12328395 (P.T.A.B. Oct. 21, 2013)

Ex Parte Peerlings et al

Patent Trial and Appeal BoardOct 21, 2013

12328395 (P.T.A.B. Oct. 21, 2013)

UNITED STATES PATENT AND TRADEMARKOFFICE UNITED STATES DEPARTMENT OF COMMERCE United States Patent and Trademark Office Address: COMMISSIONER FOR PATENTS P.O. Box 1450 Alexandria, Virginia 22313-1450 www.uspto.gov APPLICATION NO. FILING DATE FIRST NAMED INVENTOR ATTORNEY DOCKET NO. CONFIRMATION NO. 12/328,395 12/04/2008 Henricus Peerlings 15778-00174-US 6840 23416 7590 10/21/2013 NOVAK DRUCE CONNOLLY BOVE + QUIGG LLP P O BOX 2207 WILMINGTON, DE 19899-2207 EXAMINER GRESO, AARON J ART UNIT PAPER NUMBER 1726 MAIL DATE DELIVERY MODE 10/21/2013 PAPER Please find below and/or attached an Office communication concerning this application or proceeding. The time period for reply, if any, is set in the attached communication. PTOL-90A (Rev. 04/07) UNITED STATES PATENT AND TRADEMARK OFFICE ____________________ BEFORE THE PATENT TRIAL AND APPEAL BOARD ____________________ EX PARTE BAYER MATERIALSCIENCE AG Inventors: Henricus Peerlings and Juergen Winkler ____________________ Appeal 2012-008065 Application 12/328,395 Technology Center 1700 ____________________ Before FRED E. McKELVEY, RICHARD E. SCHAFER and RICHARD TORCZON, Administrative Patent Judges. McKELVEY, Administrative Patent Judge. DECISION ON APPEAL I. Background Bayer MaterialScience AG (“applicant”), the real party in interest (Brief, 1 page 1), seeks review under 35 U.S.C. § 134(a) of a final rejection dated 2 4 May 2011. 3 The application on appeal was filed in the PTO on 4 December 2008. 4 Applicant claims priority of German patent application 10 2007 058435.2, 5 filed 5 December 2007. 6 The application has been published as U.S. Patent Application Publication 7 2009/0149582 A1. 8 Appeal 2012-008065 Application 12/328,395 2 II. Prior art 1 In support of a prior art rejection, the Examiner relies on the following 2 evidence. 3 Hackl et al. “Hackl” U.S. Patent Application Publication 2005/0203244 A1 15 Sept. 2005 Finkel’shtein et al. “Finkelshtein” Molecular Spectural Analysis in the Nitrogen Industry, 15 ZHURNAL PRIKLADNOI SPEKTROSKOPII 762-765 Oct. 1971 Applicant does not contest the prior art status of the Examiner’s evidence. 4 Applicant relies on the following evidence. 5 BASF Data Sheet 1 Melapur® MC50 © 2011 We mention the following additional evidence in this opinion. 6 Farkas1 U.S. Patent 5,110,850 5 May 1992 filed 10 Apr. 1991 1 Farkas is cited in the Specification at page 2:7. Appeal 2012-008065 Application 12/328,395 3 Eckstein et al. “Eckstein” U.S. Patent 6,777,466 B2 17 Aug. 2004 filed 08 Feb. 2002 Lagneaux et al. “Lagneaux” U.S. Patent Application Publication 2003/0232933 A1 18 Dec. 2003 filed 17 June 2002 Scarso European Published Patent Application 0 389 768 A2 10 Mar. 1990 Pauling THE NATURE OF THE CHEMICAL BOND, page 449 (3d ed.) [ISBN 0-8014-0333-2] 1995 BASF Data Sheet 2 Melapur® MC25 © 2013 We have jurisdiction under 35 U.S.C. § 134(a). 1 III. Claims on appeal 2 Claims 1-6 are on appeal. Brief, page 2; Answer, 3. 3 Claim 1, which we reproduce from the Claims Appendix of the Brief, reads 4 (matter in brackets and some indentation added; principal limitation in issue in 5 italics): 6 Appeal 2012-008065 Application 12/328,395 4 A thermoplastic polyurethane based on 1 a) an organic and/or modified organic diisocyanate [e.g., 2 toluene diisocyanate (TDI) and methylene diphenyl diisocyanate 3 (MDI)]; 4 b) a polyhydroxy compound [e.g., polyhydroxy compounds 5 having 1.8 to at most 3.0 Zerewitinoff-active hydrogen atoms and an 6 Mn of from 450 to 10,000]; 7 c) a chain-lengthening agent [e.g., compounds having 1.8 to 8 at most 3.0 Zerewitinoff-active hydrogen atoms and a molecular 9 weight of from 60 to 400]; 10 d) flame-proofing agent; 11 and optionally 12 e) a catalyst; 13 f) a chain terminator; and 14 g) an auxiliary substance and/or additive; 15 wherein said flameproof agent comprises 16 [1] melamine cyanurate and 17 [2] melamine and 18 [3] optionally comprises at least one additional flameproof 19 agent. 20 IV. Rejections 21 A. Rejection 1 22 In the Answer, the Examiner has maintained the following Rejection 1: 23 Claims 1-6 stand rejected under § 102(b) as anticipated by Hackl. 24 Appeal 2012-008065 Application 12/328,395 5 In connection with Rejection 1, in the Brief applicant does not argue the 1 separate patentabilty of Claims 2-6 apart from Claim 1. Accordingly, as to 2 Rejection 1 we decide the appeal on the basis of Claim 1. 37 C.F.R. 3 § 41.37(c)(1)(vii) (2011). 4 B. New Rejection 2 5 Claims 1-6 are rejected under § 102(b) an anticipated by Eckstein. 6 Alternatively, Claims 1-6 are rejected as being unpatentable under § 103 7 over (1) Hackl, (2) Eckstein, (3) Lagneaux, (4) Scarso and (5) BASF Data Sheet 2. 8 37 C.F.R. § 41.50(b) (2011). 9 V. Description of prior art 10 A. Farkas 11 From a prior art point of view, Farkas teaches as of its April 1991 filing date 12 that a thermoplastic polyurethane (TPU) can be made flame retardant using 13 melamine. 14 Melamine has the following structure: 15 16 According to Farkas, it is important that the melamine does not include 17 “melamine derivatives.” Col. 5:53-57. 18 Appeal 2012-008065 Application 12/328,395 6 The amount of melamine to be used is in an amount of 30-40 % based on the 1 TPU. Col. 5:57-59. 2 B. Eckstein 3 From a prior art point of view, Eckstein teaches as of its February 2002 4 filing date that a thermoplastic polyurethane (TPU) can be made flame retardant 5 using melamine cyanurate. 6 Melamine cyanurate has the following structure, where the dash bonds are 7 hydrogen bonds: 8 9 Eckstein reveals that melamine cyanurate is a known flame retardant for 10 use in a TPU, but its use at high levels is said to have been avoided because of 11 detrimental effect on tensile strength and molecular weight. Col. 1:56-60. 12 Nevertheless, Eckstein states that a TPU along with melamine cyanurate can 13 “achieve good flame retardency.” Col. 2:50-53. 14 According to Eckstein, it is important that the only flame retardant used be 15 melamine cyanurate. Col. 6:62-66. 16 A suitable melamine cyanurate is described as Melapur® MC-25. 17 Col. 7:32-33. 18 Appeal 2012-008065 Application 12/328,395 7 According to BASF Data Sheet 2 (dated 2013) Melapur® MC-25 has an 1 excess melamine content of less than 0.3 wt.% (see Typical Properties). 2 The amount of melamine cyanurate to be used is in an amount of 28-50 % 3 based on the TPU. Col. 6:66 to col. 7:1. 4 C. Lagneaux 5 From a prior art point of view, Lagneaux teaches as of its 17 June 2002 6 filing date, that a mixture of melamine and melamine cyanurate may be used as a 7 flame retardant in TPU compositions. ¶ 0049. 8 The amount of flame retardant to be used is described as being from about 9 10 to about 50 parts by weight per 100 parts by weight of the TPU composition. 10 Id. 11 The Lagneaux teaching concerning the use of mixtures of flame retardants, 12 including mixtures of melamine and melamine cyanurate is consistent with a 1990 13 teaching by Scarso that in combination with other flame retardants, a mixture of 14 melamine and melamine cyanurate would function as a flame retardant in 15 polyurethanes. Page 2, col. 1: 39-46; page 4: 43-50. 16 D. Hackl 17 From a prior art point of view, as of its 21 May 2003 filing date, Hackl—18 cited by the Examiner—describes the use of melamine cyanurate as a flame 19 retardant in combination with a phosphorus compound for use in TPUs. ¶ 0040. 20 Unlike Eckstein, we have not been able to find in Hackl a description of a 21 particular source of melamine cyanurate (e.g., Melapur® MC-25). 22 Appeal 2012-008065 Application 12/328,395 8 E. Finkelshtein 1 Finkelshtein was cited by the Examiner to establish that when melamine 2 cyanurate is made by reacting melamine with cyanuric acid that melamine 3 cyanurate will have some melamine. See the second paragraph of Part 3 on 4 page 1416. 5 F. BASF Data Sheet 1 6 The BASF Data Sheet 1 (bearing a 2011 date) is relied upon by applicant to 7 rebut the Examiner’s reliance on Finkelshtein. Brief, page 5. 8 According to applicant, the BASF Data sheet discloses that melamine 9 cyanurate sold by Ciba (now BASF) as Melapur® MC50 has an excess melamine 10 content of less than 0.3% by weight. Id. 11 G. BASF Data Sheet 2 12 The BASF Data Sheet 2 (bearing a 2013 date) discloses that melamine 13 cyanurate sold by Ciba (now BASF) as Melapur® MC25 has an excess melamine 14 content of less than 0.3% by weight. Id. 15 VI. New Rejection 2 16 We start with new Rejection 2. 17 Claims 1-6 are rejected under § 102(b) an anticipated by Eckstein. 18 Alternatively, Claims 1-6 are rejected as being unpatentable under § 103 19 over (1) Farkas, (2) Eckstein, (3) Lagneaux, (4) Scarso and (5) BASF Data Sheet 2. 20 37 C.F.R. § 41.50(b) (2011). 21 A. Anticipation--Eckstein 22 Eckstein describes thermoplastic polyurethanes (col. 2:50-53) made from 23 (1) a diisocyanate (MDI), (2) a polytetramethylene ether glycol (PTMEG), 24 Appeal 2012-008065 Application 12/328,395 9 (3) a chain extender (1,4-butanediol) and (4) a flame proofing agent—melamine 1 cyanurate. Col. 13:4-14; Example 2—col. 14:11-29. A particular melamine 2 cyanurate is described as being Melapur® MC-25. Col. 7:33. 3 According to BASF, in 2013 Melapur® MC25 has less than 0.3 wt.% 4 melamine. BASF Data Sheet 2. We find that some, albeit very little, melamine is 5 present in Melapur® MC-25. It is true that BASF Data Sheet 2 is not prior art 6 given its 2013 date. However, we have no reason to believe that the composition 7 of Melapur® MC-25 has changed over the years. We find it more likely than not, 8 in the absence of evidence to the contrary, that the composition of Melapur® 9 MC 25 has remained unchanged. We note that applicant now markets Melapur® 10 MC-25 and is in a much better position vis-à-vis the PTO to establish the precise 11 melamine content of its compositions at the relevant time. 12 Claim 1 does not limit the amount of melamine vis-à-vis melamine 13 cyanurate. Accordingly, we find on the current record that the description of the 14 use of Melapur® MC-25 anticipates applicant’s claims melamine/melamine 15 cyanurate mixture. 16 B. Obviousness 17 Assuming arguendo that Eckstein does not anticipate the claims, the subject 18 matter of the claims would have been obvious under § 103 over the prior art. 19 As early as 1990, Scarso suggests the use of a mixture of melamine and 20 melamine cyanurate (in combination with other flame retardants) as suitable for 21 use in polyurethanes. 22 In 1991, Farkas discovered that thermoplastic polyurethanes may be 23 rendered flame retardant using melamine—as the sole flame retardant. Farkas 24 Appeal 2012-008065 Application 12/328,395 10 provides no comprehensive scientific reason for stating why it is important that the 1 sole flame retardant be melamine. Col. 5:53-64. 2 Nevertheless, a difference between Farkas and the subject matter of the 3 claims on appeal is that Farkas does not describe the use of a mixture of melamine 4 and melamine cyanurate. 5 Shortly after Farkas, in 1992 Eckstein discovered that thermoplastic 6 polyurethanes may be rendered flame retardant using melamine cyanurate—as the 7 sole flame retardant. Eckstein provides no comprehensive scientific for stating 8 why it is important that the sole flame retardant be melamine cyanurate. 9 Col. 6:64 66. 10 Nevertheless, a difference between Eckstein and the subject matter of the 11 claims on appeal is that Eckstein does not describe the use of a mixture of 12 melamine and melamine cyanurate. 13 In June of 2002, Lagneaux teaches that melamine, melamine cyanurate and 14 mixtures thereof can be used as flame retardants in blends of thermoplastic 15 polyurethane and blend polymer. ¶ 0049. The Lagneaux teaching is consistent 16 with the 1990 Scarso teachings. 17 While Farkas and Eckstein limit their respective discoveries to use of either 18 melamine alone or melamine cyanurate alone, as noted above, neither provides any 19 comprehensive scientific reason why it limits its invention to use of only one flame 20 retardant. Based on the combined teachings of Farkas, Eckstein, Lagneaux and 21 Scarso, as of 2006 one skilled in the art reasonably would have expected that a 22 mixture of melamine and melamine cyanurate would have been useful as a flame 23 retardant for thermoplastic polyurethanes. In re Kerkhoven, 626 F.2d 846, 850 24 Appeal 2012-008065 Application 12/328,395 11 (CCPA 1980) (it is generally prima facie obvious to combine two compositions 1 each of which is taught by the prior art to be useful for the same purpose in order 2 to form a third composition which is also used for that purpose). Scarso and 3 Lagneaux describe the use of mixtures of melamine and melamine cyanurate. 4 In resolving patentability of claims based on an application filed in Germany 5 claiming an effective filing date of 2007, the PTO is not limited to the 1991 Farkas 6 filing date or the 1992 Eckstein filing date time periods. 7 Rather, obviousness as to the claims on appeal can properly be measured 8 based on prior art available as of 2006—one year prior to applicant’s 2007 German 9 filing date. 10 The subject matter of the claims on appeal would have been prima facie 11 obvious. Applicant is using known compounds for their known purpose to achieve 12 an expected result. 13 Applicant provides some data in the Specification which we will consider as 14 rebuttal evidence. 15 The data represents results said to have obtained by mixing various flame 16 retardants with a polyurethane made from (1) MDI, (2) a polyether having an Mn 17 of about 1000, and (3) 1,4-butane diol. Specification, page 11, 16-20. 18 The data is set out in Table 1 (Specification, page 14) set out below to which 19 we have added some explanatory notes. 20 Appeal 2012-008065 Application 12/328,395 12 Table 1 Formulation Incorporation of MC/M Example MC melamine cyanurate [wt.%] M melamine [wt.%] BDP flame retardant [wt.%] IHPO flame retardant [wt.%] Single- screw extruder TSE (twin screw extruder) UL-94 flame test 1 (comparison) 25 0 7.5 3 Not possible 2 (invention) 18 7 7.5 3 X V-0 3 (comparison) 25 0 7.5 3 X V-2 4 (invention) 18 7 7.5 3 X V-0 5 (comparison) 35.5 0 0 0 X V-2 6 (invention) 25.5 10 0 0 X V-0 7 (comparison) 0 35.5 0 0 X Failed The data is not convincing under any standard of proof. 1 Invention Examples 2 and 4 are reported to have achieved a UL-94 rating of 2 V-0. However, one skilled in the art would not be able to ascertain whether the 3 V-0 rating was due to the mixture of melamine and melamine cyanurate or 4 melamine in combination with BDP and IHPO—additional flame retardants. 5 Comparison Examples 5 and 7 vis-à-vis invention Example 6 report tests 6 based on: 7 (1) melamine alone (Example 5—UL 94 = V-2), 8 (2) melamine cyanurate alone (Example 7—reported to have failed 9 UL 94) and 10 Appeal 2012-008065 Application 12/328,395 13 (3) a mixture of melamine and melamine cyanurate 1 (Example 6—said to have achieved a UL 94 of V-0). 2 We decline to give much weight to the “Incorporation of MC/M” because 3 process claims 3-4 do not call for any method of incorporation. 4 We decline to give much weight to Example 5 data because it is inconsistent 5 with the prior art. See Farkas, col. 6:10-12: “The TPU/melamine composition 6 generally achieves a V-0 classification when tested according to the UL-94 vertical 7 burn test.” Farkas Examples 1-6 report flame retardant UL-94 values of V-0 for 8 polyurethanes made from (1) MDI, (2) a polyether diol (PTMEG) having an Mn of 9 1000, and (3) 1,4-butane diol—the same diisocyantes and polyols said to have 10 been tested by applicant. Col. 6:49-51. In re Reid, 179 F.2d 998, 1002 (CCPA 11 1950) (“in no way reflecting on the good faith of the makers of the affidavits . . . 12 the failures of experimenters who have no interest in succeeding should not be 13 accorded great weight.”); In re Michalek, 162 F.2d 229, 232 (CCPA 1947) (same). 14 We likewise decline to give much weight to Example 7 data because it too is 15 inconsistent with the prior art. See Eckstein, col. 12:59-63; Table 1 (which is 16 understood to be the table in col. 15). Polyurethanes made from (1) MDI, 17 (2) polytetramethylene ethyl glycol, and (3) 1,4-butanediol have said to have 18 passed UL-1581 flame tests when 32.8 wt.% (Run 8) and 30.5 wt.% (Run 13) 19 melamine cyanurate was used. On the record before us, we are unable to compare 20 UL-94 test values with UL-1581 test values. 21 No explanation appears at this time on the record why Farkas and Eckstein 22 report and appear to achieve good flame retardant results with polyurethanes 23 similar to those described in applicant’s examples using approximately the amount 24 Appeal 2012-008065 Application 12/328,395 14 of melamine alone or melamine cyanurate alone (Examples 5 and 7). In any case, 1 the prior art expressly teaches using the mixture of MC/M for flame retardency, 2 which means that (apart from appellants’ private results) a person having ordinary 3 skill in the art would have objectively expected the MC/M mixture to have worked 4 as the appellants found. An expected result is consistent with a conclusion of 5 obviousness. Wrigley Jr. Co. v. Cadbury Adams USA LLC, 683 F.3d 1356, 1362 6 (Fed. Cir. 2012) (known synergy not unexpected). 7 We also note that flame retardant properties appear to be a function of the 8 amount of melamine cyanurate used. Compare Eckstein Run 8 (32.8 wt.% = 9 passed) with Eckstein Run 6 (14.9 wt. % = failed). Applicant’s Example 6 limited 10 to 25.5 wt.% melamine cyanurate and 10 wt.% melamine is not a showing which is 11 commensurate in scope with the breadth of the claims on appeal. Applicant has 12 not shown that it can achieve good flame retardant properties at a 14.9 wt.% level. 13 VII. Rejection 1 14 Rejection 1 is based on a finding that one skilled in the art would understand 15 that the melamine cyanurate described by Hackl is a mixture of melamine and 16 melamine cyanurate. 17 Hackl does not explicitly describe a mixture of melamine and cyanurate. 18 Rather, Hackl describes the use of melamine cyanurate. 19 It may well be that melamine cyanurate necessarily contains small amounts 20 of melamine. See BASF Data Sheets 1 and 2, both of which describe melamine 21 cyanurate having less than 0.3 wt.% melamine. 22 The claims on appeal do not require any particular amount of melamine. 23 Appeal 2012-008065 Application 12/328,395 15 Accordingly, a mixture of 99.97 melamine cyanurate and 0.3 melamine 1 would meet the mixture limitation of Claim 1. 2 We are also aware of the fact that the hydrogen bonds of melamine 3 cyanurate may not be strong bonds. See Pauling. However, we do not know 4 whether any hydrogen bond breakdown necessarily results in some melamine 5 being present in melamine cyanurate. 6 On the record before us, we are unable to discern a reasonable basis for 7 finding that melamine cyanurate necessarily contains some melamine. 8 Finkelshtein likewise does not establish that all melamine cyanurate contains 9 some melamine. While limited melamine cyanurate experimentation described by 10 Finkelshtein contains some melamine, that fact does not establish that the 11 melamine cyanurate of Hackl necessarily contains melamine. 12 Because Hackl does not describe applicant’s claimed mixture limitation, it 13 cannot anticipate the subject matter of Claim 1. 14 However, a lack of anticipation does not render Claim 1 patentable over 15 Hackl. 16 Hackl describes the use of melamine cyanurate. Like applicant, Hackl does 17 not describe a particular source for melamine cyanurate. 18 A known melamine cyanurate source as of 2002 was Melapur® MC-25. 19 Eckstein, col. 7:33. 20 As noted earlier, BASF Data Sheet 2 indicates that in 2013 Melapur® 21 MC 25 had some, albeit less than 0.3 wt.%, melamine content. Also as noted 22 earlier, we will presume it had the same melamine content in 2002. 23 Appeal 2012-008065 Application 12/328,395 16 One skilled in the art would have found it obvious to use Melapur® MC-25 1 as the melamine cyanurate for practicing the Hackl invention. Use of Melapur® 2 MC-25 would amount to the use of a known commercial product for its intended 3 use to achieve an expected result. 4 The combination of Hackl, Eckstein and BASF Data Sheet 2 render the 5 subject matter of Claim 1 unpatentable under § 103. 6 VIII. Decision 7 Upon consideration of the appeal, and for the reasons given herein, it is 8 ORDERED that the decision of the Examiner rejecting Claims 1-6 9 under § 102 as anticipated by Hackl is reversed. 10 FURTHER ORDERED that Claims 1-6 are newly rejected as being 11 unpatentable under § 103 over Hackl, Eckstein and BASF Data Sheet 2. 12 37 C.F.R. § 41.50(b) (2011). 13 FURTHER ORDERED that Claims 1-6 are newly rejected under 14 § 102 as anticipated by Eckstein, alternatively as being unpatentable under § 103 15 over (1) Farkas, (2) Eckstein, (3) Lagneaux, (4) Scarso and (5) BASF Data Sheet 2. 16 37 C.F.R. § 41.50(b) (2011). 17 FURTHER ORDERED that our decision is not a final agency 18 action. 19 FURTHER ORDERED, within two (2) months from the date of our 20 decision, applicant may further prosecute the application on appeal by exercising 21 one of the two following options: 22 Option 1: Request that prosecution be reopened by submitting 23 an amendment or evidence or both. 37 C.F.R. § 41.50(b)(1). 24 Appeal 2012-008065 Application 12/328,395 17 Option 2: Request rehearing on the record presently before the 1 Board. 37 C.F.R. § 41.50(b)(2) (2011). 2 FURTHER ORDERED that no time period for taking any 3 subsequent action in connection with this appeal may be extended under 37 C.F.R. 4 § 1.136(a)(1)(iv) (2011). 5 REVERSED 6 (New rejection under 37 C.F.R. § 41.50(b) (2011)) 7 8 bar 9 Europiisches Patentamt European Patent Office ® Publication number: o 389 768 Office europeen des brevets A2 ® EUROPEAN PATENT APPLICATION €V Application number: 90102681.5 ® Date of filing: 12.02.90 ® Priority: 29.03.89 IT 1994189 @ Date of publication of application: 03:.10.90 Bulfetln 90/40 ® Designated Contracting States: AT BE CH DE FRGB U NLSE @ Int. C1.5: COSK 13/02, COSL 75/04, !/(COSK13102,3:22,3:32,5:16) ® Applicant V.A.M.P. S.r.l. Viale TeOOorlco, 1912 1-20149 Milano MI(IT) @ Inventor: Scarso, luciano Viale Teodorico, 19/2 1-20149 Milano MI(IT) ® Representative: Trupiano, Roberto BREVETTI EUROPA S.r.l. Piazza Bernini, 6 1-20133 Milano (MI)(IT) ® Flame-retardant and smoke-suppressant composition for pOlymers and so-obtained polymeric materials. ® Flame-retardant and smoke-suppressant compo sition for polyurethane polymers and polyurethane- based materials in general, comprising A) an ammo nium phosphate andlor one or more amine phosphat!*); B) one or more nitrogen-containing organic compound(s); and C) magnesium hydroxide andlor aluminum hydroxide. Polyurethane polymers and polyurethana-based materials endowed with flame-retardant and smoke-suppressant characteris tics by means of said composition. Xerox Copy Centre EP 0 389 768 A2 2 FLAME-RETARDANT AND SMOKE-SUPPRESSANT COMPOSmON FOR POLYMERS AND SO-OBTAINED POLYMERIC MATERIALS The present invention relates to a flame-retar dant and smoke-suppressant composition for poly urethane polymers, which composition, in other terms, combines with the property of being flame retardant, the property of being "smoke-suppres sant". i.e., the property of depressing the formation and/or the emission of the toxic smokes conse quent to the heating and the thermal decomposition of polyurethane polymers. A further object of the present invention are the polyurethane polymers and the various polyurethane-based polymeric ma terials. such as fibres, coatings. elastomers and rigid and flexible foams. rendered self-extinguishing and endowed with properties of low emission of toxic smokes by means of said flame-retardant and smoke-suppressant composition. As known. a polymeric material in general is endowed with self-extinguishing properties by means of the addition of special "flame-proofing" or "flame-retardant" agents which are precisely capable of supplying the polymeric substance with the required self-extinguishlng characteristics. Such flame-retardant agents (i.e.. "flame-retar dants") are constituted by halogenated organic substances, by metal-based compounds, such as. e.g., antimony trioxide, by phosphorus and phos phorus derivatives (such as. e.g., red phosphorus, ammonium polyphosphate, phosphoric esters). by nitrogen-containing organic compounds (such as, e.g., urea, dicyandiamide, melamine and/or melamine salts, cyanuric acid, and the like), and still others. In order to reach the desired self-extinguishing features, even two or more different flame-retar dants are used in mutual association, both in order to take advantage, in combination. of specific flame-retardant characteristics of the individual pro ducts. and in order to accomplish determined "synergistic" or "combined" effects. Flame-retardant compositions known from the prior art are those based on phosphorus and nitro gen, comprising, e.g., as nitrogen-containing pro ducts, compounds selected from the group consist ing'of hydroxyalkyl derivatives of isocyanuric acid. in particular tris-(2-hydroxyethyl)-isocyanurate. melamine. cyanuric acid, melamine salts and the like, and. as phosphorus containing products. am monium polyphosphate. Such flame-retardant compositions are widely used and are particularly suitable in order to endow the polyolefinic polymers with self-extingulshment characteristics. In cese of polyurethane polymers. a serious drawback which occurs when such polymers are submitted to a heating to very high temperatures and. in particular, are exposed to the action of direct flames and the like, is. as known. the emis sion of highly toxic smokes. deriving from the ther 5 mal decomposition of the same polymer. As a consequence. the use of such materials, widely diffused in the sectors of furnishings. of transport. of the construction of structural parts. of floor fab rics. of upholstery and the like. is extremely risky 10 and can cause severe damages in case of a fire. owing to the emission of the smokes deriving from the induced heating. even if the polymer was ren dered self-extinguishing by means of the use of traditional flame-retardant products and therefore is 15 not capable of feeding the flames and of support ing the fire. The purpose of the present invention is of providing a flame-retardant composition for poly urethane polymers which simultaneously is also a 20 smoke-suppressant one. which, i.e.. is capable of "suppressing" or "depreSSing" the emiSSion of noxious smokes deriving from the decomposition of the polyurethane materials when these latter are submitted to a heating at high temperatures and/or 25 are exposed to the action of direct flames. and the like. These and still other purposes. and relevant advantages. which are set forth by the following disclosure. are advantageously achieved by a 3Q flame-retardant composition for polyurethane poly mers. for polyurethane-based copolymers. mixed polymers and polymeriC materials. which composi tion. according to the present invention. comprises the following components: 36 A. an ammonium phosphate or one or more amine phosphate(s). or a mixture constituted by an ammonium phosphate and one or more amine phosphate(s); B. a nitrogen-containing organic compound 40 (s). or a mixture of two or more nitrogen-containlng v' organic compounds selected from the group com prising urea. dicyandiamide. cyanuric acid. piperazine and piperazine derivatives. melamine. melamine cyanurate. melamine borate, melamine V V 45 sulfate. a hydroxyalkyl derivative of isocyanuric acid of formula 2 10 20 30 40 50 3 EP 0 389 768 A2 4 a-OH n w.herein R. R' and RN are alkyl radical equal to, or different, from each other, containing from 1 to 6 carbon atoms; and C. magnesium hydroxide Mg(OH)a or alu minum hydroxide AI(OH)3, or a mixture of both of them. It has been seen that the composition accord ing to the present invention, when is homoge neously and intimately incorporated in a polyure thane polymer in the form of a coating or of an either rigid or flexible foam, as well as in any other. normally used, forms. gives the same polymer high flame-retardant properties. and furthermore consid erably reduces. in some cases down to practically negligible levelS. the emission of noxious smokes when the polymer or the material. or the finished article manufactured from the polymer. is heated to high temperatures. and/or is placed into contact with direct flames or with other heat sources. such as electrical resistors. red-hot metal elements and the like. such as to cause the polymer to undergo thermal breakdown. More particularly, said hydroxyalkyH:lerivative of isocyanuric acid is constituted by tris-(2-hydrox yethyl)-isocyanurate and Is used both in monomer form. and as a homopolymer. with n being a nu meral comprised within the range of from 1 to 500. Said ammonium phosphate preferably is in the form of a polyphosphate having the general for mula (NH4.)n+2 Pn~+l wherein n Is a numeral higher than 2, of a metaphosphate-(NH4.POs)n and the like. and said amine phosphates are selected from the group consisting of dimethyl-ammonium phosphate. dlethyl-ammonium phosphate. ethylene-dlamlne phosphate. melamine ortho phosphate and melamine pyrophosphate. Still according to the present invention. said ammonium and/or amine phosphates are also used in the form of particles ~mlcroencapsulated ~according to processes known from the prior art) In a water-repellant synthetic resin or the like. In particular when the composition according to the instant invention is destined to render self-extin guishing polyurethane materials destined to uses which require low water absorptions by the same matenals. and when a high resistance to water extraction is anyway required. The amounts and the mutual ratios of the A). B) and C) components to be Incorporated in the polymer or in the polyurethane-based material in order to efficaciously endow it with self-extiguishing and smoke-suppressant characteristics. vary ac 5 cording to the type of polyurethane. In general. in order to achieve a satisfactory level of self-extin guishment. and a suitably low emiSSion of smokes in the polymer the follOWing amounts, expressed a~ percentages by weight relatively to the polyure thane endowed with self-extinguishing characteris tics, of the three components are incorporated: A) ammonium phosphate and/or amine phos phates. from 1 to 40% by weight; B) nitrogen-containing organiC compound(s). 16 from 1 to 40%; C) magnesium hydroxide and/or aluminum hydroxide. from 1 to 40%. The composition according to the instant find ing, .if referred to the total weight of the same composition. is constituted by the follOwing per centages of the three components. by weight: A) ammonium phosphate and/or amine phos phates. from 10 to 80%; B) nitrogen-containing organic compound(s). 25 from 10 to 80%; C) magnesium hydroxide and/or aluminum hydroxide. from 10 to 80%. The total amounts of the composition accord ing to the present invention, to be incorporated into the polyurethane-based materials. are of the order of from 3 to 70% by weight (relatively to the total weight). The flame-retardantlsmoke-suppressant com position according to the present invention makes it 35 possible stabilizing/antioxidant agents of known type, lubricants. dyes. foaming agents. inorganic flilers, minerai fibres. and the like. to be simulta neously used in the polymer. The constituents of the flame-retardantlsmoke suppressant composition according to the present invention are incorporated in the polyurethanes ac cording to known techniques, variable from case to case. according to the polyurethane type. As known, polyurethanes are resins with an 46 external appearance and characteristics which may be very variable, which are obtained by means of the condensation of a dlisocyanate with a com pound containing at least two activated hydrogen atoms. such as diols. diamines. bicarboxy acids. polyesters with free hydroxy groups. polyethers, and so forth. Toluene-diisocyanate and hexamethylene-diisocyanate are among the most frequently used diisocyanates. From the reaction of dllsocyanates with glycols. 55 products are obtained. which can be used in the field of textile fibres, and from the reaction of said diisocyanate with polyols. resins are prepared. which are used in the field of paints. of adhesives. 3 5 10 15 20 25 30 35 40 45 50 55 5 EP 0 389 768 A2 6 of elastomers and of foamed materials. The composition according to the present in vention can be incorporated in the polymeric prod uct, e.g.. by adding the components of the same composition, either as individual compounds, or pre-mixed with one another, to the mixture of the diisocyanate with the polyol or the diamine during the reaction step, optionally together with other additives known from the prior art. Or, according to an alternative route, said components of the com position can be previously mixed with the dlisocyanate or with the polyol, or the diamine, or they can be partially mixed with the diisocyanate and partially with the polyol or the diamine. in amounts and in mutual ratios which can vary from case to case. according to the chemical and phys ical compatibility of the individual constituents with one another. In case of thermosetting polyurethane com positions constituted by prepolymers capped with blocked isocyanic groups and suitable chain ex tenders or cross-linking agents of diaminic char acter. the flame retardant/smoke suppressant com position according to the present invention is ad vantageously incorporated in said prepolymer. op tionally together with pigments. stabilizer filters. antioxidants, foaming agents and further possible additives known from the prior art. The invention according to the present inven tion can be better set forth and disclosed by the following example of practical embodiment thereof. supplied for merely exemplifying purposes, and which in no way shall be construed as being in any way limitative of the scope of protection of the same invention. Example A mixture of polyol and toluene-diisocyanate is prepared in the ratios which are normally used in order to obtain polyurethanes for polyurethane foams production. The flame retardant/smoke sup pressant composition according to the present in vention in which the ratio of the A component. ammonium polyphosphate; to the B component. constituted by 50% by weight of a polymer of trls (2-hydroxyethyl)-isocyanurate and by 50% by weight of melamine, isocyanurate; to the C compo nent, aluminum hydroxide. is of 1 :3:2. is added to the above said mixture in an amount of 30% by weight. The so obtained product results to be flame retarded, in conformity with Class B1 according to DIN 4102, also after that the specimens of the material are submitted to extraction with hot water. Furthermore. when said product was submitted to decomposition by means of the direct action of a free flame, a development of smoke was observed, according to ASTM E 662. whose amount was reduced by at least 50% relatively to the amount of smoke developed by a similar product obtained by means of the separate addition of only one of the individual components. i.e •• of the A component or of the B component or of the C component in an amount of 30% by weight, or by means of the addition of binary combinations of said components Le.• ofA+C,orofB+CorofA+B. Furthermore, according to the present inven tion, in order to facilitate the metering (absence of dusts) and the dispersion of the flame retardant/smoke suppressant composition in the polyurethane-based materials, the same compOSi tion can be concentrated at 10-50% in a polyol or in a polymeric substance compatible with the poly urethane to which it has to be added, as well as with further optional conventional additives, such as coadjuvants, dyes. lubricants. antistatic agents, sta bilizers, foaming agents, inorganic fillers, and the like. In other terms, in this way a "concentrate" of said flame retardant/smoke suppressant agent in a suitable "carrier" is formed, which is ready to be added to the polymers. The invention, as hereinabove disclosed and exemplified. can be supplied with technically equiv alent variants, all of which fall within the scope of protection of the same invention. Claims 1. Flame-retardant and smoke-suppressant composition for polyurethane polymers and for polyurethane-based polymeric materials. character ized in that it comprises the following components: A) an ammonium phosphate or one or more amine phosphate(s). or a mixture constituted by an ammonium phosphate and one or more amine phosphate(s); B) a nitrogen-containing organic compound, or a mixture of two or more nitrogen-containing J organic compounds selected from the group com pnslng urea, dicyandiamide, cyanuric acid, piperazine and piperazine derivatives. melamine, v melamine cyan urate, melamine borate, melamine v surrate, a hydroxyalkyl derivative of isocyanurlc acid of formula 4 7 EP 0 389 768 A2 8 n w.herein R, R' and R· are alkyl radical equal to, or different, from each other. containing from 1 to 6 carbon atoms; C) magnesium hydroxide Mg(OHb or alu minum hydroxide A1(OH)s. or a mixture of both of them. 2. Flame retardant / smoke suppressant com position according to claim 1, characterized in that said (6) component is tris-(2-hydroxyethyl) isocyanurate and is used both in monomer form. and as a homopolymer, with n being a numeral comprised within the range of from 1 to 500. 3. Flame retardant/smoke suppressant compo sition according to claim 1, characterized in that said ammonium phosphate is in the form of a polyphosphate having the general formula (NH4) n+2PnOSn+l wherein n is a numeral higher than 2. of a metaphosphate (NH~P03)n and the like, and said amine phosphates are selected from the group consisting of dimethyl-ammonium phosphate, diethyl--ammonlum phosphate. ethylene-diamine phosphate, melamine orthophosphate and melamine pyrophosphate. 4. Flame retardant/smoke suppressant compo sition according' to claim 1, characterized in that said (A) component is in the form of particles microencapsulated in a synthetic resin of a type known from the prior art. compatible with the poly urethane formulations used. 5. Composition according to claim 1 character ized in that said flame retardant/smoke suppressant composition is constituted by 10 to 80'% by weight of said ammonium phosphate and/or amine phos phates (the A component). from 10 to 80% by weight of said nitrogen-contalning organic com pounds (the 6 component)and from 10 to BO% by weight of. magnesium hydroxide and/or aluminum hydroxide (the C component). 6. Composition according to claim 1, character ized in that said A. B and C components of said flame retardant/smoke suppressant composition are in mixture with from 10 to 50% by weight of a polyol or in a polymeric substance of the same nature of, or anyway compatible with, the polyure thane In which said composition is introduced. as well as with other additives such as various coad juvants, dyes. antistatic lubricants, stabilizers and foaming agents. of types known from the prior art. 5 10 15 25 35 40 45 50 55 5 7. Flame retardant/smoke suppressant compo sition according to claim 1, characterized in that said composition is incorporated in said polyure thane polymer by adding the components of the same composition. either individually, or pre-mixed with one another. to the mixture of the diisocyanate with the polyol or the diamine during the reaction step, together with any further known additives. B. Flame retardant/smoke suppressant compo sition according to claim 1, characterized in that said components of said composition are incor porated in the polyurethane polymer by being pre viously mixed with the diisocyanate, or with the polyol or the diamine, or partially with the diisocyanate and partially with the polyol or the diamine, according to the chemical and physical compatibility of the Individual constituents with one another. 9. Flame retardant/smoke suppressant compo sition according to claim 1, characterized in that In case of thermosetting polyurethane compositions constituted by prepolymers capped with blocked Isocyanic groups and by suitable chain extenders or cross-linking agents of diaminic character, said flame retardant/smoke suppressant composition is incorporated in said prepolymer. 10. Polyurethane polymers and polyurethane based polymeric materials characterized in that they are endowed with self-extinguishing and smoke-suppressant characteristics by means of the flame retardant composition according to claim 1. 11. Polyurethane polymers and polyurethane based polymeric materials according to claim 10, characterized in that they contain from 1 to 40% by weight of ammonium phosphate and/or amine phosphates selected from the group consisting of dimethyl-ammonium phosphate, diethyl-arnmonium phosphate, ethylene-diamine phosphate, melamine orthophosphate and, melamine pyrophosphate (the A component), from 1 to 40% by weight of one or if more nitrogen-containing organic compounds se- V !ected from the group consisting of urea, dicyan diamide, cyanuric acid, piperazine and piperazine derivatives, melamine, melamine cyan urate, V melamine borate, melamine suHate. a hydroxyalkyl derivative of isocyanuric acid of formula --OH n wherein R, R' and R" are alkyl radical equal to, or 9 EP 0 389 768 A2 10 different. from each other. containing from 1 to a carbon atoms (the B component); and from 1 to 40% by weight of magnesium hydroxide Mg(OH)2 or of aluminum hydroxide AI(OH)3. or of a mixture of both of said compounds (the C component). 5 10 15 211 25 311 35 411 45 fill a THE NATURE OF THE CHEMICAL BOND AND THE STRUCTURE OF MOLECULES AND CRYSTALS: An Introduction to Modem Structural Chemistry By LINUS PAITLING THIRD EDITION CORNELL UNIVERSITY PRESS Ithaca, New York Copyright 1939 and 1940, third edition © 1960, by Cornell University All rights reserved. Except for brief quotations in a review, this book. or parts thereof, must not be reproduced in any form without permission in writing from the publisher. For information, address Cornell University Press, Sage House, 512 East State Street, Ithaca, New York 14850. Third edition published 1960 by Cornell University Press. Thirteenth printing 1995. International Standard Book Number 0-8014-0333-2 PRINTED IN THE UNITED STATES OF AMERICA 8The paper in this book meets the minim urn requirements of the American National Standard for Information Services-Permanence of Paper for Printed Library Materials, ANSI Z39.48-1984. ) ( j, respec ,iosely re 0.19 A in antimony in appar re needed 3phalerite ,wo sulfur fed by six atom has 'ur atoms Those of oms, with the other 'ur atom! ;) A, bond termined. principles that have ',try,64 and ther than ry of the . Neuma.n, ! sylvanite, :Ia CryBt. 5., j and kren ,hree struo ·ally. The d the other st apprOlC'i the squat~ tds extend g the other CHAPTER 12 The Hydrogen Bond 12-1. THE NATURE OF THE HYDROGEN BOND IT was recognized some decades ago that under certain conditione an atom of hydrogen is attracted by rather strong forces to two atoms, instead of only one, so that it may be considered to be acting as a bond between them. This is called the hydrogen bond. I The bond was for some time thought to result from the formation of two covalent bonds by the hydrogen atom, the hydrogen fluoride iOll [HF2J- being as... .. signed the structure [:F:H:F: J-. It is now recognized that the hy drogen atom, with only one stable orbital (the Is orbital), can form only one covalent bond, that the hydrogen bond is largely ionic in character., and that it is formed only between the most electronegative atoms. A detailed discussion of its nature is given in the following sections. Although the hydrogen bond is not a strong bond (its bond energy, that is, the energy of the reaction XH + Y -4 XHY, lying in most cases in the range 2 to 10 kcal/mole), it has great significance in deter mining the properties of substances. Because of its small bond energy and the small activation energy involved in its formation and rupture, the hydrogen bond is especially suited to playa part in reactions oc- I Other names, such as hydrogen bridge, have also been used. A detailed discussion of the hydrogen bond is given in the book by G. C. Pimentel a.nd A. L. McClellan, The Hydrogen Bond, W. H. Freeman Co., San Francisco, 1959. Many excellent review articles have been published; among them are E. N. Lassettre, Chern. RevlI. 20, 259 (1937) j H. Hoyer, Z. Elektrochem. 49,97 (1943); J. Donohue, J. Phys. Chem. 56, 502 (1952); A. R. Ubbelohde and K. J. Gallagher, Acta Cryst. 8, 71 (1955); G. M. Badger, Rev. Pure and App. Chern. (Australia) 7, 55 (1957); C. A. Coulson, Research (London) 10, 149 (1957); M. Magat, Nuovo cimento 10,416 (1953); D. Sokolov, Tagungsber. der chem. Ge8. Dwt.ch. Oem. Rep. 11155, 10. 449 Melapur® MC25 by Ciba, now part ofBASF - SpecialChem4Adhesives Page 1 of 1 Trends & Jnnovations Materials & Solutions Online Courses Channels Community Pulse Open innovation Formulation Centers Solution Case StudIes Materials Selector Storefronts Webinars Formulations Selector Adhesion Guide Melapur® MC25 Supplier: Ciba, now part of BASF Product perfonnance: 1.2.5-triazine-2.4.6 (1H.3H.5H)-toone. compound with 1.3.5 triazine-2.4.6 triamine (1:1). Used in hotmelt, reactive. solvent based. radiation curing and water based adhesives and sealants. Acts as an effective flame retardant Offers benefits such as good economics. mechanical properties and lower specific gravity compared to compounds containing halogen and antimony flame retardant systems. halogen free. lower smoke density. lower smoke toxicity and less corrosion. ApplicatiOns I Recommended for: • ADHESIVES» Radiation Curing (UVIEB) • ADHESIVES» Hot-melts • ADHESIVES» Reactive systems • ADHESIVES» Water-based • ADHESIVES» Solvent based • PU· Polyols • PU - Isocyanates • Polyesters • PU - Polyurethane dispersions (PUDs) • PU - Thermoplastics (TPU) • Polyamides (PA) • Natural rubbers (NR) • Acrylicsl Acrylates • Ethylene co-terpolymers - solid (EVA. EMA .. ) • SEALANTS • Electrical & Electronic Bonding TYPICAL PROPERTIES VALUE UNIT fred mckelvey 0 Product type: I • Flame and Smoke Retardants » Melamine based I Chemical composition: 1.2.5-triazine-2.4.6 (1 H.3H.5H)-trione. compound with 1.3.5 triazine 2.4.6 loamine (1:1) Physical form: Powder CAS Number: 37640-57-6 Other products with same trade name: • Melapur® MCSO • Melapur® 200 • Melapur@ ME View all producls from Ciba, now part of BASF i l I I Other products: • Flame and Smoke ! Suppressants (269) 1 > Melamine based (4) D,selalmer Melamine cyanurate content Water content Excess melamine content Excess cyanuric acid content Water sOIUtlility @ 20·C Bulk density SpecWic gravity Molecular weight 99.5 %wt 0.2 %wt 0.3 %wt 0.2 %wt 0.1 g/100 ml 150 - 200 kglm3 17 g/cm3 255.2 g/mol About SoeCJalChem - About SpeciaIChem4Adhes.ves - Commercia! AcceleratIon Services - AdvertIse 'tVlth us Contact U~ - Eqrgot "lour UserlD 1 Passwotd? - Slle Map - RSS - Terms and Cond,tlons - speclal'Chern.com Copyright © 2013 SpeciatChem S.A. http://www.specialchem4adhesives.comltds/melapur-mc25/ciba-now-part-of-basfI12169/i... 10114/2013