same manner as Example 68, except that an IOA / IBA / ratio was used. AA of 76/23/1. Example 104 was prepared in the same manner as Example 103, except that 30 parts of Regalrez 3102 thickener was used. Example 105 was prepared in the same manner as Example 68, except that an IOA / IBA / ratio was used. AA of 90/8/2. Example 106 was prepared in the same manner as Example 68, except that an IOA / IBA / AA ratio of 81/17/2 was used. Example 107 was prepared in the same manner as Example 106, except that 40 parts of Regalrez 3102 thickener were used. Example 108 was prepared in the same manner as Example 68, except that an IOA / IBA / ratio was used. AA of 76/22/2. Example 109 was prepared in the same manner as Example 74, except that 10 parts of Regalrez 1094 and a monomer ratio of 90/9/1 of IOA / IBA / AA were used. 83 Example 110 was prepared in the same manner as Example 74, except that a monomer ratio of 81/18/1 IOA / IBA / AA was used. Example 111 was prepared in the same manner as Example 109, except that a monomer ratio of 76/23/1 IOA / IBA / AA was used. Example 112 was prepared in the same manner as Example 111, except that 20 parts of Regalrez 1094 were used. Example 113 was prepared in the same manner as example 109, except that 10 parts of Regalrez 3102 were used, were used. 0.09 parts of the 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -s-triazine crosslinker, N-octyl-acrylamide (NOA) was used instead of IBA, and the proportion of monomers was 89 / 10.5 / 0.5 of IOA / NOA / AA.

Example 114 was prepared in the same manner as Example 113, except that 30 parts of Regalrez 3102 were used. Example 115 was prepared in the same manner as Example 62, except that an IOA / IBA / AA ratio was used. of 95 / 4.75 / 0.25 and 25 parts of Regalrez 6108 were used. 84 Comparative Example Cl 90 parts by weight of isooctyl acrylate (IOA) and 10 parts of acrylic acid (AA) were mixed with 0.04 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator (Irgacure'5 '651, available from Ciba Geigy Corporation) and it was photopolymerized with an ultraviolet light source under a constant purge of nitrogen at a viscosity of about 3000 cps. An additional 0.16 parts of the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone and 0.15 parts of 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -s-triazine were added to the acrylate syrup, and mixed until all the components had completely dissolved. After mixing, the mixture Ettl &? s WF pm & Aíi sdbz? L &amp? S 8m d% e l? Bet lc d? Paper coated with polyethylene, treated with silicone. The compound was then exposed to ultraviolet radiation having a spectral yield of 300-400 nanometers with a maximum of 351 nanometers in a nitrogen-rich environment. An intensity of approximately 1.0 mW / cm2 was used for the first third of the exposure time, and an intensity of approximately 2.2 mW / cm2 was used for the second two thirds of the exposure time, resulting in a total energy of comparative example C2 in the same manner as comparative example Cl, except that a premix of 94 parts of IOA and 6 parts of AA was used. Comparative example C3 was prepared in the same manner as comparative example Cl, except that a premix of 100 parts of IOA and 0 parts of AA was used. The data of Examples 57-115 and the comparative examples Cl, C2, and C3 are shown in the Table III-3. The test procedures Al-III-Bl-III, and Cl-III were used to generate the data. The designation "nt" means not proven. 86 TABLE I I 1-3 87 TABLE III-3 TABLE III-3 89 TABLE III-3 90 Examples 116-114 Example 116 83 parts of IOA and 17 parts of IBA together in a vessel under a constant nitrogen purge, together with 0.04 parts of Irgacure 651 photoinitiator from Ciba Geigy Corp. (2,2-dimethoxy-2-phenylacetophenone). This mixture was exposed to a low intensity ultraviolet light under a constant nitrogen purge while stirring until a cohesive viscosity syrup was obtained. The conversion of this syrup was between 4 and 10%, and the viscosity was about 3000 cps. 0.12 parts of 2,4-bis (trichloromethyl) -6- (3,4-dimethoxyphenyl) -s-triazine and 0.16 additional parts of Irgacure 651, together with 20.5 parts of the Regalrez 6108 thickener (Hercules Company), were then added to the prepolymerized syrup. ). The ingredients were mixed perfectly until they were homogeneous and then coated by a blade to a thickness of 0.127 mm (5 mils) on a paper release liner coated with polyethylene, treated with silicone. The compound was then exposed to ultraviolet radiation which had a spectral yield of 300 to 91 400, with a maximum at 351 nanometers in a nitrogen-rich environment. The average intensity was approximately 2.05 mW / cm2 resulting in a total energy of 650 mJ / cm2. Example 117 was prepared in the same manner as example 116, except that the monomer mixture was 77 parts of IOA and 23 parts of IBA. Also, 13.6 parts of Regalrez 6108 were used. Example 118 was prepared in the same manner as example 116, except that the monomer mixture was 71 parts of IOA and 21 parts of IBA. Also, 7.5 parts of Regalrez 6108 were used. Example 119 was prepared in the same manner as example 116, except that the monomer mixture was 84 parts of IOA, 15 parts of IBA, and 1 part of AA. Also, 20.5 parts of Regalrez were used 6108. Example 120 was prepared in the same manner as Example 116, except that the monomer mixture was 81 parts of IOA, 18 parts of IBA, and 1 part of AA. Also, 17.6 parts of Regalrez were used 6108. Example 121 was prepared in the same manner as example 116, except that the monomer mixture was 72 parts of IOA, 27 parts of IBA, and 1 part 92 From aa. Also, 7.5 parts of Regalrez 6108 were used. Example 122 was prepared in the same manner as example 116, except that the monomer mixture was 83 parts of IOA and 17 parts of IBA. Also, 5 parts of Regalrez 6108 were used. Example 123 was prepared in the same manner as example 122, except that 15 parts of Regalrez 6108 were used. Example 124 was prepared in the same manner as example 122, except that 30 parts of Regalrez 6108 were used.

Comparative Example C4 94 parts of IOA and 6 parts of AA were mixed together in a vessel under a constant nitrogen purge, together with 0.04 parts of Irgacure 651 photoinitiator from Ciba Geigy Corp. (2,2-dimethoxy-2-phenylacetophenone). This mixture was partially polymerized under a nitrogen-rich atmosphere to provide a coatable syrup having a viscosity of about 3000 cps. 0.16 parts of 2,4-bis (trichloromethyl) -6- (3, 4-dimethoxyphenyl) -s-triazine and 0.16 additional parts of 93 Irgacure 651 was then added to the prepolymerized syrup, and this was then coated with a knife on a coated release paper backing to a thickness of 0.127 mm (5 mils). The resulting coating was then exposed to ultraviolet radiation having a spectral yield of 300 to 400 nanometers, with a maximum at 351 nanometers in a nitrogen-rich environment. The average intensity was approximately 2.05 mW / cm2, resulting in a total energy of 650 mJ / cm2.

Comparative example C5 was prepared in the same manner as comparative example C4, except that a premix of 10 parts of AA and 90 parts of IOA was used. In addition, 0.12 parts of triazine were used. Comparative C6 was prepared in the same manner as comparative example C4, except that a premix of 14 parts of AA and 86 parts of IOA was used.

The peel and cut data for Examples 116-124 and Comparative Examples C4, C5, and C6 are described in Table III-4. The data is 94 generated according to Test Procedures A2-III, B2-III, and C2-III.

TABLE II1-4 EXAMPLES OF PATENT FOR NPAs THICKENING FOR OILY METALLIC SURFACES TABLE III-4 PATENT EXAMPLES FOR NPAs THICKENED FOR OILY METALLIC SURFACES 97 IV. Adhesives for Vibration Damping Example 1 A composition was prepared by mixing 67 parts of isooctyl acrylate, 32 parts of isobornyl acrylate, 1 part of acrylic acid, and 0.04 parts of benzyl-dimethyl ketal photoinitiator (KB-1 of Sartomer). The mixture was partially polymerized in a nitrogen-rich atmosphere using black fluorescent lights to a syrup having a viscosity of about 300 centipoise. An additional amount of 0.16 parts of KB-1 photoinitiator and 0.15 parts of hexanediol diacrylate was added to the syrup, which was then mixed and knife coated to a thickness of about 50 microns on a paper release liner coated with polyethylene. , treated with silicone. The coated mixture was exposed to ultraviolet radiation having a greater portion of the spectral yield between 300 and 400 nanometers, with a maximum at 351 nanometers, and at an intensity of about 2 milliwatts / cm2. The total energy was approximately 650 millijoules / cm2. The resulting sheet material was then laminated to a 98 thickness panel of 0.165 mm cold rolled steel, to form a forced layer shock absorber. The forced-bed cushion was then cut to a dimension of 20.3 cm by 20.3 cm and laminated to an automotive door panel. The door panel with the damper was suspended with Tygon pipe, and an accelerometer was coupled (Model 22 of Endevco Company, San Juan Capistrano, California) to the door panel and wired to a Fast Fourier Transform (FFT) analyzer (Tektronix Model 2630 analyzer). The analyzer was then coupled to an impact hammer (obtained from PCB, DePew New York). In the test, the impact hammer was used to hit the panel, which caused various excitation or vibration modes to occur within the panel. Acceleration was then measured as a function of time, and the FFT analyzer was used to convert the results to acceleration as a function of frequency. The frequencies (FREQ) of the first eight modes were determined using the computer software (STAR Modal Software from Structural Measurement Systems, Milipitas, California). The average loss factors (AVG) for the eight modes were also calculated. 99 In comparison, the test was also conducted on the same door panel without a shock absorber, and also with a commercially acceptable shock absorber (which measures 20.3 cm x 20.3 cm) having 1.78 mm of black mastic material on an aluminum forced layer of 0.10. mm thick. All test results are found in Table IV-1. 100 The data in Table 1 show that the vibration damping compounds, for example, the forced layer dampers of the invention provide superior damping compared to commercial products, as shown by the higher loss factor. Other embodiments are within the following claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims

101 CLAIMS

1. A damping construction comprising at least one layer of a viscoelastic material applied to a solid vibrating article, said viscoelastic material comprises the reaction product of the starting materials, characterized in that it comprises: a) 3-97 parts by weight of an ester of acrylic acid of a monohydric alcohol whose homopolymer has a Tg less than 0 ° C; b) 3-97 parts by weight of a non-polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; and c) 0.5 parts by weight of a polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C, and substantially no epoxy component.

2. A damping construction, comprising at least one layer of an adhesive applied to a solid vibrating article, said adhesive is a pressure sensitive adhesive comprising the adhesive. reaction product of the starting materials characterized in that it comprises: a) 25-97 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a Tg of less than 0 ° C; b) 3-75 parts by weight of a non-polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; and c) 0.5 parts by weight of a polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C, the relative amounts of said acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the ethylenically unsaturated polar monomer are chosen such that adhesion to the 90 ° release of the reaction product to a polypropylene surface is at least 910 g / 1.27 cm (2 pounds / 0.5 inch) after a residence time of 72 hours at room temperature, as measured according to Test Procedure BI.

3. A damping construction comprising at least one layer of an adhesive applied to 103 a solid vibrating article, the adhesive is a pressure-sensitive adhesive comprising the reaction product of the starting materials, characterized in that it comprises: a) 25-97 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a Tq less than 0 ° C; b) 3-75 parts by weight of a non-polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; and c) 0.5 parts by weight of a polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C, the relative amounts of the acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the monomer ethylenically unsaturated polar, are chosen such that adhesion to the 90 ° release of said reaction product to a surface provided with 0.23 ± 0.04 mg / cm2 (1.5 ± 0.25 mg / inch squared) of oil is greater than zero after a residence time of 10 seconds at room temperature, as measured according to Test Procedure B-II. 104

4. A damping construction, comprising at least one layer of an adhesive applied to a solid vibrating article, the adhesive is a pressure sensitive adhesive, characterized in that it comprises: a) the reaction product of the starting materials comprising: i) 25-98 parts by weight of an acrylic acid ester of a monohydric alcohol whose homopolymer has a Tg of less than 0 ° C; ii) 2-75 parts by weight of a non-polar ethylenically unsaturated monomer, different from a methacrylate monomer, the homopolymer of which has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C; and iii) 0.5 parts by weight of a polar ethylenically unsaturated monomer whose homopolymer has a solubility parameter greater than 10.50 and a Tg greater than 15 ° C, b) at least one thickener that is miscible in the reaction product at room temperature, with the proviso that the pressure-sensitive adhesive does not contain essentially an emulsifier. 105

5. The damping construction according to claim 4, characterized in that the relative amounts of said acrylic acid ester, the non-polar ethylenically unsaturated monomer, and the ethylenically unsaturated polar monomer, are chosen such that adhesion to peeling at 90 ° C. said adhesive to a polypropylene surface is at least 910 g / 1.27 cm (2 pounds / 0.5 inches) after a residence time of 72 hours at room temperature as measured according to Test Procedure Bl-III.

6. The damping construction according to claim 1, characterized in that it comprises 40-85 parts by weight of the acrylic acid ester.

7. The damping construction according to claim 1, characterized in that it comprises 15-60 parts by weight of the non-polar ethylenically unsaturated monomer.

8. The damping composition according to claim 1, characterized 106 because it comprises a non-polar ethylenically unsaturated monomer different from a methacrylate monomer.

9. The damping construction according to claim 1, characterized in that it comprises a non-polar ethylenically unsaturated monomer selected from the group consisting of 3, 3, 3, 5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, N-octyl-acrylamide, t-butyl acrylate, and combinations thereof.

10. The damping construction according to claim 1, characterized in that the non-polar ethylenically unsaturated monomer is isobornyl acrylate.

11. The damping construction according to claim 1, characterized in that it comprises the reaction product of isooctyl acrylate and isobornyl acrylate.