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Glyoxal DP Improvement of Whiteness of Glyoxal treated Cotton Fabrics by Additives 2000 8 1

Glyoxal DP Improvement of Whiteness of Glyoxal treated Cotton Fabrics by Additives 2000 8 2

Glyoxal DP Improvement of Whiteness of Glyoxal treated Cotton Fabrics by Additives 2000 8 3

. 2000 8 4

100% glyoxal DP. magnesium chloride, magnesium chloride/citric acid,,. sodium tetraborate decahydrate, sodium peroxoborate tetrahydrate, sodium chlorite,. aluminum sulfate. glyoxal DP magnesium chloride magnesium chloride/citric acid, yellowing. sodium tetraborate decahydrate, sodium peroxoborate tetrahydrate sodium chlorite. sodium chlorite buffer sodium phosphate monobasic. aluminum sulfate 5

WRA(wrinkle recovery angle). 6

Abstract The crosslinking of cotton fabric by glyoxal as a nonformaldehyde crosslinking agent was investigated. Reaction was conducted in the presence of magnesium chloride or magnesium chloride/citric acid at various mole ratios of catalyst/glyoxal. The effect of sodium tetraborate decahydrate, sodium peroxoborate tetrahydrate, or sodium chlorite in treating solutions on wrinkle recovery angle, breaking strength, and C.I.E. whiteness index of treated fabrics was analyzed. The effect of the above mentioned additives was also examined when aluminum sulfate was used as a catalyst. Magnesium chloride/citric acid mixed-catalyst was proven highly effective in catalyzing the crosslinking of glyoxal with cellulose. However, mixed catalyst gave low breaking strength and whiteness. The addition of sodim tetraborate decahydrate, sodium peroxoborate tetrahydrate, or sodium chlorite to treating solutions increased breaking strength and whiteness. Surprisingly, sodium chlorite was highly effective in the presence of sodium phosphate monobasic as a buffer. The additives also improved the strength retention and whiteness of treated fabrics when aluminum sulfate was used as a catalyst. 7

--------------------------------------------------------------i Abstract --------------------------------------------------------------ii --------------------------------------------------------------iii 1. ---------------------------------------------------------------1 2. ---------------------------------------------------------------6 2.1. ---------------------------------------------------6 2.2. ---------------------------------------------------6 2.3. ---------------------------------------------------7 2.4. ----------------------------------------------------9 3. -------------------------------------------------11 3.1. --------------------------------11 8

3.2. ------------------------------------------------26 3.3. 2 -------------------------------------------------38 4. ------------------------------------------------------46 ------------------------------------------------ -----48 9

1. DP(durable press) W&W. N-methylol DP,,,. 1980 DP,, DP [1]. DP DMDHEU(dimethyloldihydroxyethylene urea [2], 10

polycarboxylic acid [3~7]. BTCA(1,2,3,4,-butanetetracarboxylic acid) polycarboxylic acid DP,, SHP(sodium hypophosphite). glyoxal DMDHEU glyoxal DP. glyoxal DP, [8~10]. glyoxal acetaldehyde ethylene glycol acetaldehyde ethylene glycol 11

dehydrogenation [11,12]. glyoxal 40%. glyoxal crosslinking 1960. Gonzales Guthrie[13] glyoxal magnesium chloride, Matsui[14] zinc fluoborate hydrogen peroxide. Worth[15,16] aluminum sulfate magnesium sulfate glyoxal reactive silicone /. glyoxal DP 1980. Welch[8~10] formaldehyde N-methylol DP glyoxal aluminum. glyoxal glycol glycol DP. glyoxal 12

,.,,, (telomer),, ( ) [1]. [17~21], DP ( ).. BTCA TEA HCl, NaBO 3 4H 2 O, NaB 2 O 4 10H 2 O [22] glyoxal. 13

100% DP glyoxal MgCl 2 citric acid MgCl 2 - -. glyoxal. [23] WRA 14

2. 2.1., Table 1. Table 1. Characteristics of cotton fabric. Composition Cotton 100% Weave Yarn Number, Ne Fabric count(ends/in Plain 30 30 68 68 picks/in) Weight(g/m 2 ) 122 15

2.2. glyoxal(taeyang Chemical Co ) aluminum sulfate(shinyo Pure Chemical Co., ), magnesium chloride(aldrich Chemical Co. citric acid(duksan Pharmaceutical Co, ). sodium tetraborate decahydrate(na 2 B 4 O 7 10H 2 O, Shinyo Pure Chemical Co., ), sodium peroxoborate tetrahydrate(nabo 3 4H 2 O, Junsei Chemical Co., ), sodium chlorite(naclo 2, Kanto Chemical Co., 1 ). 2.3. 2.3.1. 1). 16

2) Padder(Japan Yamaguchi Sankyo Ltd, YN-450 type ) 2nip-2dip wet pick-up 105 2%. 3) (Swiss Werner Mathis AG., Laboratory Drying and Curing Machine CH-815) pin frame 85 3. 4) 17

5) 50 30. 6) 15, 30, 45, 60. 2. 4. AATCC Monsanto Wrinkle Recovery Angle Tester,. 18

ASTM D ) Instron(Janpan Orientic Co., RTM-500). X-rite spectrophotometer(x-rite Incorporated D65 10. 19

20 3. 3.1. glyoxal,. WRA. TGA [24, 25].. DP.

,. [17]. DP. O O cell OH + H C C H + HO cell cat. heat cell O HO HC CH O OH cell Figure 1. Crosslinking reaction of glyoxal with cellulose. 21

3.1.2. glyoxal magnesium chloride Figure 2 ~ 4 glyoxal magnesium chloride 5%, 150, 3 MgCl 2 /glyoxal 0.05 0.35 WRA. magnesium chloride wrinkle recovery angle(wra) MgCl 2 /glyoxal 0.15 0.2. 0.05 65 82 magnesium chloride DP WRA glyoxal 22

MgCl 2 citric acid Figure 5 7 MgCl 2 /glyoxal 0.15 0.2 citric acid/mgcl 2 0.05 0.3 WRA. 5%, 150, 3. WRA citric acid citric acid/ MgCl 2 MgCl 2 /glyoxal 0.15 0.2 citric acid/ MgCl 2 citric acid/mgcl 2 MgCl 2 /glyoxal 0.15 0.2., MgCl 2 citric acid ph. 23

300 Wrinkle Recovery Angle(w+f) o 280 260 240 220 200 180 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 MgCl 2 /Glyoxal mole ratio Figure 2. Effect of catalyst concentration on wrinkle recovery angle of treated fabric. glyoxal 5%, curing 150 o C, 3min. 24

100 Retention of Breaking Strength(%) 90 80 70 60 50 40 30 20 10 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 MgCl 2 /Glyoxal mole ratio Figure 3. Effect of catalyst concentration on retention of breaking strength of treated fabric. glyoxal 5%, curing 150 o C, 3min. 25

90 80 70 Whiteness Index 60 50 40 30 20 10 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 MgCl 2 /Glyoxal mole ratio Figure 4. Effect of catalyst concentration on C.I.E. whiteness index of treated fabric. glyoxal 5%, curing 150 0 C, 3min. 26

MgCl 2 /glyoxal 0.15 0.2 MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2. citric acid/mgcl 2 WRA. 3.1.4. Figure 8 ~ 10 glyoxal 5% MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2, 130 ~ 170 C 3, 150 C 1 ~ 5 WRA. WRA 150 C.,. 150 C. 27

300 Wrinkle Recovery Angle(w+f) o 280 260 240 220 200 MgCl 2 /glyoxal mole ratio 0.15 0.20 180 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 CA/MgCl 2 mole ratio Figure 5. Effect of CA/MgCl 2 mole ratio on wrinkle recovery angle of treated fabric. glyoxal 5%, curing 150 o C, 3min. 28

70 Retention of Breaking Strength(%) 60 50 40 30 MgCl 2 /glyoxal mole ratio 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 CA/MgCl 2 mole ratio Figure 6. Effect of CA/MgCl 2 mole ratio on retention of breaking strength of treated fabric. glyoxal 5%, curing 150 o C, 3min. 29

90 80 MgCl 2 /glyoxal mole ratio 0.15 0.20 Whiteness Index 70 60 50 40 30 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 CA/MgCl 2 mole ratio Figure 7. Effect of CA/MgCl 2 mole ratio on C.I.E. whiteness index of treated fabric. glyoxal 5%, curing 150 o C, 3min. 30

WRA 150 C. WRA 3,. 3. Figure 11 ~ 13 citric acid/mgcl 150 C MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2 glyoxal 1 ~ 9% WRA. glyoxal glyoxal. WRA glyoxal glyoxal. glyoxal 5% 5%. glyoxal glyoxal 31

300 280 Wrinkle Recovery Angle (w+f) 260 240 220 200 Curing time Curing temp. 180 0 1 2 3 4 5 (temp:150 o C) time(min.) 0 130 140 150 160 170 temp( o C) (time:3min.) Curing Condition Figure 8. Effect of curing condition on wrinkle recovery angle of treated fabric. glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2 32

100 90 Retention of Breaking Strength(%) 80 70 60 50 40 30 20 Curing time Curing temp. time(min.) 0 temp( o C) 10 0 1 2 3 4 5 130 140 150 Curing Condition 160 (temp:150 o C) 170(time:3min.) Figure 9. Effect of curing condition on retention of breaking strength of treated fabric. glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2 33

90 80 Curing time Curing temp. Whiteness Index 70 60 50 40 30 0 1 2 3 4 5 (temp:150 o C) time(min.) 0 130 140 150 160 170 temp( o C) (time:3min.) Curing Condition Figure 10. Effect of curing condition on C.I.E. whiteness index of treated fabric. glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2 34

35 glyoxal.. glyoxal glyoxal odium tetraborate decahydrate odium peroxoborate tetrahydrate

300 Wrinkle Recovery Angle(w+f) o 280 260 240 220 200 Glyoxal Glyoxal+Catalyst 180 1 3 5 7 9 Glyoxal Concentration(%) Figure 11. Effect of glyoxal concentration on wrinkle recovery angle of treated fabric. MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o C, 3min. 36

100 Retention of Breaking Strength(%) 90 80 70 60 50 40 30 20 Glyoxal Glyoxal+Catalyst 10 1 3 5 7 9 Glyoxal Concentration(%) Figure 12. Effect of glyoxal concentration on retention of breaking strength of treated fabric. MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o C, 3min. 37

90 80 Whiteness Index 70 60 50 Glyoxal Glyoxal+Catalyst 40 30 1 3 5 7 9 Glyoxal Concentration(%) Figure 13. Effect of glyoxal concentration on C.I.E. whiteness index of treated fabric. MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o C, 3min. 38

1) CA/MgCl 2 glyoxal aluminum sulfate, MgCl 2 + CA. Figure. Figure 14 15 5%, MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2, Al 2 (SO 4 ) 3 /glyoxal 0.04, 150 C sodium tetraborate decahydrate(stb) sodium peroxoborate tetrahydrate(spb) WRA. WRA ph. WRA 270... 39

STB SPB, STB SPB WRA. ph 2 ph 4.2. ph,. STB SPB.. 4NaBO 3 + 5H 2 O = Na 2 B 4 O 7 +4H 2 O 2 +2NaOH Na 2 B 4 O 7 +NaO 2 +4H 2 O NaBO 2 H 2 O 2 3H 2 O + 3NaBO 2 H 2 O 2 H + + HO 2 - H 2 O 2 + 2H + + 2e H 2 O 2 + H 2 O + 2e ------------( ) -----------(Alkali ) Alkali HO - 2, H 2 O 2 40

H 2 O 2 [26]. 2) Aluminum sulfate [23] aluminum sulfate WRA. aluminum sulfate. glyoxal 5%, glyoxal aluminum sulfate 0.04, 150 C, 3 sodium tetraborate decahydrate(stb) sodium peroxoborate tetrahydrate(spb) WRA.. 41

300 Wrinkle Recovery Angle(w+f) 280 260 240 220 200 STD (CA/MgCl 2 ) SPB (CA/MgCl 2 ) STD (Al 2 (SO 4 ) 3 ) SPB (Al 2 (SO 4 ) 3 ) 180 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Concentration of additives(%owb) Figure 14. Effect of additives on wrinkle recovery angle of treated fabric. glyoxal 5%, curing 150 o C, 3min. i) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 42

70 60 Retention of Breaking Strength(%) 50 40 30 20 10 STB(CA/MgCl 2 ) SPB(CA/MgCl 2 ) STB(Al 2 (SO 4 ) 3 ) SPB(Al 2 (SO 4 ) 3 ) 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Concentration of additives(%owb) Figure 15. Effect of additives on breaking strength of treated fabric. glyoxal 5%, curing 150 o C, 3min. i) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 43

90 80 Whiteness Index 70 60 50 40 STB(CA/MgCl 2 ) SPB(CA/MgCl 2 ) STB(Al 2 (SO 4 ) 3 ) SPB(Al 2 (SO 4 ) 3 ) 30 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Concentration of additives(%owb) Figure 16. Effect of additives on C.I.E. whiteness index of treated fabric. glyoxal 5%, curing 150 o C, 3min. ii) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 44

Sodium chlorite 1) citric acid/mgcl 2 Figure 17 19 glyoxal 5%, MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2, 150 C, NaClO 2 NaClO 2 buffer NaH 2 PO 4 WRA. WRA sodium chlorite WRA. sodium chlorite, buffer sodium phosphate monobasic. sodium chlorite buffer sodium phosphate monobasic. sodium chlorite ph 3.5 buffer ph 4.7 45

. ph,. NaClO 2 80% 20 C 40%. sodium chlorite ClO 2. ph. 20 C ph 3.5 [HClO 2 ] ClO 2. ph HClO 2. 5ClO 2 + 2H + 4ClO 2 + Cl - + 2 OH - ph ClO 2 ClO 2 ClO 2 ClO 2. PH 5 NaClO 2. ph 2~3 ph 3. NaClO 2 ph 3~5 [26]. 46

2) Aluminum sulfate NaClO 2 aluminum sulfate NaClO 2. glyoxal 5%, glyoxal aluminum sulfate 0.04, 150 C, sodium chlorite(sc) buffer sodium phosphate monobasic. sodium chlorite WRA. aluminum sulfate. Figure 20 ~ 22 2 glyoxal 5%, MgCl 2 /glyoxal 0.15, citric acid/mgcl 2 0.2 47

85 15, 30, 45, 60 300 280 Wrinkle Recovery Angle(w+f) 260 240 220 200 CA/MgCl 2 +NaClO 2 CA/MgCl 2 +NaClO 2 +NaH 2 PO 4 Al 2 (SO 4 ) 3 +NaClO 2 +NaH 2 PO 4 180 0.00 0.01 0.02 0.03 0.04 0.05 Concentration of NaClO 2 (%owb) Figure 17. Effect of NaClO 2 on wrinkle recovery angle of treated fabric. glyoxal 5%, curing 150 o C, 3min. i) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 48

70 65 Retention of Breaking Strength(%) 60 55 50 45 40 35 30 CA/MgCl 2 +NaClO 2 CA/MgCl 2 +NaClO 2 +NaH 2 PO 4 Al 2 (SO 4 ) 3 +NaClO 2 +NaH 2 PO 4 25 0.00 0.01 0.02 0.03 0.04 0.05 Concentration of NaClO 2 (%owb) Figure 18. Effect of NaClO 2 on breaking strength of treated fabric. glyoxal 5%, curing 150 o C, 3min. i) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 49

90 80 Whiteness Index 70 60 50 40 CA/MgCl 2 +NaClO 2 CA/MgCl 2 +NaClO 2 +NaH 2 PO 4 Al 2 (SO 4 ) 3 +NaClO 2 +NaH 2 PO 4 30 0.00 0.01 0.02 0.03 0.04 0.05 Concentration of NaClO 2 (%owb) Figure 19. Effect of NaClO 2 on C.I.E. Whiteness index of treated fabric. glyoxal 5%, curing 150 o C, 3min. i) MgCl 2 /glyoxal mole ratio 0.15 CA/MgCl 2 mole ratio 0.2 ii) Al 2 (SO 4 ) 3 /glyoxal mole ratio 0.04 50

51 WRA STB SPB 5 SC

300 Wrinkle Recovery angle(w+f) o 280 260 240 220 200 One bath system STB : 269 SPB : 270 SC : 278 STB SPB SC 180 0 15 30 45 60 Immersing time(min.) Figure 20. Effect of immersing time on wrinkle recovery angle of treated fabric. (two-bath system) glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o C, 3min. 52

100 Retention of Breaking Strength(%) 90 80 70 60 50 40 30 20 One bath system STB : 39 SPB : 38 SC : 49 STB SPB SC 10 0 15 30 45 60 Immersing time(min.) Figure 21. Effect of immersing time on retention of breaking strength of treated fabric. (two-bath system) glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o C, 3min. 53

90 80 Whiteness Index 70 60 50 40 One bath system STB : 72 SPB : 72 SC : 72 STB SPB SC 30 0 15 30 45 60 Immersing time(min.) Figure 22. Effect of immersing time on C.I.E. whiteness index of treated fabric.(two-bath system) glyoxal 5%, MgCl 2 /glyoxal mole ratio 0.15, CA/MgCl 2 mole ratio 0.2, curing 150 o, 3min. 54

glyoxal 100% 5% magnesium chloride WRA glyoxal magnesium chloride citric acid WRA glyoxal 5% MgCl 2 /glyoxal 0.15 citric acid/mgcl 2 0.2 sodium tetraborate decahydrate(stb), sodium peroxoborate tetrahydrate(spb) sodium chlorite(sc) sodium chlorite WRA glyoxal citric acid/mgcl 2. 55

sodium chlorite buffer sodium phosphate monobasic. STB, SPB SC aluminum sulfate WRA. 1 2 1 WRA. WRA 1. 56

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