JP5586509B2 - Method for producing acid-modified olefin-based aqueous dispersion - Google Patents

Description

  The present invention relates to a method for producing an aqueous dispersion containing an acid-modified olefin polymer.

Polyolefins are light and inexpensive, and are excellent in moldability and solvent resistance, and thus have been widely used in automotive applications in recent years. Conventionally, when coating or bonding a polyolefin molded body, a paint or an adhesive in which chlorinated polyolefin is dissolved in an aromatic organic solvent such as toluene or xylene has been widely used.
However, in recent years, a paint, an adhesive, or a primer that does not contain an organic solvent has been demanded in consideration of the environment.
As a method for producing an aqueous dispersion not containing an organic solvent, a method utilizing a phase inversion phenomenon using a polymerization method or an extruder is known. References 1 and 2 specifically disclose a method using an extruder.
Patent Documents 1 and 2 disclose that an aqueous dispersion obtained using an extruder has a small average particle diameter and can be stably produced with a small amount of non-emulsified product.

Japanese Examined Patent Publication No. 7-96647 JP 2008-101156 A

However, when an aqueous dispersion of an acid-modified polymer material is produced by the methods described in Patent Documents 1 and 2, the resulting aqueous dispersion has a small particle size and a small amount of non-emulsified matter. However, the viscosity tended to be high. For this reason, the dispersibility, workability, and filterability of the paint are reduced, resulting in a decrease in work efficiency and many industrial demerits.
In addition, in the method for producing an aqueous dispersion using an extruder, if the temperature of the extruder is set to be equal to or lower than the melting point of the polymer material used for thermal degradation and energy saving of the polymer, a kneading failure occurs, and the aqueous dispersion It became difficult to get.
An object of the present invention is to provide a method for producing an acid-modified olefin-based aqueous dispersion in which the particle size of the aqueous dispersion of the acid-modified polymer material is small, the amount of non-emulsified material can be reduced, and the viscosity can be reduced.

As a result of studies to achieve the above object, the present inventors have invented the following method for producing an acid-modified olefin-based aqueous dispersion.
[1] A first kneaded product obtained by melt-kneading an acid-modified polymer material (P) containing an acid group-containing first acid-modified olefin polymer (A) and an anionic surfactant (C) The temperature of the kneading step is equal to or higher than the melting point, the basic material (D) and water (E) are added to the kneaded material, and the temperature of the second kneading step for melt kneading is equal to or lower than the melting point, A method for producing an acid-modified olefin-based aqueous dispersion, wherein the amount of addition of E) is 10 to 22 parts by mass with respect to 100 parts by weight of the first acid-modified olefin polymer (A).
[2] The first acid-modified olefin polymer (A) has an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic acid anhydride unit, an acid value of 10 mgKOH / g or more, and a mass average molecular weight. It is 2,000-30,000, The manufacturing method of the acid-modified olefin type aqueous dispersion as described in [1] characterized by the above-mentioned.
[3] Second acid modification in which the acid-modified polymer material (P) has an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit and has a mass average molecular weight of 31,000 to 50,000. The acid-modified olefin-based aqueous dispersion according to [1] or [2], containing 1 to 50 parts by mass of the olefin polymer (B) with respect to 100 parts by mass of the first acid-modified olefin polymer (A). Body manufacturing method.

  According to the method for producing an acid-modified olefin-based aqueous dispersion of the present invention, the particle size of the aqueous dispersion of the acid-modified polymer material can be reduced, the amount of non-emulsified material can be reduced, and the viscosity can be reduced. According to the aqueous dispersion obtained by this method, it is possible to improve the deterioration of dispersibility, workability, and filterability during coating.

<Acid-modified olefin-based aqueous dispersion>
The acid-modified olefin-based aqueous dispersion (hereinafter abbreviated as “aqueous dispersion”) obtained by the method for producing an acid-modified olefin-based aqueous dispersion of the present invention includes an acid-modified polymer material (P) and an anionic surfactant. It contains (C), basic substance (D), and water (E), and does not contain organic solvent and chlorine atom-containing polymer.

(Acid-modified polymer material (P))
The acid-modified polymer material (P) has an acid group, contains the first acid-modified olefin polymer (A) as an essential component, and optionally contains the second acid-modified olefin polymer (B). Contains as a component.

[First Acid-Modified Olefin Polymer (A)]
The first acid-modified olefin polymer (A) is an olefin polymer having an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit.
The olefin component unit is preferably an olefin having 2 to 4 carbon atoms, that is, ethylene, propylene, 1-butene, but may be 1-pentene, 1-hexene, 1-octene and the like. These may be used individually by 1 type and may combine 2 or more types.
Examples of the unsaturated carboxylic acid unit or the unsaturated carboxylic acid anhydride unit include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid, and anhydrides thereof. These may be used individually by 1 type and may combine 2 or more types.

  The acid value of the first acid-modified olefin polymer (A) is preferably 10 mgKOH / g or more, more preferably 20 to 55 mgKOH / g. The acid value here is the number of mg of potassium hydroxide required to neutralize 1 g of the acid-modified olefin polymer. When the acid value is 10 mgKOH / g or more, a stable aqueous dispersion can be collected during production.

The mass average molecular weight of the first acid-modified olefin polymer (A) is preferably 2,000 to 30,000, more preferably 5,000 to 28,000, and particularly preferably 10,000 to 26,000. If the weight average molecular weight is 2,000 to 30,000, a stable aqueous dispersion can be collected during production.
The mass average molecular weight Mw in the present invention is a value measured by gel permeation chromatography and converted to standard polystyrene.

  As a method for producing the first acid-modified olefin polymer (A), there are a polymerization step for polymerizing a precursor polyolefin as described in JP-A No. 2004-115712, and the precursor polyolefin is unsaturated. A method having a modification step of grafting carboxylic acid or unsaturated carboxylic acid anhydride is preferred.

  The composition of the precursor olefin polymer can be adjusted by appropriately changing the supply amount of the olefin monomer during the polymerization step. Examples of methods for adjusting the mass average molecular weight and the melting point include a method of controlling using hydrogen gas during polymerization, a method of controlling the monomer concentration, and a method of controlling the polymerization temperature.

In the modification step, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, an organic peroxide or an azonitrile can be appropriately selected and used.
Organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroxyperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. And diacyl peroxides such as oxides.
Examples of the azonitrile include azoisobutyronitrile and azoisopropylonitrile.
These radical polymerization initiators may be used alone or in combination of two or more.
The addition amount of the radical polymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the precursor polyolefin polymer.

  The method for the graft reaction may be any method as long as the first acid-modified olefin polymer (A) can be produced. Examples thereof include a method of reacting by melting and stirring without a solvent, a method of reacting by heating and kneading with an extruder, and the like. Among them, the method of graft polymerization using an extruder does not require the use of a solvent, does not require a solvent distillation step, and further has no time in the graft polymerization step, which is preferable in terms of energy advantage. .

[Second acid-modified olefin polymer (B)]
The second acid-modified olefin polymer (B) is a polymer having an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit as essential components. Here, as the olefin unit, unsaturated carboxylic acid unit or unsaturated carboxylic anhydride unit, the same as the first acid-modified olefin polymer (A) can be used.

  As the second acid-modified olefin polymer (B), a polymer having an olefin unit and an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is preferably used. The unsaturated carboxylic acid unit or unsaturated carboxylic anhydride unit is preferably 1.5 to 7.5 parts by mass with respect to 100 parts by mass of the polymer.

The mass average molecular weight of the second acid-modified olefin polymer (B) is preferably 31,000 to 50,000, preferably 35,000 to 45, because the storage stability of the aqueous dispersion becomes higher. Is more preferable.
The acid value of the second acid-modified olefin polymer (B) is preferably 20 to 60 mgKOH / g and more preferably 30 to 50 mgKOH / g because the storage stability of the aqueous dispersion becomes higher. Is more preferable.

  Since the content of the second acid-modified olefin polymer (B) is small in the amount of non-emulsified aqueous dispersion and storage stability is higher, the first acid-modified olefin polymer (A) 100 is increased. It is preferable that it is 1-50 mass parts with respect to a mass part, and it is more preferable that it is 10-40 mass parts.

(Anionic surfactant (C))
Examples of the anionic surfactant (C) include primary higher fatty acids, secondary higher fatty acids, primary higher alcohol sulfates, secondary higher alcohol sulfates, primary higher alkyl sulfonic acids, Secondary higher alkyl sulfonic acid, higher alkyl disulfonic acid, sulfonated higher fatty acid, higher fatty acid sulfuric acid ester, higher fatty acid ester sulfonic acid, higher alcohol ether sulfuric acid ester, higher alcohol ether sulfonic acid, higher fatty acid amide alkylolated sulfuric acid Examples thereof include acids such as esters, alkylbenzenesulfonic acid, alkylphenolsulfonic acid, alkylnaphthalenesulfonic acid, and alkylbenzoylimidazolesulfonic acid, and salts thereof.
Examples of higher fatty acids constituting the above anionic surfactant include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, margaric acid, stearic acid, arachidic acid, and other saturated fatty acids, Linderic acid, Tuzic acid, Examples include unsaturated fatty acids such as petroceric acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid, and mixtures thereof.
Examples of the element for forming a salt with an acid include alkali metals such as sodium and potassium. Of these, potassium fatty acid is preferred from the viewpoint of stability during production of the aqueous dispersion.
An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the anionic surfactant (C) is preferably 1 to 40 parts by mass, and 5 to 25 parts by mass with respect to 100 parts by mass of the first acid-modified olefin polymer (A). More preferred. If the amount of the anionic surfactant (C) is 1 part by mass or more, the storage stability of the aqueous dispersion is improved, and if it is 40 parts by mass or less, the average particle size of the aqueous dispersion is small and non-emulsified. The quantity is reduced.

(Basic substance (D))
The basic substance (D) is necessary for neutralizing the first acid-modified olefin polymer (A) and the second acid-modified olefin polymer (B) and the non-neutralized anionic surfactant. It is said.
Basic substances (D) include substances that act as bases in water such as alkali metals, alkaline earth metals, ammonia, and amines, alkali metal oxides, hydroxides, weak bases, hydrides, alkaline earths Examples thereof include substances that act as bases in water, such as metal oxides, hydroxides, weak bases, and hydrides, and alkoxides of these metals. Among these, potassium hydroxide is preferable from the viewpoint of storage stability.
The amount of the basic substance (D) is the amount necessary to neutralize the acid derived from the acid-modified polymer material (P) and the anionic surfactant (C) from the viewpoint of the storage stability of the aqueous dispersion. The amount is preferably 1 to 2 times the amount, more preferably 1.2 to 1.8 times the amount.

(Water (E))
The amount of water (E) is 10 to 22 parts by mass with respect to 100 parts by mass of the first acid-modified olefin polymer (A). When the amount of water (E) is less than 10 parts by mass and more than 22 parts by mass, the amount of the non-emulsified product in the aqueous dispersion increases.
In addition, since the aqueous dispersion obtained above has a solid content concentration of 80% or more and is substantially solid, it is diluted with water from the viewpoint of workability and handling when used as a paint or an adhesive. It is preferable to do. Specifically, an amount in which 34 parts by mass or more of dilution water is added to the aqueous dispersion and the solid content concentration becomes 10 to 60% by mass is preferable.

(Other ingredients)
The aqueous dispersion obtained in the present invention may contain other aqueous resins such as polyolefin resin emulsions, aqueous acrylic resins, aqueous urethane resins, aqueous epoxy resins, aqueous alkyd resins, aqueous phenol resins, aqueous amino acids as necessary. Resins, aqueous polybutadiene resins, aqueous silicone resins and the like may be included.

Moreover, the aqueous dispersion obtained by this invention may also contain a submaterial as needed.
Examples of auxiliary materials include dispersants such as cationic surfactants and nonionic surfactants, emulsifiers, stabilizers, wetting agents, thickeners, foaming agents, antifoaming agents, gelling agents, and anti-aging agents. Agents, softeners, plasticizers, fillers, colorants, flavoring agents, anti-tacking agents, mold release agents, film-forming aids, leveling agents and the like.

(how to use)
The aqueous dispersion obtained in the present invention can be used by applying to various substrates, for example.
As the base material, for example, high adhesion of the aqueous dispersion is exerted on nonpolar base materials such as paper, fiber woven fabric, plastic molded product, especially polypropylene molded product and polyethylene molded product. The nonpolar base material includes various additives such as other polyolefins (for example, ethylene / propylene copolymer rubber), inorganic fillers (for example, talc, glass fiber, calcium carbonate, etc.), stabilizers, and coloring agents. The same applies to the case where
As a coating method, for example, a method using various coating machines, a method using a spray, a brush coating, or the like can be employed.

  Since the aqueous dispersion obtained by the present invention does not contain any organic solvent, it is not necessary to distill off the organic solvent, and VOC emission can be suppressed.

<Method for producing aqueous dispersion>
The method for producing an acid-modified olefin-based aqueous dispersion of the present invention includes a twin-screw extruder in which two screws are provided in a heatable barrel, and a cooling means provided on the front end side of the twin-screw extruder. And a production apparatus comprising a barrel tip of a twin-screw extruder and a flow path for connecting a cooling means, wherein a part of the flow path comprises a connecting pipe. As a cooling means, for example, it is preferable to cool the obtained aqueous dispersion to 80 ° C. or lower using a jacketed static mixer. In addition to the static mixer with jacket, a single-screw or multi-screw extruder can be used as the cooling means.

The twin-screw extruder has an acid-modified polymer material (hereinafter referred to as “intermediate part”) from a material input port (hereinafter referred to as “input port”) at the base of the twin-screw extruder to an acid-modified polymer material ( P) and an anionic surfactant (C) are melt-kneaded to obtain a kneaded product, and the kneaded product from the middle part to the tip side of the twin-screw extruder (hereinafter referred to as “tip side”) On the other hand, a basic substance (D) and water (E) are added from an aqueous solution supply port provided in an intermediate part of the twin-screw extruder, and a second kneading step of melt-kneading is included.
In the first kneading step, the heating temperature is set to be equal to or higher than the melting point of the first acid-modified olefin polymer (A). In the second kneading step, the heating temperature is set to the first acid-modified olefin polymer (A ) Or less.
When the heating temperature in the first kneading step (hereinafter referred to as “barrel first half temperature”) is lower than the melting point of the first acid-modified olefin polymer (A), the stability during production decreases, and the particle diameter Is large, and the amount of non-emulsified product increases. When the heating temperature in the second kneading step (hereinafter referred to as “barrel latter half temperature”) exceeds the melting point of the first acid-modified olefin polymer (A), the viscosity of the obtained aqueous dispersion increases.

  The amount of the anionic surfactant (C) added in the first kneading step is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the first acid-modified olefin polymer (A). More preferably, it is -25 mass parts. If the added amount of the anionic surfactant (C) is 1 part by mass or more, the storage stability of the aqueous dispersion is improved, and if it is 40 parts by mass or less, the average particle size of the aqueous dispersion is small, The amount of emulsion is reduced.

The amount of the basic substance (D) added in the second kneading step is such that the acid derived from the acid-modified polymer material (P) and the anionic surfactant (C) is used from the viewpoint of the storage stability of the aqueous dispersion. The amount required for neutralization is preferably 1 to 2 times, more preferably 1.2 to 1.8 times.
The basic substance (D) may be added directly to the kneaded product, but is preferably added in the form of an aqueous solution of about 5 to 40% by mass.

Water (E) added in the second kneading step is water necessary for phase inversion.
The amount of water (E) added in the second kneading step is 10 to 22 parts by mass with respect to 100 parts by mass of the first acid-modified olefin polymer (A). If the amount of water (E) added is less than 10 parts by mass or more than 22 parts by mass, it becomes unstable during production and the amount of non-emulsified product increases.

  The solid content concentration of the aqueous dispersion in which the amount of water (E) added is in the above range is 80% by mass or more, and is substantially solid. Therefore, in order to apply this aqueous dispersion by the existing coating method, or in order to make it easy to mix other chemicals, 34 parts by mass or more are added to the aqueous dispersion after the second kneading step. It is preferable to have a dilution step of adding and diluting the diluted water. In the dilution step, the solid concentration is preferably 10 to 60% by mass.

In the above production method, since a large amount of water is present during emulsification of the first acid-modified olefin polymer (A), kneading is performed even when the temperature in the extruder is lower than the melting point of the first acid-modified olefin polymer (A). Defects are less likely to occur. Therefore, the particle size of the aqueous dispersion of the acid-modified polymer material can be reduced, the amount of non-emulsified material can be reduced, and the viscosity can be reduced. According to the aqueous dispersion obtained by this method, it is possible to improve the deterioration of dispersibility, workability, and filterability during coating. Further, the storage stability of the aqueous dispersion can be increased.
Moreover, in the said manufacturing method, since the organic solvent is not used, discharge | emission of VOC at the time of manufacture can be suppressed, and the organic solvent is not contained in the obtained aqueous dispersion.

Hereinafter, the present invention will be specifically described with reference to production examples, but the present invention is not limited to the following examples. In the following examples, “%” means “mass%” and “part” means “part by mass”.
The characteristics (mass average molecular weight, melting point, acid value) of the first acid-modified olefin polymer (A) and the second acid-modified olefin polymer (B) were measured as follows.

[Mass average molecular weight]: Measured by Alliance GPC V2000 type (standard material: polystyrene, solvent: orthodichlorobenzene, measurement temperature: 140 ° C., solvent flow rate: 1 mL / min) manufactured by Waters.

[Melting point]: The melting point was determined by the following method using DSC200, a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. A sample (about 5 to 10 mg) was melted at 160 ° C. for 3 minutes, cooled to −20 ° C. at a rate of 10 ° C./minute, held at −20 ° C. for 2 minutes, and then heated to 160 ° C. at 10 ° C./minute. Thus, a melting curve was obtained, and the peak top temperature of the main endothermic peak in the final temperature rising stage was obtained as the melting point.

[Measurement of Acid Value]: 200 mg of the first acid-modified propylene polymer (A) or the second acid-modified propylene polymer (B) and 4800 mg of chloroform are placed in a 10 ml sample bottle and heated at 50 ° C. for 30 minutes. And completely dissolved. Chloroform was placed in a liquid cell with NaCl and an optical path length of 0.5 mm as a background. Next, the dissolved acid-modified propylene-based polymer solution was put into a cell, and an infrared absorption spectrum was measured using FT-IR (manufactured by JASCO Corporation) at a total number of 32 times. Further, a solution in which maleic anhydride was dissolved in chloroform was measured, and the graft ratio of maleic anhydride was calculated using a calibration curve.
From the area of the absorption peak of the carbonyl group in the infrared absorption spectrum (maximum peak near 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer was calculated based on a separately prepared calibration curve. Calculated acid component content / (100-acid component content) × 1/97 (molecular weight per grafted maleic anhydride molecule) × 2 equivalents (one grafted maleic anhydride was neutralized) The acid value was calculated from the number of carboxylic acid groups at the time) × 57 (KOH molecular weight) × 1000.

An olefin polymer (AP-1) used as a precursor of the acid-modified olefin polymer was obtained by the following method.
In a 1000 mL round bottom flask, 110 mL of deionized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved by stirring. In this solution, 16.7 g of commercially available granulated montmorillonite was dispersed, heated to 100 ° C., and stirred for 2 hours. Then, it cooled to room temperature and filtered the obtained slurry, and collect | recovered the wet cake. The collected wet cake was slurried again with 500 mL of demineralized water in a 1000 mL round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.
To 4.4 g of the obtained chemically treated montmorillonite, 20 mL of a toluene solution of triethylaluminum (0.4 mmol / mL) was added and stirred at room temperature for 1 hour. To the suspension, 80 mL of toluene was added, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / mL). In a separate flask, 0.2 mmol of triisobutylaluminum was collected, and 19 mL of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8 -Tetrahydro-1-azulenyl) hafnium] 131 mg (57 μmol) of toluene diluted solution was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
Next, 2.48 L of liquid propylene and 0.05 L of liquid ethylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 85 ° C., and the stirring was continued for 2 hours at the same temperature while keeping the total pressure during polymerization at 0.60 MPa and a hydrogen concentration of 400 ppm. After completion of the stirring, the unreacted olefin was released and the polymerization was stopped. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed to obtain a propylene-ethylene copolymer toluene solution. The obtained propylene-ethylene copolymer was used as an olefin polymer (AP-1).
The olefin polymer (AP-1) had a mass average molecular weight Mw of 70,000 (in terms of polystyrene) and a melting point of 135 ° C. (see Table 1).

A modification treatment for grafting maleic anhydride onto the olefin polymer (AP-1) was performed to obtain a first acid-modified olefin polymer (A-1).
Specifically, using a twin screw extruder in which 100 parts of the olefin polymer (AP-1) was set to 170 ° C. with 2 parts of maleic anhydride and 1.8 parts of di-t-butyl peroxide. By reacting, an acid-modified olefin polymer was obtained. At that time, the inside of the extruder was deaerated to remove residual unreacted substances.
The first acid-modified olefin polymer (A-1) obtained by this reaction had a mass average molecular weight of 25,000 and an acid value of 12 mgKOH / g. The melting point is the same as that of the olefin polymer (AP-1).

Olefin polymer (AP-2), (AP-3):
Olefin polymers (AP-2) and (AP-3) were prepared in the same manner as in the method of (AP-1) except that the gas supply amount of ethylene and / or 1-butene was adjusted. The melting point of the olefin polymer was adjusted by adjusting the gas supply amount of ethylene and / or 1-butene. The melting point of the obtained olefin polymer (AP-2) was 105 ° C., and the melting point of the olefin polymer (AP-3) was 95 ° C. The mass average molecular weight was the same as that of the olefin polymer (AP-1) (see Table 1).

First acid-modified olefin polymer (A-2):
Except that the olefin polymer (AP-1) is changed to the olefin polymer (AP-2), the first acid-modified olefin polymer (A-1) is produced in the same manner as in the production of the first olefin polymer (AP-1). An acid-modified olefin polymer (A-2) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the obtained first acid-modified olefin polymer (A-2).

First acid-modified olefin polymer (A-3):
Except for changing the olefin polymer (AP-1) to the olefin polymer (AP-3), the same procedure as in the production of the first acid-modified olefin polymer (A-1), An acid-modified olefin polymer (A-3) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the obtained first acid-modified olefin polymer (A-3).

First acid-modified olefin polymer (A-4):
The first acid-modified olefin polymer (A) was produced in the same manner as in the production of the first acid-modified olefin polymer (A-1) except that the amount of maleic anhydride added was changed as shown in Table 2. -4) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the obtained first acid-modified olefin polymer (A-4).

First acid-modified olefin polymer (A-5):
The first acid-modified olefin polymer (A) was prepared in the same manner as in the production of the first acid-modified olefin polymer (A-2) except that the amount of maleic anhydride added was changed as shown in Table 2. -5) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the obtained first acid-modified olefin polymer (A-5).

First acid-modified olefin polymer (A-6):
The first acid-modified olefin polymer (A) was prepared in the same manner as in the production of the first acid-modified olefin polymer (A-3) except that the amount of maleic anhydride added was changed as shown in Table 2. -6) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the obtained first acid-modified olefin polymer (A-6).

First acid-modified olefin polymers (A-7) to (A-10):
Except having changed the modification conditions of maleic anhydride as shown in Table 2, it carried out similarly to manufacture of acid-modified olefin polymer (A-1), and acid-modified olefin polymer (A-7)-(A -10) was obtained. Table 2 shows the mass average molecular weight, acid value, and melting point of the acid-modified olefin polymer obtained.

First acid-modified olefin polymer (a-11):
An acid-modified olefin polymer (a-11) was obtained in the same manner as in the production of the acid-modified olefin polymer (A-1) except that the modification conditions of maleic anhydride were changed as shown in Table 2. . Table 2 shows the mass average molecular weight, acid value, and melting point of the acid-modified olefin polymer obtained.

The following (B-1) to (B-3) were used as the second acid-modified olefin polymer (B).
Second acid-modified olefin polymers (B-1) to (B-3):
The second acid-modified olefin polymers (B-1) to (B-3) were used except that the olefin polymer (AP-1) was used as a precursor and the modification conditions were changed as shown in Table 2. And obtained in the same manner as in the production of the first acid-modified olefin polymer (A-1). Table 2 shows the mass average molecular weight, acid value, and melting point of the second obtained acid-modified olefin polymer.

As the anionic surfactant (C), fatty acid potassium (“KS soap” manufactured by Kao) (C-1) was used.
Potassium hydroxide (D-1) was used as the basic substance (D).

Example 1
30 parts of second acid-modified olefin polymer (B-) with respect to 100 parts of first acid-modified olefin polymer (A-1) and first acid-modified olefin polymer (A-1). 1) and 16 parts of fatty acid potassium (C-1), a twin screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 type, screw diameter: 30 mm, L / D; 40, first half barrel temperature: 140 ° C., barrel The latter half temperature; 130 ° C.) was supplied from the inlet and melt kneaded.
The first acid-modified olefin polymer (A-1), the second acid-modified olefin polymer (B-1), and fatty acid potassium are supplied from an aqueous solution supply port provided in the middle part of the twin-screw extruder. With respect to the total mass of (C-1), in the form of an aqueous potassium hydroxide solution, 1.8 parts (1.5 times the amount necessary to neutralize the acid) of potassium hydroxide (D- 1) and 17 parts of water (E) were continuously press-fitted at 1.8 MPa, and melt-kneaded in a twin-screw extruder.
Then, the aqueous dispersion discharged from the tip side of the twin screw extruder is cooled to 80 ° C. or lower using a jacketed static mixer, dispersed in 150 parts of warm water, diluted, and the solid content concentration is 30. % Aqueous dispersion (AW-1) was obtained.
The storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion (AW-1) were evaluated as follows. The results are shown in Table 3.

[Storage stability test]
As storage stability evaluation, the aqueous dispersion was put in a 1 L sealable container and allowed to stand at 40 ° C. for 1 month, and the state of the aqueous dispersion was evaluated according to the following criteria.
◎: No separation and precipitation, no change in viscosity ○: Separation and precipitation are not confirmed, but thickening Δ: Separation and / or precipitation is confirmed, but can be easily dispersed by stirring ×: Separation and / or precipitation was confirmed and could not be easily dispersed by stirring Note that separation and / or precipitation was confirmed, but when it could be easily dispersed by stirring, it was judged to have storage stability.

[Average particle diameter]: The volume-based average particle diameter was measured using Microtrack (Nanotrack 150) (measuring solvent: pure water) manufactured by Nikkiso Co., Ltd.

[PH measurement]
Measured using HM-11P type manufactured by Toa Denpa Kogyo Co., Ltd.

[Measurement of unemulsified amount]
The aqueous dispersion was filtered through a 100 mesh stainless steel wire mesh, and the residue on the mesh was washed with water and dried, and then the mass of the filtered solid residue was measured. And the mass ratio of the non-emulsified thing in an aqueous dispersion was calculated | required by the following formula.
Non-emulsified mass ratio (mass%) = [mass of filtered solid residue (g) / mass of total solid (g)] × 100 (mass%)

[B type viscosity measurement]
A TVB-10 viscometer manufactured by Toki Sangyo Co., Ltd. was used. The measured values of temperature: 23 ° C., rotor: M1, and rotational speed: 60 rpm were measured.

[Measurement of residual organic solvent content]
A gas chromatograph was used. A toluene calibration curve was used to measure the organic solvent content in the aqueous dispersion.

(Example 2)
An aqueous dispersion (AW-2) having a solid concentration of 30% was obtained in the same manner as in Example 1 except that the barrel latter half temperature was changed to 80 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 3)
30 parts of the second acid-modified olefin polymer (B-) with respect to 100 parts of the first acid-modified olefin polymer (A-2) and the first acid-modified olefin polymer (A-2). 1) and 16 parts of fatty acid potassium (C-1) per 100 parts of the first acid-modified olefin polymer (A-2), a twin screw extruder (screw diameter; 30 mm, L / D; 40, first half temperature of barrel; 110 ° C., second half temperature of barrel; 100 ° C.), and melt kneaded.
The first acid-modified olefin polymer (A-2), the second acid-modified olefin polymer (B-1), and fatty acid potassium are supplied from an aqueous solution supply port provided in the middle part of the twin-screw extruder. With respect to the total mass of (C-1), in the form of an aqueous potassium hydroxide solution, 1.8 parts (1.5 times the amount necessary to neutralize the acid) of potassium hydroxide (D- 1) and 17 parts of water (E) were continuously injected at 1.8 MPa. And it melt-kneaded in the twin-screw extruder, and obtained the aqueous dispersion.
Then, the aqueous dispersion discharged from the tip side of the twin screw extruder is cooled to 80 ° C. or lower using a jacketed static mixer, dispersed in 150 parts of warm water, diluted, and the solid content concentration is 30. % Aqueous dispersion (AW-3) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

Example 4
30 parts of second acid-modified olefin polymer (B-) with respect to 100 parts of first acid-modified olefin polymer (A-3) and first acid-modified olefin polymer (A-3). 1) and 16 parts of fatty acid potassium (C-1) per 100 parts of the first acid-modified olefin polymer (A-3), a twin screw extruder (screw diameter; 30 mm, L / D; 40, first half temperature of barrel; 100 ° C., second half temperature of barrel: 90 ° C.), and melt kneaded.
The first acid-modified olefin polymer (A-3), the second acid-modified olefin polymer (B-1), and fatty acid potassium are supplied from an aqueous solution supply port provided in the middle part of the twin-screw extruder. With respect to the total mass of (C-1), in the form of an aqueous potassium hydroxide solution, 1.8 parts (1.5 times the amount necessary to neutralize the acid) of potassium hydroxide (D- 1) and 17 parts of water (E) were continuously injected at 1.8 MPa. And it melt-kneaded in the twin-screw extruder, and obtained the aqueous dispersion.
Then, the aqueous dispersion discharged from the tip side of the twin screw extruder is cooled to 80 ° C. or lower using a jacketed static mixer, dispersed in 150 parts of warm water, diluted, and the solid content concentration is 30. % Aqueous dispersion (AW-4) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 5)
The first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (A-4), and the amount of potassium hydroxide (D-1) added was changed to 1.5 parts. Except that, an aqueous dispersion (AW-5) having a solid content concentration of 30% was obtained in the same manner as in Example 1. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 6)
The first acid-modified olefin polymer (A-2) was changed to the first acid-modified olefin polymer (A-5), and the amount of potassium hydroxide (D-1) added was changed to 1.5 parts. Except that, an aqueous dispersion (AW-6) having a solid content concentration of 30% was obtained in the same manner as in Example 3. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 7)
The first acid-modified olefin polymer (A-3) was changed to the first acid-modified olefin polymer (A-6), and the addition amount of potassium hydroxide (D-1) was changed to 1.5 parts. Except that, an aqueous dispersion (AW-7) having a solid content concentration of 30% was obtained in the same manner as in Example 4. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 8)
An aqueous dispersion having a solid content concentration of 30% in the same manner as in Example 1 except that the second acid-modified olefin polymer (B-1) was changed to the acid-modified olefin polymer (B-2). AW-8) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

Example 9
An aqueous dispersion having a solid content concentration of 30% in the same manner as in Example 1 except that the second acid-modified olefin polymer (B-1) was changed to the acid-modified olefin polymer (B-3). AW-9) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 3.

(Example 10)
Except for changing the addition amount of the second acid-modified olefin polymer (B-1) to 0 part and the addition amount of potassium hydroxide (D-1) to 1.1 parts, the same as in Example 1, An aqueous dispersion (AW-10) having a solid content concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 11)
The same procedure as in Example 1 was conducted except that the addition amount of the second acid-modified olefin polymer (B-1) was changed to 0.5 part and the addition amount of potassium hydroxide (D-1) was changed to 1.1 parts. Thus, an aqueous dispersion (AW-11) having a solid concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 12)
The same procedure as in Example 1 was conducted except that the addition amount of the second acid-modified olefin polymer (B-1) was changed to 1.5 parts and the addition amount of potassium hydroxide (D-1) was changed to 1.1 parts. Thus, an aqueous dispersion (AW-12) having a solid concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 13)
Except for changing the addition amount of the second acid-modified olefin polymer (B-1) to 49 parts and the addition amount of potassium hydroxide (D-1) to 2.0 parts, the same as in Example 1, An aqueous dispersion (AW-13) having a solid content concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 14)
Except having changed the addition amount of the 2nd acid modification olefin type polymer (B-1) to 51 parts and the addition amount of potassium hydroxide (D-1) to 2.1 parts, it is the same as that of Example 1, An aqueous dispersion (AW-14) having a solid content concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 15)
An aqueous dispersion having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the addition amount of potassium hydroxide (D-1) was changed to 1.9 parts and the addition amount of water was changed to 10.5 parts. AW-15) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 16)
An aqueous dispersion (solid content concentration of 30%) was obtained in the same manner as in Example 1 except that the addition amount of potassium hydroxide (D-1) was changed to 1.6 parts and the addition amount of water was changed to 21.5 parts. AW-16) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 17)
The solid content concentration was 30 as in Example 1 except that the amount of fatty acid potassium (C-1) added was changed to 0.5 parts and the amount of potassium hydroxide (D-1) added was changed to 1.9 parts. % Aqueous dispersion (AW-17) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 18)
The solid content concentration was 30 as in Example 1, except that the addition amount of fatty acid potassium (C-1) was changed to 1.5 parts and the addition amount of potassium hydroxide (D-1) was changed to 1.9 parts. % Aqueous dispersion (AW-18) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 19)
The solid content concentration is 30% in the same manner as in Example 1 except that the amount of fatty acid potassium (C-1) added is 39 parts and the amount of potassium hydroxide (D-1) added is 1.5 parts. An aqueous dispersion (AW-19) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 20)
The solid content concentration is 30% in the same manner as in Example 1 except that the amount of fatty acid potassium (C-1) added is 41 parts and the amount of potassium hydroxide (D-1) is changed to 1.5 parts. An aqueous dispersion (AW-20) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 4.

(Example 21)
Example 1 except that the amount of potassium hydroxide (D-1) added was 1.1 parts, and the base equivalent of the components (A), (B) and (C) was changed to 0.9 times the amount of acid. Thus, an aqueous dispersion (AW-21) having a solid concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 22)
Example 1 except that the amount of potassium hydroxide (D-1) added is 1.3 parts, and the base equivalent of the components (A), (B), and (C) is 1.1 times the amount. Thus, an aqueous dispersion (AW-22) having a solid concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 23)
Example 2 except that the amount of potassium hydroxide (D-1) added is 2.2 parts, and the base equivalent to the acid of the components (A), (B), and (C) is changed to 1.9 times the amount. Thus, an aqueous dispersion (AW-23) having a solid concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 24)
Example 1 except that the amount of potassium hydroxide (D-1) added is 2.3 parts, and the base equivalent of the components (A), (B) and (C) is 2.1 times the acid. Thus, an aqueous dispersion (AW-24) having a solid content concentration of 30% was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 25)
An aqueous solution having a solids concentration of 30% was obtained in the same manner as in Example 1 except that the first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (A-7). A dispersion (AW-25) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 26)
An aqueous solution having a solid content concentration of 30% in the same manner as in Example 1 except that the first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (A-8). A dispersion (AW-26) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 27)
An aqueous solution having a solid content concentration of 30% in the same manner as in Example 1 except that the first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (A-9). A dispersion (AW-27) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Example 28)
An aqueous solution having a solid content concentration of 30% in the same manner as in Example 1 except that the first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (A-10). A dispersion (AW-28) was obtained. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 5.

(Comparative Example 1)
An aqueous dispersion (AW-29) having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the barrel latter half temperature was changed to 140 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 2)
An aqueous dispersion (AW-30) having a solid content concentration of 30% was obtained in the same manner as in Example 2 except that the barrel latter half temperature was changed to 110 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 3)
An aqueous dispersion (AW-31) having a solid content concentration of 30% was obtained in the same manner as in Example 3 except that the barrel latter half temperature was changed to 100 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 4)
An aqueous dispersion (AW-32) having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the temperature in the first half of the barrel was changed to 130 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 5)
An aqueous dispersion (AW-33) having a solid content concentration of 30% was obtained in the same manner as in Example 2 except that the barrel first half temperature was changed to 100 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 6)
An aqueous dispersion (AW-34) having a solid content concentration of 30% was obtained in the same manner as in Example 3 except that the barrel first half temperature was changed to 90 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 7)
An aqueous dispersion (AW-35) having a solid concentration of 30% was obtained in the same manner as in Example 1 except that the first half barrel temperature was changed to 130 ° C and the second half barrel temperature was changed to 140 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 8)
An aqueous dispersion (AW-36) having a solid content concentration of 30% was obtained in the same manner as in Example 2 except that the first half barrel temperature was changed to 100 ° C and the second half barrel temperature was changed to 110 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 9)
An aqueous dispersion (AW-37) having a solid content concentration of 30% was obtained in the same manner as in Example 3 except that the barrel first half temperature was changed to 90 ° C and the barrel second half temperature was changed to 100 ° C. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 10)
An aqueous dispersion (AW-38) having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the amount of water added was changed to 9.5 parts. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 11)
An aqueous dispersion (AW-39) having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the amount of water added was changed to 22.5 parts. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

(Comparative Example 12)
The first acid-modified olefin polymer (A-1) was changed to the first acid-modified olefin polymer (a-11), and the amount of potassium hydroxide (D-1) added was changed to 1.0 part. Except for the above, an aqueous dispersion (AW-40) having a solid content concentration of 30% was obtained in the same manner as in Example 1. Then, in the same manner as in Example 1, the storage stability, average particle diameter, pH, unemulsified amount, B-type viscosity, and residual organic solvent amount of the obtained aqueous dispersion were evaluated. The results are shown in Table 6.

  In the aqueous dispersions of Examples 1 to 28 within the scope of the invention according to claim 1 of the present application, the particle size of the aqueous dispersion of the acid-modified polymer material was small, the amount of non-emulsified material was small, and the B-type viscosity was low. Further, the aqueous dispersion did not contain any organic solvent and was excellent in storage stability.

In Comparative Examples 1 to 3, in which the barrel latter half temperature was higher than the melting point of the first acid-modified olefin polymer, the B-type viscosity was high although the particle size was small and the amount of non-emulsified material was small.
In Comparative Examples 4 to 6, in which the temperature in the first half of the barrel was lower than the melting point of the first acid-modified olefin polymer, it was unstable during production, the particle size was large, the amount of unemulsified material was large, and the storage stability was low.
In Comparative Examples 7 to 9, in which the first half barrel temperature was lower than the melting point of the first acid-modified olefin polymer and the second half barrel temperature was higher than the melting point of the first acid-modified olefin polymer, The amount of non-emulsified product was large, the storage stability was low, and the B-type viscosity was high.
In Comparative Examples 10 to 11 in which the amount of water (E) added was outside the range of claim 1, the amount of water (E) became unstable during production and the amount of non-emulsified product was large.
In Comparative Example 12 in which a polymer that was not an acid-modified olefin polymer was used and the amount of water added was large, the polymer became unstable regardless of the temperature during production, and the amount of non-emulsified product was large.

Claims (3)

  First kneading step of obtaining a kneaded product by melt-kneading the acid-modified polymer material (P) containing the first acid-modified olefin polymer (A) having an acid group and the anionic surfactant (C) The temperature of the second kneading step in which the basic substance (D) and water (E) are added to the kneaded material and melt kneaded is below the melting point, and the temperature of the water (E) The method for producing an acid-modified olefin-based aqueous dispersion, wherein the addition amount is 10 to 22 parts by mass with respect to 100 parts by weight of the first acid-modified olefin polymer (A).   The first acid-modified olefin polymer (A) has an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic acid anhydride unit, an acid value of 10 mgKOH / g or more, and a mass average molecular weight of 2,000. It is -30,000, The manufacturing method of the acid-modified olefin type aqueous dispersion of Claim 1 characterized by the above-mentioned. The acid-modified polymer material (P) has an olefin unit and an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit, and has a weight average molecular weight of 31,000 to 50,000. The production of the acid-modified olefin-based aqueous dispersion according to claim 1 or 2, wherein the blend (B) is contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the first acid-modified olefin polymer (A). Method.