JPS6156360B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for producing a paper sizing agent, in particular to a low polymer of one or more types of lower olefins or a low polymer of spent _C4 fraction, by adding an α,β-unsaturated dibasic acid, and After reacting with urea,
This article relates to a method for producing a sizing agent that undergoes alkali saponification. Two types of sizing agents are mainly used in paper manufacturing: rosin-based and petroleum resin-based.However, from the viewpoints of resource conservation and pollution control, recent paper mills recycle and reuse white water, reducing the salt concentration of the water used. Hydrogen ion concentration is increasing. Therefore, it has become difficult to obtain sufficient sizing effects using conventional sizing agents. On the other hand, by adding α, β-unsaturated dibasic acids to low polymers of olefins obtained in the field of petroleum distillates,
A method for producing a sizing agent by saponifying the product with an alkali has been proposed (for example, Japanese Patent Application Laid-open No. 51-35706), but
The raw material low polymer-unsaturated acid additive used in this method has a softening point of about 35 to 40°C, and a high saponification value of about 350. Therefore, the resulting sizing agent requires a large amount of sulfate ions for fixation, and as a result, the amount of sulfate ions contained in the paper increases, causing a deterioration in paper quality. Furthermore, due to the low softening point of the raw material, the sizing agent has a tendency to stick to the felt or dryer surface, which is especially noticeable when paper is made at high temperatures, such as high-quality paper or heavy-duty paper, which can reach as high as 70°C at 50°C. It is not suitable for practical use. As a result of intensive research to eliminate these drawbacks, carbon obtained by polymerizing one or more types of lower olefins such as ethylene, propylene, butylene, pentene or cyclopentene, or by polymerizing a spent _C4 fraction. When urea is reacted with an α,β-unsaturated dibasic acid adduct of a low polymer olefin having a number of 8 to 30, the softening point of the product increases by 10 to 15°C compared to the polybasic acid adduct. It has been found that the saponification value is greatly reduced, for example, in the case of maleic anhydride adducts, it is reduced to about 1/2. This is because at least one of the carboxylic acid groups in the α,β-unsaturated dibasic acid adduct of the low polymer olefin binds to urea and is blocked, and for this reason, the reaction ratio of both is ratio is preferred. The urea-modified product thus obtained can be used directly or mixed with other sizing materials such as rosin, modified rosin; petroleum resin; maleic acid-modified petroleum resin or its urea-modified product and then subjected to alkali saponification to produce excellent paper-making properties. A sizing agent is obtained. The low polymer olefin having 8 to 30 carbon atoms used as a raw material is selected from commercially available products manufactured by the petrochemical industry depending on the purpose. Typical α,β-unsaturated dibasic acids include maleic acid, maleic anhydride, and fumaric acid. The reaction between the low polymer olefin and the α,β-unsaturated dibasic is carried out using a Friedel-Crafts catalyst (e.g., AlCl ₂ , BF ₃ , FeCl ₃ ), a free radical generator (e.g., benzoyl peroxide, di-t) in a conventional manner. ―
butyl peroxide) under heat. The resulting modified low polymer olefin is mixed with urea and heated to react at a temperature of 140 to 180°C, preferably 150 to 170°C, within several hours, usually one hour. Subsequently, the urea-modified product is saponified with an alkali, using caustic soda, caustic potash, ammonia and alkanolamines. In the present invention, it is also possible to control the properties of the resulting sizing agent by adding rosin, modified rosin, petroleum resin, maleic acid-modified petroleum resin, or urea-modified product thereof during the manufacturing process. According to this invention, α, β-
Since the saponification value of the urea-modified low polymer olefin with unsaturated dibasic acid is low, only a small amount of alkali is required for the production of the sizing agent. The amount used can also be reduced. Furthermore, since the softening point of the raw material is higher than that of simple unsaturated acid-added low polymer olefin, the resulting sizing agent can be used without fear of contaminating felts and dryers. Furthermore, the sizing agent is stable against fluctuations in papermaking conditions, is less affected by increases in water hardness and the presence of filler, and has the characteristics of providing a high degree of sizing. The invention will be explained in further detail in the following examples. Example 1 213 parts of propylene pentamer was charged into a reaction vessel equipped with a condenser, and the temperature was raised to 100°C. After that, 98 parts of maleic anhydride was added and the reaction was carried out at 200°C to 210°C for 8 hours in the presence of nitrogen gas. . After the reaction is complete, increase the temperature in the system to 150℃~
After the temperature was lowered to 160°C, 60 parts of urea was gradually added, and the reaction was carried out at the same temperature for 1 hour. After the reaction was completed, unreacted materials were removed under reduced pressure to obtain a base resin with a saponification value of 173. Next, 100 parts of the obtained resin was transferred to an emulsification pot with a stirrer, 34.6 parts of a 50% aqueous caustic potassium solution was added, and the mixture was saponified by heating. A predetermined amount of water was then added to obtain a paper sizing agent with a solid content of 30%. . Comparative Example A propylene pentamer and maleic anhydride were reacted according to Example 1 to obtain a base resin with a saponification value of 350. 100 parts of base resin in 50% caustic potassium solution 70 parts
The mixture was saponified by heating and diluted with water to obtain a paper sizing agent. Example 2 213 parts of propylene pentamer and 98 parts of maleic anhydride were placed in a reaction vessel equipped with a condenser, and 1.5 parts of di-tertiary butyl peroxide was added as a catalyst, and the mixture was heated at 170°C to 180°C in the presence of nitrogen gas. The reaction was carried out for 5 hours. After the reaction is complete, reduce the temperature in the system to 150℃
After the reaction was completed, the temperature was lowered to ~160°C, 60 parts of urea was gradually added, and the reaction was continued at the same temperature for an additional hour.
Unreacted substances were removed under reduced pressure to obtain a base resin with a saponification value of 170. Next, 100 parts of the obtained resin was transferred to an emulsification pot equipped with a stirrer, and 34.6 parts of a 50% caustic potassium aqueous solution was added for saponification by heating, followed by adding a predetermined amount of water to obtain a paper sizing agent with a solid content of 30%. Example 3 After 168 parts of propylene tetramer was charged into a reaction vessel equipped with a condenser and the temperature was raised to 70°C, 98 parts of maleic anhydride was added and a reaction was carried out at 200 to 210°C for 8 hours in the presence of nitrogen gas. After the reaction was completed, 60 parts of urea was gradually added to reduce the temperature in the system to 150°C to 160°C, and the reaction was carried out at the same temperature for 1 hour. After the reaction was completed, unreacted materials were removed under reduced pressure to obtain a base resin with a saponification value of 180. Next, 100 parts of the obtained resin was transferred to an emulsification pot equipped with a stirrer, 36.0 parts of a 50% aqueous caustic potassium solution was added, and the resin was saponified by heating. A predetermined amount of water was added to obtain a paper sizing agent with a solid content of 30%. Example 4 115.5 parts of α-olefin (trade name Dialene 168, C ₁₆ - _{C 18} ) was charged into a reaction vessel equipped with a condenser and the temperature was raised to 70°C. 49 parts of maleic anhydride was added and the mixture was heated to 220°C in the presence of nitrogen gas. The reaction was carried out at 210°C for 7 hours. After the reaction was completed, the temperature in the system was lowered to 150°C to 160°C, 60 parts of urea was gradually added, and the reaction was carried out at the same temperature for 1 hour. After the reaction is complete, unreacted substances are removed under reduced pressure to determine the saponification value.
A base resin of 157 was obtained. Next, 100 parts of the obtained resin was transferred to an emulsification pot with a stirrer, and 31.4 parts of a 50% caustic potassium aqueous solution was added.
After saponifying the solid content, add a certain amount of water to reduce the solid content to 30%.
% paper sizing agent was obtained. Example 5 Polybutene (molecular weight = 350) in a reaction vessel with a cooler
After charging 350 parts and raising the temperature to 100°C, 98 parts of maleic anhydride was added and the reaction was carried out at 200°C to 210°C for 7 hours in the presence of nitrogen gas. After the reaction is complete, reduce the temperature in the system.
The mixture was cooled to 150°C to 160°C, 60 parts of urea was gradually added, and the reaction was carried out at the same temperature for 1 hour. After the reaction was completed, unreacted materials were removed under reduced pressure to obtain a base resin with a saponification value of 100. Next, 100 parts of the obtained resin was transferred to an emulsification pot with a stirrer, and 20.0 parts of a 50% caustic potassium aqueous solution was added for saponification.
A predetermined amount of water was added to obtain a paper sizing agent with a solid content of 30%. Example 6 200 parts of commercially available petroleum resin (HiResin #60) and 168 parts of propylene tetramer were placed in a reaction vessel equipped with a condenser.
After heating to 120°C, 108 parts of maleic anhydride was added and reaction was carried out at 200°C to 210°C for 7 hours in the presence of nitrogen gas. After the reaction is complete, reduce the temperature in the system to 160°C to 170°C.
60 parts of urea was gradually added and the reaction was carried out at the same temperature for 1 hour. After the reaction was completed, unreacted materials were removed under reduced pressure to obtain a base resin with a saponification value of 95. Resin obtained next
Transfer 100 parts to an emulsifying pot with a stirrer and add 17.1 parts of 50% caustic potassium aqueous solution and 5.16 parts of 50% triethanolamine aqueous solution.
After adding a certain amount of water and saponifying it, add a certain amount of water to dissolve the solid content.
A 30% paper sizing agent was obtained. Example 7 213 parts of propylene pentamer was charged into a reaction vessel equipped with a condenser and the temperature was raised to 100°C, and then 98 parts of maleic anhydride was added and the reaction was carried out at 200°C to 210°C for 8 hours in the presence of nitrogen gas. . After the reaction is completed, the temperature in the system is 150℃~160℃.
The mixture was cooled to °C, 60 parts of urea was added, and the reaction was carried out at the same temperature for 1 hour. After the reaction was completed, unreacted materials were removed under reduced pressure to obtain a base resin with a saponification value of 171. Resin obtained next
Transfer 50 parts to an emulsifying pot with a stirrer, add 50 parts of rosin, saponify by adding 24.8 parts of 50% caustic soda, then add the specified amount of water to make a paper sizing agent with a solid content of 30%. Obtained. 4 Size performance comparison test 4-1 Paper making conditions Pulp: L-BKP Beating degree: SR 30゜tsubo Amount: 60g/m ² size addition amount: 0.3 0.5 0.7% solids Fixing pH: PH4.5 at band Drying conditions: 90°C for 2 minutes (using a drum dryer) Size measurement method: JIS.P.8122 (Stekicht method)

[Table] 4-2 Paper making conditions Pulp: L-BKP Beating degree: SR 30゜tsubo Amount: 60g/m ² size addition amount: 0.8% Solid content Fixing pH: Adjusted to PH4.5 with band Hardness :0 20 40゜dH (using synthetic seawater) Drying conditions: 90℃ for 2 minutes (for drum dryer) Size measurement method: JIS.P.8122 (Stekicht method)

【table】

[Table] 4-3 Paper making conditions Pulp: L-BKP Beating degree: SR 40゜tsubo Amount: 70g/m ² size addition amount: 0.3 0.5 0.7% solids Fixing pH: Adjusted to PH4.5 with band Filler: 20% clay Drying conditions: 90°C for 2 minutes (using a drum dryer) Size measurement method: JIS.P.8122 (Stekicht method)

【table】

[Table] 4-4 Paper making conditions Pulp: L-UKP Beating degree: SR 26゜ Tsubo Amount: 80g/m ² size addition amount: 0.1 0.2 0.3% solids Fixing pH: PH5.0, 5.5 at band Drying conditions: 90°C for 2 minutes (using a drum dryer) Size measurement method: JIS.P.8122 (Stekicht method)

【table】

【table】

Claims (1)

[Claims] 1. A method for producing a paper sizing agent by adding an α,β-unsaturated dibasic acid to a low polymer olefin having 8 to 30 carbon atoms, then reacting it with urea, and saponifying the resulting product with an alkali. .