2) United States Patent Matsukawa et al. 'US006384151BL US 6,384,151 BL May 7, 2002 a0) Patent No.: (45) Date of Patent: Ga) (75) ji Matsukawa, Osaka; Tos Hayashiya, Toyono-cho; Koji Takabatake, Mino; Katsura Hayashi, Kobe; Hironori Funaki, Suita, all of 1 0 ° ox MAbeRD = 33 Water MA, o ° 0 x ° Fst MA (oo) 38 3 as as as ‘Water (me) as tS 5 1s CPD (al) m2 2 2 2 2 Ratio of re tril Fint tp) ‘Water Mola tio 120 090 MAIDCRD Mois to 150 225 Water MA, Mois to os 040 Second step MA (oo) 98 oo > o PO (a) 76 2 oom moot 6 (ot) ey 2s es 2s DEG (not) 106. os oss PA (oot 1481 a = 02 of Rito ofall fae materia cPDIMA Mola sata os auto Sate of resstion minere Before ° ar? a. ing DCPD Chance of moifed simure ‘Acid value 2 3 68 ‘Charcertin of retin composition fplexitense aie 1 aoa a O ° ° (Nowe) fel exinence ater? mothe 6 o ° Fix water existance (Ge) 280 oo sas Inpeegnatbiy 0 Be be ‘Gass pia pater ° ° ° ° (None) ister 6 0 (None) MW Ta Exe Tex? Ra ix Tet Ex) ‘WatecDcrD > 1 MAbeRD = 33 Water MA, Fist MA (mod) 98 as 4s 2: ‘ater (ae) 18 1s 2 2 CPD (al) m2 2 2 3 Ratio of ror tril (fin tp) ‘Water Mole tio 105 o8 MAIDCRD Mois to 110 073 Water MA, Mois to 035 109 Second sep MA (oo) 98 = - PG (aod) 76 35 = EG (ot) er bes DEG (et) 1061 = os a8 PA (aa!) st = 02 02US 6,384,151 BL 19 TABLE L-continued DcPDMA, Sie of ection mintue foe Mola tio ding DED ‘Charteris of died siuse Acid value ‘Chace of sexi composition Viscanty 28° 8) Say 40°C) pel exitence ster 1 mouth gol existance ster 2 months Hot water wexiance (ie) Inpregnteity isa ter ‘as pain pte Ble As is apparent from Table 1, in Test Examples 1 to 3 satisfying hoth ofthe main features according tothe prescat javention (Water/DCPD=1 and MA/DCPD= 1.2, and Water! MAS), the reaction mixture before adding dicyclopenta- diene was homogeneous. In addition, the obtained resin ‘composition had a preferable viscosity, an excellent stability (ie. the composition was not polymerized even after 2 months) and 2 good impregnatabiity to glass fiber (ie, the resulting. molded article is Tree from glass grain patero and blister). Moreover, the resulting molded atticle had a good hot water resistance ‘On the other hand, Test Example 9 was a comparative example which failed to satisfy any main feature of the preseat invention. In the Example, the reaction system on production of the modified polyester was heterogeneous 10 cause reaction problems. The obtained resin composition had a poor stability, i. it was lable to be partially poly- merized before molding. The resin composition also had a poor impregnatability © glass fiber (ie, blister and glass grain pattem were generated in the molded article) and provided a considerably poor hot waler resistance 10 the molded article. ‘Test Examples 4 to 8 satisfied either one of main features of the present invention. Test Example 4 deviated slightly from the range ofthe feature of (Water/MAS 1) but satisfied the first features of (Water/DCPD>1 anal MA/DCP ‘The resin composition of this example can be sufficiently utilized for SMC material because of its ood stability and impregoatability to the glass fiber. Test Examples 5 to 8 satisfied the feature of (Water/MA'S1) but failed to satisfy the features of (Water/DCPD>1 and MA/DCPD= 1.2). The ‘objained resin compositions of these examples were not suitable for SMC material due tothe slightly poor stability and impregaatability to glass fibers. However, the reaction systems in the examples on production of the modified polyester were homogeneous to cause no reaction problem and also the bot water resistance of the molded articles using the modltied polyester resin compositions of the examples were markedly superior than that of Test Example 9. ‘Therefore, the resin compositions in Test Examples 4 t0 8 ean be sufficiently utilized for a molding material other than SMC or MBC. ‘Test Example 10 Inthe same reaction vessel as used in Test Example 1,490 (5 mol) of maleic anhydride and 580 g (5 mol) of maleic os ss 4s ss 6s 20 as acid were charged and heated to 120° C. Then 72 (4 mol) ‘of water was added dropwise from the dropping device over 10 minutes with the mixture maintaining. a temperature of 120 t0 130° C. As a result, the obtained reaction mixture was, 44 homogeneous liquid free from a solid ‘Then, 1251 g(9 mol) of dicyclopentadiene having a purity of 95% was added dropwise from the dropping device over 2 hours with the reaction mixture maintaining the same temperature. After the dropwise adding was completed, the ‘mixture was further heated at 125° C. for 30 minutes, to dobiain a reaction product having an acid value (addition reaction degree: 97%) of 264 (frst step). To the resulting reaction product, 372 g (6 mol) of ethylene glycol was added, followed by an esterification by heating to 200° C. with removing water distillated from the reaction produet. When the acid value of the esterified product reached 26, the esterified product was cooled to 120° C. to obtaia 2570 g of a dicyclopentadiene-moditied unsaturated polyester (Second step) ‘This modified unsaturated polyester was mixed with 860 1g of styrene as a radically polymerizable monomer and 0.7 of hydroquinone to obtain a dicyclopentadiene-modified unsaturated polyester resin composition (styrene content 25%, viscosity: 2.5 stokes). ‘Test Examples 11 to 17 In the same manner as in Test Example 10, except that each amount of raw materials used in the respective reac- tions was varied as shown in Table 2 below, dicyclopentadiene-modified unsaturated polyester resin compositions were produced ‘The state of the reaction mixture before adding DCPD (ie. whether a solid deposited or not) in Test Examples 10 to 17 to produce dicyclopentadiene-modified unsaturated polyester resin compositions, and the hot water resistance (aforementioned) of the molded articles by using the resin compositions are summarized in Table 2.US 6,384,151 BL 21 22 TABLE 2 MW Tt Ex10 Text Tats i? Tet Exe MA (oo) os s 0 0 6 Male aad 5 = 2 2 ‘Wie 1s 4 5 » 4 CED (et) im2 9 5 3 4 Rata of cw sisi (at step) wien Molar tio 08 a9 a 07 BCPD MA, Molt ato 0.90, so a0 067 Second sap, £6 (aol) sa 6 6 6 - 6 () we = = = 5 A (ro) os = = = i Ratio of at ‘aw materiale DcPDMA, Molar tio 09 a9 09 os Sate of ection minuie fore ° s ° adaing DCPD (Note) Chnceitin of| oiied mine Acid vale 6 26 a 0 Chntstertin of Fexn composition Viscosity Q5° C5) as as as 30 Ho water revise (me) 20 230 20 50 MW Tet Exid Te tx is Tet xi Tet xi? Water MA = 1 © x x x int ep MA (wo), 98 6 0 0 ® Malic acid = = 2 2 ‘wie is 2 a 7 DCP (so) i202 5 3 4 Ratio of rr ase it ep) ‘wicrMa, Molar mio 03. 1 1s rr Second sep EG (ot) ena = « 6 - PG (oo) e a = = 5 PA (ro) 98 as = = 1 Sue of ection mixte fe © x xx. x ding DEPD (Not) modified ime Acid value Ey 23 » 0 Chace of etn composion Visas (25° Cs) so 28 so 32 Ho wer eniaance (@ s0 10 2 eo EG: Ealene gyoat PG: Propylene yea! PA: ope ae (Nor) ‘OPNo sold deposed ‘Ac Aalight amount f slid deposited X:A medium amooat of sod deponied XX:A lige amunt of solid deposited AS is apparent from Table 2, the results can be discussed Test Examples 10 to 14 were examples in which a ratio of as follows, water to MA in the first step was 1 or less. In theseUS 6,384,151 BL 23, Examples, the reaction mixture before adding cyclopenta- diene was fee from deposition of a sole and the resulting modified unsaturated polyester was superior in. handling because of its low viscosity. Moreover, it was found that ‘each molded article obtained from the resin compositions had an excellent hot water resistance. On the other hand, Test Examples 15 10 17 were com- parative examples in which a ratio of water to MA exceeds 1. In these Examples, a solid was deposited in the eaetion mixture before adding eyclopentadiene and the reaction system was heterogeneous, resulting in an unsatisfactory bot water resistance. Although Test Example 17 showed a better hot water resistance than the other comparative examples, it was much worse that that of Test Example 13 wherein all conditions were the same, except fr a ratio of water fo MA. ‘What is claimed 1. A dicyclopentadiene-modified unsaturated polyester produced by a process comprising the steps of: 2) reacting maeie anhyelride with water ata temperature of 100° C. to 140" C. to obiain a reaction mixtuce: +) reacting the reaction mixture with dicyclopentadiene (OCPD), a mola ratio (HO/DCPD) of water to dicy lopentadiene being greater than 1 and a molae ratio (MAVDCPD) of maleic anhydride to dicyelopentadiene being 1.2 oF more; and 6) reacting the reaction produet obtained io step b) with a polyhydric alcohol, or a polyhydric alcohol and a polybasic acid, to obtain an unsaturated polyester moditied with dicyclopentadiene, wherein the dicyclopentadiene-modlified unsaturated polyester has a weight-average molecular weight of $000 or more and a ratio of weightaverage molecular weight 0 number-average molecular weight of from 5 to 50. 2. The dicyclopentadiene-modifed unsaturated polyester ‘of claim 1, wherein in step b), sad molar ratio (MA/DCPD) 48 1.5 oF more 3. A dicyclopentadiene-modiied unsaturated polyester resin composition, comprising: 4) the dicyclopentadiene-modified unsaturated polyester of claim 1; and by a radically polymerizable monomer. 4. A molding material, comprising 4 dicyclopentadiene- modified unsaturated polyester resin composition, the resin ‘composition comprising 4) the dicyclopentadiene-modified unsaturated polyester of claim 4; and ») a radically polymerizable monomer 5. The molding material of elaim 4, further comprising a reinforcing fiber holding the dicyclopentadiene-modificd unsaturated polyester resin composition 6. A dicyclopentadiene-modified unsaturated polyester produced by a process comprising the steps of: a) reacting maleic anhyelride with water ata temperature cof 100° to 140° C. 16 obtain a reaction mixture, a molar ratio (H,O/MA) of water to maleic anhydride being, 1 or less; +) reacting the waction mixture with dieyelopentadiene; and ©) reacting the reaction product obtained in the seeond step with a polyhyrie aleobol, or & polyhydric alcohol 0 as os ss 4s ss 24 and a polybasic acid to obtain an unsaturated polyester modified with dieyelopentadiene, wherein the dicyclopentadiene-modified unsaturated polyester has 1 weight-average molecular weight of 8000 or more and a ratio of weight-average molecular weight to ‘aumber-average molecular weight of from 5 to 50. 7. A dicyclopentadiene-modified unsaturated polyester resin composition, comprising: 4) the dicyclopeatadiene-modified unsaturated polyester of claim 6; and b) a radically polymerizable monomer. 8. A molding material, comprising a dicyclopentadiene- ‘modified unsaturated polyester resin composition, the resin composition, comprising: 4) the dicyclopentadiene-modified unsaturated polyester of claim 6; and ») a radically polymerizable monomer, 9. The molding material of claim 8, further comprising a reinforcing fiber bolding the dicyclopentadiene-modified unsaturated polyester resin composition. 10. A dicyclopentadiene-modified unsaturated polyester prodluced by a process comprising the steps of 4) reacting maleic anhydride with water at a temperature ‘of 10010 140? C. to obtain a reaction mixture, a molar ration (H.O/MA) of water to maleie anbydride being 1 or less; a mixture with dicyclopentadiene, 4 io of (HO/DCPD) of water to dieyelopenta- dione being greater than one, a molar ratio of (MA! DCPD) of maleic anhydride to dieyclopentadiene being 1.2 or more; and 6) reacting the reaction product obtained in the second step wit a polyhydriealeohol, ora polyhydric aleobol and a polybasie acd, to obtain an unsaturated polyester modified with dicyclopentadiene, wherein the ieyclopentadiene-mosifed unsaturated polyester has a weightaverage molecular weight of 8,000 or more and a ratio of weightaverage molecular weight to number-average molecular weight of from 5 to 50. 1. The dieyelopentadiene-modifed unsaturated polyester resin composition of claim 10, wherein in sep b), saa molar ratio (MADCPD) is 1.5 oF more 12. A dicyclopentadiene-modiied unsaturated polyester resin composition, comprising 2) the dieyelopentadiene-modified unsaturated polyester of chim 10, and ) a radically polymerizable monomer. 13. A molding material, comprising & dicyelopentadicne- ‘modified unsaturated polyester resin composition, the resin composition, comprising: 4) the dicyclopentadiene-modified unsaturated polyester of chim 10, and +) a radically polymerizable monomer 14. The molding material of claim 8, further comprising 4 reinforcing fiber holding the dieyclopentadiene-modified unsaturated polyester resin composition.