JPS6017429B2 - Method for producing aqueous emulsion of rosin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for making stable aqueous rosin material emulsions.

Aqueous emulsions of rosin materials are widely used as excellent paper sizing agents.

U.S. Pat. No. 3,565,755 discloses a method in which a rosin material is dissolved in an organic solvent such as benzene, then neutralized and emulsified with an aqueous alkali solution, and then the organic solvent is removed to obtain an aqueous emulsion useful as a paper sizing agent. is listed. Furthermore, JP-A-50-43202 describes a method of heating and melting and emulsifying a mixture of a rosin substance, an alkylbenzene sulfonate, and water; The rosin material and the alkali metal salt of ethoxylated nonylphenol half ester of sulfosuccinic acid are mixed with water to obtain an emulsion in which the rosin material is the continuous phase and the water is the dispersed phase, and then water is added so that the water is the continuous phase. describes an inversion emulsification method to obtain emulsions in which rosin material is the dispersed phase. The aqueous emulsions of rosin substances obtained by these known methods have good long-term storage stability and stability when diluted with water, especially in rivers, water supplies, etc.
It had the disadvantage of poor stability when diluted with highly hard water such as well water. The present invention was made in order to eliminate the drawbacks of the conventional method for producing an aqueous rosin material emulsion, and it has excellent long-term storage stability and dilution stability, and is easy to handle when used as a paper sizing agent. It is an object of the present invention to provide a highly advantageous method for producing aqueous emulsions of rosin substances.

The present invention mixes a rosin material, an emulsifier, and water to obtain an emulsion in which the rosin material is a continuous phase and water is a dispersed phase, and then by adding water, the phases are inverted so that water is a continuous phase and rosin material is a dispersed phase. In the inversion emulsification method to obtain an emulsion, the general formula or proviso is, RI: an alkyl group or alkenyl group having 7 to 21 carbon atoms R2: a day or CH3 group n: an integer from 1 to 30 M: forming a water drop I salt It is expressed as a counterion.

This is a method for producing an aqueous rosin emulsion, characterized in that a mono- or di-(polyoxyalkylene fatty acid amide) ester salt of sulfosuccinic acid or a mixture thereof is used as an emulsifier. In the present invention, the rosin material is a material containing rosins and/or rosin adducts, and includes, for example, 0 to 95% by weight of rosins and 5 to 10% by weight of rosin adducts.

Examples of rosins include wood rosin, gum rosin, tall oil rosin, modified products thereof, and mixtures thereof. Examples of the modified products include hydrogenated rosin, disproportionated rosin, polymerized rosin, and aldehyde-modified rosin. be. As a rosin adduct, for example, the above-mentioned gins and 2 to 30% by weight of Q,8 monounsaturated carboxylic acid are mixed into 1
Some are obtained by heating reverse oligoreaction at a temperature of 50 to 240 qo, and Q,8-unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, itaconic acid, acid anhydrides thereof, and mixtures thereof. There is. In the present invention, the sulfosuccinate ester salt of Mono (polyoxyethylene fatty acid amide) or the sulfosuccinate ester salt of G (polyoxyethylene fatty acid amide) used as an emulsifier is synthesized by a known method.

That is, a polyoxyalkylene fatty acid amide represented by the formula is reacted with maleic anhydride or maleic acid,
Sodium acid sulfite is then added.

The fatty acids used as raw materials are saturated or unsaturated fatty acids having 8 to 22 carbon atoms, or mixtures thereof, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and coconut acid. There are fatty acids obtained from animal and vegetable oils such as oil fatty acids and tallow fatty acids, and synthetic fatty acids such as 2-ethylhexanoic acid, isostearic acid, undecylic acid, and pentadecylic acid.
I are these fatty acid residues. The amount of ethylene oxide or propylene oxide added is 1 to 30 moles, preferably 2 to 30 moles.
It is 20 moles. If the amount of the compound added is outside this range, preferred emulsifying power cannot be obtained. Counter ions that form the water-dropping salt represented by M include lithium, aluminum, sodium, ammonium, and lower alkanolamines. In the present invention, the amount of the mono- or di-(polyoxyalkylene fatty acid amide) sulfosuccinate salt used is usually 0.5 to 10% based on the rosin material to be emulsified.
% by weight, preferably in the range 1-8% by weight.

If the amount used is less than 0.5% by weight, the emulsifying power will be insufficient, and if the amount exceeds 1% by weight, the size effect will be reduced, which is not preferred. Emulsification of the rosin substance according to the present invention can be carried out, for example, by the following method.

That is, the rosin material is heated in a container equipped with a fly frame device and a heating device until it melts, thereby obtaining a molten rosin material.
The temperature at this time is usually in the range of 90 to 190 o'clock. An aqueous solution of an emulsifier is added to the hot melt rosin material thus obtained to obtain an emulsion in which water is the dispersed phase and the rosin material is the continuous phase. The amount of water used at this stage is such that the rosin material is 70-85% by weight. Next, add warm water while stirring vigorously. The amount of overflowing water added is appropriately determined so that the concentration of the rosin substance is 5 to 7% by weight, preferably 10 to 55% by weight. At this stage, the emulsion is inverted, with water becoming the continuous phase and the rosin material becoming the dispersed phase. Upon cooling, an aqueous emulsion of finely dispersed solid rosin material is obtained. The method of the invention described above can be carried out in an open container under atmospheric pressure or in a closed container under pressure. The inversion emulsification method performed by the method of the present invention can provide a more stable emulsion than the usual emulsification method in which a rosin substance and water are simply mixed and emulsified. The aqueous emulsion of rosin material obtained by the method of the present invention has a white to milky appearance at pH 3 to 6, and has excellent emulsion stability, especially storage stability and dilution stability against hard water. When the aqueous emulsion of the rosin substance obtained according to the present invention is used as a sizing agent for paper manufacturing, it can be prepared by adding it to an aqueous dispersion of pulp together with a fixing agent such as sulfuric acid at pH 4 to 6. There is a method of making paper, or a method of adding it to an aqueous dispersion of pulp together with a small amount of a fixing agent such as sulfuric acid and a very small amount of a cationic fixing aid and making paper with mottling 5 to 7.

The aqueous emulsion obtained by the present invention can also be used as a surface sizing agent, and can be used as a surface sizing agent to prevent fogging, impregnating, and
It can be applied using conventional methods such as coating. The aqueous emulsions of the present invention can also be used in other applications.
Next, the present invention will be explained in more detail with reference to Examples and Reference Examples. In the following description, parts and percentages are by weight. Reference example 1 Tall oil rosin (acid value 169) 720 ml was heated and melted,
1.0 ml of p-toluene sulfonic acid was added and mixed.

Next, a 37% formaldehyde aqueous solution was heated to 170℃ for 66 minutes.
It was dripped in 3 hours. After the dropwise addition, aging was carried out at the same temperature for about 30 minutes, 5.3 hours of a 92% aqueous sodium hydroxide solution was added, and the mixture was further aged for 2 hours to obtain a formaldehyde-modified rosin with an acid value of 162. Add 300 g of gum rosin with an acid value of 174 to 450 g of the obtained modified rosin and mix at 160 qo.
Mixed for an hour. 44.3 tons of fumaric acid was added to this mixture, and addition reaction was carried out at 190q0 for 3 hours to obtain a rosin adduct with an acid value of 205. This is used as a rosin substance.
Reference example 2 Gum.

500 g of gin (alcohol value: 174) and 190 g of fumaric acid were heated and melted, and reacted at 200° C. for 4 hours. The obtained o-gin adduct had an acid value of 283. 270 g of the thus obtained rosin adduct and 250 g of the formaldehyde-modified rosin obtained in Reference Example 1 were mixed at 16 mm for 1 hour to obtain a rosin material. Reference example Trihydrogenated rosin (acid value 16
8 Bromine number 48.5) 655 and wood rosin (Acid number 16
6) 600 yen was heated and melted at 180°C, and then fumaric acid 44 yen and maleic anhydride Shoyu were added and reacted at the same temperature for 4 hours to obtain an o-zine adduct with an acid value of 215.

This is used as a rosin substance. The test method in the examples is as follows.

Storage stability test: The product was stored at a temperature of 3 pi for 6 months, and the presence or absence of aggregates was observed.

Dilution stability test: Each emulsion was diluted with hard water (Ca/M
g = 3'2) to a 5% concentration, and the time required for the emulsion to coagulate and form flocs was measured.

Examples 1-19 Comparative Examples 1-4 100 g of the rosin material obtained in Reference Example 1 was melted in a container with baffles and heated to 14,030 g.

Table-1 heated to 90℃ in molten rosin material
Aqueous solution of emulsifier shown in (emulsifier concentration 25%)
Added within minutes. At this time, a considerable amount of water evaporates. After the addition of anchorage was completed, 25 hours of hot water of 9 pi○ was added to the W/O type (
A water-in-rosin emulsion was obtained. Next, hot peach 7M at 95° C. was added for about 1 minute while stirring vigorously to obtain a ◯/W type (rosin in water type) emulsion. This was rapidly cooled to 360 ℃ using a water-cooled condenser to obtain a milky white aqueous emulsion of rosin material. The test results are shown in Table-1. Table 1
In Table 4, A is a compound of formula 1', B is a compound of formula
is sodium dodecylbenzenesulfonate, D is the sodium salt of the rosin material of Reference Example 1, and 8 is ethoxylated nonylphenol of sulfosuccinic acid (ethylene oxade 1).
0 mol) half-ester disodium salt, CM indicates a coconut oil fatty acid residue, Tal indicates a beef tallow fatty acid residue, and the presence or absence of storage stability indicates the presence or absence of aggregates. Table 1 From the results in Table 1, all examples using the emulsifier of the present invention have good emulsion storage stability and dilution stability, but even the same type of emulsifier as in Comparative Example 1 falls outside the specified range. It can be seen that the dilution stability of the emulsion is poor when using other emulsifiers such as those in Comparative Examples 2, 3, and 4.

Examples 20 to 31 A mixed system of emulsifier A and emulsifier B was tested in the same manner as in Examples 1 to 19.

The results are shown in Table-2. This result shows that even in the mixed system of A and B, the storage stability and dilution stability of the emulsion are good. Table 2 Examples 32-4 and Comparative Examples 5-7 100 ml of the rosin material obtained in Reference Example 2 was melted in a container with a baffle plate and heated to 13,500 ml.

20 minutes of an aqueous solution of the emulsifier shown in Table 3 (emulsifier concentration 20% - Example 44 was 25%, Example 45 was 15%) heated to 95°C was added to the molten rosin material. . At this time, a considerable amount of water evaporates. After the addition of octopus was completed, 95 qo of hot water was added to the mixture for 35 minutes.
/O type (water in rosin type) emulsion was obtained. Next, 80 g of hot water of 95 q0 was added in about 1 minute while stirring vigorously to obtain a ○/W type (rosin-in-water type) emulsion. This was rapidly cooled to 35q0 using a water-cooled condenser to obtain a milky white aqueous emulsion. The results are shown in Table-3. Table 3 Examples 46 to 51, Comparative Examples 8 to 10 100 kg of the rosin material obtained in Reference Example 3 was melted in a container with baffles and heated to 135 qo.

Table 4: The molten rosin material heated to 90°C
Aqueous solution of emulsifier shown in (emulsifier concentration 30%)
Added within minutes. At this time, a considerable amount of water evaporates. After the addition was complete, 25 more 9500g hot water was added to the mixture to obtain a W/O (water in water) emulsion. Next, 80 g of 95 qo hot water was added over about 1 minute while stirring vigorously to obtain a ○/W (rosin-in-water type) emulsion.
This was rapidly cooled down to 3 C using a water cooler to obtain a milky white aqueous emulsion. The test results are shown in Table-4. Table 4 All of the aqueous emulsions obtained in the above examples had good emulsion stability, and when used as a paper sizing agent,
All showed good sizing results.

As described above, according to the present invention, it is possible to produce an aqueous rosin emulsion with excellent emulsion stability, particularly storage stability and dilution stability with hard water.

Claims (1)

[Claims] 1. A rosin substance, an emulsifier, and water are mixed to obtain an emulsion in which the rosin substance is a continuous phase and water is a dispersed phase, and then water is added to cause phase inversion, with water being a continuous phase and rosin being a continuous phase. In the inversion emulsification method to obtain an emulsion in which the substance is the dispersed phase, the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Where R^1: Alkyl group having 7 to 21 carbon atoms or alkenyl group R^2: H or CH_3- group n: integer from 1 to 30 M: mono- or di-(polyoxyalkylene fatty acid amide) ester salt of sulfosuccinic acid represented by a counter ion forming a water-soluble salt Or a method for producing an aqueous emulsion of a rosin substance, characterized in that a mixture thereof is used as an emulsifier. 2. The method for producing an aqueous rosin emulsion according to claim 1, wherein the rosin substance consists of 0 to 95% by weight of rosins and 5 to 100% by weight of rosin adducts. 3 R^1 is caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, coconut oil fatty acid, tallow fatty acid, 2-ethylhexanoic acid, isostearic acid, undecylic acid, and pentadecylic acid. The method for producing an aqueous emulsion of a rosin substance according to claim 1 or 2, wherein the rosin substance is one or more fatty acid residues selected from the following. 4. The method for producing an aqueous rosin material emulsion according to any one of claims 1 to 3, wherein M is sodium.