Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/14—Carboxylic acids; Derivatives thereof
  • D21H17/15—Polycarboxylic acids, e.g. maleic acid
  • D21H17/16—Addition products thereof with hydrocarbons
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/17—Ketenes, e.g. ketene dimers
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/62—Rosin; Derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/66—Salts, e.g. alums
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents

Definitions

• This invention relates to paper sizing compositions, method for making such compositions, processes for sizing paper products using these compositions and paper products which have been sized with these compositions.
• Paper is used, for convenience, to mean all forms of paper, paperboard and related products whose manufacture involves the employment of a sizing agent upon cellulosic or other fibres.
• Paper sizing agents are usually employed either by being added to the cellulosic or other fibre stock from which a web is later made or by being applied to the surface after the web has been formed. Rosin-based sizing agents depend for their sizing effect upon the formation of electrostatic bonds between the sizing agent and the cellulosic or other fibres of the paper stock or web.
• paper sizing agents are usually in the form of stable dispersions and they cause sizing by depositing rosin-based or other materials on to the fibre stock or the paper web, so that sizing essentially involves breaking the stable dispersion. This can occur on contact between the dispersion and the stock or web, where the latter is effective to destroy the stability of the dispersion.
• adequate sizing does not arise from mere contact of the paper sizing agent with the paper stock or web. Instead, it requires the presence of a co-reactant to break the dispersion and so cause the desired deposition of sizing components on the fibres of the paper stock or web.
• co-reactants are aluminium compounds and, especially, aluminium sulphate, papermaker's alum and the polyaluminium chlorides.
• dispersions comprising a rosin component and a co-reactant, which are stable and which impart excellent sizing properties to paper, can be prepared by the incorporation into a suitable composition of an amine or an amine salt of a rosin acid.
• a paper sizing composition which comprises an aqueous dispersion containing a rosin size component, a co-reactant and an amine or an amine salt of a rosin acid.
• Rosin is a solid resinous material which occurs naturally in the oleoresin of pine trees. It is obtained from one of three main sources, the oleoresin exudate of living pine trees, and oleoresin contained in the aged stumps of pine trees and from the tall oil produced as a by-product in the kraft paper industry. Rosin is a complex mixture of cyclic terpene carboxylic acids together with a small amount of non-acidic components. A major constituent of rosin is the tricyclic doubly unsaturated mono-carboxylic acid, abietic acid.
• rosin may therefore be reacted with dienophilic carboxylic acids such as maleic acid, maleic anhydride or fumaric acid to form a tetracyclic polycarboxylic acid. This reaction with these dienophiles is commonly termed fortification.
• the product of such reaction between rosin and a dienophile is commonly termed a fortified rosin. Fortified rosin dispersions are used as sizing compositions in the paper sizing industry and the novel dispersions of this invention may comprise either rosin or fortified rosin or a mixture of the two.
• the rosin may have been treated with formaldehyde in order to enhance their stability.
• Esterified or disproportionated rosins may also be used in the compositions of this invention.
• Esterified rosins are rosins which have been reacted with an alcohol which is 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 these types of rosin may be used in the compositions of this invention.
• the preferred rosin for use in the composition of this invention are fortified rosins.
• the preferred fortified rosins are those wherein the rosin has been reacted with from 5 to 50% of its own weight and generally about 10% by weight of a dienophile.
• Such rosins comprise a mixture of fortified and unfortified rosin. The two are normally used in combination in view of the fortification which would render the use of a product comprising fortified rosin only prohibitively expensive.
• the most preferred type of rosin is fortified tall oil rosin.
• the amine salt of the rosin acid may be produced by the neutralisation of any of the rosin or rosin derivatives described above. It may be prepared separately and added to the rosin dispersion, but more usually it will be produced in situ by the addition of sufficient amine to bring about the partial neutralisation of the acid content of the rosin.
• the amine salt is the salt of the rosin acid or acids present in the rosin component of the dispersions of this invention.
• the salt of the rosin acid may be produced by neutralising the acid either prior to or after its conversion to a rosin derivative.
• the neutralisation may be carried out using an amine having the formula: wherein substituents R1, R2 and R3, which may be the same or different, represents alkyl or alkenyl groups comprising from 1 to 4 carbon atoms or a hydrogen atom, with the proviso that at least one of the substituent is not a hydrogen atom.
• substituents R1, R2 and R3 represent alkyl groups and, most preferably, all three of these substituents represent alkyl groups.
• R1, R2 and R3 which represent alkyl groups may represent branched or straight chain saturated alkyl groups such as methyl, ethyl, or n- or iso- propyl, n-, sec- or tert- butyl groups or they may represent alkyl groups which contain one or more substituent groups such as hydroxyl, alkoxy, carboxy or amino groups such as 2, hydroxyethane groups or hydroxypropane groups.
• Particular amines which are useful in the composition of this invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monoethanolamine, diethanolamine and triethanolamine.
• the most preferred amine is triethanolamine.
• the amount of amine which is added to the rosin will be that which is required in order to produce the desired amount of amine salt.
• the amount of amine which is added will normally be sufficient to neutralise from 1 to 20%, preferably from 3 to 6% of the acid groups present in the rosin.
• the amount of amine salt will normally be such that the mixture comprises the same proportions of neutralised and non-­neutralised rosin acids.
• the co-reactant component of the dispersions of this invention may be of any of the aluminium salts known to be useful in the sizing of paper such as aluminium sulphate, paper maker's alum Al2(SO4)3.18H2O, polyaluminium chlorides such as those having the formula Al(OH)x(SO4)yCl z wherein x has a value in the range 1.35 to 1.65, y has a value of from 0.08 to 0.15 and z has a value of 3-(x+y), or those having the formula: Al n (OH) m Cl 3n-m wherein n has a value of from 1 to 20, m is less than 3n and is at least 2 and preferably at least 5.
• a particular type of polyaluminium chloride which is useful in the dispersions of this invention are those described in European Patent Application 145686 and those produced by the processes described in European Patent Application 181847.
• Another type of useful polyaluminium chloride are the aluminium chlorohydrates having the formula: Al x (OH) y Cl z wherein x has a value of from 1 to 4, preferably a value of 1, y and z, which may be the same or different, have values of from 0.5 to 2.5 and the ratio y:z has a value in the range 5:1 to 1:5.
• the preferred co-reactant for use in the compositions of the present invention are the aluminium chlorohydrates.
• the dispersions of the present invention may be prepared by simple admixture of the components thereof or by using any of the conventional techniques of the art.
• the dispersions may be prepared using the inversion technique.
• the rosin preferably a fortified rosin, optionally treated with para formaldehyde in the presence of a para toluene sulphonic acid to inhibit crystallisation, and optionally one which has been at least partially neutralised with an amine, may be melted and a stabilising agent or mixture of stabilising agents may then be added as a concentrated (e.g. 50% by weight solids) aqueous 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).
• a stabilising agent or mixture of stabilising agents may then be added as a concentrated (e.g. 50% by weight solids) aqueous 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).
• the emulsion On dilution with water the emulsion inverts to provide a stable oil-in-water emulsion, typically having solids content of from 20% by weight up to the maximum achievable oil-in-water concentration (often about 80% by weight solids) and preferably from 30% to 40% by weight solids.
• the rosin content of the emulsion or dispersion usually contains at least 90% of unsaponified rosin acids.
• the emulsions may then be blended with an aqueous solution of one or more co-reactants.
• the emulsions may be used for sizing paper, including alumed paper.
• the rosin dispersions may be formulated so as to comprise other ingredients known in the art.
• the dispersions may comprise one or more stabilisers.
• a variety of surface active agents or emulsifiers may be used to stabilise the dispersions either in admixture 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, an amine salt of a rosin acid, a co-reactant and a protective colloid form a preferred aspect of this invention.
• Other compounds which may be used to stabilise the dispersions include starch derivatives, cellulose derivatives such as hydroxyethyl cellulose, or polymeric materials such as polyvinyl pyrolidone.
• Anionic, non-ionic, amphoteric, or cationic surfactants may be utilised as stabilisers in the dispersions of this invention.
• anionic or non-ionic surfactants may be utilised as stabilisers in the dispersions of this invention.
• anionic or non-ionic surfactants may be utilised.
• compositions of this invention examples include:
• Sulphosuccinate half esters of fortified rosin having the formula:- H (3-m) .R. [(CH2CH2O) n -OC.C2H3SO3Na. COONa] 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 those described in European Patent Application 159794.
• R represents an alkyl group comprising from 4 to 18 carbon atoms and R′ represents an alkyl or alkenyl group comprising from 4 to 18 carbon atoms and n is an integer having a value of from 4 to 25 including all those described in United States Patent 4199367.
• Sulphosuccinate salts of ethylene oxide condensates having the general formula:- wherein R represents an alkyl group comprising from 4 to 18 carbon atoms and n is an integer having a value of from 4 to 25; including all those compounds described in United States Patent 4203776.
• Organic phosphate esters having the general formulae:- wherein R represents an alkyl an alkyl phenol, alkenyl or alkaryl group comprising from 5 to 20 carbon atoms, n has a value of from 5 to 20 and X represents a monovalent cation or hydrogen.
• Cationic resin dispersant systems may also be used to stabilise the rosin dispersion of this invention.
• suitable materials include water soluable polyaminopolyamide epichlorohydrin resins, water soluble alkylene polyamine epichlorohydrin resins or poly(diallyl-amine) epichlorohydrin resins.
• a further type of compound which can usefully be incorporated into the dispersions of this invention is that comprising ammonia or an ammonium salt or a precursor thereof such as urea, a chemically modified urea or a precursor thereof.
• ammonia or an ammonium salt or a precursor thereof such as urea, a chemically modified urea or a precursor thereof.
• compounds which are useful in the compositions of this invention include urea, thiourea, biuret.
• melamine, water-soluble urea-formaldehyde and melamine formaldehyde resins and derivates or urea especially those reaction products obtained by reacting urea with an acid selected from the group comprising sulphamic acid, phosphoric acid, trichloroacetic acid, nitric acid, sulphuric acid, hydrochloric acid, stearic acid and acetic acid as described in United States Patent 4022634 and 4093779, the reaction products of urea with a Lewis acid such a p-toluene sulphonic acid as described in United States Patent 4141750, the reaction products of urea and sulphamic acid such as are described in United States Patent 4025354 and the products obtained by the reaction of urea and formic acid as described in United States Patent 4437894.
• an acid selected from the group comprising sulphamic acid, phosphoric acid, trichloroacetic acid, nitric acid, sulphuric
• the preferred sources of ammonia or ammonium salt 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 United States Patent 4025354.
• These modified ureas may be produced by combining urea with sulphamic acid and water.
• the parts by weight of water equal the parts by weight of urea plus sulphamic acid, although the urea may be treated with the sulfamic acid with more water or with little or no water.
• the urea-sulphamic acid solution may be heated to a temperature which causes a change in the pH for example to rise in the pH to at least about 7.5.
• the temperature affecting the pH may be higher.
• a temperature of about 212° and 235°F, preferably about 215° to 230°F will increase the pH up to at least about 7.9.
• the solution boils at the temperature which changes the pH and heating should be continued until after boiling has stopped to effect an irreversible pH change.
• the pH range is an important measurement of reaction completion, a more important consideration is the acidity of the first stage product measured as parts of water (ppm).
• the desired minimum acidity is at least 1,000 ppm, with a preferred minimum 4,300.
• the actual amount of sulphamic acid is probably at least about 0.1% by weight of urea, with preferred amounts ranging from about 0.2% to about 8.0%.
• the maximum amount of sulphamic acid needed would be 15 or at most 20% by weight of 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 of between 7.9 and 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 novel size composition of this embodiment.
• the proportion of ammonia or ammonia salt (or in the preferred embodiment the precursor thereof) to rosin or fortified rosin in the dispersions of this invention may be in the range 5 to 60% and preferably 10 to 35% by weight.
• a further class of ingredients which may usefully be incorporated into the compositions of this invention are the synthetic sizes such as alkenyl succinic anhydrides and especially the alkyl ketene dimers. These reagents may be used as well as or as a partial replacement for the rosin sizes. In general the ratio of the weight of the rosin components to the synthetic size components will be in the range 2:1 to 5:1.
• novel dispersions will normally be formulated as relatively concentrated compositions which are diluted prior to their use in the sizing process.
• the dispersions will comprise from 25 to 60% and more usually from 30 to 45% by weight of the combined weight of the rosin, amine salt or co-reactant.
• compositions of the invention my be employed as an internal size or as a surface size. Their use as an internal size forms a preferred aspect of the present invention.
• Internal sizing processes comprise the dilution of the concentrated composition with water and the addition of the diluted composition to a pulp suspension.
• the amount of size composition employed is generally in the range 0.1 to 5.0% by weight of solids based on the weight of fibres in the pulp slurry.
• the emulsions may be used for sizing paper, including alumed paper.
• the emulsions may contain biocides such as bactericides, slimicides and/or fungicides or diluents such as wax.
• the fortified rosin was loaded into a one tonnne pot using an agitator speed of 300 rpm, water and 10 kg of triethanolamine was added both to cool and partially neutralise the rosin product.
• Example 2 800 kg of the 30% rosin emulsion produced in Example 2 was placed into a 3 tonne production unit. To this was added 400 kg of a 30% urea solution. The stirrer was switched on at 3,000 rpm (Greaves mixer). To this was added quickly (1-5 secs) 160 kg of an aluminium chlorohydrate solution. An additional 640 kg of the aluminium chlorohydrate solution was added over a period of one minute. The stirrer was switched off and the product filtered through a 40 mesh filter basket.
• a dispersion was produced using the ingredients and procedures described in Example 4, except a 30% Lewis acid reacted urea was substituted for the 30% urea solution.
• a dispersion was produced using the ingredients and procedures described in Example 4, with the exception that no urea was added.
• a dispersion was produced using the ingredients and procedures described in Example 4, except that a polyaluminium chloride was substituted for the aluminium chlorohydrate.
• a dispersion was produced using the ingredients and procedures described in Example 4, except that aluminium sulphate (paper maker's alum) was substituted for the aluminium chlorohydrate.
• a dispersion was produced using the ingredients and procedures described in Example 4, except that 50 mole % of the aluminium chlorohydrate was substituted with a polyaluminium chloride.

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• Adhesives Or Adhesive Processes (AREA)
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Citations (7)

• 1987
  • 1987-05-26 GB GB878712370A patent/GB8712370D0/en active Pending
• 1988
  • 1988-05-16 ES ES88304405T patent/ES2051845T3/es not_active Expired - Lifetime
  • 1988-05-16 DE DE8888304405T patent/DE3873826T2/de not_active Expired - Fee Related
  • 1988-05-16 AT AT88304405T patent/ATE79657T1/de not_active IP Right Cessation
  • 1988-05-16 EP EP88304405A patent/EP0293119B1/de not_active Expired - Lifetime
  • 1988-05-20 NZ NZ224724A patent/NZ224724A/xx unknown
  • 1988-05-23 ZA ZA883650A patent/ZA883650B/xx unknown
  • 1988-05-25 AU AU16611/88A patent/AU615444B2/en not_active Ceased
  • 1988-05-26 CA CA000567764A patent/CA1340339C/en not_active Expired - Fee Related
  • 1988-05-26 FI FI882487A patent/FI94069C/fi not_active IP Right Cessation
  • 1988-05-26 JP JP63127232A patent/JP2641253B2/ja not_active Expired - Lifetime
  • 1988-05-26 PT PT87589A patent/PT87589B/pt not_active IP Right Cessation
  • 1988-05-26 BR BR8802569A patent/BR8802569A/pt unknown

Patent Citations (7)

Non-Patent Citations (1)

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