Rosin Emulsion Research Articles

Modification of rosin resin acids to improve their hydrophobizing action on paper and cardboard

The modification of rosin resin acids, which improves their hydrophobic effect on paper and cardboard, is based on the implementation of 6 stages. Control of chemical processes at each stage is carried out by monitoring and regulating temperature and flow parameters, which determine the achievement of the required physical and chemical properties and composition of intermediates and final substance. One of the main indicators is the acid number, which for the final substance should be 60–70 mg KOH/g, which corresponds to the content of free resin acids in the functional substance of 40–45 %. The fulfillment of the specified temperature and consumption parameters for the modification of resin acids of rosin and the achievement of the necessary physicochemical properties of intermediates at each stage ensures the production of a functional substance with an improved hydrophobic effect on paper and cardboard. Compared to the traditionally used TM adhesive-paste, the developed functional substance in the production of paper with absorbency at one-sided wetting of not more than 21 g/m2 provides a reduction in the content of particles of the dispersed phase of the rosin emulsion by 1.4–2.0 times, which indicates its improved properties, and maximum preservation of the original strength of the paper by reducing the distance between the fibers due to a 3.3–3.8 times reduction (from 4200–5000 to 1100–1480 nm) in the size of sizing complexes.

Features of the coagulating and peptizing action of weakly basic and strongly basic cationic polyelectrolytes on rosin emulsions

It has been shown for the first time that cationic polyelectrolytes (weakly basic (polyamide-polyamine-epichlorohydrin resin (PPER)) and strongly basic (polydimethyldiallylammonium chloride (PDMDAAC) and copolymer of acrylamide with methylene chloride dimethylamminopropylacrylamide (CA MC DMAPA)), widely used in paper and cardboard technology as flocculants (existing technology), additionally participate in the processes of coagulation and peptization (proposed technology). It has been established that the coagulating ability of polyelectrolytes decreases in the series CA MC DMAPA > PDMDAAC > PPER, while the peptizing ability, on the contrary, increases. Peptizable coagulants with the size and ξ-potential that do not exceed 5200 nm and +15 mV, respectively, are formed in the presence of PPER, when its content in the dispersed system does not exceed 0.15 parts by weight / parts by weight of the dispersed phase of the rosin emulsion (RE). The first region of electrolytic coagulation RE (proposed technology) corresponds to the ratio of RE : electrolyte in the range from 1: 0.3 to 1: 0.6, while with an increased content of electrolyte in the dispersed system (existing technology), which is in the range of 1: 2.4 to 1: 3.0 , the coagulation process proceeds in the second region (the resulting coagulates are electrically neutral and coarse (size exceeds 5200 nm) and are not able to peptize). The peptization process proceeds in the dispersed system “RE (1.0 wt. parts) – PPER (0.04 wt. parts) – electrolyte (0.6 wt. parts)”. The presence of PPER promotes an increase in the ξ-potential of peptized particles from +35 to +50 mV. Unlike coagulates, such particles provide a shift in the sizing process from the traditional mode of homocoagulation to a more efficient mode of heteroadagulation. This results in an increase in the hydrophobicity and strength of paper (cardboard) by 29–36 and 28–38 %, respectively, as well as in an improvement in the printing properties of coated products by 12–15 %.

Разработка способа повышения эффективности применения слабоосновных катионных полиэлектролитов в технологии бумаги и картона

The article considers the effect of weak cationic polyelectrolytes on the structure- and paper-forming properties of glued fibrous suspensions and the quality of glued and coated paper and cardboard samples obtained from them. It is shown for the first time that the efficiency of using cationic polyelectrolytes increases by 2…3 times due to a change in the sequence of its introduction into glued fibrous suspensions (cellulose and waste paper) in relation to rosin emulsion and electrolyte, as well as by «correction» their dosages. It is found that the use of the developed technology allows cationic polyelectrolytes to participate not only in the process of flocculation, but also in the formation of new sizing complexes in the form of finely dispersed positively charged peptized particles. It is revealed that the replacement of the sizing process in the homocoagulation mode with a more efficient mode of heteroadagulation of peptized particles due to the use of weakly basic cationic polyelectrolytes provides an increase in hydrophobicity and strength of the glued types of paper and cardboard. The expediency of using cationic polyelectrolytes to obtain high-quality products in the developed resource-saving and ecologically safe technology of glued types of paper and cardboard is substantiated based on the established increase in the degree of retention of fibers and sizing complexes and the simultaneous decrease in the content of suspended solids in recycled water. It is determined that the coating of glued paper and cardboard samples obtained with weakly basic cationic polyelectrolytes improves the printing properties of the resulting products. Recommendations are given for replacing the traditionally used complex of natural compounds in the coating paste formulation, including oxidized starch (2,0 parts by weight), sodium carboxymethyl cellulose (0,7 parts by weight) and casein glue (2,0 parts by weight), for one synthetic binder — modified urea-formaldehyde oligomer (3,2 parts by weight).

Effects of Rosin Sizing Agent on the Fixation of Boron in <i>Styrax tonkinensis</i> Wood

The aim of this study was to evaluate the effect of rosin upon fixing boron in Styrax tonkinensis (Piere) wood treated with mixtures of 3% boric acid and 1% rosin sizing agent. After treatment, wood samples were also analyzed by scanning electron microscope observation and energy-dispersive X-ray spectroscopy (SEM-EDX). The results showed that all boron-rosin formulations impregnated Styrax tonkinensis wood evenly penetrated into the wood blocks. Boron-rosin treatment decreased by 16% the amount of boron leaching from treated wood samples compared with those from the samples treated with boric acid alone. The SEM-EDX analysis proved that the boron element was still in the cell lumens of leached wood blocks. Results indicated that rosin emulsion sizing agent can have an effect on the fixation of boron in wood. This signifies that using of rosin as fixing agents may contribute to lead to wood treated with boron based preservatives being more widely used.

Hydrogenated rosin ester latexes/waterborne polyacrylate blends for pressure‐sensitive adhesives

ABSTRACTDiethylene glycol ester of hydrogenated rosin (DGE‐HR) emulsion was prepared via phase inversion method and then blended with waterborne (wb) polyacrylate for pressure‐sensitive adhesives (PSAs). The preparation conditions of DGE‐HR emulsion were studied. DGE‐HR emulsion with an average particle size of about 220 nm was obtained. Furthermore, the thermal, adhesive, and viscoelastic properties and the morphology of DGE‐HR/polyacrylate composite were investigated. Thermal analysis indicated that glass transition temperatures (Tg) of the DGE‐HR/polyacrylate blends became higher as the DGE‐HR content increased and DGE‐HR did not have a significant influence on thermal stability of the blend films. Atomic Force Microscopy (AFM) observation revealed that the DGE‐HR particles added had a good miscibility with acrylic particles. Additionally, for these tackified acrylic PSAs, positive correlations between mechanical performance and viscoelastic response at bonding and debonding frequencies were also found. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42965.

Polyurethane-Acrylate Composite Emulsion Applying to the Pre-Coated Adhesive Film

This paper studied on the application mechanics and characteristics of the polyurethane-acrylate composite emulsion applying to the pre-coated adhesive film of paper and plastic laminating. The formula design and synthesis method of the polyurethane-acrylate composite emulsion was researched, and the physical properties of the copolymer emulsion was tested by infrared spectroscopy (IR), particle size analysis, gel permeation chromatography (GPC). According to mix the waterborne polyurethane acrylate emulsion to the waterborne rosin emulsion, the hot melt pre-coated adhesive was obtained. The experimental results based on the physical properties and image analysis of the pre-coated adhesive film of paper and plastic laminating showed that: the adhesive film coated by this hot melt adhesive had a high gloss and adhesive force, it improved the application performance of the pre-coated adhesive film of paper and plastic laminating in the printing and packaging industry.

The Effects of Cationic Polymer Addition on Size Retention and Paper Sizing Performance in Rosin Emulsion Sizing

近年，古紙配合量の増加，用水原単位の低下により，白水循環系中のピッチ，アニオントラッシュが増加し，内添薬品の効果低下や，原料歩留の低下，断紙トラブルなど，生産性，操業性に関わるトラブルが発生している。この問題に対し，有機凝結剤によるアニオントラッシュ処理が重視され，その適用が広まりつつある。一方，繊維への定着不良や過剰添加によって系内に濃縮した内添薬品は，新たな阻害物質となり，様々なトラブルを誘発していると考えられる。そこで今回，内添薬品であるロジンサイズ剤の定着に着目し，サイズ剤の定着とサイズ発現効果に与えるカチオン性ポリマー物性の影響について検討を行った。その結果，高いカチオン荷電を持つポリマーを定着剤として用いると，良好なサイズ定着効果を示すものの，カチオン荷電の低いポリマーに比べてサイズの発現効果が低く，サイズの発現性は，シート中のサイズ剤含有量だけでなく，定着剤として使用するポリマーの物性にも依存することや，サイズ発現には最適な分子量域があることがわかった。また，定着剤の添加場所について検討を行ったところ，填料の有無や，定着剤添加からサイズ剤添加までの攪拌時間がサイズ剤の定着量に影響を与えることから，定着剤は，サイズ剤の後に添加する方が望ましいことがわかった。

Application of cationic polymer prepared from sulfuric acid lignin as a retention aid for usual rosin sizes to neutral papermaking

Cationic polymers that acted as the retention aids for usual rosin sizes in neutral papermaking were prepared from sulfuric acid lignin (SAL), one type of acid lignin. To convert SAL to the cationic polymer (MP-SAL), SAL was phenolated and then treated by the Mannich reaction to introduce the amino groups. In the MP-SAL single system, MP-SAL exhibited high sizing effectiveness in neutral papermaking with the rosin emulsion size. However, MP-SAL showed no sizing effectiveness when soap rosin size was used. MP-SAL showed increased sizing effectiveness as the pK a of the introduced amino group increased. From this and comparison of the sizing degrees of MP-SAL and polyethylenimine, which possesses a linear structure, it was suggested that the sizing effectiveness was not only affected by the charge density and molecular weight, but also by the basicity of the introduced amino groups and the molecular structure of the retention aid. In the alum–MP-SAL dual system, alum and MP-SAL synergistically enhanced the sizing effectiveness in the rosin emulsion sizing at neutral pH. In turn, this allowed a decrease in the MP-SAL dosage and resulted in a small decrease in brightness.

Supramolecular structure and sizing performance of rosin-based emulsion size microparticles

Abstract Compared with conventional acidic rosin emulsion size, neutral rosin size has good sizing efficiency under neutral–alkaline conditions of paper manufacture because its emulsion particles are stable to the action of hydroxide ions. Therefore, the sizing efficiency of emulsion-type rosin sizes, i.e. their ability to increase resistance to fluid penetration, was considered to be related with their particulate structure. The supramolecular structure of the neutral glycerin rosin ester–rosin size microparticles and acidic rosin size microparticles were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) absorption spectroscopy, and electron spectroscopy for chemical analysis (ESCA) techniques in this study. The results indicated that the neutral glycerin rosin ester–rosin size is quite distinct from the acidic rosin sizes in their particulate supramolecular structure. A glycerol dirosinate bilayer existed in the particle structure is hypothesized for the neutral glycerin rosin ester–rosin size microparticles. The results also suggest that the glycerol dirosinate bilayer distributes on the outermost layer of the neutral rosin size microparticles, covering the rosin acid molecules, so as to prevent the dissociation of rosin by hydroxide ions under neutral–alkaline conditions. Consequently, the difference in the supramolecular structure of the rosin sizes particles resulted in their different stabilities and retention characteristics.

Roles of Aluminum Sulfate in Rosin Sizing

Roles of aluminum components originating from aluminum sulfate (alum) in rosin sizing were investigated by X-ray photoelectron spectroscopy, X-ray fluorescence analysis and pyrolysis gas chromatography. Handsheets were prepared with 1% alum and 1% anionic rosin emulsion, where the stirring time of pulp suspensions at pH 6.7 or pH 4.5 between the alum and size additions varied from 3 to 3000 min. Sizing effects of the handsheets prepared at pH 6.7 decreased rapidly as the stirring time proceeded, although the sizing appearance of the handsheets prepared at pH 4.5 was observed even at an addition interval of 50 hrs. Under the neutral papermaking conditions, the Al components once adsorbed on pulp fibers were immediately counteracted by OH- ions, followed by the Al desorption and the drop in rosin retention. On the other hand, the acidic circumstances preserved the Al retention and performance, resulting in higher rosin content and better sizing efficiency. The Al components present on pulp surfaces were then aggregated gradually, and the ability as a retention aid eventually became absent, although the Al content remained almost unchanged. However, the Al components that had lost the above function could make a great contribution to sizing appearance by tub-sizing the Al-containing handsheets with the same rosin emulsion. Therefore, alum in rosin sizing must play two individual roles in sizing response: a retention enhancer as which Al cations act at the wet end, and a sizing promoter as which non-ionic Al components perform in the dried paper sheet.

Sizing mechanism of rosin emulsion size-alum systems

Sizing mechanism of rosin emulsion size-alum systems

Function mechanisms of polyamines in rosin sizing under neutral papermaking conditions

AbstractThe surface analyses of the papers sized with a rosin emulsion (RE) and five typical polyamines, polyallylamine (PAAm), polyvinylamine (PVAm), polyethyleneimine (PEI), poly(diallyldimethylammonium chloride (PDADMAC), and poly(dimethylamino ethyl methacrylate) (PDMAEMA), were performed using a X‐ray photoelectron spectrometer. The results show that the chemical states of the polyamines on the outermost surfaces of the papers changed significantly during the neutral rosin sizing. The five polyamines could react with carboxyl groups of the fibers to form urethane linkages at 400.0 ± 0.1 eV, which resulted in absorption of the polyamines onto the fibers. Only PAAm and PVAm could combine with RE to form urethane linkages at 400.7–0.1 eV, which were related deeply to sizing effectiveness. The polyamines distributed mainly on the surfaces of the fibers. The concentrations of PAAm and PVAm on the surfaces of the sized papers were much larger than those of PEI, PDMAEMA, and PDADMAC. A larger sizing degree was related to a larger C1 component at 285.0 eV (CC) in the C1s XPS spectra of the sized papers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2185–2190, 2001

Sizing Performance of the Cationic Rosin Emulsion Size at Near Neutral Conditions

Recently, for the internal sizing, the rosin emulsion sizes are often used. There are two types of rosin emulsion size corresponded to the acidic conditions and the higher pH conditions. For the latter, the rosin ester-type emulsion sizes are well known. The sizing performance of this type is not satisfactory at near neutral conditions, because of the dependence upon the amount of alum used. The high performance rosin emulsion size, more reasonable price and easier to use than AKD and ASA, is required, under neutral papermaking is advanced in order to improve the quality of paper and reduce the cost. We investigated a new size in terms of the components of resin and the ionicity of polymer surfactant, and found that the size, formed by dispersing the fortified rosin and petroleum resin mixture with a cationic surfactant, is excellent in comparison with rosin-ester size.

Effects of polyamine structure on rosin sizing under neutral papermaking conditions

The sizing effectiveness of rosin size with four typical polyamines, polyvinylamine (PVAm), polyallylamine (PAAm), poly(dimethylamino ethyl methacrylate) (PDMAEMA), and polyethyleneimine (PEI), was investigated under neutral papermaking conditions. The polyamines with linear structures were more effective than was PEI with a branched structure. The smaller the side chains of the linear polyamine, the larger was the sizing degree of the rosin emulsion size (RE) with the polyamine. The polyamine with smaller molecular geometric size could retain more rosin size on the pulp and form smaller rosin-polyamine complexes.

内添による紙の機能性発現機構について

Wet-end additives can give new functionalities to papersheet efficiently in the papermaking process. The additives have various forms ; molecular-order compounds, emulsions, their coagulants and others. The appearance of functionalities on papersheet is also various, depending on the way to coagulate the wet-end additives and/or that to adsorb the coagulated compounds on pulp fiber surfaces in wet-end. The research fields of wet-end additives have remarkably advanced, as the new methods for determining wet-end additives in papersheet have been established recently, such as pyrolysis-gas chromatography and SEM-EDXA.In the case of reactive sizes such as AKD and ASA, the chemical structures to react with water is necessary for efficient sizing of papersheet. Surface charges of the emulsion particles of the reactive sizes turn from cationic to amphoteric in wet-end, and thus efficient retention of the reactive sizes can be achieved. Furthermore, lower coagulation behavior of size components on pulp fiber surfaces is maintained by the water-reactivity of reactive sizes in press and drying processes, and sizing features appears efficiently on papersheet thereby.Sizing and retention mechanisms of rosin soap, rosin emulsion and rosin-ester sizes also have been studied using new analytical techniques, from the aspects of structures of rosin molecules in papersheet and roles of alum in wet-end and in papersheet.

Recent Progress of Sizing Agents

The recent technical trends of internal paper sizes are reviewed. The selection of adequate sizes for each different papermaking conditions and to increase the fixing rate of the sizes are the most important role in using the sizes. To satisfy these requirements, the basic mechanisms of the absorption and retention of sizes are summarized.To review the recent technical trend, the rosin emulsion sizes with polymer based emulsifier for acid papermaking, and AKD, ASA and cationic polymer sizes for alkaline papermaking are selected. The characteristic point and the recent technical trend of selected sizes are described. In addition to those selected sizes, the rosin based neutral sizes, which are now widely accepted and used for the PPC grade paper production, is specially described for its design philosophy, using methods with fixing agents and alum, and its characteristics.The review also described the new development of the rosin based sizes for acid-neutral papermaking (applicable pH range is between 5 to 7), to meet the recent industrial situation, increased use of recycled paper containing calcium carbonate.

新規なロジンエマルションサイズ剤

New type of rosin emulsion, stabilized with a synthetic anionic polymer, recently came into the market. The new rosin emulsion shows better mechanical, chemical (dilution with hard water), and freeze-thaw stability, better re-dispersibility of dried emulsion, less foaming in paper making system, and better sizing efficiency than conventional ones, which are stabilized with anionic low-molecular-weight surfactant.In this article, the performances of this rosin emulsion were introduced and the protectivity of the stabilizers are also discussed.