WO2003000992A2

WO2003000992A2 - Paper sizing agent

Info

Publication number: WO2003000992A2
Application number: PCT/BR2002/000089
Authority: WO
Inventors: Rubens Chaves De Oliveira
Original assignee: Universidade Federal de Viçosa
Priority date: 2001-06-22
Filing date: 2002-06-24
Publication date: 2003-01-03
Also published as: BR0103827B1; BR0103827A; AU2002312664A1; WO2003000992A3

Abstract

The present patent refers to a product used in internal paper sizing. Its addition is conducted in the mass minutes before the sheet formation. This product (PDS-SIZE) has the objective to delay liquid absorption and diffusion by the paper. Paper industries use some sizes with the same objective, being these: rosin size used in acid systems and the imported sizes ASA and AKD in neutral/alkaline systems. The sizes are used in the emulsion form. The present size 'PDS-SIZE' developed in this patent uses fattys acids extracted from soybean oil and is also used in the emulsion form. The PDS-SIZE is constituted of three substances: fattys acids, starch and aluminium sulfate. Associating these three substances in the emulsification unity, a emulsion is produced consisting of small particles of PDS-SIZE, for an optimum sizing performance.

Description

" PDS-SIZE"

The resistance to liquid penetration and diffusion (water, paint, blood, milk, juices, oils, fats, etc.) is of fundamental importance in the utilization and commercialization of many paper types and its products. This

5 process is obtained through internal sizing of the pulp.

Internal sizing consists in the addition of a water repellent material to the pulp during the stage of mass preparing for paper production. The sizing stage has the function to difficult or delay liquid penetration or diffusion 10 in the formed papers. The procedure consists in mix the size to the mass, so the hydrophobic agent involves the cellulose fiber. The internal sizing, beyond to promote paper hydrophobic, gives better retention of charges, fibers and other materials added during mass preparation, as well as 15 promote more stability and resistance to the formed sheet.

In the passed years, the internal sizing process of printing and writing papers in neutral and alkaline conditions has been the most used technology, in Europe and in the United

States of America. Lately, the referred technology has been

20. evaluated in Asia and Latin America.

Among the many existing paper types, some of them for its characteristics do not require sizing. Others require a moderate sizing and for some it is necessary an intense sizing. Following, there is a classification of the most well

25 known types of these papers :

(a) Not sized papers: towel paper; tissue paper; filling paper; newspaper; coffee filters and filter papers for laboratory use. (b) Sizing papers: money paper (highly sized); linerboard; supermarket bags; offset paper; copy paper; basis for coating; rotule paper (highly sized) ; food packages (highly sized) ; envelopes . The text bellow describes some products highly used in paper sizing.

Rosin is a size agent used in internal paper sizing systems since 1804. It consists in a natural product, solid and resinous, insoluble in water, transparent, color amber, extracted from trees of the panacea family. Its formula consists in a complex mixture of organic compounds mutually soluble with 80 to 90 % of resinous acids and 10 to 20 % of neutral material. It is usually divided into two groups: abietics and pimarics. Figure 1 shows the resinous acids formulas actually used in sizing on the rosin basis: 1- Neoabietic acid and 2- Pimaric acid. These are natural surfactants, having in its chain a polar hydrophilic structure and a nonpolar hydrophobic structure. Sizing with rosin has been the main choice on acid conditions . Soap formation with alkali converts the rosin in a form easily soluble in water, allowing its addition to the mass system. The reaction with aluminum salts, forming a compound with positive charge, possibility the adsorption and retention of this compound in the cellulose fiber surface. The sizing emulsions using rosin acid can be cationic or anionic and can have variations and chemical improvements, which aim to facilitate its manipulation, retention in the sheet and better reaction with the aluminum. These variations are : 1) Fortified rosin sizing: the efficiency of the rosin sizing is improved when reacted with the aleic anhydride or with the fumaric acid, resulting in a product much more reactive;

2) Anionic disperse rosin sizing: the resinate particles are dispersed and stabilized by surfactants, starch, polymers or proteins, with cationic characteristics.

The ASA size (Alkenyl Succinic Anhydride) is a patented size and is an anhydride of unsaturated fatty acid. The alkaline sizing agent (ASA) is constituted by a long hydrocarbon chain containing a group reactive to the cellulose. Its origin comes from an isometric olefin derived from the fractioning process of petroleum refining. Its main characteristic is to contain unsaturated reactions along the chain. The product of this olefin reaction with the maleic anhydride is the ASA agent (Alkenyl Succinic Anhydride) used as the active agent in sizes already patented) , an oleaginous material (Figure 2) . This size must be emulsified at the local and be used right after its fabrication. It also uses the cationic starch as medium for emulsification. The AKD size (Alkyl Ketene Dimer) is another patented size very much used on internal paper sizing systems. The AKD sizing agent chemical structure can be generalized as showed in Figure 3. The AKD sizing agent is a solid fatty, presenting a 55DC fusion point. Usually it is commercialized in the form of emulsions, with approximately 5 to 15 % of solids content, and a size agent active fraction ranging from 30 to 50% of the solids content. Its production process constitutes basically in the dimerization of the aliphatic acids with cloridric acid, which usually has as main composition the commercial stearic acid. This size also presents in its constitution, the cationic starch.

The present invention refers to a development of a sizing agent (PDS-SIZE) (Soybean Derived Product - PDS) utilizing Brazilian national product derived from soybean, generating a new substance for paper industries which can be added to the mass system in a paper industry with the objective to delay liquid absorption and diffusion by the paper. The size PDS is developed using an emulsifier, the emulsification is processed in the presence of three substances: soybean derived product, cooked starch and aluminum sulphate.

Nowadays, Brazil imports 100% of products utilized in internal sizing, as well as all its technology. With the aim to revert this situation, it was developed the present invention, so Brazil can have sufficient competitiveness in the international market.

Soybean is a leguminous plant, and its beans give valuable products (oil and flour) . The given peculiarity of the fattys oils present in the soybean oil through emulsification it is possible to add them to the cellulose pulp giving hydrophobic to the formed paper sheet. This new product, initially named as Soybean Derived Product - PDS, can be used in acid, neutral or alkaline paper sizing.

The fattys acids of natural occurrence in oils and fats, in general, have a long chain constituted by carbon atoms and hydrogen (hydrocarbon chain) and a terminal group called "carboxyl group", characteristic of the organic acids. These acids differ one from another by the size of the hydrocarbon chain and by the number of double bonds. Fattys acids of natural occurrence, with few exceptions, contains "pair" number of carbon atoms and present a flat hydrocarbon chain, it is, without ramifications. The fattys acids with "odd" carbon numbers - or ramified chain - are called "uncommon fattys acids" . They sustain certain functional groups (-OH, - CO, ...) and can be found in determined plants or in microorganisms. However, they can occur in animal fats, in quantities rarely exceeding 1-2%. Some seeds, certain fruit pulps, and germs of some cereals are the most important source of oils.

"Saturated" fattys acids are the ones that have simple bonds among carbon atoms, each carbon being linked to two hydrogen atoms. On the other hand, "unsaturated" fattys acids have double bonds between the carbon atoms, each carbon being linked only to one hydrogen atom. These different compounds differ basically one from another by the size of the hydrocarbon chain and by the number and position of the double bonds. They are represented generally by the formula R-COOH, where R represents any hydrocarbon chain. However, the register claim for invention patent for PDS sizing agent (PDS-SIZE) has three substances in its constitution as follows:

(1) a mixture of fattys acids extracted from soybean with the following average constitution: Palmitic acid (13%) , Stearic acid (5%) , Oleic acid (22%) , Linoleic acid (50%) , Linolenic acid (8% maximum) . These substances are extracted from soybean seed by means of brute oil distillation.

(2) Starch: this product is^" already used in other sizes with the same function. (3) Aluminum sulphate.

In the formulation of PDS-SIZE, the percentages referent to each substance are: 12,69% of fattys acids, 4,72% of starch, 6,09 % of aluminum sulfate and 76,5% of water. These percentages can vary for more or for less. The PDS-SIZE fabrication stages are:

(1) Cooking of the starch at 5% of solids (ebullition for 20 minutes with constant mechanical agitation) , cooling at ambient temperature; (2) Heating of the fatty acid in steam bath, at 35°C temperature;

(3) Formulation of 160 grams of cooked starch (4,72% of starch and 76,5% of water), 25 grams of fattys acids at 35DC (12,69%) and 12 grams of aluminum sulfate (6,09%). Allocating all the weighted mass in the emulsifier container and operating it at the maximum velocity for 20 minutes promoting the emulsification.

Two great advantages of this product are its biodegradable organic characteristic and its renewable source, since soybean is cultivated in Brazil in large scale.

Table 1:

Structure of main saturated and unsaturated fattys acids present in the oil vegetable,

Saturated Carboxylic Acid Unsaturated Carboxylic Acid

CH CH COOH CH₃[CH₂]₅ [CH₂]_?COOH

\ /

Caprylic Acid HC=CH

CH₃[CH₂]₈COOH Palmitoleic Acid

Capric Acid CH₃[CH₂]₇ [CH₂]₇COO \ / CH₃[CH₂]₁₀COOH HC-CH

Lauri Acid Oleic Acid CH₃[CH₂]₁₂COOH CH₃[CH₂] i CH₂ [CH₂]₇COOH

Myristic Acid \ / \ / HC=CH HC=CH CH₃[CH₂l COOH Linoleic Acid

Palmitic Acid CHJCHJ CH₂ CH₂ [CHJ.COOH

CH CH ⁴ \ / \ / \ / * '

2^J 1β COOH HC=CH HC=CH HC=CH Stearic Acid Linolenic Acid

Table 2: Fattys acids of anyone vegetable oil and fats.

Palm tree Babassu Sesame Oormen

Fat and Oil Snfiron Cotton Peanut Rice Buriti Canol« Coconut Sunflonvr Intlai* Linrced λlacnύba . „ Corn Olive Palm oil Soybean oil oil wheat bullet

Caproic C:6:0 3-6 5-11

Caprylic C:8:0 4-7 5-10 12 6

F Capric C:10:0 10 5 a Laurie C: 12:0 44-46 45-50 44 44 t

Mristic C:14:0 1-2 1-2 1-3 1 15-20 18-20 11 9 1-2 1 1 1 t y Palmitic C: 16:0 5-8 18-25 35-43 17-12 15 6-9 16 4 5-10 6-8 14 7 7 4-6 5 25-30 7-11 5-15 48 6-14 s

Stearic C: 18:0 3-5 1-2 3-5 2-6 2 3-5 1 2 1-4 2-5 4 3,3 3 2-3 2 30-35 3-4 1-4 4 2-7

A Araquidic C:20:0 1-3 1 1 c Palmitoleic C:16:l (9) 1 0,4 0,1 0,4 i d 01eic C:18:l (9) 15-20 17-37 34-56 30-58 45 14-19 79 60 6-8 45-50 20 14 13 13-28 26 35-40 23-2567-83 38 10-23 s Linoleic C: 18:2 (9,12) 50-27 44-55 9-11 21-37 36 1 19 1-3 40-45 55 75 2 3 2-4 50-57 7-12 9 50-59 Linolenic C:18:3 (9,12,15) 1 10 7 46-61 4-9

Others 1-2 1-2 1-2 2-3 1-2 1-2 2-3 1-2 1

Claims

CLAIMS 1. "PDS-SIZE", characterized by a constitution of 5 fattys acids extracted directly from the soybean oil from agriculture.

2. "PDS-SIZE", characterized for passing through an emulsifier the following substances: fattys acids extracted from soybean, starch and aluminum sulfate.

3. "PDS-SIZE" characterized for also using fattys acids extracted from another plants presented in Table 2, as well as the utilization of isolated fattys acids.