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1 Carbon Letters Vol. 10, No. 1 March 2009 pp Carbon Fibers(III): Recent Technical and Patent Trends Min-Kang Seo 1, Sang-Hee Park 2, Shin Jae Kang 2 and Soo-Jin Park 1, 1 Dept. of Chemistry, Inha University, 253, Nam-gu, Incheon , Korea 2 Jeonju Institute of Machinery and Carbon Composites, 750-1, Deokjin-gu, Jeonju , Korea a sjpark@inha.ac.kr (Received February 12, 2009; Accepted march 11, 2009) Abstract Carbon fibers are a new breed of high-strength materials. The existence of carbon fiber came into being in 1879 when Edison took out a patent for the manufacture of carbon filaments suitable for use in electric lamps. However, it was in the early 1960s when successful commercial production was started, as the requirements of the aerospace industry for better and lightweight materials became of paramount importance. In recent decades, carbon fibers have found wide applications in commercial and civilian aircraft, along with recreational, industrial, and transportation markets as the price of carbon fiber has come down and technologies have matured. The market for carbon fiber has experienced a good growth in recent years. The growth rate for the last 23years was about 12%. The article reviewed 9,641 Korea, U.S., Japan, Europe patents issued in the carbon fibers in order to offer additional insight for researchers and companies seeking to navigate carbon fiber patent landscape. This article will provide you with all the valuable information and tools you will need to investigate your study successfully within the carbon fiber field. This article also will save you hundreds of hours of your own personal research time and will significantly benefit you in expanding your business in the carbon fiber market. Keywords : Carbon fibers, Patent, Research, Business, Market 1. ˆ o ˆ o p v opp 90% p p p lv oqp ˆ q k (Polyacrylonitrile, p PAN), o Ë ˆ ˆ q p (Pitch, kdž ) pmp rs o ˆp o r ~ v (Precursor, ˆ eˆ rp v)p o l l l llv o p, r ~p s l PAN m [1-5]. ˆ op vp o l p ˆ q p s, s v o ˆp p q, l, r k r, r lr, rlž} l kr, r,, X Œ, rqž, ~, ol p n vp v pp, (activation) s l n n l [6-10]. ˆ o rs p, ˆ o p q pqˆ p q p l r p te v q n op, pqˆ p 300 GPa p p o Typep ˆ (HM, ˆ o 99% p ) ˆ o, pq 4.0 GPa p p o Typep (HT, ˆ o 92% p ) ˆ o, p l} m p rs l v [11-20]., PAN ˆ o, ˆ p n l p ~ p ~ q Ënt, d n l n l m p p p 1 sq rn o e ˆ op p ˆ o rs l n~ p l p qp eq l l ~ Table 1l ˆ m p, Torayca T800H, Magnamite IM-6, IM-7, Besfight IM-500 p tˆ ˆ o ež p CFRPn r 2 ˆ op n p l PAN n p 2 p 7GPa, r e 2.4% s p pl 2.0% }pp l p ˆ op Torayca T1000p p l e l. pp e p e p l t l. ˆ o q l k l, e d Ë r n p l Ënt p r kl n l m. q ˆ op p p l qp ~ q n l p. l v l p k }l d l rv q l n nvpp p, p }l d q p l l PAN ˆ o n eq m. rp r pp p o ~r p el ˆ o

2 44 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) Table 1. rsl~ PAN ˆ o rsl~ Grade (GPa) Toray Toho Tenax Mitsubishi Rayon Heracules Torayca Besfight Pyrofil Magnamite T800H T1000H T1000 IM-400 IM-500 IM-600 MR-40 MR-50 MR-60K IM-6 IM-7 IM-8 IM-9 n e pp, e rp ~r Žp ~ q k l r or ožp, l v p p p o ~ pnp o., p v ˆ o ~p ~ q l n l eqp p r [21-27]. ˆ op n e v eˆ o p p lv p. Š Ë l kl n p lv nl krp rp m. v q p n ˆ o r p p l p l n p, pn k d n kl t p l m pn kp k o p n rp p lrk p. l ˆ om r tep (Patent Mapping)p q s l ˆ ol v v 30l p p pm p, op p p no p tn p k p ~ rp p f e pn l p p p ˆ op p Žk q m. 2. Š m l ˆ (GPa) e (%) ˆ ol r p r l o l r r p pd tp l,, p, o p p mp, qp p l opp tp m [28]. l e ˆo p ˆ om pm, ˆ o rs ˆ o p n l p ee mp, n rp l Fig. 1. o ( n). rp p rp s l p r bottom-up ep v m. p e p ˆo n el e, p ˆo v rp l l ep q p f e pn l ˆ kp p r m., p p m e o l p lr l t pp, rl l r kl o p rp ˆ v kk, kl p r p lvv kpp p p k p l l k e. p p s ˆ o r p 10,000l plp, r p o l t pv( ˆo p lp p n lv ) r ˆ o p l tl r v kp p f sr p p 9000l p l krp p r rp np p r p l p v m. r p ol, op l, rop v p p l mp, r p p p Žk m. 3. Š }k r~ (1) o ˆ op o p Fig. 1l k p p p p 1981 q v o ˆ o

3 Carbon Fibers (III): Recent Technical and Patent Trends 45 Fig. 2. ol o ( n). Fig. 4. ol o ( ). Fig. 3. op o ( n). p r~ p 9,641 p 79%(7,680 ) v p, pl, o, p 10%(986 ), 7%(636 ), 4%(339 ) v p. p p ˆ ol p l p p o k ppp lt p. (2) o l o Fig. 2 p,, o l o ˆ o o l Š, p eqp 1990 v o t v mp, 1990 l 770 p q p o l. eq l 1996 l 123 p p o 1997 e o v eq l 2000 l 465 p o lp, e 2002 l 2 p op l. (3) op o Fig. 3p ˆ o r~ o (9,641 ) op l o 7o v, op rp p plp, 1,912 p o l r~ o p k 20% v p. op tp 1o p 576 p o mp, { e pm m d Fig. 5. op o ( ) p o l 2om 3o v m. (4) r (IPC) o v m p,, o l o 9,641 p ˆ o r (IPC), r~ o p 50%l 4,844 p o 10 p l, t q pp p v p D01F(ps, o, p r sl pl r vp ;ˆ rsl r q ) r~ 9,641 t 1,405 p v m (1) o l o Fig q v l o 339 p ˆ o o l p 20l p o p Š p ( )l o m 1990 ( )l o 1980 l 73 p o p 21.5%, p o p 70% v pp

4 46 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) Table 2. tn opp o ( ) '81 '85 '86 '87 '88 '89 '90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 Mitsubishi Rayon Toray Saehan POSCO RIST Daewoo Heavy Ind Dow Chemical Fig. 6. r o p( )., 2000 p 28 p 8.5% ˆ o r~ p r. p l o ˆ o 1990 l o lpp ˆ, p e l ˆ o p q l lpp p. (2) op o l o ˆ op tn op p, Fig. 5 m p p lp { e pm p 13 jp q p op m, p, d, l l p 11, p p p. p p { e pmp n Table 2l ˆ p o 13 t 10 p 1980 l o p 3 p 2000 l o 1990 l l o v kk. v, l p nl 1990 q v l p v kv t o p p k pp, n t lp 1995 o 5 p p v p k 1990 t p l p ˆ o l l q mpp k p. (3) r o Fig. 6p l o ˆ o p opp p n pp, n p opp e r ˆ p. r~ op t, n pp v pp 53% 47%p p o p p tp v p p ˆ. n p op pp r e l p p 31.3%m 15.0% v m, pp m, d, dod p o Fig. 7. ol o (p ). p op pp ~ 6% p ˆ, p p o ropp n pp k pl n (1) p ( ) o l o Fig. 7p 1981 q v p l o 7,680 p ˆ o o p ˆ p. p p n 1990 p tp p ˆ p vp o 4,769 p r~ o p 62% v p v 3 k o 149 p tl 1997 e o l p ˆ l. ( ) op (p ) Fig. 8p v p l o ˆ o op, o 7 p p p ˆ., r~ ˆ o o p 7,680 p 22%l 1,680 p p 7 l p o l. o q p r~ p 6.2%l 479 p o p mp,

5 Carbon Fibers (III): Recent Technical and Patent Trends 47 Fig. 8. op o (p ). Fig. 10. op o ( ). Fig. 9. ol o ( ). { e pm, k m d p 357, 210, 203 p p. (2) ( ) o l o Fig v l o 986 p ˆ o o l ˆ p. p n 1980 l 391, 1990 l 589 p o l pr l vt op v k pr o o v, 20l l ~ t o p. p p p n ˆ ol l r l p lv p k t v rp p lv ppp lt p. ( ) op o Fig. 10p 1981 q v l o 986 p ˆ o op, o 7 Fig. 11. ol o (o ). t 7 p p p ˆ p, r ~ ˆ o o p 986 p 9%l 89 p p 7 l p o l. o q p r~ p 3.1%l 31 p o p mp, { e pm m 23, 18 p o l 2om 3o v p. (3) o ( ) o l o Fig. 11p v o l o 636 p ˆ o o p ˆ, o p n p l qv v 20l k p rn o v p p ˆ p., 2001 l 46 p o l, p p 1980 o l p 5 v p.

6 48 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) Fig. 12. op o (o ). ( ) op o ˆ ol o p op o p p, v Fig. 12} o 7 o 139 p ˆ o r~ 636 p 22% v p. 139 p 81%l 113 p p l p o p, t q p o opp p p p 53 p o m ˆ o q o 2006 p ˆ o q l o 7 p p p ˆ o pƒ, o,, n r l Table 3l ˆ l. r~ 98 t ˆ o l k 9%, d v 12%, t q 3%, q 24%, 16%, ˆ 36% ˆ p, o q p pƒ ˆ om v Fig. 13. ˆ o q r m (X : op, Y : o, o: op t, / /p /o, '05~'03, '02~'00, '99~'97... '75~'73, ~72) p, j e pm, Š d r~ o p 65% v m ˆ o r m p ˆ o e l o (Y ) m op (X ) p l, o p r Žk m p, op m o v r, op kr o Table 3. p ˆ o q (2006 ) «ƒ l l l y n ƒ¹ n ƒ¹ «Toray Mitsubishi Rayon Toho Tenax Teijin Techno product Honda Motor Mitsubishi Heavy Ind Mitsubishi Eng. Plastics Etc p(%)

7 Carbon Fibers (III): Recent Technical and Patent Trends 49 Fig. 14. ˆ o q l n p rop (X : ol, Y : rop, o: op t,, ~'95, '96~'98, '05~'07). Table 4. vl l t v ~1987~1990~1993~1996~1999~2002~2005~2007 n e p} r t ~ 2 2 ~ r r * o : op t,, ~'87, '88~'90, '03~'05, '06~'07 * op n rp op 18 op l p l l 06~ 07 o l p r~rp r m v., op m o s p l r Žk l Fig. 13l ˆ Fig. 15. p vl v. l. ˆ o, q rs k l 1990 o op v p ˆ, q ˆ o ql l p v p r l p p Ž p vl r p t opp e l vl o, n p r, v p l vl Žk m. Table 4l ˆ m p vl l p, 1990 rp o p eq lp, 2003 ~2005 l op q p l. vl ne p op q kp, ˆ op p r p 6o v p p s l. Fig. 14 ˆ op l n pp o p ˆ p, 2001 v n r opp o pp 30%r v mp, 2002 p n p p op v l 2005 p 40% p v p ˆ. p ˆ o q p o n l p eqp r o n l o p v eˆ l p Ž. Fig. 15 ˆ o q rs r~l r vt o v (Activity Index) vl e p p 1 nl r p p p., tm p vt q kp, vl v p 6.2 q k p n p k pp, pp r rp ˆ l.

8 50 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) Fig. 16. p tn Ž (X : op r, Y : Ž /Ž ) p eq Fig. 16p t p op r Ž m Ž p. p rp Ž p l,, n o p r l p ˆ, Ž o, p eq p ˆ v n., p Ž Ž ˆ kl p eq p v o l p q p v p Žk p PAN ˆ ol tn op PAN ˆ ol tn opp k r v ˆ o l tn e lp p m j e pm v m. p l o l p '76 ~'06 v 314 p o mp, p v 279 p o p p tn ˆ eqp p p ˆ p, l l rp l 2 p o m. j e pm l o l j e pm 75 ~ 06 v 254 p o mp, o p p 230 p p o pm v p p tn eqp r mp, l l rp op l 2 p o m. p e opp o ˆ o rs o r ~ p v mp, pp ˆ l 81 p v m. 4. l vp p,, o l o ˆ o l p q m. o, p p r ~ o p 79%l op mp, o, p 10%, 7% 4% v m. p} o l k p p ˆ o l p l o p l p p o p r rp o p ˆ o l o p Žk pp, ˆ o p v r Ž k p. o o l p, 1980 l o kp 1990 l o p ˆ p l e op l p p p, p p p l, nt rp n ˆ op n 1990 r~rp se mv, l ˆ op, p p e n p l špl q, s v p Š k, CNG, rn p, oe, p p p ~ l v l v k,, p n k, k e r or } k, p, p v, r r, l n p k l kl rnp p lv p. kp n k kl ˆ o o n p Ž l 1990 l t l p 2000 p l n n p ˆ p p., ˆ o q rs k o op v r l r p p k Ž, eq re ql p q o kl op re n. p p p pr l p e n, pl, l r p vop p lrk p Ž. p lr ~ p n qp p p e q 7s o l p ˆ q eql ˆ l p n k p. m l o p vop 21 Ž ll l ( l v l )p p p ld. y [1] Donnet, J. B.; Bansal, R. C. Carbon Fibers, Marcel Dekker, New York, 1984S 125U

9 Carbon Fibers (III): Recent Technical and Patent Trends 51 [2] Fitzer, E. Carbon Fibers and Their Composites, Springer, Berlin, 1985S 62. [3] Cato, A. D.; Edie, D. D. Carbon 2003, 41, [4] Bahl, O. P.; Manocha, L. M. Carbon 1974, 12, 417. [5] Johnson, D. J.; Tyson, C. N. Brit. J. Appl. Phys. 1969, D2, 787. [6] Hong, L. L.; Moshonov, A.; Muzzy, J. D. Polym. Compos. 1991, 12, 191. [7] Drzal, L. T.; Madhukar, M. J. Mater. Sci. 1993, 28, 569. [8] Dresselhaus, M. S.; Dresselhaus, G. Adv. Phys. 1981, 30, 139. [9] Kim, S.; Jung, Y.; Park, S. J. Colloids Surf. A. Physicochem. Eng. Aspects 2008, , 220. [10] Kim, B. J.; Lee, Y. S.; Park, S. J. Int. J. Hydrogen 2008, 33, [11] Toray Industries, Inc., Process for producing high-strength, high-modulus carbon fibers, US [12] Toray Industries, Inc., Carbon fibers and process for the production thereof, JP [13] Toray Industries, Inc., Carbon-fibers and a method of producing them, US [14] Toray Industries, Inc., Ultrahigh strength carbon fibers, US [15] Mitsubishi Rayon Co., Ltd., Production device for carbon fibers and production method therefor, JP [16] Mitsubishi Rayon Co., Ltd., Carbon fibers having modified surfaces and process for producing the same, US [17] Mitsubishi Rayon Co., Ltd., Carbon fibers having high tenacity and high modulus of elasticity and process for producing the same, US [18] Toho Rayon Co., Ltd., Acrylic fiber strand suitable for use in carbon fiber production and process for producing the same, US [19] Toho Rayon Co., Ltd., Method for producing carbon fiber reinforced thermoplastic resin product, US [20] Toho Rayon Co., Ltd., Treatment of acrylic fiber strands, EP [21] Savage, G. Eng. Fail. Anal. 2007, 14, 321. [22] Kelkar, A. D.; Tate, J. S.; Bolick, R. Mater. Sci. Eng. B 2006, 132, 79. [23] Park, S. J.; Seo, M. K. Carbon 2001, 39, [24] Park, S. J.; Seo, M. K.; Lee, J. R. Carbon 2002, 40, 835. [25] European Community, Composites, applications, and process for manufacturing said composites, EP [26] The Boeing Company, Composites containing amideimide sized fibers, US [27] Daimler Chrysler AG, C/SiC-composites and a process for producing holes in the same, EP [28]

국9308.fm

국9308.fm Carbon Letters Vol. 9, No. 3 September 2008 pp. 218-231 Carbon Fibers (I): General Understanding and Manufacturing Techniques of Carbon Fibers Min-Kang Seo 1, Kyeong-Eun Choi 2, Byung-Gak Min 3 and Soo-Jin