NZ224250A

NZ224250A - Rosin emulsions and paper sizing compositions

Info

Publication number: NZ224250A
Application number: NZ224250A
Authority: NZ
Inventors: Ian Richard Hiskins; Robert John Britton; William Robert Bussell; Nicholas Stuart Morgan
Original assignee: Albright & Wilson
Priority date: 1987-05-08
Filing date: 1988-04-14
Publication date: 1990-12-21
Also published as: ATE85098T1; FI882073A0; AU1568388A; GB8710918D0; DE3877820D1; PT87284A; EP0292124B1; FI882073A; EP0292124A1; JPS63288297A; MX167998B; ZA882946B; ES2037221T3; DE3877820T2; AU611432B2; BR8802194A; PT87284B

Abstract

Aqueous rosin dispersion paper sizing compositions containing an ammonium salt or a precursor thereof, such as urea, a chemically-modified urea or a precursor of the latter.

Description

New Zealand Paient Spedficaiion for Paient Number £24250 r w f 22 42 5 0 Complete Specification Filed: Class: 2 I DEC 1990 Publication Date: P.O. Journal. No: 126??.

NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION ROSIN EMULSIONS rr,« -HWe, ALBRIGHT & WILSON LIMITED, a British Company, 210-222 Hagley Road West, Oldbury, Warley, West Midlands, iJby UNB> United Kingdom hereby declare the invention for whichHE-/ we pray that a patent rn^ji^^Nr be granted to-F»«-/us, and the method by which it is to be perforrraM, v • ( to be particularly described in and by the following statement:-^ tUAPRlWS - i - (followed by page la) .n >! I i % € '■"vv' 22 4 2 5 0 1a- This invention relates to paper sizing compositions, method for making such compositions, processes for sizing paper products using these compositions and products which have been sized with 5 the compositions. More particularly, this invention relates to aqueous paper sizing compositions, methods for their manufacture, processes for their use and sized products made by use of the compositions, the compositions being in the form of rosin dispersions. 10 Rosin comprises a complex mixture of cyclic terpene carboxylic acids and is relatively insoluble in water. In order to be usable in the form of aqueous sizing compositions, rosin must either be taken into solution (as a rosin soap) or dispersed as fine 15 droplets in water (as a rosin dispersion). Rosin soap solutions comprise systems in which the rosin acid functionality has been almost completely neutralised with a base, which enables the insoluble rosin acids to be taken into solution. In practice, the degree of 20 neutralisation employed is usually of the order of 90% of the available acidity, the unsaponified acid components remaining and any neutral components present in the rosin being held in the soap structure. Rosin dispersions comprise fine particles of rosin and also 25 include a stabiliser which acts to prevent destabilisation of the dispersion. The stabiliser is commonly a surface-active agent (which may be a soap, in particular a rosin soap, a protective colloid or a mixture of the two). Where a rosin soap is employed, 30 the dispersion may be formed by neutralising from about 1 % to about 10% of the total rosin acids present.

It has been now been found that rosin dispersions which have not been reported previously nor, it is believed, even formed can be made and are 35 very suitable for use as paper sizing compositions. 3? m m. ^'w' 'm m f r , s&4256 2 The ability of urea and various chemically-modified derivatives of urea to act as precursors for ammonia or ammonium salts or to serve as useful ingredients in conjunction with ammonia and ammonium 5 salts in rosin soap sizing compositions has been described in the art. For example, US-A-4022634 and US-A-4093779 describe sizing compositions comprising a /-s, rosin soap and a reaction product of urea with an acid selected from sulphamic acid, phosphoric acid, 10 trichloracetic acid, nitric acid, sulphuric acid, hydrochloric acid, stearic acid and acetic acid. US-A-4141750 describes similar compositions, in which urea has been reacted with a Lewis acid, such as paratoluene-sulphonic acid. US-A-4025354 describes 15 sizing compositions which comprise a rosin soap and a chemically-modified urea, the preferred form of which is the product obtained by reacting urea with sulphamic acid. US-A-4437894 describes sizing compositions which comprise a rosin soap and the product obtained by 20 reacting urea with formic acid. US-A-4605445 describes sizing compositions which comprise rosin, a soap and urea. 'w/ It has been discovered that the addition of urea or a chemically-modified urea or precursor thereof to 25 rosin dispersion sizing compositions is advantageous. In particular it has not only been found that the addition of these compounds is beneficial because they exhibit a degree of sizing activity when present in such dispersion sizing systems, but also because, 30 surprisingly, the dispersions are stabilised by their addition rather than being destabilised as might have been expected. According to one aspect of the invention, therefore, a paper sizing composition which comprises an aqueous rosin dispersion is provided and 35 is characterised in that it also contains urea-__or a -hhriptx**?**'*"" >$/ ■j?,, ^o'i & zz4250 % % 3 chemically-modified urea.

Rosin is a solid resinous material which occurs naturally in the oleoresin of pine trees. It is obtained from one of three main sources, namely the 5 oleoresin exudate of living pine trees, the oleoresin contained in the aged stumps of pine trees and from the tall oil produced as a by-product in the kraft paper industry. In addition to cyclic terpene carboxylic acids, rosin also includes a small amount of non-acidic 10 components.

A major constituent of rosin is abietic acid, which is a tricyclic doubly-unsaturated mono-carboxylic acid. Abietic acid undergoes Diels-Alder addition reactions with dienophiles. Rosin may therefore be 15 reacted with dienophilic carboxylic acids and their derivatives, such as maleic acid, maleic anhydride and fumaric acid, and so forms tetracyclic polycarboxylic acids. This reaction between rosin and dienophiles is commonly termed "fortification" and the reaction 20 product is commonly termed a "fortified" rosin. Fortified rosin dispersions are used as sizing compositions in the paper sizing industry. Rosin ijy dispersions according to the present invention may be based either upon rosin or a fortified rosin or a 25 mixture of the two. It is also possible to employ fortified rosins which have been treated with formaldehyde in order to enhance their stability. sw' Esterified or disproportionated rosins may also be used in the compositions of this invention. Esterified 30 rosins are rosins which have been reacted with an alcohol, preferably a polyol such as glycerol. Disproportionated rosins are rosins which have been treated by a catalytic process in order to improve their stability to oxidation. Mixtures of any of thes< types of rosin may be used in the compos^ V'V - 9 NOV J990 yj -x ' -1*^^,, 4 invention.

The preferred rosin for use in the composition of this invention are fortified rosins. The preferred i 1 fortified rosins are those wherein the rosin has been | | 5 reacted with an amount of a dienophile in the range ] j from 5% to 50% by weight and generally about 10% by | weight of the weight of the rosin. The most preferred i ) type of rosin is fortified tall oil rosin. | The rosin dispersions according to the | 10 invention preferably comprise from 2.5% to 8.0% by | weight of a soap, which is preferably a rosin acid | soap, based upon the total weight of solids in the | dispersion. The rosin acid soap may be prepared by I saponification of a rosin acid or a fortified rosin i | 15 acid with an organic or an inorganic base.

Alternatively, the soap may be formed in situ by the neutralisation of a part of the total acidity of the rosin, again using either an organic or an inorganic base. Preferably, such procedures involve the 20 neutralisation of an amount in the range from 1% to 10% and, more preferably from 3% to 6%, of the total , acidity of the rosin acids.

The rosin dispersions may be formulated using any of the conventional techniques and ingredients | 25 known in the art. In particular, the dispersions may comprise one or more stabilisers in addition to the s^) urea or chemically-modified urea. A variety of surface-active agents or emulsifiers may be used to stabilise the dispersions, either in admixture 30 with one another or with other known emulsifying agents or in conjunction with other known auxiliary stabilising agents. A preferred class of auxiliary stabilising agents are the protective colloids, such as casein, and compositions comprising rosin, urea or >*•* a chemically-modified urea, a stabiliser and v. .. r* ^ -ggi t, t s 1 w%4 a protective colloid form a preferred aspect of this invention.

Anionic, nonionic, cationic or amphoteric surfactants may be utilised as stabilisers in the 5 dispersions of this invention. In general, anionic or nonionic surfactants are preferred.

Examples of surface-active agents or surfactants which find use in the compositions of this invention include: (i) salt of sulphonic acids having the general formula: (R» ) _ - 0(C H O) -CH CH.CH SO M m ffx^r 2 4 n 2| 2 3 22 4 2 5 0 where R1 represents a hydrocarbon residue having from 4-18 carbon atoms, m is an integer having a value of 1 or 2, n is an integer having a value of 4 to 25, X represents a hydrogen atom or a .hydroxyl group and M 20 represents a monovalent cation; (ii) salts of sulphuric acid half esters having the general formula: - A - (TT) - 0(C2H40)pS03Q ' wherein r2 represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, A represents a straight-chain or branch-chain alkylene group having 2 or 3 carbon atoms, p is an integer having a value of 30 from 4 to 25 and Q is a monovalent cation, including all such compounds described in US-A-4309388; (iii) alkyl-benzene sulphonates wherein the alkyl substituent comprises from 8 to 24 carbon atoms, including all such compounds described in US-A-4157982; (iv) sulphosuccinate half esters of fortified ^^•'r^A m Z1- M 5 0 rosin having the formula: 0 (— II -j H(3-M)-R' p2CH20)n-C-C2H3S03Na.C00Na)m; wherein R is a fortified rosin acid tricarboxylate group, m has an average value of from 1.5 to 3 and n has an average value from 4.5 to 25, including all such compounds described in EP-A-159794; (v) compounds having one or other of the formulae: 0(CH2CH20)nS03 M+ and j~Rl-0(CH2CH20)nS0^j M+ wherein R represents an alkyl.group containing from 4 to 18 carbon atoms, R' represents an alkyl or alkenyl group containing from 4 to 18 carbon atoms and n is an integer having a value from 4 to 25, including all those described in US-A-4199367; (vi) sulphosuccinate salts of ethylene oxide condensates having the general formula: ? 0 1 o (ch2ch2o) nc-<j:H. ch2co .m+ so. wherein R represents an alkyl group containing from 4 30 to 18 carbon atoms and n is an integer having a value of from 4 to 25, including all those compounds described in US-A-4203776. (vii) organic phosphate esters having one or other of the general formulae: ft 3 O . - - ** O dr zm250 r^ R.O.(CH-.CK.-O) 0 2 2 n\=X and ox ^ox R.O.tCH-.CH-.O) ,o n -v \ ? n V R.o.(C3-C3-0) -» n ox 0 ''O and mixtures thereof, wherein R represents an alkyl, alkyl-phenol, alkenyl or alkaryl group containing form 5 to 20 carbon atoms, n has a value of from 5 to 20 and X represents a monovalent inorganic or organic cation or hydrogen.

Cationic resin dispersant systems may also be used to stabilise the rosin dispersions of this invention. Examples of suitable materials include water-soluble polyaminopolyamide/epichlorohydrin resins, water-soluble alkylene-polyamine/epichlorohydrin resins and poly(dially1-amine)/ephichlorohydrin resins.

Examples of chemically-modified urea compounds which are especially useful in the compositions of this invention include thiourea, biuret, melamine, water—soluble urea/formaldehyde and melamine/formaldehyde resins and acid and Lewis acid derivatives of urea, especially those reaction products obtained by reacting urea with an acid selected from sulphamic acid? phosphoric acid, 'v : V /v \ •* ./\ m9mrn^} ■a * ...w-^^m*''^'.®.'.'^-.-- ,.„,A^v-"'."-.„i m4250 A J 8 3 | trichloroacetic acid, nitric acid, sulphuric acid, "6 | hydrochloric acid, stearic acid and acetic acid, as I described in US-A-4022634 and US-A - 4 0 9 3 7 7 9 , the reaction products of urea with a Lewis acid, such as a 5 p-toluene sulphonic acid, as described in US-A-41 41 750, the reaction products of urea and sulphamic acid, as described in US-A-4025354 and the products obtained by ^ the reaction of urea and formic acid, as described in ~ US-A-4437894.

The preferred chemically-modified urea compounds for use in the compositions of the present invention are the products obtained by the reaction of urea with sulphamic acid, including all those products which are described in US-A-4025354. These modified 15 ureas may be produced by combining urea with sulphamic acid and water. Ideally, the parts by weight of water i ; equal the parts by weight of urea plus sulphamic acid, N although the urea may be treated with the sulphamic acid in conjunction with more water or with little or 20 no water. The urea-sulphamic acid solution may be | heated to a temperature which causes a change in the pH, for example a rise in the pH at least to about 7.5.

When little or no water is used, the temperature affecting the pH may be higher. In one 25 preferred embodiment, however, a 50% water-50% urea/sulphamic acid solution is used, and it has been found that a temperature of about 212° to 235°F, (100°-113°C) preferably about 215° to 23 0°F, increases the pH at least up to 7.9. Generally, the solution boils at the temperature which changes the pH and heating should be continued until after boiling has stopped in order to effect an irreversible pH change. Although the pH range is an important measurement of reaction completion, a more important'- consideration is 35 the acidity of the first stage product ipe-a^sured asj •'Tn m r~\ O aw: 9 parts of water (ppm). When the sulphamic acid is heated with the urea, undetermined reactions occur which not only raise the pH to a basic value, but also effect the acidity of the solution. The desired minimum acidity is at least 1/000 ppm, with a preferred minimum of 4,300 ppm. The actual amount of sulphamic acid most desirably employed is probably at least 0.1% by weight of the urea, with preferred amounts ranging from 0.2% to 8.0%, by weight. The maximum amount of sulphamic acid needed is generally 15% or, at most, 20% by weight of the urea, to achieve the desired results. It has been found that 5% sulphamic acid produces an acidity of about 86,000 ppm with a pH in the range from 7.9 to 8.3, when processed in a 50% water/50% urea plus sulphamic acid solution. Accordingly, sulphamic acid at 0.25% by weight of urea produces a first stage product with an acidity of 4,300 ppm. As indicated, the amount of sulphamic acid added to the solution is not as important as its resulting acidity in defining the first stage product of the size compositions of this embodiment. (3 The proportion of urea or chemically-modified urea to rosin or fortified rosin is desirably in the range from % to 60% and preferably from 10% to 35% by weight.

The dispersions of the invention will normally be formulated as relatively concentrated compositions, which are either diluted prior to their use in a sizing process or can be added in a concentrated form depending upon the conditions. In general, the dispersions advantageously comprise concentrates which contain from 20% to 60% and more desirably and usually from 3 0% to 50% by weight of the combined weight of the rosin and the urea or chemically-modified ur^S- —_ tv! «• / / >• v \ /-/ ; | II 4 / V a I -S % m 22 4 2 50 1 10 i The compositions of the invention may be | employed as internal sizes or as surface sizes. Their ' ^ use as an internal size forms a preferred aspect of the present invention. Internal sizing processes comprise 5 the dilution of the concentrated composition with water and the addition of the diluted composition to a pulp suspension. A flocculant such as, preferably, ^ papermakers alum, aluminium sulphate or polyaluminium chloride may be added to the pulp suspension prior to, j 10 simultaneously with or subsequent to the size ; composition. The amount of size composition employed is generally in the range from 0.1% to 5.0% by weight | of solids based on the weight of fibres in the pulp I slurry. The compositions of the present invention may 15 be prepared using the phase inversion process.

The rosin, preferably a fortified rosin, optionally treated with paraformaldehyde in the presence of paratoluene-sulphonic acid to inhibit crystallisation, and optionally one which has been at 20 least partially saponified with concentrated sodium or potassium hydroxide or with a volatile base such as ammonia, may be melted and the stabilising agent or w' mixture of stabilising agents may then be added as a concentrated (e.g. 50% by weight solids) aqueous 25 solution. Sufficient water is stirred in to form a creamy water-in-oil emulsion (e.g. 20% to 40% based on the weight of rosin). On dilution with water, the emulsion inverts to provide a stable oil-in-water emulsion, typically having a solids content in the 30 range from 20% by weight up to the maximum achievable oil-in-water concentration (often about 80% by weight solids) and preferably from 30% to 50% by weight solids. The rosin content of the emulsion or dispersion usually includes at least 90% of 35 unsaponified rosin acids. The emulsions may then be 1 1 blended with an aqueous solution of the urea or chemically-modified urea or precursor thereof.

The emulsions may be used for sizing paper, including alumed paper. The emulsions may contain at 5 least one biocide, such as bactericides, slimicides and/or fungicides, and/or diluents, such as wax.

The invention is illustrated by the following non-limitative Examples: Example 1 grm Tall oil rosin treated with fumaric acid 350 Caustic potash 3.5 Casein 17 Sodium tetraborate 4 1 5 The fortified rosin at 160OC was cooled to 100°C and the caustic potash was added in a minimum of water. A concentrated solution of the casein and borax was added and the mass immediately inverted. This was mixed for 5 minutes and diluted with water to a solids content of 50% by weight.

The final product was mixed with modified urea solution prepared by heating a solution of urea and sulphamic acid to its boiling point and cooling the product.

The rosin emulsion and modified urea solution were mixed in such a proportion that 25% of fortified rosin had been replaced by the modified urea.

Example 2 Laboratory hand sheets were prepared from bleached sulphite pulp beaten to a Schopper-Reigler value of 40 at 2% consistency. The pulp was treated with known quantities of the preferred size or a known industry standard dispersion size (ROSCQL A & W LTD.) and a standard level of aluminium sulphate, the pH was m 11 k 2 5 ( 3 12 adjusted to 4.9-5.0 arid sheets were made on a standard sheet former, pressed and dried by passing around a photographic drier set at 100°C.

After conditioning overnight, the sheets were 5 tested for sizing by the Cobb test. As the figures for Cobb value are grams of water picked up per square metre of sheet under the test conditions, a lower value represents improved sizing. The following results were obtained: % sizing agent, as received, on dry fibre content 1 min Cobb (grms) Standard Example 1 1.15 45.5 .0 1 .50 34.1 31 .7 2.00 27 .5 23.8 2.60 23.5 21 .8 The extended product shows an improved sizing 20 performance although the level of active content (rosin) is lower than the standard.

Example 3 Stability of the rosin dispersions was tested by an accelerated sedimentation test, which subjects 25 the product to high gravitational force for a set time and measures the extent of deposition. This is a test which has long been used and correlates well with storage under normal conditions. The extent of sedimentation reflects the extent of deposition likely 30 to occur if the emulsion is stored normally for three months. 11 4 2 5 0 Accelerated Sedimentation Standard Dispersion Size 0.5% Product of Example 1 0.3% Modified Standard Dispersion Size of larger particle size (Emulsion A) 4.0% Emulsion A blended with a modified urea of Example 1 1.8% "w1 \ \ I m 224250 14 0 O NEV PA" : s2

Claims

WHAT WE CLAIM IS:

1 . A paper sizing composition comprising an aqueous rosin dispersion, characterised in that the composition also contains urea or a chemically modified 5 urea.

2. A composition according to claim 1, wherein the dispersion comprises rosin, fortified rosins, formaldehyde-treated rosins, esterified rosins, disproportionated rosins or mixtures thereof. 10

3. A composition according to claim 2, wherein the dispersion comprises a fortified rosin in which the rosin has been reacted with an amount of dienophile in the range from 5% to 50% by weight of the weight of the rosin. 15

4. A composition according to claim 2 or 3, wherein the dispersion comprises fortified tall oil rosin or gum rosin.

5. A composition according to claim 2 or 3, wherein one or more stabilisers selected from soaps, 20 surface-active agents, emulsifiers and protective colloids is/are included.

6. A composition according to claim 5, wherein an amount in the range from 2.5% to 8.0% by weight of a rosin acid soap or other soap, based upon 25 the total weight of solids in the dispersion, is present.

7. A composition according to claim 6, wherein the soap is a rosin acid soap and is formed in situ by the neutralization of a part of the total 30 activity of the rosin acids.

8. A composition according to claim 7, wherein the rosin acid soap is formed by neutralizing 1% to 10% of the total acidity of the rosin acids.

9. A composition according to any of claims 5 35 to 8, wherein casein is included as a stabiliser. si'i-. v ess?- 224250 15

10. A composition according to any of the claims 5 to 9, wherein one or more stabilisers selected from anionic, nonionic, cationic and amphoteric surfactants is/are included. 5

11. A composition according to any preceding claim, including, as chemically modified urea, at least one of thiourea, biuret, melamine, water-soluble urea/formaldehyde and melamine/formaldehyde resins and urea derivatives obtained by reacting urea with acids 10 and Lewis acids.

12. A composition according to claim 11, which includes the reaction product of urea and sulphamic acid, with or without water.

13. A composition according to claim 12, 15 wherein the reaction product is made by heating urea and sulphamic acid to a temperature at which a change in pH occurs.

14. A composition according to any preceding claim, wherein the amount of urea or chemically 20 modified urea in the aqueous dispersion is in the range from 5% to 60% by weight of the amount of rosin.

15. A composition according to claim 14, wherein the amount is in the range from 10% to 35% by weight. 25

16. A composition according to any preceding claim, which is in the form of a concentrate suitable for dilution prior to use and containing 20% to 60% by weight of the rosin and the urea or chemically modified urea combined. 30

17. A composition according to claim 17, which contains 30% to 50% by weight of the rosin and the urea or chemically modified urea.

18. A composition according to any preceding claim, wherein at least one bactericide, slimicide, 35 fungicide or other biocide and/or at least one wax or

~,W\ li 224250 1

I

I •$*';I;1;o;O;NEW ZEALAND PATENT OFFICE;-2 NOV 1990;RECEIVES;i;16;other diluent is included.;19. A method of making a paper sizing composition which comprises an aqueous dispersion of rosin made by melting the rosin, adding at least one;5 stabiliser, agitating the mixture in the presence of an amount of water suitable for the formation of a water-in-oil emulsion, diluting the emulsion with water to cause it to invert to a stable oil-in-water dispersion, and blending the dispersion with urea or a chemically;10 modified urea or precursor thereof.;20. A method according to claim 19, wherein the dispersion contains a rosin fortified by reaction with a dienophile, the dienophile being present in an amount in the range from 5% to 50% by weight of the;15 weight of the rosin.;21. A method according to claim 20, wherein the dispersion is made from rosin which has been reacted with an amount of dienophile of about 10% by weight of the rosin.;20

22. A method according to any of claims 19 to;21, wherein an amount in the range from 2.5% to 8.0% by weight of a rosin acid or other soap, based upon the total weight of solids in the dispersion, is present.;

23. A method according to claim 22, wherein;25 the soap is a rosin acid soap and is formed in situ by the neutralization of a part of the total activity of the rosin acids.;

24. A method according to claim 23, wherein the rosin soap is formed by neutralizing from 3% to 6%;30 of the total acidity of the rosin acids.;

25. A method according to any of claims 19 to 24, wherein a chemically modified urea is blended with the dispersion, the chemically modified urea or precursor comprising at least one of thiourea, biuret,;35 melamine, water-soluble urea/formaldehyde and;m;224250;17;melamine/formaldehyde resins and urea derivatives obtained by reacting urea with acids and Lewis acids.;

26. A method according to any of claims 19 to 25, wherein the chemically modified urea comprises the;5 reaction product of urea and sulphamic acid.;

27. A method according to claim 26, wherein the reaction product is made by heating urea and sulphamic acid to a temperature at which a change in pH occurs.;10

28. A method according to claim 27, wherein a;50% water-50% urea/sulphamic acid solution is heated to a temperature in the range from 1 OO^C to 113°C {212° to 235°F) for a time sufficient to cause an increase in pH at least to 7.9.;15

29. A method according to claim 28, wherein the heating is carried out so that the solution boils and is continued until boiling stops and a pH change is thereby effected.;

30. A method according to claim 28 or 29, 20 wherein the reaction is carried out for a time sufficient to reduce the acidity of the first stage product obtained to not less than 1,000 ppm.;

31. A method according to any of claims 19 to 30, wherein the amount of urea or chemically modified;25 urea in the aqueous dispersion is in the range from 5% to 60% by weight of the amount of rosin.;

32. A composition substantially as hereinbefore described in Example 1.;

33. A method of making a paper-sizing 30 composition, the method being substantially as hereinbefore described in Example 1 .;

34. A process for the manufacture of a sized paper product, wherein a paper sizing composition is added to a pulp suspension, if required after dilution;35 with water, a flocculant is added to the pulp;NEW ZEALAND PATENT OFFICE;« 2 NOV 1990;\,y^ RECEIVED ~;j*>- SK5 224250 r\ 18 suspension before, during or after addition of the sizing composition and a paper product is made therefrom, wherein the paper sizing composition is a composition as defined in any of claims 1 to 18 and 32 5 or made by a method according to any of claims 19 to 31 and 3 3.

35. A process according to claim 34, wherein the sizing composition is employed in the range from 0.1% to 5.0% by weight of solids based upon the weight 10 of fibres in the pulp.

36. A process for the manufacture of a sized paper product, wherein a paper sizing composition is employed as a surface size, the paper sizing composition is a composition being as defined in any of 15 claims 1 to 18 and 32 or made by a method according to any of claims 19 to 31 and 33.

37. A paper product, when made by a process according to any of claims 34 to 36. o - 2/ cf-q / \ AS-l'i I - - VJ . i ktent omce ; i s2n0vtm /