JP2007321105A - Method for producing aqueous resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aqueous resin dispersion, by which the aqueous polyolefin dispersion having small dispersed particle diameters and a narrow particle diameter distribution can simply be produced, and a solvent can readily be recovered after used. <P>SOLUTION: This method for producing the aqueous resin dispersion comprising a modified polyolefin and water is characterized by comprising a dissolution process for dissolving the modified polyolefin in a solvent (a) having solubility of 1.0 to 95.0 wt.% in water at 20°C, a dispersion process for adding water to the solution to disperse the modified polyolefin, and a distillation process for distilling away at least the solvent (a). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an aqueous resin dispersion containing polyolefin, which can be used for various applications such as paints and adhesives.

  Polyolefin is inexpensive and has excellent mechanical properties, heat resistance, chemical resistance, water resistance, and the like, and is therefore used in a wide range of fields. However, such polyolefins generally have a low polarity because they do not have a polar group in the molecule, and it is difficult to paint and bond, and improvements have been desired. For this reason, as a device for imparting good paintability and adhesiveness to polyolefin, so-called modified polyolefin is applied as a primer. These modified polyolefins have been generally applied after being dissolved in an organic solvent. In recent years, however, they have been required to be applied as an emulsified aqueous dispersion in terms of safety and health and environmental pollution. .

  However, since polyolefin has a low polarity as described above, it is difficult to emulsify, and attempts have been made to emulsify using a large amount of surfactant, or to reduce the particle size using a special emulsifier. For example, an emulsion obtained by dissolving a modified polyolefin in an aromatic solvent and making it aqueous using a basic substance or a surfactant (Patent Document 1), or an aqueous resin composition using an emulsifier having a special atomization mechanism A manufacturing method (Patent Document 2) and the like have been proposed. However, the method described in Patent Document 1 has a large dispersion particle diameter of 0.5 to 7 μm or more, and has a problem in terms of dispersion stability. In addition, the method described in Patent Document 2 uses a special emulsifier, which increases costs. In practice, a surfactant or a basic substance is essential, and the particle size of the aqueous dispersion is about 0.15 μm. There was also a problem that the mixing property was poor when mixed with an emulsion having a finer particle size at the limit.

As a method for reducing the dispersed particle size, there is also a method (Patent Document 3) in which a modified polyolefin is dissolved in an ether solvent such as propylene glycol monopropyl ether, water is added dropwise in the presence of a base to disperse, and then the solvent is distilled off. Proposed. However, since ether solvents are infinitely compatible with water at ordinary temperatures from room temperature to the boiling point, water and ether cannot be liquid-liquid separated after distilling off. The entire solvent must be recovered by distillation, causing environmental and process problems.
Japanese Patent Laid-Open No. 01-256556 JP-A-11-269206 JP 2004-018659 A

  An object of the present invention is to provide a method for easily producing an aqueous dispersion of polyolefin having a fine dispersed particle size and a narrow particle size distribution without using a special emulsifier. Moreover, it aims at providing the manufacturing method which can collect | recover the solvent after use easily.

As a result of intensive studies to achieve the above object, the present inventor has dissolved the modified polyolefin in a solvent that can be mixed with a small amount of water, and then dropped water to disperse the modified polyolefin and distill off the solvent. The present inventors have found that an excellent aqueous resin dispersion as described above can be easily produced, and have reached the present invention.
That is, the present invention is a method for producing an aqueous resin dispersion containing a modified polyolefin and water, wherein the modified polyolefin is a solvent (a) having a water solubility at 20 ° C. of 1.0 to 95.0% by weight. The present invention relates to a method for producing an aqueous resin dispersion, comprising: a dissolution step for dissolving in water, a dispersion step for adding water to the dispersion, and a distillation step for distilling off at least the solvent (a).

The present invention also relates to a method for producing an aqueous resin dispersion, wherein the solvent is one or more selected from the group consisting of alcohol, ketone and ester.
Moreover, this invention relates to the manufacturing method of the aqueous resin dispersion which performs the said melt | dissolution process and / or a dispersion | distribution process under the pressure of 1 MPa or less.
Moreover, this invention relates to the manufacturing method of the aqueous resin dispersion whose 50% particle diameter of the said aqueous resin dispersion is 0.2 micrometer or less.

  According to the method for producing an aqueous resin dispersion of the present invention, an excellent aqueous resin dispersion having a fine dispersed particle diameter, a narrow particle size distribution, and stably dispersed resin particles can be easily obtained. In addition, since the surfactant can be dispersed without adding a very small amount or substantially, there is an advantage that bleeding out due to the surfactant which has been a problem in the past can be suppressed. can get. Therefore, aqueous dispersions can be used for applications that have conventionally been applied as organic solvent solutions, which is also preferable in terms of safety and hygiene. Further, since it is not an organic solvent solution, VOC (volatile organic chemical substance) emission can be reduced, which is preferable from the environmental viewpoint. In addition, an aqueous dispersion having excellent properties can be obtained without substantially containing chlorine. When chlorine is not included, there are no problems such as dioxin and toxicity, which is very preferable in terms of environment.

Moreover, since the solvent used for dispersion is easily separated from water after being distilled off, it can be easily recovered, and is useful for both reuse and disposal of the solvent.
Furthermore, the coating film obtained by applying the paint containing the resin dispersion obtained by the present invention is excellent in water resistance, moisture resistance, oil resistance (GH resistance) and chemical resistance. For this reason, it is also suitable for a coating method such as a solvent-based lacquer type paint which is finished by only one coating. The resulting coating film shows good adhesion to polyolefin materials or plastic materials containing polyolefin, etc., and is also formed on difficult-to-adhere base materials such as untreated polypropylene, which are usually difficult to paint or bond. Yes. Therefore, the resin dispersion obtained by the present invention is extremely useful as a surface treatment agent, an adhesive, a coating agent, a paint, and the like for a crystalline olefin polymer.

Moreover, the laminated body obtained in this way is excellent in coating-film adhesiveness, and can be applied to a wide range of industrial products.
In the present invention, it is not always essential to exhibit all the effects, and it is only necessary to have one or more of the effects described above.

The method for producing an aqueous resin dispersion of the present invention relates to a method for producing an aqueous resin dispersion containing a modified polyolefin and water, and the solubility of water of the modified polyolefin at 20 ° C. is 1.0 to 95.0% by weight. It includes a dissolution step of dissolving in the solvent (a), a dispersion step of adding water to the solvent and dispersing, and a distillation step of distilling off at least the solvent (a).
In other words, the modified polyolefin is once dissolved in a solvent having a water solubility in a specific range, and then dispersed by adding water, and then the solvent is distilled off, so that the dispersed particle size is fine and the particle size distribution is narrow. A stably dispersed aqueous resin dispersion can be obtained. In addition, the used solvent can be easily recovered, and the production method is very excellent in terms of environment and process.

In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved.
First, the modified polyolefin of the present invention will be described.
The modified polyolefin of the present invention means a polyolefin modified with a hydrophilic polymer and / or an acid. That is, it is a polymer (C) formed by bonding a hydrophilic polymer (B) and / or an acidic group to a polyolefin (A). Such a polymer is preferable because of its excellent dispersibility in water.

This will be described in more detail below.
[1] Polyolefin (A)
As the polyolefin (A), various known polyolefins can be used, and are not particularly limited. For example, a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, ethylene or / and propylene and other comonomers, The copolymer of these is mentioned. Examples of the comonomer include α-olefin comonomers having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 8 carbon atoms, and more preferably an α-olefin comonomer having 2 to 6 carbon atoms.

Alternatively, two or more kinds of these α-olefin comonomers can also be used.
Also, a hydrogenated product of a copolymer of two or more monomers selected from a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, and an aromatic vinyl monomer and a conjugated diene monomer. , Etc. can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer.

  Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 50% by weight or less, preferably 30% by weight or less. However, for the purpose of reducing the environmental load, it is desirable that the polyolefin (A) does not substantially contain chlorine. The phrase “substantially containing no chlorine” means, for example, that the chlorination rate of polyolefin is less than 5% by weight.

  Specific examples of the polyolefin (A) include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, and chlorinated ethylene-propylene. Examples thereof include a copolymer, a chlorinated propylene-butene copolymer, a hydrogenated product of styrene-butadiene-styrene triblock (SEBS), a hydrogenated product of styrene-isoprene-styrene triblock (SEPS), and the like. A propylene homopolymer, a propylene-ethylene copolymer, and a propylene-butene copolymer are preferable, and a propylene-butene copolymer is more preferable. These may be chlorinated.

  The polyolefin (A) preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC (Gel Permeation Chromatography) and converted with a calibration curve of each polyolefin. A more preferable value of the lower limit value is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the lower limit, the degree of stickiness tends to decrease and the adhesion to the substrate tends to increase, and as the Mw is lower than the upper limit, the viscosity tends to decrease and the resin dispersion tends to be easily prepared. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

  The molecular weight distribution Mw / Mn represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the polyolefin (A) is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. This means that the molecular weight distribution is narrow and the molecular weight of the polyolefin is uniform. By using such a polyolefin (A), it is easy to control the particle size when dispersed in water, and the dispersed particles There is an advantage that a resin dispersion having a small diameter, a narrow particle size distribution, and a stable dispersion can be obtained. Preferably Mw / Mn is 3.0 or less. However, it is usually 1.0 or more.

  The polyolefin (A) preferably has a melting point Tm of 120 ° C. or lower. More preferably, it is 110 degrees C or less, More preferably, it is 100 degrees C or less. The melting point Tm lower than 120 ° C. is preferable because the crystallinity is low and the solubility in a solvent is improved, and the emulsification / dispersion work is easily performed at a low temperature. However, the melting point Tm of the polyolefin (A) is usually 25 ° C. or higher, preferably 35 ° C. or higher. It is advantageous in terms of high heat resistance, high hardness, and non-stickiness.

The content of propylene in the polyolefin (A) is preferably 50 mol% or more, more preferably 70 mol% or more. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.
A preferable example of the polyolefin (A) is one having an isotactic structure as a whole or a part as the stereoregularity of the propylene homopolymer or copolymer. For example, not only ordinary isotactic polypropylene but also isotactic block polypropylene, isotactic block and atactic block as described in JP-A-2003-231714 and US Pat. No. 4,522,982 A stereo block polypropylene having

  Further, when the polyolefin (A) is a propylene homopolymer, the [mmmm] pentad exhibiting isotactic stereoregularity is preferably in the range of 10% to 90%. A preferable value of the lower limit is 20%, more preferably 30%, more preferably 40%. A preferred value for the upper limit is 80%, more preferably 70%, more preferably 60%, and more preferably 55%. As a method for measuring the pentad ratio, the method described in JP-A-2003-231714 can be used. There is a tendency that the degree of stickiness becomes smaller as the value is lower than the lower limit, and the degree of crystallinity becomes lower and the preparation of the resin dispersion tends to become easier as the value is lower than the upper limit.

However, when the polyolefin (A) is a copolymer, the apparent stereoregularity is higher, and for example, it can be preferably used even if the ratio of the [mmmm] pentad is larger.
Alternatively, another preferred example of the polyolefin (A) is a propylene-α-olefin copolymer. Since such a copolymer has a lower melting point than a homopolymer such as polypropylene, a resin dispersion using the copolymer has an advantage that the baking temperature after coating can be lowered. More preferably, the propylene content is 50 mol% to 95 mol%. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate. Preferably it is 60 mol% or more, More preferably, it is 70 mol% or more. However, the propylene content is 95 mol% or less. Usually, when the propylene content is lowered, the melting point of the copolymer can be lowered, and for example, there is an advantage that the baking temperature after coating can be lowered. Preferably it is 90 mol% or less, More preferably, it is 85 mol% or less. Furthermore, the molecular weight distribution Mw / Mn of the copolymer is preferably 3.0 or less.

  The α-olefin is preferably an α-olefin having 2 to 8 carbon atoms, more preferably an α-olefin having 2 to 6 carbon atoms, still more preferably an α-olefin having 2 to 4 carbon atoms, and most preferably. Is 1-butene. The 1-butene content is preferably 5 mol% to 50 mol%. More preferably, it is 10 mol% or more, More preferably, it is 15 mol% or more. More preferably, it is 40 mol% or less, More preferably, it is 30 mol% or less. At this time, the copolymer may contain a small amount of a structural unit derived from an α-olefin other than propylene and 1-butene. For example, 10 mol% or less of ethylene may be included. More preferably, it is 5 mol% or less.

Commercially available products available as copolymers include Tuffmer XM-7070 and XM-7080 manufactured by Mitsui Chemicals.
Polyolefin (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
In summary, the polyolefin (A) is preferably a stereoblock polypropylene polymer having a propylene content of 50 mol% or more and having an isotactic block and an atactic block, and propylene-α-olefin. It is a copolymer or a combination thereof.

About the manufacturing method of polyolefin (A), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.
In the case of coordination polymerization, for example, a polymerization method using a Ziegler-Natta catalyst or a polymerization method using a single site catalyst or a Kaminsky catalyst can be used. A preferable production method includes a production method using a single site catalyst. The reason for this is that single-site catalysts are generally easy to control the reaction precisely due to the ligand design, yielding a polymer with a sharp molecular weight distribution and stereoregularity distribution, and have a melting point compared to polymers based on Ziegler-Natta catalysts. This is because the resin dispersion using this polymer can lower the baking temperature after coating because it is low. As the single site catalyst, for example, a metallocene catalyst or a Brookhart catalyst can be used. C ₁ symmetric type metallocene catalyst, C ₂ symmetric, C _2V symmetric, C _S symmetric like, it may be selected preferred catalyst in accordance with the stereoregularity of the polyolefin to be polymerized. Preferably, a C ₁ symmetric type or C ₂ symmetric type metallocene catalyst can be used.

  The polymerization may be any polymerization form such as solution polymerization, slurry polymerization, bulk polymerization, and gas phase polymerization. In the case of solution polymerization or slurry polymerization, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic carbonization such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrogen, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples include alcohols such as ethanol, n-propanol, isopropanol, and n-butanol; ethers such as dibutyl ether and tetrahydrofuran; and polar solvents such as dimethylformamide and dimethyl sulfoxide. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, hexane, heptane, cyclopentane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

[2] Polymer (C1) in which an acidic group is bonded to polyolefin (A)
The acidic group in the present invention refers to an electron pair accepting group, and is not particularly limited. For example, a carboxylic acid group (—COOH), a sulfo group (—SO ₃ H), a sulfino group (—SO ₂ H), and a phosphono group. _(-PO 2 H), and the like. Of these, a carboxylic acid group is preferred. Before being dispersed in water, the carboxylic acid group is at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic anhydride group (—CO—O—OC—), and a dicarboxylic anhydride monoester group. (Hereinafter, these may be collectively referred to as a carboxylic acid derivative group.) Examples of the carboxylic acid group include a (meth) acrylic acid group, a fumaric acid group, a maleic acid group or an anhydride group thereof, an itaconic acid group or an anhydride group thereof, and a crotonic acid group.

The binding amount of the acidic group is preferably in the range of 0.4 to 5 mmol, that is, 0.4 to 5 mmol / g per 1 g of the polyolefin (A). A more preferred lower limit is 0.6 mmol / g, and a more preferred lower limit is 0.8 mmol / g. A more preferred upper limit is 3 mmol / g, and a more preferred upper limit is 1.6 mmol / g. The higher the lower limit value, the greater the polarity of the polymer (C1) and the greater the hydrophilicity, so the dispersed particle size tends to decrease. The lower the upper limit value, the greater the adhesion to the crystalline polyolefin as the substrate. . In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mols of acidic groups (or reactive groups).
About the manufacturing method of polyolefin polymer (C1), the method similar to the manufacturing method of polyolefin (A2) which a reactive group couple | bonds with polyolefin (A) mentioned later in [3-1] can be used.

[3] Polymer (C2) formed by bonding hydrophilic polymer (B) to polyolefin (A)
The ratio of the polyolefin (A) to the hydrophilic polymer (B) is usually (A) :( B) = 100: 5 to 100: 500 parts by weight. If the ratio of the hydrophilic polymer (B) is smaller than this range, the polymer (C2) may not be dispersed well in water and the dispersed particle size may be very large, or may be aggregated or separated. On the other hand, when the ratio of the hydrophilic polymer (B) is larger than this range, the adhesion with the polyolefin-based molded product tends to deteriorate.

  As a method for producing a polymer (C2) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic polymer in which a polar monomer is polymerized in the presence of the polyolefin (A) and bonded to the polyolefin (A) is usually used. For example, a method (R1) for forming a conductive polymer (B), or a method (R2) for bonding a prepolymerized hydrophilic polymer (B) to a polyolefin (A), such as a polyolefin (A) or a hydrophilic polymer. What is necessary is just to select suitably according to the kind and combination of (B), the characteristic of the target polymer (C2), etc. Further, the hydrophilic polymer (B) may be bonded directly to the polyolefin (A), or the polymer (A2) in which a reactive group is bonded to the polyolefin (A) described below is used, and the hydrophilic polymer (B) is used. The polymer (B) may be bound.

[3-1] Polyolefin (A2) in which a reactive group is bonded to polyolefin (A)
Examples of the polyolefin (A2) having a reactive group include a copolymer (A2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization, or reactive. A polymer (A2b) obtained by graft-polymerizing a radically polymerizable unsaturated compound having a group to a polyolefin (A), and a polymer (A2c) obtained by converting a polyolefin having an unsaturated end group into an element group of Groups 13 to 17 Can be used.

  The copolymer (A2a) is obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is inserted into the main chain. Copolymer. For example, it can be obtained by copolymerizing an α-olefin such as ethylene, propylene or butene and an α, β-unsaturated carboxylic acid or anhydride such as acrylic acid or maleic anhydride. Specifically as a copolymer (A2a), a propylene-butene-maleic anhydride copolymer etc. can be used, for example. These may be used individually by 1 type and may be used in combination of 2 or more type. As the manufacturing method, the method described in [1] can be similarly used.

  The polymer (A2b) is obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin (A), and the unsaturated compound having a reactive group is grafted to the main chain. Yes. For example, polyolefins such as polyethylene and polypropylene, (meth) acrylic acid, fumaric acid, maleic acid or anhydride thereof, itaconic acid or anhydride thereof, crotonic acid, 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid It is a polymer grafted with 2-hydroxypropyl, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid (2-isocyanato) ethyl, or the like. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and others are based on this.

As polyolefin (A) of this reaction, the polyolefin which does not have the above-mentioned reactive group can be used.
Specific examples of the polymer (A2b) include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified propylene-ethylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include a modified propylene-ethylene copolymer and its chlorinated product, and an acrylic acid-modified propylene-butene copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used for the graft polymerization can be appropriately selected from ordinary radical initiators, and examples thereof include organic peroxides and azonitriles. Examples of organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. Diacyl peroxides such as oxides and peroxyesters such as t-butylperoxyisopropyl monocarbonate can be used. Examples of the azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide and t-butylperoxyisopropyl monocarbonate are particularly preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

The use ratio of the radical polymerization initiator and the graft copolymer unit is usually in the range of radical polymerization initiator: graft copolymer unit = 1: 100 to 2: 1 (molar ratio). Preferably it is the range of 1: 20-1: 1.
About the manufacturing method of a polymer (A2b), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. For example, solution modification method (method of reacting by heating and stirring in a solution), melt modification method (method of reacting by melting and heating and stirring without a solvent, or method of reacting by heating and kneading with an extruder), etc. It is done.

As a solvent in the case of producing in a solution, the solvents mentioned in [1] can be used similarly.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 300 ° C. More preferably, it is in the range of 80 to 200 ° C. in the case of the solution modification method, and is in the range of 150 to 300 ° C. in the case of the melt modification method. The reaction time is usually about 2 to 20 hours. The reaction time is usually about 2 to 20 hours.

  The polymer (A2c) is usually used for producing a block copolymer. For example, as described in JP-A No. 2001-288372, a double bond of a polyolefin (A) having a terminal double bond A polyolefin (A2c1) in which a part is converted into a group 13 element group such as a boron group or an aluminum group, or a double bond part of a polyolefin having a terminal double bond as described in JP-A-2005-48172 is halogenated. Polyolefin (A2c2) converted to element or polyolefin (A2c3) in which the double bond portion of a propylene polymer having a terminal double bond is converted to a mercapto group as described in JP-A-2001-98140 is used. be able to.

Examples of the method for producing the polyolefin (A) having a double bond include a method of causing α-hydrogen elimination during olefin polymerization and a method of thermally decomposing a propylene-based polymer at a high temperature.
Examples of a method for converting a double bond portion into a boron group or an aluminum group include a method in which an organic boron compound or an organic aluminum compound is reacted with a double bond in a solvent.

As a method for converting the double bond portion into a halogen element, for example, after converting the above-mentioned polyolefin having an organic boron group (A2c1) to a propylene-based polymer having a hydroxyl group by reacting a base and hydrogen peroxide solution, There is a method in which a halogen group-containing acid halide is reacted to convert it into a halogen group-containing ester group.
As a method for converting the double bond portion into a mercapto group, for example, there is a method in which thioacetic acid is reacted in the presence of a radical initiator and then treated with a base.

The production method of the polymer (A2c) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced. Any production method may be used, but a method of heating and stirring in a solution is preferably used. As a solvent in the case of producing in a solution, the solvents mentioned in [1] can be used similarly.
The content of the reactive group in the polymers (A2a) and (A2b) formed by bonding reactive groups may be in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g per 1 g of polyolefin. preferable. A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, and particularly preferably 0.5 mmol / g.

  The content of the reactive group in the polymer (A2c) formed by bonding the reactive group is usually 1 reactive group or less per polymer molecule from the production method, and is 1 / number average molecular weight Mn (mol / g) or less. And tends to be lower than those of the copolymers (A2a) and (A2b). Accordingly, it is preferably in the range of 0.004 to 2 mmol / g per gram of polyolefin. A more preferred lower limit is 0.005 mmol / g. A more preferred upper limit is 0.2 mmol / g.

  The higher the lower limit value, the greater the amount of the hydrophilic polymer (B) bound and the higher the hydrophilicity of the polymer (C2). Therefore, the dispersed particle size tends to decrease. There is a tendency for adhesion to polyolefin to increase. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

The polyolefin (A2) may be linear or branched. Polyolefin (A2) may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, both the polyolefin (A) itself and the polyolefin (A2) formed by bonding a reactive group are used in combination with the hydrophilic polymer (B), the characteristics of the target polymer (C2), etc. It can be used as appropriate. However, it is preferable to include at least a polyolefin (A2) formed by bonding a reactive group. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B) and various reactions that can be used for binding. Only the polyolefin (A2) formed by bonding a reactive group may be used.

Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, mercapto groups, and halogen groups. More preferably, it is at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group. These carboxylic acid groups and the like are not only highly reactive and easy to bond with hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.
Any of the polymers (A2a), (A2b), and (A2c) can be used, but the polymer (A2b) is usually preferred. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).

[3-2] Hydrophilic polymer (B)
In the following, only the polyolefin (A) will be described for simplification of explanation, but the same applies to the polyolefin (A2).
In the present invention, the hydrophilic polymer means a polymer having an insoluble content of 1% by weight or less when dissolved in water at 25 ° C. at a concentration of 10% by weight. The hydrophilic polymer (B) is not particularly limited as long as the effects of the present invention are not significantly impaired, and any of synthetic polymers, semi-synthetic polymers, and natural polymers can be used. It may have a reactive group.
Although it does not specifically limit as a synthetic polymer, For example, a poly (meth) acryl resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin etc. can be used. Examples of natural polymers include, but are not limited to, starch such as corn starch wheat starch, candy starch, potato starch, tapioca starch, and rice starch, seaweed such as fungi, agar and sodium alginate, gum arabic, tragacanth gum, and konjac. Animal materials such as quality materials, glue, casein and gelatin, fermented mucilages such as pullulan and dextrin, and the like can be used. The semi-synthetic polymer is not particularly limited, and for example, starch such as carboxyl starch, cationic starch, and dextrin, viscose, cellulose such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose can be used.

  Among these, a synthetic polymer that can easily control the degree of hydrophilicity and has stable characteristics is preferable. More preferred are acrylic resins such as poly (meth) acrylic resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, and polyether resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Highly hydrophilic polyether resins are most preferred.

  The acrylic resin used in the present invention is usually obtained by polymerizing an unsaturated carboxylic acid or its ester or anhydride by radical polymerization, anionic polymerization, or cationic polymerization. The bonding method with the polyolefin (A) is not limited, but, for example, a method of radical polymerization in the presence of polyolefin, an acrylic resin having a reactive group such as a hydroxyl group, an amino group, a glycidyl group or a (anhydrous) carboxylic acid group For example, a method of reacting with a polyolefin having a reactive group.

Preferably, the unsaturated carboxylic acid or its ester or anhydride exhibiting hydrophilicity is preferably (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (dimethyl) ethyl dimethylaminoethyl (meth) acrylate. And (meth) acrylamide.
In addition, a hydrophobic radical polymerizable compound (hydrophobic monomer) can be copolymerized within a range showing hydrophilicity. Examples of the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.

  Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and the like.

Examples of the (meth) acrylic acid ester monomer having an aryl group or arylalkyl group having 1 to 12 carbon atoms include phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, and the like. It is done.
Examples of the polymerizable vinyl monomer having a hydrocarbon group having 1 to 12 carbon atoms include vinyl acetate and styrene monomer.

Preferably, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate are used.
Alternatively, a radically polymerizable unsaturated compound can be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then modified with the hydrophilic polymer (B). Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. In this case, as the polyolefin (A), a polyolefin (A2) obtained by bonding a reactive group can be used, but usually a polyolefin (A) having no reactive group is used.

The polyvinyl alcohol resin is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.
The polyvinyl pyrrolidone resin is usually obtained by polymerizing vinyl pyrrolidone.
The polyether resin is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with the polyolefin (A) is not limited. For example, a method of ring-opening polymerization of a cyclic alkylene oxide in a polyolefin (A2) having a reactive group, a polyether polyol or a poly-polyester obtained by ring-opening polymerization, or the like. Examples thereof include a method of reacting a hydrophilic polymer having a reactive group such as ether amine with a polyolefin (A2) having a reactive group.

Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.
Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.

Or as a polyetheramine, you may use Huntsman's Jeffamine M series, D series, ED series, etc.
The hydrophilic polymer (B) used in the present invention preferably has at least one reactive group capable of reacting with the polyolefin (A) before bonding with the polyolefin (A). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and preferably have at least an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, a glycidyl group, and an isocyanate group, it is easy to bond a polyolefin and a hydrophilic polymer. The amino group may be primary, secondary, or tertiary, but is preferably a primary amino group.

The number of reactive groups may be one or more, but more preferably it has only one reactive group. When there are two or more reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with the polyolefin (A), resulting in gelation.
However, even if it has a plurality of reactive groups, it is sufficient if only one reactive group is more reactive than the others. For example, a hydrophilic polymer having a plurality of hydroxyl groups and one amino group having a higher reactivity is a preferred example. Here, the reactivity is the reactivity with the reactive group of the polyolefin (A).

  The hydrophilic polymer (B) in the present invention needs to be a polymer in order to impart sufficient hydrophilicity to the polymer (C2), and is a weight average molecular weight measured by GPC and converted by a polystyrene calibration curve. It is assumed that Mw is 200 or more. The lower limit is preferably 300, more preferably 500. However, the weight average molecular weight Mw is preferably 200,000 or less. A more preferable value of the upper limit value is 100,000, and more preferably 10,000. As the Mw is higher than the lower limit, the hydrophilicity of the polymer (C2) is increased and the dispersed particle size tends to be smaller and stably dispersed, and as the Mw is lower than the upper limit, the viscosity is low and the resin dispersion tends to be easily prepared. . The GPC measurement is performed by a conventionally known method using a commercially available apparatus using THF or the like as a solvent.

  The amount of the hydrophilic polymer (B) bonded to the polyolefin (A) is preferably in the range of 0.01 to 5 mmol, ie 0.01 to 5 mmol / g, per 1 g of the polyolefin (A). A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, particularly preferably 0.5 mmol / g, and most preferably 0.3 mmol / g. The higher the lower limit value, the higher the hydrophilicity of the polymer (C2) and the smaller the dispersed particle size tends to be stably dispersed, and the lower the upper limit value, the higher the adhesion to the crystalline polyolefin as the substrate. is there.

  The polyolefin (A) and the hydrophilic polymer (B) are a graft copolymer in which the hydrophilic polymer (B) is graft-bonded to the polyolefin (A), and one or both ends of the polyolefin (A) are highly hydrophilic. There may be a block copolymer of a polyolefin (A) and a hydrophilic polymer (B) containing a state in which the molecule (B) is bonded, and a graft copolymer is preferred. There is an advantage that the content of the hydrophilic polymer (B) can be easily controlled and the content of the hydrophilic polymer (B) can be easily increased as compared with the block copolymer.

The hydrophilic polymer (B) can be bonded to the polyolefin (A) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.
Reactions using reactive groups are those in which both polyolefin (A) and hydrophilic polymer (B) have reactive groups that are reacted to form covalent bonds or ionic bonds. Is done. Examples of this reaction include (ring-opening) esterification reaction of (anhydrous) carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening of primary or secondary amino group and epoxy group Reaction, (anhydrous) carboxylic acid group and primary or secondary amino group (ring-opening) amidation reaction or imidation reaction, carboxylic acid group and tertiary amino group quaternary ammonium reaction, carboxylic acid group and isocyanate Examples include amidation reactions of groups, urea reactions of primary or secondary amino groups and isocyanate groups, urethane reactions of hydroxy groups and isocyanate groups, and the like. Among them, the ring-opening amidation reaction or imidation reaction between a carboxylic anhydride group and a primary or secondary amino group is preferable in terms of high reactivity. Furthermore, amidation is more preferable than NH group than imidation. Since the hydrophilic group of COOH group remains in the group, it is preferable from the viewpoint of easy emulsification. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted with respect to one equivalent of the dibasic acid or anhydride.

[3-3] Method for Producing Polymer (C2) As a method for producing polymer (C2) by combining polyolefin (A) and hydrophilic polymer (B), a hydrophilic radical is usually used in the presence of polyolefin. There is a method (R1) for polymerizing a polymerizable unsaturated compound to form a hydrophilic polymer (B) bonded to a polyolefin, or a method (R2) for bonding a prepolymerized hydrophilic polymer (B) to a polyolefin. .

[3-3-1] Production method (R1) of polymer (C2)
In this method, a hydrophilic polymer (B) bonded to polyolefin is obtained by polymerizing a hydrophilic radically polymerizable unsaturated compound (hydrophilic monomer) in the presence of polyolefin. As a polymerization method of the hydrophilic radically polymerizable unsaturated compound, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic radical polymerizable unsaturated compound may be copolymerized as long as a hydrophilic polymer can be formed after polymerization. In either case, the polyolefin (A) having no reactive group or the polyolefin (A2) formed by bonding a reactive group can be used as the polyolefin.

  Specifically, for example, there is a method in which a hydrophilic radical-polymerizable unsaturated compound is graft-polymerized into a polyolefin-polyacrylic graft copolymer in the presence of a polyolefin (A) and a radical polymerization initiator such as a peroxide or an azo compound. is there. Further, as described in JP-A No. 2001-288372, a hydrophilic radical-polymerizable unsaturated compound is prepared in the presence of polyolefin (A2c1) having a group 13 element group such as a boron group or an aluminum group at its terminal and oxygen. There is a method of polymerizing into a block copolymer of polyolefin and polyacryl. Further, as described in JP-A No. 2004-131620 and JP-A No. 2005-48172, a polyolefin (A2c2) having a halogen atom at the terminal, copper halide, ruthenium halide, etc. are used, and an atom transfer living radical method is used. There is a method of using a block copolymer of a propylene polymer and polyacryl. Further, as described in JP-A No. 2001-98140, a polyolefin / polyacryl block copolymer is obtained by polymerizing a radical initiator and a hydrophilic radical-polymerizable unsaturated compound in the presence of a polyolefin having a mercapto group at its terminal. There is a method.

The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples include methacrylic acid dimethylaminoethyl quaternized product, vinyl pyrrolidone and the like.
Examples of the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.

  Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and the like.

Examples of the (meth) acrylic acid ester monomer having an aryl group or arylalkyl group having 1 to 12 carbon atoms include phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, and the like. It is done.
Examples of the polymerizable vinyl monomer having a hydrocarbon group having 1 to 12 carbon atoms include vinyl acetate and styrene monomer.

Preferably, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate are used.
Reactive surfactants and reactive emulsifiers can also be used as the aqueous radical polymerizable unsaturated compound. Examples thereof include alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts and salts of sulfates thereof described in JP-A-4-53802 and JP-A-4-50204. Among them, alkyl propenyl phenol ethylene oxide 20 mol adduct, 30 mol adduct, 50 mol adduct (Daiichi Kogyo Seiyaku, Aqualon RN-20, RN-30, RN-50) and alkyl propenyl phenol polyethylene oxide 10 mol. Adduct sulfate ammonium salt and 20 mol adduct sulfate ammonium salt (Daiichi Kogyo Seiyaku, Aqualon HS-10, HS-20) are used.

  Alternatively, the radically polymerizable unsaturated compound can be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then the hydrophilic polymer (B) can be modified. For example, a method in which t-butyl (meth) acrylate is polymerized and hydrolyzed under acidity to modify poly (meth) acrylic acid, or a method in which this is further neutralized with a base, or vinyl acetate is saponified after polymerization and polyvinyl Examples include a method of modifying to alcohol. Examples of the copolymerizable hydrophobic radical polymerizable unsaturated compound include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, as the propylene-α-olefin copolymer, a polyolefin (A2) having a reactive group can be used, but usually a polyolefin (A) having no reactive group is used.

Alternatively, there is a method in which a hydrophilic polymer (B) is obtained by polymerizing a hydrophilic ring-opening polymerization monomer or the like using a polyolefin (A2) having a reactive group and using this reactive group as an initiation terminal.
Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [3-1] can be used similarly.

[3-3-2] Production method (R2) of polymer (C2)
In this method, the previously polymerized hydrophilic polymer (B) is bonded to the polyolefin (A). In this case, as the hydrophilic polymer (B), those mentioned in [3-2] can be used.
Specifically, for example, when a hydrophilic monomer is first polymerized to form a hydrophilic polymer, an unsaturated double bond is left in the molecule, and then graft polymerization is performed on the polyolefin using a radical polymerizable initiator. There is a way. In this case, the polyolefin (A2) having a reactive group can be used as the polyolefin, but the polyolefin (A) having no reactive group is usually used.

  There is also a method in which a hydrophilic polymer having a reactive group at the terminal is first polymerized, and then this is bonded to a polyolefin (A2) formed by bonding a reactive group. The hydrophilic polymer having a reactive group at the terminal can be obtained by polymerizing a hydrophilic monomer using a compound having a reactive group as an initiator or a chain transfer agent. Alternatively, it can also be obtained by ring-opening polymerization of a hydrophilic ring-opening polymerization monomer such as an epoxy compound.

As the hydrophilic monomer that can be used at this time, various hydrophilic monomers listed in [3-3-1] can be used similarly.
Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [3-1] can be used similarly.

[4] Method for Producing Aqueous Resin Dispersion of Modified Polyolefin (Polymer (C)) The method for producing an aqueous resin dispersion of the present invention comprises the above-described modified polyolefin (polymer (C)) in water at 20 ° C. A dissolving step of dissolving in a solvent (a) having a solubility of 1.0 to 95.0% by weight, a dispersing step of adding water to disperse this, and a distillation step of distilling off at least the solvent (a). Including.

The solubility of water in a certain solvent is the amount of water that is saturatedly dissolved in the solvent among the mutual solubility of the solvent and water, and is represented by the content of water in 100 g of a solution in which water is saturatedly dissolved in the solvent. As a method for measuring the solubility of water, for example, the method described in Solvents Guide (edited by C. Marsden, Cleaver Hume Press Ltd., London (1963) p. 73) can be used.
For convenience, pp. 153, “Fourth edition, Experimental Chemistry Course 1, Basic Operation 1, The Chemical Society of Japan, Maruzen Publishing” can be referred to. Stir the water and solvent well at 20 ° C to reach saturation equilibrium and let stand, wait for the two phases to completely separate, sample the upper or lower phase with a pipette, etc., and quantify with gas chromatography To do.

The solvent (a) has a water solubility at 20 ° C. of 1.0 to 95.0% by weight. This is because if the solubility of water is less than 1.0% by weight, water which is a poor solvent for the modified polyolefin does not penetrate into the solvent (a) which is a good solvent, and the polyolefin does not form fine particles. Preferably it is 3.0 weight% or more, More preferably, it is 5.0 weight% or more.
On the other hand, when the solubility of water is more than 95.0% by weight, liquid-liquid separation with water after distilling with water is insufficient. Preferably it is 70.0 weight% or less, More preferably, it is 50.0 weight% or less, More preferably, it is 40.0 weight% or less, Most preferably, it is 30.0 weight% or less.

As such a solvent having an appropriate solubility in water, one or more selected from the group consisting of alcohol, ketone and ester are preferable. Alcohols, ketones and esters are not only moderately soluble in water, but are not too reactive, such as amine solvents, and are stable without forming oxides, such as ether solvents. It's also cheap.
For example, as alcohols, 1-pentanol (7.0 wt%), cyclohexanol (11.0 wt%), isobutanol (16.0 wt%), n-butanol (20.0 wt%), 2-butanol (44.0% by weight) and the like. Examples of ketones include methyl propyl ketone (3.3% by weight), cyclohexanone (9.5% by weight), methyl ethyl ketone (10.4% by weight) and the like. Examples of the esters include butyl acetate (1.9% by weight), propyl acetate (2.9% by weight), ethyl acetate (2.9% by weight), methyl acetate (8.0% by weight) and the like. The parentheses indicate the solubility of water at 20 ° C. (Source: Solvent Handbook (Kodansha) published in 1976).

These solvents can be used alone as the solvent (a).
A mixture of two or more solvents may be used as the solvent (a). In this case, the solubility of water at 20 ° C. after mixing may be in the above range. For example, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic aliphatic hydrocarbons, halogenated hydrocarbons, esters, ketones, and the like can be arbitrarily mixed within the range.

However, in consideration of recovery after distillation, ease of reuse, etc., it is preferable to use one solvent alone as the solvent (a).
The amount of the solvent (a) used is preferably in the range of 5 to 50% by weight after the modified polyolefin is dissolved. Considering the use efficiency of the solvent, it is desirable that the amount of the solvent (a) is not excessive with respect to the amount of the modified polyolefin, and it is preferably 5% by weight or more. More preferably, it is 10% by weight or more. On the other hand, 50% by weight or less is preferable in order to perform uniform stirring without excessively high solution viscosity and to obtain a uniform dispersion. More preferably, it is 40% by weight or less.

After the dissolution step of dissolving the modified polyolefin in such a solvent (a), the process proceeds to a dispersion step of adding water to the dispersion to disperse the modified polyolefin. You may heat as needed at the time of melt | dissolution and dispersion | distribution.
It is preferable to perform a melt | dissolution process and / or a dispersion | distribution process normally in the temperature range of 20 to 150 degreeC. Generally, the higher the temperature, the easier the dissolution and dispersion. More preferably, it is 40 ° C. or higher. However, if the boiling point of the solvent to be used is low, evaporation may proceed. Therefore, it is more preferably 100 ° C. or less, and further preferably 80 ° C. or less.

  Moreover, it is preferable to perform a melt | dissolution process and / or a dispersion | distribution process under the pressure of 1 Mpa or less normally. More preferably, it is 0.5 MPa or less, More preferably, it is 0.2 MPa or less. However, the pressure is usually 0.01 MPa or more. Most preferably, it is about 0.101 MPa. In general, dissolution and dispersion are easy at high temperature and high pressure, but an expensive apparatus that can withstand high temperature and high pressure is used, or a large amount of energy is required for high temperature and high pressure. According to the method for producing an aqueous resin dispersion of the present invention, it is not necessary to use a high pressure, and the resin can be easily dispersed. Therefore, an expensive apparatus is not required and a large amount of energy is not required. It is.

  The amount of water added in the dispersion step varies depending on the boiling point of the solvent (a), but is usually in the range of solvent (a): water = 5: 95 to 95: 5 by weight ratio. The water addition rate is preferably about 0.01 to 10 hours over 100 g of water with respect to 100 g of the modified polyolefin solvent (a) solution. Although the addition method is not particularly limited, it is usually added dropwise.

Next, the solvent (a) is distilled off from the mixture of the modified polyolefin, the solvent (a), and water. The pressure at this time is not particularly limited, and although it depends on the boiling point of the solvent (a) and the temperature of the dispersion, it is usually under reduced pressure, preferably in the range of 0.101 MPa to 0.001 MPa. At this time, a part of water is usually distilled together.
The amount of the solvent (a) in the aqueous resin dispersion after evaporation of the solvent (a) is usually 10% by weight or less. Preferably it is 5 weight% or less, More preferably, it is 2 weight% or less.

Although the following (x), (y), and (z) can be considered for the order of water addition and solvent (a) distillation, any of these methods can be used.
(X) Distillation is performed after adding all the water.
(Y) A part of the solvent (a) is distilled off after partly adding water. Repeat this operation.
(Z) The solvent (a) is continuously distilled off while adding water.

By the method for producing an aqueous resin dispersion of the present invention, a dispersion having a fine dispersed particle diameter and a narrow particle size distribution can be obtained. This dispersion is also excellent in dispersion stability.
The dispersed particle diameter of the resin (modified polyolefin) in the aqueous resin dispersion obtained by the present invention is 50% of the cumulative particle diameter from the finer particle diameter (50% particle diameter or 50% average particle diameter). Is usually 10 μm or less at a 50% particle size, and preferably 1 μm or less. According to the present invention, the 50% particle size can be 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the 90% particle diameter is determined, the 90% particle diameter can be more preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. Further, a reduction in the ratio of the 90% particle diameter to the 50% particle diameter means that the particle size distribution becomes narrow, and as a result, the dispersion stability is improved.

In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved. Accordingly, there is no particular limitation on the lower limit value of the dispersed particle size.
The solid content of the aqueous resin dispersion obtained by the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% by weight or more. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The smaller the amount of solid content, the lower the viscosity, the easier it can be applied to various application methods and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  In the resin dispersion of the present invention, a water-soluble resin or a resin that can be dispersed in water can be mixed and used as necessary within a range that does not significantly impair the effects of the present invention. For example, improvement in adhesion to the base film and various physical properties, specifically improvement in the appearance of coating (glossing or matting) and reduction in tackiness, coating strength, water resistance, weather resistance, abrasion resistance It is possible to improve the properties and solvent resistance. For example, the resins mentioned as the hydrophilic polymer (B) can be used. Examples of the resin that can be dispersed in water include acrylic resin, polyepoxy resin, polyester resin, polyurethane resin, melamine resin, and alkyd resin. After these resins are mixed with the modified polyolefin, a dispersion can be formed using the production method of the present invention.

  According to the production method of the present invention, the obtained resin dispersion can usually have a surfactant content of 15 parts by weight or less based on 100 parts by weight of the polymer (C). That is, the dispersed particle diameter of the resin is very small and the surfactant is very little or substantially free of surfactant. Conventionally, particularly in aqueous resin dispersions, there has been a problem that a stable dispersion having a fine dispersed particle diameter cannot be obtained unless a large amount of surfactant is used. According to the production method of the present invention, the dispersibility is as described above. Therefore, it is not necessary to use a large amount of a surfactant. Thereby, when this resin dispersion is used as a coating material, there is an advantage that a bleed-out can be suppressed and a coated product excellent in appearance can be obtained, and this resin dispersion can be used as a coating material on the outermost surface of coating. In addition, the water resistance and oil resistance (GH resistance) of the coating can be improved, and the resulting resin dispersion has any of adhesion, water resistance, moisture resistance, oil resistance (GH resistance), and chemical resistance. Will also be excellent.

  A smaller amount of the surfactant is preferred, and the surfactant content of the resin dispersion is preferably 10 parts by weight or less with respect to 100 parts by weight of the polymer (C). More preferably, it is 5 parts weight or less, More preferably, it is 2 parts weight or less. It can also be substantially free of surfactant. “Substantially free of surfactant” means less than 1 part by weight per 100 parts by weight of the polymer (C).

  As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. As the surfactant, those having an alkyl group, alkenyl group, alkylaryl group or alkenylaryl group having 4 or more carbon atoms as a hydrophobic group are usually used. Preferably it is C8 or more, More preferably, it is C12 or more. However, it usually has 30 or less carbon atoms.

  Examples of nonionic surfactants include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene sorbitan monolaurate. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate, and the like. Examples of the cationic surfactant include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and the like. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.

Moreover, what is called a reactive surfactant etc. in which said surfactant has a radically polymerizable functional group can also be used. When a reactive surfactant is used, the water resistance of a film formed using this resin dispersion can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).
In addition, since nonionic surfactant is hard to reduce water resistance compared with other surfactant, nonionic surfactant may be included a little more. For example, when the surfactant other than the nonionic surfactant should be 5 parts by weight or less with respect to 100 parts by weight of the polymer (C), the nonionic surfactant may be 10 parts by weight or less.

Further, according to the present invention, there is an advantage that it is not necessary to use a chlorinated polyolefin and the environmental load can be reduced.
An acidic substance or a basic substance can be added to the resin dispersion of the present invention as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Basic substances such as inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine Organic bases such as diethylamine, triethylamine, tripropylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. .

It is preferable to add a basic substance when the resin has an acidic group, and an acidic substance when the resin has a basic group. There is an advantage that the hydrophilicity of the resin can be increased and the dispersed particle size can be made finer.
The resin dispersion of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors; colorants such as titanium oxide and organic pigments; conductivity imparting agents such as pigments, carbon black and ferrite, dyes, pigment dispersions Various additives such as additives, leveling agents, antifoaming agents, thickeners, preservatives, fungicides, rust inhibitors and wetting agents may be used in combination.

Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
In order to further improve various coating performances such as water resistance and solvent resistance. The crosslinking agent can be added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin in the dispersion. As the crosslinking agent, there can be used 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. Among them, an isocyanate compound, Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

  When the resin dispersion obtained by the production method of the present invention is used for applications such as primer, paint, ink, etc., a hydrophilic organic solvent other than water is used for the purpose of increasing the drying speed or obtaining a surface with a good finish. Can be blended. Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, and ethers thereof.

  The resin dispersion obtained by the production method of the present invention is applied as a coating material to a substrate and heated to form a resin layer, whereby a laminate can be obtained. The substrate may be in any shape, such as a film, sheet, or plate. This laminate can be used in various applications such as for automobiles, home appliances, and building materials.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.
In the following examples, the operation was performed under atmospheric pressure (0.101 MPa) unless otherwise specified.
<Physical property measurement method and evaluation method>
(1) Stereoregularity The stereoregularity [mmmm] of polypropylene was measured by a ¹³ C-NMR spectrum measurement method with an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a flip angle of 90 ° and a pulse interval of 5 T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, since the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition. Measurement was carried out by integrating over 20 hours.

(2) Molecular weight First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by weight of BHT was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a PTFE (polytetrafluoroethylene) filter having a pore diameter of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed by using TSKgel GM H-HT (30 cm × 4) as a column and Waters GPC150CV equipped with an RI detector. As measurement conditions, the injection amount of the sample solution: 500 μl, column temperature: 135 ° C., solvent: orthodichlorobenzene, flow rate: 1.0 ml / min were employed.

When calculating the molecular weight, use a commercially available monodisperse polystyrene as a standard sample, create a calibration curve for the retention time and molecular weight from the polystyrene standard sample and the viscosity formula of polypropylene, and calculate the molecular weight of the propylene-based polymer. went.
[Η] K · Mα is used as the viscosity formula, K = 1.38E-4 and α = 0.70 for polystyrene, and K = 1.03E− for propylene-based copolymers. 4, α = 0.78 was used.

(3) Graft rate 200 mg of the polymer and 4800 mg of chloroform are put into a 10 ml sample bottle and heated at 50 ° C. for 30 minutes to be completely dissolved. Chloroform was placed in a liquid cell having a material NaCl and an optical path length of 0.5 mm as a background. Next, the dissolved polymer solution was placed in a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation at 32 times. The graft ratio of maleic anhydride was calculated using a calibration curve prepared by measuring a solution of maleic anhydride in chloroform. Then, from the area of the absorption peak of the carbonyl group (maximum peak in the vicinity of 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer is calculated based on a separately prepared calibration curve, and this is calculated as the graft ratio ( % By weight).

(4) Dispersion particle diameter It measured using Microtrac UPA (model 9340 batch type dynamic light scattering method / laser Doppler method) by Nikkiso Co., Ltd. The dispersion time is 0.9 g / cm ³ , the particle shape is spherical, the particle refractive index is 1.50, the dispersion medium is water, and the dispersion medium is 1.33, and the measurement time is 120 seconds or 180 seconds. The 50% particle diameter and the 90% particle diameter were determined cumulatively from the finer particle diameter in terms of volume.

[Production Example 1: Production of polyolefin]
In a 1,000 ml round bottom flask, 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved with stirring. In this solution, 16.7 g of commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried overnight at 110 ° C. 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 this suspension was added 80 ml of toluene, 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 another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd.) was collected, 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- A toluene diluted solution of 131 mg (57 μmol) of 5,6,7,8-tetrahydro-1-azulenyl) hafnium was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry. According to the method described in Japanese Patent No. 002310).

  Next, 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene 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 63 ° C., and the total pressure during polymerization was kept constant at 0.65 MPa, and stirring was continued for 2 hours at the same temperature. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 11 kg (1.4 kg propylene polymer) of 12.8 wt% propylene polymer toluene solution was obtained. The resulting polypropylene had a weight average molecular weight Mw of 180,000 and stereoregularity [mmmm] of 47.5%.

[Production Example 2: Production of maleic anhydride-modified polypropylene]
Into a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 650 g of toluene and 350 g of the polypropylene obtained in Production Example 1 were placed, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After heating, 28 g of maleic anhydride was added, 14 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the system was cooled to near room temperature, acetone was added, and the precipitated polymer was filtered off. Furthermore, precipitation and filtration were repeated with acetone, and the resulting polymer was dried under reduced pressure to obtain a maleic anhydride-modified polymer in the form of a white powder. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 2.1% by weight (0.21 mmol / g as maleic anhydride groups, 0.42 mmol as reactive groups). / G). The weight average molecular weight was 95,000.

[Production Example 3: Production of polyalkylene glycol-modified polypropylene]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 30 g of maleic anhydride-modified polypropylene obtained in Production Example 2 and 70 g of toluene were added, and the mixture was heated to 110 ° C. and completely dissolved. Next, a solution prepared by dissolving 9 g (9 mmol) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) in 9 g of toluene was added at 110 ° C. For 3 hours.

After cooling, toluene was distilled off under reduced pressure to obtain 39 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride near 1784 cm ⁻¹ disappears, and the maleic anhydride-modified polypropylene and the polyetheramine are completely bonded. Observed. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

[Example 1]
To 20 g of the polyalkylene glycol-modified polypropylene obtained in Production Example 3, 80 g of isobutanol (water solubility at 20 ° C .: 16.4% by weight) was added and completely dissolved at 100 ° C. Next, the solution was cooled to 65 ° C., and 120 g of pure water was added dropwise at the same temperature over 1 hour to obtain a cloudy solution. The operation so far was performed under atmospheric pressure (0.101 MPa).

Subsequently, this liquid was cooled to 40 ° C., and distillation was started at a pressure of 0.02 MPa. Further, the pressure was gradually reduced from 0.02 MPa to 0.004 MPa, and isobutanol and water were distilled off until the resin concentration reached 25% by weight to obtain a pale yellow translucent aqueous resin dispersion. The amount of isobutanol in the dispersion was 5% by weight or less. The distillate was 140 g.
As a result of measuring the dispersed particle size, the 50% particle size was 0.015 μm, and the 90% particle size was 0.021 μm. Further, the distillate was separated into an upper isobutanol layer and a lower aqueous layer, and liquid-liquid separation was possible. The results are shown in Table-1.

[Example 2]
An aqueous resin dispersion was obtained in the same manner as in Example 1 except that isobutanol was changed to n-butanol (water solubility at 20 ° C .: 20.0 wt%) and the amount of pure water dropped was changed to 200 g. It was. The state before distilling off was a cloudy solution as in Example 1. The amount of n-butanol in the dispersion was 10% by weight or less. The distillate was 220 g.
As a result of measuring the dispersed particle size, the 50% particle size was 0.011 μm, and the 90% particle size was 0.015 μm. The distillate was separated into an upper n-butanol layer and a lower aqueous layer, and liquid-liquid separation was possible.

[Comparative Example 1]
An aqueous resin dispersion was obtained in the same manner as in Example 1 except that isobutanol was changed to THF (water solubility at 20 ° C .: infinite) and the temperature at the time of dissolution was changed to 65 ° C. The amount of THF in the dispersion was 5% by weight or less. The distillate was 140 g.
As a result of measuring the dispersed particle size, the 50% particle size was 0.011 μm, and the 90% particle size was 0.014 μm. The distillate was in a uniform layer and could not be separated.

[Comparative Example 2]
The same operation as in Example 1 was performed except that isobutanol was changed to toluene (water solubility: 0.05% by weight). As water was added dropwise, the solution became cloudy and finally solids were separated. A dispersion was not obtained.

[Comparative Example 3]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 20 g of maleic anhydride-modified polypropylene obtained in Production Example 2 and 80 g of toluene were added, and the mixture was heated to 110 ° C. and completely dissolved. Next, after cooling to 50 ° C., polyoxyethylene cetyl ether (Emulgen 220 manufactured by Kao Corporation, nonionic surfactant, HLB = 14.2) 5 g, and polyoxyethylene lauryl ether (Emulgen 147 manufactured by Kao Corporation) , 5 g of nonionic surfactant, HLB = 16.3) was added and dissolved, and then cooled to 35 ° C.

  After 100 g of water was added and sufficiently stirred, emulsification was carried out at 21000 rpm for 3 minutes using an internal shear type emulsifier CLEARMIX CLM-0.8S (manufactured by M Technique). Subsequently, an aqueous solution obtained by diluting 2-amino-2-methyl-1-propanol with water to 10% by weight was added to the system, and the pH was adjusted to 8. The crude emulsion was gradually reduced in pressure from 0.02 MPa to 0.0045 MPa at a temperature of 50 ° C., and toluene and water were distilled off to obtain a milky white aqueous resin dispersion having a concentration of 25% by weight. The amount of toluene in the dispersion was 5% by weight or less.

  As a result of measuring the dispersed particle size, the 50% particle size was 0.25 μm, and the 90% particle size was 3.1 μm. The distillate was separated into an upper toluene layer and a lower aqueous layer, and liquid-liquid separation was possible.

Claims (4)

A method for producing a resin dispersion containing a modified polyolefin and water,
A dissolving step in which the modified polyolefin is dissolved in a solvent (a) having a water solubility of 1.0 to 95.0% by weight at 20 ° C., a dispersing step in which water is added and dispersed therein, and at least the solvent ( The manufacturing method of the aqueous resin dispersion characterized by including the distillation process which distills a) away.   The method for producing an aqueous resin dispersion according to claim 1, wherein the solvent (a) is one or more selected from the group consisting of alcohol, ketone and ester.   The manufacturing method of the aqueous resin dispersion of Claim 1 or 2 which performs the said melt | dissolution process and / or a dispersion | distribution process under the pressure of 1 Mpa or less.   The manufacturing method of the aqueous resin dispersion of any one of Claims 1 thru | or 3 whose 50% particle diameter of the said aqueous resin dispersion is 0.2 micrometer or less.