JP5085151B2 - Aqueous dispersion and method for producing the same - Google Patents

Description

  The present invention relates to an aqueous dispersion mainly composed of an olefin copolymer having a low crystallinity and a method for producing the same.

Conventionally, when a polyolefin resin molded body is coated or bonded, a solvent containing a chlorinated polyolefin in a solvent has been often used. However, in consideration of recent environmental problems, a water-based dispersion that can be used as a component of a paint or adhesive containing no solvent or chlorine, or a primer is required.
Therefore, Patent Document 1 proposes an aqueous dispersion having an acid-modified polyolefin, a modified starch, and an emulsifier, and having a pH of 6 or more.
JP 2004-285227 A

However, the aqueous dispersion described in Patent Document 1 did not exhibit as much adhesion as a solvent-type paint or adhesive. In particular, when the substrate was a polypropylene molded body, the adhesion was low. In addition, the aqueous dispersion described in Patent Document 1 has insufficient water resistance of the resulting film.
The present invention has been made in view of the above circumstances, and although it does not contain an organic solvent and a chlorine atom-containing polymer, it has sufficient adhesion, particularly high adhesion to a polypropylene molded article, and the water resistance of the resulting coating is high. An object is to provide an aqueous dispersion having excellent properties and a method for producing the same.

The present invention includes the following aspects.
[1] 5 to 20 parts by mass of acid modification with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) An aqueous dispersion containing a polyolefin (B), 1 to 10 parts by weight of an anionic surfactant (C), and 0.5 to 20 parts by weight of water (D),
The propylene / 1-butene / ethylene terpolymer (A) contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and The weight average molecular weight is 120,000 to 400,000, the crystallinity is 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, and has a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. An aqueous dispersion characterized by being.

[2] 5 to 20 parts by mass of acid-modified polyolefin with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) (B) and 1-10 parts by mass of an anionic surfactant (C) are melt-kneaded with 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) to obtain a kneaded product. Process,
Adding 0.5 to 20 parts by mass of water (D) to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and further melt-kneading the kneaded product. A method for producing an aqueous dispersion having
As propylene / 1-butene / ethylene terpolymer (A), it contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and Using a weight average molecular weight of 120,000 to 400,000 and a crystallinity of 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, having a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. What is claimed is: 1. A method for producing an aqueous dispersion, comprising:

Although the aqueous dispersion of the present invention does not contain an organic solvent and a chlorine atom-containing polymer, the aqueous dispersion has sufficient adhesion, particularly high adhesion to a polyolefin molded article, and is excellent in water resistance of the resulting coating.
According to the method for producing an aqueous dispersion of the present invention, although it does not contain an organic solvent and a chlorine atom-containing polymer, sufficient adhesion, particularly adhesion to a polyolefin molded body is high, and the resulting coating has water resistance. An excellent aqueous dispersion can be produced.

"Aqueous dispersion"
The aqueous dispersion of the present invention contains a propylene / 1-butene / ethylene terpolymer (A), an acid-modified polyolefin (B), an anionic surfactant (C), and water (D). is there.

(Propylene / 1-butene / ethylene terpolymer (A))
The propylene / 1-butene / ethylene terpolymer (A) has 40 to 70% by mass of propylene units. When the propylene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 40% by mass or more than 70% by mass, the obtained aqueous dispersion is converted into a polypropylene molded product. Adhesiveness when applied to the coating is lowered, and the water resistance of the resulting coating is lowered.
Moreover, a propylene / 1-butene / ethylene terpolymer (A) contains 20-40 mass% of 1-butene units. Even if the 1-butene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 20% by mass or more than 40% by mass, adhesion, particularly adhesion to a molded product of polypropylene. And the water resistance of the resulting coating is reduced.
The propylene / 1-butene / ethylene terpolymer (A) contains 5 to 25% by mass of ethylene units. Even if the ethylene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 5% by mass or more than 25% by mass, the adhesiveness, in particular, the adhesiveness to the molded product of polypropylene can be obtained. In addition, the water resistance of the resulting coating is lowered.

The propylene / 1-butene / ethylene terpolymer (A) may contain other monomer units in addition to the above structural units within a range not inhibiting the effects of the present invention.
Examples of other monomers include conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, Non-conjugated dienes such as 5-methylene-2-norbornene and 2,5-norbornadiene; (meth) acrylic acid, (meth) acrylate, (meth) acrylate ester, vinyl acetate, vinyl alcohol, 1-undecylenic acid, Examples include polar vinyl monomers such as 1-undecenol and maleic anhydride component units; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and indene. As for another monomer, 1 type may be contained independently and 2 or more types may contain.

  The degree of crystallinity of the propylene / 1-butene / ethylene terpolymer (A) is 0.1 to 16%, preferably 0.1 to 8%. When the crystallinity of the propylene / 1-butene / ethylene terpolymer (A) exceeds 16%, the adhesion of the resulting aqueous dispersion to a polyolefin molded product, particularly a polypropylene molded product is lowered, and water resistance is also improved. Lower. On the other hand, even if the crystallinity of the propylene / 1-butene / ethylene terpolymer (A) is less than 0.1%, the adhesion and water resistance of the resulting aqueous dispersion are lowered.

  The weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) is 120,000 to 400,000. Even if the weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) is less than 120,000 or more than 400,000, the adhesiveness, particularly the adhesiveness to polypropylene molded articles is low. Become.

The production method of the propylene / 1-butene / ethylene terpolymer (A) is not particularly limited. For example, using a vanadium catalyst, a titanium catalyst containing magnesium, titanium, halogen, or the like as a component, Examples thereof include a method of copolymerizing propylene, 1-butene, ethylene and other monomers as required.
As a method for producing the propylene / 1-butene / ethylene terpolymer (A) with controlled crystallinity, it is preferable to use a metallocene catalyst. Examples of the metallocene catalyst include transition metal complexes of Groups 4 to 6 of the periodic table having at least one cyclopentadienyl skeleton. For example, a metallocene catalyst described in JP-A-9-151205 can be used.
The composition of the propylene / 1-butene / ethylene terpolymer (A) is appropriately determined according to the propylene / 1-butene / ethylene terpolymer (A) supply composition of propylene, 1-butene and ethylene during polymerization. It can be adjusted by changing.
The weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) can be adjusted by supplying hydrogen gas during polymerization and appropriately changing the supply amount.

(Acid-modified polyolefin (B))
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof. Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, and examples of the ethylenically unsaturated carboxylic acid anhydride include maleic anhydride.
Examples of the acid-modified polyolefin (B) include acid-modified polyethylene having an acid value of 3 to 80 mg / g, acid-modified ethylene-propylene copolymer, acid-modified polypropylene, and ethylene- (meth) acrylic acid copolymer. It is done.
Acid-modified polyolefin (B) may be used individually by 1 type, and may use 2 or more types together.

  The weight average molecular weight of the acid-modified polyolefin (B) is 1,800 to 35,000, preferably 1,800 to 20,000. When the weight average molecular weight of the acid-modified polyolefin (B) is less than 1,800, since the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed, an aqueous dispersion cannot be obtained, When it exceeds 35,000, adhesion and water resistance are lowered.

  The acid value of the acid-modified polyolefin (B) is 3 to 80 mg / g, preferably 10 to 70 mg / g. The acid value here is the number of mg of potassium hydroxide required to neutralize 1 g of the modified polyolefin. When the acid value of the acid-modified polyolefin (B) is less than 3 mg / g, the aqueous dispersion cannot be obtained because the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed. When it exceeds / g, adhesion and water resistance are lowered.

  The amount of the acid-modified polyolefin (B) is 5 to 20 parts by mass, preferably 5 to 10 parts by mass with respect to 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A). When the amount of the acid-modified polyolefin (B) is less than 5 parts by mass, since the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed, an aqueous dispersion cannot be obtained and 20 masses. When the amount exceeds 50 parts, the resulting aqueous dispersion has a large particle size, and adhesion and water resistance decrease.

(Anionic surfactant (C))
Examples of the anionic surfactant (C) include primary higher fatty acid salts, secondary higher fatty acid salts, primary higher alcohol sulfates, secondary higher alcohol sulfates, and primary higher alkyls. Sulfonates, secondary higher alkyl sulfonates, higher alkyl disulfonates, sulfonated higher fatty acid salts, higher fatty acid sulfate esters, higher fatty acid ester sulfonates, higher alcohol ether sulfates, higher alcohol ethers Examples thereof include sulfonates, alkylol sulfates of higher fatty acid amides, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzoylimidazole sulfonates.
Higher fatty acids constituting the above anionic surfactants include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic 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 elements for forming salts with higher fatty acids include alkali metals such as sodium and potassium.
An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. Among these anionic surfactants, potassium tallow fatty acid and potassium oleate are more preferable from the viewpoint of water resistance.

  The amount of the anionic surfactant (C) is 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A). . When the amount of the anionic surfactant (C) is less than 1 part by mass, the dispersion stability of the aqueous dispersion is lowered, and when it exceeds 10 parts by mass, adhesion and water resistance are lowered.

(Water (D))
Water (D) in the aqueous dispersion is water necessary for phase inversion, and is 0.5 to 20 parts by mass with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A). .
In addition, solid content concentration of the aqueous dispersion whose quantity of water (D) is the said range is 84 mass% or more, and is substantially solid. Therefore, in order to apply the existing coating method to this aqueous dispersion, or to make it easy to mix other chemicals, 50 parts by mass or more is added to the aqueous dispersion for the purpose of adjusting the viscosity to an appropriate range. It is preferable to add dilution water and dilute to obtain an aqueous dispersion having a solid content concentration of 10 to 60% by mass.

(Auxiliary materials)
The aqueous dispersion may contain various auxiliary materials as necessary. Secondary materials include, for example, 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.

The aqueous dispersion described above contains the acid-modified polyolefin (B), which is presumed to have an effect of uniformly dispersing the surfactant in the stage before phase inversion. As a result of the uniform dispersion of the surfactant, even if the content of the anionic surfactant (C) is as relatively small as 1 to 10 parts by mass, the average particle diameter of less than 1 μm, ethylene / 1-butene / ethylene The original copolymer (A) can be dispersed in water. As a result, the adhesion of the aqueous dispersion to the substrate can be improved, and the water resistance of the resulting coating can be improved.
In addition, since the aqueous dispersion uses water as a dispersion medium, there are few environmental problems and excellent handleability.

(how to use)
The aqueous dispersion is used by being applied to various substrates. Examples of the substrate include paper, fiber fabric, plastic molded product, wood, metal, and the like. Among these, high adhesiveness of the aqueous dispersion is remarkably exhibited for plastic molded products, particularly polyethylene molded products and polypropylene molded products. Various additions such as other polyolefins (for example, ethylene / propylene copolymer rubber), inorganic fillers (for example, talc, glass fiber, calcium carbonate, etc.), stabilizers, colorants, etc. to the polyethylene molded products and polypropylene molded products Even when an agent is included, the effect exerted is the same.
As a coating method of the aqueous dispersion, for example, a method using various coating machines, a method using a spray, a brush coating, or the like can be employed.

"Method for producing aqueous dispersion"
In the method for producing an aqueous dispersion of the present invention, a mixture containing a propylene / 1-butene / ethylene terpolymer (A), an acid-modified polyolefin (B) and an anionic surfactant (C) is melt-kneaded. To obtain a kneaded product (hereinafter referred to as the first step), and further, after adding water (D) to the kneaded product, further melt-kneaded (hereinafter referred to as the second step).

(First step)
The blending amount of the acid-modified polyolefin (B) in the first step is 100 masses of propylene / 1-butene / ethylene terpolymer (A), similar to the content of the acid-modified polyolefin (B) in the aqueous dispersion. It is 5-20 mass parts with respect to a part, Preferably it is 5-10 mass parts.
The blending amount of the anionic surfactant (C) is 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A) as in the content of the anionic surfactant (C) in the aqueous dispersion. 1 to 10 parts by mass, preferably 2 to 5 parts by mass.

When melt-kneading the propylene / 1-butene / ethylene terpolymer (A), the acid-modified polyolefin (B) and the anionic surfactant (C), for example, a kneader, a Banbury mixer, a multiaxial screw An extruder can be applied.
The melt-kneading conditions are appropriately selected depending on the physical properties of the propylene / 1-butene / ethylene terpolymer (A), but the melt-kneading temperature is preferably 160 ° C to 250 ° C. If the melt-kneading temperature is 160 ° C. or higher, the melt viscosity is sufficiently low so that it can be easily kneaded. Decomposition can be suppressed and energy consumption can be reduced.

(Second step)
In the second step following the first step, water (D) is injected into the kneaded product obtained in the first step, and propylene / 1-butene / ethylene terpolymer (A) and acid-modified Water is contained in the resin solids containing the polyolefin (B). In the addition of water (D), only water may be added, or it may be added in the form of an aqueous solution in which other additive components are dissolved. As other additive components, alkaline components such as potassium hydroxide, sodium hydroxide and organic amines are preferable because the acid-modified polyolefin (B) -derived acid can be neutralized to produce an aqueous dispersion more easily.
The amount of water (D) added is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and 2 to 10 parts by mass. It is more preferable. If the amount of water (D) added is less than 0.5 parts by mass, an aqueous dispersion cannot be obtained, and if it exceeds 20 parts by mass, the average particle size of the resin solid content of the aqueous dispersion becomes large and adheres. And water resistance are lowered.

In the melt-kneading in the second step, the phase is changed from a state in which the resin solid content contains water to a state in which the resin solid content is dispersed in water.
Also in the melt-kneading in the second step, a kneader, a Banbury mixer, and a multi-screw extruder can be applied as in the first step.
The melt kneading temperature in the second step is preferably 160 to 250 ° C. as in the first step. If the melt kneading temperature is 160 ° C. or higher, phase inversion can be easily performed, and if it is 250 ° C. or lower, the resin is not heated more than necessary, so that the deterioration and thermal decomposition of the resin are suppressed, and the energy consumption is reduced. Can be reduced.

  After completion of the second step, it is preferable to add water to the obtained aqueous dispersion to obtain a diluted aqueous dispersion. If water is further added, the viscosity of the aqueous dispersion decreases and the fluidity increases. Further, the amount of water to be added is appropriately selected depending on the purpose and method of use of the aqueous dispersion, but is preferably such that the solid content concentration of the aqueous dispersion is in the range of 10 to 60% by mass.

In other production methods other than the present invention, it is difficult to obtain an aqueous dispersion having a small average particle diameter of about 0.1 to 1 μm when the amount of the surfactant is as small as 1 to 10 parts by mass. However, according to the method for producing an aqueous dispersion, an aqueous dispersion having a small average particle diameter of about 0.1 to 1 μm can be obtained even with a small amount of surfactant of 1 to 10 parts by mass. This is because the acid-modified polyolefin (B) used in this production method is a stage in which the propylene / 1-butene / ethylene terpolymer (A) before phase inversion is a continuous phase, and the surfactant is microdispersed. It is presumed that this is to exert the effect of Accordingly, the acid-modified polyolefin (B) is an essential component in the production method. On the other hand, other dispersion methods show only a slight viscosity reduction effect and are not essential.
Moreover, the coating film formed from the aqueous dispersion obtained by the said manufacturing method becomes what was excellent in adhesiveness and water resistance.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In the following examples, “%” means “mass%” and “part” means “part by mass”.
The properties of propylene / 1-butene / ethylene terpolymer and acid-modified polyolefin in the following examples were measured as follows.
-Quantification of polyolefin unit: It was determined by measuring the molar ratio with a high resolution Fourier transform nuclear magnetic resonance apparatus JNM-AL400 manufactured by JEOL Ltd.
-Weight average molecular weight of polyolefin and acid-modified polyolefin: Measured by Alliance GPC V2000, manufactured by Waters.
Polyolefin crystallinity: Determined by a wide-angle X-ray diffractometer RAD-RX manufactured by Rigaku Corporation.
Average particle size: Measured with a Microtrac UPA manufactured by Mounttech.

In the following examples and comparative examples, the following (A-1) to (A-17) were used as the component (A).
Propylene / 1-butene / ethylene terpolymer (A-1)
A 100 L stainless steel polymerization tank equipped with a stirrer is dried under reduced pressure, hydrogen is supplied for molecular weight adjustment, and polymerized continuously by the following method to produce a propylene / 1-butene / ethylene terpolymer (A-1 )
From the bottom of the polymerization tank, hexane as a polymerization solvent is supplied at a rate of 100 L / hour, propylene is supplied at a supply rate of 10.5 kg / hour, 1-butene is supplied at a supply rate of 9.5 kg / hour, and ethylene is supplied at 5 kg / hour. Hydrogen gas was continuously supplied at a supply rate of 90 g / hour at a supply rate of time.
Moreover, the reaction mixture was continuously extracted from the upper part of the polymerization tank so that the volume of the reaction mixture in the polymerization tank was maintained at 100 L.
At the same time, a supply rate of 0.005 g / hour of dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst from the lower part of the polymerization tank. Then, triphenylmethyltetrakis (pentafluorophenyl) borate was continuously supplied at a supply rate of 0.30 g / hour and triisobutylaluminum was continuously supplied at a supply rate of 2.3 g / 10 hours.
At the same time, the reaction mixture was continuously extracted from the upper part of the polymerization tank so that the volume of the reaction mixture in the polymerization tank was maintained at 100 L.
The polymerization reaction was performed at 45 ° C. by circulating cooling water through a jacket provided outside the polymerization tank.
A small amount of ethanol was added to the reaction mixture continuously extracted from the upper part of the polymerization tank to stop the polymerization reaction, and then the monomer was removed and washed with water. Next, the solvent was removed with steam in a large amount of water and dried under reduced pressure at 80 ° C. for one day to obtain a propylene / 1-butene / ethylene terpolymer (A-1).
The composition, crystallinity, and weight average molecular weight of each monomer unit of propylene / 1-butene / ethylene terpolymer (A-1) were measured as follows. The results are shown in Table 1.

In addition, the propylene / 1-butene / ethylene ternary copolymer described above was used except that the supply rate of propylene, 1-butene and ethylene was changed so that the composition of the monomer units was as shown in Table 1 or Table 2. Propylene / 1-butene / ethylene terpolymers (A-2) to (A-17) were obtained in the same manner as in the method for producing the polymer (A-1).
Table 1 or Table 2 shows the composition, crystallinity, and weight average molecular weight of each monomer unit in the propylene / 1-butene / ethylene terpolymers (A-2) to (A-17).

As the component (B), the following (B-1) to (B-8) were used.
Acid-modified polyolefin (B-1): “TP Licocene PPMA 6252” manufactured by Clariant, which is an acid-modified polypropylene wax having an acid value of 40 mg / g and a weight average molecular weight of 3,000.
Acid-modified polyolefin (B-2): “Yumex 100TS” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 3.5 mg / g and a weight average molecular weight of 10,000.
Acid-modified polyolefin (B-3): “High Wax 2203A” manufactured by Mitsui Chemicals, which is an acid-modified polyethylene wax having an acid value of 30 mg / g and a weight average molecular weight of 2,000.
Acid-modified polyolefin (B-4): “Yumex 1010” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 52 mg / g and a weight average molecular weight of 30,000.
Acid-modified polyolefin (B-5): “Yumex 1001” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 26 mg / g and a weight average molecular weight of 40,000.
Acid-modified polyolefin (B-6): “High Wax 1105A” manufactured by Mitsui Chemicals, which is acid-modified polyethylene having an acid value of 60 mg / g and a weight average molecular weight of 1,100.
Polypropylene wax (B-7): “High Wax NP055” manufactured by Mitsui Chemicals, which is a polypropylene wax that is not acid-modified and has a weight average molecular weight of 7,000.
Acid-modified polyolefin (B-8): “Diacarna 30” manufactured by Mitsubishi Chemical, which is an α-olefin / maleic anhydride copolymer having an acid value of 110 mg / g and a weight average molecular weight of 10,000.

Example 1
Propylene / 1-butene / ethylene terpolymer (A-1), 12 parts of acid-modified polyolefin (B-1) with respect to 100 parts of propylene / 1-butene / ethylene terpolymer, propylene 3 parts of potassium oleate with respect to 100 parts of -1-butene / ethylene terpolymer are charged into a twin screw extruder (screw diameter; 30 mm, L / D; 40, barrel temperature; 200 ° C.). And melt-kneaded. The total supply rate of the three raw materials was 3,450 g / hour.
Further, a 14% potassium hydroxide aqueous solution was press-fitted at 1.8 MPa so that the amount of water relative to 100 parts of polyolefin was 4 parts from a supply port provided in the vent part of the twin-screw extruder.
The solid emulsion extruded from the tip of the twin screw extruder was dispersed in warm water to obtain an aqueous dispersion having an average particle size of 0.21 μm.

The adhesion of the obtained aqueous dispersion and the water resistance of the coating obtained from the aqueous dispersion were evaluated as follows. The results are shown in Table 3. This evaluation method was applied to other examples and comparative examples.
[Preparation of test piece]
A plate of 100 × 100 mm and a thickness of 2 mm was obtained by injection molding for “J106G” manufactured by Prime Polymer Co., which is a homo PP, and “J715M” of a block PP, respectively.
After degreasing the surface of this flat plate, No. The aqueous dispersion was applied to a thickness of 10 μm using 13 coating bars. And it dried at 70 degreeC for 20 minute (s), and left still at room temperature for 24 hours, the film was formed, and the flat plate in which the film was formed was used as a test piece.
[Adhesion test]
The cuts reaching the PP flat plate were formed on the film by a cutter so that 100 squares were formed at 1 mm intervals. Cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) was adhered to the cells, and then peeled off, and the number of cells remaining was recorded. The greater the number of remaining cells, the better the adhesion.
[Water resistance test]
The test piece placed in a metal cage was completely immersed in warm water at 40 ° C. and left for 10 days. Then, it took out from warm water, and if the abnormality was not recognized in the external appearance, the same test as the said adhesion test was performed continuously. The greater the number of remaining cells, the better the water resistance.

(Example 2)
An aqueous dispersion having an average particle size of 0.25 μm was obtained in the same manner as in Example 1 except that 6 parts of acid-modified polypropylene wax (B-1) was added to 100 parts of polyolefin. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 3)
An aqueous dispersion having an average particle diameter of 0.27 μm was obtained in the same manner as in Example 1 except that 18 parts of acid-modified polypropylene wax (B-1) was added to 100 parts of polyolefin. The adhesion and water resistance results are shown in Table 3.

Example 4
Except for using propylene / 1-butene / ethylene terpolymer (A-2) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 3.

(Example 5)
Except for using propylene / 1-butene / ethylene terpolymer (A-3) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.20 μm was obtained. The adhesion and water resistance results are shown in Table 3.

(Example 6)
Except for using propylene / 1-butene / ethylene terpolymer (A-4) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.30 μm was obtained. The adhesion and water resistance results are shown in Table 3.

(Example 7)
Except for using propylene / 1-butene / ethylene terpolymer (A-5) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.23 μm was obtained. The adhesion and water resistance results are shown in Table 3.

(Example 8)
Except for using propylene / 1-butene / ethylene terpolymer (A-6) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 7, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 3.

Example 9
Except for using propylene / 1-butene / ethylene terpolymer (A-7) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 7, An aqueous dispersion having an average particle size of 0.32 μm was obtained. The adhesion and water resistance results are shown in Table 3.

(Example 10)
An aqueous dispersion having an average particle size of 0.22 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-2) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.

(Example 11)
An aqueous dispersion having an average particle size of 0.26 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-3) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.

(Example 12)
An aqueous dispersion having an average particle size of 0.23 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-4) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.

(Example 13)
An aqueous dispersion having an average particle size of 0.25 μm in the same manner as in Example 5 except that dodecylbenzenesulfonic acid (in the table, DBS is used) is used as an anionic surfactant instead of potassium oleate. Got. The adhesion and water resistance results are shown in Table 4.

(Example 14)
An aqueous dispersion having an average particle size of 0.38 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 1.0 part. The adhesion and water resistance results are shown in Table 4.

(Example 15)
An aqueous dispersion having an average particle size of 0.33 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 15 parts. The adhesion and water resistance results are shown in Table 4.

(Comparative Example 1)
In an autoclave with an internal volume of 2 liters equipped with a stirrer, 100 parts of propylene / 1-butene / ethylene terpolymer (A-1) and 500 parts of toluene were charged and dissolved by stirring at 125 ° C. for 1 hour. And cooled to 90 ° C.
Separately, an aqueous solution containing 3 parts of potassium oleate and 600 parts of water is heated to 90 ° C. in an autoclave having an internal volume of 2 liters equipped with a stirrer, and the toluene solution of the polyolefin is stirred therein. Added under continuation. After stirring for 2 hours to disperse, the mixture was dispersed with a high speed homogenizer manufactured by SMT (HG-92) at 10,000 rpm for 10 minutes.
Next, while continuing the stirring by the stirring blade, while condensing water is refluxed, the steam is distilled for 2 hours to distill off the toluene, but as the toluene is distilled off, agglomerates are generated and the entire amount of toluene is distilled off. The aggregate reached 99 parts before and an aqueous dispersion could not be obtained.

(Comparative Example 2)
An aqueous dispersion was obtained in the same manner as in Comparative Example 1 except that the amount of potassium oleate was changed to 10 parts. However, an aqueous dispersion could not be obtained.

(Comparative Example 3)
Except that the amount of potassium oleate was changed to 20 parts, the same procedure as in Comparative Example 1 was carried out. As a result, 12 parts of aggregates were by-produced. . The adhesion and water resistance results are shown in Table 5.

(Comparative Example 4)
In the method for preparing the aqueous dispersion of Comparative Example 3, 12 parts of acid-modified polyolefin (B-1) was dissolved in toluene in the same manner as propylene / 1-butene / ethylene terpolymer (A-1), and oleic acid was dissolved. Except for adding 20 parts of potassium, the same procedure as in Comparative Example 1 was performed. As a result, 18 parts of aggregates were by-produced, but an aqueous dispersion having a concentration of 16% and an average particle size of 8.1 μm was obtained. The adhesion and water resistance results are shown in Table 5.

(Comparative Example 5)
In place of the total amount of propylene / 1-butene / ethylene terpolymer (A-1), except that 100 parts of acid-modified polyolefin (B-1) was dissolved in toluene, the same procedure as in Comparative Example 1 was conducted. Although 1 part of the product was by-produced, an aqueous dispersion having an average particle size of 0.3 μm was obtained. The adhesion and water resistance results are shown in Table 5.

(Comparative Example 6)
Except for using propylene / 1-butene / ethylene terpolymer (A-8) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 7)
Except having used propylene / 1-butene / ethylene terpolymer (A-9) instead of propylene / 1-butene / ethylene terpolymer (A-1), it was carried out similarly to Example 1, An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 8)
Except for using propylene / 1-butene / ethylene terpolymer (A-10) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.23 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 9)
Except for using propylene / 1-butene / ethylene terpolymer (A-11) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 10)
Except for using propylene / 1-butene / ethylene terpolymer (A-12) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.25 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 11)
Except for using propylene / 1-butene / ethylene terpolymer (A-13) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.26 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 12)
Except for using propylene / 1-butene / ethylene terpolymer (A-14) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 13)
Except for using propylene / 1-butene / ethylene terpolymer (A-15) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 14)
Except for using propylene / 1-butene / ethylene terpolymer (A-16) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 15)
Except for using propylene / 1-butene / ethylene terpolymer (A-17) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.28 μm was obtained. The adhesion and water resistance results are shown in Table 6.

(Comparative Example 16)
An aqueous dispersion having an average particle size of 0.24 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-5) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 7.

(Comparative Example 17)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-6) was used in place of the acid-modified polyolefin (B-1). As a result, an aqueous dispersion was not obtained.

(Comparative Example 18)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-7) was used instead of the acid-modified polyolefin (B-1). As a result, an aqueous dispersion was not obtained.

(Comparative Example 19)
An aqueous dispersion having an average particle size of 0.30 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-8) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 7.

(Comparative Example 20)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the amount of the acid-modified polyolefin (B-1) was changed to 4 parts. However, the aqueous dispersion was not diluted with warm water, but only aggregates were formed. No body was obtained.

(Comparative Example 21)
An aqueous dispersion having an average particle size of 0.29 μm was obtained in the same manner as in Example 5 except that the amount of the acid-modified polyolefin (B-1) was changed to 25 parts. The adhesion and water resistance results are shown in Table 7.

(Comparative Example 22)
An aqueous dispersion was tried to be obtained in the same manner as in Example 5 except that the amount of potassium oleate was changed to 0.4 part. However, the aqueous dispersion was not diluted with warm water but only aggregates were formed. I couldn't.

(Comparative Example 23)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 5 except that the amount of potassium oleate was changed to 12 parts. The adhesion and water resistance results are shown in Table 7.

(Comparative Example 24)
An aqueous dispersion was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 0.3 parts. No matter how much was formed, no aqueous dispersion was obtained.

(Comparative Example 25)
An aqueous dispersion having an average particle size of 0.38 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 22 parts. The adhesion and water resistance results are shown in Table 7.

A step of melt-kneading a specific propylene / 1-butene / ethylene terpolymer (A), acid-modified polyolefin (B) and an anionic surfactant (C) to obtain a kneaded product; After injecting water (D), the aqueous dispersion obtained by the production method of Examples 1 to 15 having a step of further melt-kneading was excellent in adhesion to polypropylene. Moreover, the water resistance of the film obtained from the aqueous dispersion was excellent.
In contrast, in the production methods of Comparative Examples 1 and 2 in which the polyolefin (A) was dispersed by high-speed stirring under the condition that the amount of potassium oleate was 10 parts by mass or less in the presence of a solvent, an aqueous dispersion could not be obtained. .
In the production method of Comparative Example 3 in which the amount of potassium oleate added was increased, an aqueous dispersion was obtained, but adhesion and water resistance were low.
Also in Comparative Example 4 in which acid-modified polyolefin (B) was added to the production method of Comparative Example 3, the adhesion and water resistance were low.
In the production method of Comparative Example 5 containing acid-modified polyolefin (B) but not containing polyolefin (A), an average particle size of 0.4 μm was obtained, but adhesion and water resistance were not expressed.
In the production method of Comparative Example 6 using the propylene / 1-butene / ethylene terpolymer (A) having a propylene unit of less than 40%, adhesion and water resistance were low.
In the production method of Comparative Example 7 using propylene / 1-butene / ethylene terpolymer (A) having a propylene unit exceeding 70%, adhesion and water resistance were low.
In the production method of Comparative Example 8 using the propylene / 1-butene / ethylene terpolymer (A) having a 1-butene unit of less than 20%, adhesion and water resistance were low.
In the production method of Comparative Example 9 using the propylene / 1-butene / ethylene terpolymer (A) having a 1-butene unit exceeding 40%, adhesion and water resistance were low.
In the production method of Comparative Example 10 using the propylene / 1-butene / ethylene terpolymer (A) having an ethylene unit of less than 5%, adhesion and water resistance were low.
In the production method of Comparative Example 11 using the propylene / 1-butene / ethylene terpolymer (A) having an ethylene unit exceeding 25%, adhesion and water resistance were low.
In the production method of Comparative Example 12 using the propylene / 1-butene / ethylene terpolymer (A) having a crystallinity of less than 0.1%, adhesion and water resistance were low.
In the production method of Comparative Example 13 using the propylene / 1-butene / ethylene terpolymer (A) having a crystallinity exceeding 16%, the adhesion and water resistance were low.
In the production method of Comparative Example 14 using the propylene / 1-butene / ethylene terpolymer (A) having a weight average molecular weight of less than 120,000, adhesion and water resistance were low.
In the production method of Comparative Example 15 using the propylene / 1-butene / ethylene terpolymer (A) having a weight average molecular weight exceeding 400,000, adhesion and water resistance were low.
In the production method of Comparative Example 16 using the acid-modified polyolefin (B) having a weight average molecular weight exceeding 35,000, adhesion and water resistance were low.
In the production method of Comparative Example 17 using the acid-modified polyolefin (B) having a weight average molecular weight of less than 1,800, an aqueous dispersion was not obtained.
In the production method of Comparative Example 18 using the acid-modified polyolefin (B) having an acid value of less than 3 mg / g, an aqueous dispersion was not obtained.
In the production method of Comparative Example 19 using the acid-modified polyolefin (B) having an acid value exceeding 80 mg / g, adhesion and water resistance were low.
In the production method of Comparative Example 20 in which the addition amount of the acid-modified polyolefin (B) was less than 5 parts, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 21 in which the addition amount of the acid-modified polyolefin (B) was more than 20 parts, adhesion and water resistance were low.
In the production method of Comparative Example 22 in which the amount of potassium oleate added was less than 1 part, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 23 in which the amount of potassium oleate added exceeded 10 parts, adhesion and water resistance were low.
In the production method of Comparative Example 24 in which the amount of water added was less than 0.5 part, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 25 in which the amount of water added exceeded 20 parts, adhesion and water resistance were low.

Claims (2)

5 to 20 parts by mass of acid-modified polyolefin (B) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A). ), 1 to 10 parts by weight of an anionic surfactant (C), and 0.5 to 20 parts by weight of water (D),
The propylene / 1-butene / ethylene terpolymer (A) contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and The weight average molecular weight is 120,000 to 400,000, the crystallinity is 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, and has a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. An aqueous dispersion characterized by being. 5-20 parts by mass of acid-modified polyolefin (B) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) And a step of melt-kneading 1 to 10 parts by mass of an anionic surfactant (C) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) to obtain a kneaded product,
Adding 0.5 to 20 parts by mass of water (D) to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and further melt-kneading the kneaded product. A method for producing an aqueous dispersion having
As propylene / 1-butene / ethylene terpolymer (A), it contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and Using a weight average molecular weight of 120,000 to 400,000 and a crystallinity of 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, having a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. What is claimed is: 1. A method for producing an aqueous dispersion, comprising: