'USO085S7954B2 2) United States Patent (io Patent No: US 8,557,954 B2 Hazen et al. 4s) Date of Patent: Oct. 15, 2013 (64) WATERBASED DIMERIZED ROSINS AND 44146 A # LUI98 Oech etal... SB0KE THE PROCESS TO MAKE THES ‘3ye3ns AS 84985 Olsson soit Sonsie A+ 1991. Stim Sone (75) leators: John Hazen, Maastizht (NL) 190 S783 89 19882 Mace sani Kewelaer, Maastricht (NL) oe 12002 Kobo sta Sia? 2oosdni7s AI 12200) Lockoetal ‘asta 73) Assignee: Lamter Ine. Chicago, 1. (US) Sooatzzso7e Al® {L004 Mae sak oe si oe 2ODSIOOSAS0I AL* 12005 Locko etal 527/503 (*) Notice: Subject to any disclaimer, the term ofthis 2008/0208225 AI? 92008. Ants tal a6 Patent extended or adn ndee 35, OU7OUSLSDS mer pd USC. 1540) by 476 days. Senso Teco eta iosaera8 (21) ApphNos — 120674,787 FOREIGN PATENT DOCUMENTS. (22) PCT Pied ox leesisy a 62005 oS Se ted Hy veut a + ‘Son (86) PCTNos — RETIEP20OSU7463 cB naa A © $1977 $3710, WO woosowsoe ‘Samm 2), (4) Date: Dee.7, 2010 Wo wO200502348 3/2005 (60) PCT PAR Nos Wo200sexo20 OTHER PUBLICATIONS PCT Pub, Date: Mar 26, 2009 ws) Prior Publication Data US 2011005266741 Apr.21, 2011 G0) Foreign Application Priority Data Sep.20,2007 (EP) (070758263 (1) Ince COE 102 (2006.01), CODE 1704 (2006.01), nD 1300 (200501), (52) 30/211; 5201225 (58) Fleld of Classification Search spc: ‘530/211, 212, 224, 225 See application file for complete search history. 66) References Cited USS. PATENT DOCUMENTS 1011934 Johnson ‘81935, Binap® T1982 ‘yler 11942 Hump [1943 Rommestarg 911943 Rammer Silods “Ter ta 21944. Rommel 21984 Pereyra. Spas Bast 41987 Brndwood a 1975 Parkin eta Si976 iors eis 1980 fost Tvs oles ahawos9 202.632 S071 232K681 Buses Basie "19.185 -Ausalian Feamination Report issued in Ausalisn Patent Applic: tion No. 2008300927 and dated Jan 31,2011 Eopean Communication issied! in European Patent Application 1No- 088020249 and date Sep. 9, 2010. Ineraional Preliminary Report on Ptentailiy issued in PCT. EP2008 007463 and dad Ma. 24,2010 Ineraional Search Report and Weiten Opinion issued ia PCT |FP2008 07463 and mae Jan. 22, 2009 Ottce Acton ise in Canadian Patent Applicaton No. 2.700.083 a dated Mar 30,2012 Otice Action ised in Chinese Patent Application No, 20088017089 X and dated May 18, 2012 (English relation pro ide Ottce Action with Search Report resve for Taiwan Application No, 077133645 dated Sep. 28,2012 (8 pages) English Wansaion inci Zink, Duane Ft a "Naval Stores: Production Chemisty ‘ation’ Pp Chemieal Asovaton 1989, pp 288, 85, and 708 (4 pase. Seaich Report received for Ewopean Patent Application No, 1214S dated Fab 14, 2013 ( pages). cond Office Action issed in Chinese Patent Application No 200880107899 X dated Mar 4, 2013 (10 pages. Stauffer, Don, “Disllaions: Why is Rosin Polymaiznd” Forest (Chemical Retin: (Mat pe 2002) 3 pape) * cited by examiner Primary Examiner — Liam Heincer (14) Attorney, Agen, or Firm — Foley & Larder, LLP on ABSTRACT ‘The present invention relates to a method! to prepare dimer- ‘ed rosin dispersible in water in presence of extremely lows level of dimerization acid catalyst. The present invention relates also to ts use asa tackifier resin, solid or in water, and ink resin and an adhesive composition ad ink composition comprising the sin resin 7 Claims, No DrawingsUS 8,557,954 B2 1 WATERBASED DIMERIZED ROSINS AND ‘THE PROCESS TO MAKE THEM RELATED APPLICATION DATA, This application claims the benefit of PCT Application PCT/ED2008/007463 with Iaternational Filing Date af Sep. 11, 2008, published as WO 2009/036920 A1, which further claims priority. to. European Patent Application No, EPO7075826.3 fled Sep. 2, 2007, the enirecontentsof both are hereby incorporated by referee DESCRIPTION ‘Te present invention relates to method to prepare dimer ined rosins dispersible ia water in presence of extremely low level of dimerization acid eatalyst. The present invention relates also tits use asa tackifer resi, solid or in water, and ink resin, and an adhesive composition and ink composition ‘comprising the rosin resin, "Many methods for the dimerization of rosin have been published, Previous methods describe the use of sing inor- iBanic acids, such as sulfuric acid asthe catalyst, US. Pat Nos, 2,136,525, 2,108,982, 2,307,681, 2.328,681, 2515218, 2,251,806, 2,532,120 and 4,108 462. “Altemative methods bave been described using sulfonated polymers, US. Pat. No. 4414,146, ora halogenated meth- ‘anesulfonie acid, US, Pat. Nos, 4,339,377 and 4,172,070, ‘Further alternative methods deseibe the use of form ‘asthe catalyst in US, Pat, Nos. 2,375,618, 2492, 146, 33. The prior at uses processes including a final washing and catalyst removal sep adding to the process complexity and is an object ofthe present invention to provide a process that utilizes catalyst that can be used at extremely low level andor a etalyst that ids the subsequent product plication thereby eliminating the need ofa costly washing and catalyst removal ste. The present invention solves the above identitiod deaw= backs by the use of a carboxylate sulfonic acid as catalyst produce dimerized rosin. The process eliminates the need of catalyst removal by the high activity ofthe catalyst of the invention, “The present invention relates also to an adhesive compost tion comprising a dimerizod rosin ackitier made according 10 the present method, “The prsent invention relates further to resins for ink appli= ‘ation comprising the dimerized rosin as building bloc The present iawention relates also an ink composition ‘comprising an ink resin based on the dimerized rosin. ‘The method of the invention to produce dimerized rosin is based on carboxylated sulfonic acids as catalyst. In one ‘embodiment the earboxylated sulfone acid derivatives like eg. sullosuecinie avid, Ssulfosalicyic acid or 4-sulfoph- thalie acid are used as catalyst at 0.1 to 1 weight pereent on rosin, Inthe prefered method 4-sulfosalicylie ai is used as ‘catalyst. The catalyst can be left inthe final product oroption= ally neutralized with alkali such as potassium hydroxide oF ‘The method of the invention to produce dimerized rosin, or subsequent appliction in water based dispersions such as ‘water based tackifers, is based on sulphonate surfactants as catalyst Production of water based dispersions such as water based tackifiers does require surfactants to aid the emulsification process and stabilize the final dispersion, Sulfonated surfae- 0 o 2 ‘ants are well known surfactants and widely wsed in many applications. In the embodiment process sulfonated surfac- ‘ant is used as catalyst to prodice dimerized rosin, The cate lyst dacs not require a separation step and can be wsed at higher level of 1 to $ weight percent on rosin, typical forthe stefactant level in formulations to prepare Water hased tek Tiers, In the subsequent emulsification process only alkali addition such as potassium hydroxide or amine is needed t0 produce a water based tockifer dispersion. The sulphonate Surfactant full dual role, Fist as rosin dimerization cata- Jystthen after a subsequent neutralization to form as emolsi fier to prepare water based tackfier. ‘In the preferred embodiment ofthe resent method dode- ceylbenzene sulfonic acid is used at about 3 weight percent. ‘he process makes about 30% dimerized rosin. Afterneutral- ‘vation with triethanol amine the subsequent lackiier disper siomis prepared, EXAMPLES Example 1 After the addition of 1000 g Chinese gum rosin and 20 g 4-sulfophthali acd at 135°C. ina glass reactor, the content js tired and Kept fr 4 hours, Ten the mixture is ete to 160" C. and kept for another 4 hours, ‘Analysis: softening point: 92° C. (R&B); acid value: 150, ‘ng KOFg; colour (toluene, 50%): Gardner 7: imerized rosin (GPC; RI detector: 41%. Example 2 After the aditon of 1000 y Chinese gum and 38 g doe ceylbenzenesulfonic acid at 140° C. in a glass reactor, the content is stirred and kept for 4 hours ‘Analysis: softening point: 84° C. (R&B); acid value: 152 ‘mg KOHg; colour (toluene, 50%: Gardner 8, dimerized rosin (GPC; RI detector: 20% Example 3 The rosin resin of example 2, 1000 g, is molten at 110°C in a stool eaker. While stiring, triethanolamine 25 g, is added, While stirring, water (60° C.) i added in 15 minutes time. The final dispersion is cooled “Analysis: solids 52%; viscosity 240 mPas; particle size (mean)-0.28 uM: pH: 7.5. ‘Comparative Examples Experiment using p-TSA (equimolaramount to 38g dode- eylhenzenesulfonate of exanple 2) Example 4 ‘After the addition of 1000 g Tal oil rosin (TOR) and 20 2 peTSAat 138°C. in a glass reactor, the content is sted and kept for hours. ‘The temperature is increased to 150° C, and kept for ‘another hour. 13 g KOH solution in water (50%) is added ‘Analysis: softening point: 83° C, (R&B); acid value: 146, mg KOHig:dimerized mosin (GPC; RI detector): 22% Example 5 ‘The rosin resin of example 4, 1000 gs molten at 110° C ina steel beaker. Whilestirring 1000 water at 60°C. isadded in 1S minutes time,US 8,557,954 B2 3 The content is cooled Analysis: No sign of emulsification nor inversion pont ‘Two phases wherein one being the solid rosin resin and the other wer. ‘We claim: s 1A method to produce dimerized rosin comprising con- ‘acting rosin wth catalyst comprising an alkyl substituted ary sulfonic acl to produce the dimerized rosin contining the catalyst or a salt thereof, wherein the allyl group has at least 5 carbon atoms. 0 2. The method of claim 1 futher comprising neuealizing the dimerized rosin with an alkali salt or an onganie amine then subsequently dispersing the dimerized rosin in water '3. The method of elim 2, wherein the dispersing com= prises ang a surfactant, is 44 The method of elsia 1 wherein the catalyst is present from 1 to Sweight percent based onthe Weight ofthe rosin. '. The method of claim 4 whercin the catalyst is selected from the group consisting of pentylbenzene sulfonic acid, hexylbenzene sulfonic acid, hepiylbenzene sulfonic acid, 20 ‘erslbenzene sulfonic acid, nonylbenzene sulfonic acid, ‘decylbenzene sulfonic acid, dodecylbenzene sulfonic avi, dodecyldipheny! disulfonic acid, and combinations of any two.or more thereof, 6. The method of claim 5 further comprising neutralizing 2s the dimerized rosin by an alkali salt, an onzanie amine or ammonia then subsequently dispersing the dimerized rosin in wate. 7. The method of claim § wherein the catalyst comprises dadecyTbenzene sulfonic aid i an amount of 3 weight per- 30 ‘cent hase on the weight of the rosin,