JP2010100805A - Resin dispersion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin dispersion composition which has excellent storage stability, exhibits good coating characteristics such as moisture resistance, water resistance, oil resistance and gasohol resistance, has sufficient adhesion to the substrates comprising polyolefin, is useful as a primer, coating or the like to these substrates, and is easy to perform preparing operation. <P>SOLUTION: The resin dispersion composition is obtained by dispersing resin particles having 0.1-5.0 μm of 50% particle diameter containing an epoxy resin (D) with Tg of 25-200°C and resin particles containing polyolefin (A) having a reactive group obtained by reacting with an epoxy group into water. Due to a crosslinking between the epoxy resin (D) and the polyolefin (A), a coating film having good coating characteristics such as moisture resistance, water resistance, oil resistance and gasohol resistance is formed. The epoxy resin (D) having the above specific Tg is used, and thus, good storage stability is achieved under normal storage condition at ≤40°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin dispersion composition in which resin particles containing an epoxy resin (D) and resin particles containing a polyolefin (A) are dispersed in water.

  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 low polarity because they do not have a polar group in the molecule, and it has been desired to improve them because painting and adhesion are difficult. In order to improve the paintability and adhesion of polyolefin, the surface of the molded body has been oxidized by chemical treatment, corona discharge treatment, plasma treatment, flame treatment, etc. Various methods have been tried such as. 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. By applying such a modified polyolefin to the surface of the polyolefin molded body as a surface treatment agent, an adhesive or a paint, paintability and adhesiveness can be imparted. Usually, these modified polyolefins are applied in the form of a solution in an organic solvent or a dispersion in water, but an aqueous dispersion is usually preferably used from the viewpoint of safety and environmental pollution.

  However, in order to prepare an aqueous dispersion of polyolefin, it is necessary to modify it with a highly hydrophilic polycarboxylic acid or to stabilize it in water with a surfactant having a hydrophilic group. It becomes inferior. In addition, even after the aqueous dispersion is applied to the surface of the molded body and dried to form a coating film, the dispersed particles do not completely fuse with each other, so that oil and solvent easily penetrate through the gap. There was a problem that oil resistance and gasohol resistance (mixture of gasoline and ethanol) were low.

In order to solve such a problem, Patent Documents 1 and 2 show an aqueous resin dispersion in which an epoxy aqueous dispersion is blended with an acid-modified polyolefin aqueous dispersion.
Further, Patent Document 3 discloses an aqueous resin dispersion in which an aqueous epoxy resin dispersion is blended with an aqueous polyolefin polyolefin dispersion without using an emulsifier.

JP 2001-139875 A JP 2004-2801 A JP 2008-56914 A

  In the aqueous resin dispersions described in Patent Documents 1 and 2, it is said that the acid-modified polyolefin and the epoxy resin are reacted / crosslinked to improve the moisture resistance and gasohol resistance, but the moisture resistance and gasohol resistance and storage are improved. A further improvement in stability was necessary.

  An object of the invention disclosed in Patent Document 3 is to provide an aqueous dispersion of a resin which is excellent in moisture resistance and gasohol resistance and is useful as a surface treatment agent, adhesive or paint for a polyolefin-based substrate. It is said. However, since an epoxy resin with large particles is used in order to satisfy the above characteristics, sedimentation separation occurs during storage, and there is a problem that workability such as coating is poor.

  Therefore, the present invention is excellent in storage stability, has good coating properties such as moisture resistance, water resistance, oil resistance, gasohol resistance, and has sufficient adhesion to a substrate made of polyolefin. It is an object of the present invention to provide a resin dispersion composition that is useful as a primer or paint for these substrates and that can be easily prepared.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a resin dispersion composition in which a specific epoxy resin and a polyolefin having a reactive group capable of reacting with an epoxy group are dispersed in water. The present inventors have found that it has good storage stability, is easy to prepare a resin dispersion composition, and has excellent adhesion, moisture resistance, and oil resistance to a polyolefin substrate.

  That is, the present invention is a resin particle having a 50% particle diameter of 0.1 to 5 μm including an epoxy resin (D) having a glass transition temperature (Tg) of 25 to 200 ° C., and reactivity capable of reacting with an epoxy group. The present invention relates to a resin dispersion composition obtained by dispersing resin particles containing a group-containing polyolefin (A) in water.

  Moreover, this invention relates to the said resin dispersion composition whose weight average molecular weights of an epoxy resin (D) are 300-20000.

  In the present invention, the epoxy equivalent of the epoxy resin (D) is 100 to 1000 g / eq. It is related with the said resin dispersion composition.

  Moreover, this invention relates to the said resin dispersion composition whose reactive group which can react with an epoxy group is a carboxyl group.

  The present invention also relates to the resin dispersion composition, wherein the polyolefin (A) is a polyolefin grafted with a hydrophilic polymer (B).

  The present invention also relates to the resin dispersion composition, wherein the polyolefin (A) does not substantially contain chlorine.

  Moreover, this invention relates to the said resin dispersion composition in which the resin particle containing polyolefin (A) does not contain surfactant substantially.

The resin dispersion composition of the present invention provides a coating film with good coating properties such as moisture resistance, water resistance, oil resistance, gasohol resistance, and the like because crosslinking of the polyolefin (A) by the epoxy resin (D) occurs. can do.
Furthermore, since a specific Tg resin is used as the epoxy resin (D), the storage stability is good under normal storage conditions of 40 ° C. or lower. In particular, by using an aqueous epoxy resin dispersion with a particle size in a specific range, the storage stability of the aqueous resin dispersion itself is further improved, and there are no problems such as sedimentation and separation, and the resin dispersion composition is prepared. Improved workability.

  Hereinafter, embodiments of the resin dispersion composition of the present invention will be described in detail.

  The resin dispersion composition of the present invention reacts with resin particles having a 50% particle diameter of 0.1 to 5 μm, including an epoxy resin (D) having a glass transition temperature (Tg) of 25 to 200 ° C., and an epoxy group. Resin particles containing a polyolefin (A) having a reactive group capable of being dispersed are dispersed in water.

The method for dispersing the resin particles containing the epoxy resin (D) and the resin particles containing the polyolefin (A) in water is not particularly limited, and these two resins may be mixed and then dispersed in water at the same time. Two types of aqueous resin dispersions in which each resin is dispersed in water may be prepared and mixed.
In the resin dispersion composition of the present invention, since the improvement in coating film properties is more remarkable, the resin particles containing the epoxy resin (D) and the resin particles containing the polyolefin (A) form separate particles. Therefore, it is preferable to obtain the resin dispersion composition by the latter method.

  Hereinafter, each component of the present invention will be described.

(1) Polyolefin (A)
In the present invention, the polyolefin (A) is a polyolefin having a reactive group capable of reacting with an epoxy group (hereinafter sometimes referred to as “epoxy-reactive group”). Examples of the reactive group that can react with the epoxy group include a carboxyl group, an amino group, an amide group, a hydroxyl group, and a mercapto group. Among these, the carboxyl group and the amino group may be neutralized, that is, may form a salt. Polyolefin (A) may have only 1 type of these epoxy reactive groups, and may have 2 or more types.

  As the reactive group capable of reacting with the epoxy group, a carboxyl group is particularly preferred for reasons such as reactivity with the epoxy group, ease of introduction into the polyolefin, and stability of the resulting aqueous resin dispersion.

As the polyolefin (A) having an epoxy reactive group, one kind may be used alone, or two or more kinds may be used in combination.
For the purpose of reducing the environmental load, it is desirable that the polyolefin (A) having an epoxy reactive group does not substantially contain chlorine. The phrase “substantially not containing chlorine” means that, for example, the chlorination rate of a polyolefin described later is less than 5% by mass.

  The polyolefin (A) having an epoxy reactive group is not particularly limited as long as the epoxy reactive group is bonded to the polyolefin through a covalent bond or an ionic bond.

The polyolefin (A) includes a polymer (A1) in which a small molecule having a molecular weight of less than 200 is bonded to the polyolefin main chain (A0), and a polymer (A2) in which a polymer having a molecular weight of 200 or more is bonded to the polyolefin main chain (A0). Examples of the polymer (A1) in which a small molecule having a molecular weight of less than 200 is bonded to the polyolefin main chain (A0) include, for example, an unsaturated compound having no epoxy reactive group and an epoxy reactive group. And a copolymer (A1b) obtained by graft polymerization of a radically polymerizable unsaturated compound having an epoxy-reactive group onto a polyolefin. Examples of the polymer (A2) in which a polymer having a molecular weight of 200 or more is bonded to the polyolefin main chain (A0) include a graft polymer (A2a) obtained by further reacting the polymer (A1) with a hydrophilic polymer, a polyolefin A polymer (A2b) having an epoxy-reactive group in a polymer bonded to can be used.
Here, the molecular weight is a weight average molecular weight Mw (hereinafter sometimes abbreviated as Mw) measured by GPC (Gel Permeation Chromatography) and converted by a calibration curve of each polystyrene.

  Among these, the polyolefin (A) is a graft polymer in which a hydrophilic polymer (B) described later is graft-bonded to the polyolefin, that is, a polyolefin (A2a) or polyolefin (A2b) described later. However, it is preferable in that a stable aqueous resin dispersion can be easily prepared without substantially using a surfactant that is not preferable in the use of the resin dispersion composition.

(1) -1 Polymer (A1) in which a small molecule having a molecular weight of less than 200 is bonded to the polyolefin main chain (A0).
As the polymer (A1) in which a small molecule having a molecular weight of less than 200 is bonded to the polyolefin main chain (A0) (hereinafter sometimes referred to as “polyolefin (A1)”), an unsaturated compound having no epoxy-reactive group and A copolymer (A1a) copolymerized with an unsaturated compound having an epoxy reactive group (hereinafter sometimes referred to as “polyolefin (A1a)”), and a radical polymerizable unsaturated compound having an epoxy reactive group as a polyolefin And a polymer (A1b) (hereinafter sometimes referred to as “polyolefin (A1b)”) obtained by graft polymerization.

Polyolefin (A1a) is obtained by copolymerizing an unsaturated compound having no epoxy reactive group and an unsaturated compound having an epoxy reactive group, and the unsaturated compound having an epoxy 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 with an α, β-unsaturated carboxylic acid such as acrylic acid or maleic anhydride or an anhydride thereof. Specific examples of the polyolefin (A1a) include an ethylene-acrylic acid copolymer and an ethylene-acrylic acid ester-maleic anhydride copolymer. These may be used alone or in combination of two or more.
As the method for producing the polyolefin (A1a), the method for producing the polyolefin main chain (A0) described later can be used in the same manner.

  The polyolefin (A1b) is obtained by graft polymerization of a radically polymerizable unsaturated compound having an epoxy reactive group on a prepolymerized polyolefin main chain (A0), and the radically polymerizable unsaturated compound having an epoxy reactive group is: Grafted to the main chain. For example, polyolefin 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 Examples include polymers grafted with 2-hydroxypropyl acid, (meth) acrylamide, and the like. “(Meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”, and the others are based on this.

The polyolefin main chain (A0) polymerized in advance will be described below.
As this polyolefin main chain (A0), 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 and / or A copolymer of propylene and another comonomer, for example, butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, norbornene, or other α-olefin comonomer, or Two or more types of copolymers of these comonomers can be used. The “comonomer” refers to a copolymerizable monomer compound.
Here, the α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms.

  Also, a copolymer of an α-olefin comonomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, a copolymer of an α-olefin comonomer and a comonomer such as an aromatic vinyl monomer, or a hydrogenated product thereof, a conjugate A hydrogenated product of a diene block copolymer can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer.

  Furthermore, it is desirable that these polyolefins contain substantially no chlorine for the purpose of reducing the environmental load, but chlorinated chlorinated polyolefins can also be used. The degree of chlorination of the chlorinated polyolefin is usually 5% by mass or more because it is generally easily available, and is preferably 50% by mass or less, more preferably 30% by mass from the viewpoint of adhesion to the polyolefin substrate. % Or less.

  Specific examples of the polyolefin main chain (A0) include polyethylene (ethylene homopolymer), polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, Hydrogenated chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS) (SEBS), hydrogenated product (SEPS) of styrene-isoprene-styrene block copolymer (SIS), and the like. Of these, a propylene homopolymer or a copolymer of propylene and another α-olefin comonomer is preferable, and these may be chlorinated.

  The polyolefin main chain (A0) is more preferably a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, a chlorinated polypropylene, a chlorinated ethylene-propylene copolymer, or a chlorinated propylene- A butene copolymer, more preferably a propylene homopolymer, an ethylene-propylene copolymer, and a propylene-butene copolymer.

  Preferably, the content of the structural unit derived from propylene in all the structural units of the polyolefin main chain (A0) is 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, most preferably It is a 100 mol% propylene homopolymer or a propylene-based copolymer. Usually, the higher the content of the propylene-derived structural unit of the polyolefin main chain (A0), the higher the adhesion to polyolefin, particularly polypropylene base material.

  As the polyolefin main chain (A0), one type may be used alone, or two or more types may be used in combination.

  Further, as the stereoregularity of the propylene homopolymer or copolymer of the polyolefin main chain (A0), 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 USP 4,522,982 should be used. Can do.

  Preferably, the polyolefin main chain (A0) is a propylene homopolymer or copolymer of stereoblock polypropylene having an isotactic block and an atactic block. Most preferably, it is a stereoblock polypropylene having an isotactic block and an atactic block.

In this case, the polyolefin main chain (A0) preferably has a [mmmm] pentad exhibiting isotactic stereoregularity in the range of 10% to 90%. A preferable lower limit value of [mmmm] pentad is 20%, more preferably 30%, and more preferably 40%. A preferable value of the upper limit of [mmmm] pentad is 80%, more preferably 70%, more preferably 60%, and more preferably 55%. The stickiness tends to be smaller as the value is lower than the lower limit, and the crystallinity is lowered as the value is lower than the upper limit, and the resin dispersion tends to be easily prepared.
As a method for measuring the ratio of [mmmm] pentad, the method described in JP-A-2003-231714 can be used.

  The polyolefin main chain (A0) in the present invention preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC and converted with a calibration curve of each polystyrene. A more preferable lower limit value of Mw is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value of Mw is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the above lower limit value, the stickiness degree tends to be small and the adhesion to the substrate tends to increase, and as it is lower than the upper limit value, the viscosity tends to be low and the resin dispersion tends to be easily prepared. In addition, the GPC measurement of polyolefin (A0) is performed by a conventionally well-known method using THF (tetrahydrofuran) etc. as a solvent using a commercially available apparatus.

The production method of the polyolefin main chain (A0) according to the present invention is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any production method may be used. 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 a polymer obtained by designing a single-site catalyst by ligand design are generally sharp. Here, as the single site catalyst, for example, a metallocene catalyst or a Brookhart catalyst can be used. As 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, CS symmetric type and the like. 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 reaction solvent used include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatics such as cyclohexane and methylcyclohexane. Hydrocarbons, halogenated hydrocarbons such as 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, Examples thereof include alcohols such as methanol, 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 alone or in combination of two or more.

  Specific examples of polyolefin (A1b) obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to such a polyolefin main chain (A0) include, for example, maleic anhydride-modified polypropylene and chlorinated products thereof, Maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, acrylic acid-modified polypropylene and its chlorinated product, acrylic acid-modified ethylene-propylene copolymer and its chlorinated product, acrylic Examples include acid-modified propylene-butene copolymers. These may be used alone or in combination of two or more.

  The radical polymerization initiator used for graft polymerization of the radically polymerizable unsaturated compound having a reactive group on the polyolefin main chain (A0) can be appropriately selected from ordinary radical initiators. An oxide, an azonitrile, etc. can be mentioned. 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 alone or in combination of two or more.

The use ratio of the radical polymerization initiator and the graft copolymerized unit which is a radically polymerizable unsaturated compound having a reactive group is usually a radical polymerization initiator: graft copolymerized unit = 1: 100 to 2: 1 (molar ratio). ), Preferably in the range of 1:20 to 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 polyolefin (A1b), 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, a method of reacting by heating and stirring raw material components in a solution, a method of reacting by melting and heating without solvent, a method of reacting by heating and kneading with an extruder, and the like can be mentioned.
As a solvent in the case of manufacturing in a solution, the solvent mentioned above as a reaction solvent in the case of manufacturing polyolefin main chain (A0) by solution polymerization or slurry polymerization can be used similarly.

  Of the polyolefin (A) having an epoxy reactive group, the content of the epoxy reactive group in the polyolefin (A1) is in the range of 0.01 to 5 mmol / g of polyolefin (A1), that is, 0.01 to 5 mmol / g. It is preferable that it exists in. The more preferable lower limit of the content of the epoxy reactive group is 0.05 mmol / g, more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. Moreover, the more preferable upper limit of content of an epoxy reactive group is 1 mmol / g, More preferably, it is 0.8 mmol / g, Most preferably, it is 0.5 mmol / g. The higher the lower limit value, the higher the reactivity with the epoxy resin (D) tends to improve the moisture resistance and gasohol resistance. The lower the upper limit value, the better the storage stability and the crystalline polyolefin base material. There is a tendency for the adhesion to be increased. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxyl groups in the said group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

  The polyolefin (A1) preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC and converted with a calibration curve of each polystyrene. A more preferable lower limit value of Mw is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value of Mw is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the above lower limit value, the stickiness degree tends to be small and the adhesion to the substrate tends to increase, and as it is lower than the upper limit value, the viscosity tends to be low and the resin dispersion tends to be easily prepared. In addition, GPC measurement of polyolefin (A1) is performed by a conventionally well-known method using THF etc. as a solvent using a commercially available apparatus.

  The polymer (A1) in which a small molecule having a molecular weight of less than 200 is bonded to polyolefin may be linear or branched.

(1) -2 Polymer (A2) in which a polymer having a molecular weight of 200 or more is bonded to the polyolefin main chain (A0).
As the polymer (A2) in which a polymer having a molecular weight of 200 or more is bonded to the polyolefin main chain (A0) (hereinafter sometimes referred to as “polyolefin (A2)”), the above-mentioned polyolefin (A1) is more hydrophilic. A polymer (A2a) obtained by reacting the molecule (B) (hereinafter sometimes referred to as “polyolefin (A2a)”), an epoxy in the hydrophilic polymer (B) bonded to the above-described polyolefin main chain (A0). And a polymer (A2b) having a reactive group (hereinafter sometimes referred to as “polyolefin (A2b)”). The difference between the polyolefin (A2a) and the polyolefin (A2b) is that the polyolefin main chain (A0) itself has an epoxy-reactive group (polymer (A2a)) or hydrophilicity that binds to the polyolefin main chain (A0). The polymer (B) has an epoxy reactive group (polymer (A2b)). The epoxy reactive group may be attached only to either the polyolefin main chain (A0) or the hydrophilic polymer (B), or may be attached to both, but preferably at least in the polyolefin main chain (A0). It is what is combined.

Hereinafter, the hydrophilic polymer (B) will be described.
In the present invention, the hydrophilic polymer (B) 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. The hydrophilic polymer (B) may have a reactive group.

  Of the hydrophilic polymer (B), the synthetic polymer is not particularly limited, and for example, poly (meth) acrylic resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, and the like 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, with polyether resins having high hydrophilicity being most preferred. These may be used alone or in combination of two or more.

Among the synthetic polymers of the hydrophilic polymer (B), the acrylic resin is usually obtained by polymerizing an unsaturated carboxylic acid or its ester or anhydride by radical polymerization, anionic polymerization, or cationic polymerization.
The method for bonding the acrylic resin to the polyolefin main chain (A0) is not limited. For example, a method of radical graft polymerization directly to the polyolefin main chain (A0), a hydroxyl group, an amino group, a glycidyl group, an (anhydrous) carboxyl group, etc. Examples thereof include a method in which an acrylic resin having a reactive group is reacted with a polyolefin having a reactive group such as polyolefin (A1).
The unsaturated carboxylic acid or its ester or anhydride constituting the acrylic resin is preferably (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (dimethylaminoethyl (meth) acrylate) Quaternized compounds and (meth) acrylamide are mentioned.

  Among the synthetic polymers of the hydrophilic polymer (B), the polyvinyl alcohol resin is usually obtained by saponification after polymerizing vinyl acetate to obtain polyvinyl acetate. Here, the saponification degree may be complete saponification or partial saponification.

  Among the synthetic polymers of the hydrophilic polymer (B), the polyvinyl pyrrolidone resin is usually obtained by polymerizing vinyl pyrrolidone.

Of the synthetic polymers of the hydrophilic polymer (B), the polyether resin is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine.
The method for bonding the polyester resin to the polyolefin main chain (A0) is not limited. For example, a polyether polyol obtained by ring-opening polymerization of a cyclic alkylene oxide in a polyolefin having a reactive group, ring-opening polymerization, or the like. And a method of reacting a polyester resin having a reactive group such as polyetheramine with a polyolefin having a reactive group such as polyolefin (A1).

  Here, 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 or polyalkyleneimine of the polyester resin include polyethylene oxide, polypropylene oxide, and polyethyleneimine.
Further, as the polyetheramine, Jeffamine M series, D series, ED series, etc. manufactured by Huntsman may be used.

In the polyolefin (A2), the hydrophilic polymer (B) may be referred to as a reactive group capable of reacting with the reactive group of the polyolefin main chain (A0) or the polyolefin (A1) (hereinafter referred to as “main chain reactive group”). It is preferable to have one or more. Examples of the main chain reactive group include a carboxyl 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. Have.
Amino group is highly reactive with various reactive groups such as carboxyl group, anhydrous carboxyl group, glycidyl group and isocyanate group, so it binds polyolefin main chain (A0) or polyolefin (A1) and hydrophilic polymer (B). It is easy to make. The amino group may be primary, secondary or tertiary, but is preferably a primary amino group.

The hydrophilic polymer (B) may have at least one main chain reactive group, but more preferably has only one main chain reactive group. When there are two or more main chain reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with the polyolefin (A1).
However, even if it has a plurality of main chain reactive groups, it is sufficient if only one main chain reactive group is more reactive than 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 main chain (A0) or the polyolefin (A1).

  The hydrophilic polymer (B) in the present invention can be imparted for the purpose of imparting hydrophilicity to the polyolefin (A), and its molecular weight is usually measured by GPC and the weight average molecular weight Mw converted by a polystyrene calibration curve is 200 or more. The lower limit value of Mw of the hydrophilic polymer (B) is preferably 300, more preferably 500. However, the Mw of the hydrophilic polymer (B) is preferably 200,000 or less. A more preferable value of the upper limit value of Mw of the hydrophilic polymer (B) is 100,000, and more preferably 10,000. As Mw is higher than the lower limit, the hydrophilicity of the polyolefin (A) increases, and the dispersed particle size tends to be smaller and stably dispersed. Also, the viscosity is lower as the Mw is lower than the upper limit, and a resin dispersion tends to be easily prepared. It is in. In addition, GPC measurement of hydrophilic polymer (B) is performed by a conventionally well-known method using THF etc. as a solvent using a commercially available apparatus.

  The amount of the hydrophilic polymer (B) bonded to the polyolefin (A1) or the polyolefin main chain (A0) is in the range of 0.01 to 5 mmol / g of polyolefin (A2), that is, 0.01 to 5 mmol / g. Preferably there is. The more preferable lower limit of the binding amount of the hydrophilic polymer (B) is 0.05 mmol / g, more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. Further, 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 greater the hydrophilicity of the polyolefin (A2) and the smaller the dispersed particle size tends to be stably dispersed. The lower the upper limit value, the greater the adhesion to the crystalline polyolefin as the substrate. is there.

  Moreover, it is preferable that content of the epoxy reactive group in polyolefin (A2) exists in the range of 0.01-5 mmol per 1g of polyolefin (A2), ie, 0.01-5 mmol / g. The more preferable lower limit of the content of the epoxy reactive group is 0.05 mmol / g, more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. Moreover, the more preferable upper limit of content of an epoxy reactive group is 1 mmol / g, More preferably, it is 0.8 mmol / g, Most preferably, it is 0.5 mmol / g. The higher the lower limit value, the higher the reactivity with the epoxy resin (D) tends to improve the moisture resistance and gasohol resistance. The lower the upper limit value, the better the storage stability and the crystalline polyolefin base material. There is a tendency for the adhesion to be increased. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxyl groups in the said group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

  The polyolefin (A2) preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC and converted with a calibration curve of each polystyrene. A more preferable lower limit value of Mw is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value of Mw is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the above lower limit value, the stickiness degree tends to be small and the adhesion to the substrate tends to increase, and as it is lower than the upper limit value, the viscosity tends to be low and the resin dispersion tends to be easily prepared. In addition, GPC measurement of polyolefin (A2) is performed by a conventionally well-known method using THF etc. as a solvent and using a commercially available apparatus.

  In the polyolefin (A2), a graft copolymer in which a hydrophilic polymer (B) is graft-bonded to the polyolefin main chain (A0) or the polyolefin (A1), one end of the polyolefin main chain (A0) or the polyolefin (A1) or There may be a block copolymer of a polyolefin main chain (A0) including a state in which a hydrophilic polymer (B) is bonded to both ends, and a hydrophilic polymer (B).

  The hydrophilic polymer (B) can be bonded to the polyolefin main chain (A0) or the polyolefin (A1) by various reaction forms. Although the form is not particularly limited, for example, a radical graft reaction or a reaction utilizing a main chain reactive group.

  According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.

  The reaction using the main chain reactive group has a reactive group in both the polyolefin main chain (A0) or the polyolefin (A1) and the hydrophilic polymer (B), and reacts them to bond them. Yes, a covalent or ionic bond is formed. Examples of this reaction include esterification reaction between a carboxyl group and a hydroxyl group, ring opening reaction between a carboxyl group and an epoxy group, ring opening reaction between a primary or secondary amino group and an epoxy group, carboxyl group and primary or Amidation reaction with secondary amino group, quaternary ammonium reaction with carboxyl group and tertiary amino group, urethanation reaction with carboxyl 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 carboxyl group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted for one equivalent of the dibasic acid or anhydride.

Next, the manufacturing method of polyolefin (A2) is demonstrated.
As a method for producing a polyolefin (A2a) or (A2b), a hydrophilic polymer (B) bonded to a polyolefin by polymerizing a hydrophilic monomer in the presence of a polyolefin main chain (A0) or polyolefin (A1) is usually used. There is a method (R1) of forming, or a method (R2) of bonding a prepolymerized hydrophilic polymer (B) to the polyolefin main chain (A0) or the polyolefin (A1).

(1) -2-1 Production method of polyolefin (A2) (R1)
In this method, a hydrophilic polymer (B) bonded to a polyolefin main chain (A0) or a polyolefin (A1) by polymerizing a hydrophilic monomer in the presence of a prepolymerized polyolefin main chain (A0) or polyolefin (A1). ) 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 with the hydrophilic monomer as long as a hydrophilic polymer can be formed after polymerization.

  Specifically, for example, a hydrophilic monomer (hydrophilic radical polymerizable unsaturated compound) is polymerized in the presence of a radical polymerization initiator to form a hydrophilic polymer (B) and a polyolefin main chain (A0) or There is a method of bonding to the polyolefin (A1).

  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 monomer (hydrophobic radical polymerizable compound) can be copolymerized within the range in which the resulting hydrophilic polymer (B) exhibits 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.

  Preferred examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate.

  As another method, a radically 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 the polymer portion is modified to form a hydrophilic polymer ( There is a method 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 copolymerizable hydrophobic monomers that can be used in this case include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate.

  Alternatively, polyolefin (A1) is used, and a hydrophilic monomer such as a hydrophilic radical polymerizable unsaturated compound or a hydrophilic ring-opening polymerization monomer is polymerized by using an epoxy reactive group of the polyolefin (A1) as an initiation terminal. There is a method of forming the molecule (B).

Here, the above-mentioned thing can be used similarly as a hydrophilic radically polymerizable unsaturated compound.
Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine.
Examples of copolymerizable hydrophobic monomers that can be used in this case include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

  Any of the copolymerizable monomer components may be used singly or in combination of two or more.

  The reaction method is not particularly limited as long as the polyolefin (A2) 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 mentioned above as a reaction solvent in the case of manufacturing polyolefin main chain (A0) by solution polymerization or slurry polymerization can be used similarly.

(1) -2-2 Production method (R2) of polyolefin (A2)
In this method, the previously polymerized hydrophilic polymer (B) is bonded to the polyolefin main chain (A0) or the polyolefin (A1). In this case, the aforementioned hydrophilic polymer (B) can be used.

  Specifically, for example, when a hydrophilic monomer is first polymerized into a hydrophilic polymer (B), an unsaturated double bond is left in the molecule, and then a polyolefin main monomer is used using a radical polymerizable initiator. There is a method of graft polymerization to the chain (A0) or the polyolefin (A1).

  There is also a method in which a hydrophilic polymer (B) having a main chain reactive group at the terminal is first produced and then bonded to the polyolefin (A1). 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 mentioned in the description of the production method (R1) can be used in the same manner, and the hydrophilic polymer (B) is within the range in which the hydrophilic polymer is hydrophilic. These hydrophobic monomers may be used in combination.
Any of these may be used alone or in combination of two or more.

  The reaction method is not particularly limited as long as the polyolefin (A2) 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 mentioned above as a reaction solvent in the case of manufacturing polyolefin main chain (A0) by solution polymerization or slurry polymerization can be used similarly.

(1) -3 Resin Particles Containing Polyolefin (A) The method for producing the resin particles containing polyolefin (A) contained in the resin dispersion composition of the present invention is not particularly limited. For example, polyolefin (A), water And a method of preparing an aqueous dispersion by preparing a mixture of solvents other than water and then removing the solvent from the mixture, and then adding and dispersing water after melting at a temperature above which the polyolefin (A) melts And the like, and the former method is preferred.

According to the method of preparing an aqueous dispersion by preparing a mixture of polyolefin (A), 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 this mixture, you may heat as needed. The heating temperature in this case is usually 30 to 150 ° C.

  Among these, a method of adding a solvent other than water to the polyolefin (A) and adding water after heating and dissolving as necessary is preferable because an aqueous dispersion having a finer particle size can be easily produced. The temperature when the polyolefin (A) is dissolved in a solvent or when water is added is usually 30 to 150 ° C. When the polyolefin (A) is once dissolved in a solvent other than water, the solvent may be distilled off after adding water.

  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. These may be used alone or in combination of two or more.

  As a usage-amount of solvents other than water, it is preferable to set it as 50-2000 mass parts with respect to 100 mass parts of polyolefin (A), especially 100-1000 mass parts. Moreover, it is preferable that the usage-amount of water shall be 50-1000 mass parts with respect to 100 mass parts of solvents other than water, especially 100-500 mass parts. If the amount of the solvent other than water is too small, the polyolefin (A) cannot be dissolved, and if it is too much, it takes time to remove the solvent thereafter. Further, if the amount of water used is too small, it cannot be replaced with water and cannot be formed into an aqueous resin dispersion, and if it is too much, the particle size tends to increase.

  An apparatus for producing a resin dispersion by adding water after the polyolefin (A) is dissolved or melted is not particularly limited. For example, a reactor equipped with a stirring device, a uniaxial or biaxial kneader. Etc. 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.

  The polyolefin (A) described above is very excellent in water dispersibility, and according to the method for producing a resin dispersion described above, an aqueous resin dispersion of a polyolefin (A) having a fine dispersed particle diameter can be obtained. This resin dispersion composition has a fine dispersed particle diameter, and the resin particles are stably dispersed.

  The solid content (usually composed of polyolefin (A)) content of the polyolefin (A) resin dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. 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 the solid content in the resin dispersion, the lower the viscosity, and the resin dispersion composition using the same can be applied to various coating methods and is easy to use, and the stability as a dispersion tends to be high. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

The content of the solvent other than water contained in the polyolefin (A) resin dispersion is usually 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 1% by mass. % Or less.
Therefore, in the above-described method for producing a resin dispersion, it is preferable to remove the solvent other than water by distillation or the like so that the content of the solvent other than water is not more than the above upper limit.

  The dispersion particle diameter of the resin particles containing the polyolefin (A) in the resin dispersion of the polyolefin (A) thus obtained is the polyolefin (A) in the resin dispersion composition of the present invention prepared by using this. The particle diameter is the same as the dispersed particle diameter of the resin particles containing, but this particle diameter is 50%, cumulative from the finer particle diameter in terms of volume of the particle diameter measured by a particle size dispersion measuring machine, When the particle diameter when obtained (hereinafter sometimes referred to as “50% particle diameter”) is determined, the 50% particle diameter is usually 10 μm or less, preferably 1 μm or less. In particular, according to the production method described above, the 50% particle size can be 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the resin particle containing polyolefin (A) in the resin dispersion composition of the present invention is converted into a volume, the particle diameter is accumulated from the finer one to 90% (hereinafter referred to as “90% particle diameter”). The 90% particle diameter can be preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersion particle diameter in this way, the dispersion stability of the resin particles containing the polyolefin (A) in the resin dispersion composition of the present invention is improved, and aggregation is less likely to occur, and more stably dispersed. can do. Further, a reduction in the ratio of the 90% particle size to the 50% particle size means that the particle size distribution becomes narrow, and as a result, the dispersion stability is improved. Therefore, the 90% particle diameter / 50% particle diameter of the resin particles containing the polyolefin (A) in the resin dispersion composition of the present invention is particularly preferably 5 or less, particularly preferably 2 or less.

  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. Therefore, there is no particular limitation on the lower limit of the dispersed particle size of the resin particles containing the polyolefin (A) in the resin dispersion composition of the present invention.

As described above, the polyolefin (A) can be dispersed in water without using a surfactant, and has an advantage that the dispersed particle size is very small.
However, a surfactant may be contained in the polyolefin (A) resin dispersion 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, and these are used alone. Two or more kinds may be mixed and 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. The number of carbon atoms of these hydrophobic groups is preferably 8 or more, more preferably 12 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. Examples of commercially available representative reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).

  The content of these surfactants in the resin dispersion of polyolefin (A) is usually 50 parts by mass or less, preferably 30 parts by mass or less, with respect to 100 parts by mass of polyolefin (A) in the resin dispersion. It is.

  However, one advantage of the present invention is that it is not necessary to use a surfactant when obtaining resin particles containing polyolefin (A), and thus the resin particles containing polyolefin (A) are substantially free of surfactant. Therefore, it is preferable that the amount of the surfactant in the resin dispersion of the polyolefin (A) is small, and the surfactant content of the resin dispersion is 10 parts by mass or less with respect to 100 parts by mass of the polyolefin (A). The amount is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and the surfactant can be substantially not contained. The phrase “substantially free of surfactant” means that the content of the surfactant is less than 1 part by mass with respect to 100 parts by mass of the polyolefin (A).

  Thus, by reducing the amount of the surfactant in the resin dispersion, the reactivity of the polyolefin (A) and the epoxy resin (D) is increased in the resin dispersion composition of the present invention produced using the same. The water resistance and gasohol resistance when forming a coating film are preferable. Furthermore, bleeding out, which has been a problem in the past, can be suppressed, and there is an advantage that a coated product having an excellent appearance can be obtained, and the resin dispersion composition can be suitably used as the outermost coating material for coating. Become. Further, 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 from this point.

  However, since the nonionic surfactant is less likely to lower the water resistance compared to other surfactants, the nonionic surfactant may be included in the resin dispersion a little more. 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 polyolefin (A), the nonionic surfactant may be 10 parts by mass or less.

  An acidic substance or a basic substance can also be added to the polyolefin (A) resin dispersion 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.

(2) Epoxy resin (D)
The epoxy resin (D) used in the present invention must have a glass transition temperature (Tg) of 25 to 200 ° C. The epoxy resin (D) is not particularly limited as long as it is a polymer having two or more epoxy groups in one molecule.

  Epoxy resins include glycidyl ethers obtained from polyhydroxy compounds and epihalohydrins, glycidyl ester compounds obtained from polycarboxylic acid compounds and epihalohydrins, glycidyl amines obtained from polyamine compounds and epihalohydrins, and carbon-carbon double bonds. There are types such as an olefin oxidation (alicyclic) system in which an epoxy group is introduced by oxidizing glycidyl ether, and a glycidyl ether system is common.

  Examples of the polyhydroxy compound include bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, dihydroxy diphenyl ether, dihydroxy naphthalene, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, Various phenols such as phenol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolac resin, or various phenols and benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal Obtained by condensation reaction with various aldehydes such as Various phenolic compounds of such polyhydric phenol resin to be.

  Examples of the polycarboxylic acid compound include various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid.

  Examples of the polyamine compound include various amine compounds such as diaminodiphenylmethane, aminophenol, and xylenediamine.

  The epoxy resin (D) is preferably a glycidyl ether type in that the epoxy equivalent, water resistance and storage stability are simultaneously increased.

  The glass transition temperature (Tg) of the epoxy resin (D) used in the present invention is 25 ° C. or higher, preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and particularly preferably 40 ° C. or higher. Moreover, it is 200 degrees C or less, Preferably it is 150 degrees C or less, More preferably, it is 100 degrees C or less, Most preferably, it is 80 degrees C or less. When Tg is less than 25 ° C., the reactivity during storage increases and the storage stability decreases. On the other hand, when Tg is 200 ° C. or lower, the reactivity with the polyolefin (A) during low-temperature baking of the coating film is improved, and the crosslinking effect is increased.

  The epoxy resin (D) preferably has a weight average molecular weight Mw measured by GPC and converted by a calibration curve of each polystyrene of 300 to 20000, more preferably 900 or more, still more preferably 1500 or more, and particularly preferably 2500. That's it. Further, it is more preferably 10,000 or less, particularly preferably 5000 or less. When the weight average molecular weight of the epoxy resin (D) is 300 or more, the glass transition temperature (Tg) is high, and storage stability is easily exhibited. A weight average molecular weight of 20000 or less is preferable because reactivity with the polyolefin (A) is improved and crosslinkability is increased. In addition, GPC measurement of an epoxy resin (D) is performed by a conventionally well-known method using THF etc. as a solvent using a commercially available apparatus.

  The epoxy equivalent of the epoxy resin (D) is 100 to 1000 g / eq. Is more preferable, and 150 to 500 g / eq. , Particularly preferably 200 to 400 g / eq. It is. The epoxy equivalent of the resin particles containing the epoxy resin (D) is 90 to 900 g / eq. Is more preferable, and 135 to 450 g / eq. And particularly preferably 180 to 360 g / eq. It is. Any epoxy equivalent is more than the said lower limit, and it is easy to raise storage stability. Further, when the epoxy equivalent is not more than the above upper limit value, it is easy to increase water resistance and oil resistance by crosslinking with the polyolefin (A).

  Although the manufacturing method of the resin particle containing the epoxy resin (D) contained in the resin dispersion composition of this invention is not specifically limited, For example, making an epoxy resin (D) aqueous emulsion in presence of surfactant. Thus, resin particles containing the epoxy resin (D) can be obtained as an aqueous resin dispersion of the epoxy resin (D).

  Examples of the surfactant include all anionic surfactants, nonionic surfactants, amphoteric surfactants, polymer surfactants or reactive surfactants that can be contained in this type of aqueous dispersion. These surfactants can be used, and one of these may be used alone, or two or more thereof may be mixed and used.

  Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate, sodium dodecyl polyglycol ether sulfate, sodium sulforicinone, alkali metal salt of sulfonated paraffin, and sulfonated paraffin. Alkyl sulfonates such as ammonium salts, fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine abiate, alkyl benzene sulfonates, alkyl aryl sulfonates such as alkali metal sulfates of alkali phenol hydroxyethylene, high alkyl naphthalene sulfonic acids Salt, naphthalenesulfonic acid formalin condensate, dialkyl sulfone Haq salts, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, trimethylolpropane fatty acid ester, and polyoxyethyleneoxypropylene copolymer. Examples include polymers, condensation products of ethylene oxide with fatty acid amines, amides or acids.

  Examples of the polymer surfactant include polyvinyl alcohol, sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl ( Examples thereof include (meth) acrylates, copolymers of two or more polymerizable monomers which are these polymer constituent units, and copolymers with other monomers. In addition, what are called phase transfer catalysts such as crown ethers are also useful as those showing surface activity.

As the reactive surfactant, any nonionic or anionic surfactant can be used as long as it has an unsaturated bond capable of copolymerizing with the unsaturated monomer in the molecule.
Of these surfactants, nonionic surfactants are preferred because of their high storage stability.

  It is preferable that the usage-amount of surfactant is 1-40 mass parts with respect to 100 mass parts of an epoxy resin (D), and it is especially preferable that it is 5-20 mass parts. A stable aqueous resin dispersion can be obtained when the amount of the surfactant used is at least the above lower limit. Moreover, when it is the said upper limit or less, when it is set as the resin dispersion composition of this invention, the reactivity with polyolefin (A) improves, and the water resistance and gasohol resistance at the time of using a coating film become favorable. Preferably, furthermore, bleeding out in the coating film can be suppressed, and the appearance is improved.

As an aqueous emulsion method, a known phase inversion emulsification, mechanical emulsification, or the like can be employed, whereby an aqueous resin dispersion of resin particles containing an epoxy resin (D) can be obtained.
The emulsification temperature is 30 to 95 ° C, preferably 40 to 90 ° C.

  The solid content (usually composed of the epoxy resin (D)) content in the aqueous resin dispersion of the epoxy resin (D) thus obtained is usually 30 to 90% by mass, preferably 40 to 80% by mass, and more. Preferably it is 50-70 mass%. When the solid content is equal to or higher than the lower limit, the viscosity is appropriately increased, and the resin particles do not settle or separate. Moreover, workability | operativity becomes favorable and it is preferable that it is below an upper limit.

Moreover, the dispersion particle diameter of the resin particle containing the epoxy resin (D) in the aqueous resin dispersion of the epoxy resin (D) is the same as that of the resin particle containing the epoxy resin (D) in the resin dispersion composition of the present invention. The particle diameter corresponds to the particle diameter and is usually 0.1 to 5 μm, preferably 2 μm or less, more preferably 1 μm or less, as a 50% particle diameter measured by a particle size dispersion measuring instrument. The dispersed particle size is preferably smaller in view of high storage stability. However, since the reactivity with the polyolefin (A) becomes too high and the storage stability becomes low, the lower limit is 0.1 μm.
Similarly, the 90% particle diameter of the particle diameter measured by a particle size dispersion measuring machine of the resin particles containing the epoxy resin (D) in the resin dispersion composition of the present invention is preferably 0.2 to 10 μm, more preferably 5 μm. More preferably, it is 2 μm or less.

(3) Resin dispersion composition The resin dispersion composition of the present invention is obtained by dispersing resin particles containing the above-mentioned epoxy resin (D) and resin particles containing polyolefin (A) in water. It is preferably produced by mixing an aqueous resin dispersion of resin particles containing the epoxy resin (D) and an aqueous resin dispersion of polyolefin (A).
In addition, below, content of each resin particle shall be shown by the ratio in solid content of a resin dispersion composition.

  The content of the resin particles containing the epoxy resin (D) in the resin dispersion composition of the present invention is usually 2% by mass or more, preferably 4% by mass or more, particularly preferably 6% by mass or more, and usually 50%. It is not more than mass%, preferably not more than 30 mass%, particularly preferably not more than 15 mass%. If the content of the resin particles including the epoxy resin (D) is too small, the crosslinking effect is small, and the water resistance and gasohol resistance tend to be low. If the content is too large, there are many epoxy resins (D) that cannot be crosslinked. On the contrary, the gasohol resistance tends to be low.

  The content of the resin particles containing the polyolefin (A) in the resin dispersion composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, and particularly preferably 15% by mass or more. 80 mass% or less, preferably 50 mass% or less, particularly preferably 30 mass% or less. If the content of the resin particles containing the polyolefin (A) is too small, the adhesion to the polyolefin substrate tends to be low. If the content is too large, the excess polyolefin (A) cannot be crosslinked, and conversely, gasohol-resistant Tend to be low.

  In addition, the resin particles containing the epoxy resin (D) are contained in the resin dispersion composition of the present invention, although the content ratio of the resin particles containing the epoxy resin (D) and the resin particles containing the polyolefin (A) varies depending on the application. : The mass ratio of the resin particles containing the polyolefin (A) is preferably 100: 10 to 1000, and particularly preferably 100: 50 to 500. When the resin particles containing the polyolefin (A) are at least the lower limit of this range, the adhesion to the polyolefin substrate is good, and when the resin particles are below the upper limit, crosslinking by the reaction with the epoxy resin (D) is sufficient. It is preferable because the water resistance and gasohol resistance of the film are improved.

  The resin dispersion composition of the present invention preferably has a smaller surfactant content from the viewpoint of improving the water resistance of the coating film to be formed and preventing bleeding out, and the surfactant content is preferably 30% by mass or less, More preferably, it is 20 mass% or less.

  The resin dispersion composition of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weather resistance stabilizers, heat resistance inhibitors, etc., conductivity imparting agents such as titanium oxide, carbon black, ferrite, dyes, pigment dispersants, leveling agents, antifoaming agents, Various additives such as thickeners, preservatives, fungicides, rust inhibitors and wetting agents can be contained.

  Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.

  Moreover, in order to further improve various coating film performances such as water resistance and solvent resistance, a crosslinking agent is used as a resin component in the resin dispersion composition (usually polyolefin (A) and epoxy resin (D) as necessary. 0.01-100 mass parts can be added with respect to 100 mass parts) of the below-mentioned resin (C) used correspondingly. 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. These may be used alone or in combination of two or more.

  In addition, when the resin dispersion composition of the present invention is used for applications such as primers, paints, and inks, a hydrophilic organic solvent other than water is blended 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.

  Moreover, organic or inorganic compounds other than those described above can be added to the resin dispersion composition as long as the stability of the resin dispersion composition is not impaired.

  Furthermore, in the resin dispersion composition of the present invention, a resin that can be dispersed in water using a water-soluble resin or surfactant or the like (hereinafter referred to as these, as long as the effect of the present invention is not significantly impaired). The resin may be referred to as “other resin”.) May be used in combination. The blending of these other resins is effective in, for example, improving the appearance of coating (glossing or matting) and reducing tackiness.

  Among other resins, as the water-soluble resin, for example, the resins mentioned as the hydrophilic polymer (B) can be used. For example, an aqueous solution in which these resins are dissolved in water can be mixed and used.

  Examples of the resin that can be dispersed in water using a surfactant or the like include acrylic resins, epoxy resins other than the epoxy resin (D), polyester resins, polyurethane resins, melamine resins, alkyd resins, and the like.

  The other resin is preferably at least one resin selected from the group consisting of epoxy resins other than acrylic resins, polyester resins, polyurethane resins, and epoxy resins (D). Resin dispersion compositions containing these resins are suitable for paints. Hereinafter, these other resins are collectively referred to as a resin (C).

  The method for adding the resin (C) to the resin dispersion composition is not particularly limited. For example, the resin (C) is emulsified separately from the resin particles containing the polyolefin (A) and the resin particles containing the epoxy resin (D) to prepare an aqueous dispersion, and the resin particles containing the polyolefin (A) are prepared. And an aqueous dispersion of resin particles containing an epoxy resin (D). In this method, a resin dispersion composition containing resin particles of resin (C) different from resin particles containing polyolefin (A) or epoxy resin (D) can be obtained.

  Or there exists the method of emulsifying, after mixing resin (C) and polyolefin (A) or an epoxy resin (D). In this method, a resin dispersion composition is obtained in which resin particles in which resin (C) and polyolefin (A) or epoxy resin (D) are mixed in water are dispersed in water. For example, the polyolefin (A) or the epoxy resin (D) can be mixed together during the polymerization of the resin (C), and both can be mixed, and this can be emulsified and dispersed in water to form the resin (C) in one particle. Resin particles containing polyolefin (A) or epoxy resin (D) can be formed. Alternatively, the resin (C) and the polyolefin (A) or the epoxy resin (D) can be synthesized separately and then mixed by melt-kneading or the like. Resin particles containing resin (C) and polyolefin (A) or epoxy resin (D) can be formed therein.

  In order to effectively exhibit the properties of the epoxy resin (D) and the polyolefin (A) and the resin (C), resin particles containing the polyolefin (A), resin particles containing the epoxy resin (D), and the resin (C) The resin dispersion composition in which the resin particles containing s are present separately.

  When such a resin (C) is used, the mass ratio of the polyolefin (A) and the resin (C) in the resin dispersion composition is preferably 90:10 to 10:90. That is, the total amount of polyolefin (A) and resin (C) 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. The ratio of the polyolefin (A) in the total 100 parts by mass of the polyolefin (A) and the resin (C) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. Further, when the amount of the polyolefin (A) is more than 90 parts by mass, the physical properties of the obtained coating film, specifically, the coating film strength, water resistance, weather resistance, abrasion resistance, solvent resistance and the like are insufficient. turn into. The ratio of polyolefin (A) in the total 100 parts by mass of polyolefin (A) and resin (C) is preferably 85 parts by mass or less, more preferably 80 parts by mass or less.

  The mass ratio of the total amount of the epoxy resin (D) and the resin (C) to water is preferably 5:95 to 60:40. That is, the total amount of the epoxy resin (D) and the resin (C) is 5 parts by mass or more and 60 parts by mass or less with the total amount of the epoxy resin (D), the resin (C), and water being 100 parts by mass. When the total amount of epoxy resin (D) and resin (C) in 100 parts by mass of epoxy resin (D), resin (C) and water is less than 5 parts by mass, workability such as coating and heat curing is poor and practical. Not right. This ratio is preferably 10 parts by mass or more, more preferably 15 parts by mass or more. If the total amount of the epoxy resin (D) and the resin (C) in 100 parts by mass of the epoxy resin (D), resin (C) and water is more than 60 parts by mass, the viscosity of the resin dispersion composition is high. It becomes too high, the applicability deteriorates, and a uniform coating film is difficult to form. This ratio is preferably 55 parts by mass or less, more preferably 50 parts by mass or less.

  In order to make the resin (C) into an aqueous emulsion to form an aqueous dispersion, a surfactant can be used if necessary. As surfactant, what was mentioned as surfactant used for manufacture of the aqueous dispersion of the resin particle containing the above-mentioned epoxy resin (D) can be used, for example.

  The content of the surfactant in the aqueous dispersion of the resin (C) is usually 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (C). More preferably, it is 2 parts by mass 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 polyolefin (A) or the epoxy resin (D) and the resin (C) are mixed and then emulsified.

  The dispersed particle size of the resin particles containing the resin (C) in the resin dispersion composition of the present invention is 5 to 500 nm, particularly 20 to 200 nm, as a 50% particle size of the particle size measured by a particle size dispersion measuring machine. It is preferable that If the particle size is too large, phenomena such as sedimentation and separation tend to occur, which is not preferable. If the particle size is too small, the adhesion to the polyolefin substrate tends to decrease.

  A pigment (E) can be further 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, etc. be able to. These may be used alone or in combination of two or more.

  The amount of pigment (E) added to the resin dispersion composition is 100 parts by mass of resin (total amount of polyolefin (A) and epoxy resin (D) and resin (C) used as necessary). 10 mass parts or more are preferable, More preferably, it is 50 mass parts or more. However, 400 mass parts or less are preferable, More preferably, it is 200 mass parts or less. As the added amount of the pigment (E) is larger than the lower limit, the color developability and the hiding property tend to be higher, and as the amount is lower than the upper limit, the adhesion, moisture resistance and oil resistance tend to be higher.

  When the pigment (E) is blended with the resin dispersion composition, a pigment dispersant may be used together with the pigment (E). Examples of the pigment dispersant include 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; Air Products (air product) An acetylenic diol derivative such as Surfynol T324 manufactured by Komatsu Ltd .; a water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., Ltd. These may be used alone or in combination of two or more. By using these pigment dispersants in a proportion of, for example, about 1 to 30% by mass with respect to the pigment (E), the dispersibility of the pigment (E) can be stabilized.

  In addition, the pigment (E) is preliminarily dispersed in water together with a pigment dispersant as necessary to prepare a pigment dispersion paste having a pigment (E) concentration of about 20 to 70% by mass. It is preferable to mix by mixing an aqueous resin dispersion of resin particles containing and an aqueous resin dispersion of polyolefin (A).

(4) Applications The resin dispersion composition of the present invention can be used for primers, primerless 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.

(5) Laminate The resin dispersion composition of the present invention is applied to a substrate and heated to form a resin layer to obtain a laminate.
This laminate can be used in various applications such as for automobiles, home appliances, and building materials.
In this case, the shape of the substrate is not limited, such as a film, a sheet, or a plate.

The resin dispersion composition of the present invention is applied to a thermoplastic resin molded body (F) described later, preferably a molded body (base material) of an olefin polymer having crystallinity to form a coating film satisfactorily. Can do.
Examples of the olefin polymer as the 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. Examples thereof include olefin copolymers such as copolymers, 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.

  The molded product to which the resin dispersion composition of the present invention is applied is obtained by any of the above-mentioned various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. The resin dispersion composition of the present invention may be blended with inorganic fillers such as talc, zinc white, glass fiber, titanium white, and magnesium sulfate, pigments, and the like. Even when it is, a coating film with good adhesion can be formed.

(5) -1 Production Method of Laminate As a method for forming a resin layer on a substrate using the resin dispersion composition of the present invention, a known method can be used without any particular limitation. , A method of applying the resin dispersion composition by spray, a method of applying by a roller, a method of applying by a brush, and the like.

  After the resin dispersion composition is applied to the base material, it is usually heated with nichrome wire, infrared rays, high frequency, etc. to cure the coating film, and a laminate having a desired resin coating film on the surface can be obtained. The curing conditions for the coating film are appropriately selected depending on the material and shape of the substrate, the composition of the resin dispersion composition to be 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 laminated resin layer (after curing) can be appropriately selected depending on the material and shape of the substrate, the composition of the resin dispersion composition to be used, the purpose of use of the laminate, etc., but is usually 0.1 μm or more. The thickness is preferably 1 μm or more, more preferably 5 μm or more. However, it is usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less. If the film thickness is too thin, adhesion to the polyolefin substrate may not be exhibited. If the film thickness is too thick, the coating film may dry due to evaporation of water or solvent contained during coating.

(5) -2 Thermoplastic resin molded body A thermoplastic resin molded body is desirable as the base material of the laminate.
Although it does not specifically limit as a thermoplastic resin molded object (F), For example, the molded object which consists of polyolefin resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin etc. is mentioned. In particular, the resin dispersion composition of the present invention is preferably applied to a thermoplastic resin molded body made of a polyolefin resin (hereinafter sometimes referred to as “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 and Copolymerization of propylene and other comonomers such as 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.

This 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 the b unit part is larger than the above lower limit value, and the rigidity, strength and heat resistance tend to increase as the amount is smaller than the upper limit value.

  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 according to 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.

The thermoplastic resin molded body (F) used in the present invention can 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.

Here, specific examples of the inorganic filler component include plate-like fillers such as talc, mica, and montmorillonite; fibers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, and zonolite. Filler: Potassium titanate, magnesium oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide and other needle-shaped (whisker) fillers; precipitated calcium carbonate, heavy Granular fillers such as fine calcium carbonate and magnesium carbonate; balun fillers such as glass balloons, and the like. Moreover, 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.
These inorganic filler components may be used alone or in combination of two or more.

  These inorganic filler components 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 body.

  The amount of the inorganic filler component used is selected from a wide range depending on the purpose and application of the molded body. For example, the amount is preferably 1 to 80 parts by weight, more preferably 2 to 75 parts by weight with respect to 100 parts by weight of the crystalline polyolefin. More 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 further preferably 4 to 60 kJ / m ² .

  Hereinafter, preferred fillers will be described in detail.

(A) 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. Here, the average particle size value of talc is a particle size cumulative distribution curve drawn from the measurement results 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 a cumulative amount of 50% by mass read from now on. 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 are preferably used. Moreover, 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 resin. The surface may be treated with a fatty acid metal salt, a fatty acid ester, or the like.

(B) 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 an 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. As this modified polyolefin, those modified with polypropylene as a base material are particularly preferable, and those having a modification rate of 0.1 to 10% by mass are preferably used.

(C) Mica Mica preferably has an average particle size of 2 to 100 μm and an average aspect ratio of 10 or more, more preferably an average particle size 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.

  When the thermoplastic resin molded body (F) as a base material is a crystalline polyolefin molded body, 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. These may be used alone or in combination of two or more.

  Specific examples of the elastomer component include ethylene / α-propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-hexene copolymer rubber, ethylene / 1-octene copolymer rubber, and other ethylene / α. -Olefin copolymer rubber; Ethylene / α-olefin / non-conjugated diene copolymer rubber such as ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM); Hydrogenated styrene-butadiene-styrene triblock (SEBS) ), Styrene-containing thermoplastic elastomers such as styrene-isoprene-styrene triblock hydrogenated product (SEPS).

  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.

  In addition to the above, the thermoplastic resin molded body (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, neutralizing agents, foaming agents, copper damage inhibitors, lubricants, flame retardants, other resins such as polyethylene resins, and the like.

  In order to produce the thermoplastic resin molded body (F), first, various components are blended into the above-described resin 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) can be obtained. In order to improve the dispersion of each component, a twin screw extruder is preferably used.

  When kneading and granulating, the above components may be kneaded at the same time, or a method of kneading each component separately may be employed to improve performance.

Next, the obtained thermoplastic resin composition is molded to obtain a thermoplastic resin molded body (F), and various known methods can be used for this 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.

(5) -3 Use of Laminate The laminate obtained using the resin dispersion composition of the present invention is excellent in coating film adhesion, and 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, environmental load can be reduced by not containing halogens, such as chlorine.

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

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.

<Physical property measurement method and evaluation method>
The measurement or evaluation methods of physical properties in the following examples and comparative examples are as follows.

(1) Epoxy equivalent It measured according to JIS K7236. The epoxy equivalent of the epoxy resin represents the mass of the resin containing 1 equivalent of the epoxy group, and the epoxy equivalent of the resin particle containing the epoxy resin is a resin particle containing 1 equivalent of the epoxy group (the interface other than the epoxy resin). Mass of non-volatile substances such as activators).

(2) Glass transition temperature (Tg) of epoxy resin
In a differential scanning calorimeter DSC2920 manufactured by TA Instruments Inc., the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min, and then cooled to −30 ° C. to make the heat history the same. The glass transition temperature (Tg) when the temperature was raised again to 200 ° C. at a rate of temperature increase of 10 ° C./min was measured.

(3) Storage stability of epoxy resin aqueous dispersion The epoxy resin aqueous dispersion was placed in a 20 ml sample bottle and allowed to stand at 23 ° C. for 30 days. Then, the separation state of the resin phase and the aqueous phase and the presence or absence of sediment were determined. The evaluation was made based on the following criteria.
1: No separation at all, no sediment 2: Slight separation, but no sediment 3: Separation but no sediment 4: No separation at all, but no sediment Yes 5: Slightly separated, some sediment 6: Separated, some sediment

(4) Weight average molecular weight, number average molecular weight (4) -1 Molecular weight measurement of polyolefin First, 5 mg of a sample was taken in a 10 ml vial, and 5 g of tetrahydrofuran containing 250 ppm of butyloxytoluene was added as a stabilizer. Dissolved. 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 resin concentration of 0.1% by mass. 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.
(4) -2 Weight average molecular weight measurement of epoxy resin A sample solution having a resin concentration of 1% by weight was prepared in the same manner as in (4) -1. Next, GPC measurement was performed using TSKgel SUPER HZ-H as a column, GPC HLC-8220 manufactured by Tosoh Corporation equipped with two HZ4000, one HZ3000, and HZ20001. Measurement conditions were as follows: injection volume of sample solution: 10 μl, column temperature: 40 ° C., solvent: tetrahydrofuran, flow rate: 1.0 ml / min.
In calculating the weight 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.

(5) 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 determined by measuring the absorption of carbonyl groups in a solution of maleic anhydride dissolved in chloroform, and preparing a calibration curve. And from the area of the absorption peak of the carbonyl group of the sample (maximum peak near 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer is calculated based on the calibration curve created earlier, The graft ratio (mass%) was used.

(6) Dispersion particle diameter: 50% particle diameter and 90% particle diameter (6) -1 Measurement of epoxy resin aqueous resin dispersion The dispersion was measured using LA-300 manufactured by Horiba, Ltd. The dispersion particle shape was measured with a spherical shape and the dispersion medium as water for a measurement time of 10 seconds, and as a volume conversion, a cumulative particle diameter of 50% and a particle diameter of 90% were obtained from the finer particle diameter.
(6) -2 Measurement of aqueous resin dispersion of resin other than epoxy resin The measurement was performed using Nanotrack 150 manufactured by Nikkiso Co., Ltd. The density of the dispersion was 0.9 kg / m ³ , the dispersion particle shape was spherical, the dispersion medium was water and the measurement time was 180 seconds, and the particle size was accumulated from the finer in terms of volume to 50%. The particle diameter at the time and the particle diameter at 90% were obtained.

(7) Storage stability test A resin dispersion composition is prepared by mixing an aqueous epoxy resin dispersion, an aqueous polyolefin dispersion, a pigment dispersion paste, an aqueous urethane resin dispersion, etc. And the viscosity was measured. Moreover, the following coating tests were conducted. After storing in a constant temperature bath at 40 ° C. for 10 days, pH and viscosity were measured. Moreover, the following coating tests were conducted.

(8) Coating test After the automobile exterior grade polypropylene is injection molded into 70mm x 150mm x 3mm to create a substrate, it is divided into two equal parts into a 70mm x 75mm x 3mm substrate, and the substrate surface is wiped with isopropyl alcohol. did. Next, the resin dispersion composition was spray-coated at a coating amount of about 10 g / m ^2, and this test piece was dried at 80 ° C. for 10 minutes in a safe ben dryer.
Next, a water-based metallic base paint was spray-applied so that the application amount was about 15 g / m ² and dried at 80 ° C. for 3 minutes.
Finally, solvent-based two-liquid clear was spray-coated at a coating amount of 40 g / m ² and dried at 80 ° C. for 35 minutes. The following adhesion, moisture resistance, and gasohol resistance tests were conducted after standing for 24 hours or longer.

(8) -1 Adhesiveness The prepared coating test piece is cross-cut according to the cross-cut test method described in JIS K 5400, and cellophane tape (manufactured by Nichiban Co., Ltd.) is attached to the coating film. After that, it peeled in the direction of 90 degrees. The number of grids that were not peeled out of the grid 25 was evaluated.

(8) -2 Moisture resistance After the prepared coating test piece was placed for 10 days under the conditions of 50 ° C. and 95% RH, a cross-cut test was conducted in the same manner as in (8) -1, and the cross-cut 25 was peeled off. Adhesion was evaluated by the number of grids that were not present. In addition, the presence or absence of blisters (blisters) was examined and evaluated according to the following criteria.
○: No appearance abnormality △: Small number of blisters occurred ×: Many blisters occurred

(8) -3 Gasohol resistance The edge of the prepared coating specimen is shaved with a cutter and immersed in a liquid of 20 ° C. regular gasoline: ethanol = 9: 1 (volume ratio), and peeling of the coating is 2 mm from the edge. The time when it was reached was measured.

(9) pH
The measurement was performed using a pH meter F-21 manufactured by Horiba, Ltd., which was calibrated with a pH standard solution, and the resin dispersion composition was previously adjusted to a liquid temperature of 25 ° C. in a thermostatic bath.

(10) Viscosity Using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd., No. Measurement was carried out at a speed of 60 rpm with 1 rotor attached.

[Production Example 1: Production of pigment dispersion paste]
A water-soluble acrylic resin (John Crill 683 manufactured by Johnson Polymer Co., Ltd. (resin acid value 160 mgKOH / g)) was neutralized with 2-amino-2-methylpropanol and dissolved in water.
20 g of this aqueous solution (solid concentration 25% by mass), 7.5 g of carbon black (manufactured by Mitsubishi Chemical Corporation), 60 g of titanium oxide (R-5N manufactured by Sakai Chemical Industry Co., Ltd.), antifoaming agent (Surfinol manufactured by Air Products) 440) 2.5 g, ion-exchanged water 60 g, and zirconia beads 150 g were mixed and stirred and dispersed in a paint shaker for 30 minutes. The dispersion was filtered through a 400 mesh wire mesh to obtain a pigment dispersion paste having a solid content concentration of 50% by mass.

[Production Example 2: Production of aqueous epoxy resin dispersion according to the present invention]
Into a glass flask equipped with a reflux condenser, a thermometer and a stirrer, an epoxy equivalent of 218 g / eq. After adding 540 g of orthocresol novolak type epoxy resin having a weight average molecular weight of 3,300 and Tg of 47 ° C., the inside of the container was dissolved while being replaced with nitrogen gas, and 30 g of HLB15.6 nonionic surfactant and HLB18.7 were dissolved. 30 g of nonionic surfactant and 30 g of water were added, and the temperature was adjusted to 100 ° C. Further, 65 g of water was added at 90 ° C. to perform phase inversion. Thereafter, water was further added to obtain an aqueous dispersion. The obtained epoxy resin aqueous dispersion had a solid content concentration of 61.9% by mass, a 50% particle size of 0.55 μm, a 90% particle size of 0.76 μm, and an epoxy equivalent of resin particles of 242 g / eq. Met. The evaluation results are shown in Table 1.

[Reference Example 1: Evaluation of aqueous epoxy resin dispersion according to comparative example]
Evaluation was performed in the same manner as in Production Example 2 using Epiletz 6006W70 manufactured by Hexion Co. as an aqueous epoxy resin dispersion. The epoxy resin has a molecular weight of 3,000 and a Tg of 35 ° C., and the epoxy equivalent of the resin particles is 251 g / eq. The aqueous epoxy resin dispersion had a solid content concentration of 71.7% by mass, a 50% particle size of 7.3 μm, and a 90% particle size of 14.6 μm. The evaluation results are shown in Table 1.
In addition, Tg of the epoxy resin in epoxy resin aqueous dispersion Epiretz 6006W70 was measured by separating the epoxy resin by the following method.
Epiletz 6006W70 was applied to a glass plate at 100 μm and dried at 120 ° C. for 4 hours. The solid 1.5g and 90ml water which shaved off this with the cutter were added to the 100cc sample bottle, and it stirred with the stirring bar for 2 hours. This was filtered through a 3 μm membrane filter. The operation of washing this solid with water and filtering was repeated two more times. The obtained solid was placed on an aluminum dish and dried at 120 ° C. for 2 hours to obtain an epoxy resin from which the surfactant was removed.
This epoxy resin aqueous dispersion was inferior in stability in the storage stability test because the resin settled in the lower part and a deposited layer was formed.

[Production Example 3: Production of Epoxy Resin Aqueous Dispersion According to Comparative Example]
Epoxy equivalent 209 g / eq. An aqueous epoxy resin dispersion was obtained in the same manner as in Production Example 2, except that an ortho-cresol novolak type epoxy resin having a weight average molecular weight of 1,300 and a Tg of 21 ° C. was used. The obtained epoxy resin aqueous dispersion had a solid content concentration of 61.3 mass%, a 50% particle size of 0.53 μm, a 90% particle size of 0.74 μm, and an epoxy equivalent of resin particles of 232 g / eq. Met. The evaluation results are shown in Table 1.

[Production Example 5: Production of aqueous epoxy resin dispersion according to the present invention]
Instead of the orthocresol novolac type epoxy resin, an epoxy equivalent of 915 g / eq. An aqueous epoxy resin dispersion was obtained in the same manner as in Production Example 2, except that a bisphenol A type epoxy resin having a weight average molecular weight of 2770 and Tg of 58 ° C. was used. The obtained epoxy resin aqueous dispersion had a solid content concentration of 58.6% by mass, a 50% particle size of 0.75 μm, a 90% particle size of 1.42 μm, and an epoxy equivalent of 1017 g / eq. Met. The evaluation results are shown in Table 1.

[Production Example 6: Production of aqueous epoxy resin dispersion according to the present invention]
Instead of the ortho-cresol novolac type epoxy resin, an epoxy equivalent of 1940 g / eq. An aqueous epoxy resin dispersion was obtained in the same manner as in Production Example 2, except that a bisphenol A type epoxy resin having a weight average molecular weight of 5500 and a Tg of 68 ° C. was used. The obtained epoxy resin aqueous dispersion had a solid content concentration of 60.1% by mass, a 50% particle size of 0.70 μm, a 90% particle size of 1.16 μm, and an epoxy equivalent of resin particles of 2156 g / eq. Met. The evaluation results are shown in Table 1.

[Production Example 4: Production of aqueous polyolefin dispersion]
(Melting and kneading process)
200 kg of propylene-butene copolymer (Mitsui Chemicals, Tuffmer XM7070, propylene content 74 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 Co., Ltd.) was used. , While feeding t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by Nippon Oil & Fats Co., Ltd.) halfway with a liquid pump so as to be 1 part by mass with respect to 100 parts by mass of propylene-butene copolymer, The mixture was kneaded under 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 mass (0.08 mmol / g as the maleic anhydride group, 0 as the carboxyl group). .16 mmol / g). Moreover, 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 added, 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, then 0.75 g of perbutyl I was added, and stirring was continued for 7 hours at the same temperature. Thereafter, 0.5 g of the solution was taken out, acetone was added, the precipitated polymer was filtered off, precipitation and filtration were 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 mass (0.15 mmol / g as maleic anhydride groups and 0.30 mmol / g as carboxyl groups). The weight average molecular weight was 146,000, and the number average molecular weight was 77,000 (both in terms of polystyrene).

(Graft polymerization process)
Next, after adding 129 g of toluene to the above solution for dilution, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Irga manufactured by Ciba Specialty Chemicals) Knox 1010) 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 hot water phase at the bottom and two phases, 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.

(Emulsification process)
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 mass% aqueous solution (AMP90) of 2-amino-2-methyl-1-propanol was added, and toluene, isopropanol and water were distilled off under reduced pressure until the solid content concentration became 30 mass%. As a result, a pale yellow aqueous dispersion was obtained. As a result of measuring the dispersed particle size, the 50% particle size was 0.042 μm, and the 90% particle size was 0.080 μm.

  The polyolefin in this aqueous polyolefin dispersion is composed of a maleic anhydride-modified propylene-butene copolymer (carboxyl group content 0.30 mmol / g, Mw 146,000), and a methoxypoly (oxy) having Mw 1000 as a hydrophilic polymer. Ethylene / oxypropylene) -2-propylamine is obtained by graft polymerization of 0.15 mmol / g, and the amount of carboxyl group of the polyolefin after the graft polymerization is 0.15 mmol / g and Mw is 139,000.

[Example 1]
Anionic self-emulsifying polyurethane aqueous dispersion Superflex 150 (solid content concentration 30% by mass, 50% particle diameter 75 nm, acid value 18 mgKOH / g) 9.6 g, epoxy resin aqueous dispersion of Production Example 2 3.49 g, 16.8 g of the aqueous polyolefin dispersion of Production Example 4 and 28.8 g of the pigment dispersion paste of Production Example 1 were mixed, and the resin dispersion composition was adjusted to a solid content concentration of 30% by mass with ion-exchanged water. Created.
The epoxy resin content in the solid content of this resin dispersion composition is 8.8% by mass, the polyolefin content is 20.6% by mass, and the polyurethane resin content is 11.8% by mass. The derived surfactant content is 0.8% by mass.
The evaluation results of the obtained resin dispersion composition are shown in Table 2.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that 3.01 g of the aqueous epoxy resin dispersion of Reference Example 1 was used instead of the aqueous epoxy resin dispersion of Production Example 2. The evaluation results are shown in Table 2.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that 3.49 g of the aqueous epoxy resin dispersion of Production Example 3 was used instead of the aqueous epoxy resin dispersion of Production Example 2. The evaluation results are shown in Table 2. As a result of the storage stability test, the viscosity increased 300 times or more after 10 days, and the storage stability was low.

[Comparative Example 3]
All operations were performed in the same manner as in Example 1 except that the aqueous epoxy resin dispersion of Production Example 2 was not used. The evaluation results are shown in Table 2.

[Example 2]
The same procedure as in Example 1 was performed except that 3.69 g of the aqueous epoxy resin dispersion in Production Example 5 was used instead of the aqueous epoxy resin dispersion in Production Example 2. Table 3 shows the evaluation results of the obtained resin dispersion composition.

[Example 3]
The same procedure as in Example 1 was conducted except that 3.59 g of the aqueous epoxy resin dispersion of Production Example 6 was used instead of the aqueous epoxy resin dispersion of Production Example 2. Table 3 shows the evaluation results of the obtained resin dispersion composition.

  From Tables 2 and 3, it can be seen that the resin dispersion composition of the present invention is excellent in storage stability and can form a coating film excellent in adhesion, moisture resistance, gasohol resistance and the like.

Claims (7)

  Resin particles having a 50% particle diameter of 0.1 to 5 μm including an epoxy resin (D) having a glass transition temperature (Tg) of 25 to 200 ° C., and a polyolefin having a reactive group capable of reacting with an epoxy group (A A resin dispersion composition obtained by dispersing resin particles containing) in water.   The resin dispersion composition of Claim 1 whose weight average molecular weights of an epoxy resin (D) are 300-20000.   The epoxy equivalent of the epoxy resin (D) is 100 to 1000 g / eq. The resin dispersion composition according to claim 1, wherein   The resin dispersion composition according to any one of claims 1 to 3, wherein the reactive group capable of reacting with an epoxy group is a carboxyl group.   The resin dispersion composition according to any one of claims 1 to 4, wherein the polyolefin (A) is a polyolefin grafted with a hydrophilic polymer (B).   The resin dispersion composition according to any one of claims 1 to 5, wherein the polyolefin (A) does not substantially contain chlorine.   The resin dispersion composition according to any one of claims 1 to 6, wherein the resin particles containing the polyolefin (A) do not substantially contain a surfactant.