JPS60133052A - Manufacture of rosin-based emulsion sizing agent - Google Patents

Abstract

PURPOSE:To easily obtain titled agent with assurance through an inversion process, high in stability and great in its sizing effect, by using, as dispersant, a combination of specific surfactant with water-soluble acid. CONSTITUTION:(A) A molten rosin material is admixed with (B) an acidic dispersant aq. solution (pref. a pH 2.5-3.5) containing (i) 2-10wt% based on the component (A) of a surfactant of formula (R is 8-24C hydrophobic hydrocarbon; M is monovalent cation; n is 5-25) and (ii) 5-10wt% based on said surfactant, of a water-soluble acid (e.g. hydrochloric acid, nitric acid) to form a homogeneous dispersion followed by adding, while stirring, warm water to effect phase inversion, thus obtaining the objective agent.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a new method for producing a rosin-based emulsion sizing agent mainly used in the paper manufacturing process, and more specifically, the present invention relates to a novel method for producing a rosin-based emulsion sizing agent mainly used in the paper manufacturing process. The present invention relates to a novel method for producing a rosin-based emulsion sizing agent that uses a water-soluble acid as a dispersion aid when producing the rosin-based emulsion sizing agent by dispersing the agent.

[Prior Art] Conventionally known rosin-based emulsion sizing agents are more susceptible to deterioration of the sizing effect due to deterioration of the quality of water used in the paper manufacturing process and rise in temperature, compared to similarly known saponified aqueous solution type reinforced rosin sizing agents. Recently, it has attracted particular attention because of its resistance to

However, even with this sizing agent, there are still problems in terms of the stability of the emulsion, and improvements are desired.

The manufacturing methods of rosin-based emulsion sizing agents are mainly two methods: a high-pressure emulsification method using a high-pressure homogenizer, and an inversion method in which an aqueous dispersant solution is added to a molten rosin-based material to invert the rosin-based material from a continuous phase to a dispersed phase. It is broadly divided into Although the former method can produce a rosin-based emulsion with extremely fine particle diameters, it requires a large-scale emulsification device, and it is considerably difficult to efficiently produce a fine-particle emulsion using abutment.

Emulsification of rosin-based substances was traditionally carried out by the Bewoid method, in which rosin-based substances were placed in an aqueous medium by using a small amount of alkali, such as caustic soda, in combination with a protective colloid such as casein. Recently, various synthetic surfactants have been studied as dispersants for rosin-based substances in water.

For example, as an aqueous dispersant for the inversion method of reinforced rosin materials, salts of sulfuric acid raw esters of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether (Japanese Patent Application Laid-Open No. 77206/1982) and polyoxyethylene disdyrylphenyl There are proposals such as a salt of sulfuric acid half ester of Edel (Japanese Unexamined Patent Publication No. 106534/1983). Due to the relatively high melting point of reinforced rosin materials, it was believed that it was difficult to disperse them in water using the inversion method. By using surfactants of specific chemical structure, inversion-based dispersion of reinforced rosin materials in water is possible. However, according to the inventor's additional tests, even with the use of the above-mentioned surfactant, it is still quite difficult to emulsify the reinforced rosin material, and the rosin material solidifies during the emulsification process, making emulsification impossible. There are many. Furthermore, even if emulsification is possible and an emulsion of the fortified rosin material is obtained,
It must be said that the dispersed particle size of the emulsion is large and the stability of the emulsion is extremely unsatisfactory.

The present inventors have studied various rosin substances, particularly reinforced rosin substances, their dispersants, and their emulsification methods, and have conducted research to produce rosin-based emulsions suitable as paper-making sizing agents. As a result, although the above-mentioned specific surfactants are suitable as an aqueous dispersant for reinforced rosin materials, their use alone does not provide sufficient size effects or stability to be practical as a paper sizing agent. It was not possible to obtain a rosin-based emulsion with

[Object of the Invention] Here, the present invention provides an extremely easy operation in the emulsification process by using a water-soluble acid together with the surfactant as a dispersion aid, and moreover reliably emulsifies the reinforced rosin material. The object of the present invention is to obtain an emulsion sizing agent in which the dispersed particles of the emulsion are very fine and the stability of various types of agents is also markedly excellent.

[Structure of the Invention] That is, the present invention provides a method for producing a rosin-based emulsion sizing agent in which an aqueous dispersant solution is added to a molten rosin material to uniformly flood the rosin material, and then water is added to phase invert the dispersant. The aqueous solution has the general formula R-0+CH2CH2-0+-nS0
3M, where R: hydrophobic hydrocarbon group M having 8 to 24 carbon atoms
: monovalent cation n: a surfactant represented by an integer of 5 to 25; and (b): a water-soluble acid.

[Disclosure of the Invention] According to conventional knowledge, when preparing an aqueous emulsion of a rosin-based material, it is common to use a small amount of an alkaline substance along with various surface-active substances and protective colloids/substances. The reason for this is thought to be that some of the carboxyl groups contained in rosin-based substances are saponified by alkaline substances, producing water-soluble soaps from rosin-based substances, which possess excellent surface-active properties. It's here.

However, when a rosin substance is emulsified in water by the inversion method using a surfactant represented by the above general formula as a dispersant, the presence of an alkaline substance has a completely opposite effect, making emulsification impossible. It becomes. The details of the reason are not clear at present, but the water-soluble soap generated from the alkaline substance and the rosin substance works with the surfactant to promote the penetration of water into the rosin substance. This is thought to be due to the fact that it promotes hydration crystallization, hydrolysis, etc., impairing emulsibility in water.

On the other hand, various surfactants represented by the above general formula are commercially available, but in all of them, M is an ammonium group or an alkali metal, so they are not suitable for emulsification in water by the inversion method of rosin substances. Although it is thought that it cannot act as a dispersant, when it is used together with a water-soluble acid, the action of alkaline substances such as ammonium groups and alkali metals is suppressed, and a very good dispersing effect is developed. Conceivable.

The rosin materials used in the present invention typically include fortified rosin materials suitable as sizing agents. The reinforced rosin material is obtained by a heated addition reaction between rosin and an αβ-unsaturated polybasic acid, and is generally a reinforced rosin material in which 5 to 15 parts by weight of an αβ-unsaturated polybasic acid is reacted with 100 parts by weight of rosin. is preferably used. Such a reinforced rosin material is a mixture of an equimolar addition reaction product of rosin and an αβ-unsaturated polybasic acid and unreacted rosin. Here, as the rosin, gum rosin, wood rosin, 1- to -2-ole oil rosin, modified products thereof, or mixtures thereof are used, and as the αβ/unsaturated polybasic acid, maleic acid, itaconic acid, maleic anhydride, etc. is used. Furthermore, if necessary, in addition to the above-mentioned reinforced rosin substance, various known hydrophobic substances, such as waxes such as paraffin wax and microcrystalline wax, and hydrocarbon resins such as petroleum resin and terpene resin can be mixed and used.

The surfactant serving as a dispersant for the rosin substance constituting the dispersant aqueous solution in the present invention has the general formula R-0-+
CH2Cl-12-0+-nSO3'M, where R: hydrophobic hydrocarbon group having 8 to 24 carbon atoms M: monovalent cation n: expressed as an integer from 5 to 25 and having the corresponding chemical structure Various commercially available products can be used. Specifically, R is an alkyl group such as an octyl group, a nonyl group, a lauryl group, a stearyl group, an alkylphenyl group such as a tertiarybutylphenyl group, a balaroctylphenyl group, a nonylphenyl group, or a styrenated or distyrenated phenyl group. etc., and M is an alkali metal such as Na, ammonia or various alkylamines, or an ammonium group based on alkanolamines, etc., and even if they are combined, any of them can be used. be.

Examples of water-soluble acids as dispersion aids used in combination with the above surfactants include water-soluble inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and water-soluble organic carboxylic acids such as formic acid, acetic propionic acid, and p-toluenesulfonic acid. , or water-soluble organic sulfonic acids.

In carrying out the present invention, an acidic dispersant aqueous solution containing a surfactant represented by the above general formula and a water-soluble acid is added dropwise to a melt of a rosin substance while sufficiently stirring to obtain a uniform transparent solution, or After forming a homogeneous dispersion in which the rosin substance is the continuous phase, hot water is added while stirring vigorously to cause phase inversion, thereby producing a milky white emulsion in which the rosin substance is the dispersed phase. At this time, the dispersant aqueous solution contains 2 to 10% surfactant based on the weight of the rosin material used and 5% to 5% surfactant based on the weight of the rosin material used.
It is desirable that the acidic aqueous solution containing ~10% of a water-soluble acid be 1-15 or less, preferably 2.5 to 3.5 times per day, and the total amount is based on 100 parts by weight of the molten rosin material. It is preferable to have a strength of 15 to 35 parts. Within this range, the mixture of the molten rosin material and the aqueous dispersant solution becomes a homogeneous transparent to translucent solution or a homogeneous mixed dispersion. Of course, within the range where a mixture of the two exhibits the above-mentioned appearance, or so that the mixture thereof exhibits such an appearance, -F
There is no problem in adjusting the amount of water used in the aqueous dispersant solution as appropriate. In addition, the dropping of the aqueous dispersant solution onto the melted material is generally carried out at a melting temperature that is at least 20°C higher than the melting point J of the material. It is preferable to adjust the temperature to around ℃. Thereafter, warm water at 80 to 95° C. is added dropwise under stirring and phase inversion is carried out, thereby obtaining a fine particulate rosin-based emulsion-liquid agent in which the rosin substance is a dispersed phase.

In the production of the rosin-based emulsion sizing agent according to the present invention, in addition to the above-mentioned specific surfactants, a small amount of other surfactants having the same chemical structure may also be used. When using a strongly alkaline surfactant, care must be taken as it may impede the emulsification state.If this is used as an aqueous dispersant solution, it will remain stable even in the coexistence with a water-soluble acid. You should use the one you choose.

A specific example of a surfactant that can be particularly preferably used in combination is a known alkylbenzenesulfonic acid surfactant. In this case, if an alkylbenzenesulfonic acid surfactant is used in combination in a range of 10 to 30% based on the weight of the surfactant of the general formula, the emulsification of the modified rosin material in water becomes easier, and the emulsion in the form of fine particles is further improved. In addition, when this is used as a sizing agent, the reactivity with sulfuric acid band is increased, and as a result, an even more excellent sizing effect can be exhibited.

[Effects of the Invention] The structure of the present invention is as described above, and according to the present method,
A rosin-based emulsion sizing agent with a fine particle size containing a rosin material, particularly a reinforced rosin material as a dispersoid, can be produced extremely easily and reliably by the inversion method. In addition, the rosin-based emulsion sizing agent obtained by the method of the present invention is characterized by very good stability in various ways and excellent re-ease effect due to its fine particle nature.

[Embodiments] The present invention will be specifically described below based on Examples and Comparative Examples.

[Production example] 800 parts of gum rosin was heated and melted, and 16 parts of maleic anhydride was melted.
and 32 parts of fumaric acid, and heated to 190-200°C.
By reacting at 200 to 205° C. for 2 hours and for 4 hours at 200 to 205° C., a reinforced rosin material, which is an addition reaction product of rosin and αβ-unsaturated polybasic acid, was obtained. The acid value of this fortified rosin material is 188. The softening point (ring and ball method) was 78°C.

[Example 1] 100q of the reinforced rosin material obtained in Production Example was placed in a stirrer.
Pour into a flask and heat to 130-140℃ on an oil bath.
melt.

Weigh out 5 g of a general formula surfactant, 40°C F, and 15 q of water in a separate container.
Completely dissolve to obtain an aqueous dispersant solution. The pH of this dispersant aqueous solution was 8.0. Add 0.4q of 90% acetic acid to this
was added and mixed. At this time, the pH of the dispersant aqueous solution is 3.
It dropped to 1.

This acidic aqueous dispersant solution is added dropwise over a period of 10 to 20 minutes to a flask loaded with molten toughened rosin material. At this time, the contents should be thoroughly stirred and mixed uniformly. After the dropwise addition of the dispersant aqueous solution is completed, the temperature of the contents should be 95 to 95.
ioo'c, resulting in a completely transparent homogeneous mixture.

Next, while maintaining the internal temperature at 90°C or higher, the temperature was heated to 85°C while stirring.
Dry water 90Q at ~90°C was added over 20-30 minutes.

During this time, the contents undergo further phase inversion from a milky creamy state to an aqueous emulsion having a fine particle size. Thereafter, it was cooled to an internal temperature of 30° C. or lower.

The obtained rosin emulsion sizing agent had a solid content of 50
3% PH4.0 (10 times diluted solution), viscosity 120CpS/
The temperature was 20°C.

[Example 2 and Example 3] The present invention was carried out in the same manner as in Example 1 except that the amount of surfactant used in the dispersant aqueous solution in Example 1 was changed to 3 g and 7 g. Rosin-based emulsion sizing agent 2
I got the seeds. In either case, emulsification was carried out very easily as in Example 1, and the resulting rosin-based emulsion sizing agent was a fine particulate emulsion almost identical to that obtained in Example 1.

[Comparative Example 1] All operations were carried out in the same manner as in Example 1 except that the weakly alkaline dispersant aqueous solution of pH 8 was used as it was without adding acetic acid to the dispersant aqueous solution. The enriched rosin material was emulsified. When hot water was added, the emulsification was a little rotational, but the stirring speed was increased to complete the phase inversion. The resulting aqueous emulsion of the modified rosin material was the same as the emulsion of Example 1. Compared to the above, the emulsion was more cloudy and appeared to be an unstable emulsion containing F coarse particles.

[Example 4] Instead of using the dispersant aqueous solution in Example 1, P containing τ and 1.20% sodium dodecylbenzenesulfonate was used.
A rosin-based emulsion sizing agent of the present invention was obtained by carrying out all operations in the same manner as in Example 1, except for using an aqueous dispersant solution of H3,2. Emulsification was carried out very easily, and the resulting rosin-based emulsion sizing agent was a fine particulate emulsion with an appearance as good as or better than that obtained in Example 1.

[Example 5] 100 q of the reinforced rosin material obtained in the production example is charged into a flask with a stirrer, and heated to 130 to 140°C on an oil bath to melt it. In a separate container, add 5 g of surfactant of general formula % (mixture of n-12 to 18) and 40°C.
Weigh out 150% of warm water and melt it completely, then 90%
Add 0.4Q of acetic acid to make a homogeneous and transparent dispersant aqueous solution (PI-
13,2) was obtained.

This aqueous dispersant solution was added dropwise to the flask over 10 to 20 minutes while stirring to mix uniformly. The contents of the flask had a completely transparent appearance at a temperature of 95-100°C.

Next, while maintaining the internal temperature at 90°C or higher, the temperature was heated to 85°C while stirring.
90g of warm water at ~90°C was added over 20-30 minutes.

Phase inversion occurs and 1 μl of an aqueous emulsion of the reinforcing rosin material is easily poured into the dough, which is immediately cooled to obtain the rosin-based emulsion sizing agent of the present invention. This is a stable aqueous emulsion with very good dispersion.

[Example 6] All the same procedures as in Example 5 were carried out except that instead of using the aqueous dispersant solution, an aqueous dispersant solution (PH 3, 2) containing sodium dodecylbenzenesulfonate 050 was used. A rosin-based emulsion sizing agent of the present invention was obtained in the same manner as described above, which showed a very good dispersion state.

[Comparative Examples 2 and 3] Instead of using the dispersant aqueous solution in Example 5, an acetic acid-free dispersant aqueous solution (PH 8,1) and an acetic acid-free dispersant aqueous solution containing 0.5Q of sodium dodecylbenzenesulfonate were used. Except for using each of the dispersant aqueous solutions (PH8, 2),
Emulsification of the enriched rosin material was carried out in the same manner as in Example 5. In either case, emulsification was somewhat difficult, and Comparative Example 1
In the same manner as above, the stirring speed was increased to complete the phase inversion, and two aqueous one-emulsions of the modified ginseng material were obtained. These emulsions appeared to be unstable emulsions containing coarse particles.

[Example 7] 1 q of the reinforced rosin material IOOG obtained in the production example was charged into a stirrer flask, and the temperature was raised to 130 to 140°C in an oil bath to melt it.

In a separate container, weigh out 7q of W surfactant with the general formula % and 15g of 40°C warm water, and after completely dissolving them, add 90% acetic acid O, SG to make a homogeneous transparent dispersant aqueous solution (PH2, 8) was obtained. This aqueous dispersant solution was stirred while being dropped into the flask to mix uniformly. The contents of the flask had a temperature of 95-100°C and was slightly cloudy, but fairly clear.

Next, while maintaining the internal temperature at 90°C or higher, the temperature was heated to 85°C while stirring.
~90°C dry water 90Q was added dropwise. While maintaining a homogeneous state, the contents became creamy and then underwent phase inversion, resulting in a decrease in viscosity and an emulsion with a good appearance and having finely dispersed particles.

This was cooled to 30° C. or lower to obtain a rosin-based emulsion sizing agent of the present invention.

[Comparative Example 4] Everything was the same as in Example 7, except that instead of using the dispersant aqueous solution in Example 7, a dispersant aqueous solution (PI-18, 3) was used without adding acetic acid. The reinforced rosin material was emulsified by operation to obtain a rosin-based emulsion. The appearance of this emulsion was somewhat heterogeneous containing coarse particles.

[Test Example] Each of the emulsions obtained in the above Examples and Comparative Examples was tested for stability and size effect using the following test method. Write down the results.

(Test method) Product stability: 50g of rosin emulsion was placed in a 60cc glass bottle, left in a 40'C constant water tank, and oral stability was observed. If the stability is poor, the precipitate will settle and accumulate at the bottom of the bottle along with the oral intake.

Mechanical stability: Sample 5 (1%) diluted to 1% solids
Add 0g to a household mixer (2 volumes) and repeat continuous stirring 3 times for 3 minutes each.

After that, it was filtered through a 200-mesh bag, and the residue was suspended.
It is expressed by the precipitation rate of the following formula.

Measurement of size effect: Add talc as a filler to the 2.4% valve slurry of pulp LBKPcsf400* at 20% based on the pulp and mix, then add and mix a sizing agent at 0.2% based on the pulp, and further add sulfuric acid band. Add and mix 2% of the pulp to fix the sizing agent. TAPP ■Hand-paper the paper using a standard hand-paper machine to a paper basis weight of 65 g/m. After that, press drying and humidity conditioning were carried out as usual, and the degree of sizing (Stekicht method) was measured.

(Leaving space below) Procedural amendment (method) Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office, 1985-1983 1. Indication of the case: 1982 Patent Application No. 241727 2. Name of the invention: Method for producing a rosin-based emulsion sizing agent 3 Relationship between the person making the amendment and the case Patent applicant Seiko Kagaku Kogyo Co., Ltd. 4 Agent 5 Kosato Hall, 1-18-14 Nishi-Shinbashi, Minato-ku, Tokyo Date of amendment order March 27, 1980 6 Subject of amendment Details duck

Claims (1)

[Claims] 1. Add and mix an aqueous dispersant solution to a molten rosin substance to form a homogeneous transparent solution or a homogeneous dispersion in which the rosin substance is a continuous phase, and then add water and perform phase inversion. In the method for producing a rosin-based emulsion sizing agent, the aqueous dispersant solution (a) has the general formula R-0+CHz CH20+n503
M, where R: hydrophobic hydrocarbon group having 8 to 24 carbon atoms M:
A method for producing a rosin-based emulsion sizing agent, characterized in that: a monovalent cation n; a surfactant represented by an integer of 5 to 25; and (b): a water-soluble acid. 2. The method for producing a rosin-based emulsion sizing agent according to claim 1, wherein the dispersant aqueous solution is an acidic aqueous solution with a pH of 2.5 to 3.5. 3 The dispersant aqueous solution contains 2 to 10% by weight of (a) based on the weight of the rosin substance, and 5 to 10% by weight of (b) based on the weight of (a).
) The IJ manufacturing method for a rosin-based emulsion sizing agent according to claim 1 or 2, wherein the rosin-based emulsion sizing agent contains: