JP2018168348A - Aqueous dispersion and method for producing the same - Google Patents

Abstract

To provide an acid-modified polyolefin resin aqueous dispersion that has excellent filterability, resists gelation, is uniform and has a high viscosity of 1000 mPa s or more, without using a nonvolatile water-compatibilizing auxiliary, such as an emulsifier.SOLUTION: An aqueous dispersion has an acid-modified polyolefin resin, two or more organic amine compounds, and an aqueous medium with a 25°C viscosity of 1000 mPa s or more.SELECTED DRAWING: None

Description

  The present invention relates to a high viscosity aqueous dispersion.

Acid-modified polyolefin resins are used in various applications as aqueous dispersions from the viewpoints of environmental protection, resource saving, and workability.
These aqueous dispersions may require a high viscosity type of 1000 mPa · s or more depending on the purpose. If the solid content concentration of the aqueous dispersion is increased for the purpose of increasing the viscosity, the aqueous dispersion may gel and a uniform dispersion may not be obtained, or the filter may be clogged during filtration, resulting in poor productivity. there were.

  Patent Document 1 discloses a production method in which an acid-modified polyolefin resin is dispersed in water using a polymer emulsifier.

JP 2013-234243 A

  However, since the aqueous dispersion disclosed in Patent Document 1 contains an emulsifier, there are fears that it may be inferior in various physical properties such as adhesion to a substrate, water resistance and alkali resistance.

  An object of the present invention is to provide an aqueous dispersion of an acid-modified polyolefin resin having a uniform and high viscosity that is excellent in filterability and does not gel without using a non-volatile aqueous auxiliary agent such as an emulsifier.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using an aqueous dispersion containing a specific acid-modified polyolefin resin, two or more organic amine compounds, and an aqueous medium. And reached the present invention.

That is, the gist of the present invention is as follows.
(1) An aqueous dispersion containing an acid-modified polyolefin resin, two or more organic amine compounds, and an aqueous medium, and having a viscosity at 25 ° C. of 1000 mPa · s or more.
(2) The aqueous dispersion according to (1), wherein the acid-modified polyolefin resin contains an acrylic ester component.
(3) The aqueous dispersion according to (1) or (2), wherein the organic amine compound has a boiling point of 50 ° C to 210 ° C.
(4) The aqueous dispersion according to any one of (1) to (3), wherein the volume average particle diameter of the acid-modified polyolefin resin particles is 100 nm or less.
(5) The aqueous dispersion according to any one of (1) to (4), wherein the content of the organic amine compound contained in the aqueous dispersion is 0.8% by mass or more and 5.0% by mass or less. body.
(6) The method for producing an aqueous dispersion according to any one of (1) to (5), wherein the raw material is an acid-modified polyolefin resin, two types of organic amine compounds, and an aqueous medium.

  The aqueous dispersion of the present invention is excellent in filterability and excellent in storage stability without being gelled while having a high viscosity of 1000 mPa · s or more at 25 ° C. Moreover, the coating film obtained by apply | coating the aqueous dispersion of this invention is excellent in adhesiveness and water resistance. Since the aqueous dispersion of the present invention has a high viscosity, it can be suitably used for applications requiring a high viscosity type such as a substrate having a small coating area.

Hereinafter, the present invention will be described in detail.
The aqueous dispersion of the present invention contains an acid-modified polyolefin resin, two or more organic amine compounds, and an aqueous medium.

Examples of the olefin component of the acid-modified polyolefin resin include alkenes such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and cycloalkenes such as norbornene, and a mixture thereof is used. You can also. Among these, alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene are preferable, and alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are preferable. More preferably, ethylene and propylene are particularly preferable.
The content of the olefin component is preferably 50% by mass or more of the acid-modified polyolefin resin, and more preferably 70% by mass or more. When the content of the olefin component is less than 50% by mass, characteristics derived from the polyolefin resin such as adhesion to the substrate may be lost.

The acid-modified polyolefin resin is preferably acid-modified with a maleic anhydride component from the viewpoint of adhesion to a substrate and a high viscosity of 1000 mPa · s or higher at 25 ° C.
The content of the maleic anhydride component is preferably 0.1 to 25% by mass of the acid-modified polyolefin resin, more preferably 0.5 to 15% by mass, from the viewpoint of adhesion to the substrate. 8 mass% is further more preferable and 1-5 mass% is especially preferable.
The maleic anhydride component may be copolymerized in the polyolefin resin, and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.

The acid-modified polyolefin resin preferably contains a (meth) acrylic acid ester component for the purpose of improving adhesiveness. The content of the (meth) acrylic acid ester component is preferably 40% by mass or less of the acid-modified polyolefin resin, and 35% by mass or less in order to have good adhesiveness with various thermoplastic resin substrates. More preferably, it is more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When the content of the (meth) acrylic acid ester component exceeds 40% by mass in the acid-modified polyolefin resin, the properties of the olefin-derived resin are lost, and the adhesion to the substrate may be reduced.
Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include decyl, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of adhesion to the substrate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. ("(Meth) acrylic acid" means "acrylic acid or methacrylic acid".)

  In addition to the above components, other components may be contained in an amount of about 10% by mass or less of the entire acid-modified polyolefin resin. Other components include dienes, maleic esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, alkyl vinyl ethers such as (meth) acrylic acid amides, methyl vinyl ether and ethyl vinyl ether, and vinyl esters. Examples include vinyl alcohol obtained by saponification with a basic compound, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like. It can also be used.

  The acid-modified polyolefin resin has a melt flow rate at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, usually from 0.01 to 5000 g / 10 minutes, preferably from 0.1 to 1000 g / 10 minutes, more preferably from 1 to 500 g / The thing of 10 minutes, More preferably, it is 2-300 g / 10 minutes, Most preferably, the thing of 2-200 g / 10 minutes can be used. When the melt flow rate of the acid-modified polyolefin resin is less than 0.01 g / 10 minutes, the adhesion to the substrate is lowered. On the other hand, when the melt flow rate of the acid-modified polyolefin resin exceeds 5000 g / 10 minutes, the coating film becomes hard and brittle, and the adhesiveness and the adhesion to the substrate tend to be reduced.

Commercially available products of these acid-modified polyolefin resins can be suitably used. Examples of commercially available products include “Bondaine” and “Rotada” manufactured by Arkema, “Yumex” manufactured by Sanyo Kasei, and “Chemical” manufactured by Mitsui Chemicals. , “Tuffmer” and “Auroren” manufactured by Nippon Paper Chemicals.

  The aqueous dispersion of the present invention may contain an organic solvent used when dispersing the acid-modified polyolefin resin.

  In the present invention, the acid-modified polyolefin resin can be stably dispersed in an aqueous medium without using an aqueous auxiliary agent, but a non-volatile aqueous dispersing auxiliary agent may be used as necessary.

  Here, the “aqueous auxiliary” is a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous dispersion in the production of an aqueous dispersion, and “nonvolatile” means It means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.

  In the present invention, for the purpose of using the aqueous dispersion, an aqueous dispersion aid may be used as long as the effects of the present invention are not impaired, and is 5 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. You may contain in 2 mass parts or less, More preferably, it is 0.5 mass part or less.

  Examples of the non-volatile auxiliary agent used in the present invention include an emulsifier described later, a compound having a protective colloid action, a modified wax, an acid-modified compound having a high acid value, and a water-soluble polymer.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

  Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and salt thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as an acid alternating copolymer, a (meth) acrylic acid- (meth) acrylic acid ester copolymer, and a salt thereof, polyitaconic acid and a salt thereof, amino Examples thereof include water-soluble acrylic copolymers having a group, gelatin, gum arabic, and casein, and compounds generally used as fine particle dispersion stabilizers.

The aqueous dispersion of the present invention needs to have a viscosity at 25 ° C. of 1000 mPa · s or more, and the lower limit is preferably 2000 mPa · s or more. The upper limit is preferably 5000 mPa · s or less, and more preferably 4000 mPa · s or less.
When the viscosity of the aqueous dispersion is less than 1000 mPa · s at 25 ° C., for example, in applications where the application area is small, such as a linear or dotted area, the fluidity of the aqueous dispersion is too high. May not be sufficiently secured, and adhesion may be inferior. In order to make the aqueous dispersion of the present invention have a viscosity of 1000 mPa · s or more, it is preferable to set the volume average particle diameter and the resin content of the acid-modified polyolefin resin within the preferable ranges described below.

The volume average particle diameter of the acid-modified polyolefin resin in the aqueous dispersion of the present invention is preferably 100 nm or less, in view of maintaining the viscosity of the aqueous dispersion appropriately and expressing good adhesive layer forming ability. Or less, more preferably 80 nm or less. When the volume average particle diameter of the acid-modified polyolefin resin exceeds 100 nm, the aqueous dispersion is difficult to increase in viscosity, and it is difficult to adjust the viscosity to a high viscosity of 1000 mPa · s or higher at 25 ° C., and the effect may not be sufficiently exhibited. .
Although the mechanism for making the volume average particle diameter of the acid-modified polyolefin resin in the aqueous dispersion of the present invention 100 nm or less is not well understood, it can be achieved by containing two kinds of organic amine compounds.

Specific examples of such organic amine compounds include triethylamine, N, N-dimethylethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. it can.
Organic amine compounds are classified into primary amines, secondary amines, and tertiary amines. Among them, tertiary amines are preferable from the viewpoint of increasing the viscosity of the aqueous dispersion and reducing the volume average particle size. Examples of the tertiary amine include triethylamine, N, N-dimethylethanolamine, triethanolamine and the like.

  The organic amine compound needs to be contained in the aqueous dispersion in order to reduce the particle size of the acid-modified polyolefin resin at the time of aqueous dispersion described later. From the viewpoint of improvement in water resistance and water resistance, it is preferable that they do not volatilize and remain. For the above reasons, the boiling point of the organic amine compound is preferably 50 to 210 ° C, more preferably 50 to 210 ° C, and further preferably 60 to 180 ° C. When the boiling point is less than 50 ° C., the rate of volatilization when the resin is made aqueous later described increases, and the particle diameter of the acid-modified polyolefin resin tends to increase. On the other hand, when the boiling point exceeds 210 ° C., it is difficult to volatilize the organic amine compound by a drying step after coating the aqueous dispersion, and the adhesion and water resistance of the coating film may be lowered.

  The content of the organic amine compound contained in the aqueous dispersion of the present invention includes two types of organic amine compounds from the viewpoint of improving the viscosity of the aqueous dispersion and reducing the volume average particle diameter of the acid-modified polyolefin resin in the aqueous dispersion. The total content is preferably 0.8 to 5.0% by mass, more preferably 0.8 to 3.0% by mass, and even more preferably 1.0 to 2.5% by mass. Moreover, as content of one kind each, 0.1-3.0 mass% is preferable, 0.2-2.5 mass% is more preferable, 0.2-2.0 mass% is further more preferable.

Next, the manufacturing method of the aqueous dispersion of this invention is demonstrated.
The method for producing the aqueous dispersion of the present invention is not limited as long as it is a method in which the acid-modified polyolefin resin is uniformly mixed and dispersed in an aqueous medium containing two types of organic amine compounds. The raw material resin of acid-modified polyolefin resin is stirred and heated with water or a solvent to obtain an aqueous dispersion.

In order to facilitate the dispersion of the acid-modified polyolefin resin, the aqueous medium may contain an organic solvent having a water solubility of 20% by mass or more at 20 ° C.
Specific examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, and acetic acid-n-propyl. And esters such as isopropyl acetate, methyl propionate, ethyl propionate and dimethyl carbonate, and ethylene glycol derivatives such as ethylene glycol-n-butyl ether.
The amount of the organic solvent added for dispersing the acid-modified polyolefin resin is preferably 20 parts by mass or less, more preferably 16 parts by mass or less, with respect to 100 parts by mass of the acid-modified polyolefin resin. If the organic solvent is added in an amount exceeding 20 parts by mass in the dispersion of the acid-modified polyolefin resin, the resulting aqueous dispersion may take a long time to remove the solvent, resulting in a decrease in productivity or gelation.

  In the dispersion of the acid-modified polyolefin resin, it is preferable that a part of the carboxyl group in the acid-modified polyolefin resin is neutralized with a basic compound. The carboxyl group or acid anhydride group is anionized with the basic compound, and the electrostatic repulsion of the anion prevents aggregation between the resin fine particles in the aqueous medium, thereby achieving good dispersion.

When the above organic solvent or organic amine compound is used in the production of the aqueous dispersion, a part of the resin is distilled out of the system by a solvent removal process generally called “stripping” after the resin is made aqueous. The content of organic solvents and organic amine compounds can be reduced.
Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring under normal pressure or reduced pressure to distill off the organic solvent or the organic amine compound. In addition, since the solid content concentration is increased by distilling off the aqueous medium, for example, when the viscosity increases and the workability decreases, water is added to the aqueous dispersion in advance. Also good.

  The resin content in the aqueous dispersion is appropriately adjusted depending on the film forming conditions, the desired thickness and performance of the adhesive layer, and is not particularly limited, but the viscosity of the aqueous dispersion at 25 ° C. is 1000 mPa · s or more. In addition, 1 to 50% by mass is preferable, 3 to 50% by mass is more preferable, 5 to 45% by mass is further preferable, and 5 to 40% by mass is particularly preferable.

  The aqueous dispersion of the present invention may contain a crosslinking agent for the purpose of further improving various coating film performances such as chemical resistance. As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, etc. can be used. Of these, isocyanate compounds , A melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline group-containing compound, an aziridine compound, a zirconium salt compound, a silane coupling agent, and the like are preferable.

The aqueous dispersion of the present invention can be applied to a substrate to form a coating film to produce a laminate, and two or more layers of this laminate may be laminated.
Although it does not specifically limit as a base material, For example, polyester, polyolefin, paper, glass, carbon fiber etc. are mentioned. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene terephthalate, and the like. Examples of the polyolefin include polypropylene and polyethylene. These film shapes, nonwoven fabric shapes, molded body shapes, and the like can be given. Examples of the paper include filter paper and synthetic fiber paper. Examples of the glass include glass cloth, and examples of the carbon fiber include a carbon fiber sheet.

  The aqueous dispersion of the present invention can be applied to a substrate by a known method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, dip coating, brushing. The painting method etc. are mentioned. In addition, since the aqueous dispersion of the present invention has a high viscosity, it can be applied locally using a dropper or the like. After apply | coating an aqueous dispersion to the required location of a base material, the laminated body in which the coating film was formed on the base material is obtained by drying about 60 second at 60-150 degreeC.

  The aqueous dispersion of the present invention can be used for substrates and applications that require high viscosity. For example, bonding by using “lines” or “dots” instead of “surfaces”, such as bonding substrates with three-dimensional figures such as filters and cardboards without gaps, or flocking to an adhesive layer like a floor mat Also, a thick coating such as an adhesive for transfer sheets that can adhere to an adherend with a rough surface such as paper, or an adhesive for in-mold molding that does not thin the adhesive layer with molten resin is required. Suitable for use.

  The present invention will be specifically described below with reference to examples. However, the present invention is not limited by these.

The characteristics of the aqueous dispersion were measured by the following methods.
(1) Configuration of acid-modified polyolefin resin
^It calculated | required from <1> H-NMR analyzer (JEOL ECA500, 500MHz). Tetrachloroethane (d ₂ ) was used as a solvent and measured at 120 ° C.

(2) Solid content concentration The aqueous dispersion was weighed appropriately and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.

(3) Content of organic amine compound The content of the organic amine compound in the aqueous dispersion was extracted with an acetonitrile solvent and analyzed and measured by LC / MS (Agilent 6100 LC-MS system). LC / MS analysis was performed under the following conditions.
<LC>
Column: ZORBAX SB-C18 φ2.1 × 50mm, 1.8μm
Oven temperature: 35 ° C
Mobile phase A: 10 mM ammonium acetate aqueous solution Mobile phase B: Acetonitrile gradient (B conc. (%)): 0 min (30%) → 4 min (100%) post time 4 min
Flow rate: 0.2 mL / min
<MS>
Ionization method: ESI
Drying _Gas: N 2, 12L / min
Drying gas temperature: 300 ° C
Mass range: Low 50-1000

(4) Volume average particle diameter It calculated | required using the particle size distribution measuring apparatus (Nikkiso company make Nanotac wave).

(5) Viscosity Using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at a temperature of 25 ° C. in accordance with JIS Z 8803.

(6) Filterability Using a 400 mesh stainless steel filter (wire diameter 0.025 mm, plain weave), pressure filtration (air pressure 0.2 MPa) was performed. At this time, the weight of the emulsion that was completely filtered in 1 hour was measured. Practically, it is required that the filtration weight per hour is 100 kg or more, and the greater the filtration weight, the better the filterability.

(7) Storage stability The aqueous dispersion was stored in a thermostatic chamber at 25 ° C., and the storage stability was evaluated by the presence or absence of gel generation and the viscosity after 3 months.
○: No gel is formed.
Δ: Gelation of the aqueous dispersion does not occur, but the viscosity is increased by 200 mPa · s or more, or the viscosity is increased to twice or more of the initial value.
X: A gel is formed.

(8) Contact angle (coatability)
It calculated | required from the contact angle meter (the Kyowa Interface Science company make, CA-A type | mold). An aqueous dispersion was dropped on a substrate (Embret manufactured by Unitika Ltd.), the contact angle was measured, and the coating property was evaluated by permeability. When the contact angle is low, it penetrates into the base material, which hinders the formation of an adhesive layer on the base material surface.
A: 70 degrees or more. It hardly penetrates into the substrate.
○: 50 degrees or more and less than 70 degrees. It does not penetrate much into the substrate.
Δ: 30 degrees or more and less than 50 degrees. Penetration into the substrate is observed.
X: 0 degree or more and less than 30 degree | times. Easy to penetrate into the substrate.

The properties of the coating film formed from the aqueous dispersion were measured by the following method.
(9) Adhesive strength Polyester (Embret made by Unitika), polyethylene (LDPE made by Tamapoly), and paper (chemical fiber made by Azumi filter paper) were used as the planar substrate (liner), and each of the aqueous dispersions was used. A corrugated honeycomb coated with a bar coater # 10 and overlaid with a corrugated base material (flute) made of the same type of corrugated material and dried under conditions of 90 ° C. for 60 seconds. A laminate of structure was produced.
Using a tensile / compression universal testing machine (manufactured by INTESCO), the strength when the flat substrate and the corrugated plate substrate were separated was measured, and the adhesive strength was determined. The adhesive strength of the corrugated honeycomb structure is practical if it is 0.5 N / 25 mm or more, preferably 1.0 N / 25 mm or more, and more preferably 1.5 N / 25 mm or more.

(10) Water resistance (appearance evaluation after water immersion)
An aqueous adhesive was applied to a 25 μm thick polyethylene film (LDPE manufactured by Tamapoly Co., Ltd.) with a bar coater so as to have a dry thickness of 3 μm, and dried at 100 ° C. for 60 seconds to form a laminate. The obtained laminate was cut into 5 cm square, immersed in water at 20 ° C. for 24 hours, and the appearance was observed. The water resistance was evaluated in two stages according to the following indices.
○: No swelling of coating film ×: Swelling of coating film

Example 1
90 g of acid-modified polyolefin resin [manufactured by Arkema, Bondine HX-8290 (hereinafter referred to as HX-8290)], 60.0 g of isopropanol, A glass container was charged with 3.0 g of N, N-dimethylethanolamine (hereinafter referred to as DMEA), 3.0 g of triethylamine (hereinafter referred to as TEA), and 144.0 g of distilled water. When stirring was performed at a speed of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. And the system temperature was kept at 140-145 degreeC, and also it stirred for 30 minutes.
After cooling to 25 ° C. while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is used to produce a milky white uniform aqueous dispersion E. -1 was obtained.

Example 2
Using a stirrer equipped with a 1 liter sealed glass container with a heater, 90 g HX-8290, 60.0 g isopropanol, 3.0 g DMEA, 3.0 g TEA, and 144.0 g distilled water When charged in a glass container and stirred at a rotational speed of the stirring blade of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. And the system temperature was kept at 140-145 degreeC, and also it stirred for 30 minutes.
Thereafter, 60 g of isopropanol was removed from the solvent, and the mixture was diluted with water so that the solid concentration was 30% by mass. At this time, it was confirmed that triethylamine was also distilled off and the remaining amount became 0.2% by mass.
After cooling to 25 ° C. while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is used to produce a milky white uniform aqueous dispersion E. -2 was obtained.

Example 3
The same procedure as in Example 1 was performed except that the amount of resin charged was changed to 105.0 g, the amount of distilled water charged was changed to 129.0 g, and the solid content concentration was adjusted to 35% by mass. Dispersion E-3 was obtained.

Example 4
The same procedure as in Example 1 was performed except that the amount of resin charged was changed to 111.0 g, the amount of distilled water charged was changed to 123.0 g, and the solid content concentration was adjusted to 37% by mass. Dispersion E-4 was obtained.

Example 5
The same procedure as in Example 1 was carried out except that the resin charge was changed to 117.0 g, the water charge was changed to 117.0 g, and the solid content concentration was adjusted to 39% by mass. Body E-5 was obtained.

Example 6
An aqueous dispersion E-6 was obtained in the same manner as in Example 3 except that the amount of DMEA added was changed to 6.0 g and the amount of water charged was changed to 126.0 g.

Example 7
An aqueous dispersion E-7 was obtained in the same manner as in Example 1 except that triethanolamine was added instead of DMEA.

Example 8
An aqueous dispersion E-8 was obtained in the same manner as in Example 1 except that triethanolamine was added instead of TEA.

Examples 9-10
The same operation as in Example 1 was performed except that HX-8290 was used instead of HX-8290 instead of Aurolen 250S (Example 9) manufactured by Nippon Paper Chemicals and Umex 1001 (Example 10) manufactured by Sanyo Chemical. And aqueous dispersions E-9 and E-10 were obtained.

Comparative Example 1
The aqueous dispersion E-11 was obtained in the same manner as in Example 1 except that the amount of distilled water added was changed to 147 g and TEA was not added.

Comparative Example 2
The same procedure as in Example 1 was performed except that the amount of distilled water added was changed to 144 g, the amount of DMEA added was changed to 6.0 g, and TEA was not added.
Aqueous dispersion E-12 was obtained.

Comparative Example 3
The amount of distilled water added was changed to 147 g, and the same operation as in Example 1 was carried out except that DMEA was not added to obtain an aqueous dispersion E-13.

Comparative Example 4
An aqueous dispersion E-14 was obtained in the same manner as in Example 1 except that ammonia was added instead of TEA.

Comparative Example 5
An aqueous dispersion E-15 was obtained in the same manner as in Example 3 except that ammonia was added in place of DMEA.

Comparative Examples 6-7
The same operation as in Example 1 was carried out except that the acid-modified polyolefin resin was replaced with HX-8290 by using Aurolen 250S (Comparative Example 6) manufactured by Nippon Paper Chemicals Co., Ltd. and Umex 1001 (Comparative Example 7) manufactured by Sanyo Kasei Co., Ltd. And aqueous dispersions E-16 and E-17 were obtained.

Comparative Examples 8-9
Except for adding sodium hydroxide (Comparative Example 8) and potassium hydroxide (Comparative Example 9) instead of TEA, the same operations as in Example 1 were performed to obtain aqueous dispersions E-18 and E-19. .

Comparative Example 10
An aqueous dispersion E-20 was obtained in the same manner as in Example 3 except that the acid-modified polyolefin resin was replaced with HX-8290 and Primacor 5980I manufactured by Dow Chemical Company was used.

Comparative Example 11
The same operation as in Example 3 was carried out, except that TEA was not added, to obtain an aqueous dispersion E-21.

Comparative Example 12
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 90 g of acid-modified polyolefin resin HX-8290, 18 g of solid content of 50% aqueous solution of Nichigo G polymer vinyl alcohol-based resin manufactured by Nippon Synthetic Chemical Industry Co., Ltd. When 60.0 g of isopropanol and 132.0 g of distilled water were charged into a glass container and the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and were in a floating state. It was confirmed that Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. And the system temperature was kept at 140-145 degreeC, and also it stirred for 30 minutes.
After cooling to 25 ° C. while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is used to produce a milky white uniform aqueous dispersion E. -22 was obtained.

  The composition of the acid-modified polyolefin resin used is shown in Table 1, and the characteristics and evaluation results of the aqueous dispersions of Examples and Comparative Examples are shown in Table 2.

  Like the aqueous dispersions of Examples 1 to 10, the volume average particle size can be reduced by using two types of organic amine compounds, and the viscosity at 25 ° C. is a high viscosity of 1000 mPa · s or more. The filterability was excellent. In addition, since a high-viscosity aqueous dispersion is obtained, a sufficient amount can be applied on a substrate even when the application area is small, such as application with lines and dots, and high adhesive strength. The water resistance of the coating film was also good.

On the other hand, since the aqueous dispersions of Comparative Examples 1 to 9 had one kind of organic amine compound and two kinds were not used in combination, the volume average particle diameter was out of the preferred range, the viscosity was low, and it was applied with lines and spots. When applied to a substrate having a small coating area, the adhesive strength was poor.
Although the aqueous dispersion of Comparative Example 11 had only one organic amine compound, the viscosity could be increased by increasing the solid concentration, but the filterability was low and the productivity was poor. Moreover, it was inferior in storage stability.
Since the aqueous dispersion of Comparative Example 10 did not satisfy the viscosity of 1000 mPa · s or more, the adhesive strength was inferior when applied to a substrate having a small application area that was applied with lines or dots.
The aqueous dispersion of Comparative Example 12 was a high-viscosity aqueous dispersion using an emulsifier, had low filterability, poor productivity, and poor storage stability. Moreover, it was inferior to the water resistance of the coating film.

Claims (6)

  An aqueous dispersion comprising an acid-modified polyolefin resin, two or more organic amine compounds, and an aqueous medium, and having a viscosity at 25 ° C. of 1000 mPa · s or more.   The aqueous dispersion according to claim 1, wherein the acid-modified polyolefin resin contains an acrylate component.   The aqueous dispersion according to claim 1 or 2, wherein the organic amine compound has a boiling point of 50C to 210C.   The aqueous dispersion according to any one of claims 1 to 3, wherein the volume average particle diameter of the acid-modified polyolefin resin particles is 100 nm or less.   The aqueous dispersion according to any one of claims 1 to 4, wherein the total content of the organic amine compounds contained in the aqueous dispersion is 0.8% by mass or more and 5.0% by mass or less. 6. The method for producing an aqueous dispersion according to claim 1, wherein the raw material is an acid-modified polyolefin resin, two types of organic amine compounds, and an aqueous medium.