KR830002700B1 - Preparation of aqueous emulsion of rosin substance - Google Patents

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Description

Preparation of aqueous emulsion of rosin substance

The present invention relates to the preparation of aqueous emulsions of rosin materials, and more particularly to the preparation of aqueous emulsions of rosin materials by inversion using certain dispersants.

Cellulose fiber products such as middle ear, paperboard, and fibrous fiber boards are generally agitated by adding a size agent to the aqueous solution of cellulose fiber.

As said size agent, rosin substance is used normally, Especially since it can provide the size effect of the water resistance, ink permeability, etc. which were excellent in the product from which a reinforced rosin type size agent is obtained, it is used extensively.

Moreover, as a manufacturing method of these reinforcing rosin-size agents, there are the following two types of methods. One method involves reinforcing rosin in water using a high pressure shear homogenizer in the presence of a suitable dispersant. Another method is to mix the melted rosin material with the dispersant and water to form an emulsion in which the rosin material is a continuous phase and the water is in a dispersed phase and then add water to invert the emulsion so that the rosin material is in the dispersed phase and the water is It is a so-called reversal method of obtaining a continuous aqueous emulsion.

This reversal method has the advantage that an aqueous emulsion of rosin material can be obtained without using a special equipment such as a homogenizer. However, a method for producing an aqueous emulsion of rosin material having low foamability and excellent size effect, storage stability, mechanical stability and dilution stability, and other properties by this inversion method has not been proposed yet.

It is therefore an object of the present invention to provide a method for the preparation of an aqueous emulsion of rosin material having low foamability by an inversion method.

It is another object of the present invention to provide a method for producing an aqueous emulsion of rosin material, in which the size effect is superior by the inversion method.

Still another object of the present invention is to provide a method for preparing an aqueous emulsion of a rosin material having excellent storage stability, mechanical stability, and dilution stability by an inversion method.

These and other objects of the present invention will become apparent from the following description.

The present invention forms an emulsion in which the rosin material is a continuous phase by mixing the melted rosin material with the dispersant and water, and then inverts the emulsion by adding water to the rosin material in the dispersed phase and the water is in the continuous phase. In the method for obtaining an aqueous emulsion, the dispersant is to provide an aqueous emulsion of a rosin substance, characterized in that at least one of the compounds represented by the following general formula (I) and (II).

In the above formula, R ¹ is a hydrocarbon group of 4 to 18 carbon atoms, R ² is a hydrogen atom or a lower alkyl group, A is a straight or cyclic alkylene group having 2 or 3 carbon atoms, X is a hydrogen atom or hydroxyl group, M is 1 A cation is shown, m is 1 or 2, n represents the integer of 4-25.

According to a study of the present invention, a specific sulfonic acid salt represented by the general formula (1) and a sulfuric acid partial ester represented by the general formula (2) have never been used in the preparation of an aqueous emulsion of a rosin substance of such distillation. When using at least one salt as an emulsifier and dispersing the rosin material in water by the inversion method, it was found that an aqueous emulsion of the rosin material having low bubbleability and excellent size effect and stability can be obtained.

The present invention has been completed based on these new findings.

According to the present invention, in dispersing a rosin substance in water by using an inversion method, by using one or more of the dispersant of the general formula (1) and the dispersant of the general formula (2), the following excellent effects can be expressed. There is a number.

That is, the aqueous emulsion of the rosin material obtained by the method of the present invention has an excellent size effect (a), extremely excellent storage stability, mechanical stability and dilution stability (b), extremely low bubble stability (c), and The effect of (a) and (b) is that even when the amount of one or more of the above-described dispersant of formula (1) and dispersant of formula (2) is a small amount of about 2% by weight in dry weight relative to the rosin material It can be maintained.

Therefore, the foamability of said (c) can also be reduced further. Therefore, it is economically advantageous to save time and effort for the parcel.

Such an excellent effect can be expressed only when using at least one of the above-described dispersant of the formula (1) and dispersant of the formula (2).

In addition, even a compound similar in chemical structure cannot express the above excellent effect.

In the present invention, the rosin substance used as the dispersant is usually composed of 0 to 95% by weight of rosin and 5 to 100% by weight of reinforcement rosin. It includes one thing.

As the rosin, rubber rosin, wood rosin, torol oil rosin, modified substances thereof, and mixtures thereof can be used.

Examples of the modified substances include hydrogenated rosin, disproportionated rosin, polymerized rosin, aldehyde modified rosin and the like. Among these rosins, for example, aldehyde-modified rosin usually contains rosin and 2 to 8% by weight of formaldehyde or acetaldehyde at a temperature of about 140 to 200 ° C in the presence of an acidic catalyst with sulfuric acid, paratoluenesulfonic acid and the like. It is obtained by reacting for 3 hours.

Reinforced rosin is obtained by heating the above-mentioned rosin with 2 to 30% by weight, preferably 3 to 15% by weight, of α, β-unsaturated carboxylic acid at a temperature of about 150 to 250 ° C.

Examples of α, β-unsaturated carboxylic acids that can be used include acrylic acid, maleic acid, fumaric acid, itaconic acid, anhydrides thereof, and mixtures thereof, with fumaric acid, maleic acid and maleic anhydride being particularly preferred.

Moreover, as a weighting agent mentioned above, waxes, such as a paraffin wax and a microwax wax, petroleum resin, terpene resin, hydrocarbon resins, such as these hydrogenated substances, etc. can be illustrated.

When it contains these, it is preferable that rosin substance contains 25 weight% or more reinforcement rosin normally.

In this invention, it is essential to use at least 1 sort (s) of the sulfonic acid salt represented by the said General formula (1), and the sulfuric acid partial ester salt represented by General formula (2) as a dispersing agent.

(식중, R³는 수소원자 또는 저급알킬기, 예를 들면, 메틸, 에틸, 프로필, 부틸기 등을 또, B는 탄소수 1 내지 3의 직쇄상 또는 측쇄상의 알킬렌기, 예를 들면 메틸렌, 메틸메틸렌, 디이틸메틸렌, 에틸렌, 메틸에틸렌, 트리메틸렌기 등을 나타냄)으로 표시되는 방향족 탄화수소기가 포함된다. 상기에 있어서, 이 직쇄상 또는 측쇄상의 알킬기를 나타내는 경우에 (R¹)_m로 표시되는 기의 총 탄소수는 4 내지 30, 특히 6 내지 25인 것이 바람직하다. 또 R¹이 상기식

로 표시되는 방향족 탄화수소 잔기를 나타내는 경우, m는 2인것이 바람직하다. (R¹)_m로 표시되는 기의 총 탄소수는 14 내지 20인 것이 바람직하다. 이 (R^1`)_m로 표시되는 기의 총 탄소수는 14 내지 20인 것이 바람직하다. 이 (R¹)_m로 표시되는 바람직한 기로서 대표적인 것으로서는 디스티릴기

, 디(p-메틸스틸릴)기

디(α-메틸스틸릴)기

등을 예시할 수가 있다.As the hydrocarbon residue of 4 to 18 carbon atoms defined by R ¹ in the sulfonate represented by the general formula (1), a linear or branched alkyl group having 4 to 18 carbon atoms, for example, butene, isobutyl, hexyl and octyl , Ioctyl, nonyl, isononyldodecyl, tetradecyl, hexadecyl, octadecyl group, etc. and general formula

(Wherein R ³ represents a hydrogen atom or a lower alkyl group such as methyl, ethyl, propyl or butyl group, and B is a linear or branched alkylene group having 1 to 3 carbon atoms such as methylene or methylmethylene) , Dibutylmethylene, ethylene, methylethylene, trimethylene group and the like). In the above, to indicate an alkyl group on the straight or branched total number of carbon atoms of the groups represented by (R ¹⁾ _m is preferably from 4 to 30, especially 6 to 25. And R ¹ is

When the aromatic hydrocarbon residue represented by is represented, m is preferably 2. The total number of carbon atoms of the groups represented by (R ¹⁾ _m is preferably from 14 to 20. It is preferable that the total carbon number of the group represented by this (R <^1> ) _m is ^14-20 . As a typical group represented by this (R ¹ ) _m is a distyryl group

, Di (p-methylstyryl) group

Di (α-methylstyryl) group

Etc. can be illustrated.

In the present invention, as the sulfonate represented by the general formula (1), it is particularly preferable that n is 6 to 17, and two or more kinds of n being 4 to 25 are mixed, and the average value n is 6 It is also preferable to make it to 17.

Examples of monovalent cations defined by M in the sulfonate represented by the general formula (1) include alkali metal ions such as lithium, sodium, potassium, and cesium, ammonia and trimethylamine, dimethylamine, diethylamine, and triethanolamine. And ammonium ions derived from various amines.

Moreover, as a lower alkyl group defined by R <^2> in the salt of the sulfuric acid partial ester of the said General formula (2), methyl, ethyl, a propyl, a butyl group, etc. can be illustrated. Moreover, as a C2 or C3 alkylene group defined by A, a methyl methylene, dimethyl methylene, ethylene, methyl ethylene, trimethylene group can be illustrated.

로서는 스티릴

, p-메틸스티릴

, α-메틸스티릴

등이 바람직하다. 또 n로 정의되는 1가의 양이온으로서 일반식(1)의 경우와 똑같이, 리튬, 나트륨, 칼륨, 세슘 등의 알카리금속이온, 암모니아, 트리메틸아민, 디메틸아민, 디메틸아민, 트리에탄올아민 등의 각종 아민에서 유도되는 암모늄기를 예시할 수가 있다. 또 n로서는 6 내지 20이 바람직 하다.group

As styryl

, p-methylstyryl

, α-methylstyryl

Etc. are preferable. In the same manner as in the general formula (1), as the monovalent cation defined by n, alkali metal ions such as lithium, sodium, potassium, cesium, ammonia, trimethylamine, dimethylamine, dimethylamine, triethanolamine and the like The ammonium group derived can be illustrated. Moreover, as n, 6-20 are preferable.

The dispersant of the formula (1) and at least one of the dispersants of the formula (2) are usually used in a proportion of about 0.5 to 10% by weight, preferably 1 to 8% by weight, based on dry weight, relative to the rosin material. . If it is less than 0.5% by weight, the dispersing force is not sufficient, and using an amount exceeding 10% by weight is not economical.

In particular, the dispersant composed of one or more of the sulfonate represented by the general formula (1) and the sulfate ester salt represented by the general formula (2) used in the present invention is, for example, about 1 to 2% by weight Even in the case of using a small amount, there is an advantage in that an aqueous emulsion capable of expressing the desired effect can be obtained.

In carrying out the production process of the present invention, first, a molten rosin material is prepared by heating and accompanying the reinforcement rosin together with one or both of rosin and weight agent as desired. The heating temperature at this time is preferably set to a temperature at least 20 ℃ higher than the softening point of the rosin material, the suitable temperature depends on the blending ratio of the reinforcement rosin, rosin and extender, generally in the range of 90 ° to 160 ° C.

Next, while stirring the molten rosin material, an aqueous dispersant or a dispersant and water are added thereto to form an emulsion in which the rosin material is a continuous phase and the water is a dispersed phase. The amount of water used at this time is good to adjust so that the obtained emulsion may contain about 70 to 90 weight% of solid content.

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

The phase inverted water of the emulsion is produced when the amount of water exceeds about 30% of the total amount, and the water becomes a continuous phase, whereby an emulsion in the form of a rosin substance dispersed in water is obtained. If desired, the emulsion can be diluted with water or alkaline water and / or the pH can be adjusted. It is preferable to use the said alkali usage in the range which becomes pH 6 or less of an emulsion.

The aqueous emulsion thus obtained is usually 5 to 70% by weight, preferably 30 to 55% by weight of rosin, about 0.5 to 10% by weight, and preferably 1 to 8% by weight of the rosin. It is substantially composed as negative water, and the rosin material is uniformly dispersed as particles of 1 mu or less, most of 0.5 mu or less, in this emulsion. This aqueous emulsion has a milky white appearance and has a pH of 3.5 to 6 earthquakes. It is stable for at least 2 months at room temperature, does not produce precipitate, and is usually accompanied by the use of dispersants.

The aqueous emulsion obtained by the present invention is a mixture of not only the initial cellulose of cellulose fibers but also these fibers and mineral fibers such as asbestos, rock wool and synthetic fibers such as polyesters, polyesters, and polyoleins. It can be advantageously applied when manufacturing paper, cardboard, fiber board, etc.

In the case of using the aqueous emulsion obtained in the present invention as a papermaking sizing agent, for example, a method of adding an aqueous dispersion of pulp together with a fixing agent such as sulfuric acid band and the like to produce an aqueous solution at a pH of 4 to 6 or a special public office 49-30201 As described in the publication (British Patent Publication No. 1,266,829), a method of adding an aqueous solution of pulp together with a small amount of a fixing agent such as a sulfate band and a very small amount of cationic fixing aid to produce an initial solution at a pH of 5 to 7, etc. It can be adopted.

In this case, an aqueous emulsion is used at 0.05 to 3% by weight (based on dry weight) based on the pulp. Since the aqueous emulsion obtained by this invention is excellent also in dilution stability, even if it uses water, such as a river, tap water, and well, it can fully be diluted and it is easily disperse | distributed to the water dispersion of pulp. Its dilution is stable for a long time.

The aqueous emulsion obtained by the present invention can also be used as a surface sizing agent, and can be applied to conventional wet methods such as spraying, dipping and coating.

The production method of the aqueous emulsion of the present invention will be described in more detail with reference to the following Examples. Reference Example describes a preparation example of the rosin material used in the present invention. In Examples and Reference Examples, parts and percentages are by weight unless otherwise specified. In addition, each property of an aqueous emulsion is measured by the following method.

(1) mechanical stability

50 g of an aqueous emulsion is weighed into a container of a Maron stability tester (Shinsung Industrial Co., Ltd.), subjected to mechanical shear at a temperature of 25 ° C., a load of 10 kg, and a rotational speed of 1,000 rpm for 5 minutes, and the resulting aggregates are filtered through a 100 mesh gold mesh. Stability is computed by the following formula.

(2) Dilution Stability

The aqueous emulsion is diluted to 25% concentration as water of hardness 10 ° DH at 25 ° C. After dilution, the time until the emulsion agglomerates by flocculation by visual observation is measured.

(3) foamability

The aqueous emulsion was diluted with deionized water to a concentration of 500 ppm, and the lean liquid was measured according to JIS K 3362.

Reference Example 1

1800 parts of oil oil rosin are heated and melted at 165 ° C., and 2.7 parts of p-toluenesulfonic acid monohydrate is added as a catalyst, followed by 118 parts of 37% aqueous formaldehyde solution at 160 to 170 ° C. over 90 minutes. Stirring at the same temperature for another 1 hour yields formaldehyde modified rosin. In addition, 1200 parts of rubber rosin were added to this modified rosin, and stirred and mixed at 175 ° C for 1 hour.

2950 parts of the mixture and 177 parts of fumaric acid were heated and melted to react at 200 ° C for 3 hours. The acid value of the obtained rosin substance 1 is 208, and a softening point (circulation method) is 103.5 degreeC.

Reference Example 2

1000 parts of rubber rosin and 190 parts of fumaric acid were heated and melted to 200 ° C, and reacted at the same temperature for 4 hours. The strengthening rosin obtained has an acid value of 286 and a softening point of 138.5 ° C.

The rosin material 2 is obtained by mixing 550 parts of the reinforcement rosin obtained above and 500 parts of the rubber rosin at 170 ° C. and mixing for 30 minutes.

[Examples 1 and 2]

100 parts of the rosin substance (1) of Reference Example 1 was injected into a flask with a stirrer and a thermometer, and heated to be 150 ° C. 10 parts of a 20% aqueous solution of 2-hydroxy-3- (distyrylphenoxypolyoxyethylene) propyl sulfonic acid natrum (compound represented by the formula (1), m = 2, n = 13) while stirring Each of Example 1 and 20 parts (Example 2) was added to the molten rosin material in 2-3 minutes. At this point considerable water was evaporated and the temperature dropped to 93 ° C. Next, 20 parts of hot water (95 占 폚) was added to form a creamy water-in-oil emulsion.

While stirring this emulsion vigorously, 70 parts of hot water (90 degreeC) was added to it for 1 minute, and the phase inversion occurred, and it became an oil-in-water emulsion.

This was quenched from the outside, the temperature was lowered to 30 ° C., passed through a 100 mesh gold mesh and placed in a glass bottle. No coagulum was observed in the gold mesh, and the rosin material contained in the obtained aqueous emulsion was substantially the same weight (yield 98% or more) as the used rosin material. The properties of the obtained emulsion are described in the first table.

[Comparative Examples 1 and 2]

Aqueous emulsion was obtained in the same manner except that the sodium salt of polyoxyethylene (average degree of polymerization 10) nonyltenyl ether sulfate partial ester was used instead of the dispersant represented by formula (1) used in Examples 1 and 2.

The properties of the obtained aqueous emulsion are described in the first table.

[Table 1]

One)… … … Dry Weight Criteria for Rosin Substances

2)… … … Do not measure

According to the method of the present invention from the above Table 1, by using the specific dispersant represented by the general formula (1), the mechanical stability, the dilution stability and the storage stability are superior to the case of using a known dispersant, and the foamability is considerably less. You can see that you can get an emulsion. In particular, according to the method of the present invention, it is possible to obtain a desired aqueous emulsion that is stable for at least two months by using only 2% by weight (based on dry weight) of the dispersant based on the rosin material. Fire to separate water as one day

[Practical examination 1]

When the aqueous emulsion obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was used as a papermaking agent, the size diagram of the sacred paper was measured by the stachyhit method (JIS P 8122). do.

In other words, a pulp (L-BKP) of 30 ° SR at a high degree of water was used as 1% aqueous slurry, and 0.2% or 0.5% aqueous emulsion based on pulp dry weight, followed by 2.5% sulfuric acid pulp. Add the chemicals in sequence and spread them evenly, then paper them to 60 ± 1 g / m2 using a TAPPI standard sheet machine.

This was dehydrated at a pressure of 5 g / cm &lt; 2 &gt; for 3 minutes, then dried at 80 DEG C for 5 minutes, and the stock was humidified for 24 hours at 20 DEG C. 65% RH. The results are shown in Table 2.

[Table 2]

The aqueous emulsion obtained by the method of the present invention from the second table is obtained by using 4% by weight of the dispersant of the comparative example by using only 2% by weight (dry weight basis) of the dispersant represented by the ordinary stone (1) relative to the rosin material. It is obvious that the size effect can be expressed approximately. On the other hand, the aqueous emulsion obtained by using 2 weight% of the dispersing agents of the comparative example can express only a very low size effect even when using 0.5% by the large pulp dry weight standard, and it turns out that it is practically difficult.

Example 3

Except that the amount of dispersant used in Example 1 was set to 1% of the rosin material, it was carried out in the same manner to obtain an aqueous emulsion having a size effect almost the same as the emulsion of Example 1.

Comparative Example 3

In Comparative Example 1, except that the amount of dispersant used was 1% relative to the rosin material, the phase inversion did not occur, and an oil-in-water emulsion could not be obtained.

[Examples 4 to 13]

A rosin substance (2) was used instead of the rosin substance (1), and a stable aqueous emulsion was obtained in the same manner except that the compound of Table 3 below was used as the dispersant in 4% of the rosin substance (2). The yield was about 100%, the particle size of any emulsion was 0.2 to 0.3L, the dilution stability was more than 24 hours, and stably stored for more than 2 months.

[Table 3]

The results of measuring the mechanical stability and foaming properties of these emulsions and the results of using them as size agents for papermaking according to the above-described methods are shown in Table 4, respectively.

[Table 4]

EXAMPLE 14 AND 15

100 parts of the rosin materials (1) of Reference Example 1 were supplied to a flask with a stirrer and a thermometer and heated to be 150 ° C. 10 parts (Example 14) and 20% aqueous solution of the ammonium salt of the polyoxyethylene (average degree of polymerization 11) dispirylphenylether sulfate sulfuric acid partial ester (compound represented by General formula (2), n = 11) with stirring, and 20 Each part (Example 15) was added to the molten rosin material in 2-3 minutes. At this point considerable water evaporated and the temperature dropped to 93 ° C. Next, 20 parts of hot water (95 占 폚) was added to form a creamy water-in-oil emulsion. While stirring this emulsion vigorously, 70 parts of hot water were added to this for 1 minute, and the phase inversion occurred, and it became a water vapor type emulsion. This was quenched from the outside and the temperature was lowered to 30 ° C. and placed in a glass bottle through a 100 mesh gold mesh. No coagulum was observed on the gold mesh, and the rosin material contained in the obtained aqueous emulsion was substantially the same weight (yield: 98% or more) as the used rosin material. It describes in the obtained emulsion 5th table | surface.

[Table 5]

One)… … … Dry Weight Standards for Rosin Substances

It can be seen from the above Table 5 that even when the compound represented by the general formula (2) of the present invention is used as a dispersant, an emulsion having properties equivalent to those of the emulsions obtained in Examples 1 and 2 can be obtained.

[Practical examination 2]

Using the aqueous emulsion obtained in Examples 14 and 15 as the paper size agent, the size effect was measured in the same manner as in the practical test 1, and the results are shown in Table 6.

[Table 6]

The aqueous emulsion obtained by the method of the present invention from Table 6 is an emulsion obtained by using 4% by weight of the dispersant of the comparative example only by using 2% by weight (dry weight basis) of the dispersant represented by the general formula (2) based on the rosin material. It is clear that the size effect can be expressed almost equal to (see Table 2).

Example 16

The aqueous emulsion was obtained in the same manner as in Example 14 except that the amount of the dispersant used was 1% based on the rosin material. The size effect of the obtained emulsion was almost equivalent to that of the emulsion obtained in Example 14.

[Examples 17 to 20]

A rotatable substance (2) was used instead of the rosin substance (1), and a stable aqueous emulsion was obtained in the same manner except that the compound in Table 7 below was used 6% of the rosin substance (2) as a dispersant. The yield was almost 100% and any emulsion had a particle diameter of 0.2-0.3μ.

[Table 7]

These emulsions were used as the size agent for papermaking according to the method described above, and the results are shown in Table 8.

[Table 8]

Claims (1)

Mixing the melted rosin material with the dispersant and water to form an emulsion in which the rosin material is a continuous phase and the water is in the dispersed phase and then adding water to invert the emulsion to obtain an aqueous emulsion in which the rosin material is in the dispersed phase and the water is in continuous phase. A dispersing agent is a method for producing an aqueous emulsion of rosin, characterized in that at least one selected from the compounds represented by the following general formulas (1) and (2).

(Wherein R ¹ represents a hydrocarbon residue having 4 to 18 carbon atoms, R ² represents a hydrogen atom or a lower alkyl group, A represents a straight or branched alkylene group having 2 or 3 carbon atoms, X represents a hydrogen atom or a hydroxyl group, and M represents Monovalent cation, m is 1 or 2, n is an integer of 4 to 25).