JPH03180590A - Production of aqueous emulsion of rosin substance - Google Patents

Abstract

PURPOSE:To obtain the subject emulsion useful as a sizing agent for paper-making use, achieving sizing effect over a wide pH range in paper-making process and having excellent dilution stability by dispersing a rosin substance in water in the presence of a specific dispersing agent. CONSTITUTION:The objective emulsion is produced by dispersing a rosin substance in water in the presence of a dispersing agent consisting of a compound of formula (R1 is 4-18C alkyl, alkenyl or aralkyl; R2 is H, 4-18C alkyl, alkenyl or aralkyl; R3 is H or methyl; A is 2-4C alkylene or substituted alkylene; n is 1-200; M is univalent cation).

Description

[Detailed Description of the Invention] -1! The present invention relates to a method for making an aqueous emulsion of a rosin material, and in particular to a method for making an aqueous emulsion of a rosin material using a specific dispersant.

LJ-△Technique 11 Yum Rosin substances have traditionally been used in a wide range of fields such as paper sizing agents, tackifiers, rubber emulsifiers, paints, and printing inks. From this perspective, aqueous emulsification is attracting attention in these fields. Note that in this specification, an aqueous emulsion sizing agent that is particularly desired to form an aqueous emulsion will be explained as a representative.

Cellulose fiber products such as paper, paperboard, and wood fiberboard are generally made by adding a sizing agent to an aqueous dispersion of cellulose fibers, and the sizing agent usually improves the water resistance and ink smear resistance of the product. Reinforced rosin-based sizing agents are widely used because of their ability to impart properties such as the like, but in recent years, aqueous emulsion sizing agents have been attracting attention as such sizing agents.

The aqueous emulsion sizing agent can be produced by dispersing the reinforced rosin in water using a high-pressure shearing homogenizer in the presence of an appropriate dispersant, or by preparing an emulsion of the reinforced rosin containing an appropriate dispersant. There is a method of reversing it. Conventionally, reversibility using a sulfuric ester salt of polyoxyethylene alkylphenyl ether as a dispersant to stabilize reinforced rosin (Japanese Patent Application Laid-Open No. 77206/1983);
An inversion method using a sulfosuccinate salt of polyoxyethylene alkyl phenyl ether as the dispersant (Japanese Unexamined Patent Publication No. 133259/1989), an inversion method using a sulfosuccinate salt of polyoxyethylene alkyl ether as the dispersant. (Japanese Unexamined Patent Publication No. 57-167349) etc. have been proposed.

However, the emulsions obtained by these conventional methods are still far from satisfactory in terms of stability, especially mechanical stability, and the foaming properties of the emulsions themselves, especially during paper making, are extremely poor. However, it is difficult to use a large amount of antifoaming agent during transportation and use. Furthermore, each of the emulsion sizing agents obtained by these conventional methods has the drawback that the sizing effect is significantly reduced when the papermaking pH is in the weakly acidic region of 6 to 7.

The present inventors have long developed a method for producing paper with excellent stability and a wide range of paper-making properties.
With the aim of providing a method for producing an aqueous emulsion of a rosin substance that can impart excellent size effects to paper in the H range, various studies have been carried out, particularly on dispersants for stabilizing the rosin substance 11. . However, to date, no systematic research has been conducted on dispersants for stabilizing rosin substances, and in general, even compounds with similar structures and similar surface activities have no stabilizing effect on rosin substances. Developed a dispersant that can exhibit excellent stabilizing and foam-inhibiting effects equivalent to or even superior to the dispersant described in JP-A-Sho, which is unrelated and has the same surfactant effect as the dispersant described in JP-A-Sho. It was considered difficult to do so. However, in subsequent research, when a rosin material was dispersed in water in the presence of a specific compound represented by the following general formula [I], which had never been used in the production of an aqueous emulsion of this type of rosin material, It has been discovered that it is possible to obtain an aqueous emulsion of a rosin material that meets the above objectives and has excellent stability and suitability as a sizing agent over a wide papermaking pH range, and also has low foaming properties.

The present invention was completed based on this new knowledge.

That is, in the present invention, when producing an aqueous emulsion of a rosin substance by dispersing the rosin substance in water in the presence of a dispersant, the above-mentioned dispersant has the general formula [I]: 4 to 18 alkyl group, alkenyl group, or aralkyl group, R2 is hydrogen or an alkyl group having 4 to 18 carbon atoms, alkenyl J, t-1 or an aralkyl group, R3 is hydrogen or a methyl group, A is 2 to 2 carbon atoms 4 alkylene group or substituted alkylene group,
The present invention relates to a method for producing an aqueous emulsion of a rosin material, characterized in that n is an integer of 1 to 200, and M is a monovalent cation.

According to the method of the present invention, the specific dispersant represented by the general formula [I] is used in dispersing the rosin material in water, as described above, so that the rosin material has significantly superior stability and p.
It has sizing agent permeability in a wide papermaking pH range including the weakly acidic region of H6 to 7, and has little foaming property itself, and is hardly associated with the problem of large foaming property in the papermaking system. , an aqueous emulsion of rosin material can be easily obtained.

The rosin substance used as a dispersion material in the present invention is usually 0 to 95% rosin and 5 to 10% rosin derivative.
0% by weight, and further includes those to which up to 50% by weight of a rosin derivative extender is added as necessary.

Here, as the rosin, gum rosin, wood rosin, tall oil rosin can be used alone, or a mixture thereof can be used. Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as aldehyde-modified rosin, reinforced rosin, rosin ester, and reinforced rosin ester.

Optionally enriched with rosin material 1/I
Examples of I+ include waxes such as paraffin wax and microcrystalline wax, petroleum resins, terpene resins, and hydrocarbon resins such as hydrogenated products thereof.

Rosin materials containing these usually contain at least 25% by weight.
Preferably, the composition contains a rosin derivative of.

In the present invention, it is essential to use a compound represented by formula [I] above as a dispersant. - Formula [Il
Among them, R1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, and examples of the alkyl group include butyl group, isobutyl group, pentyl group, hexyl group, heptyl J, c, octyl group, nonyl group, Decyl group,
Examples include undecyl group, dodecyl group, tridecyl group, tetradecyl J, c, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and alkenyl 3.
As ti, for example, butenyl prefecture, isobutenyl 1.
(, pentenyl group, hexenyl group, heptenyl J, t,
, octenyl J&, nonenyl group, decenyl group, undecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, heptadecenyl group, octadecenyl group, etc. Examples of the aralkyl group include styryl group, benzyl group, cumyl group, etc. and these may be a mixture.

R2 is hydrogen or an alkyl group, alkenyl group or aralkyl group having 4 to 18 carbon atoms, and the alkyl group, alkenyl group or aralkyl group may be the same as R3, or a mixture thereof may be used. R3 is hydrogen or a methyl group.

In addition, A is an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, and specific examples thereof include ethylene group, propylene group, butylene group, isobutylene group, etc., and these alkylene oxides can be added individually, randomly, etc. Either addition or block addition may be used.

n is an integer of 1 to 200, more preferably 2 to 10
It is 0. Further, as the monovalent cation defined by M, an ammonium group derived from alkali metal ions such as lithium, sodium, and potassium, ammonia, and various amines such as triethylamine, dimethylamine, and triethanolamine can be presented.

The compound represented by the general formula [1] used as the dispersant can be prepared by, for example, reacting a corresponding known alkyl, alkenyl or aralkylphenol with allyl chloride or meta-allyl chloride in the presence of a catalyst, followed by distillation under reduced pressure. It can be easily synthesized by further adding alkylene oxide to the reaction product obtained by 111, followed by sulfation with a sulfating agent such as sulfuric acid or sulfamic acid, and if necessary neutralizing with an alkali substance that becomes the cation. can.

The method of the present invention is usually carried out according to the inversion method, and when the inversion method is used, the dispersant is usually about 0.5 to 10% by weight, preferably 1 to 8% by weight, based on the dry weight of the rosin material.
Used in proportions by weight. If the amount is less than 0.5%, the dispersion force will not be sufficient, and if the amount exceeds tomfjt%, it is not economical. In particular, the dispersant represented by the general formula [I] used in the present invention has the advantage that an aqueous emulsion capable of exhibiting the desired effect can be obtained even when it is used in a small amount, for example, about 1 to 2% by weight.

The method is more specifically carried out as follows.

That is, first, a rosin derivative is heated and stirred with either or both of a rosin and an extender, if desired, to prepare a molten rosin material.

The heating temperature at this time is preferably set at least 20°C higher than the softening point of the rosin substance, and the appropriate temperature depends on the blending ratio of the rosin derivative, rosin, and filler, but is generally 90 to 160°C. is within the range of

An aqueous dispersant solution or dispersant and water is then added to the molten rosin material with stirring to form an emulsion in which the rosin material is the continuous phase and water is the dispersed phase. The amount of water used at this time is approximately 70% of the emulsion obtained.
It is preferable to adjust the solid content to 90% by weight.

Next, hot water (reverse water) at about 70-100° C. is added to the emulsion with vigorous stirring.

Phase inversion of emulsions is performed when the solid content concentration is 60 to 707i.
This occurs when water is added to give fJ, %, water becomes a continuous phase, and an emulsion in which the rosin material is dispersed in water is obtained. If desired, this emulsion can be diluted and/or pH adjusted with water or alkaline water. The amount of alkali to be used is preferably such that the pH of the emulsion is 6.5 or less. In addition, in the emulsification method using an emulsifying machine, for example, the rosin substance is first dissolved in a water-insoluble organic solvent, and the solution viscosity (25°C) is
is 1000 cps or less, preferably 500 CρS or less. In this case, the solution concentration is usually 20 to 70% by weight.
degree, preferably 40 to 60% by weight. As the water-insoluble organic solvent, those that can azeotrope with water are preferred, such as benzene, toluene, cyclohexane, and carbon tetrachloride, with benzene being particularly preferred. Next, water and a dispersant or an aqueous dispersant solution are added to the obtained organic solvent solution to pre-emulsify it, followed by emulsification at a temperature of about 10 to 80°C, preferably about 30 to 60°C. Here, the amount of water used is preferably adjusted so that the mixture of the rosin material before emulsification, the organic solvent, and the water used contains 10 to 40 rl<fft% of the rosin material. Since the emulsion thus obtained contains an organic solvent, the method then involves adding an organic solvent, preferably under reduced pressure, to about 30 to 90%
Distillation is performed at 0°C to obtain the desired aqueous emulsion. When the organic solvent is distilled off, a portion of the water is usually distilled off as well, so that the concentration of the resulting aqueous emulsion is somewhat increased.

The aqueous emulsion of the present invention can also be produced by the following method. That is, first, the rosin material is heated and dissolved, water and a dispersant or an aqueous solution of a dispersant are added thereto, or the three are heated simultaneously, and then this molten mixture is emulsified. The temperature during melting and emulsification of the rosin substance must be within a range that imparts fluidity to the rosin substance but does not cause its decomposition, and is generally about 140 to 200°C, preferably about 160 to 190°C. Temperature is used. The viscosity of the rosin material melted at this temperature should be less than 300 cps, preferably less than 100 cps. As is clear from the above description, emulsification by this method must be carried out in a closed container, and the internal pressure may be approximately 10 kg/cm.The amount of water used is determined according to the desired amount of the aqueous emulsion obtained. It is determined appropriately depending on the concentration of.

In any of the above methods, if an emulsifying machine is used, a homogenizer, a piston-type high-pressure emulsifying machine, an ultrasonic emulsifying machine, etc. can be used. Further, the water used during emulsification and which is a constituent component of the aqueous emulsion of the present invention does not need to be purified water, but it is preferable to use so-called soft water.

The aqueous emulsion thus obtained usually has a molecular weight of 5 to 701
(1) As a dispersing agent in an amount of rosin material of 30 to 55% by weight, preferably 0.5 to 10% by weight relative to the rosin material, preferably 1 to 1% by weight of the above-mentioned formula [I]
The emulsion consists of a compound represented by the following formula and 100% by weight of water, and the rosin material is uniformly dispersed in the emulsion as particles of 1 μm or less, mostly 0.5 μm or less. Moreover, the aqueous emulsion has a milky appearance, and 3.
It has a pH of 5-6.5. The aqueous emulsions of the present invention are stable at room temperature for at least two months, do not precipitate, and exhibit very little foaming typically associated with the use of dispersants. Furthermore, it has excellent mechanical stability and dilution stability as shown in the Examples below.

The aqueous emulsion obtained by the present invention can be produced not only by making cellulose fibers, but also by making a mixture of the cellulose fibers and mineral fibers, such as asbestos, rock wool, etc., or synthetic yams, such as polyamides, polyesters, polyolefins, etc., to produce paper, paperboard, etc. It can be advantageously applied when manufacturing fiberboard, etc.

When the aqueous emulsion obtained according to the present invention is used as a sizing agent for paper manufacturing, it is added, for example, to an aqueous dispersion of a bulb together with a fixing agent such as chloride sulfate.
7 or as described in Japanese Patent Publication No. 49-30201, add a fixing agent such as sulfuric acid and a small amount of a cationic fixing agent to the aqueous dispersion of bulb and make paper at pH 5 to 7. It is possible to adopt methods such as this, and it is possible to impart excellent size effects to paper over a wide papermaking pH range. In this case, the aqueous emulsion is used in an amount of about 0.05 to 3% (dry weight basis) based on the bulb. The aqueous emulsion obtained by the present invention also has excellent dilution stability, so it can be sufficiently diluted with water from rivers, taps, wells, etc., and is well dispersed in the aqueous dispersion of the valve.

Moreover, the diluted solution is stable for a long time.

The aqueous emulsion obtained according to the invention can also be used as a surface sizing agent, in which case it is applied to preformed wet paper by conventional methods such as spraying, dipping, coating, etc.

Further, among the aqueous emulsions obtained by the present invention, aqueous emulsions of rosin esters and reinforced rosin esters are effectively used as tackifiers.

EXAMPLES The method for producing an aqueous emulsion of the present invention will now be described in more detail with reference to Examples. Note that the reference example shows an example of producing a rosin substance used in the present invention.

Examples and percentages are by weight unless otherwise specified.

In addition, each property of the aqueous emulsion in the table was measured by the following method.

(1) Mechanically stable 50 g of the aqueous emulsion was weighed into a container of a Marlon Ni stability tester (manufactured by Shinsei Sangyo Co., Ltd.), and mechanically tested at a temperature of 25°C, a load of 10 kg, and a rotation speed of 1000 r, p, m for 5 minutes. After adding the mechanical shear, the resulting aggregates were filtered through a 100-mesh wire mesh, and the mechanical stability was calculated according to the following formula.

Mechanical stability (%) = Absolute dry weight of aggregates x 100 Absolute dry weight of sample emulsion (2) Foaming property (a) Dilute the aqueous emulsion with deionized water to a concentration of 5%, and for this diluted solution, The foam height (mm) was measured according to JIS 3362.

(3) Foaming property (b) Obtained by adding 5% and 2.5% aqueous emulsion (bone dry weight basis) and sulfuric acid band to a 1% aqueous slurry of bulb (L-BKP), respectively. An aqueous liquid at 1° C. was placed in a JIS K 3362 apparatus, and the contents were circulated for 10 minutes (8 squares/minute) using a pump, and then the circulation was stopped and the height (mm) of the bubbles was measured.

Reference Example 1 1800 parts of tall oil rosin was heated and melted, and 2.7 parts of p-toluenesulfonic acid monohydrate was added as a catalyst while stirring at 165°C. Then, 118 parts of a 37% formaldehyde aqueous solution was added at 160 to 170°C over a period of 90 minutes. The mixture was further stirred at the same temperature for 1 hour to obtain formaldehyde-modified rosin. Further, 1200 parts of gum rosin was added to this modified rosin, and the mixture was stirred and mixed at 175° C. for 1 hour.

2950 parts of the direct mixture and 177 parts of fumaric acid were heated and melted and reacted at 200°C for 3 hours to obtain a rosin substance (I) having an acid value of 203 and a softening point (ring and ball method) of 103.5°C.

Reference Example 2 1000 parts of gum rosin and 190 parts of fumaric acid were heated and melted to 200°C, and reacted at the same temperature for 4 hours to obtain a reinforced rosin with an acid value of 286 and a softening point of 138.5°C.

550 parts of reinforced rosin and 50 parts of gum rosin obtained above
0 part was heated to 170°C and mixed for 30 minutes to prepare the rosin substance (
n) was obtained.

Reference Example 3 1000 parts of gum rosin was heated and melted at 165°C, and while stirring, 0% p-toluenesulfonic acid monohydrate was added as a catalyst.
．． 95 parts were added. Then, 54 parts of a 37% formaldehyde aqueous solution was added at 160 to 170°C over 90 minutes. The mixture was further stirred at the same temperature for 1 hour to obtain formaldehyde-modified rosin. 4 at the same temperature.
Allowed time to react. Add 90 parts of fumaric acid to this and add 20 parts of fumaric acid.
Reacted at 0℃ for 3 hours, acid value 230, softening point 125℃
A rosin substance (III) was obtained.

Reference example 4 1000 parts of gum rosin and 80 parts of glycerin (equivalent ratio (
-08/-COOH) = 0.86), heated to 250°C under a nitrogen stream, and esterified at the same temperature for 12 hours to produce a rosin material (rV) with an acid value of 32 and a softening point of 86°C.
I got it.

Reference Example 5 A rosin material (V ) was obtained.

Reference Example 6 In the same manner as Reference Example 4, except that the amount of glycerin was changed to 120 parts (ratio = 1.29),
A rosin material (■) with an acid (i1i8) and a softening point of 88°C was obtained.

Reference Example 7 The rosin substance (IV) obtained in Reference Example 4 was kept at 180°C after completion of esterification, and 160 parts of maleic anhydride was added.
The addition reaction was carried out at 210°C for 3 hours to obtain a rosin material (■) having an acid value of 185 and a softening point of 122°C.

Reference Example 8 After the esterification, the rosin material (V) obtained in Reference Example 5 was kept at 180°C, 90 parts of maleic anhydride was added, and 21 parts of maleic anhydride was added.
Addition reaction was carried out at 0°C for 2 hours, acid value 90, softening point 210.
A rosin material (■〉〉) was obtained at °C.

Reference Example 9 The rosin material ('/l) obtained in Reference Example 6 was kept at 774,180°C after esterification, 90 parts of maleic anhydride was added, and an addition reaction was carried out at 210°C for 2 hours, resulting in an acid value of 90 and a softening point. A rosin material (IX) at 115°C was obtained.

Examples 1 to 6 100 parts of the rosin substance (I) of Reference Example 1 was charged into a flask equipped with a stirrer and a thermometer, and heated and melted to give 15
At 0° C., 20 parts of a 20% aqueous solution of a compound represented by the general formula [I] shown in Table 1 as a dispersant was added to the molten rosin material over about 3 minutes while stirring. At this point, significant water had evaporated and the temperature had dropped to 93°C. Then hot water (9
5° C.) to form a creamy water-in-oil emulsion. While stirring the emulsion vigorously, 70 parts of hot water (90° C.) was further added over 1 minute to the emulsion, causing phase inversion to form an oil-in-water emulsion.

This was rapidly cooled from the outside to a temperature of 30°C, and then passed through a 100-mesh wire mesh into a glass bottle. No coagulum was observed on the wire gauze, and the amount of rosin substance contained in the obtained aqueous emulsion was substantially the same as the rosin substance used (yield: 98% or more). The properties of the obtained emulsion are shown in Table 2.

[Left below] Comparative Example 1 In place of the dispersant represented by the general formula [I] used in Example 1, sodium salt of polyoxyethylene (average degree of polymerization 10) nonylphenyl ether sulfate half ester was used. was carried out in the same manner to obtain an aqueous emulsion. The properties of the obtained emulsion are shown in Table 2.

Comparative Example 2 The same procedure was carried out except that polyoxyethylene (average degree of polymerization 9) nonylphenyl ether sulfosucci adult bovine Nisder sodium salt was used instead of the dispersant represented by the general formula [I] used in Example 1. An aqueous emulsion was obtained. The properties of the obtained emulsion are shown in Table 2.

[Margins below] According to Table 2 of Maekita, based on the use of the specific dispersant represented by the general formula [I], according to the method of the present invention, mechanical stability is improved compared to using a known dispersant. It was found that an aqueous emulsion with excellent properties and considerably low foaming properties could be obtained.

<Practical Test 1> When the aqueous emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were used as paper sizing agents, the sizing degree (seconds) of the paper was determined by the Stekicht method (JIS P 81).
22).

In other words, based on the dry weight of the valve with a freeness of 30″SR,
．． 2% or 0.5% aqueous emulsion then 2.5%
After adding the chemicals in the order of % sulfuric acid bands and uniformly dispersing them, the pH was adjusted to a weight of 60 ± 1 g/cm3 using a TAPPI standard sheet machine.
Paper was made in steps 4 and 6. This is 5 kg/cm”
The paper stock was dehydrated for 3 minutes at a pressure of The results are shown in Table 3.

<Practical test 2> Bulb with a beating degree of 30''SR (waste paper, containing 3% calcium carbonate) was made into a 1% aqueous slurry, and an aqueous emulsion of 0.5% based on the dry weight of the bulb, then 1 After adding chemicals in the order of 0% sulfuric acid band and uniformly dispersing them, paper was made in the same manner as in Practical Test 1 at a papermaking pH of 6.5, and the size effect was measured.The results are shown in Table 3.

[Left below] Table 3 shows that the aqueous emulsion obtained by the method of the present invention not only exhibits excellent size effects under normal acidic papermaking conditions of pH 4 and 6, but also under weakly acidic papermaking conditions such as pH 6 and 5. It can be seen that the present invention also exhibits excellent size effects that cannot be obtained with aqueous emulsicone obtained using known dispersants.

Examples 7 to 14 Stable aqueous emulsions were obtained by carrying out the same operations as in Example 1 except that rosin substances (II) to (IX) shown in Table 4 were used instead of rosin substance (I). Yield is almost 100%
All emulsions have a particle size of 0.20 to 0.
It was 35μ.

The size effect of each emulsion obtained was similarly measured. The results are shown in Table 4.

[Margin below] When the aqueous emulsion obtained by the present invention is used as a sizing agent for papermaking, it can impart excellent sizing effects to paper over a wide range of papermaking pH. Furthermore, since it has excellent dilution stability, it can be sufficiently diluted using water from rivers, taps, wells, etc., and is well dispersed in the water dispersion source of the valve. Moreover, the diluted solution is stable for a long time.

Claims (1)

[Claims] (1) When producing an aqueous emulsion of a rosin substance by dispersing it in water in the presence of a dispersant, the general formula [I] is used as the dispersant: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, R_2 is hydrogen or an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, R_3 is hydrogen or a methyl group, A is 2 carbon atoms ~4 alkylene group or substituted alkylene group,
1. A method for producing an aqueous emulsion of a rosin substance, characterized in that n is an integer of 1 to 200, and M is a monovalent cation.