MXPA97004979A - Method and composition to join vid components - Google Patents

Abstract

A method for the attachment of a component to glass is described, which comprises placing a material in the form of an adhesive sheet, sensitive to the pressure between said component and the glass, such that the adhesive sheet material adheres to the component and to glass, wherein the pressure-sensitive adhesive sheet material comprises the photopolymerization reaction product of the starting materials comprising: (a) a monomeric or partially prepolymerized syrup mixture comprising at least one acrylic acid ester of an alkyl alcohol and at least one copolymerizable monomer, (b) an epoxy resin or a mixture of epoxy resins, (c) a heat activatable hardener for the epoxy resin or mixture of epoxy resins, (d) a photoinitiator, and (e) a pigment

Description

METHOD AND COMPOSITION TO JOIN COMPONENTS TO THE GLASS FIELD OF THE INVENTION The invention relates to a thermosetting, pressure-sensitive adhesive to a sheet material comprising the adhesive, and a method of joining components to the glass.

BACKGROUND OF THE INVENTION In the automotive industry, the mirror bases have been coupled to the windscreen and the body of the automobile by means of urethane in the form of paste or silicone adhesives, as well as polyvinyl-butyral films. There have been some drawbacks in the use of paste-like adhesives, including a lack of strength before curing, which can cause the base of the mirror to slide and become misaligned. There is also a tendency to flow outward under the weight of the base of the mirror, which may require an additional finishing step to remove the material that has flowed outward. Polyvinyl butyral films, on the other hand, suffer from having REF: 24963 poor resistance to moisture and heat, which can result in the base of the mirror falling from the glass plate to which it is attached. U.S. Patent No. 5,160,780 (Ono) describes the use of an organopolysiloxane material (also referred to in the industry as silicone rubbers) useful for attaching a mirror base to the glass plate. The organopolysiloxane becomes cross-linked after heating in an autoclave at elevated temperatures. However, silicone rubbers are elastomeric and may be subject to slippage during sustained loads. Pressure-sensitive thermosetting adhesive materials have been described in US Patent No. 5,086,088 (Kitano et al.). Viscoelastic materials useful in cushion constructions are described in US Pat. No. 5,262,232 (ilfong et al.).

BRIEF DESCRIPTION OF THE INVENTION A method for attaching a component to the glass comprising the placement of a pressure-sensitive adhesive sheet material, between said component and the glass, so that the adhesive sheet material is adhered to the component and the glass. The adhesive sheet material includes the photopolymerization reaction product of the starting materials, comprising: (a) a monomer mixture or partially prepolymerized syrup comprising at least one acrylic acid ester of an alkyl alcohol and at least one copolymerizable monomer; (b) an epoxy resin or a mixture of epoxy resins; (c) a heat-activatable hardener for the epoxy resin with the mixture of epoxy resins; (d) a photoinitiator; and (e) a pigment. In yet another embodiment, the starting materials further comprise a silane. The invention also provides a pressure sensitive adhesive sheet material comprising the photopolymerization reaction product of the starting materials, comprising the components (a) to (e) above, and further comprising a silane.

DETAILED DESCRIPTION The present invention provides pressure sensitive, thermosetting, colored adhesive sheet materials which change in color tone after curing. Preferred adhesives, after thermal curing, have a relatively low elasticity and are characterized by having an elongation to breaking of less than 100%, and preferably less than 75%. Cured adhesives have good vibration damping properties and show a tan delta greater than 0.1 between a range of between about 0 ° C and 170 ° C. Adhesive sheet materials are pressure sensitive in nature, for example, sticky, and have a storage mode between about 5 x 104 to about 107 dynes per square centimeter at room temperature, prior to thermal curing. Alternatively, instead of thermal curing, the adhesive can be cured by radiation. After the thermal curing of the sheet materials, the adhesives are thermoset and have a storage module greater than 2 x 107 between temperatures of -40 ° C and 100 ° C.

Preferably, the sheet material is initially prepared by coating a photopolymerizable thermosettable pressure sensitive adhesive composition on a film treated with a release coating and exposing it to ultraviolet radiation to form the sheet material. The sheet material is subsequently adhered between two objects to be bonded, and thermally cured at temperatures of about 100 ° C to 200 ° C for about 5 to 60 minutes. During the second curing process, the adhesive becomes lighter in color as measured by a HunterLab colorimeter, and indicates when sufficient healing has occurred. In a preferred embodiment, the adhesive comprises an acrylic portion, an epoxide portion, and a coloring agent. In a more preferred embodiment, the adhesive comprises an acrylic portion, an epoxide portion, a coloring agent and an organofunctional silane. In the practice of the invention, the epoxide portion comprises from about 20 to 150 parts by weight per one hundred parts of acrylate, for example, the acrylate and the copolymerizable monomers, and preferably from 40 to 120 parts of epoxy per one hundred parts of acrylate, and more preferably from 60 to 100 parts of epoxy per one hundred parts of acrylate. In a highly preferred composition, the pigment comprises a carbon black pigment or graphite. Preferred acrylic materials include photopolymerizable mixtures of prepolymer or monomeric acrylate. Useful acrylic materials include monoethylenically unsaturated monomers having a vitreous transition temperature of the homopolymer of less than 0 ° C. Preferred monomers are monofunctional acrylic or methacrylic esters of non-tertiary alkyl alcohols having from 2 to 20 carbon atoms, and preferably 4 to 12 carbon atoms in the alkyl portion. Useful esters include n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, lauryl acrylate, octadecyl acrylate, and mixtures thereof. The acrylate portion may optionally include a copolymerizable reinforcing monomer. The reinforcing monomer is selected to have a glass transition temperature of the homopolymer, higher, than a homopolymer only the acrylate monomer. Useful reinforcing monomers include isobornyl acrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl piperidine, N, N-dimethylacrylamide, and acrylonitrile. A small amount of an acidic monomer, such as acrylic acid, may also be included in the acrylic portion, as long as it does not adversely affect the cure of the epoxy portion or the total desired performance of the adhesive. If used, the amount of acid is preferably less than about 2 weight percent of the acrylic portion, for example, the total weight of the acrylate, the copolymerizable reinforcing monomer and the acid monomer. When the prepolymer or monomer mixture includes an acrylate and a reinforcing monomer, the acrylate will generally be present in an amount of about 50 to 95 parts and the reinforcing monomer will be present in a corresponding amount of 50 to 5 parts by weight. Adhesive compositions also preferably include a free radical photoinitiator that is activated by ultraviolet radiation. An example of a useful photoinitiator is benzyl-dimethyl ketal (Irgacure ™ 651 available from Ciba Geigy). The photoinitiator is typically used in amounts from about 0.01 to 5 parts by weight per 100 parts of the acrylate monomers. The adhesives of the invention also preferably include an acrylate crosslinking agent. The crosslinking agent increases the modulus of the adhesive in the pressure sensitive state, so that when it is used to attach an object to a surface with pressure, either from the weight of the object or from an external source, it resists the flow outwards and around the object during thermal curing. Useful crosslinking agents are those that are polymerizable by free radicals from acrylate monomers such as divinyl ethers and multifunctional acrylates that do not interfere with the cure of the epoxy resin. Examples of multifunctional acrylates include, but are not limited to, 1,6-hexanediol diacrylate, tri-methylolpropane triacrylate, pentaerythritol tetraacrylate, and 1,2-ethylene glycol diacrylate. Amounts of up to about 1 part per 100 parts of acrylate monomers, and amounts of 0.01 to 0.2 parts are preferred. Useful epoxy resins are selected from the group of compounds containing an average of more than one, and preferably at least two, epoxy groups per molecule. The epoxy resin can be either solid, semi-solid, or liquid at room temperature. Combinations of different types of epoxy resins can be used. Representative epoxy resins include, but are not limited to, epoxy phenolic resins, epoxy bisphenol resins, hydrogenated epoxy resins, aliphatic epoxy resins, halogenated bisphenol epoxy resins, novolac epoxy resins, and mixtures thereof. Preferred epoxy resins are those formed by the reaction of bisphenol A with epichlorohydrin. Examples of commercially available epoxy resins include EponRM 828 and EponRM 1001 from Shell Chemical Co. Epoxy resins are cured with any type of an epoxy hardener, preferably a heat activatable hardener. The hardener is included in an amount sufficient to affect the curing of the epoxy under heat. Preferably, the hardener is selected from a group comprising dicyandiamide or polyamine salts. The heat activatable hardener will typically be used in an amount of about 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of the acrylate monomers. In cases where oven curing temperatures may be insufficient to fully cure the epoxy resin, it is useful to include an accelerator in the adhesive composition before the sheet material is processed, so that the resin can be completely cured at a higher temperature. low, or within a shorter period of time. The imidazole and urea derivatives are particularly preferred as accelerators because of their ability to extend the shelf life of sheet materials. Examples of preferred imidazoles are 2,4-diamino-6- (2'-methyl-imidazoyl) -ethyl-s-triazine isocyanurate, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6 - (2'-methyl-imidazolyl) -ethyl-s-triazine, hexakis- (imidazole) -nickel phthalate, and toluene-bisdi-ethylurea. An accelerator may be used in amounts of up to about 20 parts by weight per 100 parts by weight of the acrylate monomers. In a preferred embodiment, the pigment that is selected to modify the adhesive formulation preferably shows good light transmittance below 400 nm. The transmittance of light depends on the concentration of the pigment; the higher the pigment load, the smaller the amount of light that will be able to penetrate into the center of the adhesive mass. The light transmittance can be measured using a UV-visible spectrophotometer such as the Hewlett Packard HP8452A UV-visible Diode Array Spectrophotometer. In practice, the amount of light transmittance below 400 nm must be measurable (eg,> 0%), especially in the region where the photoinitiator shows absorbance. This ensures that the detectable light energy is penetrating through the thickness of the adhesive mass, and that it allows the absorption characteristics of the photoinitiator to perform its initiation function by absorbing light energy. A pigment is any substance that imparts color to another substance or mixture. Preferred pigments include carbon black, and graphite pigments. A useful commercially available pigment is a dispersion of 18% graphite in phenyloxyacrylate sold under the tradename PenncoRM 9B117 by Penncolor, Doylestown, PA. Carbon black and graphite show uniform transmittance as a function of wavelength across the visible and UV regions of the electromagnetic spectrum. They also show a decrease in transmittance as the pigment concentration increases. The amount of the pigment used must not exceed a concentration threshold that unduly interferes with the achievement of acceptable cure of the adhesive composition through its thickness. In practice, the adequate amount of pigment is influenced by the intensity of the light source and the thickness of the adhesive mass. Since the polymerization rate for polymerization reactions photoinitiated by free radicals is proportional to the square root of the luminous intensity, and the molecular weight is inversely proportional to the intensity of the light, it follows that the incorporation of a pigment Carbon black or graphite in a UV curing adhesive with a thick cross section will influence the ability to achieve healing, as well as the resulting physical properties of the adhesive. In a preferred embodiment, the adhesive of the invention also includes an organofunctional silane. The silanes have the following general formula R * R1 (-CH-) n-Si-R2 R4 Silanes which are useful in the practice of the present invention include those having the following organic functional groups wherein R 1 is either vinyl, halogen, epoxy, acrylate, methacrylate, amine, mercapto, styryl or ureido; and R2, R3 and R4 is halo, ethoxy, ethoxy, propoxy, or beta-methoxyethoxy; and n is an integer between 0 and 8. / Silanes with organic functional group are commercially available from sources such as Hulls, America. The silanes are incorporated in a way to impart specific performance and visual characteristics to the construction in ribbon form. It has been found that the incorporation of organic functional group silanes provides unexpected properties highly beneficial to hybrid acrylate / epoxy adhesive compositions. Most silanes participate exclusively in either thermal curing or ultraviolet light. Silanes can participate in both thermal and ultraviolet light steps if a combination of silanes is used, or if the particular silane has functional groups that participate in both healing steps. The silanes are used in sufficient quantities to affect the desired properties. The specific function of the silane is to alter the properties of the tape after curing with ultraviolet light or after the thermal cure step. A property of this type is the modulus or stiffness of the adhesive, which can be changed from a semi-structural adhesive to a structural adhesive, simply by the incorporation of a silane. The color tone of the tape after the final cure can also be changed with the incorporation of silanes with organic functional group. This is an unexpected discovery that makes it possible for someone to easily determine the point at which the final healing is achieved during the thermal healing process. It has been observed that at certain temperatures of thermal curing, the pitch change in the tape is a gradual change occurring in the course of seconds when the construction of the tape is maintained at a given thermal cure temperature. The use of silanes in the construction of hybrid tape epoxy / acrylate also enables the tape constructions for a given simply by adjusting the amount of silane in a given formulation color optimized. The manner in which the pitch change occurs during thermal curing is not a gradual change over time at a given temperature. The change occurs very quickly, presumably once phase separation has occurred at the end of the epoxy healing process, which indicates the end of healing. Organosilanes can also be used to crosslink the acrylate phase through various methods. One method involves allowing the individual silane with vinyl or acrylate functional groups to condense with another identical silane molecule. Yet another method involves the incorporation of an inorganic filler such as fumed silica, glass bubbles or other inorganic fillers that are capable of condensing with the silane functional group, which creates a scaffolding of inorganic crosslinking. These two procedures achieve the desired function of gelation of the acrylate phase of the hybrid adhesive tape construction. In another preferred embodiment, the acrylate portion is supposedly left uncrosslinked. The purpose of this is to impart thermally induced mass flow characteristics to the entire adhesive composition. In this specific case, the acrylate species and the epoxy species are movable and able to flow when exposed to the thermal cure step. The advantage of this is to impart the filling of the empty spaces and the sealing properties to the tape construction. In this specific case, the use of silanes with vinyl or acrylate functional groups could be avoided due to their tendency to self-condense, and with this, crosslink the acrylate phase. The use of silanes with glycidyl functional group could be used in this case. A preferred method for manufacturing the inventive tape constructions of the present invention involves four distinct steps. The first step involves the dissolution, mixing, and dispersion of the epoxy and curative resins in the acrylate monomers or in the syrup together with any fillers and silanes. The second step involves coating the composite formulation on a single support liner, or between two liners at a given thickness, and exposing the formulation to healing radiation. Sufficient radiation must be used to achieve a complete content of non-volatile materials that is >95%, as measured by the thermogravimetric analysis. The third step involves the conversion of the tape to rolls and the assembly of the tape to the adherendos. The final step involves the exposure of the assembly attached to the heat, which initiates the mechanism of epoxy curing and results in the conversion and gelation of the epoxide portion of the composition. During this step phase separation of the epoxy occurs, resulting in a two-phase morphology. The formation of the two-phase morphology is what is believed to cause the change of tone in the construction of tape through a dispersion mechanism. The function of the silanes is to specifically adjust and design this phase separation, and the resulting domain size in such a way as to achieve the specific objective properties in the final tape construction. The discovery that if silanes can radically alter the final appearance of the tape in pigmented systems, it is a simple and easy means of ensuring that uniform performance on the tape product is achieved on a consistent basis. Other additives that can be used include fibers, woven and non-woven fabrics, glass or polymer microspheres, and fillers such as silica. The observation that organic dyes are capable of achieving a change of tone during the thermal cure step, but do not demonstrate ability to adjust the tone of the tape, is attributed to the solubility of the dye in the individual phases in the tape. In contrast, inorganic pigments that are particulate by nature are selectively excluded from the discontinuous phase during the phase separation process. The function of the silane is to control the resulting morphology (eg, domain size and distribution) which makes it possible to alter the distribution of the pigment particles in the ribbon, which leads to a change in the final tone of the ribbon. This is achieved through a simple modification in the formulation. The adhesives of the invention are useful for joining a wide range of objects to various surfaces. The objects and surfaces may include glass, ceramics, metals, sintered glass, plastics and the like. In particular, the adhesives are useful in attaching objects to glass plates, such as automotive windshields, or other optically transparent substrates, so that the color change can be used as an indication of sufficient cure. The color of the adhesive can also be modified to provide an aesthetically pleasing surface when viewed through the window. The adhesives of the invention are also particularly useful in bonding non-transparent surfaces together, when it is desirable to provide a particular color in the bond line with adhesive. Objects that can be attached to glass substrates include mirror bases for rear-view mirrors, horns, interior lights and the like. In a preferred method of practicing the invention, a pressure-sensitive adhesive sheet material having a thermally curable pigmented adhesive is adhered to a mirror base which is then attached to a glass plate. The compound is then heated to a temperature sufficient to cure the adhesive to a thermoset state, and effect a visible color change. The color change is noted as a decrease in color intensity or an increase in the "L" value of the color, as measured with a HunterLab colorimeter. For example, a black leaf material before final curing and having an "L" value between 10 and 15 will turn a gray color after thermal curing with an "L" value between 20 and 40.

Test Procedures Adhesion to the 90 ° detachment A 1.27 cm by 15.2 cm strip of sheet material is laminated to a 0.13 mm thick strip of anodized aluminum. The aluminum strip is then laminated to a cold-rolled stainless steel panel (304-BA) cleaned with three rubs of a 50/50 mixture of water and isopropanol, and laminated with 2 passes of a 6.8 kg roller. The panel is then attached to an accessory in a jaw Tester Instron, so that the aluminum strip is pulled at a 90 ° angle at a speed of 30.48 cm / minute.

Adhesion to detachment is recorded in pounds per half inch, and converted to Newtons per decimeter (N / dm).

Cut resistance The cut resistance of the adhesive is determined by the adhesion of a 1.27 cm by 2.54 cm strip of sheet material between overlapping ends of panels covered with DE-500 E available from ACT (Advenced Coatings Technology, Hilsdale MI), which they measure 2.54 cm by 7.5 cm, such that the free ends of the panels extend in opposite directions. The 2.54 cm dimension of the sheet material is placed across the width of the panels. The composite is laminated with two passes of a 6.8 kg roller, then cured in an oven at 140 ° C for 25 minutes. The sample is then cooled to room temperature and tested by extending the free ends of the panel into the jaws of an Instron Traction Tester and separating the jaws at a rate of 5 cm / minute. The results are recorded in pounds per inch and are reported in MegaPascals (Mpa).

Resistance to Traction and Elongation after Final Healing The sheet material is thermally cured for 25 minutes at 177 ° C and cooled to room temperature. A test sample conformed to the ends with more section than the central body (prepared according to ASTM D-412) is held in the jaws of an Instron Traction tester and the jaws are separated at a speed of 50.8 cm per minute. Tractive force is required to break the test sample as shown in the tables in MegaPascals (Mpa). The elongation until the break is reported in percent of the original length (%).

Color "L" The color of a sample before and after curing is determined using a HunterLab colorimeter. The color value "L" is a HunterLab scale of luminosity and darkness in color in which high numbers, for example, close to 100 are white, and low numbers, for example, close to 0 are black. The test is performed according to the manufacturer's instructions on a "L" Colorimeter 100 and an Optical Sensor D25A, both available from HunterLab Associates, Reston, VA. The instrument is calibrated with a white slab having a WL value "of 92, and a black slab having an X, L" value close to 0. A gray slab having an "L" value of 30.9 is verified for comparison. The pressure-sensitive adhesive sheet materials are measured for the "L" values before thermal cure, by removing one of the polyester films from a 152.4 cm by 152.4 cm sample, and placing the adhesive surface exposed to the sensor. To cure the adhesive, one of the polyester films from a 152.4 cm by 152.4 cm sample is removed, and the adhesive is placed in a flat bottom aluminum container with the other polyester film against the container. The adhesive in the container is then heated to 140 ° C for 25 minutes, and then cooled to room temperature. The other film is removed from the adhesive, and the glossy side of the cured sheet material is measured for the value X, L. The adhesives of the invention consistently show an increase in the "L" value after thermal cure, which indicates that the cured adhesives have a lighter color than the uncured sheet material.

Break Test This test is a measure of how well a mirror base (also called a mirror button) adheres to a glass plate. The U-shaped sintered stainless steel mirror button measuring 22 mm by 28 mm, obtained from SSI, Janesville, (isconsin) is lightly cleaned by sandblasting and cleaned either by loosening with acetone, or cleaning in a ultrasonic cleaner. A clear tempered glass plate measuring 12.7 cm by 5.08 cm by 0.396 cm (available from Abrisa Industrial Glass, Ventura CA) is cleaned by rubbing three times with a 50/50 mixture of distilled water and isopropanol. The plate is heated in an oven at 82 ° C for at least 10 minutes. A U-shaped piece of pressure-sensitive adhesive sheet material, cut slightly smaller than the mirror button, is applied to the mirror button. The button for mirror is then adhered to the glass plate and laminated using a hot plate set at 177 ° C and pressurized by an air cylinder with an inline pressure of 550 kiloPascals of pressure for 6 seconds. The assembly is then heated in an oven at 140 ° C for 25 minutes. The sample is then conditioned at room temperature and at 40-60% relative humidity for at least 24 hours before the test. The glass plate is then mounted vertically in a test attachment on a clamp of an Instron A Traction Tester. A lever arm of 70 mm length is attached to the mirror button so that it extends horizontally. The lever arm is then clamped in the Instron apparatus, and the lever arm is pulled in an upward direction at a speed of 2.5 millimeters per minute. The maximum value until the break, for example, when the button for mirror is broken and released from the glass plate, is recorded in pounds and converted to Newtons.

Example 1 A composition was prepared by mixing 29 parts of n-butyl acrylate with 29 parts of N-vinyl caprolactane, heated to about 50 ° C to form a solution. The following components were added to the solution: 42 additional parts of n-butyl acrylate, 25 parts of diglycidyl ether oligomer of bisphenol A (Epon 1001F available from Shell Chemical Co.), and 45 parts of diglycidyl ether of bisphenol A (Epon 828 available from Shell Chemical Co.). The mixture was mixed with a high-cut mixer for about 2 hours as the temperature increased to about 52 ° C. The temperature was reduced below about 38 ° C, and the following ingredients were added and mixed for approximately 30 minutes : 0.28 parts of benzyl-dimethyl-ketal (Irgacure 651 available from Ciba Geigy), 0.1 parts of stabilizer (Irganox 1010 available from Ciba Geigy), 0.05 parts of hexanediol diacrylate, and 0.38 parts of black pigment (PenncoMTB117). The following ingredients were added using a high-cut mixer for about 1 hour: 7 parts of micronized dicyandiamide (DYHARD available from SKW Chemical Co.), 2. 7 parts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine (Curezol 2MZ-Azine from Air Products), 8 parts of hydrophilic silica (Cab-O-Sil M- 5 available from Cabot Corp.). An additional 0.1 part of the black pigment was added to the composition and mixed for approximately 45 minutes. The composition was then degassed under vacuum, and coated to a thickness of about 0.51 millimeters between two polyester films that had been coated with a silicone release liner. The coated compound was then irradiated by both the upper part and the lower part of the compound, with ultraviolet light lamps which have 90% emissions between 300 and 400 nanometers (nm), and a maximum emission of 351 nanometers as measured with a UVIRAD radiometer (Model No. VR365CH3) available from EIT (Electronic Instrumentation & Technology, Inc.). The intensity was approximately 2 milliwatts / square centimeter (mW / cm2), and the energy above and below the coated compound was 350 milliJoules / square centimeter (mJ / cm2), and the total energy was 700 mJ / cm2 . The coated sheet was tested according to the test methods described above, and the test results are shown in Table 1. The adhesive sheet material was cured at 177 ° C for 25 minutes and the thermomechanical properties of the adhesive were determined using a Rheometrics Solids Anlyzer II (RSA II), available from Rheometrics, Inc, at a frequency of 1 Hz. Samples were screened from -40 ° C to 120 ° C at 2 ° C incremental increments, and a soaking time of 60 seconds. The adhesive had a storage modulus greater than about 2 x 107 dynes / cm2 in a range of -40 ° C to 100 ° C. The effective damping range, for example, where tan delta is greater than 0.1, was approximately - 7o C to approximately 160 ° C.

Examples 2-16 Leaf materials were prepared as in Example 1, except that varying amounts of two types of silanes with organic functional groups, and a mixture of varying amounts of the silanes, were added to the composition of the quantities per hundred parts of acrylate and monomers bristling copolls (pph) as shown in Table 1. Effective sheet thicknesses are also shown. The silanes used were methacryloxy-propyl-tri-ethoxysilane (M8550 available from Huís America) and designated MPTS in the table, and glycidoxy-propyl-trimethoxy-silane (Dynasylan-glymo CG6720 available from Huís, America) and designated GPTS in the table, and a mixture of each of the silanes. For Examples 9-14, the diglycidyl ether oligomer of bisphenol A was mixed with butyl acrylate in a ratio of 2: 1 before addition to the composition. The additional amount of butyl acrylate was adjusted to 29.5 parts, so that the composition, except for silanes and pigment, was the same as in Example 1.

TABLE 1 Quantity Thickness Resis- Resis- Enlarge- Adhesion Color Color Test E-i # silane < * e ^ e the tension to the "" "L" silane blade to the cut% Before- After Rompipph mm MPa Drive to the MPa at 9 ° Cure Healing Ne tons N / dm 0 0.47 22.1 7.6 52 104 14.4 30.6 455 2 GPTS 2 0.59 13.7 9.9 17.3 115 15.1 34 781 3 GPTS 4 0.54 14.9 10.4 1938 124 15.2 34.5 568 4 GPTS 6 0.64 13.3 9.3 27.6 112 15.3 34.9 253 or GPTS 8 0.60 14.5 8.8 25.4 110 16 36.7 80 6 GPTS 10 0.67 13.9 7.9 31.2 107 16 38.4 85 7 MPTS 2 0.56 9.2 6.8 13.9 96 15.2 33.3 342 8 MPTS 10 * 3.5 * * 91 15.7 20 * * 9 GPTS 0.5 0.71 10.4 8.5 19 168 14.1 36 667 10 GPTS 1 0.70 11.0 9.9 14.5 120 13.2 29.1 689 11 MPTS 0.05 0.70 14.7 10.3 15.5 113 12.7 34.3 565 GPTS 0.5 TABLE 1 (Continued) Amount Thickness Resis- Resis- Enlarge- Adhesion Color Color Test Ex. SÜanO ^ e ^ tency to the "L" "L" of silane sheet to cut the% after- Before After Rompi- pph mm MPa tensile stress MPa at 90 ° cure healing Newtons N / dm 12 MPTS 0.05 0.70 7.8 1.5 141 11.7 153 GPTS 1 13 MPTS 0.5 0.69 8.4 4.3 18 139 13.3 35.2 591 GPTS 0.5 14 MPTS 4 6.7 96 15.3 25.5 ) GPTS 3 15 MPTS 4 0.66 7.3 4.7 104 15.7 26 * * GPTS 4 16 MPTS 5 0.59 5.6 87 16.8 23.3 * * GPTS 5 * Not tested - the sample was too fragile ** Not tested - no adhesion to the mirror base Data not available The data in Table 1 show that the physical properties of the adhesive sheet materials of the invention can be changed with the addition of silanes to make adhesives of different modules. The color change after thermal curing was consistently from a black color to varying shades of gray (indicated by the "L" Color values before and after curing), which shows that the final color of the adhesive can also be modified by selecting the type and quantities of silanes.

Examples 17-28 The sheet materials for examples 17-19 were prepared as in Example 1, except that the amount of black pigment was varied as shown in TABLE 2. The sheet materials for examples 20-22 were prepared as in Example 1, except that a blue pigment, potassium cupric sulfate, was used in the amounts indicated in TABLE 2. The sheet materials for examples 23-27 were prepared as in Example 9, except that red dye was used ( for (1, 2, 2-cyanoethenyl) -N, N-diethyl-aniline). Silanes with organic functional groups of Examples 24-27 were used, as follows: Example 24 - 0.5 pph GPTS; Example 25 - 0.05 pph MPTS; Example 26 - 0.05 pph MPTS and 1.0 pph GPTS; and Example 27 - 0.5 pph MPTS and 0.05 pph GPTS TABLE 2 Ex. Colc Thickness Resist- Resist Adhesive% Color "L" Color "L" Proof of pph of the Cia to the Cagea Before the After Break of the blade Cutting of the tensile strength mm MPa MPa d Healing Curing Ne tons at 90 ° N / dm 17 0.2 .051 7.6 10.1 15.3 144 21.7 39.2 761 18 0.38 0.48 6.5 9.0 15.1 156 14.6 31.4 721 19 0.6 0.51 6.6 10.8 22.2 126 11 26.7 623 0.2 0.48 8.9 11.2 19.3 125 55.9 72.7 890 21 0.4 0.51 8.8 10.4 15.6 137 55.3 72.3 836 22 0.6 0.51 8.5 11.6 20.4 106 55.4 72.6 805 23 0.05 0.75 44.3 70.9 24 0.05 0.75 43.8 71.3 25 0.05 0.75 41.3 72.7 26 0.05 0.75 41.6 72.5 27 0.05 0.75 42.4 72.8 The data in TABLE 2 show that the color changes can be effected by pigments and dyes, and the amount of change can be controlled by the amount of pigment and the use of silanes.

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 (10)

1. A method for attaching a component to the glass, characterized in that the method comprises placing a pressure-sensitive adhesive sheet material between the component and the glass, so that the adhesive sheet material is adhered to the component and to the glass, in wherein the adhesive sheet material comprises the photopolymerization reaction product of the starting materials comprising: (a) a monomeric or partially prepolymerized syrup mixture comprising at least one acrylic acid ester of an alkyl alcohol and at least one copolymerizable monomer . (b) an epoxy resin or a mixture of epoxy resins; (c) a heat-activatable builder for the epoxy resin or mixture of epoxy resins; (d) a photoinitiator; and (e) a pigment

2. The method according to claim 1, characterized in that the initial materials also comprise a crosslinking agent.

3. The method according to claim 1, characterized in that the starting materials further comprise a silane with an organic functional group.

4. The method according to claim 1, characterized in that the monomer mixture or partially prepolyzed syrup comprises: (a) from about 50 to about 95 parts by weight of at least one acrylic acid ester of an alkyl alcohol selected from isooctyl acrylate , isononyl acrylate, decyl acrylate, dodecyl acrylate, butyl acrylate, ethylhexyl acrylate, a hexyl acrylate; and (b) from about 50 to about 5 parts by weight of at least one copolymerizable monomer selected from isobornyl acrylate, N-vinyl-caprolactam, N-vinyl-pyrrolidone, -vinyl-piperidine, N, N-dimethylacrylamide and acrylonitrile.

5. The method according to claim 1, characterized in that the pigment results in a reaction product by photopolymerization having a black or gray color.

6. The method according to claim 1, characterized in that the pigment is carbon black or graphite pigment.

7. The method according to claim 1, characterized in that the initial materials comprise from about 25 to 40 parts by weight of epoxy resin or mixtures of epoxy resins.

8. A pressure sensitive adhesive sheet material, comprising the reaction product by photopolymerization of the starting materials, characterized in that they comprise: (a) a monomer mixture or partially prepolymerized syrup comprising at least one acrylic acid ester of an alkyl alcohol and at least one copolymerizable monomer; (b) an epoxy resin or a mixture of epoxy resins; (c) a heat activatable builder for the epoxy resin or epoxy resin mixture. (d) a photoinitiator; (e) a pigment; and (f) a silane with an organic functional group

9. The method according to claim 1, characterized in that the method further comprises the additional step of heating the pressure sensitive adhesive sheet material after the adhesive sheet material has been adhered to the component and the glass.

10. The method according to claim 1, characterized in that the method further comprises the additional step of exposing the pressure sensitive adhesive sheet material to ultraviolet radiation after the adhesive sheet material has been adhered to the component and the glass.