Jou rnal of Scicnt ili c & Industr ia l Resea['eh

Vol. 61. Dece mber 2002. PI' 1046- 1050

Development of Specialty Papers is an Art : Wax Match Tissue Paper from Indigenous Raw Materials - Part I

Dharm Dutt" '. J S Upadhyaya, A K Ray and R S Malik

Indi an Institutc ofTL'dlilology. Saharanpur CI [lJPlI S. Department o f Papel' Tcchnology. I'o~ t l30x 83 . Saharanpur 2-+ 7 00 1

and

M K Upadhyaya

Star Paper Mill s Ltd . Sahara llpur 2-+ 7 001

Rece ivcd:08.!\pril 2002: accepted : 0-+ Orloher 2002

. _ In present in ves ti~ation'llI c mpt s havc hec n made to lIlanufariLire wax match paper from locall y avail ah le hardwoous like 1:."CU/lptIlS tNetICOr/II S wit h SO IllC proportio ns of D(' l ldmell/wIII IS st r ictlls ( l3amhoo) allu P illils ros/J/Ir~ /I il. These raw mat en ,i/ s arc mos l~ y, ulilIl.c~ [n Inu[a in dillcrc nl proportions. The i'CS UllS of labo ratory made wax Illalch li ss u~ papL' r arc vc ry ploml slllg .II1U [n tc les tlng 1 he con ve rtcd paper lullil propose 01 enu users.

Introduction

Wax match ti ss uc papcr is a hi ghl y spec iali zed machine fini shed and un gla/,cd Ixtpcr uscd to manufac ture 'Vesta '. which is a kind of short match. espec iall y with wax shaft for safety matches in 40146 g/m2

• from low freencss pulp, hut with hi gh tcnsile strength and the absc ncc of pin holes. I3lcached krart pulp used for wax match is prepared from a blend of hardwood and soft wood s. Soft wood fibres (r ive thc

b

mcc hanical strength where as hard wood fibres imparts softn ess to papcr. The pulp must be a clcaned, free frolll spcc k and dirt particles and beaten to 45 °SR' d . tn or er to deve lop toughness 01 wax shaft. The typ ica l basis we ight range is betwcen 40-45 g/Jl1 2

. The wax match ti ss ue paper is rirst passed through a bath of paraffin wax ha ving Illelting point 57 °C and then the impregnated paper is subj ected to cy linder di scs where it is converted in to WJX stemmed cy lindcr on a spec ial ves tas-mJnufacturing mach ine. The match head is put on in a sepJrate operat ion fo r beading with vari ous infl am mable ingred ients. When vesta is to set fire the paper may burn in very short time and cause se ri ous acc idents. No paper manufJctured from ce llulose ribre ca n be mJde fireproof; it will burn if

"Author lo r correspondance. Tel: 0 132 7 1 17-+0 E lIlail: dharlll_du1l 0)yahoo .coll1

suffi cient heat is suppli ed. Paper can he madc fire res istant so that it wil l not support combusti on: it will burn if it is brought in contact with flame but it \V iii cease to burn when flame is withura wll. Howeve r. in the casc of vcsta the WJX stemmcd cy linuer should bu rn Jt a vc ry slo\V but cont ro ll cd rate in orde r to avo id rire acc ident and othcr hazard s.

Fire RC/(frt!r/lll s os F/(ff lle Prooflllg Mm erio/

The chemi ca ls useu as fire retardan t arc generall y ammonium sa lt s such as ammontum phosphate, ammon i um su I pham<lle. polyphos­phorylalll ide or ammonium sul phate:. Jmmonium ca rbonate, aluminum hydrox iue, zinc sul phate. magnes iulll sul phate, ammonium phosp hate. zinc chl oride, and urea. It was observed that borax-boric acid or boric aci d and sodi um borate mi xture are a better f:j 'e retardant compared to chcmical s like tetra ki s hyd roxy methyl phos phonium ch loride (THPC) and THPC with bromoform-tr ia ll yl phosphate pol ymer, metall ic ox ide pi us ch lorinated hyd roca rbon or urea phosphate compound U

Many more compounds arc used as rire retardants, such as 5-15 pCI' cent soluti on of phenoli c res in containing oxy fiu oborate and L! piaslici/.er. such as a wa ter-so luble polyethylene glyco l. ApJ rt from bora x and ammonium chl oriJ e. other flame proofi ng

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D TT (" 01. : WAX MATel1 T ISSUE P,.\PER 1047

agents are di-ammonium phosphate and di ­ammonium ethyl phos phate. There are wa ter-soluble res in s about 15 per cent on the we ight of the paper to give adequate fire protec ti on and prevent after glow. A mi xture oCBori c acid and sodium borate require around 25 per cent to obta in fire retardancy. but it docs not protect aga inst aft er glow. Ammonium sulphate needs 15-20 per ce nt by we ight of sheet and gives exce ll ent fire retardancy and fair after glow characteri st ics. As a II these agents have the di sadvantages of being water-so luble and any severe wetting reduces or eliminates the retardant charac teri stics .

Flaille retardant can al so be formulat ecl from chlorinated pa raffin or an timony ox ide and works onl y when the organi c matt er content and pi gment is in the rati o of I: I. Chl orin ated ru bbe r, appli ed fro m a to luene solution. has found highl y success ful.

Zinc borate deve loped during World - War II has we ll fired retardant property and al so ex hibit s water res istance and a definite fun gic idal act ion agai nst co mmon ce llulose degradin g fun gi. Sod ium tun gs tate and sodium stannate. alulll , mi xture of bora x and MgC I:!. MgB0.107 and {Sn(ONa).1 I

Na2B.107 + MgCl:! ~ MgB.107 + 2NaCI

Sn (ONa ).1 + 2 (N H.1) SO.1 ~ Sn (0 H.1).1+2 Na2Sn Sn (ONH.1).1 + 4H20 H Sn (O H).1 + 4N H.10H

MgCl2 + MnSiO, ~ MgS i03 + 2M nCI

(H2C)2N-PO-N(CH,)-(CH2)2-N(C H,)-PO-(CH):, + Zinc borate

N,N' -e thl ylene-bis I PI P' -{ azirhidinyll-N- meth yl­Phosphinamide.

A mi xture of ferri c pyrophos phate and Ti , Zr. or Sb ox ide can be used as fi re retardant. But wax match tissue paper along with the above fire retardatns when impregnated with paraffin wax turn s in to black or blui sh colour. These chemi cal s are di ssolved in water and appl ied either at size press or at the ca lendar. It can be used in beater in some situati ons.

The tes t fo r fire retardancy consists of burning paper in cont act with a l"lan'e produced by burning gas with a spec ified energy content in a burner with requi site charac teri sti cs . Afte r 12 s the flame is withdraw n and the time during whi ch it continues to glow is measured along with the length of char that is prod Llc cd.1.

The paper is supplied in the form of ree ls or narrow bobb ins on customer requi rements. The mos t. important properti es for wax match ti ss ue paper are as foll ows:

• Uniform formati on of the paper is ve ry important as it influences many other important properties. like compress ibility. poros ity. opacity and surface smoothness.

• Even thickness must be maintained. Paper should be free from lumps as it is direc tl y linked to rLlnn ability of spec ial vestas-manu fac tu ring machine .

• Optical properti es. like bri ghtness and opac ity arc of utmost importance for wax match tissue paper. No shade variati on is accepted. Shade of the paper should be bright and white.

• The paper should be free from specks, pinholes. dirt parti cles and two sidedness . Anything whi ch tends to form pinholes, like air in stock. di spersed air in the forlll of bubbles, foam, poor sheet release from wire, press roll s. dryers. therefore, should be avoided.

• Hi gh tear strength is frequentl y used to evaluate toughness. Whi le stress/s train curve and TEA (Tensil e energy absorpti on) are also equall y important.

• Tensil e strength is another criteri on, as cylinder fo rmati on operati on requires high MD/CD strength rati o. Thi s is poss ibl y with hi ghl y oriented fibres. Thi s gives a good CD elonga tion, which allows the wax stemmed paper to foll ow the shape of a cylinder.

• As the wax match ti ss ue paper is subj ected to illlpregnati on with wax, water klemn va lues (penetrat ion of melted wax through capillaries into the paper) and castor oil penetrati on (paper able to retain me lted wax in it) are essenti all y required.

• Wet strength res in is frequentl y lI sed in order to keep relati ve ly strong the rather low strength di splayed by thi s base paper after wetting.

• [n order to retain res ins and mi croni zed soap stone alum (A ll (SO.1) 3 14-1 8 H20 ) is added to pH 6.5. The alum must be free from iron as Fe+++ turn s paper into blackish or blui sh whil e dipping in wax.

1048 J SCIINO RES VOL 61 DECEMBER 2002

Thc study aims at developing wax match tissue from indigenous hard woods, like Eucalyptus tereticornis with some proporti ons of Delldrocn!all1us strictus (Ba mboo) and Pinus rosburghii. In order to develop water klcmn values, hard wood pulp is blended with softwood pulp; the former gives formation and smoothness and later deve lop strength. The important properties required for wax match ti ss ue paper stri ctly fulfil the requirements of end users.

Expe.-imental Methodology

PilIp Chantcterislics

Bleached mill pulp of brightness 82.0 DpV (Photo volt) is undertaken for stud y. The approximate compositi on of Pine : Bamboo: Eucalyptus bei ng 1:2.3: II.

Blending and Stock Preparation

Softwood bl eachcd pulp of brightness 87.5 DpV was beaten to 34 and 4S °SR, respectively, in laboratory va lley beater. In the similar manner, bl eached mill pulp was beaten to 34 and 4S °SR. respecti ve ly. 81eached mill pulp and imported softwood pulp of similar freeness level was mixed in the rat io of 4: I. The blended pulp is now divided into four sets:

Set J - In the first se t of pulp ha ving freeness leve l of 34 !lSR Ile pcr ce nt mclamine formaldehyde, n. l per cent te tra -k i.~- h ydroxyl methyl phosphonium chl oride (THPC) with bromoform-triallyl phos phate polymer were added to retard the burning rate. 0.1 per cen t sod ium he"' J meta phosphate al so added for uniform mi xing of non-fibrous additives. A final pH level of 6.5 was maintained with the help of non­rerric alulll by thoroughly mi xing in laboratory disintegrator wi til controll ed rpm of the rotor.

Sct 2 - [n second set of pulp ha ving a freeness leve l of 34 °SR . all the non-fibrous additives, as menti oned in set I. along withlO per cent mi croni zed soapstone powder of brightness 9S DpV were added. A pH level of 6.5 was also maintained with the help . f nOll -ferric alum by uniform mixing.

Stt -' -111 he (hiI'd se t of pul p ha ving a freeness level of 45 {'SR. all the non-fibrous additives were added accord ing to set I.

Sct 4 - In the fourth set of pulp, hav ing a freeness leve l of 4S DSR, all the non-fibrous add iti ves were added according to set 1.

Sheet Preparation a/ld Evaluation

The chemicals were thorough ly mixed with the pulp in laboratory disintegrator prior to sheet forming . Laboratory hand-sheets of basis we ight 4S g/m" on Briti sh sheet fonner were prepared. The hand-sheets were air dried, conditioned and tested as per BIS specification. The properties of laboratory hand -sheets are reported in Tabl e [. The results are compared with mi II made wax match ti ss ue papers obtained fro m those Indian mill s and shown there in.

Results and Discussion

In the present study, a pulp blend having 40 per cent imported softwood fibre and 60 per cent mill pulp of composition of pine, bamboo and euca lyptus in the rati o [ : 2.3 : I [ was fo und sui table to impart optimum properties for wax match tiss ue paper. Th is composition can give hi gh st rength properties like tear and tensile strength (to form shaft), elonga ti on and toughness (to give proper shape to cy linder of a vesta ).

Mi croscopic examination shows that some wax match ti ss ue sa mples consi st of 40 per cent jute fibre, 10 per cent so ftwood fibre, and remai ning 50 per cent hardwood fibre . In other wax match ti ss ue paper samples the softwood fibres are found up to 70 per cent. The rest mi ght be hard wood and other fibres.

Table I shows the comparison of laboratory made wax match ti ssue paper with mill made wax match ti ssue paper. When the chosen pulp blend is beaten to 34 °SR separately and thoroughl y mi xed wi th I per cent melamine forma ldehyde to deve lop sufficie nt wet strength during impreg nati on, O. J per cent tetra-kis-hydroxyl methyl phosphonium chloride with bromoform-triallyl phosphate to slow down burning of ves t shaft, 0.1 per cent sod ium hex a meta­phosphate for uniform di stributi on of non- fibrous additi ves and non-ferric alum to maintain pH 6.5 to enhance interlink with MF res in with fibres. The converters require 4.5 per cent ash in Vl<lX malch -#

tissue paper and suffi cient opac ity and brightness after impregnation with paraffin W;! x. Therefo re. it is necessary to add microni zed soapstone in to the furni sh and the veS La becomes bri ghter aft er impregn,lt lon with paraffi n wax.

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DUll el at. : WAX MATCH TISSUE PAPER 1049

Table I - Compari son of laboratory made wax match ti ssue with mill made wax match paper

Parameters Laboratory made hand- sheet Mill made wax match tiss lle paper

Freeness 34 Os R Freeness 45 °SR Mill-A Mill-B Mill -C

Pulp with I per Pulp with I per cent Pulp with I per Pulp with I per ce nt cent M F res in M F resin + 10 per cent cent M F resin M F resin + 10 per

MSS4> cent MSS4>

Bas is we ight. g/ml 43 45 40 42 47 45 46 Thickness . 11m 80 84 77 76 7 1 72 75 Bulk, cm3/g 1.86 1.87 1.93 1.8 1 1.51 1.66 1.67 Burst index . kPam2/g 3.43 3 04 3 726 3. 138 2.255

Breaking length. m MD 3970 8014 6660 CD 2835 4864 3950

Average 4320 3260 4833 3650 2903 6439 5350

Tear index. mN m2/g MD 5.785 7.45 9.807 CD 6.276 8386 11.474

Average 7.747 7.159 7.3 55 657 6.080 7.94 18.05

DOllbl e fold . no 34 18 62 24 98 102

Brightness. per cent 8 1.2 83 .4 80.2 82.5 83.5 76 Dpy

Opacity. per cent 770 79.2 76.2 779 78.3 72

Water ke lmn. mm/4mi n MD II 7 6 CD 10 8 7

Ave rage 2 1 22 13 15 10.5 7.5 6.5

Air porosit y Gurl ey. sl lOO mL 8 8 42 36 76

Wet strength . g/cm MD 120 CD 85

Average 120 11 3 133 127 103

COP. second s TS 6 6 12 10 8 WS 5 5 10 7 18

Avera(.!c 5.5 5.5 II 8.5 13

Ash. per cent 2.0 4.5 2.0 3.9 5.3

4> MSS = Mi croni zed soap stone. MD = Machine directioll . CD = Cross direction. TS = Top side. WS = Wire side

In SCl 2. len per cent microni zed soapstonc of brightness 95 (JpV was added along with other non­fibrous (Jdditi ves as stated in se t I. However, all other propertics are rem(Jincd constant but breaking length drops sharpl y from 4320 to 3260 m. It is generall y observed that approximate ly 10-15 per cent of strength properti es of laboratory made hand-shcet reduces in paper machi ne operati on due to mi xing of broke and white water.

In another set the pulp was beaten to 45 °SR to enhance strength properti es . rn set 3, all non-fibrous (Jdditives except micronized soapstone in the similar proportions were added. A breaking length of 4833 m. tcar index 7.355 mNm2/g, double fold 62 numbers. water kelmn v(Jlues 13 mm/4min , COP Illl O sand wet strength 133 g/cm were obtained in the labora tory made hand-sheets.

lOS() J SC I IND RES VOL 61 DECEM BER 2002

In se t 4. ten per cent mi croni zed soa pstone al ong with other non-fi brous additi ves was added. However. a ll ot her strength properti es, like COP. wet strength and wate r ke lmn remained almos t constant but break in g lem;t h dec reases from -+833 to 36S0 (2-+ .5 per ce71t ) ~1I;d tear index 7.3SS to (1.57 II1N Ill2/g (a bout 107 per ce nt ).

T here is no I3IS stand ard for wax 1ll ~ lch ti ss ue pa per availa ble. Thercrore. paper co uld not be compared with the spec ifiGlti on stipul ated by the regul atory author it ies. In thi s situati on co mpari son ca n be made onl y with the res ult s of the 1e~l d in g wax match tiss ue pa per manufacturers. In the present stud y the bboratory mad e result s are compared with samples rro m dilTere nt mill s. The result s show the c lose prox imity with mill s m~lde wax match ti ss ue paper. In so me cases the laborat ory made paper is supe ri or 10 mill made wax match ti ss ue and fulfil the requirement s of end use rs.

Conclusions

I. A pulp blend ha ving 4(} per ce nl imported so ft wood fihre and 60 per ce nt mill pulp o f compos iti on o f pine. bamboo. and eucal yptus in the rati o I : 2.3 : II . beate n to -+5 tiSR. was found suita ble for wax ma tc h paper.

2. Ten per cent loading of soapstone to ge t 6 ± I per ce nt ash in pape r. 1.0 per cent melamine formaldehyde res lll. 0. 1 per ce nt tetra -kis­hydroxy l l11ethyl phosphonium chlorid e with bromoform- triall yl phosphate to slow dow n burning o f ves t sharI. 0. 1 per ce nt sodium hexa meta phosphate for uniform di stribu tion o f non­fibrous additi ves, and non-ferri c alu l11 to mai ntain pH 6.5 to enhance interlink with NlF resin with fibres was round suitable fo r "vax match ti ss ue paper.

3. Non- k rri c alum dosin g tu ge t 6.5 pH was added as a retenti on aid to entrap fil le rs and to enhance res in cross- linking without an y adverse crkct

-+. T he propert ies o f laborat ory made hand-sheet we re found to be excellent with those from machine made papers. In some cases . even supe ri or properties are obtai ned. T he reo ult s arc fo und ve ry promi sing.

References

Liekson J. ("(/11 IJo I 5(j.j() .j2. ScplcmhL'r :10. 1959

2 Rohcns() n J. liS Pm 2S-I25 10 .I uly 8. 1958.

:l Sanuholl.c r M vV. / \ 11/ /)\'('.1'1111/ N <,pl. .+~ ( t ) 195 9. :17-'+1 .

.+ T~lppi Tesling. Proccdun:s. "1".+6 1. 1972