JPH0629327B2 - Method for producing aqueous emulsion - Google Patents

Description

The present invention relates to a sizing agent for papermaking, cement or gypsum, which comprises dispersing a rosin or a modified rosin in the presence of a water-soluble cationic resin or a cationic aqueous emulsion. The present invention relates to a method for producing an aqueous emulsion used as a waterproofing agent or the like.

(Prior Art) In recent years, reuse of waste paper has been avoided in the paper manufacturing industry, which has caused various harmful effects. In particular, calcium carbonate is used as a filler and pigment for color-coated paper, and therefore the content of calcium carbonate in the waste paper is increasing. Currently, anionic sizing agents are mainly used in the paper manufacturing industry, and in recent years anionic rosin emulsion sizing agents have been used. Is often used. Further, in the anionic type sizing agent, a sulfuric acid band is generally used as a fixing agent for the sizing agent. The use of the sulfuric acid band causes a very serious problem in the paper manufacturing industry, such as the problem of foaming due to the generation of CO ₂ which reacts with the calcium carbonate in the waste paper, the precipitation of the generated gypsum and the desired size performance, and the like. ing. Under such circumstances, the industry has long eagerly anticipated the appearance of a sizing agent that can achieve an excellent sizing effect even when the sulfate band is extremely reduced.

(Means for Solving the Problem) The present invention is to add a α, β unsaturated polybasic acid to a petroleum resin, and then to react with a polyalkylene polyamine or an N, N dialkyl polyalkylene diamine. Provided is a method for producing an aqueous emulsion, which comprises reacting an agent, an inorganic acid or an organic acid to make it water-soluble, and dispersing a rosin or a modified rosin using the obtained water-soluble cationic resin as a dispersant. A cationic aqueous resin emulsion obtained by emulsion-polymerizing a styrene monomer and an acrylic monomer using the water-soluble cationic resin as a dispersant can also be used as a dispersant for rosin or modified rosin.
Further, the water-soluble cationic resin and the cationic aqueous resin emulsion are each used in combination with a cationic surfactant or a nonionic surfactant such as trimethyl chloride of higher fatty acid to disperse rosin or modified rosin. It can be used as a sizing agent for papermaking.

The present inventors have conducted earnest research to meet the demands of the industry, and intend to provide it this time.

The petroleum resin used in the present invention is a by-product when naphtha is decomposed. C ₅ fraction and C ₉ fraction were polymerized using a Friedel-Crafts type catalyst to have a softening point of 30 ° C to 120 ° C and a bromine number of 2
0-100 Preferably softening point 50-80 degreeC Bromine number 40-
The one of 60 is used.

As the α, β unsaturated polybasic acid added to the petroleum resin, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the like are used.

As the polyalkylene polyamine used in the present invention, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, etc. are used.
As the dialkyl alkylene diamine, 1,1 dimethyl propylene diamine, 1,1 diethyl propylene diamine, 1,1 diethyl ethylene diamine and the like are used.

Benzyl chloride, ethylene chlorohydrin or epichlorohydrin is used as the quaternizing agent, and hydrochloric acid, sulfuric acid, formic acid, acetic acid and the like are used as the inorganic and organic acids.

On the other hand, as the surfactant used as necessary, general nonionic surfactants such as polyoxyethylene nonylphenol ether and polyoxyethylene alkyl ether are used. Further, as the cationic surfactant, an alkyl trimethyl chloride quaternary salt or the like is used.

On the other hand, as the styrene-based and acrylic-based monomers, styrene, α-methylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxy acrylate, acrylate, etc. can be used.

If necessary, protective colloids such as polyvinyl alcohol, methyl cellulose and cationic starch can be used in combination. Further, if necessary, treatment with a high-pressure emulsifying machine is also effective for stabilizing the emulsion.

Examples will be described below, but the present invention is not limited to this range.

Example 1 92 parts of a petroleum resin having a softening point of 65 ° C. and a bromine number of 50 was charged into a reaction kettle, heated and melted, and when the temperature in the system reached 190 ° C., 8 parts of maleic anhydride was added to the reaction vessel at 200 ° C. to 220 ° C. Reaction was carried out for 5 hours.

After completion of the reaction, the temperature inside the system was adjusted to 180 ° C to 190 ° C, and 10.6 parts of 1,1 diethylpropylenediamine was added to 1
The reaction was carried out at 80 ° C to 190 ° C for 3 hours.

Then, the temperature in the system was cooled to 160 ° C to 170 ° C, 6.6 parts of ethylene chlorohydrin was added, and the mixture was heated at 160 ° C to 170 ° C for 3
After reacting for a time, the temperature in the system is adjusted to 120 ° C to 130 ° C.
The temperature was lowered to 60 ° C., and warm water at 60 ° C. was added to obtain a cationic resin solution having a solid content of 40%.

The obtained resin liquid is referred to as liquid A.

Next, 80 parts of 5% maleated rosin (95 parts of rosin / 5 parts of maleic anhydride reacted at 200 ° C. for 2 hours) was charged in an emulsification kettle, the temperature was adjusted to 160 ° C., and 50 parts of the above-mentioned solution A was added under stirring. Then, 120 parts of 90 ° C. warm water was gradually added to emulsify and disperse, and then cooled to 40 ° C. to obtain a cationic rosin emulsion having a solid content of 40%.

Example 2 75 parts of solution A and 250 parts of water were charged into an emulsification kettle, the temperature inside the system was adjusted to 80 ° C., 0.5 part of α, α azobisisobutyronitrile was added to 40 parts of styrene and 30 parts of methyl acrylate. Dissolve in the mixed solution of, and add dropwise over 30 minutes, the system temperature 80
The reaction was carried out at ℃ to 85 ℃ for 3 hours. The obtained emulsion (solid content: 25%) is referred to as B.

Next, 70 parts of 9% fumarized rosin was charged into an emulsification pot and 160
After melting by heating at ℃
Then, 10 parts of warm water of 0 ° C. was injected under pressure and then cooled to 40 ° C. to obtain a 50% solid content cationic rosin emulsion.

Example 3 5 parts of maleic anhydride was added to 95 parts of a petroleum resin having a softening point of 62 ° C. and a bromine number of 45, and the reaction was carried out at 200 ° C. to 210 ° C. for 6 hours.

Then add 7.6 parts of triethylene tetraamine and add 200
The reaction was carried out at ˜210 ° C. for 3 hours.

After the completion of the reaction, the temperature in the system was cooled to 100 to 110 ° C., 10 parts of glacial acetic acid was added, and then warm water at 80 ° C. was added to emulsify and disperse to obtain a cationic resin emulsion having a solid content of 40%. The obtained resin emulsion is referred to as liquid C.

Next, charge 80 parts of 6% maleated rosin into the emulsification kettle 16
After heating and melting at 0 ° C, 2% of formalin and modified rosin was added and reacted for 20 minutes, then 50 parts of the above liquid C was added under pressure, followed by addition of 116 parts of warm water at 80 ° C to emulsify and disperse, and then system temperature 40 The mixture was cooled to 0 ° C. to obtain a cationic rosin emulsion having a solid content of 40%. Then, 0.5% of cation starch to rosin was added as a protective colloid, and the mixture was passed once using a high-pressure emulsifier at a pressure of 200 kg / cm ² to obtain a cationic rosin emulsion having a solid content of 35%.

Performance Test- (1) This test is a performance test for observing the influence of the sizing agent used when the sulfuric acid band is reduced (that is, when the fixing pH value is high) on the sizing degree.

Paper was produced using the cationic rosin emulsion sizing agent of the present invention obtained in Examples 1 to 3, and the obtained paper was
The size degree was measured by the Steckigt method (JIS-P-8122). As a control, a paper obtained in the same manner using a conventional commercial anionic sizing agent was used.

The paper was manufactured under the following conditions.

Pulp: L / N (7/3) BKP Beating degree: CSF = 460 m Basis weight: 80 g / m ² Fixing pH: Adjusted to pH 4.5 and 6.0 by adding sulfuric acid band Sizing agent added amount: solid content conversion 0.3% by weight and 0.
Prepared to 5% by weight (pulp weight basis) Drying condition: 90 ° C for 2 minutes Papermaking process: disaggregation → (5 minutes) → band → (5 minutes) → size → (5 minutes) → papermaking temperature: 40 ° C (result ) The test results are shown in the table below.

As can be seen from the above table, the sizing degree of the paper made using the sizing agent of the present invention is better than that of the control, and is particularly excellent at a high pH value of pH 6.0.

Performance Test- (2) This test is a performance test of sizing degree when using a magazine waste paper containing calcium carbonate as a pulp raw material.

Using magazine waste paper containing calcium carbonate as a pulp raw material, paper was made using the cationic rosin emulsion sizing agent of the present invention obtained in Examples 1 to 3, and the obtained paper was prepared by the Steckigt method (JIS -P-8122) was used to measure the sizing degree. As a control, a paper obtained in the same manner using a conventional commercial anionic sizing agent was used.

The paper was manufactured under the following conditions.

Pulp: Magazine waste paper (containing 4% of CaCO ₃ ) Beating degree: CSF = 350 m Basis weight: 100 g / m ² Fixing pH: Adjusted to pH 6.0 by adding sulfuric acid band Sizing agent addition amount: 0 in terms of solid content. 3% by weight and 0.
Prepared to 5% by weight (pulp weight basis) Drying condition: 90 ° C for 2 minutes Papermaking process: disaggregation → (5 minutes) → band → (5 minutes) → size → (5 minutes) → papermaking temperature: 40 ° C (result ) The test results are shown in the table below.

As can be seen from the above table, the sizing degree of the paper made with the sizing agent of the present invention was significantly superior to that of the control.

(Effect of the Invention) By using the aqueous cationic rosin emulsion of the present invention as a paper sizing agent, a good sizing degree can be obtained even when the pH value of the paper is high. Further, when the waste paper containing calcium carbonate is recycled, by using the aqueous cationic rosin emulsion of the present invention as a sizing agent for recycled paper, a good sizing degree can be obtained even if the amount of sulfuric acid band used is reduced.

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Claims (4)

[Claims] 1. An α, β unsaturated polybasic acid is added to a petroleum resin and then reacted with a polyalkylene polyamine or an N, N dialkyl polyalkylene diamine, and then benzyl chloride, ethylene chlorohydrin, an inorganic acid or an organic acid. To make it water-soluble, and disperse the rosin or modified rosin with the resulting water-soluble cationic resin as a dispersant. 2. The method for producing an aqueous emulsion according to claim 1, which comprises dispersing a rosin or a modified rosin in combination with a nonionic or cationic surfactant or a protective colloid in the water-soluble cationic resin. 3. A water-soluble cationic resin according to claim 1 is used as a dispersant to emulsion-polymerize styrene or a styrene derivative and an acrylic monomer, and the resulting cationic aqueous resin emulsion is used as a dispersant to prepare a rosin or a modified rosin. A method for producing an aqueous emulsion, which comprises dispersing to obtain an aqueous emulsion. 4. The method for producing an aqueous emulsion according to claim 3, wherein the cationic aqueous resin emulsion is combined with a nonionic or cationic surfactant or a protective colloid to disperse a rosin or a modified rosin.