MXPA00004774A - Pressure-sensitive flame retardant adhesive - Google Patents

Abstract

A pressure-sensitive, flame-retardant adhesive is disclosed comprising a composition fabricated with the polymerization of acrylicesters, dibromostyrene, and vinyl phosphonic acid, with or without acrylic acid, mixed with dispersions of antimony trioxide. The adhesive composition preferably is an emulsion polymer fabricated with dibromostyrene, 2-ethylhexyl acrylate, n-butyl acrylate, and vinyl phospohonic acid, mixed with Sb2O3 in an approximate ratio of 100 parts polymer per about 8-12 parts Sb2O3. Preferred polymers are those containing at least about 11.6%to 15.6%bromine and from 0.25%to 2.5%phosphorous. The adhesive is particularly advantageous in fabricating optical circuit devices.

Description

RETARDANT ADHESIVE OF. FIELD SENSITIVE FLAME FIELD OF THE INVENTION The present invention relates to a flame retardant, pressure sensitive adhesive and is particularly related to an adhesive composition comprising the polymerization of an emulsion or solution of one or more acrylic esters, dibromostyrene and vinylphosphonic acid, composed of an antimony trioxide. BACKGROUND OF THE INVENTION A pressure sensitive adhesive can be defined as a material which, in its dry form, is aggressively and permanently glued at room temperature, so that a variety of different surfaces can be firmly adhered by contact without needing more. that the pressure of a finger or a hand (a little pressure). The molecular weights of the polymers used as pressure sensitive adhesives cover a wide range depending on their type, composition, structure and polymerization method. They are available in a variety of base chemicals and are advantageously formulated by having a particular balance of tack, adhesive, cohesive and elastic properties, along with good chemical and thermal stability. They are available in both emulsions (latex) and solution polymers. Properties such as adhesion strength, shear and adhesion resistance can be adjusted by changing the molecular weight and chemistry of the polymers or by adding fillers or plasticizers. Adhesion of the adhesive refers to its ability to form an instantaneous bond upon flow and dry on the substrate virtually without applying pressure. The adhesion can be measured by a variety of methods that are known in the field, including a clamp adhesive, a ball bearing adhesive or the like. A number of test methods known in the field are identified as the Test Methods of the Council of Pressure Sensitive Tapes (PSTC), which includes an adhesion test of the PSTC-5 instant adhesives. The adhesive properties refer to the last adhesion for a period of time according to a rolling pressure. A PSTC-1 test comprises a 180 ° degree of peel adhesion test using stainless steel panels and a 2.04 kg rubber roller. (4.5 lbs.) For contact pressure. Adhesion tests are often carried out after time intervals of 0, 15 minutes, 24 hours, 72 hours and 168 hours at the specified temperature and humidity conditions. An increase in adhesion over time is indicative of the relative "moisture removal" of the adhesive. The cohesion reflects the internal resistance of the pressure-sensitive adhesive and is measured by shear strength tests, such as PSTC-7 (a shear test with dead load) and other tests known in the field, including shears. superimposed, adhesion breaking temperature by shearing (SAFT) and Williams plasticity (compression resistance). Pressure-sensitive acrylic adhesives are permanently sticky soft polymers, preferably manufactured to have glass transition temperatures (Tg) of about -15 ° C to -55 ° C, as discussed in US Pat. No. 3,579,490, issued to Kordinzinski et al. on May 18, 1971, entitled "Resin Production Method for Adhesive Use", which is incorporated herein by reference. The glass transition temperature (Tg) is the temperature at which the polymer changes from a hard vitreous material to a soft elastic material. Pressure-sensitive acrylic adhesives have specific attributes that increase their usefulness in various applications. Its beneficial attributes include resistance to oxidation and ultraviolet radiation, high optical clarity without color or little color, high bond strength for a variety of substrates and formulation versatility for cohesive strength, a thermal resistance, and a resistance to chemicals and solvents. Pressure-sensitive acrylic adhesives may be prepared with latex polymerization techniques or a solution having molecular weights of less than 10 or greater than 106 in solution polymers comprising polymers with a lower molecular weight. As a result of its benign attributes, it is found that pressure sensitive acrylic adhesives have a utility in a wide variety of applications, including graphic arts and for use in the manufacture of decals, labels, tapes, switches, membrane, medical devices and other applications for protection and concealment work. However, the combustibility of adhesives is a concern in some applications, including electrical devices and appliances, electrical tape and in the manufacture of flexible optical circuits or multi-wire boards. The challenge with the use of pressure sensitive adhesives in such applications has developed materials that have adhesive properties with optimal or desired levels and are no longer combustible. Pressure sensitive adhesives based on acrylates or polyacrylates, for example, have excellent pressure-sensitive adhesive properties, but they are also combustible. A common approach to reduce the combustibility of a pressure sensitive adhesive is to mix additives that inhibit combustion in the adhesive. Many flame retardant adhesives contain bromine, such as brominated diphenyl or brominated diphenyl oxide compounds. For example, decabromodiphenyl oxide is often used, which has good flame retardant properties in view of its high bromine content. Another additive commonly used is antimony trioxide, which can be used in combination with halides, such as titanium tetrachloride, the halogen radicals provided by these additives react to form hydrogen halides, which interfere with the chain mechanism of radicals in the combustion process, by which the combustion cycle is broken. Antimony acts as a synergistic element to increase the effectiveness of halides. However, adding materials that inhibit combustion can break the sensitive balance of adhesive properties, such as stickiness, cohesion, strength, solvency and stability. Typical flame retardant systems, such as those based on decabromodiphenyl oxide and antimony oxide, tend to consolidate the acrylic and adhesive coatings and opaque the polymer and decrease its adhesive properties. In addition to the halogen-containing flame retardants, phosphates have also been used to develop flame retardants, particularly flame retardants of the condensed phase flame in oxygen-containing polymers. See M. Robert Christy, Standards, Bans, and Retardant Faye, PLASTICS COMPUNDING (Sept./Oct.93), at 59. A pressure sensitive adhesive containing phosphate is disclosed in U.S. Pat. No. 3,515,578 issued to Tomita et al. on June 2, 1970, entitled "Pressure Sensitive Adhesive Tape" and assigned to Minnesota Mining and Manufacturing Co. (3M). The 3M patent discloses pressure sensitive adhesives comprising polyacrylates modified by tri- (halogenated alkyl) phosphates and antimony trioxides and described as being preferred to tri- (halogenated alkyl) phosphates with alkyls • dibromosubstituted having three carbon atoms and, in particular, tri- (2,3-dibromopropyl) phosphates, although it has been determined that these phosphates are carcinogenic and prohibited by the Environmental Protection Agency of the E.U.A. It is mentioned as a flame retardant the use of brominated phosphates in Spotlight, Customer Demands: Synergistic Flame-Retardant Systems, PLASTICS CO POUNDING (Jan / Feb. 1994), which discloses a study related to a compound comprising 16.7 % of a brominated polycarbonate oligomer and 12% of a triphenyl phosphate or 6% brominated phosphate (60% bromine, 4% phosphorus). In this example, phosphates are used as fillers when mixed in polycarbonate compounds. The use of phosphates has been discouraged since it affects the mechanical properties of the materials, particularly when presented as filler. See Favstrits et et al., In the U.S. Patent. No. 5,100,986, entitled "Coatings Based on Brominated Retardant Styrene of the Flame", issued March 31, 1992, which is incorporated herein by reference. While phosphates show good flame retardancy and clarity, they tend to be insoluble in water, and when used in conjunction with a polymer, they tend to plasticize the polymer and migrate to the surface, depending on their compatibility with the polymer. polymer and other additives, ie certain phosphates will greatly weaken the cohesive properties of the adhesives. An advantageous approach to developing a flame retardant pressure sensitive adhesive is to react a flame retardant in a polymer structure, as compared to the flame retardants additives mixed in the polymer. There is limited success with such integrated polymers, as discussed in Wang & Favstritsky, Flame-Retardants Brominated Styrene-Based Polymers, JOURNAL OF COATINGS TECHNOLOGY, Vol. 68, No. 853 (February 1996), pp 41-47, on page 41. For example, the copolymers of acrylonitrile, vinylidene chloride and chloride of vinyl are of this type have flame retardant and adhesive properties. However, chloride is less effective than bromine or phosphorus in producing the flame retardant properties and, consequently, chlorinated compounds are not effective as compositions incorporating bromine or phosphorus. Also chlorinated polymers are less stable thermally and hydrolytically than brominated polymers. The development of flame retardant polymers comprising dibromostyrene is described in Wang & Favstritsky, JOURNAL OF COATINGS TECHNOLOGY, mentioned above and Wang & Favstritsky, Novel Fíame Retardant Dibromostyrene-Based Lattices: Synthesis, Characterization, and Applications, presented at the Symposium of Water Propagated Coatings, with a high content of Solids and Dust, (Feb. 22-24, 1995) (hereinafter referred to as present the "Symposium Document"). Wang et al. discloses polymers of dibromostyrene and butadiene or dibromostyrene and a plurality of monomers selected from the group consisting of styrene, butadiene, methacrylic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, and itaconic acid, with the selection of a monomer that depends on the application. See the Symposium Document on page 1. See also Patents of the U.S.A. No. 5,066,752 issued to Favstritsky et al., On November 19, 1991, entitled "Polymers Based on Brominated Retardant Styrene of the Flame", Patent of the U.S.A. No. 5,100,986 mentioned above; the U.S. Patent No. 5,290,636 issued to Rose et al. on March 1, 1995, entitled "Coatings Based on Brominated Retardant Styrene of the Flame" and Patent of the U.S.A. No. 5,438,096 issued to Wang et al. on August 1, 1996, entitled "Latex Based Brominated Retardant Flame Styrene", all of which were assigned to Great Lakes Chemical Corp. and are incorporated herein by reference. An application for using flame retardant pressure sensitive adhesives includes optical circuit devices. The optical circuits are tested for the flame retardant capacity according to the standards known in the industry for measuring the combustibility of plastics used in electronic devices and devices, mainly the standard 94 of Underwriters' Laboratory (UL). The UL standards are well known and are also described in M Robert Christy, Standards, Bans, and Faith Retardants, PLASTICS COMPOUNDING (Sept./Oct.93), on pages 59-61. The UL94 vertical standard (UL94V) has been applied to optical circuit devices, including UL94V test and 94VTM test, the latest test (94VTM) is applicable for thinner materials prone to distortion. The difficulty with the adhesives used in the optical circuits has developed materials that satisfy the coefficients of UL Standard 94 while maintaining the desired levels of their adhesion capacity. In order for the circuits to satisfy the desired levels of flame retardant capacity, additives that inhibit combustion in a percentage greater than 25% of the total solids will be required. This will decrease the adhesion of the adhesives at the point where they can no longer meet the tolerances of placement of the desired fiber. The adhesives used in the optical circuit devices will have a peel strength of at least two pounds per inch; they will have enough adhesion for a curved fiber with a radius of 2.54 cm (one inch) to be held in place without allowing the fiber to relax and uncoil and will be held in place roughly 1 mil after it is Pressed into the adhesive with an approximate force of one quarter pound, it will remain stable when exposed to normal environmental tests as known in the industry; it will not contain reactive constituents that could degrade the compound; and will not require the use of special procedures, such as gloves or ventilation, to handle the adhesive at temperatures up to 100 ° C. Accordingly, there remains a need for a non-combustible improved pressure sensitive adhesive in which the flame retardants are reacted in the polymer structure having high flame retardant properties with good adhesion, cohesion and stickiness. There is a particular need for such an adhesive that can be used for the manufacture of flexible optical circuit devices. The adhesives of this invention satisfy this need, although a utility was also found in other applications, such as electrical tape or in electronic devices and apparatus. Additional major advantages may appear when considering the description provided below. BRIEF DESCRIPTION OF THE INVENTION The invention comprises an adhesive composition consisting of the polymerization of an emulsion or solution of acrylic esters, dibromostyrene and vinylphosphonic acid, with or without acrylic acid and having dispersions of antimony trioxide mixed in the polymer. In a preferred embodiment, a latex adhesive composition is worked up with 2-ethylhexyl acrylate, dibromostyrene, n-butyl acrylate and vinylphosphonic acid, and are mixed again with Sb203 preferably in an approximate proportion of 100 parts of the copolymer by 8 to 10. Sb203 parts. Preferred compositions are those that contain at least 11.65 to 15.5% bromine and approximately 0.25% to 2.5% phosphorus. The pressure sensitive adhesives according to the invention further comprise compositions represented by the formula (I): wherein n is an integer having an approximate value of 1 to 200, x = 1 to 4, y = 1 to 5, z = 0 to 1, R1 is hydrogen or methyl; R2 is hydrogen or alkyl having from one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, hexyl, isoctyl and 2-ethylhexyl. When the latex polymerization (emulsion) techniques are employed, z = 0. The pressure sensitive adhesives according to the invention further comprise compositions represented by the formula (II): where n is an integer that has an approximate value of 1 to 200, x = 4, w = 1 to 4, y = 1 to 5, z = 0 to 1, R1 is hydrogen or methyl, R2 is hydrogen or alkyl having from one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, hexyl, isoctyl and 2-ethylhexyl. With latex polymerization techniques (emulsion), z = 0. The polymers of the invention have an average molecular weight of at least 75,000 and glass transition temperatures (Tg) of about -15 ° C to -55 ° C. BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the invention, reference is made to the accompanying drawings, in which: Figure 1 reflects the results of a gel infiltration chromatography analysis for the solution polymer prepared following the EXAMPLE 3 of the present; and Figure 2 reflects the results of a differential scanning calorimetry analysis for the solution polymer of Figure 1. DETAILED DESCRIPTION OF THE INVENTION The invention provides a flame retardant pressure sensitive adhesive in which the flame retardant capacity of the flame retardant the flame is reacted in the polymer structure. With this invention, a series of acrylic polymers based on dibromostyrene (or dibro oethenylbenzene) incorporating phosphorus are provided. In general, the adhesive composition comprises a polymerization of an emulsion or solution of dibromostyrene, acrylic esters and vinylphosphonic acid. With the polymerization of a solution, acrylic acid is also incorporated into the polymerization mixture. Preferred acrylic esters comprise butyl acrylate and 2-ethylhexyl acrylate. However, other acrylates and / or methacrylates can be used, including one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, hexyl acrylate, acrylate isoctyl and vinyl acetate. The resulting copolymer is again mixed with dispersions of antimony trioxide (Sb203) preferably in an approximate proportion of 100 parts of the copolymer by 8 to 10 parts of Sb203. The high bromine content of the adhesive provides good flame retardant properties, while the aromatic quality of the compound ensures good thermal and hydrolytic stability. The phosphorus content increases the effectiveness of the flame retardant at the point where only relatively small amounts of Sb203 may be needed to obtain the desired levels of flame retardant capacity, so that the adhesive adhesion of the composition remains at a level Suitable for use in optical circuits and other applications that have similar restrictions. The best combination of the flame retardant capacity and adhesive amounts is obtained when the polymerization of an emulsion is used. Emulsion polymers are preferred to solution polymers due to the kinetic reaction. Dibromostyrene tends to react more slowly with the acrylic esters of a solution than those of an emulsion and tend to form dibromostyrene homopolymers instead of the desired copolymer compositions. PreferablyWith the polymerization of an emulsion 2-ethylhexyl acrylate is the predominant acrylic ester with an approximate ratio of 2-ethylhexyl acrylate to 2: 1 butyl acrylate. With the polymerization of a solution, approximately equal parts of 2-ethylhexyl acrylate and butyl acrylate have proven advantageous. Small amounts of vinylphosphonic acid are incorporated into the polymerization mixture of an emulsion or solution, with a percentage of the vinylphosphonic acid which is about 1 to 5% of the total monomers charged. Preferred compositions for the polymerization of an emulsion have percentages by weight of about: 1 percent vinylphosphonic acid, 50 percent 2-ethylhexyl acrylate, 26 percent n-butyl acrylate, 23 percent dibromostyrene. For polymerization, the percentages by weight comprise 5 percent vinylphosphonic acid, 35 percent 2-ethylhexyl acrylate, 35 percent n-butyl acrylate, 23 percent dibromostyrene, and 2 percent acrylic acid. The composition obtained with the polymerization can be represented by the formula (I): wherein n is an integer having an approximate value of 1 to 200, x = 1 to 4, y = 1 to 5, z = 0 to 1, R1 is hydrogen or methyl; R2 is hydrogen or alkyl having from one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, hexyl, isoctyl and 2-ethylhexyl. When latex polymerization (emulsion) techniques are used, z = 0.

The composition obtained with the polymerization includes a vinyl acetate monomer which can be represented by the formula (II): where n is an integer having an approximate value of 1 to 200, x = la, w = 1 to 4, y = 1 to 5, z = 0 to 1, R1 is hydrogen or methyl, R2 is hydrogen or alkyl having one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen- or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, hexyl, isoctyl and 2-ethylhexyl. With latex polymerization (emulsion) techniques, z = 0. The monomers specified in the specifically mentioned proportions herein can be advantageously used or mixed with vinyl acetate and acrylic esters (such as acrylate and methacrylate esters) in such proportions to provide the copolymers having glass transition temperatures (Tg) of about -15 ° C to -55 ° C. The latex polymers are preferably used with an average molecular weight of at least 150,000 or the solution polymers with an average molecular weight of about 76,000. The approximate bromine content is preferably at least 11.6 to 15.6 percent and the approximate phosphorus content is preferably 0.25 to 2.5 percent. A dibromostyrene monomer suitable for use in polymerizations is made available by the Great Lakes Chemical Company in West Lafayette, Indiana, under the Great Lakes DBS brand. It is an amber liquid containing 58 to 59 percent bromine with a formula weight of 261.9. When the test is carried out, it results in 99% brominated styrene. The dibromostyrene monomer contains approximately 85 percent dibromostyrene, 10-15 percent monobromattyrene (primarily parabromostyrene) and 5-6 percent tribromostyrene by weight. The polymerization is preferably carried out at high temperatures, ie approximately 80 to 100 ° C. The polymerization techniques are well known. Suitable initiators include those used for free radical polymerization, such as persulfates, peroxides, or azo compounds. diazo Suitable emulsifiers include anionic, cationic, nonionic or amphoteric. A bath of solvent or deionized water, such as toluene, is charged and flowed overflowing with nitrogen, and the monomers (comprising dibromostyrene, acrylic esters, vinylphosphonic acid and acrylic acid) are pumped into the bath for a period of time , while the composition is stirred or rotated, with an increasing temperature. Cross-linking additives can be added and the finished polymer mixed with the appropriate dispersions of Sb203. Care must be taken that the Sb203 is well dispersed. For optical circuit applications, the adhesive can be emptied onto a silicone release liner. Wet adhesive films can be air dried and cured at temperatures of 48.40 to 119.90 ° C (120-125 ° F), and then transferred to a KAPTON ™ film or other suitable film used for optical circuits. The adhesive layer preferably has a thickness of 1 mil in dry, but can be coated with no less than 0.5 to 5.0 mil in dry. Now the invention will be further described with reference to the following Examples. However, it is understood that these Examples are illustrative and of a non-limiting nature. EXAMPLE 1 Polymerization of an emulsion was carried out using 1% vinylphosphonic acid (18 gr.), 50% of 2-ethylhexyl acrylate (900 g.), 26% of n-butyl acrylate (468 g.) And 23% of dibromostyrene (414 g.) (The percentages are by weight). A reactor was charged with 954 deionized water and purged with nitrogen while heating to 80 ° C. A polymerization initiator consisting of 9.0 gr. Was added to the reactor. of ammonium persulfate dissolved in 45.0 gr. of deionized water. Fifteen minutes after the addition of the initiator, the monomer pre-emulsion consisting of 414 gr. of deionized water, 45.0 gr. of RHODAPEXCO-436 (a mark for an ammonium salt of sulphonated nonylphenoxy (ethyleneoxy) ethanol sulfate available by Rhone Poulenc), 14.4 gr. of aqueous ammonium (29%), 18.0 gr. of vinylphosphonic acid, 900 gr. of 2-ethylhexyl arylate, 468 gr. of n-butyl acrylate and 414 gr. of dibromostyrene. This pre-emulsion was added equally over a period of four hours (9.47 grams per minute) with the reactor under nitrogen. The reactor bath was maintained at approximately 81 ° C plus / minus 1 ° C. The contents of the reactor were maintained at 80.1 ° C plus / minus 1 ° C during monomer feed and stirring varied from 150 to 200 r.p.m. as needed. 108 gr. of deionized water at the end of the feed as a rinse, and the reactor was maintained at 80 ° C for an additional 45 minutes. The emulsion was then cooled to 50 ° C. Four dispersants were added as follows: Dispersing composition # 1 # 2 # 3 # 4 Deionized water, gr. 6.01 6.01 6.01 6.01 70% t-Butyl hydroperoxide, gr. 0.83 - 0.83 Sodium formaldehyde sulfoxylate, gr. - 0.83 - 0.83 The dispersant # 1 was added after cooling to 50 ° C. Dispersant # 2 was added five minutes after dispersant # 1. Dispersant # 3 was added 20 minutes after dispersant # 2. Dispersant # 4 was added 5 minutes after dispersant # 3. The reactor was maintained at 50 ° C for a total of 60 minutes, beginning 20 minutes after the addition of dispersant # 2. The finished emulsion was cooled to approximately 35 ° C and 5.63 gr. of KATHON LX (1.5%) BIOCIDE (available by Rohm & Haas Company), a 4-izotiazoline-3-one compound used as a microbiocide was added before being packaged in a barrel or container. The total charge of the rector was 3422.39 gr. The latex was 53.6% non-volatile with a viscosity of about 20-34 cps at 25 ° C and a pH of 5.91. The average particle size was measured at approximately 295 nanometers. The filterable solids (coagulated substance) were 3 parts per million in a 100 mesh, 9 ppm in a 200 mesh, and 15 ppm in a 325 mesh. EXAMPLE 2 2326 gr. of the product of Example 1 were prepared with 6.3 g. 29% NH4OH. 4-65 gr. of DREWPLUS L-475 (a brand of a non-ionic defoamer comprising a mixture of mineral oils and silica derivatives sold by Dre Industrial Division), 94.6 gr. of ALCOGUM L-31 (a mark for a thickener of a copolymer of an acrylic emulsion, sold by Aleo Chemical Corp.) and 20 gr. of deionized water. The product was 52.1% non-volatile with a viscosity of 2015 cps at 25 ° C and a pH of 8.41. This product had the properties listed below in Table I, Column 1. The composite product was dispersed with Sb203 in a proportion of 100 parts of copolymer solids per 12 parts of Sb203 solids (192.3 g of the copolymer prepared in the manner described above) was mixed with 20 gr. of AQUAMIX 104 (a brand for an aqueous dispersion containing 60% Sb203, sold by Har ick Chemical), to produce 212.3 gr. The wet adhesive was poured over a bleached Kraft paper silicone release liner, allowed to air dry for 15 minutes, cured for 6 minutes at 92.40 ° C (200 ° F) and transferred to a 2 mil film. KAPTON ™. The KAPTON ™ film coated adhesive was tested to obtain the UV 94 standard classifications. Of twenty samples tested, six obtained a VO classification and 13 obtained a VI classification. The resulting product had the adhesive properties listed in 1-a Table I, column 2. EXAMPLE 3 Intermediate Polymer Solution A Polymerization of a solution was initiated using 5% vinylphosphonic acid (60 gr.), 35% acrylate 2- ethylhexyl (420 gr.), 35% n-butyl acrylate (420 g.), 23% dibromostyrene (138 g.) and 2% acrylic acid (24 g.) with 520.5 g. of toluene and 1.25 gr. of TRIGANOX 29 (1, 1-di- (t-butylperoxy) -3, 3, 5- (trimethylcyclohexane), dissolved in 50 g of toluene.This solution was added to a 2 1/2 stainless steel reactor. gallons purged with nitrogen with an agitation of (120 to 130 rpm) The contents of the reactor were heated to 103/104 ° C and maintained at 104 ° C for 15 minutes A feeding of the dilated monomer solution consisting of 60 gr of vinylphosphonic acid, 420 g of 2-ethylhexyl acrylate, 420 g of n-butyl acrylate, 414 g of dibromostyrene and 14 g of acrylic acid, with 668.9 g of toluene and 1.51 g of TRIGANOX 29, dissolved in 50 g of toluene was added evenly to the reactor (114 g / min.) Over a period of three hours with stirring, while maintaining the flow of nitrogen and the temperature of the contents of the reactor was maintained at 100 °. C plus / minus 1 ° C. The reaction continued at this temperature for an additional period of 6 hours after the solution was added. n monomeric dilated. The reaction was completed with three individual additions of each compound 2.0 gr promoter. of TRIGANOX 29 dissolved in 50 gr. of toluene added at three hour intervals beginning at the end of the 6 hour maintenance period. Three and a half hours after the third promoter was added, the reactor was cooled to approximately 60 ° C and 515.4 g was added. of isopropanol. The solution polymer was further cooled to 40 ° C and packaged in a barrel. The polymeric base of a solution that was not formed into a compound (a polymeric base of a solution A) had a solids content of 54.1% and a Gardner Holdt viscosity of 14.9 Stokes (about 1640 cps) at a temperature of 25 ° C. . The total materials charged comprised 4363 gr. Intermediate Polymer Solution B The polymeric base of solution A was mixed with metallic chelate cross-linked with the additives as follows: 2.4 gr. of aluminum acetylacetonate (0.6% polymer solids)3.7 gr. of 2,4-pentanedione (approximately 1.5 times the charged aluminum acetylacetonate) and 24.5 gr. of toluene (10 times the charged aluminum acetylacetonate), were previously dissolved and added as a masterbatch of 30.6 gr. mixing in 765.5 gr. of the intermediate polymer solution A (approximately 409.3 g of solids). This product had the adhesive properties listed below in Table I, Column 3. Final Polymer Solution of Compound C Intermediate polymer solution B was prepared with dispersions of Sb203 at a ratio of 100 parts of resin solids per 10 parts of Sb203 . 11.8 gr. from an Harwick Matermix antimony oxide containing 85% Sb203 (approximately 10 g of Sb203) to 192.3 g. of the intermediate polymer solution B containing the crosslinking additives (approximately 100 grams of solids) mixing until it becomes homogeneous. The resulting product had the adhesive properties listed below in Table I, Column 4. The solution polymer of EXAMPLE 3 was analyzed using gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) analysis. Liquid sample for the GPC was prepared by adding 0.02 gr. from the polymer of the solution to 10 ml of tetrahydrofuran; it was then kept at 25 ° C for 24 hours to dissolve the polymer, filtered through a 4.5 μm filter and injected with a 100 μl injection into a series of 7 column Waters HMW 6e / HMW with a mobile phase of THF of 1 ml / min. The results are reported in Figure 1 and reflect a molecular weight of 76,610. The DSC reflects a Tg of -49 extrapolated from a thermal profile of 20 ° C / minute from -100 ° C to 250 ° C reported in Figure 2. As noted, the copolymers and intermediate polymers obtained through the described processes in Examples l-3 were cast on release liners, air-dried for fifteen minutes and cured at approximately 92.40 ° C (200 ° F) to comprise 1-mil adhesive films, which were transferred to substrates of MYLARm of 2 mils and tested on the basis of its flame retardant capacity and adhesive, cohesive and tack properties. The compositions were found to have the properties listed below in Table I: TABLE I ADHESIVE PROPERTIES SENSITIVE TO PRESSURE OF EXAMPLES I-III RELATED TO TRANSFER OF ADHESIVE FILMS OF 1 THOUSAND INCH DRY • COVERED IN A MYLAR TYPE SUBSTRATE OF 2 THOUSAND INCHES. CURING: 15 MINUTES, DRY IN THE AIR FOR 6 MINUTES. @ 92.40 ° C (200 ° F) Example 2 Example 2 Example 3 Example 3 (without Sb2? 3) (with Sb2? 3 in (without Sb2? 3> (with Sb2? 3 in 10 a ratio of 100/12 ratio ) 100/10) • Adhesive Properties PSTC-1, Adhesion to peeling 180 ° c, pounds / inch 15 Interval Interval, (prog.) 2.0 C 2.6C 2.5 c Interval at 15 '(prom.) 3.5C / 4 0PT 2.0C 3.2C 3.7C 24 hour interval (avg.) 7.13 / 6 2PT 2.6C 3.6C 3.7C Adhesion properties: PSTC-5, Immediate adherence 20 (average) 0.9C 0.7C 1.6C / 0.7Z Adhesion by clamp pounds (average) 0.8 PSTC-7, adhesion to shear, hours 25 1"X 1/2" X 1000 gr. (prom.) 0.05 1/2"X 1/2" X 5000 gr. .) 0.11S 0.97S 0.46S 1/2"X 1/2" X 1000 gr. (Avg.) 0.25S 0.1S Code of Deficiencies of Adhesive C = Transparency, Deficiency in adhesive PT = Partial Transfer S = Separation Z = Closing It is understood that the modalities described herein are only exemplary and that a person with experience In the art, it can effect variations and modifications without departing from the spirit and scope of the invention. All variations and modifications are intended to be included within the scope of the appended claims.

Claims (19)

1. CLAIMS CLAIMS: 1. An adhesive composition comprising the polymerization of one or more acrylic esters selected from the group consisting of butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, nitrile acrylate, -butyl, n-butyl methacrylate, hexyl acrylate, isoctyl acrylate, and vinyl acetate; a dibromostyrene monomer or a vinylphosphonic acid monomer.
2. 2. The composition of claim 1, further comprising antimony trioxide (Sb203) mixed with the polymer in a proportion of about 100 parts of the polymer by 6 to 15 parts of Sb203.
3. 3. The composition of claim 1, wherein the polymerization comprises the. polymerization of a solution and about one to five percent acrylic acid by weight.
4. 4. The composition of claim 1, wherein the acrylic esters comprise 2-ethylhexyl acrylate and n-butyl acrylate.
5. The composition of claim 1, wherein the polymer comprises at least about 11.6 to 15.6% bromine and about 0.25 to 25% phosphorus by weight.
6. 6. The composition of claim 4, comprising the polymerization of an emulsion of 2-ethylhexyl acrylate and n-butyl acrylate, wherein the ratio of 2-ethylhexyl acrylate to n-butyl acrylate is approximately 2: 1 .
7. The composition of claim 3, comprising the polymerization of an emulsion of 2-ethylhexyl acrylate and n-butyl acrylate, wherein the ratio of 2-ethylhexyl acrylate to n-butyl acrylate is about 1. :1.
8. The composition according to claim 1, having an average molecular weight of at least about 75,000 and a glass transition temperature Tg of about -15 ° C to -55 ° C.
9. 9. The composition according to claim 1, comprising about 1 to 5% by weight of vinylphosphonic acid.
10. 10. The composition of claim 6, which consists of about 1% by weight of vinylphosphonic acid, 50% by weight of 2-ethylhexyl acrylate, 26% by weight of n-butyl acrylate and 23% by weight dibromostyrene.
11. The composition of claim 7, which comprises approximately by weight of vinylphosphonic acid, 35% by weight of 2-ethylhexyl acrylate, 35% by weight of n-butyl acrylate, 23% by weight dibromostyrene and 2% by weight Acrylic acid 12.
12. A pressure sensitive adhesive comprising a polymer represented by the formula: where n is an integer that has an approximate value of 1 to 200, x = l to 4, w = 0 to 4, y = l to 5 / z = 0 15 to 1, R1 is hydrogen or methyl; R2 is hydrogen or alkyl having from one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, Hexyl, isoctyl and 2-ethylhexyl.
13. The pressure sensitive adhesive of claim 12, wherein = 1 to 4 and comprising the polymerization of the vinyl acetate monomer.
14. 14. A pressure sensitive adhesive comprising a polymer represented by the formula: wherein n is an integer having an approximate value of 1 to 200, x = 1 to 4, y = 1 to 5, z = 0 to 1, R1 is hydrogen or methyl, R2 is hydrogen or alkyl having one to four carbon atoms; R3 and R4 taken independently of each of R3 and R4 is hydrogen or methyl; R5 taken independently from each of R5 is selected from the group consisting of methyl, ethyl, n-butyl, hexyl, isoctyl and 2-ethylhexyl.
15. 15. The adhesive composition according to claim 12, further comprising dispersions of antimony trioxide mixed with the polymer.
16. 16. An adhesive composition according to claim 14, comprising an emulsion polymer in which Z = 0.
17. 17. The adhesive composition according to claim 12, which further comprises an antimony trioxide (Sb203) mixed with the polymer in an approximate proportion of 100 parts of the polymer by 6 to 15 parts of Sb203.
18. The adhesive composition according to claim 14, further comprising antimony trioxide (Sb203) mixed with the polymer in a proportion of about 100 parts of the polymer by 6 to 15 parts of Sb203.
19. 19. The adhesive composition according to claim 1, comprising a polymer represented by the formula of claim 12.