JPS5980467A - Preparation of rosin ester emulsion - Google Patents

Abstract

PURPOSE:To prepare an emulsion easily and stably, without using an emulsifier, taking advantage of the self-emulsifiability of a rosin, by dispersing a specific oligoester of a rosin and its derivative with polyethylene glycol in an alkaline aqueous solution under agitation. CONSTITUTION:An oligoester having an acid value of <=100 and composed of (A) a rosin (preferably gum rosin) and its derivative (preferably a rosin derivative modified with maleic acid, or a rosin obtained by modifying a part of the above derivative with a polyhydric alcohol) and (B) a polyethylene glycol having a molecular weight of about 180-1,000, is dispersed in an alkaline aqueous solution of 7-11pH under agitation without using an emulsifier. The esterification with polyethylene glycol may be carried out by using a polyhydric alcohol or a polyhydric alcohol and a polybasic acid such as maleic acid as a part of th raw materials.

Description

[Detailed Description of the Invention] A large number of esters of alcohols, polybasic acid adducts, and the like are known as rosin compounds, and there are many shapes ranging from solids to liquids. Depending on the purpose of use, some are used as solids or liquids, some are used after being dissolved in water or other organic solvents, and some are used as emulsions by dispersing them using emulsifiers. It is well known. However, it has not been known to date that emulsions can be stably and easily made using self-emulsifying properties without using emulsifiers. If it were possible to easily produce a stable emulsion without using an emulsifier, it would be possible to use emulsions for a variety of purposes in the fields of adhesives, paints, printing inks, etc., and the characteristic of emulsions is that they are convenient to handle. In addition, by easily making an emulsion immediately before use, it not only saves a lot of money on transportation costs and container costs for the emulsion, but also prevents the deterioration of properties caused by the use of emulsifiers. was strongly requested.

The present invention was completed based on the results of numerous experiments in order to meet this demand.

Regarding rosin, various rosins (gum, wood, tall oil and mixtures thereof) obtained from conventional rosin manufacturing operations, known polymerized rosins, hydrogenated rosins, disproportionated rosins or rosins made based on these rosins are used. Any of these mixtures may be used. The rosin used can be used depending on the purpose, but it is generally preferable to use gum rosin, which can be used for a variety of purposes and is relatively inexpensive. The rosin derivative may be one obtained by adducting maleic acid (and anhydride) or fumaric acid to an unsaturated double bond contained in rosin, or a mixture thereof. Alternatively, a part of the adducted acid may be esterified with a polyhydric alcohol.

All of these have been made using known methods for a long time.

The polyethylene glycol for making the above rosin and rosin derivative and oligoester has a molecular weight of 180 to 100.
Use 0. This product is also already commercially available and readily available, and is not specially created for the present invention. The esterification reaction of polyethylene glycol and rosin may be carried out by a conventional method (e.g., JP-A-57-1999).
25991P533, Example 1), the esterified product can be easily obtained. However, in order to achieve self-emulsifying property and easy dispersion in an alkaline aqueous solution with a pH of 7 to 11, which is the objective of the present invention, K is set to 0.8 to 2.0% in terms of hydroxyl group per equivalent of acid functional group.
It is desirable to use 0 equivalent, and the obtained oligoester has a softening point of 100°C or less and an acid value of 100 or less, preferably a softening point of 50°C or less and an acid value of 50 or less.

For esterification with polyethylene glycol,
It is also possible to partially use a polyhydric alcohol. Furthermore, it is also possible to add a polybasic acid such as maleic acid before or simultaneously with the esterification reaction.

Further, it is also possible to further add it for the purpose of adjustment after the completion of esterification. In any case, depending on the purpose of use, rosin,
The types of unsaturated dibasic acid and polyethylene glycol and the proportions of each component to be used are determined.

The obtained product takes a form ranging from a very viscous liquid to a solid at room temperature, and can be stored and handled relatively easily in that state.

Emulsification is extremely easy. In particular, liquid materials can be emulsified at room temperature, and solid materials with a high softening point require some heating, but there is no need to heat them to 100° C. or higher.

Emulsification is easy, and it is easily emulsified at an ester concentration of 50% or less (preferably 40% or less) by normal stirring. Although high-speed shear stirring using a homomixer or the like is not necessarily required, this does not preclude its use.

The particle size obtained can be changed by changing the stirring conditions and temperature. It is also possible to use an oligoester with a low softening point as a dispersion aid for the oligoester with a high softening point.

The water used is desirably alkaline and needs to have a PI of 7 or higher.The pH can be adjusted by simply adding a common inorganic alkaline substance and is not particularly limited.

The resulting emulsion is milky white and exhibits excellent stability, with good shelf life for several months.

Examples are shown below. Parts represent parts by weight.

Example (1) 1050 parts of gum rosin was added to a stirring device, an inert gas inlet,
The mixture was charged into a 2,000 W/volume four-eye flask equipped with a formed water removal port, and heated to 200°C while blowing N2 gas to dissolve the rosin. Next, 400 parts of polyethylene glycol (molecular weight: 210) was gradually added,
The temperature was raised to 250°C, and the reaction was continued until the acid value reached 25. When the acid value reached 25, the pressure was maintained at reduced pressure for 1 hour, unreacted polyethylene glycol was removed, and the viscosity (100°C,
A rosin ester having a CPS) of 65, a color number (Gardner) of 7, an acid value of 22, and a hydroxyl value of 480 was obtained.

150 parts of the above rosin ester, 6 parts of 25% ammonia water
Pour 50 parts of well water into a beaker with a capacity of 1000 V and stir uniformly at room temperature (500 R, P, Yyl, blade turbine type 5.). Next, stir at room temperature (500 r, p, m
, vane turbine type 5 bacteria), 300 parts of well water was gradually added to obtain a homogeneous dispersion. This rosin ester emulsion has a solid content (weight%) of 30 and a viscosity (25°C, cps
) 2500, pH 9.5.

Example (2) 1050 parts of tall rosin was charged into a four-eye flask similar to that in Example (1), and heated to 200°C while blowing N2 gas to dissolve the rosin.

Next, 30 parts of maleic anhydride was added and kept at 200°C for 1 hour, and then polyethylene glycol (molecular weight: 210
) 340 parts were gradually added. Subsequently, the temperature was raised to 250 °C, and the reaction was continued until the acid value reached 25. When the acid value reached 25, the pressure was maintained for 1 hour to remove unreacted polyethylene glycol, and the viscosity (100 °C, cps) A rosin ester having a color number of 150, a color number (Gardner) of 8, an acid value of 21, and a hydroxyl value of 26 was obtained.

150 parts of the above rosin ester, 5% ammonia water
Stir 20 parts of well water in a 10001/volume beaker (
500f, p8ms impeller turbine type 5(7)) and then heated to 50°C with high speed stirring (1500r,
200 parts of well water was gradually added to the flask while using a vane turbine (p0mz) to obtain a homogeneous dispersion. On this day, gin ester emulsion [S1 min, (wt%) 40, viscosity (25℃
, CPs) aoo, PH9.6.

Example (3) 1050 parts of wood rosin was placed in a four-eye flask similar to that in Example (1), and heated to 200° C. while blowing N2 gas to dissolve the rosin. Then maleic anhydride 3
After adding 0 part of polyethylene glycol (molecular weight:
210) 490 parts and 30 parts of glycerin were gradually added. Subsequently, the temperature was raised to 250°C, and the reaction was continued until the acid value reached 5. When the acid value reached 5, the pressure was maintained for 1 hour to remove unreacted polyethylene glycol and glycerin, and the viscosity (100°C, cps) 100, number of colors (Gardner) 7
A rosin ester having an acid value of 3 and a hydroxyl value of 720 was obtained.

150 parts of the above rosin ester, 6 parts of 25% ammonia water
1 part and 20 parts of well water were charged into a 100 Q ml beaker and stirred uniformly at room temperature (500 r, p, mz blade turbine type 55I). Next, stir at room temperature (500r, p, m%
Vane turbine type5. ,,)L, 200 parts of well water was gradually added to obtain a homogeneous dispersion. Rosin ester emulsion with tlW content (weight it%) 40, viscosity (25℃,
CPS) 200, pH 9.5.

Example (4) 1050 parts of hydrogenated rosin was charged into a four-eye flask similar to that in Example (1), and heated to 200° C. while blowing N2 gas to dissolve the rosin. Then maleic anhydride 3
After 0 parts of glycerin was added and the mixture was maintained at 200°C for 1 hour, 30 parts of glycerin was added.

Subsequently, the temperature was raised to 250°C, the reaction was continued until the acid value reached 150, and when the acid value reached 150, it was cooled to 200°C and polyethylene glycol (molecular weight: 210) 290
1 part was gradually added, the temperature was raised again to 250°C, and the reaction was continued until the acid value reached 25. When the acid value reached 25, it was kept under reduced pressure for 1 hour, unreacted glycerin and polyethylene glycol were removed, and the viscosity (100°C, CPS) was 15.
0. A rosin ester with a color number (Gardner) of 7, an acid value of 22, and a hydroxyl value of 38 was obtained.

150 parts of the above Rosin Nisdel, 6% 25% ammonia water
50 parts of well water was heated to 50°C while stirring (5,0 Or, p0ms blade turbine type 5 increments) in a 1000117mm beaker, and then heated at 50°C with high speed stirring (3000 r,
220 parts of well water was gradually added to the dispersion to obtain a homogeneous dispersion.

The rosin ester emulsion with solids content (wt%) is 3
5. Viscosity (25°C, CPS) 300. The pH was 9.6.

Example (5) 1050 parts of disproportionated rosin was charged into a four-way flask similar to that in Example (1), and heated to 200° C. while blowing N2 gas to dissolve the rosin.

Then polyethylene glycol (molecular weight: 210) 3
25 parts of glycerin were gradually added, the temperature was raised to 250°C, and the reaction was continued until the acid value reached 25. Acid value is 25
At that point, the pressure was maintained at reduced pressure for 1 hour, unreacted polyethylene glycol and glycerin were removed, and the viscosity (100°C,
A rosin ester with CPS) 75, color number (Gardner) 7, acid value 21, and hydroxyl value 41 was obtained.

150 parts of the above rosin ester, 8 parts of 25% ammonia water
Stir 50 parts of well water in a 10001/volume beaker (
500r, p0ms blade turbine type 5m) while 50
℃, then high-speed stirring (3000 r, p,
m1 blade turbine type5. , )L, 300 parts of well water was gradually added to obtain a homogeneous dispersion. This rosin ester emulsion had a solid content (wt%) of 30 and a viscosity (25°C, c
pS) 2500, P H9.7.

Comparative Example (1) 1050 parts of hydrogenated rosin was charged into a four-way flask similar to Example (1), and heated to 200° C. while blowing N2 gas to dissolve the rosin. Then glycerin 12
5 parts were added, the temperature was raised to 270°C, and the reaction was continued until the acid value reached 7. When the acid value reaches 7, it is kept under reduced pressure for 1 hour to remove unreacted glycerin, and the softening point (ring and ball method, °C) is 8.
A rosin ester having a hue (USDA) of N1, an acid value of 5, and a hydroxyl value of 40 was obtained.

200 parts of the above rosin ester, emulsifier (nonionic)
3 (1. Stir 20 parts of xylene, 2 parts of 25% ammonia water, and 50 parts of well water in a 1000117 volume beaker (50 parts
0r, p, mz blade turbine type 5m) while heating,
Next, 200 parts of well water was gradually added to the mixture at 50°C while stirring at high speed (300°C, p, m1 blade turbine type 5f) to obtain a homogeneous dispersion. This rosin ester emulsion
Solid m content (CM amount%) 40, viscosity (25°C, cps) 400
, PH was 9.2.

The rosin ester emulsion of the present invention produced in Examples (1) to (5) above has a particle size and long-term stability comparable to the rosin ester emulsion of Comparative Example (1) using an emulsifier. It is useful as a tackifier, a spreading agent, a dispersion aid, a sizing agent, etc.

Claims (1)

[Claims] 1) Rosin type and its derivatives and molecular weight of about 180 to 10
An oligoester with an acid value of 100 or less consisting of polyethylene glycol of
A method of making a stable emulsion by stirring and dispersing in an alkaline aqueous solution. 2. An emulsion using gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, etc. as the rosin system according to claim 1. 3) A maleic acid modified rosin/derivative obtained by adducting maleic acid (and anhydride) and fumaric acid to the rosin system described in claim 2 as the rosin derivative described in claim 1, or a part thereof. An emulsion using a maleic acid-polyhydric alcohol denatured rosin derivative which is denatured with a polyhydric alcohol. 4) An emulsion in which a part of the polyethylene glycol according to claim 1 is used in combination with a polyhydric alcohol. 5) An emulsion in which a part of the polyethylene glycol according to claim 1 is used in combination with a polyhydric alcohol and a polybasic acid such as maleic acid.