JP2010053188A - Resin dispersion composition including polyolefin resin, primer contain the same, coating material and laminate thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin dispersion composition which excels in stability, improves the adhesion to a coating film other than polyolefins, has good coating film properties such as moisture resistance, water resistance, oil resistance (GH resistance), chemical resistance, and resistance to scuffing, and has sufficient adhesion to a base material composed of a polyolefin polymer, and is useful as a primer and a coating material for polyolefin polymers and the like. <P>SOLUTION: The resin dispersion composition is obtained by dispersing a polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) at a ratio (weight ratio) of (A):(B)=100:5 to 100:500 and an acrylic resin having an acid value of 0-80 mgKOH/g and/or a urethane resin having an acid value of 0-40 mgKOH/g into water. A primer, a coating material, and a laminate which use this resin dispersion composition are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin dispersion composition containing a polyolefin-based resin, a primer containing the same, a paint, and a laminate thereof.

  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. Usually, an aqueous dispersion is preferably used from the viewpoint of health and safety and environmental pollution.

The present applicant has shown good adhesion to polyolefin materials or plastic materials containing polyolefin, etc., and is usually coated on difficult-to-adhere substrates such as untreated polypropylene, which is difficult to paint or bond. Patent Document 1 discloses a resin dispersion obtained by dispersing a polymer obtained by bonding a hydrophilic polymer to a polyolefin so that water can be formed.
On the other hand, when these modified polyolefins are used as a primer or a paint, the adhesion with a coating film other than the polyolefin is improved, water resistance, oil resistance (GH resistance), chemical resistance, abrasion resistance, etc. In order to improve the coating properties, it is necessary to add a resin dispersion made of an acrylic resin, a urethane resin or the like. However, since these components generally do not have high adhesion to a polyolefin substrate, even if a modified polyolefin resin dispersion alone can form a coating film having sufficient substrate adhesion, There was a problem that the adhesion of the base material was greatly lowered after mixing of resin, urethane resin and the like.

In order to solve such problems, Patent Document 2 discloses an aqueous resin dispersion in which an acrylic resin, a urethane resin, or the like is blended with a polymer containing a propylene-based polymer. Patent Document 3 discloses a coating composition in which an anionic urethane emulsion is blended with an aqueous dispersion of an aqueous non-chlorinated polyolefin.
JP2007-246871 JP2007-39645A JP 2008-56914 A

The inventions disclosed in Patent Documents 2 and 3 provide an aqueous dispersion of a resin that is fine and stable in dispersion particle size, bleed-out is suppressed, and is useful as a surface treatment agent, an adhesive, or a paint for a polyolefin-based substrate. It is intended to provide.
However, when an acrylic resin, a urethane resin, or the like is blended, the adhesiveness of a polymer containing a propylene-based polymer or an aqueous dispersion of non-chlorinated polyolefin itself becomes lower, resulting in a sufficiently strong primer or paint. The problem that adhesion was not obtained remained.

  Therefore, the present invention has excellent stability, improved adhesion to coating films other than polyolefin, and has coating film properties such as moisture resistance, water resistance, oil resistance (GH resistance), chemical resistance, and abrasion resistance. The present invention provides a resin dispersion composition that is useful and has sufficient adhesion to a base material made of polyolefin, and is useful as a primer or a paint for a polyolefin-based polymer.

As a result of intensive investigations to achieve the above object, the present inventors have found that a polymer in which a hydrophilic polymer is bonded to polyolefin at a predetermined ratio and a resin dispersion composition in which a specific resin is dispersed in water are polyolefins. It has been found that it has excellent adhesion to the substrate, moisture resistance and oil resistance, and has led to the present invention.
That is, the gist of the present invention is that 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) ( And C) and an acrylic resin having an acid value of 0 to 80 mgKOH / g and / or a urethane resin having an acid value of 0 to 40 mgKOH / g.

The present invention also relates to a resin dispersion composition in which the acrylic resin is a nonionic acrylic resin and the urethane resin is a nonionic urethane resin.
Moreover, this invention relates to the resin dispersion composition whose Tg of the said acrylic resin and / or the said urethane resin is 40 degrees C or less.
The present invention also relates to a resin dispersion composition in which the polymer (C) and the acrylic resin and / or urethane resin are dispersed by forming separate particles.

The present invention also relates to a resin dispersion composition in which the polymer (C) is a graft copolymer in which a hydrophilic polymer (B) is graft-bonded to a polyolefin (A).
Another gist of the present invention relates to a primer and a paint comprising the resin dispersion composition.
Another gist of the present invention relates to a laminate in which a resin layer is formed by applying the resin dispersion composition, the primer, or the paint to the thermoplastic resin molded body (F).

Since the resin dispersion composition of the present invention contains an acrylic resin and / or a urethane resin, adhesion with a coating film other than polyolefin is improved, moisture resistance, water resistance, oil resistance (GH resistance), chemical resistance It is possible to provide a coating film having good coating properties such as property and abrasion resistance.
Furthermore, the coating film made of the resin dispersion composition of the present invention contains an acrylic resin and / or a urethane resin that does not have high adhesion to a base material made of polyolefin, and the hydrophilic polymer is added to the polyolefin. Compared with a coating film made of a resin dispersion obtained by dispersing only the polymer to be bonded in water, it exhibits strong adhesion to a polyolefin substrate without significantly reducing the substrate adhesion. Therefore, the coating film of the present invention shows good adhesion to a polyolefin material, particularly a plastic material containing a propylene material or a propylene-based polymer material, and is usually made of untreated polypropylene which is difficult to paint or adhere. It can also be formed on such hard-to-adhere substrates.

Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents.
The resin dispersion composition of the present invention is obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio). A polymer (C) and an acrylic resin having an acid value of 0 to 80 mgKOH / g and / or a urethane resin (D) having an acid value of 0 to 40 mgKOH / g are dispersed in water.

  The form of the resin dispersion composition containing the polymer (C) and the acrylic resin and / or urethane resin (D) is not particularly limited. For example, there is a method of emulsifying and mixing the polymer (C) and the acrylic resin and / or the urethane resin (D). In this method, particles made of the polymer (C) and particles made of the acrylic resin and / or the urethane resin (D) are separately formed to obtain a resin dispersion composition dispersed in water.

  Or there exists the method of emulsifying, after mixing a polymer (C), an acrylic resin, and / or a urethane resin (D). In this method, a resin dispersion composition in which particles in which the polymer (C) and the acrylic resin and / or the urethane resin (D) are mixed in one particle is dispersed in water is obtained. For example, the polymer (C) can coexist when the acrylic resin and / or urethane resin (D) is polymerized, and both can be mixed, emulsified and dispersed in water, and the acrylic resin and / or urethane resin (D) in one particle. And a polymer (C) can be formed. Alternatively, the acrylic resin and / or the urethane resin (D) and the polymer (C) can be mixed separately and then mixed by melt-kneading and the like. Particles containing the combined (C) can be formed.

  Resin dispersion composition in which particles made of polymer (C) and particles made of acrylic resin and / or urethane resin (D) exist separately in order to effectively exhibit the properties of polymer (C) and resin. Things are preferred. Such a resin dispersion composition includes, for example, a dispersion obtained by emulsifying and dispersing a polymer (C) in water, and a dispersion obtained by emulsifying and dispersing an acrylic resin and / or a urethane resin (D) in water. It is obtained by mixing the body.

Hereinafter, the component used for the resin dispersion composition of this invention is demonstrated.
[1] Polyolefin (A)
As the polyolefin (A) used in the resin dispersion composition of the present invention, polyolefin (A1) having no reactive group or polyolefin (A2) having 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, ethylene or propylene homopolymer, ethylene and propylene copolymer, ethylene or propylene and others Or a copolymer with an α-olefin comonomer having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene and norbornene, or these comonomers Two or more types of copolymers 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. Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by mass or more, preferably 10% by mass or more, and the chlorination degree is usually 50% by mass or less, preferably 30% by mass or less.

  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.

Preferably, the content of propylene in the polyolefin (A1) is 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and most preferably 100 mol%. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.
Polyolefin (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the stereoregularity of the propylene homopolymer or copolymer, those having an isotactic structure in whole or in part are preferable. For example, not only normal isotactic polypropylene but also isotactic block polypropylene, stereo block polypropylene, etc. as described in JP-A-2003-231714 and US Pat. No. 4,522,982 should be used. Can do.

Preferably, the polyolefin (A1) is a stereoblock polypropylene homopolymer or copolymer having an isotactic block and an atactic block. Most preferred is a stereoblock polypropylene polymer having an isotactic block and an atactic block.
Preferably, the [mmmm] pentad exhibiting isotactic stereoregularity is 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.

  The polyolefin of the present invention 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 polystyrene. 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 tetrahydrofuran (THF) or the like as a solvent.

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. This is because the molecular weight distribution and stereoregularity distribution of single-site catalysts are generally sharp due to the ligand design. Moreover, as a single site catalyst, a metallocene catalyst and a Brookhart type catalyst can be used, for example. For the metallocene catalyst, a preferable catalyst may be selected according to the stereoregularity of the polyolefin to be polymerized, such as C1 symmetric type, C2 symmetric type, C2V symmetric type, and CS symmetric type. Preferably, a C1 symmetric type or C2 symmetric type metallocene catalyst can be used.

The polymerization may be any polymerization form such as solution polymerization, slurry polymerization, bulk polymerization, and gas phase polymerization. In the case of solution polymerization or slurry polymerization, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic carbonization such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrogen, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples include alcohols such as ethanol, n-propanol, isopropanol, and n-butanol; ethers such as dibutyl ether and tetrahydrofuran; and polar solvents such as dimethylformamide and dimethyl sulfoxide. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, hexane, heptane, cyclopentane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.
The polyolefin (A1) may be linear or branched.

[1-2] Polyolefin (A2) having a reactive group
Examples of the polyolefin (A2) having a reactive group include a copolymer (A2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization, or reactive. A polymer (A2b) obtained by graft polymerization of a radically polymerizable unsaturated compound having a group to a polyolefin can be used.

  The copolymer (A2a) is obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is inserted into the main chain. Copolymer. For example, it can be obtained by copolymerizing an α-olefin such as ethylene, propylene or butene and an α, β-unsaturated carboxylic acid or anhydride such as acrylic acid or maleic anhydride. Specific examples of the copolymer (A2a) include an ethylene-acrylic acid copolymer and an ethylene-acrylic acid ester-maleic anhydride copolymer. 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, polyolefin (A1) 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 ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include modified polypropylene and chlorinated products thereof, acrylic acid-modified ethylene-propylene copolymers and chlorinated products thereof, and acrylic acid-modified propylene-butene copolymers. 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.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 200 ° C. The reaction time is usually about 2 to 20 hours.

About the manufacturing method of a polymer (A2b), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. 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.
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 polyolefin (A2) having a reactive group is preferably in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g per 1 g of polyolefin. A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, and particularly preferably 0.5 mmol / g. The higher the lower limit value, the more the hydrophilic polymer (B) is bound and the higher the hydrophilicity of the polymer (C). Therefore, the dispersed particle size tends to decrease. The lower the upper limit value, the lower the crystallinity of the base material. There is a tendency for adhesion to polyolefin to increase. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

The polyolefin (A2) may be linear or branched.
Polyolefin (A2) may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, 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.

For the purpose of reducing the environmental load, it is desirable that the polyolefin (A) does not substantially contain chlorine. “Substantially no chlorine” means, for example, that the chlorination rate of polyolefin is less than 5% by mass.
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 (A) has at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic anhydride group, and a dicarboxylic anhydride monoester group. These carboxylic acid groups and the like are not only highly reactive and easy to bond with hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.
Moreover, although both a polymer (A2a) and a polymer (A2b) can be used, a polymer (A2b) is preferable normally. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).

[2] Hydrophilic polymer (B)
The hydrophilic polymer used in the resin dispersion composition of the present invention refers to a polymer having an insoluble content of 1% by mass or less when dissolved in water at 25 ° C. at a concentration of 10% by mass. The hydrophilic polymer (B) is not particularly limited as long as the effects of the present invention are not significantly impaired, and any of synthetic polymers, semi-synthetic polymers, and natural polymers can be used. It may have a reactive group.

  Although it does not specifically limit as a synthetic polymer, For example, a poly (meth) acryl resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin etc. can be used. Examples of natural polymers include, but are not limited to, starch such as corn starch wheat starch, candy starch, potato starch, tapioca starch, and rice starch, seaweed such as fungi, agar and sodium alginate, gum arabic, tragacanth gum, and konjac. Animal materials such as quality materials, glue, casein and gelatin, fermented mucilages such as pullulan and dextrin, and the like can be used. The semi-synthetic polymer is not particularly limited, and for example, starch such as carboxyl starch, cationic starch, and dextrin, viscose, cellulose such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose can be used.

  Among these, a synthetic polymer that can easily control the degree of hydrophilicity and has stable characteristics is preferable. More preferred are acrylic resins such as poly (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl pyrrolidone 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 particularly limited. For example, a method of radical graft polymerization directly on the polyolefin, an acrylic resin having a reactive group such as a hydroxyl group, an amino group, a glycidyl group, or an (anhydrous) carboxylic acid group is used. And 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.
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 particularly limited. For example, a method of ring-opening polymerization of a cyclic alkylene oxide in a polyolefin having a reactive group, a polyether polyol or a polyether amine obtained by ring-opening polymerization, etc. And a method of reacting a hydrophilic polymer having a reactive group with a polyolefin 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 one or more reactive groups 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 polyolefin. 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 esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned. 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, the hydrophilic polymer (B) bonded to the polyolefin (A) is obtained by polymerizing the hydrophilic monomer in the presence of the polyolefin (A). 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 monomer may be copolymerized as long as a hydrophilic polymer can be formed after polymerization.

Specifically, for example, there is a method in which a hydrophilic radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a hydrophilic polymer (B) and bonded to the polyolefin (A). 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.
The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples include methacrylic acid dimethylaminoethyl quaternized compounds, vinyl pyrrolidone and the like.

In addition, a hydrophobic radical polymerizable compound 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, there is a method in which a radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then modified to obtain a 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 monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. 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.

Alternatively, a polyolefin (A2) having a reactive group is used, and a hydrophilic radical polymerizable unsaturated compound, a hydrophilic ring-opening polymerization monomer, or the like is polymerized by using the reactive group as a start terminal to form a hydrophilic polymer (B). There is a way to get it.
As the hydrophilic radical-polymerizable unsaturated compound, those described above can be used similarly. Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [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 Polymer (C) Dispersion The method for producing the polymer (C) dispersion is not particularly limited. For example, the polymer (C), water, and a mixture of solvents other than water are used. After preparation, a method of preparing an aqueous dispersion by removing the solvent from the mixture, a method of melting the polymer (C) at a temperature higher than the melting point, and then adding water to form a dispersion, etc. It is done. 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 mass or more in water is preferable, and more preferably 5% by mass 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] Dispersion of polymer (C) The polymer (C) used in the present invention is very excellent in water dispersibility, and according to the method for producing a dispersion of the polymer (C) described above, dispersed particles are used. Since an aqueous resin dispersion having a small diameter can be obtained, the resin dispersion composition of the present invention obtained by mixing these has the 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 dispersion of the polymer (C) is referred to as 50% cumulative particle diameter (50% particle diameter or 50% average particle diameter) from the finer particle diameter in terms of volume. .) 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 dispersion of the polymer (C) has a solid content of preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more based on the whole. Moreover, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass 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, when the resin dispersion composition of the present invention is used as, for example, 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 dispersion of the polymer (C) has an advantage that the 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 and cetyl trimethyl ammonium bromide. 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 mass of the polymer (C) is usually 50 parts by mass or less, preferably 30 parts by mass or less.

  However, one of the advantages of the present invention is that it is not necessary to use a surfactant. Therefore, it is preferable that the amount of the surfactant is small, and the surfactant content of the resin dispersion is 100 masses of the polymer (C). It is preferable that it is 10 mass parts or less with respect to a part. More preferably, it is 5 mass parts or less, More preferably, it is 2 mass parts or less. It can also be substantially free of surfactant. “Substantially free of surfactant” means less than 1 part by mass relative to 100 parts by mass 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 mass or less with respect to 100 parts by mass of the polymer (C), the nonionic surfactant may be 10 parts by mass or less.

Another advantage of the present invention is that it is not necessary to use chlorinated polyolefin and the environmental load can be reduced.
An acidic substance or a basic substance can be added to the dispersion of the polymer (C) as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of basic substances include inorganic bases such as sodium hydroxide and potassium hydroxide, triethylamine, diethylamine, diethylethanolamine, and 2-methyl-2-amino-propanol.

[6] Acrylic resin and / or urethane resin (D)
(D-1) Acrylic resin having an acid value of 0 to 80 mgKOH / g The acrylic resin used in the resin dispersion composition of the present invention is an anionic or nonionic acrylic resin having an acid value of 0 to 80 mgKOH / g. There is no particular limitation. The acrylic resin refers to a homopolymer or copolymer of (meth) acrylic acid and / or its ester. In addition, (meth) acryl refers to acryl and / or methacryl.

  Specific examples of (meth) acrylate esters include (meth) acrylate 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 acid Hexyl, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, or carbon (Meth) acrylic acid ester having an aryl group or an aralkyl group having 6 to 12 atoms, for example, Meth) phenyl acrylate include benzyl (meth) acrylate and the like.

  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 a (meth) acrylic oligomer is usually used in the range of 1 to 80 parts by mass per 100 parts by mass of the (meth) acrylic acid and / or its ester.

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 the case of an acrylic resin, the acid value is usually 0 mgKOH / g or more and 80 mgKOH / g or less, preferably 45 mgKOH / g or less, more preferably 35 mgKOH / g or less, more preferably 25 mgKOH / g or less, more preferably 5 mgKOH / g or less. It is. When the content is 80 mgKOH / g or less, the adhesion of the resin dispersion composition obtained by dispersing the polyolefin polymer (C) and the acrylic resin to the polyolefin substrate becomes high, and the water resistance of the resulting coating film also becomes good. preferable. From the viewpoint of adhesion, it is particularly preferable to use a nonionic acrylic resin.

Here, the anionic acrylic resin indicates an acid value of 5 mgKOH / g or more, and the nonionic acrylic resin indicates an acid value of less than 5 mgKOH / g.
As a method for introducing an acid group into an acrylic resin, it is common to emulsion-polymerize acrylic acid or methacrylic acid with other (meth) acrylic acid esters in water.
When the acrylic resin is dispersed in water to form a dispersion, an anionic or nonionic surfactant may be used when the acrylic resin itself has low emulsifiability or emulsion polymerization.

When using a 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 anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, and sodium polyoxyethylene lauryl sulfate.

Examples of nonionic surfactants include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene sorbitan monolaurate.
The amount of the anionic surfactant is preferably 10 wt% or less, more preferably 5 wt% or less, based on 100 parts by weight of the acrylic resin. If it is 10 wt% or less, the hydrophilicity is not too high, and the water resistance of the coating film is good, which is preferable.

The amount of the nonionic surfactant is preferably 30 wt% or less, more preferably 20 wt% or less with respect to 100 parts by weight of the acrylic resin. If it is 30 wt% or less, the hydrophilicity is not too high and the water resistance of the coating film is good, and the surfactant does not bleed out and the appearance is good.
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 mass or more, more preferably 1 part by mass or more per 100 parts by mass of the acrylic resin. However, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the acrylic resin. 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.

The acrylic resin used in 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 acrylic resin dispersion used in the present invention is 0.01 μm to 0.5 μm, more preferably 0.05 μm to 0.3 μm. Moreover, it is preferable that resin solid content is 15-70 mass%. The liquid viscosity is preferably 1 to 50,000 mPa · s.

(D-2) Urethane resin having an acid value of 0 to 40 mgKOH / g The urethane resin used in the resin dispersion composition of the present invention is an anionic or nonionic urethane resin having an acid value of 0 to 40 mgKOH / g. Although not particularly limited, for example, (i) a component containing an average of two or more active hydrogens in one molecule, (ii) a urethane polymer obtained by reacting with a polyvalent isocyanate component, or the above ( Examples thereof include urethane polymers obtained by reacting an isocyanate group-containing prepolymer obtained by reacting component i) and component (ii) under an excess of isocyanate groups with a chain extender such as diol. In the case of an anionic urethane resin, an acid component (acid residue) is generally contained, and in the case of a nonionic urethane resin, a polyethylene glycol chain is generally contained.

When the urethane resin is dispersed in water to form a dispersion, an anionic or nonionic surfactant may be used if the emulsifiability of the urethane resin itself is low.
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 ring opening 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 the case of an anionic urethane resin, it is general to contain an acid component (acid residue) and to exhibit water dispersibility with its neutralized ionicity. The acid residue content is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less as the acid value of the urethane resin. When the acid value is 5 or more, water dispersibility is sufficient, while when the acid value is 40 mgKOH / g or less, the composition comprising the polyolefin polymer (C) and the urethane resin dispersion has high adhesion to the polyolefin substrate, The water resistance of the coating film is also good, which is preferable. From the viewpoint of adhesion, it is particularly preferable to use a nonionic urethane resin.

Here, the anionic urethane resin indicates an acid value of 5 mgKOH / g or more, and the nonionic urethane resin indicates an acid value of less than 5 mgKOH / g.
As a method for introducing an acid group into a urethane resin, a conventionally used method can be used without any particular limitation. For example, dimethylolalkanoic acid is a part of the glycol component described in (2) to (4) above or A method of introducing an acid group by introducing a carboxyl group into a polyether diol, polyester diol, polyether ester diol or the like in advance by replacing all of them is preferable. Examples of the dimethylolalkanoic acid used here include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid.

When the nonionic urethane resin is dispersed in water, it is common to use a non-ionic surfactant containing a polyethylene glycol chain and exhibiting hydrophilicity and water dispersibility.
The amount of polyethylene glycol is 20 to 80 wt%, preferably 30 to 70 wt%, more preferably 40 to 60 wt% in the urethane resin. If it is 20 wt% or less, sufficient water dispersibility is exhibited and the particle size becomes fine, and if it is 80 wt% or less, the hydrophilicity is not too high and the water resistance of the coating film is improved, which is preferable.

When using a surfactant when dispersing the urethane resin in water, it can be used in the same manner as the acrylic resin.
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.
The particle diameter of the urethane resin particles in the aqueous resin dispersion of this urethane resin is 0.01 μm to 0.5 μm, more preferably 0.05 μm to 0.3 μm. The resin solid content is 15 to 70% by mass. It is preferable. The liquid viscosity is preferably 1 to 10,000 mPa · s.

The glass transition temperature (Tg) of the acrylic resin and / or urethane resin (D) is preferably 40 ° C. or lower. Preferably it is 20 degrees C or less, More preferably, it is 0 degrees C or less. When the temperature is 40 ° C. or lower, the composition of the polyolefin polymer (C) and the acrylic resin and / or the urethane resin (D) tends to have high adhesion to the polyolefin substrate, which is preferable.
The blending ratio of the polyolefin polymer (C) and the acrylic resin and / or the urethane resin (D) is not particularly limited, but the solid content ratio of the resin dispersion composition is (C) :( D) = 1: 0. It is preferable to mix in the range of 1-1: 20 (weight ratio). (C) When it exceeds 0.1 part by weight with respect to 1 part by weight, the oil resistance and rubbing resistance of the coating film tend to be improved, and (C) with respect to 1 part by weight, (D) 20 Below the part by weight, the adhesion to the polyolefin substrate is good.

[7] Other components The resin dispersion composition of the present invention may 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, etc .; conductivity imparting agents such as titanium oxide, carbon black, ferrite, dyes, pigment dispersants, leveling agents, antifoaming Various additives such as additives, 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, there can be used a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, etc. Among them, an isocyanate compound, Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

  When the resin dispersion composition of the present invention is used for primer, paint, ink, etc., a hydrophilic organic solvent other than water is added for the purpose of increasing the drying speed or obtaining a surface with a good finish. Can do. 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.

[7-1] Combined use of other resins The resin dispersion composition of the present invention is mixed with a water-soluble resin or a resin that can be dispersed in water 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 resins other than (D-1), polyepoxy resins, polyester resins, urethane resins other than (D-2), melamine resins, alkyd resins, and the like. 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 in which particles in which these resins and the polymer (C) are mixed in one particle is dispersed in water is obtained. 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. 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 mass ratio of the component (A) and 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 mass, and the amount of polyolefin (A) is 10 parts by mass or more, preferably 90 parts by mass or less. When the amount of the polyolefin (A) is less than 10 parts by mass, the adhesion to the polyolefin-based substrate is insufficient. Preferably it is 15 mass parts or more, More preferably, it is 20 mass parts or more. When the amount of the polyolefin (A) is larger than 90 parts by mass, the physical properties of the coating film obtained from such a composite aqueous resin dispersion, specifically, the strength, water resistance, weather resistance, abrasion resistance, Solvent property will become insufficient. Preferably it is 85 mass parts or less, More preferably, it is 80 mass parts or less.

  The mass ratio of the total amount of the component (C) and the other resin and water is preferably 5:95 to 60:40. That is, the total amount of the component (C) and other resin and water is 100 parts by mass, and the total amount of the component (C) and other resin is preferably 5 parts by mass or more and 60 parts by mass or less. The amount of 5 parts by mass or more is preferable because workability such as coating and heat curing is improved. More preferably, it is 10 mass parts or more, More preferably, you may be 15 mass parts or more. When the content is less than 60 parts by mass, the viscosity of the resin dispersion composition does not become too high, the coating property becomes good, and a uniform coating film can be formed. More preferably, it is 55 mass parts or less, More preferably, it is 50 mass parts 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 mass or less with respect to 100 parts by mass of the resin. Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 2 mass parts 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.
[7-2] Addition of pigment The pigment (E) can be added to the resin dispersion composition of the present invention. The resin dispersion composition 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 may be used in combination.

  The amount of the pigment (E) added to the resin dispersion composition is preferably 10 parts by mass or more with respect to 100 parts by mass of the resin (the total amount of the polymer (C) and other resins). More preferably, it is 50 parts by mass or more. However, 400 mass parts or less are preferable, More preferably, it is 200 mass parts 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 manufactured by BASF Japan; an acidic block copolymer such as BYK-190 manufactured by Big Chemie; a styrene-maleic acid copolymer; a surface manufactured by Air Products (Air Products) Examples thereof include acetylenic diol derivatives such as Nord T324; water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., Ltd. By using these pigment dispersants, a stable pigment paste can be prepared.

  The resin dispersion composition 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.

[8] Laminate The resin dispersion composition of the present invention, a primer containing the same, or a paint can be applied to a substrate to form a resin layer to obtain 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 composition of the present invention can be applied to a molded body (base material) of an olefin polymer having crystallinity 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 composition of the present invention is applied may be any of the above-mentioned various polymers or resins, which are known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be formed by.
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.

[8-1] Method for Producing Laminate The method for forming the resin layer on the substrate is not particularly limited, and any known method can be used. For example, a resin dispersion or a paint is applied by spraying. Examples thereof include a method, a method of applying with a roller, and a method of applying with a brush.
After applying the resin dispersion composition, primer, or paint, it is usually possible to cure the coating film by heating with nichrome wire, infrared rays, high frequency or the like to obtain 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.

[8-2] Thermoplastic resin molding (F)
The base material of the laminate of the present invention is preferably a thermoplastic resin molded body. 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).

  The polyolefin molded body is usually a crystalline polyolefin molded body, and various known polyolefins can be used, and are not particularly limited. For example, ethylene or propylene homopolymer, ethylene and propylene copolymer, ethylene or Copolymerization of propylene with other comonomers, for example, butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and α-olefin comonomers having 2 or more carbon atoms such as norbornene A combination or two or more copolymers 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) of 2 g / 10 min or more, more preferably 10 g / 10 min or more, and particularly preferably 25 g / 10 min. 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 crystalline polypropylene. Crystalline polypropylene is a propylene homopolymer and / or a propylene / ethylene copolymer. Here, the propylene / ethylene copolymer is a propylene / ethylene random copolymer and / or a propylene / ethylene block copolymer, and preferably a propylene / ethylene block copolymer.

Here, the propylene / ethylene block copolymer is composed 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 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, particularly preferably 40 g / 10 min or more. . However, it is preferably 500 g / 10 min or less, more preferably 400 g / 10 min or less, 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 mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. However, it is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass 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.
Although there is no restriction | limiting in particular about the quantity of a unit part and b unit part, Generally a unit part becomes like this. Preferably it is 95 mass% or less of the whole quantity, More preferably, it is 50-95 mass%, More preferably, it is 60-90 mass%. , B unit part is preferably adjusted to 5% by mass or more of the total amount, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass. 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 using the orthodichlorobenzene.
Since the ratio of the amount of the a unit part to the 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 above 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 phase polymerization method, a liquid phase bulk polymerization method, a slurry polymerization method or the like. 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.
The propylene homopolymer and propylene / ethylene block copolymer of the present invention preferably have excellent mechanical properties and high rigidity and impact resistance in order to be used as a structural material. 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 has excellent impact resistance and is 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.

[8-3] Inorganic filler component The thermoplastic resin molded article (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-shaped 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 article, but is preferably 1 to 80 parts by mass, more preferably 2 to 75 parts by mass, and more preferably 100 parts by mass of the crystalline polyolefin. Preferably it is 5-60 mass parts.

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 still more 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 mass. 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 obtained by mechanically pulverizing the talc 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. In order to adjust the pulverized talc to the above average particle size, wet or dry classification is performed once or repeatedly in an apparatus such as a cyclone, a cyclone air separator, a micro separator, or a sharp cut separator.

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 preferable, and those having a modification rate of 0.1 to 10% by mass are preferably used.

(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.

[8-4] 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 of the molded product can be improved.
Examples of the elastomer component include ethylene / α-olefin random copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer.

  Specific examples include ethylene / α-olefin copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-hexene copolymer rubber, ethylene / 1-octene copolymer rubber and the like. Polymer rubber; Ethylene / α-olefin / non-conjugated 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.

[8-5] Other components In addition to the above, the thermoplastic resin molded article (F) can contain any additive or compounding component 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.

[8-6] 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.

[8-7] 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 bleed-out 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 sufficient performance for practical use as thinned, highly functional, and enlarged parts / materials. .
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) Propylene content The propylene content [P] in the propylene-butene copolymer was calculated from the results measured by a 13C-NMR spectrum measurement method with an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a 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 are described in J. Org. C. Randall, Macromolecules, 11, 592 (1978) was used for calculation.

(2) Weight average molecular weight, number average molecular weight First, 5 mg of a sample is collected in a 10 ml vial, 5 g of tetrahydrofuran containing BHT 250 ppm is added as a stabilizer, and completely dissolved at 50 ° C. After cooling to room temperature, the mixture was filtered through a filter having a pore diameter of 0.45 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed using Tosoh Corp. GPC HLC-8020 equipped with a guard column TSK guard column H _XL- H to TSK gel GMH _XL- L (30 cm × 2) as a column. Measurement conditions were as follows: injection volume of sample solution: 50 μl, column temperature: 40 ° C., solvent: tetrahydrofuran, flow rate: 1.0 ml / min.

  In calculating the weight average molecular weight and the number average molecular weight, a commercially available monodisperse polystyrene standard sample was measured as a standard sample, and a calibration curve was created from the retention time and molecular weight of the standard sample.

(3) Graft rate 200 mg of the polymer and 4800 mg of chloroform were placed in a 10 ml sample bottle and heated at 50 ° C. for 30 minutes for complete dissolution. 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 ( Mass%).

(4) Dispersion particle diameter It measured using Nikkiso Co., Ltd. Microtrac UPA. The density of the dispersion is 0.9 kg / m ³ , the shape is spherical, the dispersion medium is water and the measurement time is 180 seconds, and the cumulative particle size is 50%, 90% The particle size was determined.

(5) Peel strength After the automobile exterior grade polypropylene was injection-molded into 70 mm × 150 mm × 3 mm to prepare a substrate, this was divided into two equal parts to prepare a 70 mm × 75 mm × 3 mm substrate. After applying a masking tape of about 1 cm so that the modified polyolefin composition was not applied to one end, the substrate surface was wiped with isopropyl alcohol. Next, the modified polyolefin composition was applied by spraying so that the coating amount was about 10 g / m ^2, and this test piece was dried at 90 ° C. for 3 minutes in a safe ben dryer, and then the masking tape was peeled off.

Next, a two-component polyurethane paint was spray-applied so that the application amount was about 100 to 150 g / m ² . Next, the coated test piece was dried in a safe ben dryer at 90 ° C. for 30 minutes.
A 1.5 cm width was cut with a cutter from above the cured two-component polyurethane paint of the laminate that was allowed to stand at 25 ° C. for 24 hours or more after baking.
Using a FUDOH rheometer, the notched end was sandwiched between one jig and the other side of the substrate was sandwiched between the other jig and pulled in a 180 ° direction at a pulling speed of 50 mm / min. The peel strength at the time was measured, and the peel strength was converted per 1 cm.

[Production Example 1]
(Melting and kneading process)
200 kg of propylene-butene copolymer (Mitsui Chemicals, Tuffmer XM7080, propylene content 80 mol%) and 5 kg of maleic anhydride were dry blended with a super mixer, and then a twin-screw extruder (TEX54αII manufactured by Nippon Steel) The kneading part while feeding t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) halfway with a liquid pump so that the amount becomes 1 part by weight per 100 parts by weight of the propylene-butene copolymer. Were kneaded under the conditions of a cylinder temperature of 200 ° C., a screw rotation speed of 125 rpm, and a discharge rate of 80 kg / hour to obtain a pellet-shaped product.

  The maleic anhydride group content (graft ratio) of the maleic anhydride-modified propylene-butene copolymer thus obtained was 0.8% by weight (0.08 mmol / g as maleic anhydride group, as carboxylic acid group). 0.16 mmol / g). The weight average molecular weight was 156,000, and the number average molecular weight was 84,000 (both in terms of polystyrene).

(Solution denaturation process)
Next, a reflux condenser, a thermometer, a nitrogen gas blowing pipe and a stirrer were installed in a 2 L glass flask equipped with a bottom extraction valve and an oil circulation jacket heater, and then 150 g of the above maleic anhydride-modified propylene-butene copolymer. And 150 g of toluene were charged, and the mixture was heated and stirred until it reached 110 ° C. while blowing nitrogen gas.

  After raising the temperature, 2.25 g of maleic anhydride was added and dissolved, 0.75 g of perbutyl I was added, and stirring was continued at the same temperature for 7 hours. Thereafter, 0.5 g of the solution was extracted, acetone was added, the precipitated polymer was filtered, and precipitation and filtration were further repeated with acetone, and the finally obtained polymer was dried under reduced pressure. The content (graft ratio) of maleic anhydride groups of this modified polymer was 1.5% by weight (0.15 mmol / g as maleic anhydride groups and 0.30 mmol / g as carboxylic acid groups). The weight average molecular weight was 146,000, and the number average molecular weight was 77,000 (both in terms of polystyrene).

(Emulsification process)
Next, 129 g of toluene was added to the solution for dilution, and then tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Irganox 1010 manufactured by Ciba Specialty Chemicals) ) 0.075 g was added. The jacket temperature (external temperature) was lowered to 75 ° C., 15 g of isopropanol was further added and stirred for 1 hour, and then 600 g of hot water at 70 ° C. was added and stirred. After stirring for 15 minutes, the mixture was allowed to stand to separate into a toluene solution phase at the top and a warm water phase and a two phase at the bottom, so warm water was extracted from the bottom extraction valve. After the washing operation with warm water was repeated once more, the toluene solution was mixed with methoxypoly (oxyethylene / oxypropylene) -2-propylamine (a polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value) ) Was added dropwise over 1 hour in a solution of 22.5 g (22.5 mmol) in 405 g isopropanol and 101 g water.

  A process of installing a Dean-Stark tube between the reflux condenser and the flask, depressurizing the liquid obtained at a jacket temperature of 90 ° C., distilling off 120 g of the solvent, and adding 90 g of water was repeated 5 times. Thereafter, 1.5 g (15 mmol) of 90% aqueous solution (AMP90) of 2-amino-2-methyl-1-propanol was further added, and toluene, isopropanol and water were distilled off under reduced pressure until the solid content became 30% by weight. An aqueous dispersion was obtained. As a result of measuring the dispersed particle size, the 50% particle size was 46 μm, and the 90% particle size was 64 μm.

[Reference Example 1]
The aqueous polyolefin dispersion of Production Example 1 (solid content 30 wt%) was applied to the substrate by the method described above, and the peel strength was evaluated. The results are shown in Table 1.

[Example 1]
Nonionic self-emulsifying polyurethane aqueous dispersion manufactured by Dai-ichi Kogyo Co., Ltd. Superflex 500M (solid content 45 wt%, particle size d50 150 nm, Tg-39 ° C. (catalog value)) and polyolefin aqueous dispersion of Production Example 1 (solid) After adjusting 15 g (min. 30 wt%) to pH 7.5 or more, they were mixed to prepare a resin dispersion composition, and the dispersed particle size was measured.
The obtained resin dispersion composition was applied to a substrate by the method described above, and the peel strength was evaluated. The results are shown in Table 1. Good adhesion was exhibited without lowering the adhesion as compared with Reference Example 1 in which Superflex 500M was not used.

[Example 2]
Instead of Superflex 500M of Example 1, 20 g of nonionic forced emulsification type polyurethane aqueous dispersion Superflex E4000 (solid content 45 wt%, particle size d50 280 nm, Tg-58 ° C. (catalog value)) manufactured by Daiichi Kogyo Co., Ltd. A resin dispersion composition was prepared and evaluated in the same manner as in Example 1 except that it was used. The results are shown in Table 1. Good adhesion was shown without lowering the adhesion as compared to Reference Example 1 in which Superflex E4000 was not used.

[Example 3]
An anionic polyurethane aqueous dispersion Superflex 150 (solid content 35 wt%, particle size d50 75 nm, Tg 40 ° C. (catalog value)) manufactured by Daiichi Kogyo Co., Ltd. was used in place of Superflex 500M of Example 1. A resin dispersion composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. Compared with the reference example 1 which does not use the superflex 150, the adhesiveness showed favorable adhesiveness, without falling significantly.

[Comparative Example 1]
An anionic polyurethane aqueous dispersion Superflex 210 (solid content 35 wt%, particle size d50 29 nm, Tg 41 ° C. (catalog value)) manufactured by Daiichi Kogyo Co., Ltd. was used in place of Superflex 500M in Example 1. A resin dispersion composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. Compared with the reference example 1 which does not use the superflex 210, adhesiveness fell significantly.

[Example 4]
Example except that an anionic acrylic aqueous dispersion Jonkrill 1980 (solid content 40 wt%, particle size d50 51 nm, Tg 69 ° C. (catalog value)) manufactured by BASF Japan Ltd. was used instead of Superflex 500M in Example 1. A resin dispersion composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
Compared with the reference example 1 which does not use Jonkrill 1980, favorable adhesiveness was shown, without adhesiveness falling significantly.

[Comparative Example 2]
Example except that an anionic acrylic aqueous dispersion Joncryl 1535 (solid content 41 wt%, particle size d50 62 nm, Tg 50 ° C. (catalog value)) manufactured by BASF Japan Ltd. was used instead of Superflex 500M of Example 1. A resin dispersion composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
Compared with the reference example 1 which does not use Jonkrill 1535, adhesiveness fell significantly.

[Comparative Example 3]
A method similar to Example 1 except that BASF Japan's anionic acrylic aqueous dispersion Jonkrill 57J (solid content 37 wt%, Tg 67 ° C. (catalog value)) was used instead of Superflex 500M of Example 1. A resin dispersion composition was prepared and evaluated. The results are shown in Table 1. Compared with the reference example 1 which does not use Jonkrill 57J, adhesiveness fell significantly.

[Reference Example 2]
A chlorinated PP aqueous dispersion EH-801 (solid content 30 wt%, chlorination degree 16 wt%, Mw 45,000) manufactured by Toyo Kasei Co., Ltd. was prepared and evaluated by the same method as in Example 1. did. The results are shown in Table 1.

[Comparative Example 4]
Resin was prepared in the same manner as in Example 1 except that chlorinated polypropylene aqueous dispersion EH-801 (solid content 30% by weight) manufactured by Toyo Kasei Co., Ltd. was used instead of the aqueous polyolefin dispersion of Production Example 1 in Example 1. Dispersion compositions were made and evaluated. The results are shown in Table 1. When EH-801, which is an aqueous dispersion of a polymer that does not have a hydrophilic polymer, was used, the adhesion was significantly reduced as compared to Reference Example 2 in which Superflex 500M was not used.

  The resin dispersion composition of the present invention is extremely useful as a surface treatment agent, primer, adhesive, coating agent, paint, etc. for an olefin polymer having crystallinity. Moreover, the laminated body of this invention is excellent in coating-film adhesiveness, and can be applied to a wide range of industrial products.

Claims (8)

  A polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio); A resin dispersion composition obtained by dispersing an acrylic resin having an acid value of -80 mg KOH / g and / or a urethane resin having an acid value of 0-40 mg KOH / g in water.   The resin dispersion composition according to claim 1, wherein the acrylic resin is a nonionic acrylic resin, and the urethane resin is a nonionic urethane resin.   The resin dispersion composition of Claim 1 or 2 whose Tg of the said acrylic resin and / or the said urethane resin is 40 degrees C or less.   The resin dispersion composition according to any one of claims 1 to 3, wherein the polymer (C) and the acrylic resin and / or urethane resin are dispersed by forming separate particles.   The resin dispersion composition according to any one of claims 1 to 4, wherein the polymer (C) is a graft copolymer in which a hydrophilic polymer (B) is graft-bonded to a polyolefin (A).   The primer which comprises the resin dispersion composition in any one of Claims 1-5.   The coating material which comprises the resin dispersion composition in any one of Claims 1-5.   The resin dispersion composition according to claim 1, the primer according to claim 6, or the paint according to claim 7 is applied to the thermoplastic resin molded body (F), and the resin layer is A laminated body formed.