JP2008138090A - Aqueous resin dispersion, coating comprising the same, adhesive, laminated product and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin dispersion that is excellent in various properties such as stability, water resistance and oil resistance, exhibits excellent adhesiveness to both a polyolefin and a material of a different kind and is useful as a coating, an adhesive and the like. <P>SOLUTION: The aqueous resin dispersion comprises a resin particle (D), dispersed in water, which comprises a polymer (C) comprised of a polyolefin (A) and a hydrophilic polymer (B) bonded thereto, where at least a part of the resin particle (D) contains a constituting unit derived from a (meth)acrylic ester. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous resin dispersion containing a polyolefin-based resin, a coating material containing the same, an adhesive, and a method for producing the same.

  Polyolefins such as propylene polymers and propylene-α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are used in a wide range of fields. . However, such polyolefins generally have a low polarity because they do not have a polar group in the molecule, and it is difficult to paint and bond, and improvements have been desired. For this reason, various methods have been tried, such as chemically treating the surface of a molded product of polyolefin with a chemical or the like, and oxidizing the surface of the molded product by a method such as corona discharge treatment, plasma treatment, or flame treatment. Yes. However, these methods require not only a special apparatus but also an effect of improving paintability and adhesiveness.

  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 modification Chlorinated polypropylene has been developed. Such a modified polyolefin is applied as a surface treatment agent, an adhesive, a paint or the like to the surface of the polyolefin molded body. The modified polyolefin is usually applied in the form of a solution of an organic solvent or a dispersion in water. Usually, an aqueous dispersion is preferably used from the viewpoint of health and safety and environmental pollution.

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

On the other hand, there is a demand to improve the adhesion between polyolefin and different materials such as adhesives and primers, and it is proposed to use other resins such as polyolefin and acrylic resin, or to use chlorinated polyolefin. ing. For example, it is a method (Patent Documents 4 and 5) in which an acrylic resin is blended with a polyolefin resin (Patent Document 3), or a polyolefin is modified with (meth) acrylic acid ester to be an aqueous resin. In addition, a chlorinated polyolefin or an aqueous resin composition obtained by emulsion polymerization of a radical polymerizable monomer in the presence of an aqueous resin composition of polyolefin (Patent Documents 6 and 7) may be used.
JP-A-10-231402 Japanese Patent Laid-Open No. 6-256592 JP 2004-115712 A JP 2005-126482 A JP 2006-036920 A JP 2002-308921 A JP 2004-91559 A

  An object of the present invention is to provide an aqueous resin dispersion that is excellent in various properties such as stability, water resistance and oil resistance, has high adhesion to both polyolefin and different materials, and is useful as a paint, an adhesive, and the like. To do.

  As a result of intensive studies to achieve the above object, the present inventor has found that a part of the resin particles containing a polymer in which a hydrophilic polymer is bonded to polyolefin in a predetermined ratio are structural units derived from (meth) acrylic acid esters. It has been found that such an aqueous resin dispersion has excellent adhesion to a polyolefin substrate and adhesion between a polyolefin and a different material, and has led to the present invention.

That is, the present invention provides a resin dispersion in which resin particles (D) containing a polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) are dispersed in water, and the resin The aqueous resin dispersion is characterized in that at least a part of the particles (D) contains a structural unit derived from a (meth) acrylic acid ester.
The present invention also relates to an aqueous resin dispersion in which at least a part of the polymer (C) has a structural unit derived from the (meth) acrylic acid ester.
The present invention also relates to an aqueous resin dispersion in which at least a part of the structural unit derived from the (meth) acrylic acid ester forms a (meth) acrylic polymer.

In the present invention, the polyolefin (A) has at least one reactive group selected from the group consisting of an unsaturated carboxylic acid group, an unsaturated dicarboxylic acid anhydride group, and an unsaturated carboxylic acid anhydride monoester group. It has an aqueous resin dispersion.
Preferably, the reactive group content is 0.01 to 1 mmol per 1 g of the polyolefin (A). Also preferred is a polyether resin in which the hydrophilic polymer (B) has one or more reactive groups per molecule. Preferably, the polyolefin (A) contains 50% or more of propylene.

The present invention also relates to an aqueous resin dispersion in which the polyolefin (A) satisfies the following.
(1) Molecular weight distribution Mw / Mn is 3.5 or less.
(2) Melting | fusing point Tm is 50 degreeC or more and 120 degrees C or less.
The present invention also relates to an aqueous resin dispersion in which the polyolefin (A) is a propylene polymer.

Moreover, this invention relates to the aqueous resin dispersion whose weight ratio of the said polyolefin (A) and the structural unit derived from the said (meth) acrylic acid ester is 90: 10-10: 90.
In the present invention, the polymer (C) binds the hydrophilic polymer (B) to the polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio). The aqueous resin dispersion which becomes.
The present invention also relates to an aqueous resin dispersion in which the polymer (C) is a graft copolymer obtained by grafting a hydrophilic polymer (B) to a polyolefin (A).

The present invention also relates to an aqueous resin dispersion in which the resin particles (D) have a 50% particle diameter of 0.5 μm or less and are dispersed in water.
Preferably, the weight ratio of the total amount of the resin particles (D) to water is 5:95 to 70:30.
Preferably, the surfactant content is less than 10% by weight based on the total amount of the resin particles (D).

The present invention also relates to a paint comprising the aqueous resin dispersion.
The present invention also relates to an adhesive comprising the aqueous resin dispersion.
Furthermore, the present invention is a method for producing the aqueous resin dispersion, wherein the mixture of the polyolefin (A) and the (meth) acrylic acid ester is reacted, and then the hydrophilic polymer (B) is mixed and reacted. Then, the present invention relates to a method for producing an aqueous resin dispersion, which is dispersed in water.

Furthermore, the present invention provides a polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) and a structural unit derived from a (meth) acrylic acid ester on a thermoplastic resin molded body (F). It has a resin layer containing the resin particle (D) containing, It is related with a laminated body characterized by the above-mentioned.
Moreover, this invention relates to the manufacturing method of a laminated body characterized by apply | coating the said aqueous resin dispersion or the said coating material to a thermoplastic resin molded object (F), and heating and forming a resin layer.

  Since the polymer of the present invention is excellent in dispersibility in water, an aqueous dispersion having excellent stability with a fine dispersed particle diameter can be obtained with a small amount of surfactant or without adding a surfactant. Therefore, the coating film obtained from the aqueous resin dispersion in which the resin particles (D) containing the structural unit derived from the polymer (C) and the (meth) acrylic acid ester of the present invention are dispersed is an interface that has been a problem in the past. There is an advantage that the bleed-out of the activator can be suppressed, and as a result, a coated product having an excellent appearance can be obtained.

In addition, this coating film shows good adhesion to polyolefin materials or plastic materials containing polyolefin, etc., and even on difficult-to-adhere substrates such as untreated polypropylene, which is usually difficult to paint or bond. In addition, it can be formed and has high adhesion to substrates other than polyolefin, and thus is excellent as an adhesive between both substrates and a primer for paints.
Furthermore, since this coating film is excellent in water resistance, moisture resistance, oil resistance (gasohol resistance), and chemical resistance, it is also suitable for coating methods such as solvent-based lacquer type paints that are finished only once. is there.

Therefore, the aqueous resin dispersion of the present invention is extremely useful as a surface treating agent, a coating agent, a paint, an adhesive and the like for an olefin polymer having crystallinity.
In the present invention, it is sufficient that one or more of the effects described above are sufficient even if not all the effects are exhibited.

The aqueous resin dispersion of the present invention (hereinafter sometimes referred to as an aqueous dispersion, an aqueous dispersion, or a resin dispersion) is a polymer obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) ( A resin dispersion obtained by dispersing resin particles (D) containing C) in water, wherein at least a part of the resin particles (D) contains a structural unit derived from a (meth) acrylic ester. To do. Thereby, an aqueous resin dispersion which is excellent in various properties such as stability, water resistance and oil resistance, and has high adhesion to both polyolefin and different materials can be obtained.
In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are dispersed by extremely small particles, and a state that can be said to be substantially dissolved.

In the present invention, the structural unit derived from (meth) acrylic acid ester refers to a (meth) acrylic acid ester monomer or a group formed by reaction of the monomer. For example, units corresponding to (meth) acrylate monomers in (meth) acrylic polymers obtained by polymerization of (meth) acrylate monomers, (meth) acrylate monomers are other monomers and polymers It is a unit corresponding to the (meth) acrylic acid ester monomer in the compound obtained by reacting with.
In addition, (meth) acrylic acid ester is the concept showing acrylic acid ester and / or methacrylic acid ester.

In the aqueous resin dispersion of the present invention, at least a part of the resin particles (D) dispersed in water contains the structural unit derived from the polymer (C) and the (meth) acrylic acid ester in the same particle. It is characterized by. Hereinafter, such particles are referred to as composite resin particles (E).
According to the present invention, compared with the case where the polymer (C) and the structural unit derived from the (meth) acrylic acid ester are contained in separate particles, they are different even if the structural unit derived from the (meth) acrylic acid ester is small. Adhesive strength with the material can be sufficiently obtained, and furthermore, since the amount of the polymer (C) is sufficiently large, the adhesive strength with respect to the polyolefin is also high, so that sufficient adhesive strength can be obtained simultaneously with respect to both substrates. Therefore, it is considered important to contain both resin components in the same particle.

The form of the composite resin particle (E) is not particularly limited, but preferably, the form in which the polymer (C) itself has a structural unit derived from a (meth) acrylic acid ester and forms a resin particle ( Such particles are referred to as (E1).) Or a structural unit derived from a (meth) acrylic acid ester forms a (meth) acrylic polymer, and the (meth) acrylic polymer and the polymer (C ) Are mixed to form resin particles (such particles are referred to as (E2)).
In (E1), the structural units derived from the (meth) acrylic acid ester contained in the polymer (C) are polymerized to form a (meth) acrylic acid ester chain (hereinafter referred to as a (meth) acrylic chain). It may be.

  The composite resin particles (E1) can be obtained, for example, by reacting the polyolefin (A) or the polymer (C) with a (meth) acrylic acid ester monomer, and then dispersing the obtained polymer in water. The composite resin particle (E2) can be obtained, for example, by polymerizing a (meth) acrylic acid ester monomer to obtain a (meth) acrylic polymer, mixing with the polymer (C), and then dispersing in water. . It is also possible to obtain both (E1) and (E2) by polymerizing the (meth) acrylic acid ester monomer in the presence of the polyolefin (A) and the polymer (C).

(E1) is simple because it can be obtained by mixing and reacting with a (meth) acrylic acid ester monomer when the polyolefin (A) or the polymer (C) is modified.
(E2) can be obtained by mixing and dispersing the (meth) acrylic ester polymer produced separately from the polymer (C), so that the polymerization and modification conditions of the polymer (C) can be freely set. Excellent in that precise control is possible. Further, since it does not affect the polymerization and modification conditions of the polymer (C), the range of selection of (meth) acrylic acid ester monomers and polymers is widened, and there is an advantage that the most preferable one can be selected according to the purpose.
One type of structural unit derived from (meth) acrylic acid ester may be used, or two or more types may be used simultaneously.

The polymer (C) has a structure in which the hydrophilic polymer (B) is bonded to the polyolefin (A). Since this polymer (C) is very excellent in water dispersibility, the dispersion particle size is small and the particle size distribution is narrow and the particles are stably used by using a very small amount or no surfactant. A dispersed aqueous dispersion can be obtained.
As a method for producing the polymer (C), usually, a method (R1) of forming a hydrophilic polymer (B) bonded to the polyolefin (A) by polymerizing a hydrophilic monomer in the presence of the polyolefin (A), Alternatively, a method (R2) of bonding a prepolymerized hydrophilic polymer (B) to a polyolefin (A) can be mentioned, and the types and combinations of polyolefin and hydrophilic polymer, the characteristics of the target polymer (C), etc. What is necessary is just to select suitably according to. Moreover, as polyolefin (A), polyolefin (A1) which does not have a reactive group, or polyolefin (A2) which has a reactive group can be used.

Hereinafter, each case will be described separately.
[1] Polyolefin (A)
As the polyolefin (A) of the present invention, a polyolefin (A1) having no reactive group or a modified polyolefin (A2) having a reactive group can be used.

[1-1] Polyolefin having no reactive group (A1)
As the polyolefin (A1), various known polyolefins and modified polyolefins can be used, and are not particularly limited. For example, a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, ethylene or / and propylene and Copolymers with other comonomers may be mentioned. Examples of the comonomer include α-olefin comonomers having 2 or more carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, and norbornene. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 8 carbon atoms, and more preferably an α-olefin comonomer having 2 to 6 carbon atoms. Alternatively, two or more types of these α-olefin comonomers can also be used.
Also, a hydrogenated product of a copolymer of two or more monomers selected from a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, and an aromatic vinyl monomer and a conjugated diene monomer. , Etc. can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. The polyolefin (A1) may be linear or branched.

  Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 50% by weight or less, preferably 30% by weight or less. However, for the purpose of reducing the environmental load, it is desirable that the polyolefin (A1) does not substantially contain chlorine. The phrase “substantially containing no chlorine” means, for example, that the chlorination rate of polyolefin is less than 5% by weight.

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

  The polyolefin (A1) preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC (Gel Permeation Chromatography) and converted with a calibration curve of each polyolefin (polypropylene conversion). A more preferable value of the lower limit is 10,000, more preferably 15,000, particularly preferably 30,000, particularly preferably 50,000. A more preferable value of the upper limit value is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the lower limit, the degree of stickiness tends to decrease and the adhesion to the substrate tends to increase, and as the Mw is lower than the upper limit, the viscosity tends to decrease and the resin dispersion tends to be easily prepared. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

  The molecular weight distribution Mw / Mn represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the polyolefin (A1) is preferably 3.5 or less, more preferably 3.0 or less. This means that the molecular weight distribution is narrow and the molecular weight of the polyolefin is uniform. By using such a polyolefin (A1), it becomes easy to control the particle size when dispersed in water, and the dispersed particles There is an advantage that a resin dispersion having a small diameter, a narrow particle size distribution, and a stable dispersion can be obtained. Preferably Mw / Mn is 3.0 or less. However, it is usually 1.0 or more.

The polyolefin (A1) preferably has a melting point Tm of 120 ° C. or lower. More preferably, it is 100 degrees C or less, More preferably, it is 90 degrees C or less. The melting point Tm lower than 120 ° C. is preferable because the crystallinity is low and the solubility in a solvent is improved, and the emulsification and dispersion operations are easily performed at a low temperature. However, the melting point Tm of the polyolefin (A1) is usually 50 ° C. or higher, preferably 60 ° C. or higher. It is advantageous in terms of high heat resistance, high hardness, and non-stickiness.
The content of propylene in the polyolefin (A1) is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.

  A preferable example of the polyolefin (A1) is one having an isotactic structure as a whole or a part of the stereoregularity of the propylene homopolymer or copolymer. For example, not only ordinary isotactic polypropylene but also isotactic block polypropylene as described in Japanese Patent Application Laid-Open No. 2003-231714 (US 2004-162403) and US Pat. No. 4,522,982, Stereoblock polypropylene having a tactic block and an atactic block can also be preferably used.

When the polyolefin (A1) is a propylene homopolymer, the [mmmm] pentad exhibiting isotactic stereoregularity is preferably in the range of 10% to 90%. A preferable value of the lower limit is 20%, more preferably 30%, more preferably 40%. A preferred value for the upper limit is 80%, more preferably 70%, more preferably 60%, and more preferably 55%. As a method for measuring the pentad ratio, the method described in JP-A-2003-231714 (US2004-162403) can be used. There is a tendency that the degree of stickiness becomes smaller as the value is lower than the lower limit, and the degree of crystallinity becomes lower and the preparation of the resin dispersion tends to become easier as the value is lower than the upper limit.
However, when the polyolefin (A1) is a copolymer, the apparent stereoregularity is higher, and for example, it can be preferably used even if the ratio of the [mmmm] pentad is larger.

  Alternatively, another preferred example of the polyolefin (A1) is a propylene-α-olefin copolymer. Since such a copolymer has a lower melting point than a homopolymer such as polypropylene, a resin dispersion using the copolymer has an advantage that the baking temperature after coating can be lowered. More preferably, the propylene content is 50 mol% to 95 mol%. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate. Preferably it is 60 mol% or more, More preferably, it is 70 mol% or more. However, the propylene content is 95 mol% or less. Usually, when the propylene content is lowered, the melting point of the copolymer can be lowered, and for example, there is an advantage that the baking temperature after coating can be lowered. Preferably it is 90 mol% or less, More preferably, it is 85 mol% or less.

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

Commercially available products available as copolymers include Tafmer XM-7070 and XM-7080 manufactured by Mitsui Chemicals, Wintech series manufactured by Nippon Polypro Co., Ltd., Ricocene PP series manufactured by Clariant Co., Ltd. and Nippon Paper Chemicals Co., Ltd. Part of the Super Clon series manufactured by Toyo Kasei Kogyo Co., Ltd.
Polyolefin (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.
In summary, the polyolefin (A1) is preferably a stereoblock polypropylene polymer having a propylene content of 50 mol% or more and having an isotactic block and an atactic block, and propylene-α-olefin. It is a copolymer or a combination thereof.

About the manufacturing method of polyolefin (A1) of this invention, if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, What kind of manufacturing method may be sufficient. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.
In the case of coordination polymerization, for example, a method of polymerizing with a Ziegler-Natta catalyst or a method of polymerizing with a single site catalyst or a Kaminsky catalyst can be mentioned. A preferable production method includes a production method using a single site catalyst. The reason for this is that single-site catalysts are generally easy to control the reaction precisely due to the ligand design, yielding a polymer with a sharp molecular weight distribution and stereoregularity distribution, and have a melting point compared to polymers based on Ziegler-Natta catalysts. This is because the resin dispersion using this polymer can lower the baking temperature after coating because it is low. As the single site catalyst, for example, a metallocene catalyst or a Brookhart catalyst can be used. C ₁ symmetric type metallocene catalyst, C ₂ symmetric, C _2V symmetric, C _S symmetric like, it may be selected preferred catalyst in accordance with the stereoregularity of the polyolefin to be polymerized. Preferably, a C ₁ symmetric type or C ₂ symmetric type metallocene catalyst can be used.

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

[1-2] Polyolefin (A2) having a reactive group
As the polyolefin (A2) having a reactive group, for example, a copolymer (A2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polyolefin polymerization, or a reaction A polymer (A2b) obtained by graft-polymerizing a radically polymerizable unsaturated compound having a functional group to a polyolefin, and a polymer (A2c) obtained by converting a polyolefin having an unsaturated end group to an element group of Groups 13 to 17 Can do.

  Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, and isocyanate groups. More preferably, the polyolefin (A2) preferably has at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic anhydride group, and a dicarboxylic anhydride monoester group. These carboxylic acid groups and the like are not only highly reactive and easy to bond with hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.

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

  The polymer (A2b) is obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin, and the unsaturated compound having a reactive group is grafted to the main chain. For example, (meth) acrylic acid, fumaric acid, maleic acid or its anhydride, itaconic acid or its anhydride, crotonic acid, 2-hydroxyethyl (meth) acrylate or (meth) acrylic, such as polyolefins such as polyethylene and polypropylene It is a polymer grafted with 2-hydroxypropyl acid, (meth) acrylamide, (dimethylamino) ethyl (meth) acrylate, glycidyl (meth) acrylate, (2-isocyanato) ethyl (meth) acrylate and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and others are based on this. As polyolefin of this reaction, the polyolefin which does not have the above-mentioned reactive group can be used.

  Specific examples of the polymer (A2b) include, for example, maleic anhydride modified polypropylene and its chlorinated product, maleic anhydride modified propylene-ethylene copolymer and its chlorinated product, maleic anhydride modified propylene-butene copolymer and its chlorine. And acrylic acid-modified polypropylene and its chlorinated product, acrylic acid-modified propylene-ethylene copolymer and its chlorinated product, acrylic acid-modified propylene-butene copolymer and its chlorinated product, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

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

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

  The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 300 ° C. More preferably, the temperature is in the range of 80 to 200 ° C. in the case of the solution modification method, and the range of 150 to 300 ° C. in the case of the melt modification method. The reaction time is usually about 2 to 20 hours. The reaction time is usually about 2 to 20 hours.

  The polymer (A2c) is usually used when a block copolymer is produced. For example, as described in JP-A No. 2001-288372 (US2003-055179), a polyolefin having a terminal double bond is used. A polyolefin (A2c1) in which a double bond portion is converted into a group 13 element group such as a boron group or an aluminum group, and two polyolefins having a terminal double bond as described in JP-A-2005-048172 (EP16454576A1). Polyolefin (A2c2) in which a double bond is converted to a halogen element, and a double bond of a propylene-based polymer having a terminal double bond as described in JP-A No. 2001-098140 (US6451901) is converted to a mercapto group. Converted polyolefin (A2c3) can be used.

Examples of the method for producing a polyolefin having a double bond include a method of causing α-hydrogen elimination during olefin polymerization and a method of thermally decomposing a propylene-based polymer at a high temperature.
Examples of the method for converting the double bond portion into a boron group or an aluminum group include a method in which an organic boron compound or an organic aluminum compound is reacted with a double bond in a solvent.
As a method for converting the double bond portion to a halogen element, for example, after converting the polyolefin having an organic boron group (A2c1) to a propylene-based polymer having a hydroxyl group by reacting a base and hydrogen peroxide water, There is a method in which a halogen group-containing acid halide is reacted to convert it into a halogen group-containing ester group.
As a method for converting the double bond portion into a mercapto group, for example, there is a method in which thioacetic acid is reacted in the presence of a radical initiator and then treated with a base.

  The production method of the polymer (A2c) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced. Any production method may be used, but a method of heating and stirring in a solution is preferably used. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

The content of reactive groups in the polymers (A2a) and (A2b) formed by bonding reactive groups may be in the range of 0.01 to 5 mmol / g of polyolefin, ie 0.01 to 5 mmol / g. preferable. A more preferred lower limit is 0.05 mmol / g, still more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, and particularly preferably 0.5 mmol / g.
The content of the reactive group in the polymer (A2c) formed by bonding the reactive group is usually 1 reactive group or less per polymer molecule from the production method, and is 1 / number average molecular weight Mn (mol / g) or less. And tends to be lower than those of the copolymers (A2a) and (A2b). Accordingly, it is preferably in the range of 0.004 to 2 mmol / g per gram of polyolefin. A more preferred lower limit is 0.005 mmol / g. A more preferred upper limit is 0.2 mmol / g.

The higher the lower limit value, the greater the amount of the hydrophilic polymer (B) bound and the higher the hydrophilicity of the polymer (C2). Therefore, the dispersed particle size tends to decrease. There is a tendency for adhesion to polyolefin to increase. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.
Polyolefin (A2) may be used individually by 1 type, and may be used in combination of 2 or more type. Further, as the polyolefin (A2), any of (A2a), (A2b), and (A2c) can be used, but the polymer (A2b) is usually preferable. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).

  In the present invention, as the polyolefin (A), both the polyolefin (A1) having no reactive group and the polyolefin (A2) having a reactive group are combined with the hydrophilic polymer (B) or the desired heavy weight. It can be used as appropriate according to the characteristics of the coalesced (C). However, it is preferable to include at least a polyolefin (A2) having a reactive group. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B) and various reactions that can be used for binding. Only the polyolefin (A2) having a reactive group may be used.

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

  Although it does not specifically limit as a synthetic polymer, For example, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin etc. can be used. Examples of natural polymers include, but are not limited to, starch such as corn starch wheat starch, candy starch, potato starch, tapioca starch, and rice starch, seaweed such as fungi, agar and sodium alginate, gum arabic, tragacanth gum, and konjac. Animal protein such as glue, casein and gelatin, fermented mucilage such as pullulan and dextrin, and the like can be used. Although it does not specifically limit as a semisynthetic polymer, For example, starch substances, such as carboxyl starch, cationic starch, dextrin; Celluloses, such as viscose, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, etc. 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 polyvinyl alcohol resins, polyvinyl pyrrolidone resins, and polyether resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Highly hydrophilic polyether resins are most preferred.

The polyvinyl alcohol resin used in the present invention is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.
The polyvinyl pyrrolidone resin used in the present invention is usually obtained by polymerizing vinyl pyrrolidone.

The polyether resin used in the present invention is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with the polyolefin (A) is not limited. For example, a method of ring-opening polymerization of a cyclic alkylene oxide in a polyolefin (A2) having a reactive group, a polyether polyol or a poly-polyester obtained by ring-opening polymerization, or the like. Examples thereof include a method of reacting a hydrophilic polymer having a reactive group such as ether amine with a polyolefin (A2) having a reactive group.
Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.

Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.
Alternatively, as the polyetheramine, Jeffamine M series, D series, ED series, Surfonamin L series, etc. manufactured by Huntsman may be used.
The hydrophilic polymer (B) used in the present invention preferably has at least one reactive group capable of reacting with the polyolefin (A) before bonding with the polyolefin (A). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and preferably have at least an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, a glycidyl group, and an isocyanate group, it is easy to bond a polyolefin and a hydrophilic polymer. The amino group may be primary, secondary, or tertiary, but is preferably a primary amino group.

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

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

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

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

The hydrophilic polymer (B) can be bonded to the polyolefin (A) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.

  Reactions using reactive groups are those in which both polyolefin (A) and hydrophilic polymer (B) have reactive groups that are reacted to form covalent bonds or ionic bonds. Is done. Examples of this reaction include (ring-opening) esterification reaction of (anhydrous) carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening of primary or secondary amino group and epoxy group Reaction, (anhydrous) carboxylic acid group and primary or secondary amino group (ring-opening) amidation reaction or imidation reaction, carboxylic acid group and tertiary amino group quaternary ammonium reaction, carboxylic acid group and isocyanate Examples include amidation reactions of groups, urea reactions of primary or secondary amino groups and isocyanate groups, urethane reactions of hydroxy groups and isocyanate groups, and the like. Among them, the ring-opening amidation reaction or imidation reaction between a carboxylic anhydride group and a primary or secondary amino group is preferable in terms of high reactivity. Furthermore, amidation is more preferable than NH group than imidation. Since the hydrophilic group of COOH group remains in the group, it is preferable from the viewpoint of easy emulsification. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or its anhydride, 1 mol of the dibasic acid or its anhydride is calculated as 2 equivalents. May be.

[3] Polymer (C)
The polymer (C) is obtained by bonding the hydrophilic polymer (B) to the polyolefin (A). The ratio of the polyolefin (A) to the hydrophilic polymer (B) is preferably (A) :( B) = 100: 1 to 100: 300 (weight ratio). By setting (B) to 1 part by weight or more, the dispersibility of the polymer (C) in water can be improved, and the dispersed particle size can be reduced without causing aggregation or separation. By making (B) 300 parts by weight or less, it is possible to improve the adhesion to the polyolefin substrate.
As a method for producing a polymer (C) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) and bonded to the polyolefin (A). There is a method (R1) for forming the hydrophilic polymer (B) or a method (R2) for bonding the previously polymerized hydrophilic polymer (B) to the polyolefin (A). In any case, the polyolefin (A) can be used together with a polyolefin (A1) having no reactive group or a polyolefin (A2) having a reactive group.

[3-1] Method for producing polymer (C) (R1)
In this method, a hydrophilic polymer (B) bonded to polyolefin is obtained by polymerizing a hydrophilic radical polymerizable unsaturated compound (hydrophilic monomer) in the presence of polyolefin. As a method for polymerizing the hydrophilic monomer, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic radical polymerizable unsaturated compound (hydrophobic monomer) may be copolymerized as long as a hydrophilic polymer can be formed after polymerization. In either case, the polyolefin (A1) having no reactive group or the polyolefin (A2) formed by bonding a reactive group can be used as the polyolefin.

  Specifically, for example, there is a method in which a hydrophilic radical-polymerizable unsaturated compound is graft-polymerized into a polyolefin-polyacrylic graft copolymer in the presence of a polyolefin (A) and a radical polymerization initiator such as a peroxide or an azo compound. is there. Further, as described in JP-A No. 2001-288372 (US 2003-055179), a hydrophilic radical in the presence of a polyolefin (A2c1) having a group 13 element group such as a boron group or an aluminum group at its end and oxygen. There is a method of polymerizing a polymerizable unsaturated compound to obtain a block copolymer of polyolefin and polyacryl. Further, as described in JP-A No. 2004-131620 (US 2004-110903) and JP-A No. 2005-048172 (EP 1645576A1), a polyolefin having a halogen atom at its terminal (A2c2), a copper halide, a ruthenium halide, etc. And a block copolymer of a propylene polymer and a polyacryl by an atom transfer living radical method. Further, as described in JP-A-2001-098140 (US Pat. No. 6,451,901), a polyolefin is obtained by polymerizing a radical initiator and a hydrophilic radical-polymerizable unsaturated compound in the presence of a polyolefin having a mercapto group at the terminal. And polyacryl block copolymer.

The hydrophilic monomer is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethyl (meth) acrylate Examples thereof include aminoethyl quaternized products and vinyl pyrrolidone.
As the copolymerizable hydrophobic monomer, those mentioned in [2] can be used in the same manner.

  Reactive surfactants and reactive emulsifiers can also be used as the aqueous radical polymerizable unsaturated compound. For example, alkylpropenylphenol polyethylene oxide adducts and alkyldipropenylphenol polyethylene oxides disclosed in JP-A No. 04-053802 (US Pat. No. 5,332,854) and JP-A No. 04-050204 (US Pat. No. 5,324,862). Examples include adducts and sulfate salts thereof. Among them, alkyl propenyl phenol ethylene oxide 20 mol adduct, 30 mol adduct, 50 mol adduct (Daiichi Kogyo Seiyaku, Aqualon RN-20, RN-30, RN-50) and alkyl propenyl phenol polyethylene oxide 10 mol. Adduct sulfate ammonium salt and 20 mol adduct sulfate ammonium salt (Daiichi Kogyo Seiyaku, Aqualon HS-10, HS-20) are used.

Alternatively, a radically polymerizable unsaturated compound can be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to a polyolefin, and then the hydrophilic polymer (B) can be modified. For example, a method of hydrolyzing (meth) acrylic acid-t-butyl after polymerization to modify poly (meth) acrylic acid, a method of neutralizing this with a base, or saponifying vinyl acetate after polymerization. Examples include a method of modifying to polyvinyl alcohol. Examples of the copolymerizable hydrophobic radical polymerizable unsaturated compound include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, as the polyolefin (A), a polyolefin (A2) formed by bonding a reactive group can be used, but usually a polyolefin (A1) having no reactive group is used.
Alternatively, there is a method in which a hydrophilic polymer (B) is obtained by polymerizing a hydrophilic ring-opening polymerization monomer or the like using a polyolefin (A2) having a reactive group and using this reactive group as an initiation terminal.

Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone. Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

[3-2] Method for producing polymer (C) (R2)
In this method, the previously polymerized hydrophilic polymer (B) is bonded to the polyolefin (A). In this case, as the hydrophilic polymer (B), those mentioned in [2] can be used.
Specifically, for example, when a hydrophilic monomer is first polymerized to form a hydrophilic polymer, an unsaturated double bond is left in the molecule, and then the polyolefin (A) is converted into a polyolefin (A) using a radical polymerizable initiator. There is a method of graft polymerization. In this case, polyolefin (A2) having a reactive group may be used as polyolefin (A), but polyolefin (A1) having no reactive group is usually used.

Further, there is a method in which a hydrophilic polymer having a reactive group at the terminal is first polymerized, and then this is bonded to a polyolefin (A2) having a reactive group. The hydrophilic polymer having a reactive group at the terminal can be obtained by polymerizing a hydrophilic monomer using a compound having a reactive group as an initiator or a chain transfer agent. Alternatively, it can also be obtained by ring-opening polymerization of a hydrophilic ring-opening polymerization monomer such as an epoxy compound.
As the hydrophilic monomer that can be used at this time, various hydrophilic monomers listed in [3-1] can be used in the same manner.

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

[4] Structural unit derived from (meth) acrylic acid ester In the present invention, the structural unit derived from (meth) acrylic acid ester refers to a (meth) acrylic acid ester monomer or a group formed by reaction of the monomer. For example, units corresponding to (meth) acrylate monomers in (meth) acrylic polymers obtained by polymerization of (meth) acrylate monomers, (meth) acrylate monomers are other monomers and polymers It is a unit corresponding to the (meth) acrylic acid ester monomer in the compound obtained by reacting with.
The amount of the structural unit derived from (meth) acrylic acid ester in the present invention is preferably polyolefin (A): structural unit derived from (meth) acrylic acid ester = 90: 10 to 10:90 (weight ratio).

That is, when the total amount of the polyolefin (A) and the structural unit derived from the (meth) acrylic acid ester is 100 parts by weight, the polyolefin (A) is 10 parts by weight or more and 90 parts by weight or less. By setting the amount of the polyolefin (A) to 10 parts by weight or more, adhesion to the polyolefin-based substrate is improved. More preferably, it is 20 parts by weight or more, and further preferably 30 parts by weight or more. Further, when the amount of polyolefin (A) is 90 parts by weight or less, the effect of adding (meth) acrylic acid ester appears, and the physical properties of the coating film obtained from such an aqueous resin dispersion, specifically, coating The film strength, water resistance, weather resistance, abrasion resistance, solvent resistance and the like are improved. Preferably it is 80 weight part or less, More preferably, it is 70 weight part or less.
[4-1] (Meth) acrylic acid ester In the present invention, the (meth) acrylic acid ester that is the basis of the structural unit derived from the (meth) acrylic acid ester is not particularly limited. For example, an alkyl group, an aryl group, Examples include (meth) acrylic acid esters having an aralkyl group. These alkyl group, aryl group and aralkyl group may have a substituent containing a hetero atom. Examples of the hetero atom include oxygen, nitrogen, fluorine and the like.

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meta ) (Meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms such as lauryl acrylate and stearyl (meth) acrylate; 6 to 12 carbon atoms such as phenyl (meth) acrylate and benzyl (meth) acrylate (Meth) acrylic acid ester having an aryl group or an aralkyl group.

  Alternatively, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meta ) Carbon containing heteroatoms such as 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, adduct of (meth) acrylic acid and polyethylene oxide (Meth) acrylic acid ester having an alkyl group having 1 to 20 atoms; trifluoromethyl methyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid-2-perfluoro Having an alkyl group having 1 to 20 carbon atoms containing a fluorine atom such as ethylethyl ( Data) acrylic acid ester, and the like.

In addition to the above (meth) acrylic acid esters, a monomer having a double bond at the end of a molecule called a so-called macromonomer may be used in combination. These (meth) acrylic macromonomers usually have a weight average molecular weight in the range of about 200 to 50,000.
When (meth) acrylic macromonomers are used in combination, the amount used is usually in the range of 1 to 50 parts by weight per 100 parts by weight of the (meth) acrylic acid ester.
After reacting such a (meth) acrylic acid ester with the polyolefin (A) or the polymer (C), the resultant polymer is dispersed in water, whereby composite resin particles (E1) can be obtained. .
In addition, (meth) acrylic acid ester couple | bonded with polyolefin (A) or a polymer (C) may mutually superpose | polymerize, and the (meth) acryl chain may be formed. In this case, the molecular weight, structure, and the like of the (meth) acryl chain are the same as those of the (meth) acrylic polymer in [4-2].

[4-2] (Meth) acrylic polymer The (meth) acrylic polymer of the present invention is obtained by polymerizing the (meth) acrylic acid ester as described above. The polymer may be a homopolymer of a single (meth) acrylate monomer, or may be a copolymer of two or more types of (meth) acrylate monomers. Moreover, it is good also as a copolymer with monomers other than a (meth) acrylic acid ester monomer as needed. For example, a (meth) acrylic acid monomer etc. are mentioned.

  The (meth) acrylic polymer of the present invention preferably has a number average molecular weight of 1,000 or more and 1,000,000 or less. The lower limit of the molecular weight is more preferably 5,000, still more preferably 20,000. The upper limit of the molecular weight is more preferably 500,000, still more preferably 200,000. When the molecular weight is equal to or higher than the lower limit value, the adhesion to the base material tends to be improved.

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

The method for producing the (meth) acrylic polymer of the present invention may be any conventional polymerization method for (meth) acrylic acid ester monomers using a radical polymerization initiator, and is not particularly limited.
In the present invention, a monomer may be polymerized separately from the polymer (C) to obtain a (meth) acrylic polymer and then mixed with the polymer (C). The mixing method will be described in [4-3].
Or you may obtain the mixture of a polymer (C) and a (meth) acrylic-type polymer by superposing | polymerizing a monomer in coexistence of polymer (C), such as polyolefin (A).

[4-3] Mixing method of polymer (C) and (meth) acrylic polymer When the (meth) acrylic polymer is mixed with the polymer (C), prior to the production of the aqueous resin dispersion. Or, mix at the same time.
Although the mixing method of a polymer (C) and a (meth) acrylic-type polymer is not specifically limited, For example, both are dissolved and mixed in a solvent. The solvent used in this method may be any solvent that can dissolve both the polymer (C) and the (meth) acrylic polymer. For example, aromatic hydrocarbons such as toluene and xylene; hexane, octane Aliphatic hydrocarbons such as decane; cycloaliphatic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride and chlorobenzene; methyl acetate, ethyl acetate, propyl acetate, Esters such as butyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, Cyclohexanol, ethylene glycol, prop Alcohols such as pyrene glycol and butanediol; ethers such as dipropyl ether, dibutyl ether and tetrahydrofuran; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone Organic solvents having two or more functional groups such as alcohol; polar solvents such as dimethylformamide and dimethyl sulfoxide.

Alternatively, the polymer (C) and the (meth) acrylic polymer can be heated and melt mixed. Although the apparatus used for this is not specifically limited, For example, a reaction kettle with a stirring apparatus, a uniaxial or biaxial kneader, etc. can be used. The reaction kettle is preferably one that can be sealed and mixed under pressure. The stirring speed at that time varies slightly depending on the selection of the apparatus, but is usually in the range of 10 to 1,000 rpm.
The heating temperature is usually above the melting point or softening point of the resin to be mixed. Generally, it is 100 degreeC-300 degreeC, Preferably it is 120 degreeC-250 degreeC, More preferably, it is 150 degreeC-230 degreeC. If it is too low, the resin will not melt sufficiently, and if it is too high, thermal decomposition of the resin may occur.

[4-4] Polymerization of (meth) acrylic acid ester in the presence of polyolefin (A) or polymer (C) Polymerizing (meth) acrylic acid ester in the presence of polyolefin (A) or polymer (C) Thus, both a polymer (C) having a (meth) acrylic chain and a (meth) acrylic polymer can be obtained. When this is dispersed in water, both composite resin particles (E1) and (E2) can be obtained, which is preferable.
The object to be mixed may be any of a polyolefin (A1) having no reactive group, a polyolefin (A2) having a reactive group, and a polymer (C) having a hydrophilic polymer (B). (Meth) acrylic acid ester may be mixed and then polymerized.
As a preferred method, a mixture of polyolefin (A) and (meth) acrylic acid ester is reacted, then mixed with and reacted with hydrophilic polymer (B), and then dispersed in water.
In this method, a part of the (meth) acrylic acid ester is graft-polymerized to the polyolefin to form a (meth) acrylic chain, so compared with the case where the polymer (C) and the (meth) acrylic polymer are simply mixed. Composite resin particles having a higher degree of complexness can be obtained, and it is considered preferable that adhesion between the polyolefin base material and the dissimilar material is further enhanced.

[5] Method for Producing Aqueous Resin Dispersion The method for producing a resin dispersion according to the present invention is not particularly limited. For example, resin (polymer (C) or polymer (C) and (meth) acrylic polymer) Mixture), water, and a mixture of a solvent other than water, and then removing the solvent from the mixture to form an aqueous dispersion, adding water after melting the resin at or above the melting temperature And a dispersion method.
Among the production methods, a method of preparing an aqueous dispersion by preparing a mixture of resin, water, and a solvent other than water and then removing the solvent from the mixture is preferred.
According to the method of preparing an aqueous dispersion by preparing a mixture of a resin, water, and a solvent other than water and then removing the solvent from the mixture, an aqueous dispersion having a fine particle size can be easily produced. When preparing a mixture, you may heat as needed. The temperature is usually 30 to 150 ° C. The final ratio of the solvent other than water in the resin dispersion is usually 50% or less. It is preferably 20% or less, more preferably 10% or less, and particularly preferably 1% or less.

  Among them, the method of adding a solvent other than water to the resin and adding water after heating and dissolving it as necessary facilitates the formation of an aqueous dispersion having a finer particle diameter, and is more preferable. The temperature at the time of dissolution in a solvent or at the time of addition of water is usually 30 to 150 ° C. Moreover, when dissolving once in solvents other than water, after adding water, you may distill a solvent off. The ratio of the solvent other than water in the resin dispersion is as described above.

Examples of the solvent other than water used in the present method include the solvents mentioned in [4-3].
Among them, a solvent that dissolves 1% by weight or more in water is preferable, and more preferably 5% by weight or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol , Isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.

  The apparatus for producing the resin dispersion by adding water after the solvent is dissolved and in the molten state is not particularly limited. For example, a reaction kettle with a stirring device, a uniaxial or biaxial kneader, or the like 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 1,000 rpm.

  Moreover, the mixing process of [4-3] and the manufacturing process of an aqueous dispersion can also be performed simultaneously. That is, the polymer (C) and the (meth) acrylic polymer may be dissolved in a solvent by the method [4-3], and then water may be added as it is to remove the solvent to produce an aqueous dispersion. Alternatively, the polymer (C) and the (meth) acrylic polymer may be heated and melt-mixed by the method [4-3], and then water may be added as it is to produce an aqueous dispersion.

[6] Aqueous resin dispersion The polymer (C) of the present invention is very excellent in water dispersibility, and according to the method for producing a resin dispersion of the present invention, an aqueous resin dispersion having a fine dispersed particle size is obtained. Therefore, the aqueous resin dispersion of the present invention has an advantage that the dispersed particle diameter is fine and the resin is stably dispersed. Therefore, when this is used, a coated product having an excellent appearance can be obtained.
As described above, in the present invention, hydrophilic property is imparted to polyolefin by bonding hydrophilic polymer to polyolefin chain, and water dispersion becomes possible without substantially using a surfactant. In addition, according to this method, since the amount of carboxylic acid grafted can be reduced as compared with the production method in which a polyolefin is modified with a carboxylic acid without using a hydrophilic polymer, neutralized with a basic substance, and dispersed in water. There is an advantage that adhesion to the material and water resistance are excellent.

The dispersed particle diameter of the resin in the resin dispersion is referred to as 50% cumulative particle diameter (50% particle diameter, 50% average particle diameter, volume average particle diameter, or median diameter) from the smaller particle diameter in terms of volume. ) Is usually 10 μm or less, preferably 1 μm or less, with a 50% particle size. According to the present invention, the 50% particle size can be 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the 90% particle diameter is determined, the 90% particle diameter can be more preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is less likely to occur, and the dispersion can be more stably dispersed. 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.
In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved. Accordingly, there is no particular limitation on the lower limit value of the dispersed particle size.

  In the aqueous resin dispersion of the present invention, the amount of resin relative to the whole (total amount of structural units derived from the polymer (C) and (meth) acrylic acid ester) is preferably 5% by weight or more, more preferably 10% by weight or more. More preferably, it is 20% by weight or more. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The smaller the amount of resin, the lower the viscosity, the easier it can be applied to various application methods, the easier it is to form a uniform coating film, and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the amount of resin is large so that a large amount of energy and time are not required for drying water after coating.

[6-1] Resin particles (D)
When the polymer (C) is dispersed in water, an aqueous dispersion in which the resin particles (D) are dispersed is obtained by allowing a structural unit derived from a (meth) acrylic acid ester to coexist. At least a part of the resin particle (D) is a composite resin particle (E) containing a structural unit derived from (meth) acrylic acid ester. The resin particles (D) do not necessarily have to be composite resin particles (E). For example, some of the resin particles (D) may not contain a structural unit derived from (meth) acrylic acid ester. However, preferably, substantially all the resin particles (D) are composite resin particles (E).

The composite resin particles may be only (E1) or (E2), or (E1) and (E2) may be used in combination. Further, the structural unit derived from (meth) acrylic acid ester may be one kind, or two or more kinds may be used simultaneously.
The composite resin particles (E1) can be obtained, for example, by reacting the polymer (C) with a (meth) acrylic acid ester monomer and then dispersing the polymer (C) in water. The composite resin particle (E2) can be obtained, for example, by polymerizing a (meth) acrylic acid ester monomer to obtain a (meth) acrylic polymer, mixing with the polymer (C), and then dispersing in water. . It is also possible to obtain both (E1) and (E2) by polymerizing the (meth) acrylic acid ester monomer in the presence of the polymer (C).

[6-2] Surfactant The aqueous resin dispersion of the present invention has an advantage that a surfactant is not used and the dispersed particle size is very small. However, a surfactant may be included as necessary according to other purposes and applications.
As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. As the surfactant, those having an alkyl group, alkenyl group, alkylaryl group or alkenylaryl group having 4 or more carbon atoms as a hydrophobic group are usually used. Preferably it is C8 or more, More preferably, it is C12 or more. However, it usually has 30 or less carbon atoms.

Examples of the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, and sodium polyoxyethylene lauryl sulfate. Examples of the cationic surfactant include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and the like. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.
In addition, a so-called reactive surfactant having a radical polymerizable functional group can be used for the above-mentioned surfactant, and when a reactive surfactant is used, a film formed using this resin dispersion is used. Water resistance can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemul S-180 (manufactured by Kao Corporation).

The ratio of the surfactant to 100 parts by weight of the polymer (C) is usually 50 parts by weight or less, preferably 30 parts by weight or less.
However, it is one of the advantages of the present invention that it is not necessary to use a surfactant. Accordingly, it is preferable that the amount of the surfactant is small, and the surfactant content of the resin dispersion is 100 weights of the polymer (C). It is preferable that it is 10 weight part or less with respect to a part. More preferably, it is 5 parts weight or less, More preferably, it is 2 parts weight or less. It can also be substantially free of surfactant. “Substantially free of surfactant” means less than 1 part by weight per 100 parts by weight of the polymer (C). Most preferably, no surfactant is included.

By reducing the amount of the surfactant, there is an advantage that a bleed out that has been a problem in the past can be suppressed and a coated product having an excellent appearance can be obtained, and the present resin dispersion can be used as a coating on the outermost surface of the coating. Moreover, since the water resistance of the coating tends to decrease when a surfactant is contained, it is desirable that the amount of the surfactant is small in this respect as well.
However, since the nonionic surfactant is less likely to lower the water resistance compared to other surfactants, the nonionic surfactant may be included in a slightly larger amount. For example, when the surfactant other than the nonionic surfactant should be 5 parts by weight or less with respect to 100 parts by weight of the polymer (C), the nonionic surfactant may be 10 parts by weight or less.
Another advantage of the present invention is that the amount of surfactant can be reduced without using chlorinated polyolefin, and the environmental load can be reduced.

[6-3] Combined use of other resins The resin dispersion of the present invention can contain a water-soluble resin or a resin that can be dispersed in water as required, as long as the effects of the present invention are not significantly impaired. For example, it is effective in improving the appearance of coating (glossing or matting) and reducing tackiness. It may be a resin that can be dispersed using a surfactant. As the water-soluble resin, for example, the resins listed as the hydrophilic polymer (B) can be used. For example, an aqueous solution obtained by dissolving these resins in water is mixed with the resin dispersion of the present invention.
Examples of the resin that can be dispersed in water include acrylic resin, polyepoxy resin, polyester resin, polyurethane resin, melamine resin, and alkyd resin. For example, the resin particle which consists only of the (meth) acrylic-type polymer obtained by superposition | polymerization of the above-mentioned (meth) acrylic acid ester monomer may be contained.

In particular, acrylic resins, polyurethane resins, and polyester resins are preferred for reasons such as weather resistance, abrasion resistance, and economy. The method for obtaining the aqueous dispersion of the resin is not particularly limited, and a known method can be used. A method of emulsion polymerization in the presence of a surfactant, a method of mechanically forcibly emulsifying a resin obtained in advance using a surfactant, and neutralizing hydrophilic groups such as carboxylic acid groups contained in the resin Then, there is a method of dispersing in an aqueous medium.
These resins can usually be used in an amount of 10 to 1,000 parts by weight per 100 parts by weight of the polymer (C). Preferably it is 20 weight part or more, More preferably, it is 50 weight part or more. Moreover, it is preferably 500 parts by weight or less, more preferably 300 parts by weight or less.

[6-4] Pigment A pigment can be added to the resin dispersion of the present invention. An aqueous resin dispersion containing a pigment is suitable as a paint.
The pigment that can be used is not particularly limited. For example, inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, and perinone pigments. , Perylene pigments, quinacridone pigments, isoindolinone pigments, indigo pigments, organic pigments such as phthalocyanine pigments, etc .; extenders such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate ; Conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; non-colored or colored metallic luster such as aluminum, copper, zinc, nickel, tin, aluminum oxide, or other metals or alloys 1 type, or 2 or more types may be used in combination.

  The amount of the pigment added to the resin dispersion is preferably 10 parts by weight or more with respect to 100 parts by weight of the resin (the total amount of the polymer (C) and other resins). More preferably, it is 20 parts by weight or more. However, it is preferably 200 parts by weight or less, more preferably 100 parts by weight or less. As the addition amount is larger than the lower limit value, the color developability and the hiding property tend to be higher, and as the addition amount is smaller than the upper limit value, the adhesion, moisture resistance and oil resistance tend to be higher.

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

[6-5] Other additives An acidic substance or a basic substance can be added to the resin dispersion of the present invention as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Basic substances such as inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine Organic bases such as diethylamine, triethylamine, tripropylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. .

It is preferable to add a basic substance when the resin has an acidic group, and an acidic substance when the resin has a basic group. There is an advantage that the hydrophilicity of the resin can be increased and the dispersed particle size can be made finer.
The resin dispersion of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; colorants such as titanium oxide and organic pigments; conductivity imparting agents such as pigments, carbon black and ferrite, dyes, pigment dispersions Various additives such as additives, leveling agents, antifoaming agents, thickeners, preservatives, fungicides, rust inhibitors and wetting agents may be used in combination.
Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.

  To further improve the performance of various coatings such as water resistance and solvent resistance. The crosslinking agent can be added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin in the dispersion. As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, and the like can be used. Of these, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

When the resin dispersion of the present invention is used for applications such as primers, paints, and inks, a hydrophilic organic solvent other than water can be blended for the purpose of increasing the drying speed or obtaining a good surface finish. . Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, and ethers thereof, N-methylpyrrolidone, and the like. Preferred are isopropanol, ethanol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and N-methylpyrrolidone. These contents are usually 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total amount of water and the organic solvent.
[6-6] Use of aqueous resin dispersion The resin dispersion of the present invention can be used for primers, primer-less paints, adhesives, inks, and the like. The present invention is particularly useful as a primer, a paint, or an adhesive. It is particularly suitable for bonding between a polyolefin substrate and a different material. For example, it can be used for automobile paints for automobile interiors and exteriors, primers, paints for home appliances such as mobile phones and personal computers, paints for building materials, heat sealants and the like.

[7] Laminate A resin layer can be formed by applying the aqueous resin dispersion of the present invention or a paint containing the same to a substrate and heating it to form a laminate. This resin layer is a layer containing a polymer (C) formed by bonding a hydrophilic polymer (B) to a polyolefin (A) and resin particles containing a structural unit derived from a (meth) acrylic acid ester in the same particle. is there.
This resin layer contains little or no surfactant, and has excellent adhesion to both the polyolefin substrate and the different types of substrates, so this laminate is excellent in adhesion between layers and has an appearance. Good, excellent in water resistance and oil resistance.

This laminate can be used in various applications such as for automobiles, home appliances, and building materials. The substrate may be in any shape, such as a film, sheet, or plate.
The hardness of the resin layer can be soft or hard by selecting the types and amounts of (A) and (B) according to the application. For example, a hard performance is required for an automobile exterior paint, so it is hard, and a soft performance is required for an automobile interior, so a soft selection is made. The hardness can be evaluated by tensile elasticity or bending elasticity.
The resin dispersion of the present invention can be applied to a crystalline olefin polymer molding (base material) to form a coating film. Examples of the olefin polymer as a base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene, and other olefin polymers, ethylene / propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, propylene-based polymers are preferably used. Also, molded articles made of polypropylene and synthetic rubber, molded articles made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded articles such as bumpers for automobiles, and for steel plates and electrodeposition treatment It can also be used for surface treatment of steel plates and the like.

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

[7-1] Method for Producing Laminate A method for forming a resin layer on a substrate is not particularly limited, and any known method can be used. For example, a resin dispersion or a paint is applied by spraying. Examples thereof include a method, a method of applying with a roller, and a method of applying with a brush.

  After applying the resin dispersion or paint, it is usually heated with nichrome wire, infrared rays, high frequency or the like to cure the coating film, thereby obtaining a laminate having a desired coating film on the surface. The curing conditions for the coating film are appropriately selected depending on the material and shape of the substrate, the composition of the paint used, and the like. Although there is no restriction | limiting in particular in hardening temperature, Considering practicality, it is 50 degreeC or more normally, Preferably it is 60 degreeC or more. However, it is usually 150 ° C. or lower, preferably 120 ° C. or lower.

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

[7-2] Thermoplastic resin molding (F)
The base material of the laminate of the present invention is preferably a thermoplastic resin molded body. Although it does not specifically limit as a thermoplastic resin molded object (F), For example, it is a molded object which consists of polyolefin resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin etc. In particular, the present invention is preferably applied to a thermoplastic resin molded body (F) made of a polyolefin resin (hereinafter referred to as a polyolefin molded body).

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

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

  The polyolefin preferably has a melt flow rate (MFR) of 2 g / 10 min or more, more preferably 10 g / 10 min or more, and particularly preferably 25 g / 10 min. However, it is preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less. If the MFR is higher than the lower limit, the flowability of the polyolefin tends to increase. Conversely, if the MFR is lower than the upper limit value, the mechanical properties tend to increase. The MFR of the polyolefin may be adjusted at the time of polymerization, or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after the polymerization.

  More preferred as the polyolefin is crystalline polypropylene. Crystalline polypropylene is a propylene homopolymer and / or a propylene-ethylene copolymer. Here, the propylene-ethylene copolymer is a propylene-ethylene random copolymer and / or a propylene-ethylene block copolymer, preferably a propylene-ethylene block copolymer.

Here, the propylene-ethylene block copolymer consists of a crystalline polypropylene part (a unit part) and an ethylene-propylene random copolymer part (b unit part).
The a unit is usually obtained by homopolymerization of propylene, and in some cases, by copolymerizing a small amount of other α-olefin with propylene.
The MFR 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 weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. However, it is preferably 85% by weight or less, more preferably 80% by weight or less, and still more preferably 75% by weight or less. When the propylene content is within this range, the dispersibility and glass transition temperature are within an appropriate range, and the impact characteristics tend to be good. The propylene content can be adjusted by controlling the concentration ratio of propylene and ethylene during the polymerization of the propylene-ethylene random copolymer portion.
The molecular weight of the propylene-ethylene random copolymer part of the b unit part is not particularly limited, but in consideration of dispersibility and impact resistance, the weight average molecular weight (Mw) is preferably 200,000 to 3,000,000, more preferably Is 300,000-2,500,000, more preferably 400,000-2 million.

  The amount of the a unit part and the b unit part is not particularly limited, but in general, the a unit part is preferably 95% by weight or less, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight of the total amount. , B unit part is preferably adjusted to 5% by weight or more of the total amount, more preferably 5 to 50% by weight, still more preferably 10 to 40% by weight. The impact resistance characteristics tend to increase as the amount of b unit part is equal to or greater than the lower limit, and the rigidity, strength, and heat resistance tend to increase as the amount is less than the upper limit.

In the present invention, the amount of b unit part is measured using a temperature rising elution fractionation method. That is, the a unit part does not elute at 100 ° C. or lower in the extraction with orthodichlorobenzene, but the b unit part elutes easily. Therefore, the composition of the propylene / ethylene block copolymer after production is determined by extraction analysis using the orthodichlorobenzene.
Since the ratio of the amount of the a unit part and 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 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.
In order to use the propylene homopolymer and the propylene-ethylene block copolymer of the present invention as a structural material, it is preferable that they have excellent mechanical properties and high rigidity and impact resistance. That is, the flexural modulus is preferably 300 MPa or more, more preferably 500 to 3000 MPa, and still more preferably 1000 to 2000 MPa. By being in this range, it will be excellent in rigidity and suitable as a structural material. The IZOD impact strength is preferably 1 kJ / m ² or more, more preferably ^{2 to} 100 kJ / m ² , still more preferably 5 to 80 kJ / m ² , and particularly preferably 8 to 60 kJ / m ² . By making it within this range, it 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.

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

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

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

<Elastomer component>
When the thermoplastic resin molded body (F) used in the present invention 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-nonconjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene-α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Polymer rubber; ethylene-α-olefin-nonconjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM); hydrogenated product of styrene-butadiene-styrene triblock (SEBS), styrene -Styrene-containing thermoplastic elastomer such as hydrogenated product (SEPS) of isoprene-styrene triblock body can be exemplified.

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

<Other ingredients>
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, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, and other resins such as polyethylene resins.

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

When kneading and granulating, the above components may be kneaded at the same time, or a method of kneading the components separately may be employed in order to improve performance.
Next, the thermoplastic resin composition is molded to obtain a thermoplastic resin molded body (F), and various known methods can be used as the molding method.
For example, 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, etc. 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.

[7-3] Use of Laminate The laminate of the present invention has excellent physical properties balance in terms of coating film adhesion and rigidity and impact resistance. Moreover, when the resin layer which comprises a laminated body does not contain surfactant substantially, since a bleed-out does not arise, it is excellent also in an external appearance. Moreover, since it is not necessary to contain halogens, such as chlorine, an environmental load can be reduced.
Therefore, the laminate of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, has performance sufficient for practical use as parts / materials that are thinned, highly functional, and large. . Similarly, it can be used as a living material such as a film or a sheet.

  For example, automobile 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, and as various living materials such as a packaging material, an agricultural film, a gas barrier film, and synthetic paper.

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. Unless otherwise stated,% represents% by weight.
<Physical property measurement method and evaluation method>
(1) Weight average molecular weight [Mw] and molecular weight distribution [Mw / Mn]
(1) -1 Method for measuring molecular weight in terms of polypropylene First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by weight of BHT was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a PTFE (polytetrafluoroethylene) filter having a pore diameter of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed by using TSKgel GM H-HT (30 cm × 4) as a column and Waters GPC150CV equipped with an RI detector. As measurement conditions, a sample solution injection amount: 500 μl, a column temperature: 135 ° C., a solvent: orthodichlorobenzene, and a flow rate: 1.0 ml / min were employed.

In calculating the molecular weight, a commercially available monodispersed polystyrene is used as a standard sample, a calibration curve relating to the retention time and the molecular weight is created from the viscosity formula of the polystyrene standard sample and polypropylene, and the propylene-α-olefin copolymer The molecular weight was calculated.
[Η] = K · M ^α is used as the viscosity formula, K = 1.38E-4 and α = 0.70 for polystyrene, and K for propylene-α-olefin copolymer. = 1.03E-4, α = 0.78 was used.
Moreover, molecular weight distribution Mw / Mn was computed from the value of the obtained weight average molecular weight Mw and the number average molecular weight Mn.

(1) -2 Method for measuring molecular weight in terms of polystyrene First, 5 mg of a sample is collected in a 10 ml vial, 5 g of tetrahydrofuran containing 250 ppm of BHT is added as a stabilizer, and completely dissolved at 50 ° C. After cooling to room temperature, the mixture was filtered through a filter having a pore diameter of 0.45 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed using Tosoh Corp. GPC HLC-8020 equipped with a guard column TSK guard column H _XL- H to TSK gel GMH _XL- L (30 cm × 2) as a column. As measurement conditions, an injection amount of the sample solution: 50 μl, a column temperature: 40 ° C., a solvent: tetrahydrofuran, and a flow rate of 1.0 ml / min were employed.
When calculating the 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.

(2) 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 to completely dissolve. Chloroform was placed in a liquid cell having a material NaCl and an optical path length of 0.5 mm as a background. Next, the dissolved polymer solution was put into a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation at a total number of 32 times. The graft ratio of maleic anhydride was calculated using a calibration curve prepared by measuring a solution of maleic anhydride in chloroform. Then, from the area of the absorption peak of the carbonyl group (maximum peak in the vicinity of 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer is calculated based on a separately prepared calibration curve, and this is calculated as the graft ratio ( % By weight).

(3) Dispersion particle diameter It measured using Nikkiso Co., Ltd. Microtrac UPA (model 9340 batch type dynamic light scattering method / laser Doppler method). The density of the dispersion was 0.87 kg / m ³ , the shape was spherical, the dispersion medium was water and the measurement time was 180 seconds, and the 50% particle size and 90% particle size were determined.

(Primer suitability evaluation)
(4) Adhesion (polypropylene)
A substrate (test piece) was produced by injection-molding 70 mm × 150 mm × 3 mm of automotive exterior grade polypropylene, and the substrate surface was wiped with isopropyl alcohol. Here, the aqueous resin dispersion was applied by spraying so that the coating amount (dry weight after coating) was about 5 to 10 g / m ² . Next, the test piece after this application was dried at 80 ° C. for 5 minutes in a safe ben dryer. Next, an acrylic polyol urethane paint as a base coat from the top of the coating film; Retan PG80III (manufactured by Kansai Paint Co., Ltd.), a predetermined curing agent, a viscosity adjustment with a dedicated thinner, and a dry coating amount of 25 to 30 g / m ² was applied by spraying and baked at 90 ° C. for 30 minutes to obtain a coated plate.
After leaving at 23 ° C. for 24 hours, apply a grid according to the method of grid pattern test described in JIS K 5400, and paste cellophane tape (Nichiban Co., Ltd.), then peel in 90 degrees direction. The number of grids that were not peeled out of the 25 grids was evaluated.
◎: No peeling ○: Remaining number 90% or more △: Remaining number 50% or more and less than 90% ×: Remaining number 50% or less

(5) Gasohol resistance Dip a coated plate prepared in the same way as in the adhesion test into a mixed solution of regular gasoline and ethanol (weight ratio: regular gasoline / ethanol = 9/1) kept at 20 ° C. Then, the time until peeling occurred in the coating film was measured and evaluated as follows.
○: 30 minutes or more Δ: 15 minutes or more and less than 30 minutes ×: less than 15 minutes

(Evaluation of coating material suitability)
(6) Adhesion (polymethyl methacrylate and polypropylene)
A substrate (test piece) obtained by molding polymethyl methacrylate into 70 mm × 150 mm × 1 mm was prepared, and the substrate surface was wiped with isopropyl alcohol. Here, 5 g of isopropyl alcohol is added and diluted with respect to 10 g of the aqueous resin dispersion whose solid content is adjusted to 25% so that the coating amount (dry weight after coating) becomes about 3 g / m ^2. It was coated with a bar coater (No. 16) and dried in a safe ben dryer at 80 ° C. for 3 minutes. After leaving at 23 ° C. for 24 hours, a test piece with a grid pattern was prepared in accordance with the grid pattern test method described in JIS K 5400, and cellophane tape (Nichiban Co., Ltd.) was applied, It peeled in the direction of 90 degree | times and evaluated by the grid number which was not peeled among 25 grids.
Similarly, the adhesion to the automobile exterior grade polypropylene substrate used in (4) was also evaluated.
◎: No peeling ○: Remaining number 90% or more △: Remaining number 50% or more and less than 90% ×: Remaining number 50% or less

(7) Tackiness A coated plate prepared by applying an aqueous resin dispersion in the same manner as in the adhesion test is left at 40 ° C for 1 day, cooled to 23 ° C, and then the surface of the coating film is touched with a finger. Judgment was made as follows.
○: Even if touched with a finger, there is no tack ×: Touched with a finger causes a tack

(8) Bleed-out A coated plate prepared by applying an aqueous resin dispersion in the same manner as in the adhesion test is left at 40 ° C. for 1 day, cooled to 23 ° C., and then visually bleeded onto the coating surface. The outer appearance was observed and judged as follows.
○: No bleed out △: Slightly bleed out ×: Quite bleed out

[Production Example 1: Production of maleic anhydride-modified propylene-butene copolymer]
Propylene-butene copolymer polymerized using a metallocene catalyst (Tafmer XM7070 manufactured by Mitsui Chemicals; propylene content 74 mol%, melting point 80 ° C., weight average molecular weight (Mw) 240,000 (polypropylene equivalent), molecular weight distribution (Mw / Mn) 2.2) 200 kg of maleic anhydride and 5 kg of maleic anhydride were dry blended with a super mixer, and then 1 weight with respect to 100 parts by weight of propylene-butene copolymer using a twin screw extruder (TEX54αII manufactured by Nippon Steel Works). Kneaded under the conditions of a cylinder temperature of the kneading section of 200 ° C., a screw rotation speed of 125 rpm, and a discharge rate of 80 kg / hour while feeding perbutyl I in the middle with a liquid pump so as to obtain a pellet-like product. .
The maleic anhydride group content (graft ratio) of the maleic anhydride-modified propylene-butene copolymer thus obtained was 0.8% by weight (0.08 mmol / g as maleic anhydride group, as carboxylic acid group). 0.16 mmol / g). The weight average molecular weight was 156,000, and the number average molecular weight was 84,000 (both in terms of polystyrene).

[Example 1]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 70 g of the maleic acid-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 0 ° C. to dissolve the propylene-butene copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride, 30 g of ethyl methacrylate (EMA) and 1.0 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, a byproduct derived from maleic anhydride was removed.
Subsequently, 14 g (14 mmol; 20 weights per 100 parts by weight of polyolefin) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1,000 (nominal value)) A solution in which 280 g of isopropanol (IPA) was dissolved was added dropwise and reacted at 70 ° C. for 1 hour. Further, 1.4 g (15.6 mmol) of 2-amino-2-methyl-1-propanol (AMP) was added. Thereafter, 280 g of water was added dropwise with stirring while maintaining the temperature at 70 ° C., and toluene and IPA were removed under reduced pressure to obtain a milky white aqueous resin dispersion having a resin solid concentration of 28% by weight.
As a result of measuring the dispersed particle size, the 50% particle size was 0.165 μm, and the 90% particle size was 0.250 μm. The evaluation results of the obtained aqueous resin dispersion are shown in Table-1.

A part of the reaction solution before reacting with Jeffamine M-1000 was taken out, and acetone was added to separate the precipitated polymer. The obtained polymer was washed and then dried under reduced pressure to obtain a white powdery polymer. As a result of measuring the infrared absorption spectrum of this polymer, the content (graft ratio) of maleic anhydride groups was 1.6% by weight (0.16 mmol / g as maleic anhydride groups and 0.32 mmol / g as carboxylic acid groups). )Met.
Further, methoxypoly (oxyethylene / oxypropylene) -2-propylamine (Jefamine M-1000) has an insoluble content of 1% by weight or less when dissolved in water at 25 ° C. at a concentration of 10% by weight, and is hydrophilic. Functional polymer.

[Example 2]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 50 g of the maleic acid-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 0 ° C. to dissolve the propylene-butene copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride, 50 g of methyl methacrylate (MMA) and 1.0 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the by-product derived from maleic anhydride was removed, and then a solution prepared by dissolving 20 g of Jeffamine M-1000 (20 mmol, corresponding to 40 parts by weight with respect to 100 parts by weight of polyolefin) in 280 g of IPA was added dropwise. For 1 hour. Further, 1.4 g (15.6 mmol) of AMP was added. Thereafter, 280 g of water was added dropwise with stirring while maintaining the temperature at 70 ° C., and toluene and IPA were removed under reduced pressure to obtain a milky white aqueous resin dispersion having a resin solid content concentration of 26% by weight.
As a result of measuring the dispersed particle size, the 50% particle size was 0.186 μm, and the 90% particle size was 0.269 μm. The evaluation results of the obtained aqueous resin dispersion are shown in Table-1.

[Comparative Example 1]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 g of the maleic acid-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 0 ° C. to dissolve the propylene-butene copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride and 0.5 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the by-product derived from maleic anhydride was removed, and then a solution prepared by dissolving 20 g of Jeffamine M-1000 (20 mmol, corresponding to 20 parts by weight with respect to 100 parts by weight of polyolefin) in 280 g of IPA was added dropwise. For 1 hour. Further, 1.4 g (15.6 mmol) of AMP was added. Thereafter, while maintaining the temperature at 70 ° C., 280 g of water was added dropwise with stirring, and toluene and IPA were removed under reduced pressure to obtain a light yellow translucent aqueous resin dispersion having a resin solid content concentration of 30% by weight. .
As a result of measuring the dispersed particle size, the 50% particle size was 0.026 μm, and the 90% particle size was 0.042 μm. The evaluation results of the obtained aqueous resin dispersion are shown in Table-1.

[Comparative Example 2]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 70 g of the maleic acid-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 0 ° C. to dissolve the propylene-butene copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride, 30 g of EMA, and 1.0 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, after cooling to 60 ° C., 25 g of polyoxyethylene cetyl ether; nonionic surfactant (Emulgen 220, HLB = 14.2, manufactured by Kao Corporation), polyoxyethylene lauryl ether; nonionic surfactant 25 g of an agent (Emalgen 147 manufactured by Kao Corporation, HLB = 16.3) was added and dissolved. After adding 20 g of distilled water, the mixture was emulsified with a homomixer at 12000 rpm for 5 minutes. Subsequently, an aqueous solution in which 1.5 g of AMP was diluted with 400 g of water was added to the system, and the pH was adjusted to 8. The crude emulsion was gradually reduced in pressure at 50 ° C. to distill off toluene and water to obtain a milky white aqueous resin dispersion having a concentration of 25% by weight.
As a result of measuring the dispersed particle size, the 50% particle size was 0.254 μm, and the 90% particle size was 0.515 μm. The evaluation results of the obtained aqueous resin dispersion are shown in Table-1.

[Comparative Example 3]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 70 g of the maleic acid-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 0 ° C. to dissolve the propylene-butene copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride, 30 g of EMA, and 1.0 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, a by-product derived from maleic anhydride was removed, and a solution obtained by dissolving 2.8 g (31.2 mmol) of AMP in 280 g of IPA was added dropwise and stirred at 70 ° C. Thereafter, while maintaining the temperature at 70 ° C., 280 g of water was added dropwise with stirring, but the polymer became a gel-like lump on the way, and an aqueous resin dispersion could not be obtained.

According to the present invention, it is possible to obtain a stably dispersible aqueous resin dispersion without substantially using a surfactant, and the coating film has adhesion to not only a polyolefin substrate but also other substrates. In addition, water resistance and gasohol resistance are good. Therefore, the aqueous resin dispersion of the present invention is useful as a paint, a primer, and an adhesive.

Claims (15)

  A resin dispersion in which resin particles (D) containing a polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) are dispersed in water, wherein the resin particles (D) At least one part contains the structural unit derived from a (meth) acrylic acid ester, The aqueous resin dispersion characterized by the above-mentioned.   The aqueous resin dispersion according to claim 1, wherein at least a part of the polymer (C) has a structural unit derived from the (meth) acrylic acid ester.   The aqueous resin dispersion according to claim 1 or 2, wherein at least a part of the structural unit derived from the (meth) acrylic acid ester forms a (meth) acrylic polymer.   The polyolefin (A) has at least one reactive group selected from the group consisting of an unsaturated carboxylic acid group, an unsaturated dicarboxylic acid anhydride group, and an unsaturated carboxylic acid anhydride monoester group. 4. The aqueous resin dispersion according to any one of items 1 to 3. The aqueous resin dispersion according to any one of claims 1 to 4, wherein the polyolefin (A) satisfies the following.
(1) Molecular weight distribution Mw / Mn is 3.5 or less.
(2) Melting | fusing point Tm is 50 degreeC or more and 120 degrees C or less.   The aqueous resin dispersion according to any one of claims 1 to 5, wherein the polyolefin (A) is a propylene polymer.   The aqueous resin dispersion according to any one of claims 1 to 6, wherein a weight ratio of the polyolefin (A) to the structural unit derived from the (meth) acrylic acid ester is 90:10 to 10:90.   The polymer (C) is obtained by bonding the hydrophilic polymer (B) to the polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio). 8. The aqueous resin dispersion according to any one of items 1 to 7.   The aqueous resin dispersion according to any one of claims 1 to 8, wherein the polymer (C) is a graft copolymer obtained by grafting a hydrophilic polymer (B) to a polyolefin (A).   The aqueous resin dispersion according to any one of claims 1 to 9, wherein the resin particles (D) are dispersed in water with a 50% particle diameter of 0.5 µm or less.   A paint comprising the aqueous resin dispersion according to any one of claims 1 to 10.   An adhesive comprising the aqueous resin dispersion according to any one of claims 1 to 10. A method for producing the aqueous resin dispersion according to any one of claims 1 to 10,
An aqueous resin dispersion characterized by reacting a mixture of the polyolefin (A) and (meth) acrylic acid ester, then mixing and reacting with the hydrophilic polymer (B), and then dispersing the mixture in water. Body manufacturing method.   Resin particles comprising a polymer (C) obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) and a structural unit derived from a (meth) acrylate ester on a thermoplastic resin molded body (F) (D A laminate having a resin layer containing). Applying the aqueous resin dispersion according to any one of claims 1 to 10 or the paint according to claim 11 to the thermoplastic resin molded body (F) and heating to form a resin layer. A method for producing a laminate, which is characterized.