CA1069410A

CA1069410A - Emulsified lipophilic paper sizing

Info

Publication number: CA1069410A
Application number: CA236,531A
Authority: CA
Inventors: Claris D. Roth; Charles S. Nevin
Original assignee: Tate and Lyle Ingredients Americas LLC
Current assignee: Primary Products Ingredients Americas LLC
Priority date: 1974-11-04
Filing date: 1975-09-26
Publication date: 1980-01-08

Abstract

ABSTRACT OF THE DISCLOSURE

Aqueous emulsions containing lipophilic sizing agents, are used for sizing paper. Volatile nitrogen containing bases, such as ammonium hydroxide and tertiary amines, are used as emul-sifying agents to aid in forming aqueous emulsions of lipophilic sizing agents. Preferred lipophilic sizing agents are hetero-cyclic organic compounds which are formed by the reaction of a dicarboxylic acid anhydride and a long chain hydrocarbon.

Description

The present invenkion relates generally to sizing agent emulsions and to a process for the sizing of paper.
More particularly, the present invention relates to novel emulsifying agents for preparing emulsions of sizing agents and fox use of the emul~ions in the sizing of paper and paper-board products and to the improved paper prepar~d there~rom.
As used herein, the terms "paper~' and "paperboard"
refer to sheet-like materials and molded product~ made from ~ibrous cell~llosic materials and which may co~ain minor amounts of synthetic fiber~ such as polyamide, polye~ter and polyacrylic resin fibers, a~ well as mineral fibers such as asbestos and glass .
It is well known to incorporate sizing materials into paper and paperboard products for the purpose o~ increasing ~heir resistance to penetration by liquids, particularly water. Un-sized paper more readily absorbs liquids.
Rosin, variou~ hydrocarbon and natural waxes, ~tarchss, ~o~ium silicate, glues, casei}l, syIlthetic resin~, rubbQr ~atex, ~..~, .
fatty ketenes, and substituted cyclic dicarboxylic anhydrides

2 0 are among ~he ma~erials which have been used or have beel~ sug-gested for use as sizing agents. The sizing agents may be added direc:tly to the aqueous paper stock in a beater, or the formed paper sheet may be run through a size solution or over a roll we ted with a sizing agent. The process of siZing by ~he addition of a si~ing agent to the paper fiber in a beater is referred to as "~n~ernal sizing". The process of sizing wherein a iEormed pa~e~ she2t is cont~cted with a sizing solution is referred to as "external sizing". The siZing agent emul~ions o~ the present invention are us~f~l in both internal sizing and external sizing -. 30 proce~ses.
Ma~y of th~ sizing agents here~ofore used, have been diff~cult to emulsify and require large capikal inve~tment cost . ' ." ,, .
2 ~ ~ .

to provide equipment adequate to effect proper emulsification of the sizing agent. Emulsification is desirable for sizing agents so that the sizing agent is uniformly dispersed throughout the furnish in an internal sizing operation. It is desirable that the sizing agent be uniformly dispersed throughout th~
furnish in a~ small a par~icle size as is possible.
Accordingly, it is the principal object of the present inventian to provide an emulsifyi~g agent for use with sizing agen~s. It is another ob~ect o~ the present invention to pxovide sizing agent emulsions whose use results in the preparation of paper and paperboard products which are characterized by i~creased re~istance to penetration by liquids, particularly watex7 A further object o~ the present in~ention is to provide emulsifying agents for use in prepari~g emulsions of sizing agents which emulsions may be employed with all types of paper pulp oYer the complete range of pH conditions wh~h are normally encountered in paper manufacturing~ A still further ob~ect of :- the present invention is to provide emulsifying agents which are compatible with various sizing agents and with alum and with various other components, such as fillers, pigments and other chemicals which may ~e added to paper.
These and sther objects o the present invention will become more apparent from the ~ollowin~ detailed description.
Generally, the emul~ifying agents of the invention for use in preparing emulsions of sizing agents are sele~ted from the gxoup consisting of trialkyl amines wherein:the alkyl moiety is methyl or ethyl and ammonium hydroxide. Particularly :
preferrad amines for use as emulsifying agents are trimethyl ~:
amine~ trie~hyl amine and mixtures thereof.
The emulsifyi~g agents of the invention may be used to form aqueous emulsions of sizin~ agents. Preferably the aqueous emulsions herein are romprised of heterocyclic, organic

- 3 -si2ing agents which have at least one long hydrocarbon chain of about 8 to 30 c~rbon atoms attached thereto with the heterocyclic s~ructure of said sizing agent containing an oxy group bridging two carbon atoms wherein both the carbon atoms which are attached to the oxy group contain a divalent bond, i~e,, the group = ~ =. Suitable heterocyclic organic sizing agents include maleated ~riglycerides, maleated alpha=rolefins, maleated fatty acid ester~, alkyl ketene dimers, mixtures thex~of and the like.
The emulsifying agents are pa~ticularly useful to orm aque~us emulsions of sizing agents which comprise the reaction product o~ maleic anhydride a~d an unsaturated tri-~lyceride oil wherein the triglyceride oil has an iodine value of at least ~bout 50. Thus, the triglyceride oil may be par-tially hardened. By the term "triglyceride oil" is meant the triester Q~ glycerol and the same or mixed fatty acids.
Fatty acids reer to straight chain monocarboxylic acids having a carbon chain length of from C8 to C30.
5pecific examples of such preferred sizing agents include the condensation reaction product o~ maleic anhydride with soy bean oil, cottonseed oil, corn oil, safflower oil, fish oil, linseed oil, peanut oil, oi~icica oil, dehydrated castor oil, hempseed oil, and mixture thereo~. A particularly preferred sizing agent is obtained from the reaction product of maleic anhydride and soy bean oil. Various aspects of ~he present invention will be hereinafter described wi~h particular reference to the preparation of aqueous emulsions of the reaction product of maleic anhydride and soy bean oil.
~owever, it should be understood that the emulsi~ying agents of he invention are suitable for pse with the reaction pro-duct of maleic anhydxide with o~her triglyceridas oils and with other organic heterocyclic sizing agents. : -: ~. . , .. ,, , . :

Although the emulsion~ may be u~ed as an external sizing agent ~e.g., applied ~o wet or dry formed paper webs~, they are particularly useful as an internal sizing agent.
Internal sizing is best achieved by uniformly dispersing the si~i~g agent throughout the fiber furnish. Disper~al of the sizing agent throughout the furnish is prefercibly attain~d by adding the sizing age~t as an emulsion.
In pr~paring emulsions of the sizing agent, the emul-sifying agent is preferably first dispersed in the sizing agent and the sizing agent is then added to the water with agitation.
The sizing agent is generally present in the emulsion at a level of from about 1 to about 20 percent by weight. The trialkyl amine emulsifying agent is used at a level of from about .5 to a~out 2.5 percent, preferably from about 1 to about 2 percent, by weight of the sizlng agent. The ammonium hydroxide is used at a level of from about .05 to about 1 percent by weigh~ (on , . .
an ammonia bas~s) by weight of ~he sizing agent. The ammonium :-hydroxide is preferably used at a level of from about .1 to ~-about .6 percent by weight of the ~izing agentO . ~ .
It is a surprising result of the use o~ the trialkyl amine and ammonium hydroxide emulsifying agents of the invention, that sizing agent emu}sions can be prepared with lessened amounts - ; .
and intensity of agitation. High shear agitation conditions are ~ :
not required. Stable emulsions can be formed using low shear mixing co~ditioDs. As used herein ~he term l-low shear mixing conditions" refers to the use of low shear mixing apparatus, such as a pxopellor mixer, operated at moderate speeds of less .~ :
than about 1,500 x.p.m. This is a significant benefit of the use of the emulsifying agents of the invention~ since sizing agent emulsion can be prepared with simple equipment and high capital costs are avoidedA

The sizing agent emulsions o~ the pre~ent invention may be used in combination with a cativnic agent. Cationic agents refer to materials which are capable of ionizing or dis~ciating in such a manner as o produce one or more cations or other positively charged moieties~ Suitable cationic agents are alum, long chain fatty amines, sodium aluminate, aluminum chloride, cationic s~arch derivative~, polyacryl ami<le, chromic sulfate, and polyamide polymers. The cationic agent may be added ~o the furnish prior ~o, at the same time a9, or after the addition of the sizing aqent emulsio~. It is preferred that the cationic agent be added either subsequent to ar in direct combination with the sizing agent emulsion. However, the addition to the paper stsck of ei~her the cationic agent or the sizing agent emulsion may take place at any point in the papermaking process prior to forming the wet pulp into a dry sheet. ~ :
The sizing agent emulsions of the invention may be used for sizing of paper prep~red from all type~ of cellulosic pulps. The cellulosic pulps which are con~empl~ted or use include bleached and unbleached sulfite pulps, bleached and un- ~;
bleached soda pulp5, bleached and unbleached sulfate pulp~
neutral sulfite pulp, semi-chemical pulp, chemi-ground~wood pulp, ground wood pulp, a~d any combination of these pulps.
The cellulose pulp may contain minor amounts of synthetic fibers :~:
of the polyamide, polyester, polyacrylic, viscous rayon and ~ -regenerated cellulose types~ : :
The sizing agen~ emulsions of the present inventio~
are compatible wi~h all types of pigments and fillers which are normally used or added to the paper which is to be sized.
Such materials include titanium dioxide, ealcium carbonate9 clay, ~alc, calcium culfa~ei diatomaceous earths and the ca~
ionic agents previou~ly described.

: - 6 -The sizing agent emulsions of the invention are used at levels sufficient to provide from abo~t ~1 to about 5 parts by weight o~ the sizing agent per 100 p~rts by weight of the cellulose pulp, dry solids basis . Pref~rably, from about O . 5 to about 1. 5 parts by weight of the sizing agent pt-r 100 parts by weight of pulp are used. The amount of sizing agent to ,be used depends upon the type of pulp which is being sized and the specific properties desired in the finished paper or paper product. Paper which requires yood water resistance or ink 10 resistance requires the use of higher concentrations of sizing agent than does paper which is used where relatively low water resistance or ink resi~tance is required. In general, from about 1 to about 15 parts by weight of a cati~nic agent are used per S parts by weight of sizing agent.
In prepari~g maleic anhydride reaction product siæing :~
agent~, the txiylyceride oil, wh~ch may be partially hardened but which ha~ an iodine value of more ~han 50, is first heated to a temperature in the range of from about ~00F to about ~50F.
Thereafter, the maleic anhydride is added to ~he triglyceride -~.
2a oil while the triglyceride oil is ~eing agitated to efect a ::
condensation reaction~ ~he maleic anhydride is maintained in contact with ~he triglyceride oil at the elevated temperature for a time of from about 2U minutes to about 40 minutes as the triglyceride oil is bei~g agitated. Thereafter, the reaction mixture is pe~mitted to cool ~o ambisnt temperature to provide the s~zing agent. Oxygen and water should be excluded from the reactio~ mixture during ~he reaction. For this reason, it is preerred to blanket the surface of the triglyceride oil with : an inert gas during the reactio~ or to conduct the reaction in 3Q a vacuumO
In gen~ral9 the maleic anhydride is added to the tri~
glycPride ~il at a levPl o~ from about 0.9 to about 2 mols per - - - . . . - . - . - - - , . . -- . . . - , . . , , ~ . .. . .-mol o~ triglycPride oil. At levels of addition of maleic anhy-dride less than the above range the resultant reackion mixture is less effective for use as a sizing agent. Higher levels of addition of maleic anhydride than the above identified range can be u~ed but there is no advantage to the use of such higher level~
and the resultant cost of the sizing agent is increased.
The ef~iciency o the maleated oil siæing agents is directly related to the retention of the maleic anhydride moieties in the non-hydrolyzed form. For this reason, it is ::
preferred that emulsions of the sizing agent have a pH of between about 5 to about 8.5. At higher or lower pH, the maleic anhy-dride moieties ~end to hydrolyze.
. The following example further illustrates various features of the presen~ invention, but is intended to in no way limit the scope of the invention wh~ch is defined in the appended claims.
EXAMPLE I
A sizing agent emulsio~ in accoxdance with the present - :
invention ? S prepared, and is used to effect sizing of a paper product. The siæing agent emulsion is used i~ combination with alum as a cationic agen~ and the water resistance of paper re- :
sulting from the use of the sizing agent is determined.
- 880 kgs of pure soy bean oil having an iodine value - of about 125 is charged into a covered reactor. The head ~pace in the reactor is blanketed with nitrogenO The soy bean oil i~
heated to a temperature of 430~F. Thereafter~ maleic anhydride is dded to the soy bean oil in th% reactor as the soy bean oil is being agitated. The maleic anhydride is added at a level of 1~25 mols of maleic an~ydride p~r mol of soy bean oil~ The reaction mixture after the last addition of maleic anhydride is maint~ined at a temperature of 430F for 30 minutes. There-after, the reaction mixture is allowed to covl to provide a maleated oil sizing agent.

EXAMPLE II
Various paper samples, as set forth in Table I below were prepar~d using a sizing agent emulsion prepared with the emulsifying agents of ~he invention. In each sample, except one, the emulsi~ying agent is added to a maleated soy bean oil sizing agent prepared in accordance with the foregoing. In the case of sample 8? ~he sizing agent consistad of maleated linseed oil pre-pared in accordance with the foregoing procedure for preparing maleated soy bean oil~ In examples 1-7~ the sizing agent is malea~ed soy bean oil having a molar ratio of maleic anhydride to soy bean oil as set forth bel~w in Table I. Fox each sample, an emulsifying agent of the invelltion is added to the maleated oil sizing agent. The sizing agent containing the emulsifying agent is then added to water as the water is a~itated by a pro-peller mixer to provide an aqueous emulsion of the sizing agent.
The sizing agent is added to the water at a level sufficient to provide an emulsion having 5 percent by weight of the sizing :
agentl ., The aqueous emulsion of th~ sizing ag~nt is then added to a furnish of bleached sulfit~ pulp having a pH of about 6 . 5 . . .
Alum and a quaternary amine starch derivative are previ~usly added to ~he pulp. For all of the samples, except sample 1, the alum and the quaternary amine starch deriva~ive are each present in the furnish at a ratio on a weight basis to the si2ing agent of 1:1. In sample 1, alum is present at a ratio of 1.5:1 and the quaternary amine starch is present at a ratio ;:
of 1:1. The sizing agent is added o the furnish at a level sufficient to provide .5 percent by wei~ht of the sizing agent in the furnish based on ~he dry weight of the pulp.
~ Hand sheets are formed and dried in accordance with TAPPI standards. The water resistance of the hand sheets is .
determined by the KBB test. In this test, the dried hand sheet :~
is placed on an imperfora~e platen having an electrical lead connected thereto. A second porous pla~en, also having an electrical lead connectea thereto, is saturated with moisture and placed in contact with the hand sh~et on the first platenO
The time required to establish a current of 80 milliamps betwe~n the second platen and the first platen is measured. This time period in seconds is a mea~uxe o the ef~ective~ess of the sizing of the paper; tha~ is, the longer the time required to establish an 80 milliamp current, the better ~h~ water x~sistivity o~ the paper. :
The oll~wing Table I sets foxth data on the various hand sheets in respect to the ratio of maleic anhydride to tri-glyceride oil, the emulsifying agent used, the level of the emul- :
sifying agent and ~he filler used, if any. In each case where a filler is us~d, the clay ~iller is used at a level of 10 percent by weight of th~ fiber, dry basis, and titanium dioxid~ is used at a le~el of S percent by weiqht of ~he fiber, dry ba~is.

TABLE I

Le~el of emulsify-Ratio o~ ing agent maleic - percent : anhydride by weight : to tri- based on KBB t~st value - seconds : glyc~ride the weight 1 day - S~mple oil (mols~ Emulsify- of ~he siz- Filler i~mediately after No. mol) ing agen~ ng agent ty~ af~er drying dryin~

1 1.25 NH40H .33 Clay 50 45 (as NH3) and 2 1.25 NH40~ .08 None 32 35 ( 3 3 1025Tri~ethyl- 055 None 53 57 1.25 " 1.0 None 58 56 1,25Triethyl- 1.0 Clay 66 61 amine 6 0~5 " 1.0 Cl~y 13 30 :.
7 1.5 " 1.75 Clay 3~ 39 8 1.25 " 1~0 Clay 44 50 -- 10 ~

EX~LE III
190 ml. o:E 110F tap water, 10.0 g. of alkenyl ~uc:cinic anhydride and Q.3 g. of trie~lyl amine were added to a house-hold-type blender. An emulsion was fo~med by op~rating the blender for 1 minute. In a simular manner an amulsion of alkyl ketene dimer was prepared. Both of ~he aqueous emulsions were stable and were used to prepare hand sheets.
EX~MPLE IV
A sizing agent emulsion was prepared using a laboratory wat~r aspirator attached to a water line provided with water at 60 psig pressure. A water flow rate of 18,000 ml./minO was maintained through the aspira~or~ A malea~ed soy bean oil pre- -pared in accordance with Example I was fed throu~h the side arm of the aspirator. The maleated soy bean oil contained 1~75 per-cent trie~hyl amine dissolved ~h~rein, A stable emulsion of the maleated soy bean oil was provided by the mixing action attained by ~eeding the maleated soy ~ean oil through the side arm of the aspirator into the stream of water flo~ing through the aspirator. Sufficient maleated soy bean oil was fed to the 2Q side arm of th~ aspirator to provide an aqueous emulsion having ~ ;
1.5 percent by w~ight of maleated so~ bean oil.
The resultan emulsion was uniformly dispersed in a paper fur~ish containing paper maker`'s alum and cationic starch in accordance wi~h the method described in Example II. Hand sheets were made with the emulsion used as an internal sizing ag~nt. -~ :
The level of sizing agent used, level of alum uxed, cationic starch level, KBB sizing value ~or the hand sh~ets produced in accordance with Examples III and IV get forth belo~ :~
in Table II.

TABLE I I

Cationic Handsheets Sizing Agent A.lum Starch XBB
made by ~/ton (dry #/ton #/ton Sizing-Example basis~ (dry basis~ (dry basis) ~ Sec.
III lo~O 10 10 6.5 91 IV 8.8 10 lû 6.5 72 The amulsifying agents of the present inven~ion are highly effective to provide emul~ions of sizing agents, particular-ly malea~ed oil size agents, by simple low shear mixing. The emulsifying agent of the invention provides ~he paper manufac~urer with an easy and effective means, requiring little capital cost, to prepar~ sizlng ag~nt emulsions and to utilize the sizing agent emulsions in the sizing of paper.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method for providing an emulsion of a sizing agent comprising the steps of adding an emulsifying agent selected from the group consisting of a trialkyl amine at a level of from about 0.5 to about 2.5 percent by weight of said sizing agent and ammonium hydroxide at a level of about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent and a sizing agent at a level of from about 1 to about 20 percent of the total emulsion weight to water to provide a mixture, and agitating said mixture to provide an emulsion.

2. A method in accordance with claim 1 wherein said emulsifying agent is a trialkyl amine selected from the group consisting of trimethyl amine and triethyl amine.

3. A method in accordance with claim 1 wherein said emulsifying agent is ammonium hydroxide.

4. A method in accordance with claim 1, 2 or 3 wherein said sizing agent is selected from the group consisting of maleated triglycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers.

5. A method in accordance with claim 1, 2 or 3 wherein said sizing agent is the reaction produce of maleic anhydride and an unsaturated triglyceride oil having an iodine value of at least about 50.

6. An aqueous emulsion of a sizing agent suitable for sizing paper comprising an emulsifying agent selected from the group consisting of a trialkyl amine at a level of from about 0.5 to about 2.5 percent by weight of said sizing agent and ammonium hydroxide at a level of about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent and a sizing agent at a level of from about 1 to about 20 percent of the total emulsion weight.

7. An emulsion in accordance with claim 6 wherein said emulsifying agent is a trialkyl amine selected from the group consisting of trimethyl amine and triethyl amine.

8. An emulsion in accordance with claim 7 wherein said trialkyl amine is triethyl amine.

9. An emulsion in accordance with claim 7 wherein said trialkyl amine is trimethyl amine.

10. An emulsion in accordance with claim 6, 8 or 9 wherein said sizing agent is selected from the group consisting of maleated triglycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers.

11. An emulsion in accordance with claim 6, 8 or 9 wherein said sizing agent is the condensation reaction product of maleic anhydride and an unsaturated triglyceride oil having an iodine value of at least about 50.

12. An emulsion in accordance with claim 6 wherein said emulsifying agent is ammonium hydroxide.

13. A method for internal sizing of paper comprising adding to paper furnish an emulsion comprising a sizing agent at a level of from about 1 to about 20 percent of the total emulsion weight and an emulsifying agent selected from the group com-prising of a trialkyl amine at a level of from about 0.5 to about 2.5 percent by weight of said sizing agent and ammonium hydroxide at a level of about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent.

14. The method of claim 13 wherein said emulsifying agent is a trialkyl amine selected from the group consisting of trimethyl amine and triethyl amine.

15. The method of claim 14 wherein said trialkyl amine is triethyl amine.

16. The method of claim 14 wherein said trialkyl amine is trimethyl amine.

17. The method of claim 13, 15 or 16 wherein said sizing agent is selected from the group consisting of maleated tri-glycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers.

18. The method of claim 13 wherein said sizing agent is the condensation reaction product of maleic anhydride and an unsaturated triglyceride oil having an iodine value of at least about 50.

19. The method of claim 18 wherein said emulsifying agent is ammonium hydroxide.

20. The method of claim 19 wherein said ammonium hydroxide is present in said emulsion at a level of from about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent.

21. A method for preparing an internal paper sizing emulsion which comprises adding at a level of from about 1 to about 20 percent of the total emulsion weight, a water-insoluble, non-hydrolyzed, heterocyclic sizing agent characterized as having at least one long hydrocarbon chain of about 8 to 30 carbon atoms with the heterocyclic structure of said sizing agent containing an oxy group bridging two carbon atoms wherein both the carbon atoms which are attached to the oxy group contain a divalent bond, and an emulsifying agent selected from the group consisting of a trialkyl amine at a level of from about 0.5 to about 2.5 percent by weight of said sizing agent and ammonium hydroxide at a level of about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent to water at a pH between about 5.0 to about 8.5 to provide a mixture, and agitating said mixture to provide said emulsion wherein said sizing agent is uniformly dispersed and emulsified in said water by said emulsifying agent.

22. The method in accordance with claim 21 wherein said emulsifying agent is a trialkyl amine selected from the group consisting of trimethyl amine and triethyl amine.

23. A method in accordance with claim 21 wherein said emulsifying agent is ammonium hydroxide.

24. A method in accordance with claim 21 wherein said sizing agent is selected from the group consisting of maleated triglycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers.

25. A method in accordance with claim 24 wherein said sizing agent is the reaction product of about 0.9 to about 2 moles maleic anhydride and one mole of unsaturated triglyceride oil, the non-hydrolyzed reaction product has an iodine value of at least about 50 and the internal paper sizing emulsion is uniformly dispersed throughout a cellulose paper furnish in an amount, on a dry solids weight basis, ranging from about 0.5 to about 1.5 parts by weight reaction product for each 100 parts by weight cellulose pulp.

26. An aqueous emulsion of a sizing agent suitable for sizing paper comprising a water-insoluble, non-hydrolyzed, heterocyclic sizing agent characterized as having at least one long hydrocarbon chain of about 8 to 30 carbon atoms attached thereto with the heterocyclic structure of said sizing agent containing an oxy group bridging two carbon atoms wherein both the carbon atoms which are attached to the oxy group contain a divalent bond, said sizing agent being present at a level of from about 1 to about 20 percent of the total emulsion weight, and said sizing agent being emulsified with an emulsifying agent selected from the group consisting of a trialkyl amine at a level of from about 0.5 to about 2.5 percent by weight of said sizing agent and ammonium hydroxide at a level of from about 0.05 to about 1 percent by weight, on an ammonia basis, by weight of said sizing agent.

27. The emulsion in accordance with claim 26 wherein said trialkyl amine is triethyl amine.

28. The emulsion in accordance with claim 26 wherein said trialkyl amine is trimethyl amine.

29. The emulsion in accordance with claim 26, 27 or 28 wherein said sizing agent is selected from the group consisting of maleated triglycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers.

30. The emulsion in accordance with claim 26, 27 or 28 wherein said sizing agent is the condensation reaction product of about 0.9 to about 2.0 moles maleic anhydride and one mole unsaturated triglyceride oil and the reaction product has an iodine value of at least about 50 and the internal paper sizing emulsion is uniformly dispersed throughout a cellulosic paper furnish (on a dry solids weight basis) in an amount ranging from about 0.5 to about 1.5 parts by weight reaction product for each 100 parts by weight cellulose pulp.

31. A method for internal sizing of paper comprising adding to a cellulose pulp an internal paper sizing emulsion having a pH between about 5.0 to about 8.5, said emulsion comprising water, emulsifying agent and a water-insoluble, non-hydrolyzed, heterocyclic sizing agent at a level from about 1 to about 20 percent of the total emulsion weight, said heterocyclic sizing agent being characterized as having at least one long hydrocarbon chain of about 8 to 30 carbon atoms attached thereto with the heterocyclic structure of said sizing agent containing an oxy group bridging two carbon atoms wherein both the carbon atoms which are attached to the oxy group contain a divalent bond and the emulsifying agent for said sizing agent is selected from the group consisting of a trialkyl amine at a level from about 0.5 to about 2.5 percent of the sizing agent weight and ammonium hydroxide at a level of about 0.05 to about 1 percent, (on an ammonia weight basis), of said sizing agent weight to provide an internally sized paper furnish, and converting said furnish to a dry, internally sized paper product.

32. The method of claim 31 wherein said emulsifying agent is a trialkyl amine selected from the group consisting of trimethyl amine and triethyl amine and the internal paper sizing emulsion is added to the paper furnish at a level ranging from about 0.1 to about 5 parts by weight sizing agent for each 100 parts by weight of the cellulose pulp.

33. The method of claim 32 wherein said trialkyl amine is present in said emulsion at a level of from about 1 to about 2 percent by weight of said sizing agent.

34. The method of claim 33 wherein said trialkyl amine is triethyl amine.

35. The method of claim 33 wherein said trialkyl amine is trimethyl amine.

36. The method of claim 31 wherein said sizing agent is selected from the group consisting of maleated triglycerides, maleated alpha-olefins, maleated fatty esters, and alkyl ketene dimers and the heterocyclic sizing agent is added to the paper furnish in an amount (based on the dry solids weight) ranging from about 0.1 to about 5.0 parts by weight heterocyclic sizing agent for each 100 parts by weight cellulose pulp.

37. The method of claim 36 wherein said sizing agent is the condensation reaction product of about 0.9 to about 2 moles maleic anhydride and one mole of unsaturated triglyceride oil and the reaction product has an iodine value of at least about 50.

38. The method of claim 37 wherein said emulsifying agent is ammonium hydroxide.

39. The method of claim 38 wherein said ammonium hydroxide is present in said emulsion at a level of from about 0.1 to about 0.6 percent by weight, on an ammonia basis, by weight of said sizing agent.