JPS6330439B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention describes the use of special quaternization products of fatty acids and basic resin amides derived from polyalkylene polyamines and/or technical mixtures thereof in the form of aqueous preparations having a melting point higher than 30°C. This invention relates to a sizing agent for paper. So-called resin sizes based on abietic acid are commonly used as pulp sizing agents for paper. However, these sizing agents are not completely satisfactory insofar as they require alum as an additive, so other pulp sizing agents that do not require the addition of alum, such as fatty acid anhydrides or ketenes of fatty acids, isocyanates, etc. or chlorocarbonyl derivatives have been developed. The disadvantages common to all these known sizing agents are that they are difficult to emulsify, that cationic additives generally have to be used to obtain a satisfactory sizing, and also that ketene, The sensitivity of anhydride or isocyanate groups to water means that they can be stored in aqueous emulsions at room temperature for only a limited period of time. Stearic acid, or reaction products of fatty acid amines and maleic anhydride, can also be used as pulp sizing agents, but they are effective only when used in large amounts or when alum is added. According to DE 1771243, reaction products of polymeric fatty acids and polyamines are also
If they react with precisely defined amounts of epichlorohydrin, they can be used as pulp sizing agents. However, although materials such as these are eminently suitable for surface sizing, they have only a weak pulp sizing effect. The following amides containing on average two additional basic amino groups are particularly useful as sizing agents, especially when 0.05 to 5% by weight, based on solids, of electrolyte are added to their aqueous formulations. It has now been found that it is eminently suitable for use as a pulp sizing agent. The amides are composed of oligomeric alkylene amines containing more than two nitrogen atoms and C ₁₀ -C ₂₆ fatty acids that are solid at room temperature, especially
The reaction product with a _C12 to _C18 fatty acid, such as lauric acid, myristic acid, palmitic acid and preferably stearic acid) is quaternized with 0.5 to 2 equivalents of epichlorohydrin in the presence of water. (Note that the above equivalent weights refer to the amino groups in the amides to be quaternized). They are used in the form of aqueous solutions, suspensions or emulsions, optionally mixed with other sizing agents. For example, when using stearic acid, which melts at about 69°C, the corresponding amide compounds provide effective pulp sizing agents, whereas similar compounds produced using, for example, oleic acid, which is liquid at room temperature, It was found that the effect was insufficient. The proposal so far (Japanese Unexamined Patent Publication No. 147205/1989) is 30
The present invention relates to the use of sizing agents for paper in the form of preparations of salts and/or quaternization products of basic fatty acid amides derived from fatty acids having a melting point above .degree. Crystalline fatty acids and general formula H ₂ N−(R′NH) _o −
RNH ₂ linear polyamines and/or the reactants which are on average dibasic from their technical mixtures are treated according to the invention with approximately stoichiometric amounts of epichlorohydrin in the presence of water. When quaternized using
Surprisingly, the present invention represents a considerable improvement over this previous proposal, as it gives a product with a significantly improved efficacy, i.e. a good sizing effect can be obtained using considerably smaller amounts of linear amines. Has a point. Furthermore, the possibility of using technical mixtures of amines has the advantage that expensive separation steps for producing frame-pure linear amines can be omitted. Another advantage is that the present invention allows the addition of electrolytes, which surprisingly reduce the viscosity of aqueous sizing agent formulations considerably without appreciable loss of activity, thus making it easier to handle them at a given concentration. Improve. Therefore, the present invention provides fatty acids having a melting point higher than 30°C and fatty acids of the general formula H ₂ NR-(NH-R') _o -NH ₂ [wherein R and R' are the same or different] and each represents an alkylene group of 2 or 3 carbons, and n has a value of 1 to 6] and up to 80% by weight of rings having approximately the same industrial boiling range. Formula and/or branched amines, e.g.

Amides of average dibasic nature obtained from tertiary aminoalkylamines or aminoalkylpiperazines of the formula, which may contain accompanying substances consisting essentially of The amides are quaternized with 0.5 to 2 equivalents of epichlorohydrin (based on the amino group in the basic amide) in the presence of water, and then optionally an aqueous preparation of quaternized basic fatty acid amides, which may be further diluted to a solids concentration of
A sizing agent for paper having an electrolytic value of 0.05 to 5% by weight is provided. The above-mentioned concomitant substances of the industrial amines may further contain small amounts of unidentified by-products so as not to impair the production and effectiveness of the sizing agent according to the invention. Suitable main fatty acids are fatty acids having a melting point above about 30 DEG C. having 10 to 26 carbon atoms, preferably 12 to 18 carbon atoms, or mixtures of these individual fatty acids. Stearic acid or stearic acid-containing fatty acid mixtures are particularly suitable. However, other fatty acids,
For example, tallow acid, cocinic acid
It is also possible to use palmitic acid, apietic acid, arachidic acid and behenic acid, hydrogenated oleic acid or other fatty acids obtained by oxo synthesis or similar methods. Amines or technical amine mixtures suitable for the production of basic fatty acid amides are preferably polyethylene polyamines, such as diethylene triamine,
They are triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. The corresponding propylene amines are also suitable. Of particular interest is technical triethylenetetramine. By-products produced due to their similar boiling point properties in industrial polyethylene polyamines are, for example, aminoethylpiperazine, trisaminoethylamine, N,N'-bis-aminopipepyrazine,
Aminoethylated N- in the form of different isomers
aminoethylpiperazines and a number of other non-fixed impurities, most of which
The amount is less than 10% by weight. The amount of linear compounds according to the formula is at least 20% by weight, and preferably
Should be at least 40% by weight. Mixtures of technical polyalkylene polyamines with different boiling ranges can also be used in the process. For conversion to the quaternization product, epichlorohydrin is used in an amount of 0.5 to 2 equivalents, based on the amino groups present in the basic amide, preferably 0.5
An amount of ~1.5 equivalents is used. Larger amounts of epichlorohydrin can easily be used, but they do not provide any significant effect enhancement. Other quaternizing agents such as dimethyl sulfate, diethyl sulfate, propane sultone,
Benzyl chloride, alkylene oxide or chloroacetamide may optionally also be considered, but these are not critical. Based on the amount of amine used, the fatty acids required for the preparation of the preliminary amide for the sizing agent according to the present invention are such that the resulting basic amide contains on average about 2 basic amino groups per molecule. For example, about 2 moles of stearic acid are reacted per mole of triethylenetetramine. Basic amides can be prepared by various methods known to those skilled in the art, such as by heating stoichiometric amounts of stearic acid and an amine to 180°C to 220°C, optionally under a nitrogen atmosphere, and It can be produced by slowly distilling off the water produced during amide production. The amidation product should have an acid number of less than 20, preferably less than 5. After cooling to a suitable temperature range, e.g. around the melting point of the amide, which is usually in the range of about 60°C to 130°C, the resulting basic amide melt is reacted with a quaternizing agent in water. and after a reaction time of 0.5 to 10 hours, optionally with the addition of another amount of water, preferably still hot, and after stirring for a further 0.1 to 10 hours at 60 to 130°C, 5 to 40 wt. %, preferably 10 to 25% by weight, as a suspension or emulsion. This is generally accomplished by simple stirring, but in some cases it may be desirable to use mechanical emulsifying means. In one variant of the process for producing the sizing agent according to the invention, a small amount of quaternizing agent, i.e. up to 50% by weight of the total amount of epichlorohydrin required, is added to the molten basic amide before the first addition of water. Add. In this method, the emulsifier is produced in situ, which allows the water added immediately before the main quaternization reaction to be distributed more uniformly in the reaction medium. It has been demonstrated that the amount of water present during the quaternization reaction should be less than the amount of water subsequently contained in the aqueous sizing agent formulation, because this method This is because adjustment of the required concentration of the agent can be optimally combined with the addition of electrolyte. In many cases, it has proven sufficient and preferred from a processing standpoint to initially add only about 100 to 900% by weight of water, based on the amount of basic amide used, during the quaternization reaction. I am forced to do so. However, even without the addition of water, a final product with surprisingly reduced activity is obtained. At solids contents of more than 10% by weight, the aqueous sizing agent formulations described above often have a tackiness that causes handling problems. According to the invention, in these cases, 0.05
~5% by weight, preferably 0.1-1% by weight of electrolyte can be added to the formulation. This is best done by dissolving the required amount of electrolyte in the water used for final dilution during the final dilution of the sizing agent formulation and adding the electrolyte in this manner. The electrolyte can also be added at the beginning or during the first or second addition of water, and it has been found to be most effective to add the electrolyte at the beginning or during the first or second addition of water. However, it has been found that it is most effective to add the electrolyte as late as possible in the dilution process. The formulation obtained in this way is a thin liquid for a solids content of more than 10% by weight and does not thicken afterwards. Besides organic salts such as ammonium or alkali formates, acetates, benzoates, phosphates or sulfonates, suitable electrolytes are preferably inorganic salts such as ammonium chloride, potassium chloride, calcium chloride, chloride zinc, aluminum chloride or more preferably sodium chloride,
However, in principle also soluble chlorides, nitrates, sulphates, phosphates and carbonates of other elements and their acids or bases are suitable.
In many cases, even hard water or mineral-containing tap water produces adequate electrolyte effects. The aqueous sizing agent formulations obtained in this way are ready for use and have a solids concentration of 5 to 40% by weight, preferably 10 to 25% by weight. The formulations are further diluted during their application to the specific concentration required, for example to a concentration lower than 0.5% by weight of the type commonly used in paper sizing. The sizing agents according to the invention have the advantage that in the form of their aqueous formulations they can be stored in a constant state without significant loss of activity and do not require the addition of alum or cationic or anionic auxiliaries. ing. However, such additives can also be used and should be taken into account, for example cationic starches, quaternized polyamines, quaternized polyamidoamines, quaternized basic formaldehyde resins, methylcellulose, carboxymethylcellulose, lignin sulfonic acids, starches and polysaccharides of different origins, pullulan, chitosan; polymers or copolymers of (meth)acrylic acid, maleic acid, fumaric acid and itaconic acid. or other polymers or copolymers with carboxylic or sulfonic acid groups optionally present in salt form, collagen, gelatin, alginates and caragenates (made from seaweed) Mention may be made of the addition of auxiliaries based on natural polysaccharides). Their effectiveness is not adversely affected by white toners or cationic and especially anionic dyes, but is even improved; furthermore, aqueous formulations can also be formulated without emulsification aids. The sizing agents according to the invention are used on their own or in combination with other sizing agents which are particularly suitable for pulp sizing of paper, but they can of course also be used for surface sizing. They can be used not only for thioyoke-containing or kaolin-containing papers, but also for papers containing no fillers or containing other types of fillers, such as talc or gypsum. They are also suitable for sizing cellulosic materials such as cardboard, textile materials, cardboard or wood chip paper and insulating paper and leather. The invention is further illustrated by the following examples.
The parts and percentages quoted therein are by weight unless otherwise specified. Example 1 (Comparative Example) As an example of prior art for comparison,
"Sizing agent 2" described in Example 2 of the specification of No.-147205 was produced as follows. Sizing agent 2 146 parts of triethylenetetramine and 569 parts of stearic acid were refluxed at 180°C under nitrogen atmosphere for 5 hours.
heated for an hour. All fractions that are volatile at that temperature are then distilled off with thorough stirring. After cooling to 95°C, a solution of 5210 parts of 90 parts of acetic acid in water, which had been preheated to 90°C, was added to the resulting basic amide with thorough stirring. This resulted in an emulsion, which was cooled while stirring. It could be used as a linear sizing agent. Its solids content was approximately 10%. Example 2 Preparation of dibasic amide: 170 parts of stearic acid were melted and stirred with 43.8 parts of triethylenetetramine (molar ratio, approximately 2:1). Then the temperature was increased to 190℃ under nitrogen atmosphere.
and all volatile fractions were distilled off. An acid value of 1.9 was reached after 6 hours. The resulting amide had a melting point range of 87-107°C. Production of sizing agent A 480 parts of the basic amide produced above was heated at 120°C.
and then stirred with 240 parts of water to form a pasty mixture under gentle reflux. next
86.4 parts of epichlorohydrin (0.67 mol/amino group) were added with stirring as quickly as possible, followed by stirring for 1 hour under gentle reflux. Next, 1080 parts of water was added, and the mixture was stirred for an additional hour under gentle reflux. The resulting paste is then cooled to approximately 50°C and then 5.6 parts NaCl (0.5% on solids basis)
967 parts of a solution in water was added. An approximately 20% emulsion, which is a thin liquid at room temperature, was obtained, which was used as a sizing agent. Example 3 Sizing Agent B 201 parts of the basic amide prepared according to the method set forth in Example 2 were stirred at 120° C. with 3.7 parts of epichlorohydrin for 30 minutes. about 95
Then add 1252 parts of water that has been preheated to
Then 32.3 parts of epichlorohydrin was added. Stirring for 1.5 h under gentle reflux gives a thick emulsion with a solids content of 16%, which then evaporates to about 30%
Cooled to ℃. To produce a thin liquid emulsion, the thick emulsion thus obtained is divided into 2.3
diluted with a solution of 92 parts NaCl in water to a solids content of 15%. This emulsion could be used as a sizing agent. Example 4 Sizing Agent C 201.6 parts of the basic amide prepared according to the method set forth in Example 2 were stirred at 120° C. with 3.7 parts of epichlorohydrin for 30 minutes. 70
1 part of water and then 32.3 parts of epichlorohydrin were added, followed by stirring at 100°C to 120°C for 1 hour. Next, add 1182 parts of water that has been preheated to about 95°C.
The resulting emulsion was then stirred under gentle reflux for about 1 hour. After cooling to about 40°C, 1.2 parts of
A 92 parts solution of NaCl in water was added to the pasty emulsion to produce a thin liquid sizing formulation with a solids content of approximately 15%. The standard used for evaluating sizing agents is the so-called ink float test. In this exam,
A piece of paper sized with the sizing agent to be tested is placed on the surface of a dish filled with a standard ink according to DIN53 126 and the ink penetrates through the side of the paper facing the observer. Measure the time spent. In standardized form, this test is a very valid evaluation method for various sizing agents. Compared to common reactive sizing agents, the sizing agent according to the invention can be stored almost unchanged in the form of an aqueous formulation, and this is technically advantageous. A comparison with the resin size (sizing agent 1) reveals another technical advantage of the sizing agents according to the invention, namely their high effectiveness. Another significant advantage is that the sizing agent of the present invention does not contain alum, which has very little effect on resin sizing, and on paper which may optionally contain a clarifying agent. However, it does show a considerable effect. Therefore, the sizing according to the invention was also tested, for example, on an alum-free paper containing chiyoke. 5 g of a mixture consisting of 50 g of pine sulphite pulp, 50 g of western beech sulphate pulp and 25 g of chiyoke
was suspended in 200 ml of tap water. Then x% (solids content based on pulp and filler) of sizing agent was added with stirring. The suspension was then made up to about 1 with water without a binder and paper was made on a paper making machine. The paper thus produced was filtered with suction, compressed and dried on a drying cylinder at 100° C. for 5 minutes. Pieces of the paper (2 cm x 6 cm) were cut out for the ink float test. The ink float times shown in the table below were observed. Alum-containing test paper sized using a commercially available resin size was used for comparison.

Table: The results of the ink float test show a significantly better sizing effect of the sizing agent according to the invention on thioyoke-containing paper. Example 12 The test was carried out in the same manner as in Example 11, except that the paper used contained kaolin instead of thioyoke. An ink float time of 10 minutes was measured. Example 13 The test was conducted in the same manner as in Example 9 except that the paper contained talc instead of tyoke. An ink float time of 12 minutes was measured. Example 14 The test was conducted in the same manner as in Example 10, except that the paper contained mechanical wood pipe instead of western beech sulfate pulp. An ink float time of 11 minutes was measured. Example 15 (Comparative) A basic amide was prepared in the same manner as shown in Example 2, except that the molar ratio of stearic acid to amine was 3:1. This amide is treated in the same manner as in the preparation of sizing agents A, B or C to give an emulsifier which, when used in amounts less than 1% according to Examples 5-11, gives an ink float time of less than 2 minutes. , it was deemed inappropriate. Example 16 A mixture of 710 parts stearic acid and 189 parts tetra-ethylenepentamine (approximately 2.5:1 molar ratio) was reacted to form an amide according to the method set forth in Example 2. Acid value: 3.8, melting point: 65-66°C Sizing agent D 240 parts of the above amide were mixed at about 100°C with 120 parts of water and 65 parts of epichlorohydrin (about 1 mole/
(amino group) for 1 hour. Next, 593 parts of water were added, followed by stirring for an additional hour under gentle reflux. Then 350 parts of water were added and the mixture was cooled to about 45° C. with stirring. The product is then treated with 1.5 parts of NaCl to produce a thin liquid emulsion.
Diluted with 203 parts of a solution in water to approximately 18% solids content. This emulsion was used as a sizing agent. Sizing tests conducted according to Examples 9-11 gave an ink float time of 16 minutes for 0.45% sizing. The following examples were carried out using technical amines.

[Table] Example 17 Amines E to K using the same formulation according to Example 2
Basic amides were produced from Amides, all with acid numbers less than 5, were further treated in the following manner: 201.6 parts of the amide were melted at 120°C, then at 80°C.
The mixture was stirred with 1252 parts of hot water while cooling to . A microparticle suspension was produced by adding 36 parts of epichlorohydrin to the resulting suspension at 80°C, which was then stirred at 80°C for 2 hours. Then lower the temperature to 40°C and add 1.15 parts NaCl
A solution of 92 parts of in water was added to the paste with thorough stirring. A thin liquid particulate suspension with a solids content of approximately 15% was produced, which was used as sizing agent EK. The ink float times shown in the table below were observed. An alum-containing test paper sized using a commercially available resin size (sizing agent 1) was used for comparison.

[Sizing agent (example of the present invention)]

A suspension was made by stirring 101 g of amide with 625 g of water at 80°C, to which 18 g of epichlorohydrin was added under vigorous stirring, and then 80 g of water was stirred at 80°C.
Stirring was continued for 2 hours at 0.degree. C. and cooled to 50.degree. C. while stirring. A solution of 0.6 g NaCl in 50 g water was added to this and the mixture was cooled to room temperature under stirring. [Sizing agent (example of the present invention)] A suspension was prepared by stirring 101 g of amide with 625 g of water at 80°C, and 18 g of epichlorohydrin was added to this under strong stirring, and then 80 g of amide was stirred at 80°C.
Stirring was continued for 2 hours at 0.degree. C. and cooled to 50.degree. C. while stirring. A suspension of 0.6 g CaCO ₃ in 50 g water was added to this and the mixture was cooled to room temperature under stirring. [Sizing agent (known example)] A solution was made by heating 101 g of amide and 625 g of ethanol to 80°C, and 18 g
of epichlorohydrin and stirred at 80°C for 4 hours, then 675g of water was added and ethanol was
Distillation was carried out under reduced pressure at 60°C. [Sizing agent (known example)] A solution was prepared by heating 101 g of amide and 238 g of ethanol to 80°C, and 18 g of ethanol was added to the solution.
of epichlorohydrin was added, stirred at 80°C for 4 hours, then 625g of water was added, and the ethanol was mixed with approx.
Distillation was carried out under reduced pressure at 60°C. [Sizing agent (known agent)] Make a solution by heating 101 g of amide and 119 g of ethanol to 80°C, and add 18 g of ethanol to this solution.
of epichlorohydrin was added, stirred at 80°C for 4 hours, then 625g of water was added, and the ethanol was mixed with approx.
Distillation was carried out under reduced pressure at 60°C. All of the above sizing agents are heated at 125°C.
The fixed content was approximately 14% by weight, as determined by evaporation at . Paper with a weight of 80 g/m ² was manufactured using an experimental paper making machine according to the following processing method. [A] Grinding degree 35~ consisting of 50 parts by weight of bleached birch sulfate pulp and 50 parts by weight of bleached pine sulfate pulp
Using 100 parts by weight of 40°SR wood pulp, an aqueous pulp liquor with a solids content of 2.5% was prepared and diluted with water to give a solids content of 1.7%. [B] Grinding degree 35~ consisting of 50 parts by weight of bleached birch sulfate pulp and 50 parts by weight of bleached pine sulfate pulp
100 parts by weight of 40°SR wood pulp and China
An aqueous pulp liquor with a solids content of 2.5% was prepared using 25 parts by weight of clay and diluted with water to give a solids content of 1.7%. After uniformly mixing the sizing agent ~ into the pulp liquid [A] and [B], paper is made,
It was dried at 100°C for 150 seconds. The amount of sizing agent used (solids percentage relative to paper pipe) is shown in Table 3.
Shown below. [Ink float test] Cut the sized paper to a size of 9 cm long and 2 cm wide, place it on top of the blue test ink (DIN53 126), leave it in contact for 1 minute, then remove it from the ink and cut it on blotting paper. After 15 minutes of pressing from the back side, the ink penetration into the paper (ie, sizing effect) was observed and qualitatively evaluated using the following 5-step method. 1: The ink does not penetrate at all 2: The ink penetrates up to 5% 3: The ink penetrates 5 to 15% 4: The ink penetrates approximately 50% 5: The ink penetrates completely (100%) [Water absorption test ] Cut the sized paper into pieces 9 cm long and 2 cm wide, measure the air dry weight, and soak in water at 20°C.
After soaking for a minute and then pressing between sheets of paper, the weight was measured again. Increased weight of paper in g/m ²
The water absorption amount was expressed in units. The results of the test are shown in Table 3.

[Table] From the results in Table 3, it can be seen that the sizing agent (and) of the present invention is different from the sizing agent (and) of the known example.
It can be seen that the sizing effect is extremely superior compared to the sizing effect.

Claims (1)

[Scope of Claims] 1 (a) a fatty acid or a mixture of fatty acids having a melting point higher than 30°C, and (b) a fatty acid having the general formula H ₂ NR-(NH-R') _o -NH ₂ [wherein, R and R' are the same or different and each represents an alkylene group having 2 or 3 carbon atoms, and n has a value of 1 to 6. / or technical mixtures of the above amines which may contain concomitant substances consisting essentially of cyclic and/or branched amines having approximately the same technical boiling range up to 80% by weight; On average dibasic amides obtained from Aqueous formulations of quaternized basic fatty acid amides, which have been quaternized and optionally further diluted with water to the desired solids concentration, and their solids content. A sizing agent for paper consisting essentially of 0.05 to 5% by weight of electrolyte. 2. The sizing agent according to claim 1, wherein stearic acid or a stearic acid-containing fatty acid mixture is used as the fatty acid or fatty acid mixture. 3. The sizing agent according to claim 1 or 2, which uses polyethylene polyamine as the amine. 4. Use of technical mixtures of polyethylene polyamines as amines, which contain branched and/or cyclic amines in addition to the linear main component;
The sizing agent according to claim 1 or 2. 5. The sizing agent according to claim 1 or 2, which uses industrial triethylenetetramine as the amine. 6. The sizing agent according to any one of claims 1 to 5, which uses sodium chloride as an electrolyte.