JPH03180589A - Production of water-soluble emulsion - Google Patents

Abstract

PURPOSE:To obtain the subject emulsion useful as a sizing agent exhibiting stable sizing effect independent of the kind of waste paper and the pH variation of raw pulp by dispersing an alkylketene dimer using a specific dispersing agent. CONSTITUTION:(A) A (1,1-dialkyl)polyalkylene polyamine or its mixture is made to react with (B) a substance selected from a 12-22C (un)saturated fatty acid, an alpha,beta-unsaturated polybasic acid addition salt and their mixture and the obtained reaction product is quaternarized by reacting with (C) an epihalohydrin in molten state or in water. The resultant water-soluble polyalkylene polyamine.fatty acid.epihalohydrin condensation product or water- soluble polyalkylene polyamine.alpha,beta-unsaturated polybasic acid-added olefin.epihalohydrin condensation product is used as a dispersing agent to disperse an alkylketene dimer in acidic state.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is directed to a water-soluble polyalkylene polyamine, a fat e<or α,β-unsaturated polybasic acid-added olefin yjet+fat used in combination or alone), and an epihalohydrin condensate. The present invention relates to a method for producing a water-soluble emulsion comprising dispersing an alkyl ketene dimer as a dispersant.

(Prior Art) Conventionally, in the paper manufacturing industry, the recycling rate of white water has increased due to wastewater regulations, and it has become difficult to obtain the desired sizing degree with anionic sizing agents.

Particularly in recent years, the popularity of coated paper has been remarkable, and calcium carbonate has been increasingly used as a filler in coated paper due to cost and quality considerations. As the amount of waste paper containing calcium carbonate increases, it becomes increasingly difficult to obtain the desired sizing degree using anionic sizing agents.

Moreover, the reuse of waste paper has recently been discouraged worldwide, and there is a strong demand in the industry for a sizing agent that can develop sizing properties under such circumstances. In particular, the performance of conventional AKD-based, ASA-based resin, and fatty acid-based sizing agents varies depending on the type of pulp, and none of them have the expected effect on GP-based sizing agents.In recent years, the industry has It exhibits excellent effects on the GP system. In particular, there is a strong desire for the emergence of a neutral sizing agent that can provide a constant sizing degree even under fluctuations in pH, including waste paper.

The present invention is confidently provided to meet the needs of the paper manufacturing industry.

Furthermore, the present invention is not only used as a sizing agent in the paper manufacturing industry, but also exhibits excellent water resistance when added during molding and papermaking of cement-based, gypsum-based, or rock wool boards.

(Means for solving the problem '(+')) The present invention provides polyalkylene polyamine/1,1-dialkyl polyalkylene polyamine or a mixture thereof and G.
tz~022 saturated fatty acids, Qxz~C22 unsaturated fatty acids, α,β-unsaturated polybasic acid addition olefin resins, and mixtures thereof, and then reacted in the melt or in water. Dispersing agent for water-soluble polyalkylene polyamine/fatty acid/shrimp halohydrin condensate or water-soluble polyalkylene polyamine/α,β-unsaturated polybasic acid addition olefin/epihalocedrin condensate obtained by reacting and quaternizing shrimp halohydrin with The present invention provides a method for producing a water-soluble emulsion, which comprises dispersing an alkyl ketene dimer under acidic conditions.

Examples of the 012-022 saturated fatty acids and C12-C22 unsaturated fatty acids used in the present invention include lauric acid, palmitic acid, stearic acid, oleic acid, and behenic acid.

As α,β-unsaturated polybasic addition olefin resin, carbon number Qxz ~ (3O α-olefin is 150'C~2
Refers to the addition reaction of maleic anhydride, fumaric acid, or itaconic acid under heating at 50°C.

Next, as polyalkylene polyamines, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, 1,1-diethylethylenetriamine,
Examples include 1,1-dimethylethylenetriamine, 1,1-diethylethylenetetraamine, and F,1-dimethylpropylenetriamine.

Furthermore, epichlorohydrin and shrimp frommohydrin are used as quaternizing agents.

Examples of emulsifiers that may be used as necessary include fatty acid esters of polyoxyethylene (fluoropylene) alkylphenol, alkyl esters of ethylene (propylene) oxide adducts of 5ec-alcohol, and the like.

The present invention uses 1.0 to 3.0 moles of fatty acid per 1.0 mole of polyalkylene polyamine or 1.1-dialkyl polyalkylene polyamine.
``GK is heated to perform a dehydration reaction.

In addition, when using a polybasic addition olefin resin, the amount is 1.0 mol to 3 mol in terms of polybasic acid per 1.0 mol of polyamine.
．． An amount equivalent to 0 mol is added and a heated lower arm water reaction is carried out in the same manner as for fatty acids.

Next, shrimp halohydrin k 0 was added to the active amino group (-NH-) of the amidated product obtained by the above method.
．． 5 moles to 3.0 moles'? :80°C to 100'C The above amide compound is dispersed in hot water of 70°C to 90°C, then shrimp halohydrin is added and the reaction is carried out at 60'C to 80'C.

The cationic aqueous solution obtained by such a method is referred to as 'k(A)', and is hereinafter referred to as (A).

As mentioned above, the greatest feature of the present invention is that it exhibits an excellent GP effect in the paper manufacturing industry, and is stable regardless of the type of waste paper or unaffected by pH fluctuations of the raw material pulp. This means that a size effect can be obtained. In addition, regarding the production of the present invention, the ratio of AKD (alkyl ketene dimer) and dispersant (the dispersant itself also exhibits a size effect), which was previously thought to be completely impossible, can be made as desired if the ratio '&(A) is 5 wt% or more. The emulsion obtained is also stable.

The ratio of AKD and (A) can be arbitrarily changed within the range of (A) being 5% or more, but preferably 11-<Ayn30~
80%, and (A) in the range of 70-20%.

The present invention will be described below with reference to examples, but the scope is not limited thereto.

Example (1) 189 g of tetraethylene pentamine was charged into a reaction vessel equipped with a distillation tube, and while introducing N2 gas, the temperature in the system was raised to 60°C, and 568 g of stearic acid was gradually added, followed by stirring. , the temperature was raised and the reaction was carried out at 200 to 2109 C for 4 hours, and the reaction was carried out in a case with an acid value of 3 or less.

After the reaction was completed, the temperature in the system was adjusted to 80°C after dispersing in 2884g (20%) of 60°C warm water, and 277.5g of epichlorohydrin and 2773.5g of clean water were added, and the mixture was heated to 70°C.
After the reaction was completed at 80° C. for 4 hours, the mixture was cooled and infiltrated to obtain a cationic aqueous solution having a solid content of 15% (referred to as dispersant A).

Next, add 133.3g of dispersant A (solid content 15%) to the emulsification pot.
Add 287.9 liters of fresh water (including the amount of HCI) and use HCl to make PHY 3.5. After that, the temperature inside the system was increased to 70℃.
Add 80g of AKD and melt and disperse. Next, use a piston-type high-density emulsifier to make the primary E250~. Secondary EE
The solution was rapidly cooled and infiltrated twice at 50% to obtain a 20% solution.

Example (2) 203 g of 1.1-diethyltriethylenetetraamine was charged into a reaction vessel, the temperature inside the system was raised to 50°C, 568 g of stearic acid was charged, and a heating dehydration reaction was carried out at 2000 C for 4 hours while introducing N2 gas.

After the reaction was completed, the mixture was dispersed in 4165 g of 40'C hot water, and 1039 g of fresh water was added to adjust the temperature in the system to 460°C, and the reaction was carried out at 190.460°C for 6 hours. The resulting 15% cationic aqueous solution was mixed with a dispersant (
B) and ding.

Next, add 15% dispersant (B) Y 466, 7 to the emulsification pot.
After adjusting the PHY to 3 using HCl'Y and raising the temperature in the system to 70°C, 30 g' of AKD was charged and melted and dispersed. Thereafter, the mixture was rapidly cooled and infiltrated twice through a piston-type high-quality emulsifying machine using a L.

Example (3) In Example (1), the cationic aqueous solution (A) was added to the emulsification pot at 191
and 1 g of oleyl ester of polyoxyethylene nonylphenol, HGI, and a total of 410 g of fresh water (pH 3.
After adjusting the temperature in the system to 65℃, AKD60
g was added and melted and dispersed, and then passed once through primary EE30 (l) using a piston-type high-pitched emulsifier to obtain a product with a diameter of 15 φ.

Example (4) 103 g of diethylenetriamine was charged to the reaction vessel N.
While introducing two gases, the temperature in the system was raised to 80°C.

Next, in addition to 322J' of a pre-produced maleic anhydride adduct of α-olefin with a carbon number of Cts (322 g of α-olenoin and 98.9' maleic anhydride reacted at 200 to 210°C for 5 hours), 200 ℃～210℃
A dehydration reaction was carried out for 3 hours. The obtained diethylenetriamine-maleic anhydride olefin amide resin Y2306. ! i' was dispersed in warm water (90°C). (Solid content: 15 g) Next, 1048 g of clean water and 185 g of epichlorohydrin were added, and a reaction was carried out for 4 hours at 75 g. The resulting cationic aqueous solution was added to 0 dispersant (C)' with 333.
A total of 117 g of HCl and water was charged into an emulsifying pot (adjusted to pH 3.5) and the temperature in the system was adjusted to 70°C.

After that, 50g of AKD was added and melted and dispersed, using a piston-type high-pressure emulsifier to give a primary pressure of 300 to 1? , Secondary EEO*/
After passing it through a C-metal once, it was rapidly cooled and the solid content was adjusted to 20φ.

Size performance test paper making conditions - (1) Valve: L-BKP Beating degree: C3F420 door 6 Basis weight: 65,! i'/m2 Amount of sizing agent added: 0.1%, 0.3% H1id filler:
CaGO3 vs. valve 30% Drying: 90%-50 (Tofum dryer) Paper temperature
: 40'C Size measurement method: Paper making conditions according to JIS P8122 (Stekicht method) - (2) Valve: Newspaper waste/magazine waste paper = 515 Beatness: C3F 230m1 Basis weight: 80g/m2 Amount of sizing agent added: 0.2φ, 0.3% 5olid dry
: 90℃-50” (drum dryer) Paper temperature: 4
0°C Size measurement method: Test results according to JIS P8122 (Stekicht method) Paper making conditions - (1) Paper making conditions - (2) 0.
1 more 0.3% 0.2 more 0.3% Example-(1)
13'5 31'4 11"330'4 Example-(
2) 7"0 21"4 9"821"4 Example-(3) 9#3 26'7 10"327'1
Example-(4) 9"0 29''4 9"728'9 Commercially available AKD system 6'l 18"7 0'2
As a result of the 7 measurements, it was found that the sizing agent of the present invention was superior to commercially available AKD products.

Claims (1)

[Claims] 1. Polyalkylene polyamine, 1,1-dialkyl polyalkylene polyamine or a mixture thereof and C_1
_2~C_2_2 saturated fatty acids, C_1_2~C_2_
2 unsaturated fatty acids, α,β-unsaturated polybasic acid-added olefin resins and mixtures thereof, and then quaternized by reacting with epihalohydrin in the melt or in water. , the obtained water-soluble polyalkylene polyamine/fatty acid/epihalohydrin condensate or water-soluble polyalkylene polyamine/α,β-
A method for producing a water-soluble emulsion, which comprises dispersing an alkyl ketene dimer under acidic conditions using an unsaturated polybasic acid-added olefin/epihalohydrin condensate as a dispersant. 2. The method according to claim 1, wherein an emulsifier selected from the group consisting of fatty acid esters of polyoxyalkylene alkylphenols, alkyl esters of alkylene oxide adducts of sec-alcohols, and mixtures thereof is used in combination with the water-soluble condensate.