US 2009026O768A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0260768 A1 Kim (43) Pub. Date: Oct. 22, 2009

(54) PAPER COMPRISING FIBER OF CITRUS Publication Classification PEEL (51) Int. Cl. (76) Inventor: Hae Gon Kim, Jeju-do (KR) D2 IIH II/2 (2006.01) (52) U.S. Cl...... 162A148 Correspondence Address: (57) ABSTRACT THE WEBB LAW FIRM, P.C. 700 KOPPERS BUILDING, 436 SEVENTH A paper containing citrus peel fiber contains 20 to 60 weight AVENUE parts of citrus peel fiber with respect to 100 weight parts of PITTSBURGH, PA 15219 (US) paper mulberry fiber. The citrus peel fiberis a peel fiber of one selected from the group consisting of mandarin orange, (21) Appl. No.: 12/374,450 lemon, orange, Kiyomi and Dekopon. The paper containing citrus peel fiber is excellent in tensile strength, tear strength, (22) PCT Filed: Mar. 20, 2007 bursting strength and folding endurance, and has Superior preservability with pH close to neutrality. The paper contain (86). PCT No.: PCT/KR2007/OO1347 ing citrus peel fiber of the invention also has a yellowish and/or reddish aesthetic color, excellent tactile sensation and S371 (c)(1), high vapor transmission, and thus is adequate to be used as (2), (4) Date: Jan. 20, 2009 high grade wall paper and window paper. Furthermore, since the paper containing citrus peel fiber of the invention is manu (30) Foreign Application Priority Data factured by using by-products created in the course of pro cessing citruses, it is possible to reduce manufacturing costs Aug. 4, 2006 (KR) ...... 10-2006-OO73753 as well as decrease waste, thereby preventing pollution.

ANARE EE AER AAARNE EE PAER

EMO-E. 8 NEE PAPER 2

CRAG. FE. FAER ORANGE EE AER 2

KYOPEE PAR xYCW E PARE

Eixip. F. PAEF Ex-PCN REE, AR

COMON OREAM AR Patent Application Publication Oct. 22, 2009 Sheet 1 of 2 US 2009/026O768 A1

Figure 1)

Paper Patent Application Publication Oct. 22, 2009 Sheet 2 of 2 US 2009/026O768A1

Figure 2)

MANDAR NE PEEL PAPER 1 MANDAR NE PEEL PAPER 2

EMON PEE TENEEE PAPER PAPER 2 PAPER 3

ORANGE PEEL PAPER ORANGE PEE PAPER 2

KYOM PEEL PAPER KYOM PEEL PAPER 2

DEKOPON PEE PAPER DEKOPON PEEL PAPER 2

COMMON KOREAN PAPER US 2009/0260768 A1 Oct. 22, 2009

PAPER COMPRISING FIBER OF CITRUS terns, by using fiber produced from citrus peels as raw mate PEEL rials of the paper. Another object of the invention is to utilize waste outputted in the course of processing citruses as TECHNICAL FIELD resources in order to reduce manufacturing costs while pre venting pollution. 0001. The present invention relates to a paper containing citrus peel fiber, and more particularly, to a paper containing Technical Solution peel fiber of a citrus such as mandarin orange, lemons, orange, Kiyomi and Dekopon (Shiranuhi) together with mul 0007. The present invention relates to a paper containing peel fiber of a citrus such as mandarin orange, lemon, orange, berry fiber. Kiyomi and Dekopon (Shiranuhi) together with mulberry fiber. BACKGROUND ART 0008. In the present invention, the terminology "citrus” 0002 Traditional Korean paper, also referred to as collectively refers to mandarin orange, lemon, orange. “Hanji,” is manufactured by processing bast fiber, which is Kiyomi, Dekopon and so on. The terminology "citrus peel obtained from peels of paper mulberry trees or mulberry fiber” collectively refers to fibers prepared by cooking peels trees, and has high texture strength and excellent fibrous of citruses such as mandarin orange, lemon, orange, Kiyomi connection since the length of the fiber is significantly longer and Dekopon in a sodium hydroxide solution to remove cel than those of common pulps. Common paper is hydrolyzed as lulose oil therefrom, cleaning the cooked citrus peels, and time passes due to its strong acidity of about pH 4 to pH 5.5, beating the cleaned citrus peels together with water in a and thus becomes less conservable. However, Korean paper beater. has a long lifetime and remains highly hygroscopic (i.e., has 0009. In the present invention, mulberry fiber is prepared high vapor transmission). In addition, Korean paper is evalu by impregnating, cooking and beating mulberry wood ated as a high grade paper due to texture properties with according to the same process as for common Korean paper. natural beauty. However, the usage of Korean paper is gradu 0010. An adhesive may be added to disperse fiber and ally decreasing, and to date, being applied to restricted fields prevent entanglement, thereby facilitating paper forming. such as industrial arts and interiors. Thus, Korean paper making basis weight uniform, and enhancing paper strength. merely keeps itself in existence. In order to widen the usage, Examples of the adhesive may include polyethylene oxide various types of Korean paper are consistently introduced, (PEO), polyamide and so on. which include functional Korean paper where oak charcoal. 0011. The paper containing citrus peel fiber of the inven lacquer poison and the like are added. tion is manufactured by mixing an adhesive into 100 weight 0003. In the meantime, a massive amount of citrus peels parts of paper mulberry fiber and 20 to 60 weight parts of are produced in the course of processing citruses in Jeju, citrus peel fiber, the paper mulberry fiber prepared by beating Korea. A portion of the citrus peels are utilized as feeds and mulberry wood, the citrus peel fiber prepared from peels of herb medicines, but a majority of the citrus peels are dis citruses such as mandarin orange, lemon, orange, Kiyomi and carded. Sometimes, the citrus peels are even thrown away Dekopon; and forming the mixture into paper, and compress illegally. Thus, it is necessary to devise an approach which ing and drying the paper. can utilize the citrus peels as resources in order to prevent land and marine pollution and newly create added values. ADVANTAGEOUS EFFECTS 0004 Prior to the present invention, the inventor previ (0012. The paper containing citrus peel fiber of the inven ously filed Korean Patent Application No. 10-2006-0004265, tion is excellent in tensile strength, tear strength, bursting titled “Korean Paper Made of Citrus Peel.” In this document, strength and folding endurance, and has superior preservabil the inventor proposed a Korean paper manufacturing process ity with pH close to neutrality. The paper containing citrus using the citrus peels where pulverized citrus peel powder is peel fiber of the invention also has a yellowish and/or reddish added in a beating procedure. Korean paper manufactured aesthetic color, excellent tactile sensation and high vapor using the citrus peels assumes unique color and fragrance of transmission, and thus is adequate to be used as high grade citruses while maintaining the quality of common Korean wall paper and window paper. Furthermore, since the paper paper. containing citrus peel fiber of the invention is manufactured 0005. However, the citrus peel power does not have excel by using by-products created in the course of processing lent fibrous connection with mulberry fiber, and thus Korean citruses, it is possible to reduce manufacturing costs as well as paper containing the citrus peels are thicker and more bulky decrease waste, thereby preventing pollution. but have a lower density with respect to common Korean paper manufactured by inputting an adhesive material in the DESCRIPTION OF DRAWINGS same amount. In addition, Korean paper containing the citrus 0013 FIG. 1 is a sectional view illustrating a vapor trans peels also have relatively lower tensile strength, bursting mission cup prepared for vapor transmission test; and strength, tear strength and folding endurance. (0014 FIG. 2 is pictures illustrating the surface of paper manufactured according to Examples 1 to 12, taken with an DISCLOSURE imaging device. Technical Problem MODE FOR INVENTION 0006. Accordingly, the present invention has been made to Example 1 solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to manufacture Manufacturing of Mandarin Peel Paper 1 high grade paper, which is excellent in strength, vapor trans (0015, 200g of dried mandarin orange peels (also referred mission and preservability, and have aesthetic colorful pat to as “mandarin peels') were placed into a 5% sodium US 2009/026O768 A1 Oct. 22, 2009

hydroxide solution, and cooked at 100° C. for 30 minutes to Example 8 soak out cellulose oil. The cooked peels were cleaned with water three times, placed into a Holland beater together with Manufacturing of Kiyomi Peel Paper 1 1.8 kg of water, and beaten for 20 minutes, thereby producing 0023 Kiyomi peel paper 1 was manufactured in the same fiber of mandarin peel or mandarin peel fiber. process as in Example 1 except that mandarin oranges were 0016 10kg of mulberry fiber (90 wt % moisture) prepared substituted by Kiyomis. by cooking mulberry wood, 2 kg of the mandarin peel fiber prepared as above and 45 g of PEO were mixed and stirred. Example 9 The stirred mixture was placed into a paper-making tank and formed into a sheet of paper by a twin-wire sheet former. The Manufacturing of Kiyomi Peel Paper 2 paper was dewatered and compressed in a dehydrator to have a uniform basis weight. The compressed and half-dried paper 0024 Kiyomi peel paper 2 was manufactured in the same (40 wt % moisture) was swept with a drying brush, attached process as in Example 2 except that mandarin oranges were in a stack-by-stack manner, and dried in a hot plate dryer, substituted by Kiyomis. thereby producing Mandarin peel paper 1. Example 10 Example 2 Manufacturing of Dekopon Peel Paper 1 Manufacturing of Mandarin Peel Paper 2 0025 Dekopon peel paper 1 was manufactured in the same process as in Example 1 except that mandarin oranges were 0017 Mandarin peel paper 2 was manufactured in the substituted by Dekopons. same process as in Example 1 except that 10 kg of the mul berry fiber prepared by beating mulberry wood, 4 kg of the Example 11 mandarin peel fiber and 45 g of PEO were mixed. Manufacturing of Dekopon Peel Paper 2 Example 3 0026 Dekopon peel paper 2 was manufactured in the same process as in Example 2 except that mandarin oranges were Manufacturing of Lemon Peel Paper 1 substituted by Dekopons. 0018. Lemon peel paper 1 was manufactured in the same process as in Example 1 except that mandarin oranges were Example 12 substituted by lemons. Manufacturing of Common Korean Paper Example 4 0027 Mulberry fiber prepared by cooking mulberry wood was formed into a sheet of paper by a twin-wire sheet former Manufacturing of Lemon Peel Paper 2 in a paper-making tank. The paper was dewatered and com pressed in a dehydrator to have a uniform basis weight. The 00.19 Lemon peel paper 2 was manufactured in the same compressed and half-dried paper (40 wt % moisture) was process as in Example 2 except that mandarin oranges were swept with a drying brush, attached in a stack-by-stack man substituted by lemons. ner, and dried in a hot plate dryer, thereby producing common Korean paper. Example 5 0028 Papercontaining citrus peel fiber of the invention manufactured according to Examples 1 to 11 had anaesthetic Manufacturing of Lemon Peel Paper3 pattern with a yellowish or reddish color, which is not observed in common Korean paper, and gave excellent tactile 0020 Lemon peel paper 3 was manufactured in the same sensation. The following experiments were carried out to test process as in Example 4 except that 10 kg of the mulberry physical properties of the citrus peel paper according to fiber prepared by beating mulberry wood, 6 kg of the manda Examples 1 to 11. rin peel fiber and 45g of PEO were mixed together. Experiment 1 Example 6 Measurement of Physical Properties of Paper Manufacturing of Orange Peel Paper 1 0029 Specimens of the respective paper manufactured 0021 Orange peel paper 1 was manufactured in the same according to Examples 1 to 12 were extracted according to process as in Example except that mandarin oranges were TAPPI standard test T400, and humidified for 24 hours Substituted by oranges. according to T402 om-83 in a constant temperature and humidity chamber having a temperature 20+1° C. and a rela Example 7 tive humidity 65+5%. Then, tests were carried out to measure the physical properties of the paper Such as basis weight (oven Manufacturing of Orange Peel Paper 2 drying method), thickness, tensile strength, bursting strength, tear strength and folding endurance. The physical properties 0022 Orange peel paper 2 was manufactured in the same of the paper were measured according to the test methods process as in Example 2 except that mandarin oranges were reported in Table 1 below, using devices reported in Table 2 Substituted by oranges. below, and the results are reported in Tables 3 and 4 below. US 2009/026O768 A1 Oct. 22, 2009

in the cup up to a height 2-0.5 cm from the opening. Paper TABLE 1. manufactured according to Examples 1 to 12 was placed, respectively, on the opening of the vapor transmission cup, Item Method and maintained with a relative humidity 32.8% in a constant Thickness and density TAPPI Standard T200 om-83 temperature and humidity chamber at a temperature 25°C., Tensile strength TAPPI Standard T494 om-81 and the vapor transmissions of the paper were measured. Bursting strength TAPPI Standard T403 om-85 Tear strength TAPPI Standard T414 Om-82 Vapors migrate from inside the vapor transmission cup of a Folding endurance TAPPI Standard TS11 om-83 relative humidity 84.3% through the individual paper to the constant temperature and humidity chamber. After two (2) hour passed from the beginning of the test, the weight of the vapor transmission cup was measured for twenty four (24) TABLE 2 hours with one (1) hour interval in order to calculate the Item Device amount of vapors migrated. The results are reported in Table 6 below. Thickness Model 49-70, Tester Machines INC. Tensile strength Instrun Mini 44, Instron Corporation, USA Tear strength Thwing-Albert Instrument Co., USA Experiment 5 Bursting strength Daeil-Machinery Co., Korea Folding endurance Tester Sangyo Co. LTD, Japan Surface Analysis of Paper 0033. The paper manufactured according to Examples 1 to Experiment 2 12 was diced into 1 cmx1 cm pieces. The paper pieces were photographed by an imaging device (Kenko KCM-Z3. Measurement of Optical Properties of Paper Japan), at a magnifying power 200x and a luminance 5000 0030 Specimens of the respective paper manufactured Lux, and the photographed images were analyzed by an according to Examples 1 to 11 were extracted according to image analysis program (BMI plus, BumMi Universe Co., TAPPI standard test T400, and humidified for 24 hours LTD., USA). The results are shown in FIG. 2. according to T402 om-83 in a constant temperature/humidity room having a temperature 20+1° C. and a relative humidity TABLE 3 65+5%. Then, tests were carried out on the paper specimens to measure their whiteness with a Hunter whiteness analyzer Basis weight Thickness Density Volume (Model S4-M, Technidyne Corporation New Albany, India. Paper type (g/m) (Lm) (g/cm) (cm/g) USA) and their chromaticity with a spectrophotometer (NF Mandarin peel 1 23.6 84.8 O.28 3.59 Mandarin peel 2 27.8 89.2 O.31 3.21 333, Nippon Denshoku Ind. Co., LTD). The results are Lemon peel 1 22.2 92.8 O.24 4.18 reported in Table 5 below. Lemon peel 2 21.7 90.3 O.24 4.16 Lemon peel 3 20.1 85.5 O.24 4.25 Experiment 3 Orange peel 1 23.0 88.5 O.26 3.84 Orange peel 2 25.2 95.6 O.26 3.79 Measurement of pHs of Paper Kiyomi peel 1 23.5 85.5 0.27 3.64 Kiyomi peel 2 24.6 93.5 O.26 3.80 0031. The paper manufactured according to Examples 1 to Dekopon peel 1 29.8 98.8 O.30 3.32 12 was diced into 1 cm x1 cm pieces. 1.0 g of the individual Dekopon peel 2 23.2 85.2 0.27 3.67 paper pieces were placed into a 200 ml Erlenmeyer flask Common Korean 25.6 76.3 O.34 2.98 together with 100 ml of ion exchange water, and hot water paper extraction was carried out for 2 hours, followed by cooling. The resultant products were measured of pH, and the results 0034. According to the results reported in Table 3 above, it are reported in Table 5 below. is found that those paper containing citrus peel fiber decreased in density with respect to common Korean paper. It Experiment 4 is believed that spaces occupied by citrus peels make fibrous connections rather sparse but increase the Volume. The paper Measurement of Vapor Transmission of Paper containing mandarin peels and Dekopon peels showed a rela 0032. A vaportransmission cup shaped as shown in FIG. 1 tively higher density, which is similar to that of common was prepared according to KSF2607 specification, with an Korean paper. The paper containing lemon peels, however, opening area 0.005 m or more, and distilled water was filled showed lowest density.

TABLE 4 breaking elongation Tear Folding length rate Bursting strength endurance km % strength mNm/S. times Paper Type A. B A B (kPam/g) A B A B Mandarin peel 1 4.7 4.7 8.2 8.5 5.4 49.O 421 246 6 Mandarin peel 2 4.0 3.9 5.3 6.1 5.3 43.8 32.6 344 16 Lemon peel 1 7.2 2.9 3.5 6.6 5.4 SO.4 41.7 50 1 US 2009/026O768 A1 Oct. 22, 2009 4

TABLE 4-continued breaking elongation Tear Folding length rate Bursting strength endurance km % strength mNng times

Paper Type A. B A B (kPam'/g) A B A. B Lemon peel 2 6.5 4.8 4.2 5.9 5.3 50.3 41.1 53 1 Lemon peel 3 O.7 O.2 3.4 4.2 4.4 39.4 37.3 6 1 Orange peel 1 13.6 11.6 5.4 6.O 6.4 78.1 53.6 496 17 Orange peel 2 11.8 4.32 4.6 6.6 5.8 51.9 44.5 877 16 Kiyomi peel 1 9.2 6.2 2.2 2.9 S.O 43.9 32.4 252 6 Kiyomi peel 2 5.2 5.2 3.7 3.7 4.8 43.9 37.6 322 33 Dekopon peel 1 10.9 4-S 5.6 7.2 S.6 46.O 45.0 164 34 Dekopon peel 2 13.3 4.0 3.4 5.1 5.5 48.9 38.2 97 30 Common Korean paper 8.9 3.O 7.0 10.2 6.5 57.9 41.1 235 13 Note: A: Lengthwise direction B: Lateral direction

0035. According to the results in Table 4 above, the paper containing orange peels, Dekopon peels and Kiyomi peels TABLE 5-continued reportedly increased in tensile strength due to shorter break ing length with respect to common Korean paper. However, Whiteness Chromaticity except for the paper containing Lemon peel 3, other citrus peel paper generally showed excellent tensile strength: even if pH (%) L 8. b the tensile strength was lower than that of Korean paper, the Dekopon peel 2 8.37 35.7 79.58 -0.01 17.8O difference was not significant. The extension ratio showed Common Korean 7.88 81.5 88.42 -0.61 3.10 correlation with tensile strength. That is, extension ratio is paper low at high tensile strength, but high at low tensile strength. 0036. In terms of bursting strength, the citrus peel paper 0039. In Table 5 above, L=100 indicates white, but L=0 generally showed lower values with respect to common indicates black. A larger +a is more reddish, but a larger-ais Korean paper, but the difference was not significant. The more greenish. In addition, a larger+b is more yellowish, but paper containing Orange peel 1 showed fine bursting strength a larger-b is more bluish. similar to that of common Korean paper. All of the citrus peel 0040. According to the results of Table 5 above, the citrus paper showed substantially fine bursting strength. peel paper had yellowish color and lower whiteness with 0037. In terms of tear strength, the paper containing respect to common Korean paper. The paper containing Orange peel 1 showed a higher value over common Korean Kiyomi peel 2 and Dekopon peel 1 were slightly reddish. In paper. Although most of the citrus peel containing paper terms of pH, most of the citrus peel paper was slightly higher showed tear strength lower than common Korean paper, the than common Korean paper, but the paper containing the difference was not significant. Thus, the citrus peel paper Lemon peels 1 and 2 was slightly lower than common Korean generally was reported with excellent tear strength. paper. It was judged that the most citrus peel paper has excel 0038. In terms of folding endurance, the paper containing lent preservability since the pH of the most citrus peel paper Mandarin peels 1 and 2, Orange peels 1 and 2 and Kiyomi was close to neutrality. peel 1 showed a higher value over common Korean paper, the paper containing Kiyomi peel 2 showed folding endurance TABLE 6 similar to that of common Korean paper, and the paper con Vapor taining Dekopon peels 1 and 2 and Lemon peels 1 and 2 Vapor Trans- Index of showed folding endurance lowerthan that of common Korean Trans- mission Vapor Vapor paper. mission per area Resistivity Transmission

TABLE 5 Mandarin peel 1 O.19894 38.558 O.308 3.247 Mandarin peel 2 O.19528 38.222 O.311 3.215 Whiteness Chromaticity Lemon peel 1 O.21042 42,084 O.282 3.546 Lemon peel 2 O.20228 40.456 O.294 3.4O1 pH (%) L 8. b Lemon peel 3 O.19099 38.198 O.311 3.215 Orange peel 1 O.20473 40.946 O.290 3.448 Mandarin peel 1 8.25 38.4 80.24 -0.29 14.78 Orange peel 2 O.19688 69.376 O.302 3.311 Mandarin peel 2 8.37 37.4 82.85 -0.26 17.41 Kiyomi peel 1 O.22947 45.894 O.259 3.861 Lemon peel 1 7.66 46.3 82.08 -O35 10.86 Kiyomi peel 2 O.2O861 41.722 O.285 3.509 Lemon peel 2 7.74 42.7 79.98 -0.48, 10.84 Dekopon peel 1 O.19279 38.558 O.308 3.247 Lemon peel 3 7.86 30.3 75.36 O.O2 14.82 Dekopon peel 2 O.19111. 38.222 O.311 3.215 Orange peel 1 8.15 56.3 86.19 -0.10 6.88 Common Korean O.2O007 40.014 O.297 3.367 Orange peel 2 8.17 39.1 78.83 -0.19 9.62 paper Kiyomi peel 1 8.32 43.2 82.80 -0.43 12.29 Kiyomi peel 2 7.85 45.0 81.29 O.17 11.58 Dekopon peel 1 8.36 44.8 81.89 O.S3 12.63 0041 According to the results of Table 6 above, the paper containing Lemon peels 1 and 2. Orange peels 1 and 3 and US 2009/026O768 A1 Oct. 22, 2009

Kiyomi peels 1 and 2 had a higher vapor transmission with as tensile strength, tear strength, bursting strength, folding respect to common Korean paper, and the paper containing endurance, vapor transmission and preservability, which are Mandarin peels 1 and 2, Lemon peel 3 and Dekopon peels 1 close to those of common Korean paper. and 2 had a slightly lower vapor transmission with respect to 1. A paper comprising 20 to 60 weight parts of citrus peel common Korean paper. Since all of the citrus peel paper was fiber and 100 weight parts of paper mulberry fiber. high in terms of vapor transmission, it was judged that they 2. The paper according to claim 1, wherein the citrus peel are adequate to be used as a wall paper or window paper. fiber is prepared by cooking citrus peels in a sodium hydrox 0042. As shown in FIG. 2, when the paper manufactured ide solution to remove cellulose oil therefrom, cleaning the according to Examples 1 to 12 was analyzed with an image cooked citrus peels, and beating the cleaned citrus peels analyzer, the citrus peel paper was more yellowish and/or together with water in a beater. reddish than common Korean paper. In addition, due to citrus 3. The paper according to claim 1 or 2, wherein the citrus peels distributed between fibers, less inter-fiber pores were peel fiber is a peel fiber of one selected from the group found in the paper according to Examples 1 to 12 than in consisting of mandarin orange, lemon, orange, Kiyomi and common Korean paper. Dekopon. 0043. In view of the aforementioned results, the citrus peel paper of the invention have excellent physical properties Such