JPS5948031B2 - Aqueous emulsion of rosin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous emulsion for paper-making size, and more particularly, to an aqueous emulsion for paper-making size comprising a rosin substance, an emulsifier, and water, the object of which is to have excellent mechanical stability and dilution stability; The object of the present invention is to provide a new aqueous emulsion that has low foaming properties and exhibits excellent performance as a sizing agent for paper manufacturing.

Aqueous emulsions of rosin substances are already known.

For example, JP-A-50-36703 discloses that the rosin material is a water-soluble cationic polymer such as a water-soluble polyaminopolyamide-epichlorohydrin resin, a water-soluble alkylene polyamine-epichlorohydrin resin, a water-soluble poly(diallylamine)-epichlorohydrin resin; A method is described for emulsifying a rosin material in water to obtain an aqueous emulsion of a rosin material useful as a paper sizing agent. U.S. Pat. No. 3,565,755 discloses that a rosin material is dissolved in an organic solvent such as benzene, then mixed with an aqueous alkaline solution in an amount to neutralize a small amount of the rosin material, and the resulting heterogeneous mixture is emulsified. It is also described that an aqueous emulsion useful as a paper sizing agent can be obtained by distilling off the organic solvent. Furthermore, JP-A-50-4
Publication No. 3202 describes that an aqueous emulsion of a rosin substance useful as a paper-making sizing agent is obtained by mixing the same rosin substance and an aqueous solution of an alkali metal salt of an alkylbenzenesulfonic acid and emulsifying the mixture under heating in a molten state. There is. Although these known aqueous emulsions have relatively good performance as paper sizing agents, the stability of the emulsion itself is not satisfactory.

Emulsions for various uses, not just sizing agents, are subjected to mechanical suring, often by pumps, in various steps from manufacture to use. Therefore, such emulsions are required to have mechanical stability, but all of the aqueous emulsions proposed above are poor in this stability and, for example, when subjected to mechanical suring, the particles become coarse or severe. In such cases, the emulsion may be destroyed and aggregates may be formed, and great care is required in handling them. Moreover, since the above-mentioned aggregates and the like deposit and adhere to the pumps, transport lines, etc. that transport the emulsion, it is necessary to frequently stop the operation and clean them. In addition, the water used for papermaking is
ll, water from taps, wells, etc., and is often highly hard water. Therefore, it is preferable that the sizing agent for paper manufacturing has stability in hard water. In addition, it is usually considered to be highly concentrated due to transportation costs, and when used in paper manufacturing,
Since a very small amount of the sizing agent is added to the aqueous pulp dispersion, it is usually diluted to about 5% by weight to improve the dispersion of the sizing agent and then added to the aqueous pulp dispersion. However, the proposed aqueous emulsion of the rosin material has poor dilution stability and stability in hard water. Therefore, it must be uniformly diluted and added to the aqueous pulp dispersion immediately before use and within a short period of time, requiring special dilution equipment for this purpose. Furthermore, the above-mentioned known aqueous emulsion,
In particular, aqueous emulsions obtained using alkali metal salts of alkylbenzenesulfonic acids as emulsifiers have a high foaming property, and when such aqueous emulsions are used as sizing agents for papermaking, they have the disadvantage of causing various adverse effects during the papermaking process. has.

That is, foaming on the wire has the disadvantage of creating pinholes in the paper, and foaming of white water under the wire during paper making causes foam to accumulate in the white water pit, making it difficult to circulate and use the white water. becomes. Compared to the aqueous emulsions proposed above, the present invention has significantly superior mechanical stability and hard water dilution stability, has low foaming properties, and is extremely advantageous in handling when used as a sizing agent for paper manufacturing. The object of the present invention is to provide a new aqueous emulsion of a rosin material that can be used economically and favorably.

That is, the present invention provides a paper-size aqueous emulsion comprising a rosin substance, an emulsifier, and water, in which the emulsifier contains 8 to 10
A hydrophilic moiety having at least 4 carboxyl groups as pendant groups on a main chain consisting of 0 carbon atoms, and an alkyl sulfide group or alkyl sulfoxide group bonded to one end of the main chain constituting the hydrophilic moiety. The present invention relates to an aqueous emulsion of a paper-size rosin material, which is an oligomer or an alkali salt thereof having a hydrophobic portion consisting of an alkyl sulfone group or an alkyl sulfone group.

In the present invention, the rosin substance is preferably 0 to 95% by weight of rosin and an addition reaction product of the above rosin and α-β-monounsaturated carboxylic acid (hereinafter referred to as “rosin adduct”).
5 to 100% by weight can be used.

Here, as the rosin, gum rosin, oil rosin, tall oil rosin, modified products thereof, and mixtures thereof can be used. Examples of the above-mentioned modified products include hydrogenated rosin, disproportionated rosin, polymerized rosin, and aldehyde-modified rosin. Among these rosins, aldehyde-modified rosins are particularly preferred because their crystallization is suppressed. This is usually done by mixing rosin and 2 to 8% by weight of formaldehyde or acetaldehyde in the presence of an acidic catalyst such as sulfuric acid or para-toluenesulfonic acid at about 140 to 200°C.
．． It can be obtained by reacting for 5 to 3 hours. Rosin adduct is also referred to as reinforced rosin in the industry.
Generally, the rosin (particularly preferably aldehyde-modified rosin) and the α,β monounsaturated carboxylic acid are mixed at a concentration of 150 to 250%.
Obtained by heating reaction at a temperature of about ℃. α used
, β-unsaturated carboxylic acids include various types, but acrylic acid, maleic acid, fumaric acid, itaconic acid, anhydrides thereof, and mixtures thereof are preferred, particularly fumaric acid, maleic acid, and maleic anhydride. is optimal. The rosin material used in the present invention preferably contains 2 to 30% by weight, more preferably 3 to 15% by weight of the addition-reacted α,β monounsaturated carboxylic acid, based on the total weight of the rosin.
Contains % by weight. This rosin material can be obtained directly by reacting a predetermined amount of α,β-monounsaturated carboxylic acid within the above range with rosin, or by reacting an appropriate amount of α,β-monounsaturated carboxylic acid with rosin. It can also be obtained by mixing rosin with the rosin adduct obtained by the process. In this case, the amount of rosin mixed is preferably up to 95% by weight, and during mixing, the amount of α,β monounsaturated carboxylic acid added to the mixture is preferably 2 to 30% based on the total weight of the rosin. The content is preferably 3 to 15% by weight. If the amount of the α,β unsaturated carboxylic acid subjected to the addition reaction is too small, the stability and size effect of the resulting aqueous emulsion will deteriorate, which is undesirable. The paper size aqueous emulsion of the present invention is produced by emulsifying the above rosin material in water using a specific emulsifier.

In the present invention, the emulsifier has a hydrophilic moiety having at least 4 carboxyl groups as pendant groups on a main chain composed of 8 to 100 carbon atoms, and a hydrophilic moiety bonded to one end of the main chain constituting the hydrophilic moiety. It is essential to use an oligomer having a hydrophobic moiety consisting of an alkyl sulfide group, an alkyl sulfoxide group, or an alkyl sulfone group or an alkali salt thereof.

The oligomer itself is a known compound described in US Pat. No. 3,668,230 and US Pat. No. 3,839,405, but there are no examples of its use in emulsifying rosin substances. The present invention provides that when the above-mentioned oligomer or its alkali salt is used to emulsify a rosin substance, it exhibits an extremely excellent emulsifying effect, has outstanding mechanical stability and dilution stability, and has a low foaming property. It was discovered and perfected that it can give emulsion. The reason why an aqueous emulsion with such excellent properties can be obtained by using the above oligomer or its alkali salt is not clear at present, but the above oligomer is general in that it has a hydrophilic part and a hydrophobic part. It is thought that this is because the hydrophilic part is a low molecular weight polycarboxylic acid, and it also has the property of acting as a protective colloid. In any case, the above oligomer or its alkali salt has never been used to emulsify a rosin substance,
In addition, known emulsifiers of rosin substances, such as fatty acid salts, salts of rosin substances, and ordinary anionic surfactants such as alkylbenzene sulfonates, perform the desired emulsification by an essentially different mechanism. It is possible to obtain an aqueous emulsion that has excellent stability and low foaming properties that are impossible to achieve with known emulsifiers, and also has excellent size characteristics, and is therefore extremely advantageous as a sizing agent for paper manufacturing. The oligomer used as an emulsifier in the present invention preferably has a hydrophilic moiety of the formula [where R is H, CH3
or COOH and R2 are H, CH3 or CH2COOH
4 to 50 units of at least one type represented by the formula [wherein R3 and R4 are the same or different and are H or C
H3 and x are CONH2, OCH3, OC2H5,'-
A hydrophobic compound consisting of 0 to 46 of at least one type of unit represented by the following formula, the sum of the above two units being 50 or less, and consisting of an alkyl sulfide group, an alkyl sulfoxide group, or an alkyl sulfone group. Examples include those in which the alkyl group constituting the moiety is a linear or branched alkyl group having 5 to 20 carbon atoms.

For convenience, the above-mentioned preferred oligomer is expressed by the following formula. In the above formula, R is a linear or branched alkyl group having 5 to 20 carbon atoms, preferably 6 to 12 carbon atoms, n is o or an integer of 1 to 2, preferably 0a is o or an integer of 1 to 46, and b is 4-5
An integer of 0, a+b represents an integer of 4 to 50, R, ~R4
and X are the same as above.

However, the two units represented by [ ] in the above formula are randomly distributed in the molecule, and there are a and b units in the molecule, and the units in [ ] do not need to be the same. In the above, when a is o, b is preferably 4 to 30,
When a is an integer other than o, b is preferably 5 to 30.

In addition, the molar fraction represented by a/a+b depends on the water solubility of the obtained oligomer or its alkali salt, for example,
In the case of strong hydrophilic groups such as ONH2, it is usually 0.02 to 0.9.
2 Most preferably 0.7 to 0.867, and when X is a weakly hydrophilic group, it is usually 0.02 to 0.6, especially CN
and CON [0.3 to 0.5 is most preferable in the case of ICH2OH, and 0.02 to 0.5 in the case of weakly hydrophilic groups other than the above.
It is better to set it to 0.3. The oligomer represented by the above formula [I] usually has a molecular weight of about 400 to 5,000.
Among the oligomers represented by the above formula [I], those particularly suitable for the present invention are represented by the following formulas [old to [old]. [In the formula, w is a linear alkyl group of C6~, 2 preferably C8~, 0, W2 is H or CH3 is preferably H, and b is 4~5
0 preferably 4 to 30, more preferably 4 to 10,
In addition, n is the same as above] [In the formula, R', n and W2 are the same as above, and a'+b' is 5 to 30, preferably 12 to 30
and a'/a'+b' is 0.033 to 0.6, preferably 0.2 to 0.55, more preferably 0.3 to 0.5] [In the formula, Bi is C6-20, preferably C6 ~12 linear alkyl groups, N, R4 and R2 are the same as above, a″+
bl is 5 to 30, preferably 12 to 30, and a! ′
+b″ is 0.033 to 0.867, preferably 0.6 to 0
．． 867] Representative examples of the above-mentioned preferred oligomer and other oligomers used in the present invention are as follows.

The oligomer represented by the above formula [I] can be easily produced by the method described in the above-mentioned US patent or in accordance therewith. Specifically, for example, a lower alcohol such as methyl alcohol or ethyl alcohol is used as a solvent, and about 20
A desired oligomer having an alkyl sulfide group at the end can be obtained by addition polymerizing a desired monomer using lauroyl peroxide, ammonium persulfate, etc. as an initiator in the presence of an alkyl mercaptan at a temperature of ~60°C. It can be obtained quantitatively, that is, with a narrow molecular weight distribution. Alternatively, the above oligomer may be converted into an alkali salt if necessary, and then oxidized in water at a temperature of about 30 to 100°C using an oxidizing agent such as hydrogen peroxide or ozone, depending on the amount of the oxidizing agent used. A desired oligomer whose terminal end is an alkyl sulfoxide group or an alkyl sulfone group can be obtained.
Examples of the monomers used above include monomers having a carboxyl group such as acrylic acid, methacrylic acid, β-methylacrylic acid, α,β-dimethylacrylic acid, itaconic acid, maleic acid, and fumaric acid; Monomers with hydrophilic groups such as acrylamide, methacrylamide, vinyl methyl ether, vinyl ethyl ether, allyl alcohol and vinylpyrrolidone; monomers with weakly hydrophilic groups such as hydroxyethyl acrylate,
Hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N
Examples include -methylol acrylamide, N-methyl acrylamide, N-ethylacrylamide, N-isopropylacrylamide, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylonitrile, vinyl acetate, and vinyl propionate. Particularly preferred monomers are acrylic acid, acrylonitrile, acrylamide, itaconic acid, methacrylic acid and methacrylamide. When using the oligomer 1 in the present invention, it may be used as it is in the form of an acid, but it is preferable to partially or completely neutralize it with an alkali and use it in the form of a salt.

For alkali neutralization, especially when the number of alkali-neutralized acid groups in formula [1] is B, B/a+b is 0.0.
It is preferable to neutralize with alkali so that the number becomes 5 or more. The alkali salt is not particularly limited, but for example, alkali metal salts such as lithium, sodium, potassium, etc.; ammonia and organic amine salts such as monoethanolamine, ethylamine, diethanolamine, dimethylamine, pyridine, triethanolamine, etc. are preferred, especially sodium salt, or potassium salts are optimal. In the present invention, the amount of the oligomer or its alkali salt (hereinafter sometimes simply referred to as an emulsifier) used is usually 0.25 to 10% by weight, preferably 0.5 to 3.0% by weight based on the rosin material to be emulsified.
The range is by weight%.

The use of emulsifiers in amounts greater than 10% by weight may improve the mechanical stability of the resulting aqueous emulsion, but
On the other hand, it tends to reduce its performance as a sizing agent for papermaking, that is, its sizing effect.

In the present invention, it is also possible to use up to the same amount of a nonionic surfactant or other known anionic surfactant together with the emulsifier.

In particular, when a nonionic surfactant is used in combination, the mechanical stability of the aqueous emulsion and the dilution stability against hard water are further improved. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene Glycol fatty acid esters, polyoxyethylene alkylamines, fatty acid monoglycerides, sorbitan fatty acid esters, pentaerythritol fatty acid esters, propylene glycol fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, fatty acid alkanolamides and amine oxides, etc. Generally nonionic surfactants Examples include those known as agents. Examples of known anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl sulfonates. Examples include enyl ether sulfate, sodium N-lauroyl sarcosine, and sulfonate of naphthalene-formalin condensate. When emulsifying a rosin substance using the emulsifier of the present invention, since the rosin substance has a softening point of about 80°C or higher, it is preferable to employ the following emulsification method.

That is, first, a rosin substance is dissolved in a water-insoluble organic solvent to form a solution having a solution viscosity (25 C of water) of 1000 cps or less, preferably 500 cps or less. In this case, the solution concentration is usually about 20 to 70% by weight, preferably about 40 to 60% by weight. In the above, the water-insoluble organic solvent is preferably one that can azeotrope with water, such as benzene, toluene, cyclohexane, carbon tetrachloride, etc., with benzene being particularly preferred. Next, water and an emulsifier or an aqueous emulsifier solution are added to the organic solvent solution obtained above to pre-emulsify it, and then emulsification is carried out 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, organic solvent and water before emulsification contains 10 to 40% by weight of the rosin material. Since the emulsion thus obtained contains an organic solvent, the organic solvent is then dissolved, preferably under reduced pressure, to about 30 to 90%
Distillation is performed at 0°C to obtain the desired aqueous emulsion. Hereinafter, this method will be referred to as the solvent method. In this solvent process, when the organic solvent is distilled off, a portion of the water is usually also distilled off, so that the concentration of the aqueous emulsion obtained is somewhat increased. The above solvent method has the advantage of being able to produce a stable aqueous emulsion with a particle size of 1 μm or less, and furthermore, since the emulsifier used in the present invention has low foaming properties, the solvent removal operation after emulsification is extremely easy. Yes, it is preferable. The paper size aqueous emulsion of the present invention can also be produced by the following method. That is, first the rosin material is heated and melted and water and an emulsifier or an aqueous solution of one emulsifier are added thereto, or the three are heated simultaneously and the molten mixture is then 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 180°C. Adopted. The viscosity of the rosin material melted in this temperature range should be less than 300 cps, preferably less than 100 cps. Further, the amount of water used is appropriately determined depending on the desired concentration of the aqueous emulsion to be obtained. Hereinafter, this method will be referred to as a melting method, and when this method is carried out, it is particularly preferable to use the above-mentioned alkali metal salt of the oligomer as an emulsifier. In both the solvent method and the melt method, a homogenizer such as a piston emulsifier or an ultrasonic emulsifier can be used as the emulsifier.

A piston-type emulsifying machine is particularly suitable, and has a structure in which a pre-emulsified emulsion is pumped by a piston to a homovalve whose shear pressure is adjusted to 50 to 700 kg/CTIt for shear emulsification. From Gaulin Corporation in the United States, “MOdel”
It is commercially available under the names of "15M-8TA" and "MOdel31M-3TA." When emulsifying using this piston type emulsifier, the shear pressure is 100 to 600! <9/
It is preferable to employ Cd of 200 to 400 kg/Cd. The water used during emulsification and which is a 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 for papermaking size of the present invention thus obtained has a size of 1 to 6.
0% by weight preferably 30-45% by weight of rosin material, 0.25-10% by weight of rosin material preferably 0.
Preferably, the rosin material is adjusted to contain 5-3.0% by weight of emulsifier, and the rosin material is present in the emulsion in an amount of 0.0% by weight.
It is dispersed as particles of about 0.03 to 4 μm.

The aqueous emulsion has a white to milky appearance and a pH value of 3 to 6.5. It is stable at room temperature for at least 6 months, does not form precipitates, has excellent mechanical stability and hard water dilution stability, and has low foaming properties as shown in the Examples below. When using the aqueous emulsion of the present invention as a sizing agent for paper manufacturing, the method is to add it to an aqueous dispersion of pulp together with a fixing agent such as sulfuric acid and make paper at a pH of 4 to 6, or according to Japanese Patent Publication No. 49-30201. As described, it is added 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.
A method of making paper in steps 5 to 7 can be adopted.

In this case, the aqueous emulsion of the present invention is used in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight (based on dry weight), based on the pulp. As mentioned above, the aqueous hand-mulsillon of the present invention has excellent hard water dilution stability, so it can be sufficiently diluted with water from rivers, taps, wells, etc., and is well dispersed in an aqueous pulp dispersion. Moreover, the diluted solution is stable for a long time. Therefore, special equipment and space for dilution are not required, unlike when using the proposed known aqueous emulsion. Furthermore, the aqueous emulsion of the present invention has low foaming properties, causes no trouble during paper making, and can provide paper with good paper quality. The aqueous emulsion of the present invention can also be used as a surface sizing agent, and is applied to preformed wet paper by conventional methods such as spraying, dipping, and coating.

The aqueous emulsion of the present invention will be explained in more detail with reference to Examples below.

Note that the reference example shows an example of a method for producing the rosin substance and emulsifier used in the present invention. Example middle and %
Based on weight unless otherwise specified. Moreover, the softening point was measured by the ring and ball method. Reference example 1 Tall oil rosin (acid value 170, softening point 76°C) 2520
f1 was heated and melted and p was added as a catalyst while stirring at 165°C.
- Add 3.89 g of toluenesulfonic acid monohydrate.

Then, 160% 38% formaldehyde aqueous solution 2319
Addition takes 2 hours at ~170°C. The mixture was stirred at the same temperature for 30 minutes, and then 1.79% of sodium hydroxide dissolved in 16.89% of water was added to neutralize only the catalyst.
After stirring for 5 hours, a formaldehyde-modified rosin having an acid value of 164 and a softening point of 77° C. is obtained. In addition to this modified rosin 18009, gum rosin (acid value 175, softening point 77°C) 120
0f! and stirred and mixed at 175°C for 30 minutes. Said mixture 2950f! and 6% fumaric acid 177f for the mixture! is heated and melted and subjected to an addition reaction at 200°C for 3 hours.

The rosin adduct thus obtained has an acid value of 208 and a softening point of 103.5°C. This will be referred to as rosin substance A. Reference example 2 Gum rosin (acid value 175, softening point 77°C) 10009
and 190 g of fumaric acid were heated and melted to 200° C., and reacted at the same temperature for 4 hours.

The resulting rosin adduct had an acid value of 286 and a softening point of 138.
It is 5. Rosin adduct 5509 obtained above and formaldehyde modified rosin 5009 obtained in Reference Example 1
Heat to 170°C and mix for 30 minutes.

The rosin material thus obtained contains about 9.1% added fumaric acid, based on the total weight of gum rosin and modified rosin. This will be referred to as rosin substance B. Reference example 3-hydrogenated rosin (acid value 166, softening point 70.5°C, bromine number 49
) 18009 and Utudrozin (acid value 167, softening point 7
5°C) 12009 is heated and melted to 170°C, then fumaric acid 1209 and maleic anhydride 609 are added and reacted at the same temperature for 4 hours.

The acid value of the rosin material thus obtained is 210 and the softening point is 9.
8° C. and the amount of fumaric acid and maleic anhydride added is about 6% based on the total weight of hydrogenated rosin and wood rosin. This will be referred to as rosin material C. Reference Example-A-L Acrylic acid 388.89 (5.4 mol) and acrylonitrile 286 were placed in a five-bottle flask installed on a water bath and equipped with a stirrer, reflux condenser, drip load, thermometer, and nitrogen inlet tube. .29 (5.4 mol), octyl mercaptan 98.6 g (0.675 mol), and methyl alcohol 110.79 g were charged, the temperature of the reaction system was maintained at 35 ± 2 ° C. under stirring in a nitrogen stream, and the temperature of the reaction system was kept at 35 ± 2 ° C. .5
300 f of a methyl alcohol solution containing g of ammonium persulfate! was added dropwise for about 9 hours, and after the addition was completed, the temperature was kept at the same temperature for an additional hour to complete the reaction.

The reaction mixture has a pale yellow-green color and a non-volatile content of 65.0% (theoretical value 65.3%). Next, methyl alcohol was distilled off from this reaction mixture under reduced pressure (1000C/2mmH9×3
0 minutes), air-dried and washed with methyl alcohol, acetone,
A white powder is obtained which is soluble in methyl ethyl ketone and cyclohexanone. The results of the analysis are as follows. From this, it can be seen that the main component of the product is a compound represented by the following formula.

40.49 (0.72 mol) of potassium hydroxide and 1,276.69 of water were added to the oligomer 1159 (about 0.1 mol) obtained as above, and the mixture was stirred at a temperature of about 70°C. An aqueous solution with a concentration of 10% as a potassium salt is obtained, in which about 90% of the acid groups of the potassium salt are neutralized.

This is called emulsifier A. By selecting appropriate raw materials and reaction conditions in the above, each oligomer listed in Table 1 below is obtained.

The obtained oligomers were converted into a 10% aqueous alkali salt solution in the same manner as above to obtain emulsifiers BL, respectively. Table 1 also shows the degree of neutralization and the type of alkali salt. Reference Example M-Q Powdered oligomer 1159 in the free acid state obtained in Reference Example A (approximately 0.1 mol), potassium hydroxide 40.49 (0.72 mol), and water 1281.39 were added to Reference Example A. After stirring and dissolving in a nitrogen stream, reduce the temperature by 30% from the dropwise load while being careful not to let the temperature of the reaction system exceed 15℃.
A hydrogen peroxide solution having a concentration of 11.39 (0.1 mol) is added dropwise.

After dropping, the temperature was maintained at 60°C for about 1 hour to complete the reaction. Thus, a 90% neutralized product of the oligomer 1 represented by the following formula is used as the emulsifier M. In the above process, a 10% aqueous alkaline salt solution of the oligomer listed in Table 2 is obtained using appropriate raw materials.

These are designated as emulsifiers N-Q, respectively, and their neutralization degrees and types of salts are also listed in Table 2. Reference Example R-U Powdered oligomer 1159 in free acid state obtained in Reference Example A
(about 0.1 mol), potassium hydroxide 40.4f! (0.
72 moles), and 1285.9 f of water! was placed in the same flask as Reference Example A, stirred and dissolved in a nitrogen stream, and then
The temperature of the reaction system is 15. 30% concentration hydrogen peroxide solution 22.79 (0.2
mol) dropwise.

After completion of the dropwise addition, the mixture is kept at 90 to 100°C for about 1 hour to complete the reaction. In this way, a 10% aqueous solution containing as a main component a 90% potassium neutralized oligomer represented by the following formula is obtained.

(-ノ0'-1-1) This is referred to as emulsifier R.

In the above procedure, a 10% aqueous alkaline salt solution of the oligomer listed in Table 3 is obtained using appropriate raw materials.

These are each referred to as emulsifier S-U, and their degree of neutralization and type of salt are also listed in Table 3. Example 1 The rosin substance AlOO9 obtained in Reference Example 1 was mixed with benzene 100
9 and then diluted with soft water a predetermined amount of the emulsifier obtained in the above reference example to add an aqueous solution designated as 2009.

This mixture was heated to 40°C and homomixer (5000r
After pre-emulsifying at F x 1 minute), shear pressure 30 at the same temperature.
Piston type high pressure emulsifier adjusted to 0k9/Cd "MOd
el15M-8TA") twice to emulsify. Benzene is distilled off from the obtained emulsion at 40° C. under reduced pressure to obtain aqueous emulsion preparations 1 to 12 of the present invention. Type and amount of emulsifier used in the production of each emulsion (
(as non-volatile content) are shown in Table 4, and the properties and storage stability after 6 months (25°C) of each emulsion obtained are shown in Table 5.
Shown in the table. For comparison, each table also shows the case where the gum rosin used in Reference Example 1 was used instead of the rosin material A in the above, and the case where water-soluble polyaminopolyamide-epichlorohydrin, which is a known water-soluble cationic polymer as an emulsifier, is shown. A modified resin (an epichlorohydrin-modified product of polyaminopolyamide obtained by condensing adipic acid and diethylenetriamine by a conventional method), a potassium salt of rosin substance A, and a sodium salt of dodecylbenzenesulfonic acid were obtained in the same manner using predetermined amounts, respectively. The emulsions are also listed as Comparative Emulsion Boiled 13-16. Example 2 The rosin material AlOOg obtained in Reference Example 1 and the predetermined amounts of emulsifiers B and S obtained in Reference Examples B and S were diluted with soft water to give 20 g.
The aqueous solution adjusted to 0g was charged into an autoclave connected to the piston-type high-pressure emulsifier described in Example 1, heated to 180°C, stirred at the same temperature for 1 hour, pre-emulsified, and the resulting emulsion was subjected to a shear pressure of 300kg/ The resulting aqueous emulsion is passed through the emulsifier adjusted to d and cooled in a water-cooled condenser.

The obtained aqueous emulsion was boiled in the emulsion of the present invention 17
-18 are shown in Tables 4 and 5. In addition, an aqueous emulsion obtained by repeating the same operation using a predetermined amount of sodium salt of dodecylbenzenesulfonic acid as an emulsifier is also listed in Tables 4 and 5 as Comparative Emulsion Boiled 19. Stability test of emulsion> The mechanical stability and dilution stability of each emulsion boiled 1 to 19 obtained in each of the above examples are measured.

(1) Mechanical stability Each emulsion 509 was weighed into a container of a Marlon stability tester (manufactured by Shinsei Sangyo Co., Ltd.), and the temperature was 25°C and the load was 10.
kg, rotation speed 1000 rpm? After applying mechanical suture for 5 minutes, the resulting aggregates were collected with a 100-mesh stainless steel screen, and the mechanical stability was calculated according to the following formula.

The results are shown in Table 6.

(2) Dilution stability Each emulsion has a hardness of 5, 10 or 20 D at 25°C.
Dilute to 5% concentration with dilution water with H.

After dilution, the time required for the emulsion to coagulate and form flocs is measured with the naked eye. The results are shown in Table 6. Foamability Test> The foamability of each of the emulsions ▲1 to 19 obtained in each of the above examples was measured.

Each emulsion 10d has an inner diameter of 1.65C! Place in a test tube with RL and length of 16 crfL, cap tightly, shake vigorously 50 times in the vertical direction of the test tube, and leave it vertically at 25°C.

Measure the height from the original liquid level to the top of the foam 5, 10 and 30 minutes after shaking. However, the height from the liquid level to the stopper is 10 degrees. The results are shown in Table 6 below. Practical Test> The degree of sizing (seconds) of paper when the aqueous emulsion boils 1 to 19 obtained in each of the above examples are used as a sizing agent for paper manufacturing is measured by the Stekicht method (JISP8122).

That is, SR pulp (LBKP) with a freeness of 30 is mixed with tap water (
Make a 1% slurry with a DH of approximately 4.5 mm, add chemicals in the order of (a) or (x) below, and after uniformly dispersing it, use a TAPPI standard sheet machine to make a 1% slurry with a weight of 60 ± 19 mm. Paper is made so that /A is obtained.

This was dried at 80℃ for 5 minutes, and the paper stock was heated to 65% at 20℃.
The size effect is measured after 24 hours of humidity control in a constant temperature and humidity atmosphere of RH. (a) Emulsion (0.2 or 0
．． 5%) → Sulfate band (2.5%) (b) Emulsion (0.2 or 0.5%) → Sulfate band (0.5%) →
Cationic fixing aid (0.05%) The amount of each chemical added above represents the non-volatile content % of each chemical added based on the dry weight of the pulp.As a cationic fixing aid, The same water-soluble polyaminopolyamide-epichlorohydrin modified resin used in Example 1 was used.

The size effects obtained (in seconds) are shown in Table 7 below, depending on the order of addition of the chemicals used and the amount of emulsion added.
Example 3 The rosin substance BlOO9 obtained in Reference Example 2 was mixed with cyclohexane 100f! Then, an aqueous solution prepared by diluting predetermined amounts of several kinds of emulsifiers obtained in Reference Examples with soft water and making it 2009 is added.

This mixed solution was heated to 55°C and pre-emulsified using the homomixer described in Example 1, and then subjected to a shear pressure of 300 kg at the same temperature.
The mixture is emulsified by passing it twice through the piston-type high-pressure emulsifier described in Example 1, which is adjusted to /d. Cyclohexane was distilled off from the obtained emulsion at 55° C. under reduced pressure to obtain the aqueous emulsion E. Obtain 2O to ▲24. Table 8 shows the type and amount of emulsifier used in each emulsion (as nonvolatile content), and Table 9 shows the properties of each emulsion obtained and the storage stability at 25° C. after 6 months. For comparison, each table also shows the emulsions obtained when the respective predetermined amounts of the potassium salt of rosin substance B and the sodium salt of dodecylbenzenesulfonic acid were used as emulsifiers in the same manner as described above, and the comparative emulsion E. 25 and boiled 26. Example 4 An aqueous solution of 2009 obtained by diluting the rosin substance BlOO9 obtained in Reference Example 2 and a predetermined amount of the emulsifier F obtained in Reference Example F with soft water was prepared in an autoclave connected to the piston-type high-pressure emulsifier described in Example 1. The mixture was heated to 190°C and stirred at the same temperature for 1 hour to pre-emulsify.

The pre-emulsion is then passed through the emulsifier adjusted to a shear pressure of 500 kg/CTl, and the resulting aqueous emulsion is cooled in a water-cooled condenser to obtain boiled emulsion 27 of the present invention. This is also listed in Tables 8 and 9. The stability test for emulsion boiled 20 to 27 obtained in each of the above examples,
The results of the foamability test and practical test are shown in Tables 10 and 11 below.

Example 5 The rosin material ClOOfl obtained in Reference Example 3 was mixed with 10% of toluene.
09, and then add an aqueous solution prepared by diluting predetermined amounts of several types of emulsifiers obtained in the above-mentioned reference examples with soft water to make 200 g.

This mixed solution was pre-emulsified at 30° C. using the homomixer described in Example 1, and then passed twice through the piston-type high-pressure emulsifier described in Example 1 adjusted to a shear pressure of 200 kg/Cd at the same temperature to emulsify. The resulting emulsion was heated to 40°C under reduced pressure.
The toluene was distilled off to obtain boiled aqueous emulsions 28 to ▲33 of the present invention. Table 12 shows the type and amount of emulsifier used in each emulsion (as nonvolatile content), and Table 13 shows the properties and storage stability (25° C.) of each emulsion obtained after 6 months. For comparison, each table also lists emulsions obtained when predetermined amounts of the potassium salt of rosin substance C and the sodium salt of dodecylbenzenesulfonic acid are used in the same manner as the emulsifiers described above as comparative emulsions 34 and 35. do. Example 6 An aqueous solution of 2009 obtained by diluting the rosin substance ClOO9 obtained in Reference Example 3 and a predetermined amount of the emulsifier P obtained in Reference Example P with soft water was prepared in an autoclave connected to the piston-type high-pressure emulsifier described in Example 1. The mixture is heated to 160°C and stirred at the same temperature for 30 minutes to pre-emulsify.

The pre-emulsion is then passed through the emulsifier adjusted to a shear pressure of 3001<9/CTl, and the resulting aqueous emulsion is cooled in a water-cooled condenser. The obtained aqueous emulsion is shown in Table 12 and Table 1 as Emulsion ▲36 of the present invention.
Also listed in Table 3. Boiled emulsion 2 obtained in each of the above examples
The results of steps 8 to 36 are shown in Tables 14 and 15 below.

Claims (1)

[Scope of Claims] 1. A paper-size aqueous emulsion comprising a rosin substance, an emulsifier, and water, in which the emulsifier has at least 4 carboxyl groups as pendant groups in the main chain consisting of 8 to 100 carbon atoms. and a hydrophobic portion consisting of an alkyl sulfide group, an alkyl sulfoxide group, or an alkyl sulfone group bonded to one end of the main chain constituting the hydrophilic portion, or an alkali salt thereof. Aqueous emulsion of rosin material. 2 The oligomer has at least 4 to 50 units of one type represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_3 and R_4 are the same or different and are H or CH
_3 and X are CONH_2, OCH_3, OC_2H_
5. CH_2OH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, COOC_2H_4OH, COOC_3H_6OH,
CONHCH_2OH, CONHCH_3, CONHC
_2H_5, CONHC_3H_7, COOCH_3,
COOC_2H_5, CN, OOCCH_3 or OOC
C_2H_5]
an alkyl group consisting of 0 to 46 species, having a hydrophilic moiety in which the sum of the above two units is 50 or less, and constituting a hydrophobic moiety consisting of an alkyl sulfide group, an alkyl sulfoxide group, or an alkyl sulfone group; Carbon number 5
2. The aqueous emulsion of claim 1, wherein the aqueous emulsion is 20 linear or branched alkyl groups. 3. Claim 1 in which the oligomer has a hydrophilic portion composed of at least one unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, R_2 represents H, CH_3, or CH_2COOH) The aqueous emulsion according to item 1 or 2. 4 The oligomer has at least one type of unit represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R_2 represents H, CH_3 or CH_2COOH) and the formula ▲ Numerical formula,
There are chemical formulas, tables, etc. Claims 1 or 2 which have a hydrophilic part consisting of a unit represented by ▼
Aqueous emulsion as described in Section 1. 5 Oligomers have formulas▲There are mathematical formulas, chemical formulas, tables, etc.▼
(In the formula, R_2 represents H, CH_3 or CH_2COOH) and a unit represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Claims that have a hydrophilic moiety. The aqueous emulsion according to item 1 or 2. 6. Claim 1 or 2, wherein the alkyl group constituting the hydrophobic portion is a linear alkyl group having 6 to 12 carbon atoms.
Aqueous emulsion as described in Section 1. 7. The aqueous emulsion according to claim 1, wherein the emulsifier is an alkali metal salt of an oligomer. 8. The rosin substance is 0 to 95% by weight of at least one rosin selected from gum rosin, wood rosin, tall oil rosin, and hydrogenated products, disproportionate products, polymers, or aldehyde modified products of such rosins, and the above rosins. α, β−
Addition reaction product with unsaturated carboxylic acid 5-100% by weight
The aqueous emulsion according to claim 1, which consists of: 9. An aqueous emulsion according to claim 1, containing a rosin material in a concentration of 1 to 60% by weight and an emulsifier in an amount of 0.25 to 10% by weight based on the rosin material. 10 A patent claim obtained by dissolving a rosin substance in a water-insoluble organic solvent, dispersing the resulting organic solvent solution in water in the presence of the emulsifier described in claim 1, and then removing the organic solvent. The aqueous emulsion according to item 1. 11. The aqueous emulsion according to claim 1, which is obtained by mixing a heated molten rosin substance, water, and the emulsifier according to claim 1, and emulsifying the resulting molten mixture.