JPS6114249A - Preparation of resin emulsion - Google Patents

Abstract

PURPOSE:To prepare a resin emulsion which has uniform fine particle diameters, causes little foaming, and is stable, by emulsifying a resin such as a rosin ester or a terpene resin in the presence of a specified emulsifying agent. CONSTITUTION:0.4-10wt% (of the resin on a solid basis) emulsifying agent comprising an alkaline solution of a styrene-acrylic copolymer having an acid value of 100-300 and a weight-average molecular weight of 3,000-30,000 in water is added to a solution of a resin selected from among rosin ester, terpene resin, petroleum resin, cumarone resin, and dammar in a solvent such as toluene, which is roughly emulsified with a homogenizer and is then subjected to high-pressure emulsification under a pressure of 50-500kg/cm<2>; and the solvent is removed under reduced pressure to give a resin emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a resin emulsion, in particular a resin emulsion selected from the group consisting of rosin esters, terpene resins, petroleum resins, coumaron resins and dammers. The present invention aims to provide a new method for producing emulsified resin emulsions.

BACKGROUND OF THE INVENTION Resins such as rosin esters, terpene resins, petroleum resins, coumaron resins, and dammar resins are widely used as materials for various adhesives, coating agents, and the like.

The above-mentioned resins used in applications such as adhesives are usually used as a solution dissolved in an organic solvent or in a hot melt form. However, there are occupational hygiene problems such as organic solvent poisoning, the risk of flame generation, fire protection and environmental regulations associated with exhaust gas treatment, and economical issues such as solvent consumption and thermal energy consumption for melting. However, in recent years, there has been a desire for use in aqueous systems, and the use of resin emulsions made by emulsifying these resins has been increasing.

Problems to be Solved by the Invention However, these resin emulsions have the following drawbacks and various other problems.

That is, conventional resin emulsions have been unstable in that it is not possible to obtain a uniform emulsion with small particle diameters, poor in various types of stability, especially mechanical stability, and agglomeration of resin particles is likely to occur. Furthermore, depending on the type of emulsifier, the resulting resin emulsion often foams, causing problems in workability.

Means for Solving the Problems As a result of extensive research in order to solve the above-mentioned problems, the inventors of the present invention have found that by using a specific emulsifier, a product with a fine and uniform particle size and low foaming can be obtained. Stable resin 1
It was discovered that a marsion can be obtained, and the present invention was completed.

That is, the present invention provides rosin ester, terpene resin,
When producing a resin emulsion by emulsifying a resin selected from the group consisting of petroleum resins, coumaron resins, and dammers, as an emulsifier, a styrene monomer content of 30% by weight or more, an acid value of 100 to 300, and a weight average This is a method for producing a resin emulsion, characterized by using an alkaline aqueous solution of a styrene/acrylic polymer having a molecular weight in the range of 3000 to 3'oooo.

The present invention will be specifically explained below.

First, as the emulsified resin used in carrying out the method according to the present invention, there are rosin esters, which are esters of rosin components and alcohol components, and compounds. Gum rosin, tall oil rosin, wood rosin, or These include asymmetric rosin, hydrogenated rosin, polymerized rosin, maleic acid- or acrylic acid-modified rosin, and alcohol components of rosin esters include n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, and stearyl alcohol. Monohydric alcohols such as alcohol, dihydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, etc., trihydric alcohols such as glycerin, trimethylolpropane, etc. al-1-l,
Examples include tetrahydric alcohols such as pentaerythrol and diglycerin, and hexahydric alcohols such as dipentaerythrol. In particular, esters of rosin and polyhydric alcohols having two or more hydrities generally have a high viscosity and are usually solid at room temperature, making them difficult to emulsify. A rosin ester emulsion with good properties can be obtained.

As the terpene resin as the emulsified resin, there are terpene resins obtained by polymerizing gum turpentine oil, wood turpentine oil, etc., containing α-pinene and β-pinene as main components;
and their phenolic adducts.

In addition, petroleum resins include 0 or more aliphatic, alicyclic, and aromatic residual olefins from the cracked oil, excluding C2-Q olefins, such as ethylene, propylene, and butadiene from naphtha cracking. Examples include resins obtained by polymerizing.

In addition, resins such as coumaron-based resins made of coumaron and indene polymers, which are coal tar distillates, dammar, and copal can be used.

When the resin to be emulsified was emulsified using the other agent of the present invention,
Rosin ester emulsions have the smallest particle size and excellent mechanical stability, and are most preferred for use in adhesives and the like.

Further, the emulsifier used in the present invention is an alkaline aqueous solution of a styrene/acrylic polymer having a styrene motumer content of 30% by weight or more, an acid value in the range of 100 to 3000, and a weight average molecular weight in the range of 3000 to 30,000. . These styrene/acrylic polymers are styrene or α
The essential components are styrene derivatives such as methylstyrene and vinyltoluene, and acrylic acid or methacrylic acid.
It is a polymer obtained by copolymerizing monomers that can be copolymerized as necessary.

Examples of the monomers that can be co-combined include acrylic acid esters, acrylamide, acrylonitrile crotonate esters, maleic acid diesters, fumaric acid diesters,
Examples include itaconic acid diester, dibasic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid, anhydrides, and monoesters of these dibasic acids.

The styrene monomer content in these styrene/acrylic polymers needs to be 30% by weight or more; if it is less than 30% by weight, the resulting emulsion will have a large particle size and poor mechanical stability. .

Further, the acid value of the styrene/acrylic polymer as an emulsifier needs to be in the range of 100 to 300.

If the acid value is less than 100, the water solubility of the polymer is poor,
Its function as an emulsifier is insufficient. Also, the acid value is 300
Exceeding this results in deterioration of the water resistance of the resulting resin emulsion.

The weight average molecular weight of the styrene/acrylic polymer must be in the range of 3,000 to 30,000, more preferably in the range of 5,000 to 25,000. If the molecular weight is less than 3,000, the desired performance as an emulsifier in the present invention cannot be obtained, the emulsion dispersibility is poor, and it becomes difficult to obtain a stable emulsion. Moreover, when it exceeds 30,000, the viscosity of the obtained emulsion increases significantly, causing various problems in use. .
'・As the alkali used to make the styrene/acrylic polymer water-soluble, ammonia, sodium hydroxide, potassium hydroxide, alkanolamine, alkylamine, morpholine, etc. can be used, but in terms of water resistance, ammonia Volatile organic amines such as are preferred.

The appropriate amount of the emulsifier used in the present invention is approximately 0.4 to 10% by weight, calculated as solid content, based on the resin to be emulsified in the ammonia aqueous solution of the styrene/acrylic polymer. If it is less than 0.4% by weight, the particle size of the emulsion will be large and the mechanical stability of the emulsion will be poor.If it exceeds 10% by weight, the emulsion will thicken, making it unfavorable for operation.
It also has poor water resistance.

When emulsifying the resin to be emulsified, first dissolve the resin to be emulsified in a suitable solvent such as 1-helene to create a resin solution, and then create a resin emulsion using an inversion emulsification method or a high-pressure emulsification method. Manufacture. In the case of the inversion emulsification method, the resin solution to be emulsified and water containing an emulsifier are mixed and stirred to form a W10 type emulsion, water is added to this W10 type emulsion, stirred and mixed, and phase inversion is performed. O/W
Form a mold ■mulsion and remove the solvent under reduced pressure. In the case of the high-pressure emulsification method, water containing an emulsifier is added to a solution of the resin to be emulsified, coarsely emulsified with a homosyner, and the mixture is mixed with a
High-pressure emulsification is performed at a pressure of 00 kq4, and the solvent is removed under reduced pressure.

Furthermore, both the inversion emulsification method and the high-pressure emulsification method can be carried out without a solvent.

Among the emulsification methods mentioned above, the high-pressure emulsification method is easy to obtain a resin emulsion consisting of uniform and fine particles with a small amount of emulsifier, so the resulting resin emulsion has excellent stability and water resistance, and is effective. It is.

EXAMPLES More specific examples of the present invention will be described below.
The present invention is not limited to these examples.

Example 1 Glass reaction vessel equipped with a stirrer, cooler and thermometer (
500ml volume) with an acid value of 4. o1 Glycerol ester of asymmetric rosin having a constant softening point of 75.0°C was
0Q, 128 g of toluene was charged and stirred at 100°C for 1 hour to obtain a toluene solution of rosin ester (hereinafter referred to as resin liquid). Then a glass beaker (1000x
400 g of the resin liquid in Q volume) and 25 g of ammonium salt (solid content 28%) of styrene-acrylic acid copolymer (70 parts styrene, 30 parts methacrylic acid, acid value 195, weight average molecular m 10000) as an emulsifier. After adding ion-exchanged water to 293 (+) and adjusting the temperature to 30°C, it was coarsely emulsified with a homogenizer for 2 minutes.The obtained rough emulsion was heated to 300M
High-pressure emulsification was performed at a pressure of J to obtain an emulsion of 700'o. Next, 650 g of the emulsion was placed in a glass vacuum distillation device, and the solvent was removed for 4 hours under the conditions of a vacuum degree of 110 ml11 and a temperature of 47°C, resulting in a solid content of 50% and a toluene content of 4.0.
An emulsion of asymmetric rosin glycerin ester with a quality of % was obtained.

Example 2 In Example 1, except that pentaerythritol ester of disproportionate rosin (acid value 15, softening point 90°C) was used instead of glycerin phosphorus ester of disproportionate rosin. 5 The same operation as in Example 1 was carried out to obtain an emulsion of disproportionated rosin pentaerythritol ester having a solid content of 50% and a toluene content of 3.0%.

Example 3 The same operation as in Example 1 was carried out, except that a glycerin ester of hydrogenated rosin (acid value 8, softening point 73°C) was used in place of the glycerin ester of disproportionated rosin. An emulsion of hydrogenated rosin glycerin ester having a solid content of 51% and a toluene content of 2.5% was obtained.

Example 4 In Example 1, instead of the glycerin ester of the disproportionated rosin, polyterpene resin
182 Tsua, 8□Yu, below, softening point 100℃
) was used, but the same operation as in Example 1 was performed to obtain a polyterpene resin emulsion having a solid content of 49.5% and a toluene content (6) of 3.5%.

Example 5 In Example 1, aliphatic petroleum resin (Quinton D-100 manufactured by Nippon Zean Co., Ltd., softening point 100 ° C., molecular weight 160
The same operation as in Example 1 was performed except that 0) was used to obtain a petroleum resin emulsion having a solid content of 50.5% and a toluene content of 3.0%. Example 6 In Example 1, petroleum resin (Mitsui Petrochemical Co., Ltd. PE1-
Rosin PR-120. The same operation as in Example 1 was performed except that a softening point (softening point: 12'O<0>C) was used to obtain a petroleum resin emulsion having a quality of 50.3% solid content and 3.0% toluene content.

Example 7 In Example 1, Cumaron resin (G-75 manufactured by Nippon Steel Chemical Co., Ltd., acid value 0.2, softening point 78.0°C) was used in place of the glycerin ester of the disproportionated rosin. Other than that, the same operation as in Example 1 was carried out, and the solid content was 49.5%.
An emulsion of coumaron resin having a quality of 4.0% toluene content was obtained.

Example 8 The same operation as in Example 1 was carried out except that Dammar resin (produced in Sumatra) was used instead of the glycerin ester of the disproportionated rosin, and the solid content was 50.2%.
An emulsion of Dammar resin having a toluene content of 4.5% was obtained.

Example 9 In Example 1, styrene-acrylic copolymer (70 parts styrene, 30 parts methacrylic acid, acid value 195, weight average molecular weight +0000) ammonium salt was used as the emulsifier in place of the ammonium salt of styrene-acrylic copolymer. Combined (35 parts styrene, 35 parts methyl methacrylate, 3 parts acrylic acid)
The same operation as in Example 1 was carried out except that an ammonium salt with an acid value of 233 and a weight average molecular weight of 15,000 was used. A quality emulsion of asymmetric rosin glycerin ester was obtained.

Example 10 In Example 1, the amount of emulsifier used was reduced from 25 g to 4 g (l!! is the same operation as in Example 1, and the quality with solid content of 50.2% and toluene content of 3.8% was obtained. have,
An emulsion of asymmetric rosin glycerin ester was obtained.

Example 11 In Example 1, the emulsification pressure was changed from 300kq4 to 50k
The same operation as in Example 1 was performed except that the emulsion was lowered to iJ to obtain an emulsion of disproportionated rosin glycerin ester having a quality of 50.5% solid content and 2.5% toluene content.

Example 12 In Example 1, the amount of rosin ester charged was 350
(The amount of toluene was increased to 629, the amount of ion-exchanged water was decreased to 2559, the crude emulsification humidity was increased to 80°C, and the solvent removal step was omitted. Solid content 50.3%, 1 to luene content 8.2%
An emulsion of disproportionated rosin glycerine ester having the quality of

Example 13 A stainless steel reaction vessel (30 mm) equipped with a stirrer and a thermometer
A 100% glycerin ester of asymmetric rosin having an acid value of 4.5 and a constant softening point of 76°C was charged into a 100°C solution, stirred at 200°C for 3 hours to dissolve, and cooled to 130°C. After pressurizing the inside of the reaction vessel to a pressure of 2 kiJ with an inert gas, 91 kg of ion-exchanged water and a styrene-acrylic acid copolymer (70 parts of styrene, 30 parts of methacrylic acid, acid value 195, weight average molecular weight 10,000) were added as an emulsifier. )
ammonium salt (solid content 28%) 9-
The temperature was adjusted to 95°C, and the mixture was forcibly charged into the reaction vessel. Thereafter, the internal temperature was raised to 13.0°C, and the mixture was emulsified for 10 minutes.
The mixture was cooled to 30° C. using a cooler to obtain an emulsion of asymmetric rosin glycerin ester having a solid content of 50%.

Comparative Example 1 In Example 1, polyoxyethylene nonylphenol ether (active ingredient 100%, HL8
The same operation as in Example 1 was performed except that 7 g of 17.1) was used, and the solid content I! 19°8%, toluene content 3.2%
A 4-emulsion of disproportionated rosin glycerin ester having the quality of 1 was obtained.

Comparative Example 2 In Example 1, a polyterpene resin (YS Resin PX manufactured by Yasushi Oil Industries Co., Ltd., acid value 1 or less, softening point 100°C) was used in place of the asymmetric glycerin ester in Example 1, and as an emulsifier. The same operation as in Example 1 was performed except that polyoxyethylene nonylphenol ether (100% active ingredient, HLB 17.1) was used, and the quality was 42.3% solids and 3.8% toluene content.
An emulsion of polyterpene resin was obtained.

Comparative Example 3 In Example 1, a petroleum resin (Quinton D-100 manufactured by Nippon Zeon Co., Ltd., softening point 100°C, molecule 11600) was used instead of the glycerin ester of the disproportionated rosin, and polyoxyethylene was used as an emulsifier. Lennonylphenol 1-thyl (100% active ingredient, I-IL817.1
) was used, but the same operation as in Example 1 was performed to obtain a petroleum resin emulsion having a solid content of 40.5% and a toluene content of 3.2%.

Comparative Example 4 In Example 1, a petroleum resin (Vetrozin PR-120 manufactured by Mitsui Petrochemical Co., Ltd., softening point 120°C) was used instead of the glycerin ester of the disproportionated rosin, and polyoxyethylene nonylphenol ether (
The same operation as in Example 1 was carried out except that 7 g of 100% active ingredient and 7 g of HLB 17.1) was used, and a petroleum resin emulsion having an image quality of 40°8% solid content and 3.8% toluene content was prepared. Obtained.

Comparative Example 5 In Example 1, an acrylic copolymer (
15 parts of methyl methacrylate, 70 parts of ethyl acrylate,
Acrylic acid 15 parts, acid value 116, weight average molecule 1120
The same operation as in Example 1 was carried out except that an ammonium salt of 000> was used, and the solid content was 49.0% and the toluene content was 4.
An emulsion of asymmetric rosin glycerin ester having a quality of 0% was obtained.

Comparative Example 6 Same as Example 1 except that ammonium salt of styrene-acrylic acid copolymer (70 parts of styrene, 30 parts of methacrylic acid, acid value 190, weight average molecular weight 50,000) was used as an emulsifier. performed the operation. As a result, an emulsion with a solid content of 49.3% and a toluene content of 4.0% was obtained, but the emulsion was excluded from evaluation because it significantly thickened and caused problems in handling.

Comparative Example 7 In Example 1, a styrene-acrylic acid copolymer (36 parts of styrene, 55 parts of methyl methacrylate, 10 parts of acrylic acid, acid value 83, weight average molecular weight 100) was used as an emulsifier.
The same operation as in Example 1 was performed except that the ammonium salt of 00) was used, but emulsification could not be achieved.

As mentioned above, regarding the emulsions obtained in each example and comparative example,
The following items were evaluated and the results are shown in the table.

(1) Average particle size The obtained emulsion was coated on aluminum foil, air-dried, placed on a sample stand, and vapor deposited to obtain a measurement sample.

The sample for measurement is exposed to electronics at a magnification of 10,000 times.
゛′ Microscopic photographs were taken, particles were counted according to particle size, and the average particle size was determined by calculation.

(2) Amount of resin deposited After removing the solvent, the obtained emulsion was filtered through a 200-mesh wire mesh, and the weight of the residue was expressed as a percentage of the amount of emulsified resin.

(3) 30cc of foamable emulsion in a measuring cylinder with a stopper (100 volumes)
After shaking with a shaker for 1 minute, the samples were allowed to stand, and the samples were differentiated based on the amount of increase in volume. Those with a volume increase of less than 10% were evaluated as ○, those with a volume increase of 10 to 20% were evaluated as Δ, and those with a volume increase of 20% or more were evaluated as ×.

(4) 509 samples of mechanical stability emulsion were measured using a Marlon stability tester.
The system was operated under the conditions of hJ, 1000 r, I), and 1 R for 5 minutes, and the amount of precipitated resin generated during that time was expressed as φ% with respect to the amount of resin to be emulsified.

As shown in the table of effects of the invention, the emulsions of various resins such as rosin esters, terpene resins, and petroleum resins obtained by the present invention have small particle sizes, a small amount of resin precipitated during solvent removal, and emulsification. It has excellent stability.

Claims (1)

[Claims] 1. When emulsifying a resin selected from the group consisting of rosin esters, terpene resins, petroleum resins, coumaron resins, and dammers, as an emulsifier, the styrene monomer content is 30% by weight or more, and acid Method 2 for producing a resin emulsion, characterized by using an alkaline aqueous solution of a styrene/acrylic polymer having a molecular weight of 100 to 300 and a weight average molecular weight of 3,000 to 30,000. Method 3 for producing a resin emulsion according to claim 1, characterized in that the resin to be emulsified is a polyhydric alcohol ester of a disproportionated rosin. Method 4 for producing a resin emulsion according to claim 2. Production of a resin emulsion according to claim 1 or 2, wherein the resin to be emulsified is a polyhydric alcohol ester of hydrogenated rosin. Method