JP4623236B2 - Aqueous resin dispersion and method for producing the same, paint, laminate and method for producing the same - Google Patents

Description

  The present invention relates to an aqueous dispersion containing a polyolefin resin and a coating material containing the same.

  Polyolefins such as propylene polymers and propylene-α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are 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, various methods have been tried, such as chemically treating the surface of a molded product of polyolefin with a chemical or the like, and oxidizing the surface of the molded product by a method such as corona discharge treatment, plasma treatment, or flame treatment. Yes. However, in these methods, not only a special apparatus is required but also the effect of improving paintability and adhesiveness is not always sufficient.

  Therefore, as a device for imparting good paintability and adhesiveness to polyolefins such as propylene polymers by a relatively simple method, so-called chlorinated polypropylene, acid-modified propylene-α-olefin copolymers, and further acid-modified chlorine Polypropylene has been developed. Such a modified polyolefin is applied as a surface treatment agent, an adhesive, a paint or the like to the surface of the polyolefin molded body. The modified polyolefin is usually applied in the form of a solution of an organic solvent or a dispersion in water. In general, an aqueous dispersion is preferably used from the viewpoint of health and safety and reduction of environmental pollution.

  For example, an aqueous resin in which acid-modified chlorinated polypropylene is made aqueous using a surfactant and a basic substance (Patent Document 1) or an aqueous resin in which acid-modified polyolefin is made aqueous using a surfactant and a basic substance (Patent Document 2). However, in these methods, it is necessary to add a large amount of a surfactant in order to reduce the dispersed particle size. As a result, there is a problem that paints using such an aqueous dispersion have poor water resistance and chemical resistance. there were. Further, the surfactant may bleed out to the painted surface after coating, resulting in poor appearance, and further improvement has been desired.

  There is also an aqueous resin (Patent Document 3) in which a polymer obtained by block copolymerization of a functional segment with a polyolefin segment is dispersed in water, but the dispersed particle size is not sufficiently fine, and no surfactant is used. However, there was a demand for further improvement.

JP-A-3-182534 Japanese Patent Laid-Open No. 6-256592 JP 2001-288372 A

  INDUSTRIAL APPLICABILITY The present invention is an aqueous dispersion of a resin that is fine and stable in dispersion particle size, is suppressed as a bleed-out due to a surfactant, and is useful as a surface treatment agent, an adhesive or a paint for a crystalline olefin polymer A body and a method for producing the same are provided.

As a result of intensive studies to achieve the above object, the present inventor has found that a resin dispersion having excellent characteristics can be obtained by bonding a hydrophilic polymer to polyolefin in a predetermined ratio and dispersing it in water. The present invention has been reached.
That is, in the present invention, the hydrophilic polymer (B) which may have a reactive group in the polyolefin (A) having a reactive group is converted into (A) :( B) = 100: 5 to 100: 500 ( The polymer (C) bonded at a ratio of (weight ratio) is a resin dispersion in which water is dispersed with a 50% particle diameter of 1 μm or less, and the hydrophilic polymer (B) is a polyether resin. It is related with the resin dispersion characterized by being.

The present invention also relates to the polymer (C) is a resin dispersion you are dispersed in water in less than 90% particle size 1 [mu] m.

The present invention also relates to a resin dispersion in which the hydrophilic polymer (B) has a reactive group, and the reactive group is an amino group .

The present invention further relates to a resin dispersion in which the polyolefin (A) is a copolymer of ethylene and / or propylene and another comonomer.

Moreover, this invention relates to the resin dispersion whose weight average molecular weight Mw of the said hydrophilic polymer (B) is 200-200,000 .

The present invention also relates to a resin dispersion in which the polyolefin (A) has a reactive group, and the reactive content is 0.01 to 5 mmol per 1 g of polyolefin. Further, the present invention provides the polyolefin (A) having a propylene content of 50 mol% or more and having a stereoblock polypropylene polymer having an isotactic block and an atactic block, and / or a propylene-α-olefin copolymer. The present invention relates to a resin dispersion which is a polymer. Furthermore, the present invention relates to a resin dispersion in which the polyolefin (A) has a carboxylic acid derivative group as a reactive group, and the polyolefin (A) is a carboxylic acid group or a dicarboxylic acid anhydride. And a resin dispersion having one or more reactive groups selected from the group consisting of a group and a dicarboxylic anhydride monoester group.

Moreover, this invention relates to the resin dispersion whose surfactant content of a resin dispersion is 20 weight part or less with respect to 100 weight part of polymers (C) .

The present invention also relates to a resin dispersion in which the melting point Tm of the polyolefin (A) is 120 ° C. or less . Furthermore, this invention relates to the resin dispersion whose molecular weight distribution Mw / Mn of the said polyolefin (A) is 5 or less.

  According to the present invention, since the polymer (C) is extremely excellent in water dispersibility, there is an advantage that the dispersed particle diameter is fine and can be dispersed stably. Moreover, since it can disperse | distribute without adding surfactant substantially, there exists an advantage which can suppress the bleed-out by the surfactant which was a problem conventionally, and, as a result, the coated article of the outstanding external appearance is obtained. 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.

Further, according to the method for producing a resin dispersion of the present invention, an excellent aqueous resin dispersion having a fine dispersed particle diameter and stably dispersing resin particles can be easily obtained.
Furthermore, the coating film obtained by applying the paint containing the resin dispersion of 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.
Further, when the polymer (C) of the present invention is used in combination with another resin to form a composite aqueous resin dispersion, the physical property value derived from the other resin is improved, specifically, the strength, water resistance, and weather resistance of the coating film. Property, abrasion resistance, solvent resistance and the like can be improved.

Therefore, the resin dispersion of 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.
Further, the laminate of the present invention is excellent in coating film adhesion 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 resin dispersion of the present invention is a polymer obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio). (C) is dispersed in water. That is, a resin dispersion having excellent characteristics can be obtained by bonding a hydrophilic polymer to polyolefin at a predetermined ratio and dispersing it in water.
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.

  The ratio of the polyolefin (A) to the hydrophilic polymer (B) is (A) :( B) = 100: 5 to 100: 500 (parts by weight). As the ratio of the hydrophilic polymer (B) is larger, the polymer (C) is more easily dispersed in water, and the dispersed particle size is smaller and stably dispersed. For this reason, the ratio of (B) is made larger than (A) :( B) = 100: 5. On the other hand, the smaller the ratio of the hydrophilic polymer (B), the higher the adhesion with the polyolefin substrate. For this reason, the ratio of (B) is made smaller than (A) :( B) = 100: 500.

  As a method for producing a polymer (C) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) and bonded to the polyolefin (A). Examples include the method (R1) for forming the hydrophilic polymer (B), or the method (R2) for bonding the prepolymerized hydrophilic polymer (B) to the polyolefin (A). The combination may be appropriately selected according to the characteristics of the target polymer (C). Moreover, as polyolefin (A), polyolefin (A1) which does not have a reactive group, or polyolefin (A2) which has a reactive group can be used.

Hereinafter, each case will be described separately.
[1] Polyolefin (A)
As polyolefin (A) of this invention, polyolefin (A1) which does not have a reactive group, or polyolefin (A2) which has a reactive group can be used.
[1-1] Polyolefin having no reactive group (A1)
As the polyolefin (A1), various known polyolefins and modified 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 Copolymers with other comonomers may be 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. The polyolefin (A1) may be linear or branched.

  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 (A1) 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 (A1) include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, and chlorinated ethylene-propylene copolymer. Polymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SBS) (SEBS), styrene-isoprene-styrene block copolymer ( SIS) hydrogenated product (SEPS). Preferably, it is a propylene homopolymer or a copolymer of propylene and another α-olefin, and these may be chlorinated. More preferred are propylene homopolymer, ethylene-propylene copolymer, propylene-butene copolymer, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, or chlorinated propylene-butene copolymer. More preferred are propylene homopolymer, ethylene-propylene copolymer, and propylene-butene copolymer.

  The polyolefin (A1) 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 to the number average molecular weight Mn of the polyolefin (A1) is preferably 10 or less, more preferably 5 or less, and even more 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 (A1), it becomes 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 (A1) 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 (A1) 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 (A1) 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 (A1) is one having an isotactic structure as a whole or a part of 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

  When the polyolefin (A1) 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 (A1) 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 (A1) 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 (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.
In summary, the polyolefin (A1) 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 (A1) of this invention, if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, What kind of 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. It can be preferably used C ₁ symmetric type, C ₂ symmetric metallocene catalyst.

  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.

[1-2] Polyolefin (A2) having a reactive group
As the polyolefin (A2) having a reactive group, for example, 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 polyolefin polymerization, or a reaction A polymer (A2b) obtained by graft-polymerizing a radically polymerizable unsaturated compound having a functional group to a polyolefin, and a polymer (A2c) obtained by converting a polyolefin having an unsaturated end group to an element group of Groups 13 to 17 Can do.

  Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, and isocyanate groups. More preferably, the polyolefin (A2) has 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 (hereinafter collectively referred to as a carboxylic acid derivative group). Sometimes.). These carboxylic acid derivative groups are not only highly reactive and easy to bind to hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.

  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 [1-1] 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, and the unsaturated compound having a reactive group is grafted to the main chain. 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 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 its chlorine. And acrylic acid-modified polypropylene and its chlorinated product, acrylic acid-modified propylene-ethylene copolymer and its chlorinated product, acrylic acid-modified propylene-butene copolymer and its chlorinated product, and the like. 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, What kind of 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 manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 300 ° C. More preferably, the temperature is in the range of 80 to 200 ° C. in the case of the solution modification method, and the temperature 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 in the production of a block copolymer. For example, as described in JP-A-2001-288372, a double bond part of a polyolefin having a terminal double bond is boron. Group, a polyolefin (A2c1) converted to a group 13 element group such as an aluminum group, and a double bond portion of a polyolefin having a terminal double bond as described in JP-A-2005-48172 is converted to a halogen element Polyolefin (A2c3), as described in JP-A-2001-98140, a polyolefin (A2c3) obtained by converting a double bond portion of a propylene-based polymer having a terminal double bond into a mercapto group can be used.

  Examples of the method for producing a polyolefin 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, and 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 manufacturing in a solution, the solvent quoted in [1-1] 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, still 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.

Polyolefin (A2) may be used individually by 1 type, and may be used in combination of 2 or more type. Further, as the polyolefin (A2), any of (A2a), (A2b), and (A2c) can be used, but the polymer (A2b) is usually preferable. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).
In the present invention, as the polyolefin (A), both the polyolefin (A1) having no reactive group and the polyolefin (A2) having a reactive group are combined with the hydrophilic polymer (B) or the desired heavy weight. It can be used as appropriate according to the characteristics of the coalesced (C). However, it is preferable to include at least a polyolefin (A2) having 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) having a reactive group may be used.

[2] Hydrophilic polymer (B)
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. 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) formed by bonding a reactive group can be used, but usually a polyolefin (A1) having no reactive group is used.

  The polyvinyl alcohol resin used in the present invention 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 used in the present invention is usually obtained by polymerizing vinyl pyrrolidone.

  The polyether resin used in the present invention 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 more preferably is 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 must be a polymer in order to impart sufficient hydrophilicity to the polymer (C), 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 (C) is increased and the dispersed particle size tends to be smaller and stably dispersed. 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 (C) 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] Polymer (C)
As a method for producing a polymer (C) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) and bonded to the polyolefin (A). There is a method (R1) for forming the hydrophilic polymer (B) or a method (R2) for bonding the previously polymerized hydrophilic polymer (B) to the polyolefin (A). In any case, the polyolefin (A) can be used together with a polyolefin (A1) having no reactive group or a polyolefin (A2) having a reactive group.

[3-1] Method for producing polymer (C) (R1)
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 method for polymerizing the hydrophilic monomer, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic radical polymerizable unsaturated compound (hydrophobic monomer) may be copolymerized as long as a hydrophilic polymer can be formed after polymerization. In either case, the polyolefin (A1) 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. Also, as described in JP-A-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 monomer is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethyl (meth) acrylate Examples thereof include aminoethyl quaternized products and vinyl pyrrolidone. 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, a radically polymerizable unsaturated compound can be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to a polyolefin, 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.

  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. 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 polyolefin (A), a polyolefin (A2) formed by bonding a reactive group can be used, but usually a polyolefin (A1) 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.

  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 [1-1] can be used similarly.

[3-2] Method for producing polymer (C) (R2)
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 (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 the polyolefin (A) is converted into a polyolefin (A) using a radical polymerizable initiator. There is a method of graft polymerization. In this case, polyolefin (A2) having a reactive group may be used as polyolefin (A), but polyolefin (A1) having no reactive group is usually used.

  Further, there is 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) having 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 [3-1] can be used in the same manner. 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 [1-1] can be used similarly.

[4] Method for Producing Aqueous Resin Dispersion The method for producing a resin dispersion according to the present invention is not particularly limited. For example, after preparing a mixture of polymer (C), water, and a solvent other than water, Examples thereof include a method of forming an aqueous dispersion by removing the solvent from the mixture, and a method of adding water to form a dispersion after melting at a temperature equal to or higher than the temperature at which the polymer (C) melts.

  The former is preferred. According to the method of preparing an aqueous dispersion by preparing a mixture of a polymer, water, and a solvent other than water and then removing the solvent from the mixture, an aqueous dispersion having a fine particle size can be easily produced. When preparing a mixture, you may heat as needed. The temperature is usually 30 to 150 ° C. The final ratio of the solvent other than water in the resin dispersion is usually 50% or less. It is preferably 20% or less, more preferably 10% or less, and particularly preferably 1% or less.

  Among these, a method of adding a solvent other than water to the polymer (C) and adding water after heating and dissolving as necessary is more preferable because an aqueous dispersion having a finer particle size can be easily produced. The temperature at the time of dissolution in a solvent or at the time of addition of water is usually 30 to 150 ° C. Moreover, when dissolving once in solvents other than water, after adding water, you may distill a solvent off. The ratio of the solvent other than water in the resin dispersion is as described above.

  Examples of the solvent other than water used in the present method include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic systems such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrocarbons, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol and other alcohols, dipropyl alcohol Organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, etc. , Polar solvents such as dimethylformamide and dimethyl sulfoxide.

  Among them, a solvent that dissolves 1% by weight or more in water is preferable, and more preferably 5% by weight or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol , Isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.

  An apparatus for producing a resin dispersion by adding water after being dissolved in a solvent and in a molten state is not particularly limited. For example, a reaction kettle with a stirring device, a uniaxial or biaxial kneader can be used. The stirring speed at that time varies slightly depending on the selection of the apparatus, but is usually in the range of 10 to 1000 rpm.

[5] Aqueous resin dispersion The polymer (C) of the present invention is very excellent in water dispersibility, and according to the method for producing a resin dispersion of the present invention, an aqueous resin dispersion having a fine dispersed particle size is obtained. Therefore, the aqueous resin dispersion of the present invention has an advantage that the dispersed particle diameter is fine and the resin is stably dispersed. Therefore, when this is used, a coated product having an excellent appearance can be obtained. The dispersed particle diameter of the polymer (resin) in the resin dispersion is 50% cumulative from the finer particle diameter in terms of volume (also referred to as 50% particle diameter, 50% average particle diameter, or volume average particle diameter). .) Is usually 10 μm or less, preferably 1 μm or less, with a 50% particle size. 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 resin dispersion of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and still more 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.

  As described above, the aqueous resin dispersion of the present invention has an advantage that a surfactant is not used and the dispersed particle diameter is very small. However, a surfactant may be included as necessary according to other purposes and applications. 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 the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, and sodium polyoxyethylene lauryl sulfate. 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.

  In addition, a so-called reactive surfactant having a radical polymerizable functional group can be used for the above-mentioned surfactant, and when a reactive surfactant is used, a film formed using this resin dispersion is used. Water resistance can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao). The ratio of the surfactant to 100 parts by weight of the polymer (C) is usually 50 parts by weight or less, preferably 30 parts by weight or less.

  However, it is one of the advantages of the present invention that it is not necessary to use a surfactant. Accordingly, it is preferable that the amount of the surfactant is small, and the surfactant content of the resin dispersion is 100 weights of the polymer (C). It is preferable that it is 10 weight part or less with respect to a part. 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).

  By reducing the amount of the surfactant, there is an advantage that a bleed out that has been a problem in the past can be suppressed and a coated product having an excellent appearance can be obtained, and the present resin dispersion can be used as a coating on the outermost surface of the coating. Moreover, since the water resistance of the coating tends to decrease when a surfactant is contained, it is desirable that the amount of the surfactant is small in this respect as well. However, since the nonionic surfactant is less likely to lower the water resistance compared to other surfactants, the nonionic surfactant may be included in a slightly larger amount. 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.

  Another advantage of the present invention is that the amount of surfactant can be reduced without using 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. To further improve the performance of various coatings 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, 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, or the like can be used. Of these, isocyanate compounds, 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 of the present invention is used for applications such as primers, paints, and inks, a hydrophilic organic solvent other than water can be blended for the purpose of increasing the drying speed or obtaining a good surface finish. . 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. In addition, organic or inorganic compounds other than those described above can be added to the resin dispersion as long as the stability of the resin dispersion is not impaired.

[5-1] Combined use of other resins In the resin dispersion of the present invention, a water-soluble resin or a resin that can be dispersed in water is mixed and used as necessary within a range that does not significantly impair the effects of the present invention. Can do. For example, it is effective for improving the appearance of the coating (glossing or matting) and reducing tackiness. It may be a resin that can be dispersed using a surfactant. As the water-soluble resin, for example, the resins listed as the hydrophilic polymer (B) can be used. For example, an aqueous solution obtained by dissolving these resins in water is mixed with the resin dispersion of the present invention.

  Examples of the resin that can be dispersed in water include acrylic resin, polyester resin, polyurethane resin, epoxy resin, vinyl ester resin, melamine resin, and alkyd resin. The form of the resin dispersion containing these resins and the polymer (C) is not particularly limited. For example, there is a method of emulsifying and mixing these resins and the polymer (C). In this method, particles made of these resins and particles made of the polymer (C) are separately formed, and an aqueous resin dispersion dispersed in water is obtained.

  Or there exists the method of emulsifying, after mixing these resin and a polymer (C). In this method, an aqueous resin dispersion is obtained in which particles in which the resin and the polymer (C) are mixed in one particle are dispersed in water. For example, when the polymer (C) is allowed to coexist during polymerization of the resin, both can be mixed, and emulsified and dispersed in water to form particles containing the resin and the polymer (C) in one particle. Also, the resin and the polymer (C) can be mixed separately by synthesizing the resin and the polymer (C), and the both can be mixed. The particles containing the resin and the polymer (C) in one particle can be emulsified and dispersed in water. Can be formed.

  In order to effectively exhibit the properties of the polymer (C) and the resin, an aqueous resin dispersion in which particles made of the polymer (C) and particles made of the resin are present separately is preferable. Such an aqueous resin dispersion can be obtained, for example, by mixing a dispersion obtained by emulsifying and dispersing the polymer (C) in water and a dispersion obtained by emulsifying and dispersing the resin in water. The weight ratio of the polyolefin (A) to the other resin is preferably 90:10 to 10:90. That is, the total amount of the polyolefin component and other resin is 100 parts by weight, and the amount of polyolefin (A) is 10 parts by weight or more, preferably 90 parts by weight or less. When the amount of the polyolefin (A) is less than 10 parts by weight, the adhesion to the polyolefin-based substrate becomes insufficient. Preferably it is 15 parts by weight or more, more preferably 20 parts by weight or more. When the amount of the polyolefin (A) is larger than 90 parts by weight, the physical properties of the coating film obtained from such a composite aqueous resin dispersion, specifically, the coating film strength, water resistance, weather resistance, abrasion resistance, Solvent property will become insufficient. Preferably it is 85 weight part or less, More preferably, it is 80 weight part or less.

  The weight ratio of the total amount of the polymer (C) and the other resin and water is preferably 5:95 to 60:40. That is, the total amount of the polymer (C) and the other resin is 5 parts by weight or more and 60 parts by weight or less with the total amount of the polymer (C), other resin and water being 100 parts by weight. If it is less than 5 parts by weight, workability such as coating and heat curing is poor and impractical. Preferably it is 10 weight part or more, More preferably, it is 15 weight part or more. When it is larger than 60 parts by weight, the viscosity of the aqueous resin dispersion becomes too high, the applicability is deteriorated, and a uniform coating film is difficult to form. Preferably it is 55 weight part or less, More preferably, it is 50 weight part or less.

In order to emulsify the other resin as described above into an aqueous dispersion, a surfactant can be used as necessary. As the surfactant, for example, those listed in [5] can be used.
The content of the surfactant is usually 20 parts by weight or less with respect to 100 parts by weight of the resin. The amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 2 parts by weight or less. The smaller the surfactant content, the less the surfactant bleed out. Most preferably, substantially no surfactant is used.

  The surfactant can also be used in a production method in which the polymer (C) and the resin are mixed and then emulsified. The other resin is preferably at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, epoxy resin, and vinyl ester resin. Resin dispersions containing these are suitable for paints. Hereinafter, these are collectively referred to as the resin (D).

(D-1) Acrylic resin The acrylic resin of the present invention is not particularly limited as long as it is a (meth) acrylic polymer, but a homopolymer or copolymer of acrylic acid and / or an ester thereof, methacrylic acid and / or Or the homopolymer or copolymer of the ester. In addition, (meth) acryl refers to acryl and / or methacryl.

Specific examples of the (meth) acrylate ester include (meth) acrylate ester monomers having an alkyl group having 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Hexyl acid, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, or the like, or (Meth) acrylic acid ester having an aryl group or an aralkyl group having 6 to 12 carbon atoms, such as Meth) acrylate, phenyl (
And benzyl (meth) acrylate.

  Alternatively, (meth) acrylic acid esters having a C 1-20 alkyl group containing a hetero atom, such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid- 2-aminoethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid hydroxybutyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3- Methoxypropyl, (meth) acrylic acid and polyethylene oxide adducts, etc., (meth) acrylic acid esters having a C 1-20 alkyl group containing a fluorine atom, such as trifluoromethyl methyl (meth) acrylate , (Meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic 2 Pa - fluoroethyl ethyl and the like, (meth) acrylamide monomers such as (meth) acrylamide, and the like (meth) acrylic dimethyl amide, respectively.

  In addition to the above (meth) acrylic acid and / or esters thereof, those having a double bond at the end of a molecule called a so-called macromonomer are also included. These (meth) acrylic macromonomers usually have a weight average molecular weight in the range of several hundred to 50,000. Such (meth) acrylic oligomer is usually used in the range of 1 to 80 parts by weight per 100 parts by weight of the above (meth) acrylic acid and / or esters thereof.

  In addition to the above macromonomer, caprolactone modified (meth) acrylic oligomer, terminal hydroxyl group-containing (meth) acrylic oligomer, oligoester (meth) acrylic oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, etc. It is done. In order to impart water resistance, heat resistance, solvent resistance, and chemical resistance to the acrylic resin, a crosslinkable functional group can be introduced and a crosslinking agent can be used in combination. For example, a copolymer having an epoxy group such as glycidyl (meth) acrylate and a polyfunctional carboxylic acid or polyfunctional amine as a crosslinking agent, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid hydroxybutyl, etc. A copolymer having a different hydroxyl group and a polyfunctional isocyanate, or a copolymer having a carbonyl group such as diacetone acrylamide or acrolein and a crosslinking system such as a polyfunctional hydrazine such as adipic acid dihydrazide or sebacic acid dihydrazide. be able to. Among these, a cross-linking system using a carbonyl group and a polyfunctional hydrazine is preferable because it can be stored at one temperature but can be cured at room temperature. These crosslinkable functional groups preferably have 0.5 parts by weight or more per 100 parts by weight of acrylic resin, and more preferably 1 part by weight or more. However, it is preferably 20 parts by weight or less per 100 parts by weight of acrylic resin, more preferably 10 parts by weight or less. The higher the lower limit value, the easier it is to obtain a sufficient crosslinking effect, and the lower the upper limit value, the higher the storage stability and the like.

Although it does not specifically limit as a polymerization method for manufacturing the above acrylic resins, For example, methods, such as solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, can be used. In order to emulsify the acrylic resin obtained by solution polymerization and bulk polymerization into an aqueous emulsion to form an aqueous dispersion, emulsification and dispersion are performed by mechanical force such as colloid mill in the presence or absence of the solution, and then necessary The residual solvent may be distilled off under reduced pressure or atmospheric pressure.
If emulsion polymerization or suspension polymerization is used, the polymer can be obtained directly as an aqueous emulsion. A preferred form is an aqueous emulsion obtained by emulsion polymerization. Examples of commercially available products include Rikabond manufactured by Chuo Rika Kogyo Co., Ltd. and Acronal manufactured by BASF Japan Co., Ltd.

  The acrylic resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 500,000 or less. The particle diameter of the acrylic resin particles in the aqueous resin dispersion of the acrylic resin is preferably 0.01 μm to 0.5 μm. Moreover, it is preferable that resin solid content is 15 to 70 weight%. The liquid viscosity is preferably 1 to 50,000 mPa · s.

(D-2) Polyurethane resin The urethane resin of the present invention is not particularly limited. For example, (i) a component containing two or more active hydrogens in average in one molecule and (ii) a polyvalent isocyanate A urethane polymer obtained by reacting a component, or an isocyanate group-containing prepolymer obtained by reacting the component (i) and the component (ii) under an isocyanate group-excess condition and a chain extender such as a diol. The urethane polymer obtained by making it react is mentioned. These urethane polymers may contain an acid component (acid residue).

  The chain extension method of the isocyanate group-containing prepolymer may be a known method. For example, water, a water-soluble polyamine, glycols or the like is used as the chain extender, and the isocyanate group-containing prepolymer and the chain extender component are used. May be reacted in the presence of a catalyst as necessary. The component containing an average of 2 or more active hydrogens in one molecule of the component (i) is not particularly limited, but preferably has a hydroxylic active hydrogen. Specific examples of such compounds include the following.

  (1) Diol compound: ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5- Pentanediol, neopentyl glycol, 1,6-hexane glycol, 2,5-hexanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclodecane dimethanol, 1,4- Cyclohexanedimethanol and the like.

  (2) Polyether diols: alkylene oxide adducts of the above diol compounds, ring-opening (co) polymers of alkylene oxides and cyclic ethers (tetrahydrofuran, etc.) such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol (block) Or random) copolymer, glycol, polytetramethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, and the like.

  (3) Polyester diol: Dicarboxylic acid (anhydride) such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, and ethylene glycol, propylene glycol as mentioned in (1) above , 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol and other diol compounds obtained by polycondensation under hydroxyl group-excess conditions. Specifically, ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-adipic acid condensate, ethylene glycol-propylene glycol-adipic acid condensate, or lactone is opened using glycol as an initiator. Examples thereof include polymerized polylactone diol.

  (4) Polyether ester diol: (anhydrous) dicarboxylic acid as exemplified in the above (3), an ether group-containing diol (polyether diol or diethylene glycol of (2) above) or a mixture of this with another glycol And a product obtained by reacting an alkylene oxide in addition to, for example, a polytetramethylene glycol-adipic acid condensate.

(5) Polycarbonate diol: General formula HO—R— (OC (O) —O—R) _x —OH (wherein R is a saturated fatty acid diol residue having 1 to 12 carbon atoms, x is a molecular The compound etc. which show the number of repeating units, and are the integers of 5-50 normally.). These include a transesterification method in which a saturated aliphatic diol and a substituted carbonate (diethyl carbonate, diphenyl carbonate, etc.) are reacted under the condition that the hydroxyl group is excessive, the saturated aliphatic diol and phosgene are reacted, or as necessary. Then, it can be obtained by a method of further reacting with a saturated aliphatic diol.

  The compounds as exemplified in the above (1) to (5) can be used alone or in combination of two or more. As the polyisocyanate component (ii) to be reacted with the component (i), an aliphatic, alicyclic or aromatic compound containing an average of two or more isocyanate groups in one molecule can be used.

  The aliphatic diisocyanate compound is preferably an aliphatic diisocyanate having 1 to 12 carbon atoms, and examples thereof include hexamethylene diisocyanate and 2,2,4-trimethylhexane diisocyanate. The alicyclic diisocyanate compound is preferably an alicyclic diisocyanate having 4 to 18 carbon atoms, and examples thereof include 1,4-cyclohexane diisocyanate and methylcyclohexylene diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.

  In addition, those containing acid residues in the urethane-based polymer can be dispersed in water without using a surfactant or in a small amount, so that the water resistance of the coating film is improved. There is expected. The content of the acid residue is preferably in the range of 25 to 150 (mgKOH / g), preferably 30 to 100 (mgKOH / g) as the acid value of the urethane polymer. If the acid value is less than 25, the water dispersibility tends to be insufficient, and it is often necessary to use a surfactant. On the other hand, if the acid value is more than 150, the water resistance of the coating film tends to be poor.

  As a method for introducing an acid group into a urethane polymer, a conventionally used method can be used without any particular limitation. For example, dimethylolalkanoic acid is one of the glycol components described in (2) to (4) above. A method of introducing an acid group by introducing a carboxyl group into a polyether diol, a polyester diol, a polyether ester diol or the like in advance by substituting a part or all of them is preferable. Examples of the dimethylolalkanoic acid used here include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid. Examples of commercially available products include Hydran and Bondick from Dainippon Ink Industries, Ltd., and Superflex from Daiichi Pharmaceutical Co., Ltd.

  The urethane resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less. When manufacturing the water dispersion of this urethane resin, the manufacturing method is not specifically limited, It can manufacture according to the manufacturing method of the water dispersion of the above-mentioned acrylic resin. As for the particle size of the urethane resin particle in the aqueous resin dispersion of this urethane resin, 0.01 micrometer-0.5 micrometer are preferable. Moreover, it is preferable that resin solid content is 15 to 70 weight%. The liquid viscosity is preferably 1 to 10,000 mPa · s.

(D-3) Polyester resin The polyester resin of the present invention is not particularly limited, and examples thereof include dicarboxylic acids such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, and phthalic acid, and the like. / Or anhydrides thereof and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol, or ether group-containing diols (polyethylene glycol) And polypropylene glycol, polytetramethylene glycol, and the like).

  Specific examples include an ethylene glycol-adipic acid condensate, a butanediol-adipine condensate, a hexamethylene glycol-succinic acid condensate, an ethylene glycol-propylene glycol-phthalic acid condensate, and a polyethylene glycol-adipic acid condensate. . An aqueous dispersion of the polyester resin can be obtained by emulsifying these in the presence or absence of a surfactant. Although the manufacturing method is not specifically limited, it can manufacture according to the manufacturing method of the aqueous dispersion of the above-mentioned acrylic resin. Examples of commercially available products include Vylonal MD-1200 and MD-1245 manufactured by Toyobo.

  The polyester resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 5,000 or more. However, 500,000 or less is preferable, and more preferably 100,000 or less. As for the particle size of the urethane resin particle in the aqueous resin dispersion of this urethane resin, 0.01 micrometer-0.5 micrometer are preferable. Moreover, it is preferable that resin solid content is 15 to 70 weight%. The liquid viscosity is preferably 1 to 10,000 mPa · s.

(D-4) Epoxy resin The epoxy resin of the present invention is not particularly limited as long as it is a polymer having one or more epoxy groups in one molecule. For example, by reacting polyhydric phenol with epichlorohydrin in the presence of alkali. Examples thereof include polyhydric glycidyl ethers of phenol that can be produced, and epoxy group-containing polymers obtained by reacting such polyhydric glycidyl ethers of phenol with the above polyhydric phenols.

  Examples of the polyhydric phenol that can be used here include bis (4-hydroxyphenyl) -2,2-propane, 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, Bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-t-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, etc. Can be mentioned.

  Instead of these polyhydric phenols, hydrogenated compounds obtained by adding hydrogen to part or all of the double bonds of the phenyl nucleus can also be used. Further, as the epoxy resin, polyglycidyl ether of phenol novolac resin and polyglycidyl ether of polyhydric alcohol can also be used. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerol. , Bis (4-hydroxycyclohexyl) -2,2-propane, sorbitol and the like.

  An aqueous dispersion of an epoxy resin is obtained by emulsifying these in the presence or absence of a surfactant. Although the manufacturing method is not specifically limited, it can manufacture according to the manufacturing method of the aqueous dispersion of the above-mentioned acrylic resin. Typical examples of commercially available products are Novolak type epoxy resin obtained by adding epichlorohydrin to phenol novolak resin and forcibly emulsified with a surfactant (emulsifier). Resin Co., Ltd. Epiletts 6006W70, 5003W55, Toto Kasei Co., Ltd. WEX-5100, etc. are mentioned.

Similarly, bisphenol-type epoxy resin obtained by adding epichlorohydrin to bisphenol was forcibly emulsified with an emulsifier. 3540WY55 etc. are mentioned. Further, as an alkyl type epoxy resin in which epichlorohydrin is added to a polyol such as sorbitol, pentaerythritol, glycerin, etc., Denars EX-611, EX-614, EX-411, EX-313 manufactured by Nagase Chemtech Co., Ltd. and the like can be mentioned.
The epoxy resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less.

(D-5) Vinyl ester-based resin The vinyl ester-based resin of the present invention is a copolymer containing a vinyl ester single polymer or a polymer of a vinyl ester monomer and another radical polymerizable monomer. is there. Examples of the radical polymerizable monomer include ethylene, (meth) acrylic acid ester, aromatic vinyl, unsaturated nitrile, acrylamide, (meth) acrylic acid, α, β-unsaturated dicarboxylic acid and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acid having 8 to 10 carbon atoms, so-called vinyl versatate (for example, trade name: Veova 10 manufactured by Shell Chemical Co., Ltd.). And alkyl acid vinyl esters. Of these, vinyl acetate is preferable, and the vinyl ester resin is particularly preferably a vinyl acetate homopolymer or an ethylene-vinyl acetate copolymer.

  The weight ratio of the ethylene unit and the vinyl ester unit in the copolymer is preferably in the range of 5 to 70 parts by weight of the ethylene unit contained in the polymer when the vinyl ester unit is 100 parts by weight. 10-50 weight part is more preferable. When the ethylene unit is more than 5 parts by weight, the initial adhesiveness and water resistance are improved.

  A copolymer emulsion can be usually produced by emulsion polymerization of the monomers constituting the ethylene units and vinyl ester units. Examples of the emulsifier used in the emulsion polymerization include water-soluble polymer compounds such as hydroxymethyl cellulose and carboxymethyl cellulose, and protective colloids such as partially saponified or completely saponified polyvinyl acetate emulsifiers. In the present invention, the partially saponified polyvinyl acetate emulsifier is used. Among these partially saponified polyvinyl acetate emulsifiers, those partially saponified at an average polymerization degree of about 100 to 3000 and an average saponification degree of 80 to 98 mol% are more preferable.

  Specific examples of the vinyl ester resin emulsion include Sumikaflex 400, 401, 305, 455, 500, 510, 700, 751, 900 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000, OM-4200. (Above, manufactured by Kuraray Co., Ltd.), Polysol EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59, P-900 (above, Showa Polymer ( Co., Ltd.), Denka EVA-Tex # 20, # 30, # 40M, # 60, # 81, # 82 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), etc., commercially available aqueous emulsions of ethylene-vinyl ester copolymers May be used as they are.

[5-2] Addition of pigment Pigment (E) can be added to the resin dispersion of the present invention. The aqueous resin dispersion containing the pigment (E) is suitable as a paint.

  The pigment that can be used is not particularly limited. For example, inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, and perinone pigments. , Perylene pigments, quinacridone pigments, isoindolinone pigments, indigo pigments, organic pigments such as phthalocyanine pigments, etc .; extenders such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate ; Conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; non-colored or colored metallic luster such as aluminum, copper, zinc, nickel, tin, aluminum oxide, or other metals or alloys 1 type, or 2 or more types thereof may be used in combination.

  The amount of the pigment (E) added to the resin dispersion is preferably 10 parts by weight or more with respect to 100 parts by weight of the resin (total amount of the polymer (C) and other resins). More preferably, it is 50 parts by weight or more. However, it is preferably 400 parts by weight or less, and more preferably 200 parts by weight or less. As the addition amount is larger than the lower limit value, the color developability and the hiding property tend to be higher, and as the addition amount is smaller than the upper limit value, the adhesion, moisture resistance and oil resistance tend to be higher.

  At this time, a pigment dispersant may be used. For example, an aqueous acrylic resin such as Jonkrill Resin manufactured by Johnson Polymer Co .; an acidic block copolymer such as BYK-190 manufactured by Big Chemie; a styrene-maleic acid copolymer; Surfynol T324 manufactured by Air Products Co., Ltd. Acetylene diol derivatives: water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., etc. By using these pigment dispersants, a stable pigment paste can be prepared.

  The resin dispersion of the present invention can be used for primers, primer-less paints, adhesives, inks and the like. The present invention is particularly useful as a primer, a paint, or an adhesive. Particularly suitable for polyolefin substrates. For example, it can be used for paints for automobiles such as automobile interiors and exteriors, primers, paints for home appliances such as mobile phones and personal computers, and paints for building materials.

[6] Laminate A resin layer can be formed by applying the resin dispersion of the present invention or a paint containing the same to a substrate and heating it to form a laminate. This resin layer is a layer containing a polymer (C) in which a hydrophilic polymer (B) is bound to a polyolefin (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio). It is.

  This laminate can be used in various applications such as for automobiles, home appliances, and building materials. The substrate may be in any shape, such as a film, sheet, or plate. The resin dispersion of the present invention can be applied to a crystalline olefin polymer molding (base material) to form a coating film. Examples of the olefin polymer as a base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene and other olefin polymers, ethylene-propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene-butene copolymers, and propylene-butene copolymers. Of these olefin copolymers, propylene-based polymers are preferably used. Also, molded articles made of polypropylene and synthetic rubber, molded articles made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded articles such as bumpers for automobiles, and for steel plates and electrodeposition treatment It can also be used for surface treatment of steel plates and the like.

  In addition, the molded body to which the resin dispersion of the present invention is applied is formed by any of the above-described various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be what was done. A coating film with good adhesion can also be formed when these molded bodies are blended with inorganic fillers such as talc, zinc white, glass fiber, titanium white, and magnesium sulfate, and pigments.

[6-1] Manufacturing Method of Laminate The method for forming the resin layer on the substrate is not particularly limited, and a known method can be used. For example, various coating methods such as spray coating, bar coating, spin coating, dip coating, and gravure coating may be used as the resin dispersion or paint. In general, coating by spray coating is applied to large molded bodies such as automobile bumpers and home appliances, and coating by gravure coating or bar coating is performed on plastic films and sheets.

  After applying the resin dispersion or paint, it is usually heated with nichrome wire, infrared rays, high frequency or the like to cure the coating film, thereby obtaining a laminate having a desired coating film on the surface. The curing conditions for the coating film are appropriately selected depending on the material and shape of the substrate, the composition of the paint used, and the like. Although there is no restriction | limiting in particular in hardening temperature, Considering practicality, it is 50 degreeC or more normally, Preferably it is 60 degreeC or more. However, it is usually 150 ° C. or lower, preferably 130 ° C. or lower.

  The thickness of the resin layer to be laminated (after curing) can be appropriately selected depending on the material and shape of the substrate, the composition of the paint used, etc., but is usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm. That's it. However, it is usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less.

[6-2] Thermoplastic resin molding (F)
As the base material of the laminate of the present invention, a thermoplastic resin molded body is desirable. Although it does not specifically limit as a thermoplastic resin molded object (F), For example, it is a molded object which consists of polyolefin resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin etc. In particular, the present invention is preferably applied to a thermoplastic resin molded body (F) made of a polyolefin resin (hereinafter referred to as a polyolefin molded body), and in particular, a thermoplastic resin molded body (F) made of a propylene polymer (hereinafter referred to as a polyolefin molded body). It is preferably applied to a propylene-based polymer molded product).

  The polyolefin molded body is usually a crystalline polyolefin molded body, and various known polyolefins can be used, and is not particularly limited. For example, ethylene or propylene homopolymer, ethylene and propylene copolymer, ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene , Cyclohexene, and a copolymer with an α-olefin comonomer having 2 or more carbon atoms such as norbornene, or a copolymer of two or more of these comonomers can be used.

  The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms. Copolymers of α-olefin monomers and comonomers such as vinyl acetate, acrylic acid esters and methacrylic acid esters, copolymers of comonomers such as aromatic vinyl monomers or hydrogenated products thereof, and conjugated diene block copolymers A hydrogenated product or the like can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. The polyolefin may be modified as necessary.

  These can be used alone or as a mixture depending on the application. The polyolefin preferably has a melt flow rate (MFR: 230 ° C., 2.16 kg load) of 2 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and particularly preferably 25 g / 10 minutes. However, it is preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less. If the MFR is higher than the lower limit, the flowability of the polyolefin tends to increase. Conversely, if the MFR is lower than the upper limit value, the mechanical properties tend to increase. The MFR of the polyolefin may be adjusted at the time of polymerization, or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after the polymerization.

  More preferred as the polyolefin is a propylene polymer molded body. The propylene-based polymer molded body is usually a crystalline propylene-based polymer molded body, and known ones can be used. For example, a propylene homopolymer, propylene and other comonomers such as ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene. Copolymers with one or more α-olefin comonomers can be used.

  A propylene homopolymer and / or a propylene / ethylene copolymer is preferable. Here, the propylene-ethylene copolymer is a propylene / ethylene random copolymer and / or a propylene-ethylene block copolymer, more preferably a propylene-ethylene block copolymer. Here, the propylene-ethylene block copolymer consists of a crystalline polypropylene part (a unit part) and an ethylene-propylene random copolymer part (b unit part).

  The a unit is usually obtained by homopolymerization of propylene, and in some cases, by copolymerizing a small amount of other α-olefin with propylene. The MFR (230 ° C., 2.16 kg load) of the polypropylene homopolymer of a unit part is preferably 10 g / 10 min or more, more preferably 15 g / 10 min or more, still more preferably 20 g / 10 min or more. Preferably it is 40 g / 10 minutes or more. Further, it is preferably 500 g / 10 min or less, more preferably 400 g / 10 min or less, and still more preferably 300 g / 10 min or less.

  As this MFR is higher than the lower limit, the flowability tends to increase. Conversely, the mechanical properties tend to increase as the MFR is lower than the upper limit. On the other hand, the b unit is a rubbery component obtained by random copolymerization of propylene and ethylene. The propylene content of the propylene-ethylene random copolymer part of the b unit part is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. However, it is preferably 85% by weight or less, more preferably 80% by weight or less, and still more preferably 75% by weight or less. When the propylene content is within this range, the dispersibility and glass transition temperature are within an appropriate range, and impact characteristics tend to be good. The propylene content can be adjusted by controlling the concentration ratio of propylene and ethylene during the polymerization of the propylene-ethylene random copolymer portion.

  The molecular weight of the propylene-ethylene random copolymer part of the b unit part is not particularly limited, but in consideration of dispersibility and impact resistance, the weight average molecular weight (Mw) is preferably 200,000 to 3,000,000, more preferably Is 300,000-2,500,000, more preferably 400,000-2 million. The amount of the a unit part and the b unit part is not particularly limited, but in general, the a unit part is preferably 95% by weight or less, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight of the total amount. , B unit part is preferably adjusted to 5% by weight or more of the total amount, more preferably 5 to 50% by weight, still more preferably 10 to 40% by weight. The impact resistance characteristics tend to increase as the amount of b unit part is equal to or greater than the lower limit, and the rigidity, strength, and heat resistance tend to increase as the amount is less than the upper limit.

  In the present invention, the amount of b unit part is measured using a temperature rising elution fractionation method. That is, the a unit part does not elute at 100 ° C. or lower in the extraction with orthodichlorobenzene, but the b unit part elutes easily. Therefore, the composition of the propylene-ethylene block copolymer after production is determined by extraction analysis with the orthodichlorobenzene. Since the ratio of the amount of a unit part and b unit part is determined by the polymerization amount of the propylene homopolymer part and the polymerization amount of the propylene-ethylene random copolymer part, it can be adjusted by controlling the respective polymerization times.

  The production method of the propylene homopolymer or the propylene-ethylene block copolymer is not particularly limited, and is appropriately selected from known methods and conditions. As the propylene polymerization catalyst, a highly stereoregular catalyst is usually used. For example, a catalyst comprising a combination of a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors, an organoaluminum compound and an aromatic carboxylic acid ester ( JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), and a supported type in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide. Examples thereof include catalysts (see JP-A-57-63310, JP-A-63-43915, and JP-A-63-83116). Furthermore, a metallocene catalyst as shown in WO91 / 04257 and the like can also be mentioned. The metallocene-based catalyst may not contain alumoxane, but is preferably a so-called Kaminsky-based catalyst in which a metallocene compound and an alumoxane are combined.

  The propylene-ethylene block copolymer is obtained by first polymerizing propylene alone in the presence of the catalyst by applying a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, or a slurry polymerization method, and then propylene and ethylene. Can be obtained by random polymerization. In order to obtain a propylene-ethylene block copolymer having the above-described melting characteristics (MFR), it is preferable to perform multistage polymerization using a slurry method or a gas phase fluidized bed method. Alternatively, it can be obtained by a method in which propylene homopolymerization is performed in multiple stages and then propylene and ethylene are randomly polymerized. When producing a propylene-ethylene block copolymer having a large number of b units, the gas phase fluidized bed method is particularly preferred.

The propylene homopolymer is obtained by polymerizing propylene alone in the presence of the catalyst by applying a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, or a slurry polymerization method. In order to obtain a propylene homopolymer having the above-described melting characteristics (MFR), it is preferable to perform multistage polymerization using a slurry method or a gas phase fluidized bed method. In order to use the propylene homopolymer and the propylene-ethylene block copolymer of the present invention as a structural material, it is preferable that they have excellent mechanical properties and high rigidity and impact resistance. That is, the flexural modulus is preferably 300 MPa or more, more preferably 500 to 3000 MPa, and still more preferably 1000 to 2000 MPa. By being in this range, it will be excellent in rigidity and suitable as a structural material. The IZOD impact strength is preferably 1 kJ / m ² or more, more preferably ^{2 to} 100 kJ / m ² , still more preferably 5 to 80 kJ / m ² , and particularly preferably 8 to 60 kJ / m ² . By making it within this range, it is excellent in impact resistance and suitable as a structural material. A thermoplastic resin molding may be used individually by 1 type, and may be used in combination of 2 or more type.

[6-3] Inorganic filler component The thermoplastic resin molded product (F) used in the present invention may contain an inorganic filler component. In particular, mechanical properties such as bending elastic modulus and rigidity of the molded body can be improved by blending the crystalline polyolefin with an inorganic filler component. Specifically, plate fillers such as talc, mica and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber and zonolite; potassium titanate, magnesium Needle-like fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Granular fillers; balun fillers such as glass balloons; Inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate can also be used. Of these, talc, mica, glass fiber, and whisker are preferable from the balance between physical properties and cost, and talc, mica, and glass fiber are more preferable.

  The inorganic filler component may be surface-treated with a surfactant, a coupling agent or the like. The surface-treated filler has an effect of further improving the strength and heat-resistant rigidity of the molded product. The amount of the inorganic filler component used is selected from a wide range depending on the purpose and application of the molded product, but is preferably 1 to 80 parts by weight, more preferably 2 to 75 parts by weight, more preferably 100 parts by weight of the crystalline polyolefin. Preferably it is 5-60 weight part.

By including the inorganic filler component, the flexural modulus of the crystalline polyolefin can be improved to preferably 1000 MPa or more, more preferably 1500 to 10000 MPa, and still more preferably 2000 to 8000 MPa. The IZOD impact strength can be improved to preferably 1 kJ / m ² or more, more preferably ^{2 to} 80 kJ / m ² , and further preferably 4 to 60 kJ / m ² . An inorganic filler component may be used individually by 1 type, and may be used in combination of 2 or more type.
Hereinafter, preferred fillers will be described in detail.

(1) Talc The average particle diameter of talc used in the present invention is usually 10 μm or less, preferably 0.5 to 8 μm, more preferably 1 to 7 μm. The average particle size value is a cumulative amount obtained by drawing a particle size cumulative distribution curve from a measurement result obtained by a laser diffraction method (for example, LA920W manufactured by Horiba, Ltd.) or a liquid layer sedimentation method light transmission method (for example, CP type manufactured by Shimadzu Corp.). The particle size value is 50% by weight. The value in the present invention is an average particle diameter value measured by a laser diffraction method.

As the talc, fine particles obtained by further finely classifying naturally-produced talc that has been mechanically pulverized are used. What was once coarsely classified may be further classified. Examples of the mechanical crushing method include a method using a crusher such as a jaw crusher, a hammer crusher, a roll crusher, a screen mill, a jet crusher, a colloid mill, a roller mill, and a vibration mill. The pulverized talc is subjected to wet or dry classification once or repeatedly in an apparatus such as a cyclone, a cyclone air separator, a micro separator, or a sharp cut separator to adjust the average particle size.

  As a method for producing talc of the present invention, it is preferable to perform a classification operation with a sharp cut separator after pulverization to a specific particle size. These talcs are modified polyolefins, fatty acids grafted with various organic titanate coupling agents, organic silane coupling agents, unsaturated carboxylic acids or their anhydrides for the purpose of improving the adhesion or dispersibility with the polymer. The surface treatment may be performed with a fatty acid metal salt, a fatty acid ester, or the like.

(2) Glass fiber It is common to use glass chopped strand as glass fiber. The length of the glass chopped strand is usually 3 to 50 mm, and the fiber diameter is usually 3 to 25 μm, preferably 8 to 14 μm. As the glass chopped strand, it is preferable to use a surface-modified one with a silane compound or a surface treatment with a sizing agent such as polyvinyl alcohol, polyvinyl acetate, polyurethane, epoxy resin, or olefin component.

  Examples of the olefinic component as the sizing agent include unsaturated carboxylic acid-modified polyolefins and low molecular weight polyolefins. In the present invention, a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof may be blended in order to improve mechanical strength by interfacial adhesion between the crystalline polyolefin and the glass fiber. In particular, those obtained by modifying polypropylene as a base material are preferred, and those having a modification rate of 0.1 to 10% by weight are preferred.

(3) Mica Mica preferably has an average particle diameter of 2 to 100 μm and an average aspect ratio of 10 or more, more preferably an average particle diameter of 2 to 80 μm and an average aspect ratio of 15 or more. When the average particle diameter of the mica is within the above range, the scratch resistance and impact strength of the molded product can be further improved and deterioration of the appearance can be suppressed.

  The mica may be any of so-called white mica, gold mica, black mica, etc., but gold mica and white mica are preferable, and white mica is more preferable. The method for producing mica is not particularly limited, and the mica is produced by a method according to the aforementioned talc. However, dry pulverization / wet classification or wet pulverization / wet classification is preferable, and wet pulverization / wet classification is more preferable.

[6-4] Elastomer Component When the thermoplastic resin molded product (F) used in the present invention is a crystalline polyolefin molded product, an elastomer component can be further contained. Thereby, the impact strength strength of a molded object can be improved. Examples of the elastomer component include ethylene-α-olefin random copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene-α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Polymer rubber; ethylene-α-olefin-nonconjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM); hydrogenated product of styrene-butadiene-styrene triblock (SEBS), styrene -Styrene-containing thermoplastic elastomer such as hydrogenated product (SEPS) of isoprene-styrene triblock body can be exemplified.

  These elastomers can be produced as follows. The MFR (230 ° C., 2.16 kg load) of these elastomer components is preferably 0.5 to 150 g / 10 minutes, more preferably 0.8 when considering an automobile exterior material which is one of the main uses of the present invention. It is 7 to 100 g / 10 minutes, and more preferably 0.7 to 80 g / 10 minutes. An elastomer component may be used individually by 1 type, and may be used in combination of 2 or more type.

[6-5] Other components In addition to the above, the thermoplastic resin molded article (F) can contain arbitrary additives and blending components as long as the effects of the present invention are not significantly impaired. Specifically, pigments for coloring, antioxidants such as phenols, sulfurs and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, dispersion Agents, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, and other resins such as polyethylene resins.

[6-6] Method for Producing Thermoplastic Resin Molded Body (F) Various components are blended into the resin described above as necessary, and mixed and melt-kneaded. The kneading method is not particularly limited, and the heat of the present invention is obtained by kneading and granulating using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader. The thermoplastic resin composition which comprises a plastic resin molding (F) is obtained. In order to improve the dispersion of each component, a twin screw extruder is preferably used.

  In this kneading and granulation, the above components may be kneaded at the same time, or a method of dividing and kneading each component in order to improve performance may be employed. Next, the thermoplastic resin composition is molded to obtain a thermoplastic resin molded body (F), and various known methods can be used as the molding method. Examples include injection molding (including gas injection molding), compression molding, injection compression molding (press injection), extrusion molding, hollow molding, rotational molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, and the like. It is done. Preferably, injection molding, compression molding, and injection compression molding are used, and injection molding is particularly preferable in consideration of productivity and the like.

[6-7] Use of Laminate The laminate of the present invention is excellent in coating film adhesion and further has a physical property balance excellent in rigidity and impact resistance. Moreover, when the resin layer which comprises a laminated body does not contain surfactant substantially, since a bleedout does not arise, it is excellent also in an external appearance. Moreover, since it is not necessary to contain halogens, such as chlorine, an environmental load can be reduced.

Therefore, the laminate of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, has performance sufficient for practical use as parts / materials that are thinned, highly functional, and large. .
For example, automotive parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tanks, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat lids, water tanks and other toiletry parts, It can be used as a molding material for various industrial parts such as parts around the bathroom such as a bathtub, bathroom wall, ceiling, and drain pan.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.
<Physical property measurement method and evaluation method>
(1) Stereoregularity (1-1) Stereoregularity of polypropylene Stereoregularity [mmmm] of polypropylene was measured by a ¹³ C-NMR spectrum measurement method using 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 5T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group. Therefore, under this measurement condition, the recovery of the magnetization of all the carbons is 99% or more. Measurement was carried out by integrating over 20 hours.

(1-2) Propylene content in propylene-butene copolymer [P]
The propylene content [P] in the propylene-butene copolymer was measured by a ¹³ C-NMR spectrum measurement method using 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 pulse angle of 90 °, a pulse interval of 10 seconds, and an integration count of 6000. The chemical shift and content of propylene and butene were calculated with reference to the description of JCRandall, Macromolecules, 11,592 (1978).

(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, a sample solution injection amount: 500 μl, a column temperature: 135 ° C., a solvent: orthodichlorobenzene, and a 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 retention time and molecular weight from the polystyrene standard sample and the viscosity formula of polypropylene, and calculate the molecular weight of the propylene 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 put into a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation at a total number of 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 kg / m ³ , the particle shape is spherical, the particle refractive index is 1.50, the dispersion medium is water, the dispersion medium is 1.33, and the measurement time is 120 seconds or 180 seconds. In terms of volume, 50% and 90% of the cumulative particle diameter was determined from the finer particle diameter.

(5) Storage stability After adjusting the concentration of the resin dispersion so that the solid content is 20% by weight, the resin dispersion is placed in a sealed container with a capacity of 50 ml and stored in a thermostatic chamber at 40 ° C. for 3 months. Was measured. A sample in which there was almost no change in the dispersed particle size before and after storage was marked with ○, and a sample with a large dispersed particle size (aggregated) was marked with ×.

(6) Adhesiveness A substrate obtained by injection-molding automotive exterior grade polypropylene into 70 mm × 150 mm × 3 mm was prepared, and the substrate surface was wiped with isopropyl alcohol. Here, the resin dispersion whose concentration was adjusted so as to have a solid content of 20% by weight was spray-coated so that the coating amount was about 5 to 10 g / m ² . Next, the coated test piece was dried at 80 ° C. for 10 minutes in a safe ben dryer and then allowed to stand at 25 ° C. for 1 hour. Next, acrylic polyol urethane paint Retan PG80III (manufactured by Kansai Paint Co., Ltd.) as a base coat is blended with a predetermined curing agent, the viscosity is adjusted with a special thinner, and the dry coating amount is 50 to 60 g / m ^2. Was applied by spraying and baked at 80 ° C. for 30 minutes to obtain a coated plate.

  After leaving at 25 ° C. for 24 hours, a test piece with a grid pattern was prepared in accordance with the grid pattern test method described in JIS K 5400, and cellophane tape (Nichiban Co., Ltd.) was applied, It peeled in the direction of 90 degree | times and evaluated by the number of grids which were not peeled among the grids 100. FIG.

(7) Water resistance A coated plate produced in the same manner as in the adhesion test was immersed in warm water at 40 ° C. for 10 days, and the appearance of the coating was visually determined. Further, a cross-cut test was performed, and the cross-cut 100 out of the cross-cut 100 was evaluated by the number of cross-cuts.

(8) GH resistance A coated plate produced in the same manner as in the adhesion test is immersed in a mixed liquid of regular gasoline and ethanol (volume ratio: regular gasoline / ethanol = 9/1) maintained at 20 ° C., The time until peeling reached 5 mm was measured.

(9) Bleed-out A substrate obtained by injection-molding an automotive interior grade polypropylene into 70 mm × 150 mm × 3 mm was prepared, and the substrate surface was wiped with isopropyl alcohol. Here, the sample was spray-coated so that the dry weight after coating was about 15 g / m ² . Next, the coated test piece was baked at 70 ° C. for 20 minutes in a safe ben dryer to obtain a coated plate. After leaving it to stand at 40 ° C. for 3 days, the appearance of the coated plate was visually and touched, and the presence or absence of the bleed-out of the surfactant on the coating film surface and the state thereof were determined according to the following criteria.
○: No bleed-out of surfactant △: Slightly bleed-out surfactant ×: Surfactant is bleed-out and sticky when touched with a finger

<Production example>
[Production Example 1: Production of polypropylene]
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 at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.

  To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To 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- 1-Azulenyl) hafnium 131 mg (57 μmol) in toluene was added, and the mixture was stirred at room temperature for 10 minutes to obtain a catalyst slurry (see JP-A 2004-002310 for the method for producing the catalyst).

  Subsequently, 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 67 ° 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 (1.5 kg propylene polymer) of a 13.5 wt% propylene polymer toluene solution was obtained. The weight average molecular weight of the obtained polypropylene was 191,000, and the stereoregularity [mmmm] was 45.8%.

[Production Example 2: Production of maleic anhydride-modified polypropylene-1]
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 raising the temperature, 14 g of maleic anhydride was added, and 4.7 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued by stirring at the same temperature for 10 hours. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.25% by weight (0.125 mmol / g as maleic anhydride groups, 0.25 mmol as reactive groups). / G). The weight average molecular weight was 120,000.

[Production Example 3: Production-2 of maleic anhydride-modified polypropylene]
The same procedure as in Production Example 2 was carried out except that the amount of maleic anhydride was 28 g and the amount of t-butylperoxyisopropyl monocarbonate was 9.3 g. The content (graft rate) of maleic anhydride groups was 2.4% by weight (0.24 mmol / g as maleic anhydride groups, 0.48 mmol / g as reactive groups). The weight average molecular weight was 100,000.

[Production Example 4: Production of maleic anhydride-modified polypropylene-3]
The same procedure as in Production Example 2 was conducted except that the amount of maleic anhydride was 21 g and the amount of t-butylperoxyisopropyl monocarbonate was 7.0 g. The content (graft ratio) of maleic anhydride groups was 1.6% by weight (0.16 mmol / g as maleic anhydride group, 0.32 mmol / g as reactive group). The weight average molecular weight was 110,000.

[Production Example 5: Production of pigment dispersion paste]
A water-soluble acrylic resin (John Crill 683 manufactured by Johnson Polymer Co., Ltd. (resin acid value 160 mgKOH / g)) was neutralized with 2-amino-2-methylpropanol and dissolved in water. 20 g of this aqueous solution (solid concentration 25% by weight), 7.5 g of carbon black (manufactured by Mitsubishi Chemical Corporation), 60 g of titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., R-5N), antifoaming agent (manufactured by Air Products Co., Surfynol) 440) 2.5 g, ion-exchanged water 60 g, and zirconia beads 150 g were mixed and stirred and dispersed in a paint shaker for 30 minutes. The dispersion was filtered through a 400 mesh wire mesh to obtain a pigment dispersion paste having a solid content concentration of 50% by weight.

[Production Example 6: Production of maleic anhydride-modified polypropylene solution]
Polypropylene was produced in the same manner as in Production Example 1 except that the polymerization temperature was 71 ° C. and the hydrogen concentration in the system was 8600 ppm, and a 15.5 wt% toluene solution of a propylene polymer was added in an amount of 11%. 0.3 kg (corresponding to 1.75 kg of propylene polymer) was obtained. The weight average molecular weight of the obtained polypropylene was 38,000, and the stereoregularity [mmmm] was 38.9%.

  In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 300 g of the obtained polypropylene and 200 g of toluene were placed, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After the temperature increase, 9.0 g of maleic anhydride was added, 4.5 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I) was added, and the reaction was continued for 7 hours at the same temperature. . After completion of the reaction, 250 g of toluene was added to dilute the solid concentration to 40% by weight, and the liquid temperature was adjusted to 60 ° C.

  1,200 g of 60 ° C. warm water was added and stirred vigorously for 30 minutes, then allowed to stand to separate into a toluene layer and an aqueous layer, the aqueous layer was removed, and unreacted maleic anhydride and by-products derived from maleic anhydride Things were removed (washed with warm water). This warm water washing was further repeated three times, and then the resulting toluene layer was heated and dehydrated to obtain a toluene solution of maleic anhydride-modified polypropylene (solid content concentration: 40% by weight).

  A portion of this modified polymer was sampled, dried by heating and measured for infrared absorption. As a result, the content of maleic anhydride groups (graft ratio) was 1.2% by weight (0.12 mmol / g as maleic anhydride groups). The reactive group was 0.24 mmol / g), and the weight average molecular weight was 35,000.

[Production Example 7: Production of maleic anhydride-modified propylene-butene copolymer]
Into a twin screw extruder (PCM40 manufactured by Ikegai Iron Works Co., Ltd.) having a diameter of 45 mm, 10 kg of propylene-butene copolymer (Mitsui Chemicals, Tuffmer XM7070) (of which 1 kg is obtained by freezing and pulverizing pellets to form powder) A blend of 0.2 kg maleic anhydride and 0.1 kg perbutyl I (manufactured by NOF Corporation) was melt-kneaded under the following extrusion conditions.
-Cylinder temperature: 200 ° C-Screw rotation speed: 200 rpm
・ Push out amount: 10kg / hour
As a result of measuring the infrared absorption spectrum of the resulting modified polymer, the content (graft ratio) of maleic anhydride groups was 0.6% by weight (0.06 mmol / g as maleic anhydride groups, 0 as reactive groups). .12 mmol / g) and the weight average molecular weight was 78,000.

<Example>
[Example 1]
In a glass flask equipped with a reflux condenser, a thermometer and a stirrer, 30 g of maleic anhydride-modified polypropylene synthesized in Production Example 2 (maleic anhydride group content: 3.75 mmol) and 60 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Next, 7.5 g (7.5 mmol, 100 parts by weight of polyolefin (A) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) Solution corresponding to 25 parts by weight of the hydrophilic polymer (B) in 10 g of toluene was added and reacted at 110 ° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure to obtain 37 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride in the vicinity of 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.

  75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. This was cooled to 40 ° C., and the pressure was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 25% by weight to obtain a translucent light yellow resin dispersion. It seems to be translucent due to the small dispersed particle size.

  As a result of measuring the dispersed particle size, the 50% particle size was 0.068 μm. Adhesion, water resistance and GH resistance were evaluated. The results are shown in Table-1. The methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000) used in Example 1 was dissolved in water at 25 ° C. at a concentration of 10% by weight. Sometimes the insoluble content is 1% by weight or less, and it is a hydrophilic polymer.

[Example 2]
As maleic anhydride-modified polypropylene, 30 g of maleic anhydride-modified polypropylene obtained in Production Example 3 (maleic anhydride group content: 7.2 mmol) was used, and 14.4 g (14.4 mmol, polyolefin ( A) 44 g of a yellow polymer was obtained in the same manner as in Example 1 except that 100 parts by weight of the hydrophilic polymer (B) corresponded to 48 parts by weight). A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

  80 g of THF was added to 20 g of the obtained yellow polymer and completely dissolved at 60 ° C. 100 g of pure water was added dropwise at the same temperature over 1 hour to obtain a yellow solution. This was cooled to 40 ° C., the pressure reduction degree was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 20% by weight to obtain a transparent yellow resin dispersion. The dispersed particle size is so fine that it appears to be almost transparent. The dispersed particle size was measured, and the 50% particle size was 0.011 μm. In the same manner as in Example 1, adhesion, water resistance, and GH resistance were evaluated. The results are shown in Table-1.

[Example 3]
In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 30 g of maleic anhydride-modified polypropylene synthesized in Production Example 4 (maleic anhydride group content: 4.8 mmol) and 70 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Next, 4.5 g (4.5 mmol, equivalent to 15 parts by weight of the hydrophilic polymer (B) with respect to 100 parts by weight of the polyolefin (A)) of Jeffamine M-1000, and a solution dissolved in 4.5 g of toluene were added at 110 ° C. For 1 hour. Thereafter, 0.4 g (4.5 mmol) of morpholine was added and reacted at 110 ° C. for 1 hour.

After cooling, toluene was distilled off under reduced pressure to obtain 34 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, it was confirmed that 90% of the peak corresponding to maleic anhydride near 1784 cm ⁻¹ disappeared, and maleic anhydride-modified polypropylene and polyetheramine were bonded. Observed. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

  75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. This was cooled to 40 ° C., and the pressure was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 25% by weight to obtain a translucent light yellow resin dispersion. It seems to be translucent due to the small dispersed particle size. As a result of measuring the dispersed particle size, the 50% particle size was 0.086 μm. In the same manner as in Example 1, adhesion, water resistance, and GH resistance were evaluated. The results are shown in Table-1.

[Example 4]
Instead of maleic anhydride-modified polypropylene, maleic anhydride-modified chlorinated polypropylene (manufactured by Toyo Kasei Co., Ltd., maleic anhydride group content (graft ratio) is 2.1 wt% (0.21 mmol / g)), Jeffer Yellow 9 was used in the same manner as in Example 1 except that 9 g of Min M-1000 (9 mmol, equivalent to 30 parts by weight of the hydrophilic polymer (B) with respect to 100 parts by weight of the polyolefin (A)) was dissolved in 9 g of toluene. 39 g of polymer were obtained. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified chlorinated polypropylene is formed.

75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 100 g of pure water was added dropwise at the same temperature over 1 hour to obtain a yellow solution. This was cooled to 40 ° C., the pressure reduction degree was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off under reduced pressure to a concentration of 20% by weight to obtain a transparent yellow resin dispersion. The dispersed particle size is so fine that it appears to be almost transparent.
The dispersed particle size was measured, and the 50% particle size was 0.098 μm. In the same manner as in Example 1, adhesion, water resistance, and GH resistance were evaluated. The results are shown in Table-1.

[Comparative Example 1: Dispersion of maleic anhydride-modified polypropylene with surfactant]
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 heated to 110 ° C. to be completely dissolved. After cooling to 50 ° C., 3 g of polyoxyethylene cetyl ether (nonionic surfactant, Emulgen 220 manufactured by Kao Corporation, HLB = 14.2) and polyoxyethylene lauryl ether (nonionic surfactant, Kao ( Emulgen 147, HLB = 16.3) 3 g was added and dissolved, and then cooled to 35 ° C.

  After adding 140 g of water little by little here and stirring sufficiently, emulsification was carried out at 21000 rpm for 3 minutes using an internal shear type emulsifier CLEARMIX CLM-0.8S (manufactured by M Technique Co., Ltd.). 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 a pressure of 0.02 MPa to 0.0045 MPa at a temperature of 45 ° C., and toluene was distilled off to obtain a milky white resin dispersion having a concentration of 25% by weight.

  As a result of measuring the dispersed particle size, the 50% particle size was 0.25 μm. In the same manner as in Example 1, adhesion, water resistance, and GH resistance were evaluated. The results are shown in Table-1. Both 50% particle size and 90% particle size were remarkably larger than the Examples, and aggregation was observed after storage for 3 months. Moreover, water resistance was also inferior.

[Comparative Example 2: Reaction of maleic anhydride-modified polypropylene with non-hydrophilic polymer]
30 g of maleic anhydride-modified polypropylene obtained in Production Example 2 (maleic anhydride group content 3.75 mmol) was added to 7.5 g of polyester polyol (P-2010 manufactured by Kuraray Co., Ltd., molecular weight 2000 (nominal value)). .75 mmol, equivalent to 25 parts by weight of polyolefin (A) as 100 parts by weight), and 37 g of dimethylbenzylamine were added in the same manner as in Example 1 to obtain 37 g of a yellow polymer. A graft copolymer is formed by grafting polyester polyol to maleic anhydride-modified polypropylene.

  80 g of THF was added to 20 g of the obtained yellow polymer and completely dissolved at 60 ° C. When 100 g of pure water was added dropwise at the same temperature over 1 hour, the yellow polymer was separated and a resin dispersion could not be obtained. The polyester polyol used in Comparative Example 2 (P-2010 manufactured by Kuraray Co., Ltd.) has a hydrophilic polymer that has an insoluble content exceeding 1% by weight when dissolved in water at 25 ° C. at a concentration of 10% by weight. is not.

[Examples 5 to 8, Comparative Example 3]
10 g of the resin dispersion (solid content concentration: 25% by weight) of Examples 1 to 4 and Comparative Example 1 and 10 g of the pigment dispersion paste (solid content concentration: 50% by weight) of Production Example 5 and the aqueous acrylic resin dispersion ES- 20 (Rikabond ES-20 manufactured by Chuo Rika Kogyo Co., Ltd., solid content concentration: 44%, resin Tg: 47 ° C.) was added and mixed to prepare a paint. The same as in Example 1, adhesion, water resistance, GH resistance and bleed out were evaluated. The results are shown in Table-2.

[Example 9]
Into a glass flask equipped with a reflux condenser, thermometer and stirrer, 650 g of toluene and 350 g of propylene-butene copolymer (Mitsui Chemicals Co., Ltd., Toughmer XM7070) were placed, the inside of the container was replaced with nitrogen gas, and the temperature was changed to 110 ° C. The temperature rose. After heating, 35 g of maleic anhydride was added, 10.7 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued by stirring at the same temperature for 10 hours. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing 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 carboxylic acid groups). g). The weight average molecular weight was 110,000.

  Next, 30 g (maleic anhydride group content: 6.3 mmol) of the obtained maleic anhydride-modified polymer and 70 g of toluene were added to a glass flask equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Next, 6 g of Jeffamine M-1000 (6 mmol, equivalent to 20 parts by weight of the hydrophilic polymer (B) per 100 parts by weight of the copolymer (A)) was added to a solution of 6 g of toluene, and the reaction was performed at 110 ° C. for 1 hour. I let you. Thereafter, 0.53 g (6 mmol) of morpholine was added and reacted at 110 ° C. for 1 hour.

A small amount was collected from the reaction solution, toluene was distilled off under reduced pressure, and infrared absorption spectrum analysis was performed. As a result, 90% of the peak corresponding to maleic anhydride near 1784 cm ⁻¹ disappeared, and the maleic anhydride-modified polymer and polyether It was observed that the amine was bound. A graft copolymer in which polyetheramine is graft-bonded to the maleic anhydride-modified polymer is formed.

  The temperature of the obtained reaction liquid was kept at 60 ° C., and a mixed liquid of 120 g of isopropanol and 30 g of water was added dropwise over 1 hour with heating and stirring to obtain a light yellowish liquid. Further, a mixed solution of 30 g of isopropanol and 160 g of water was added dropwise over 1 hour while keeping the temperature of the reaction solution at 60 ° C. to obtain a translucent yellow solution. This was cooled to 45 ° C., and the degree of vacuum was gradually reduced from 0.02 MPa to 0.004 MPa, and toluene, isopropanol and water were distilled off under reduced pressure until the polymer concentration reached 25% by weight. A dispersion was obtained. It seems to be transparent because the dispersed particle size is fine.

  As a result of measuring the dispersed particle size, the 50% particle size was 0.099 μm, and the 90% particle size was 0.184 μm. Table 3 shows the evaluation results of the adhesion of the obtained aqueous resin dispersion. In addition, the propylene content of the used propylene-butene copolymer (Mitsui Chemicals, Tuffmer XM7070) is shown. In addition, the adhesive evaluation in a present Example was performed as follows.

A substrate (test piece) was produced by injecting automobile exterior grade polypropylene into 70 mm × 150 mm × 3 mm, and the substrate surface was wiped with isopropyl alcohol. Here, the sample was spray coated so that the coating amount (dry weight after coating) was about 15 g / m ² . Next, the coated specimen was dried and baked at 80 ° C. for 40 minutes in a safe ben dryer to obtain a coated plate.

  After leaving at 23 ° C. for 24 hours, a test piece with 25 squares (5 × 5) grids was prepared at intervals of 2 mm in accordance with the grid pattern test method described in JIS K 5400, and cellophane tape (Nichiban) The product was peeled in the direction of 90 degrees and evaluated by the number of grids that were not peeled out of the 25 grids.

[Comparative Example 4: Reaction of maleic anhydride-modified polypropylene with morpholine]
In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 30 g of maleic anhydride-modified polypropylene synthesized in Production Example 4 (maleic anhydride group content: 4.8 mmol) and 70 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Next, 2 g (23 mmol) of morpholine was added and reacted at 110 ° C. for 1 hour.

After cooling, toluene was distilled off under reduced pressure to obtain 32 g of a yellow polymer.
75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. When 84 g of pure water was dropped at the same temperature over 1 hour, the yellow polymer was separated, and a resin dispersion could not be obtained. Although morpholine is a hydrophilic compound, it has a molecular weight of 89 and is not a hydrophilic polymer.

[Comparative Example 5: Dispersion of Unmodified Polypropylene with Surfactant]
All operations were performed in the same manner as in Comparative Example 1 except that the polypropylene obtained in Production Example 1 was used to obtain a resin dispersion.

  As a result of measuring the dispersed particle size, the 50% particle size was 0.32 μm. Met. Next, when the adhesion was evaluated in the same manner as in Example 1, peeling was observed between the base coat and the coating film at all grids, and the result was 0/100.

[Comparative Example 6: Dispersion of Unmodified Polypropylene with Jeffamine M-1000]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 25 g of the polypropylene obtained in Production Example 1 and 70 g of THF were added, and the temperature was raised to 60 ° C. to completely dissolve. A solution prepared by dissolving 9 g (9 mmol) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (Jefamine M-1000) in 27 g of THF was added thereto, and the temperature was set to 60 ° C. Subsequently, when 84 g of pure water was added dropwise at the same temperature over 1 hour, the solution became cloudy during the dropping, and the resin was separated, and a resin dispersion could not be obtained. That is, Jeffamine M-1000 has no ability to disperse unmodified polypropylene and is not a surfactant.

[Example 10]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 600 g of a maleic anhydride-modified polypropylene toluene solution obtained in Production Example 6 (maleic anhydride-modified polypropylene content: 240 g) was added, and the temperature was adjusted to 110 ° C. The temperature was raised, and a solution obtained by dissolving 36.0 g of Jeffamine M-1000 (36.0 mmol, corresponding to 15 parts by weight with respect to 100 parts by weight of the propylene polymer) in 54.0 g of toluene was added and reacted at 110 ° C. for 1 hour. I let you.

A part of the reaction solution was collected after cooling, and as a result of infrared absorption spectrum analysis of the polymer obtained by distilling off toluene under reduced pressure, the peak corresponding to maleic anhydride in the vicinity of 1784 cm ⁻¹ decreased. It was confirmed that maleic acid-modified polypropylene and polyetheramine were bound. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.
Next, 100 g (polymer content 40 g) of the obtained polyalkylene glycol-modified polypropylene in toluene was added to a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised to 65 ° C.

A mixed solvent of 120 g of isopropyl alcohol (IPA) and 30 g of distilled water was added dropwise over 1 hour at the same temperature to obtain a translucent pale yellow solution. The pressure was gradually reduced, and 120 g of a toluene / IPA / water mixed solvent was distilled off under reduced pressure.
Subsequently, a mixed solvent of 15 g of IPA and 135 g of distilled water was dropped at 65 ° C. over 30 minutes, and then the solvent was distilled off under reduced pressure by the same operation to obtain a white resin dispersion having a solid content concentration of 25% by weight. It was.
As a result of measuring the particle diameter, the 50% particle diameter was 0.142 μm. Moreover, the particle diameter after 3 months was measured and storage stability was evaluated. The results are shown in Table-4.

[Example 11]
A pale yellow translucent resin dispersion was obtained in the same manner as in Example 10 except that the first drop mixed solvent was a mixture of 120 g of IPA, 30 g of distilled water, and 0.4 g of 2-amino-2-methyl-1-propanol. Got the body.
As a result of measuring the dispersed particle size, the 50% particle size was 0.084 μm. The results are shown in Table-4.

[Example 12]
A pale yellow translucent resin dispersion was obtained in the same manner as in Example 10 except that the first drop mixed solvent was changed to a mixture of 120 g of IPA, 30 g of distilled water, and 0.4 g of N, N-dimethylethanolamine. .
As a result of measuring the dispersed particle size, the 50% particle size was 0.076 μm. The results are shown in Table-4.

[Example 13]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 g of maleic anhydride-modified propylene-butene copolymer produced in Production Example 7 (maleic anhydride group content 6 mmol) and 200 g of toluene are added, and the temperature is adjusted. The temperature was raised to 65 ° C. Next, 12 g (12 mmol) of Jeffamine M-1000 was added and reacted at the same temperature for 1 hour.

  A mixed solvent of 120 g of IPA and 30 g of distilled water was prepared, and a solution in which 1.1 g of 2-methyl-2-amino-1-propanol was added to a quarter thereof was prepared and added dropwise over 30 minutes. Subsequently, the remaining mixed solvent of IPA and distilled water was added dropwise at the same temperature over 1 hour to obtain a translucent pale yellow solution. The pressure was gradually reduced, and 120 g of a toluene / IPA / water mixed solvent was distilled off under reduced pressure.

  Subsequently, a mixed solvent of 15 g of IPA and 135 g of distilled water was dropped at 65 ° C. over 30 minutes, and then the solvent was distilled off under reduced pressure by the same operation to obtain a white resin dispersion having a solid content concentration of 25% by weight. It was. As a result of measuring the particle diameter, the 50% particle diameter was 0.132 μm. The results are shown in Table-4.

Claims (12)

The hydrophilic polymer (B) which may have a reactive group in the polyolefin (A) having a reactive group is a ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio). The polymer (C) bonded in the above is a resin dispersion in which water is dispersed with a 50% particle diameter of 1 μm or less, and the hydrophilic polymer (B) is a polyether resin. A resin dispersion.   The resin dispersion according to claim 1, wherein the polymer (C) has a 90% particle diameter of 1 µm or less and is dispersed in water.   The resin dispersion according to claim 1 or 2, wherein the hydrophilic polymer (B) has a reactive group, and the reactive group is an amino group. The resin dispersion according to any one of claims 1 to 3, wherein the polyolefin (A) is a copolymer of ethylene and / or propylene and another comonomer.   The resin dispersion according to any one of claims 1 to 4, wherein the hydrophilic polymer (B) has a weight average molecular weight Mw of 200 or more and 200,000 or less.   The resin dispersion according to any one of claims 1 to 5, wherein the polyolefin (A) has a reactive group, and the content of the reactive group is 0.01 to 5 mmol per 1 g of polyolefin. .   The polyolefin (A) is a stereoblock polypropylene polymer having a propylene content of 50 mol% or more and having an isotactic block and an atactic block, and / or a propylene-α-olefin copolymer. The resin dispersion according to any one of 1 to 6. The resin dispersion according to any one of claims 1 to 7, wherein the polyolefin (A) has a carboxylic acid derivative group as a reactive group. Polyolefin (A) is a carboxylic acid group, a dicarboxylic acid anhydride group, and having at least one reactive group selected from the group consisting of dicarboxylic anhydride monoester group, any one of claims 1 to 8 The resin dispersion described in 1. The resin dispersion according to any one of claims 1 to 9 , wherein the surfactant content of the resin dispersion is 20 parts by weight or less with respect to 100 parts by weight of the polymer (C). The resin dispersion according to any one of claims 1 to 10 , wherein the polyolefin (A) has a melting point Tm of 120 ° C or lower. The resin dispersion according to any one of claims 1 to 11 , wherein the polyolefin (A) has a molecular weight distribution Mw / Mn of 5 or less.