JP2011046777A - Aqueous dispersion of polyolefin-based conjugated resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a dispersion-stable polyolefin-based conjugated resin without using a large amount of a surfactant. <P>SOLUTION: The aqueous dispersion of a polyolefin-based conjugated resin in which conjugated resin particles having a core/shell structure are dispersed in water is characterized in that the shells (outside) of the conjugated resin particles contain a polyolefin-based resin (A) as a main component; the cores (inside) of the particles contain a polymer (B1) prepared by polymerizing a radically polymerizable monomer (B) except the olefin as a main component; and the core:shell weight ratio of the conjugated resin particles is 95:5 to 5:95. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composite resin aqueous dispersion containing a polymer obtained from a radically polymerizable monomer typified by a polyolefin-based resin and (meth) acrylic acid ester, 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 have a low polarity because they do not have a polar group in the molecule, and are often difficult to paint or bond, and improvements have been desired.

  In this regard, various techniques have been tried, such as chemically treating the surface of a polyolefin molded body with a chemical agent, etc., and oxidizing the surface of the molded body by techniques such as corona discharge treatment, plasma treatment, and flame treatment. Yes. However, these methods require not only a special apparatus but also an effect of improving paintability and adhesiveness.

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

  Examples of the aqueous dispersion of the modified polyolefin include a resin dispersion in which acid-modified chlorinated polypropylene is dispersed in water using a surfactant and a basic substance (Patent Document 1), and an acid-modified polyolefin is surface-active. A resin dispersion (Patent Document 2) dispersed in water using an agent and a basic substance is known.

  When a polyolefin resin is used as an adhesive or paint, the physical properties of the polyolefin alone are insufficient, and there are many examples in which other resins such as an acrylic resin are used in combination. Examples of this include a method of blending an acrylic resin with a polyolefin resin (Patent Document 3), a method of modifying a polyolefin with a (meth) acrylic acid ester to make an aqueous resin (Patent Documents 4, 5, and 8), a chlorinated polyolefin, Alternatively, a method of obtaining an aqueous resin composition by emulsion polymerization of a radical polymerizable monomer in the presence of an aqueous polyolefin resin composition (Patent Documents 6 and 7) is known.

JP-A-10-231402 Japanese Patent Application Laid-Open No. 06-256592 JP 2004-115712 A JP 2005-126482 A JP 2006-036920 A JP 2002-308921 A JP 2004-091559 A JP 2008-138090 A

  However, in the methods described in Patent Documents 1 and 2, it is necessary to add a large amount of a surfactant in order to make the dispersed particle diameter fine. As a result, the paint using such an aqueous dispersion has a problem of poor water resistance and chemical resistance. Furthermore, the surfactant may bleed out to the painted surface after coating, resulting in poor appearance, and further improvements have been desired.

  Further, the methods described in Patent Documents 3 to 8 have a problem that a large amount of a surfactant is contained in the polyolefin aqueous resin composition, and are not sufficient.

  Then, an object of this invention is to obtain the polyolefin-type composite resin aqueous dispersion from which a stable dispersion state is obtained, without using a large amount of surfactant.

  As a result of intensive studies to achieve the above object, the present inventor has obtained an aqueous polyolefin-based composite resin dispersion in which composite resin particles having a core / shell structure are dispersed in water, and the shell ( The outer side contains a polyolefin resin (A) as a main component, and the core (inner side) contains a polymer (B1) obtained by polymerizing a radical polymerizable monomer (B) other than olefin as a main component, And the said objective can be achieved by using the polyolefin-type composite resin aqueous dispersion characterized by the weight ratio of core: shell in this composite resin particle being 95: 5-5: 95. I found it.

  Furthermore, a polyolefin-based composite resin aqueous dispersion in which composite resin particles containing a polymer obtained by polymerizing a polyolefin-based resin (A) and a radical polymerizable monomer (B) other than olefin are dispersed in water. Then, a self-emulsifiable olefin polymer (E) is used as the polyolefin resin (A), and in the aqueous dispersion of this self-emulsifiable olefin polymer (E), a radical polymerizable monomer other than olefin is used. An aqueous polyolefin-based composite resin dispersion in which the composite resin particles obtained by emulsion polymerization of (B) are dispersed in water can be used.

  Further, as the polyolefin resin (A), the hydrophilic polymer (C) is bonded to the olefin polymer (A1) at a ratio of (A1) :( C) = 100: 1 to 100: 300 (weight ratio). The olefin polymer-hydrophilic polymer copolymer (D) is used, or the olefin polymer (A1) is hydrophilic polymer (C) as the self-emulsifying olefin polymer (E). (A1) :( C) = 100: 1 to 100: 300 (weight ratio) can be used, and an olefin polymer-hydrophilic polymer copolymer (D) can be used.

  Furthermore, a monomer containing a (meth) acrylic acid ester can be used as the radical polymerizable monomer (B).

  The olefin polymer (A1) constituting the polyolefin resin (A) has a propylene content of 50 mol% or more, a molecular weight distribution [Mw / Mn] of 4.0 or less, and a melting point [Tm] of 125. A propylene-based polymer having all the characteristics of ° C. or lower can be used.

  Furthermore, as the olefin polymer-hydrophilic polymer copolymer (D), a graft copolymer obtained by grafting a hydrophilic polymer (C) to the olefin polymer (A1) can be used.

  Furthermore, a polyether resin can be used as the hydrophilic polymer (C).

  Further, the composite resin particles having a dispersed particle diameter of 0.5 μm or less can be dispersed in water.

  Furthermore, the aqueous polyolefin-based composite resin dispersion obtained can be used as a paint, primer, ink, and adhesive.

  In addition, as a method for producing an aqueous dispersion of a polyolefin-based composite resin, a radically polymerizable monomer (B) other than olefin is mixed and dispersed in a solvent to obtain a mixed liquid, and then the mixed liquid is converted into a polyolefin-based resin (A). To an aqueous dispersion of a polyolefin resin (A) composed of a self-emulsifiable olefin polymer (E) so that the weight ratio of the monomer to the radical polymerizable monomer (B) is 95: 5 to 5:95. A method characterized by adding and then emulsion-polymerizing the radically polymerizable monomer (B) can be employed.

  Furthermore, the laminated body which formed the resin layer formed using the polyolefin-type composite resin aqueous dispersion on the thermoplastic resin molding (F) can be obtained.

  Since the composite resin particles having a core / shell structure according to the present invention are excellent in water dispersibility, the dispersed particle diameter is small with little or no addition of a surfactant. An aqueous resin dispersion excellent in stability is obtained. Therefore, the aqueous polyolefin-based composite resin dispersion according to the present invention has an advantage that bleeding out due to the surfactant which has been a problem can be suppressed, and as a result, a molded article having an excellent coating appearance can be obtained.

  Moreover, the coating film obtained by applying this dispersion is excellent in water resistance, moisture resistance, oil resistance, and chemical resistance. For this reason, it is suitable also for the coating method like a lacquer type paint which finishes by only one coating.

  Furthermore, the resulting coating film exhibits good adhesion to polyolefin materials or resin materials containing polyolefin, etc., especially on difficult-to-adhere substrates such as untreated polypropylene, which are usually difficult to paint or bond. Can also be formed.

  Furthermore, since it is a resin aqueous dispersion containing a radically polymerizable monomer such as (meth) acrylic acid ester different from polyolefin as a structural unit, it improves physical properties, specifically, the strength of the coating film, water resistance In addition, weather resistance, abrasion resistance, solvent resistance, adhesion with different materials different from polyolefin, compatibility and the like can be improved.

  Therefore, the aqueous polyolefin-based composite resin dispersion of the present invention is extremely useful as a surface treatment agent, primer, paint, ink, adhesive, compatibilizer, etc. for crystalline olefin polymers. In the present invention, it is only necessary to have at least one of the above-described effects even if not all the effects are manifested.

The transmission electron micrograph about the ultra-thin section obtained in Example 6-2 is shown.

  Hereinafter, embodiments of the aqueous polyolefin-based composite resin dispersion according to the present invention will be described in detail. However, the following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these. It is not limited to the contents.

  The polyolefin-based composite resin aqueous dispersion of the present invention (hereinafter also referred to as “composite resin dispersion”) is a polyolefin-based resin (A) (hereinafter also referred to as “resin (A)”). And composite resin particles containing a polymer (B1) obtained by polymerizing a radical polymerizable monomer (B) other than olefin (hereinafter sometimes referred to as “polymer (B1)”) are dispersed in water. Being done.

[Composite resin particles]
The composite resin particles are a polymerization of a resin (A) and a radical polymerizable monomer (B) other than an olefin (hereinafter sometimes simply referred to as “radical polymerizable monomer (B)”). It is the particle | grains with which the polymer (B1) formed by this was compounded. The composite resin particles preferably have a two-layer structure (core / shell structure) in which a shell as a skin layer is formed on the outer side of the inner core. At this time, the resin (A) is included as a main component as a shell, while the polymer (B1) is included as a main component as a core. The “main component” refers to a component containing 50% by weight or more, preferably 70% by weight or more.

  The weight ratio of the polymer (B1) to the resin (A) in the composite resin particles is (B1) :( A) (in the case of having a core / shell two-layer structure, core: shell), and 95: 5: 5: 95, preferably 90: 10-10: 90, more preferably 80: 20-20: 80, and even more preferably 70: 30-30: 70. When the amount of the resin (A) (or shell) is less than 5% by weight, the adhesion to the polyolefin-based substrate tends to be insufficient. On the other hand, when the amount of the resin (A) (or shell) is more than 95% by weight, the physical properties of the coating obtained from such a composite resin dispersion, specifically, the strength of the coating, water resistance, weather resistance, Rubbing resistance, solvent resistance, etc. tend to be insufficient.

[Polyolefin resin (A) (resin (A))]
The polyolefin-based resin (A) (resin (A)) refers to a polymer having an olefin as a main monomer, and an olefin-based polymer (A1) (hereinafter referred to as an olefin homopolymer or copolymer). , Sometimes referred to as “polymer (A1)”) and self-emulsifying olefin polymer (E) (hereinafter referred to as “self-emulsifying polymer (A1)”). E) "and so on.

[Olefin polymer (A1) (polymer (A1))]
As the olefin polymer (A1) (polymer (A1)), an olefin polymer (A11) having no reactive group (hereinafter sometimes referred to as “polymer (A11)”) or the like. And a modified olefin polymer (A12) having a reactive group (hereinafter sometimes referred to as “polymer (A12)”).

Preferable embodiments of the polymer (A1) include propylene polymers that satisfy the following (1) to (3).
(1) The propylene content is 50 mol% or more, more preferably 60 mol% or more, and most preferably 70 mol% or more.
(2) The molecular weight distribution [Mw / Mn] is 4.0 or less, more preferably 3.0 or less.
(3) Melting point [Tm] is 125 ° C. or lower, more preferably 100 ° C. or lower, more preferably 90 ° C. or lower. Furthermore, the lower limit of Tm is preferably 60 ° C. or higher.

[Olefin polymer having no reactive group (A11) (polymer (A11))]
As the olefin polymer (A11) (polymer (A11)) having no reactive group, various known olefin polymers and olefin copolymers can be used. Examples of this include, but are not limited to, homopolymers of ethylene or propylene; copolymers of ethylene and propylene; ethylene or / and propylene and other comonomers such as butene-1, pentene-1, hexene-1, Copolymers of α-olefin comonomers having 2 or more carbon atoms such as heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene, or copolymers of two or more of these comonomers; α-olefin monomers and vinyl acetate , Copolymers with comonomers such as acrylic esters and methacrylic esters; copolymers with comonomers such as aromatic vinyl monomers or hydrogenated products thereof; conjugated diene block copolymers or hydrogenated products thereof .

The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 4 carbon atoms.
In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 40% by weight or less, preferably 30% by weight or less.

  Specific examples of the polymer (A11) include, for example, polyethylene, polypropylene, ethylene-butene copolymer, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorine. Polypropylene, chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene- Examples thereof include a hydrogenated product (SEPS) of a styrene block copolymer.

  What is preferable as the polymer (A11) is a propylene homopolymer or a copolymer of propylene and another α-olefin, which 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. Most preferred are a propylene homopolymer not containing chlorine, an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer.

  These polymers (A11) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polymer (A11) is preferably a propylene-based polymer containing propylene as a constituent component. The propylene content in the propylene-based polymer is 50 mol% or more, more preferably 60 mol% or more, and most preferably 70 mol% or more. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.

  Preferred propylene polymers include those having an isotactic structure in whole or in part. For example, it is a homopolymer or copolymer of a stereoblock polypropylene having an isotactic block and an atactic block as described in JP-A No. 2003-231714 and US Pat. No. 4,522,982. Most preferably, it is a stereoblock polypropylene polymer having an isotactic block and an atactic block.

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

  The weight average molecular weight Mw of the polymer (A11) is preferably 5,000 to 500,000 as measured by GPC (Gel Permeation Chromatography) and converted to the calibration curve of each polyolefin. A more preferable value of the lower limit value is 10,000, more preferably 20,000, and particularly preferably 30,000. A more preferable value of the upper limit value is 300,000, more preferably 200,000, particularly preferably 150,000. 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 composite resin dispersion tends to be easily prepared.

  The molecular weight distribution Mw / Mn represented by the weight average molecular weight Mw / number average molecular weight Mn of the polymer (A11) is preferably 4.0 or less, more preferably 3.0 or less. If the molecular weight distribution is narrow and uniform, the particle size at the time of dispersion can be easily controlled, the particle size becomes small, and the particle size distribution becomes narrow. Moreover, when the obtained composite resin particle is used for a paint or an adhesive, high performance can be obtained. In addition, the measurement of the number average molecular weight Mn can be performed using GPC, for example similarly to the measurement of the weight average molecular weight Mw.

  By the way, the GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

  In addition, the melting point Tm of the olefin polymer (A11) is preferably 125 ° C. or less. A more preferable value of the lower limit value is 60 ° C. or more, a more preferable value of the upper limit value is 100 ° C. or less, and a more preferable value is 90 ° C. or less. If the melting point is lower than the lower limit, the resin is sticky and unsuitable for use as a paint, and if it is higher than the upper limit, a high temperature is required for drying and baking, which is not preferable.

  About the manufacturing method of the said olefin type polymer (A11), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.

In the case of coordination polymerization, for example, a method using a Ziegler-Natta catalyst or a method using a single site catalyst may be used. A preferable production method includes a production method using a single site catalyst. This is because the single-site catalyst can sharpen the molecular weight distribution and the stereoregularity distribution by the ligand design. Moreover, as a single site catalyst, a metallocene catalyst and a Brookhart type catalyst can be used, for example. C ₁ symmetric type metallocene catalyst, C ₂ symmetric, C _2V symmetric, C _S symmetric like, it may be selected a suitable catalyst according to the stereoregularity of the polyolefin to be polymerized.

  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, heptane, and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, halogens, and the like. Hydrocarbons, esters, ketones, ethers and the like. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, heptane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type. The olefin polymer (A11) may be linear or branched.

[Modified Olefin Polymer Having Reactive Group (A12) (Polymer (A12))]
Examples of the modified olefin polymer (A12) having a reactive group include a copolymer (A12a) obtained by copolymerizing an olefin and an unsaturated compound having a reactive group at the time of polymerization, and a radical polymerizable property having a reactive group. Examples thereof include a graft polymer (A12b) obtained by graft polymerization of an unsaturated compound onto an olefin polymer.

  The copolymer (A12a) is a copolymer obtained by copolymerizing an olefin and an unsaturated compound having a reactive group, and having an unsaturated compound having a reactive group inserted into the main chain. For example, what copolymerized (alpha)-olefins, such as ethylene, propylene, butene, and (alpha), (beta) -unsaturated carboxylic acid or anhydrides, such as acrylic acid and maleic anhydride, is mention | raise | lifted. Specific examples of the copolymer (A12a) include an ethylene-acrylic acid copolymer and an ethylene-acrylic acid ester-maleic anhydride copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type. As the manufacturing method, the method described in (A11) can be similarly used.

  The graft polymer (A12b) can be obtained by graft polymerization of a radical polymerizable unsaturated compound having a reactive group to an olefin polymer. Examples of the reactive group include a carboxyl group, an amino group, an epoxy group, an isocyanato group, a sulfonyl group, and a hydroxyl group. Among them, preferred reactive groups are carboxyl groups and anhydrides thereof, for example, polyolefins such as polyethylene and polypropylene, (meth) acrylic acid, fumaric acid, maleic acid or anhydrides thereof, itaconic acid or anhydrides thereof, and crotonic acid. , 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 the olefin polymer used for the graft polymer (A12b), the above polymer (A11) can be used. Specific examples of the graft polymer (A12b) include maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, acrylic Examples include acid-modified polypropylene and chlorinated products thereof, acrylic acid-modified ethylene-propylene copolymers and chlorinated products thereof, and acrylic acid-modified propylene-butene copolymers. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used for graft polymerization can be appropriately selected from ordinary radical polymerization initiators, and examples thereof include organic peroxides and azonitriles. Examples of the organic peroxide include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di (t-butyl) peroxide, benzoyl Examples thereof include diacyl peroxides such as peroxides, and peroxyesters such as t-butyl peroxyisopropyl monocarbonate. 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 1:20 to 1: 1 range. The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 200 ° C. The reaction time is usually about 2 to 20 hours.

  About the manufacturing method of a polymer (A12b), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. As a solvent in the case of producing in a solution, the solvent described for the polymer (A11) can be used in the same manner.

  The content of the reactive group in the polymer (A12) is preferably in the range of 0.01 to 1 mmol, ie 0.01 to 1 mmol / g, per 1 g of the olefin polymer. A more preferable lower limit is 0.05 mmol / g, and further preferably 0.1 mmol / g. A more preferred upper limit is 0.5 mmol / g, and even more preferably 0.3 mmol / g. The higher the lower limit value, the higher the hydrophilicity and the smaller the dispersed particle size. The lower the upper limit value, the higher the adhesion to the crystalline polyolefin as the base material.

  When the reactive group of the polymer (A12) is an acidic group such as a carboxyl group or its anhydride or a sulfonyl group, the acidic group is neutralized with a basic compound, whereby the self-emulsifying weight It can be used as a kind of combined (E). Examples of the basic substance include inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, triethylamine, diethylamine, ethanolamine, dimethylethanolamine, 2-methyl-2-amino-propanol, triethanolamine, morpholine, pyridine and the like. Is mentioned. The neutralization rate with the basic compound is not particularly limited in the range of 1 to 100 mol% as long as dispersibility in water is obtained, but is preferably 50 mol% or more. If the neutralization rate is low, the dispersibility in water decreases.

[Self-emulsifying olefin polymer (E)]
The self-emulsifying olefin polymer (E) (hereinafter sometimes referred to as “self-emulsifying polymer (E)”) is a polyolefin resin having a hydrophilic group in the resin (A). , Refers to a copolymer that can be dispersed in water at 10% by weight or less of a surfactant.

  Examples of the self-emulsifying polymer (E) include a neutralized product of the polymer (A12) and an olefin polymer-hydrophilic polymer obtained by binding a hydrophilic polymer (C) to the polymer (A1). Examples thereof include a polymer copolymer (D) (hereinafter sometimes referred to as “copolymer (D)”).

  When the neutralized polymer (A12) is used as the self-emulsifying polymer (E) and the polymer (A12) is produced by graft polymerization, that is, when the graft polymer (A12b) is used, The conversion ratio is preferably 3% by weight or more, and preferably 5% by weight or more. If it is less than 3% by weight, the self-emulsifying property may be insufficient. On the other hand, the upper limit of the grafting rate is preferably 20% by weight, and more preferably 10% by weight. When it is larger than 20% by weight, water resistance and adhesion to polyolefin may be deteriorated.

[Olefin polymer-hydrophilic polymer copolymer (D)]
As described above, the copolymer (D), which is a kind of the self-emulsifiable polymer (E), can be obtained by bonding the hydrophilic polymer (C) to the polymer (A1).

  The amount of the hydrophilic polymer (C) to be bonded to the polymer (A1) is preferably in the range of 0.01 to 1 mmol, ie 0.01 to 1 mmol / g, per 1 g of the polymer (A1). A more preferable lower limit is 0.05 mmol / g, and further preferably 0.1 mmol / g. A more preferred upper limit is 0.5 mmol / g, and even more preferably 0.3 mmol / g. The higher the lower limit value, the more hydrophilic the hydrophilic polymer (C), and the smaller the dispersed particle size tends to be stably dispersed. The lower the upper limit value, the higher the adhesion to the crystalline polyolefin as the substrate. It tends to increase.

  The weight ratio of the polymer (A1) and the hydrophilic polymer (C) is preferably (A1) :( C) = 100: 1 to 100: 300, and 100: 5 to 100: 50. preferable. If (A1) :( C) is greater than 100: 1, the self-emulsifying property may be insufficient. On the other hand, when (A1) :( C) is smaller than 100: 300, water resistance and adhesion to polyolefin may be deteriorated.

[Hydrophilic polymer (C)]
The hydrophilic polymer (C) refers to 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 (C) can be used without particular limitation 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. Usually, the number average molecular weight Mn is preferably 300 or more.

  Although it does not specifically limit as said synthetic polymer, For example, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin etc. can be used. Although it does not specifically limit as said natural polymer, For example, starch, gum arabic, tragacanth gum, casein, gelatin, dextrin etc. can be used. The semi-synthetic polymer is not particularly limited, and for example, carboxylated starch, cationized starch, dextrin, ethyl cellulose, carboxylated methyl cellulose, hydroxyethyl cellulose, cationized cellulose and the like can be used.

  Among them, 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. Of these, polyether resins having high hydrophilicity are most preferable.

  The hydrophilic polymer (C) 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.

  The polyether resin is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine.

  Since the hydrophilic polymer (C) used in the present invention is bonded to the polymer (A1), it preferably has at least one reactive group capable of reacting with the polymer (A1). 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 an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, an epoxy group, and an isocyanato group, it is easy to bond a polyolefin and a hydrophilic polymer. The amino group may be primary, secondary, or tertiary, but more preferably is a primary amino group.

  The number of reactive groups is one or more, but more preferably one having 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 polymer (A1), 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.

  Examples of such hydrophilic polymer (C) include polyetheramine, polyether polyol, polyalkylene oxide, polyalkyleneimine, and polyetheramine.

  The 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. The polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.

  Furthermore, polyethylene oxide, polypropylene oxide, and polyethyleneimine are preferable as the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity. Furthermore, as the polyetheramine, Jeffamine M series, D series, ED series, Surfonamin L series, etc. manufactured by Huntsman may be used.

  The hydrophilic polymer (C) preferably has a weight average molecular weight Mw measured by GPC and converted by a polystyrene calibration curve of 200 to 100,000. A more preferable value of the lower limit value is 300, and more preferably 500. A more preferable value of the upper limit is 50,000, and more preferably 10,000. When the Mw is higher than the lower limit, the hydrophilicity of the hydrophilic polymer (C) increases, and the dispersed particle size tends to be smaller and stably dispersed. The lower the upper limit, the lower the viscosity, and a composite resin dispersion is prepared. It tends to be easy to do. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using THF or the like as a solvent.

[Production Method of Copolymer (D)]
As a method for producing the copolymer (D) by bonding the polymer (A1) and the hydrophilic polymer (C), for example, a hydrophilic monomer is polymerized in the presence of the polymer (A1). A method (R-1) for producing a copolymer (D) by forming a polymer (C), or a copolymer obtained by bonding a preformed hydrophilic polymer (C) to a polymer (A1) Examples thereof include a method (R-2) for producing (D).

[Production Method 1 (R-1) of Copolymer (D)]
In the method (R-1) for producing a copolymer (D) by polymerizing a hydrophilic monomer in the presence of the polymer (A1), the hydrophilic monomer is polymerized by, for example, addition polymerization, condensation polymerization, or ring opening. Polymerization or the like can be used. At this time, a hydrophobic monomer may be copolymerized as long as a hydrophilic polymer can be formed after polymerization. Specifically, for example, there is a method in which a hydrophilic radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a hydrophilic polymer (C) and bonded to the polymer (A1). The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, Examples include (meth) acrylic acid dimethylaminoethyl quaternized product, vinylpyrrolidone and the like.

  Further, the polymer (A12) is used to polymerize a hydrophilic radical polymerizable unsaturated compound, a hydrophilic ring-opening polymerization monomer or the like with the reactive group of the polymer (A12) as a start terminal, and a hydrophilic polymer. There is a method of obtaining (C). As the hydrophilic radically polymerizable unsaturated compound, those described above can be used in the same manner. 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 by the said polymer (A11) can be used similarly.

[Production Method 2 (R-2) of Copolymer (D)]
In the method for producing the hydrophilic polymer (C) formed in advance by bonding to the polymer (A1), the hydrophilic polymer (C) is a term that details the hydrophilic polymer (C). The following polymers can be used.

  As a bonding method, 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 a polymer ( The polymer (A1) and the hydrophilic polymer (C1) can be graft-copolymerized with the polymer (A1) or the polymer (A1) is bonded to one or both ends of the polymer (A1). And the like are subjected to block copolymerization. Among these, from the viewpoint of easy control of the content of the hydrophilic polymer (C) and easy increase of the content of the hydrophilic polymer (C), the method by graft copolymerization is more than the method by block copolymerization. Is preferred.

  When the graft copolymerization is performed, for example, the hydrophilic polymer (C) is obtained by a method of ring-opening polymerization of a cyclic alkylene oxide in a polyolefin having a reactive group using the polyether resin, ring-opening polymerization, or the like. Examples thereof include a method of reacting a hydrophilic polymer having a reactive group such as polyether amine and polyether polyol obtained with a polyolefin having a reactive group.

  In the graft copolymerization, the polymer (A11) can be used as the polymer (A1) to be used, but the polymer (A12) is usually used.

  When the graft copolymerization is performed, various reaction forms such as a radical graft reaction and a reaction utilizing a reactive group can be given as the reaction form of the bond. According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed. The reaction using a reactive group has a reactive group in both the polymer (A1) and the hydrophilic polymer (C), and reacts them to bond, and it is a covalent bond or an ionic bond. Is formed. Examples of this reaction include esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted with respect to one equivalent of the dibasic acid or anhydride.

  In this production method, as the hydrophilic polymer (C), the polymers described in the section detailing the hydrophilic polymer (C) can be used, and as the hydrophilic monomer, (R-1 The various hydrophilic monomers mentioned in the above can be used similarly. Any of these may be used alone or in combination of two or more. The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted by the polymer (A11) can be used similarly.

[Aqueous dispersion of self-emulsifying polymer (E)]
As a method of dispersing the self-emulsifiable polymer (E) obtained by the above-mentioned method in water to obtain an aqueous dispersion, a solvent other than water is added to the self-emulsifiable polymer (E), and if necessary Examples include a method in which water is added after dissolution by heating to obtain an aqueous dispersion.

  In a method in which a solvent other than water is added and water is added after heating and dissolving as necessary, an aqueous dispersion having a fine particle size is easy to make. The temperature at the time of dissolution in a solvent or at the time of addition of water is usually 30 to 150 ° C, preferably 50 to 100 ° 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 aqueous dispersion is usually 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 1% by weight or less. As the solvent, the above-mentioned solvents can be used. Among them, a solvent capable of dissolving 1% by weight or more in water is preferable, and more preferably 5% by weight or more. For example, methyl ethyl ketone, cyclohexanone, n-propanol , Isopropanol, n-butanol, isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, and 2-ethoxypropanol are preferred.

  The apparatus for producing an aqueous dispersion by adding water after dissolving in a solvent is not particularly limited, and 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 1000 rpm.

  Since the hydrophilic polymer (C) is very excellent in water dispersibility, when the copolymer (D) is used as the self-emulsifying polymer (E), the composite resin dispersion of the present invention is dispersed. There is an advantage that the 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.

  Thus, the copolymer (D) imparts hydrophilicity to the polymer (A1) by binding the hydrophilic polymer (C) to the polymer (A1), thereby substantially adding a surfactant. Water dispersion is possible without using it. In addition, since the amount of carboxylic acid grafted is smaller than in the production method in which the carboxylic acid group is directly neutralized with a basic substance and dispersed in water without using the hydrophilic polymer (C), the polyolefin base material is reduced. There are advantages such as excellent adhesion to water and water resistance.

  In the present invention, the term “dispersion” is a concept that includes a state in which dispersed particles are extremely small and dispersed in a single molecule, that is, a state that can be said to be substantially dissolved. Accordingly, the lower limit value of the dispersed particle size is not particularly limited and may be 0 μm. The aqueous dispersion of the self-emulsifiable polymer (E) used in the present invention has a solid content of preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% by weight or more based on the whole. is there. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. The smaller the solid content, the lower the viscosity and the easier it can be applied to various application methods and the higher the stability as an aqueous dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  The dispersed particle diameter of the polymer (resin) in the aqueous dispersion of the self-emulsifiable polymer (E) is usually 3 μm or less, preferably 1 μm or less at a 50% particle diameter. According to the present invention, the 50% particle diameter can be 0.5 μm or less, more preferably 0.2 μm or less. More preferably, the 90% particle diameter can be 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. The dispersed particle diameter can be measured by a dynamic light scattering method / laser Doppler method or the like.

  As described above, with the self-emulsifiable polymer (E), an aqueous dispersion can be obtained without using a surfactant, and therefore, the advantage of being able to suppress bleed-out conventionally caused by the surfactant. One. 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. The ratio of the surfactant to 100 parts by weight of the self-emulsifiable polymer (E) is less than 10 parts by weight, preferably 5 parts by 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 self-emulsifiable polymer (E). Most preferably, no surfactant is included.

  An acidic substance or a basic substance can be added to the aqueous dispersion of the self-emulsifiable polymer (E) used in the present invention, if necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of basic substances include inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, triethylamine, diethylamine, ethanolamine, dimethylethanolamine, 2-methyl-2-amino-propanol, triethanolamine, morpholine, pyridine and the like. Can be mentioned.

[Radical polymerizable monomer other than olefin (B)]
The radical polymerizable monomer (B) other than olefin (radical polymerizable monomer (B)) is not particularly limited, and (meth) acrylic such as (meth) acrylic acid and (meth) acrylic acid ester. Monomers; aromatic monomers such as styrene and α-methylstyrene; vinyl monomers such as vinyl acetate, vinyl propionate and vinyl versatate; amides such as (meth) acrylamide and dimethyl (meth) acrylamide Monomer, (meth) acrylonitrile and the like. Of these, (meth) acrylic acid esters are preferred.

  Specific examples of the (meth) acrylic acid ester include (meth) acrylic acid ester monomers having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate and ethyl (meth) acrylate. , (Meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid Hexyl, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, or the like, or (Meth) acrylic acid ester having an aryl group or aralkyl group having 6 to 12 carbon atoms, for example, (meth) acrylate Le benzyl, and the like.

  Further, (meth) acrylic acid esters having a C 1-20 alkyl group containing a hetero atom, such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid- 2-aminoethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid -3-Methoxypropyl, (meth) acrylic acid and polyethylene oxide adducts, etc. (meth) acrylic acid esters having an alkyl group containing 1 to 20 carbon atoms, such as (meth) acrylic acid tri Fluoromethylmethyl, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylate Le acid 2 Pas - fluoroethyl ethyl and the like. Among these, butyl acrylate and methyl methacrylate are preferable.

  The number average molecular weight of the polymer (B1) obtained by polymerizing the radical polymerizable monomer (B) is preferably 1,000 or more and 1,000,000 or less. The lower limit of the number average molecular weight is more preferably 5,000 or more, and further preferably 20,000 or more. The upper limit of the number average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. When the number average molecular weight is less than or equal to the lower limit value, the adhesion to the substrate tends to decrease, and when it is greater than or equal to the upper limit value, emulsification becomes difficult.

  In addition, the glass transition temperature (Tg) of the polymer (B1) can be arbitrarily set by changing the type of radical polymerizable monomer according to the intended use, such as paint, adhesive, ink, and pressure-sensitive adhesive. A range can be obtained. Although there is no restriction | limiting in particular in a glass transition temperature (Tg), Generally it is the range of -100 degreeC-100 degreeC, Preferably it is the range of -60 degreeC-80 degreeC. In general, if a monomer having a low glass transition temperature is used, the minimum film-forming temperature (MFT) can be lowered, and can be adapted to applications such as pressure-sensitive adhesives. If a monomer having a high glass transition temperature is used, the minimum The film forming temperature (MFT) can be increased, and a coating film having no surface tack or blocking can be obtained.

In addition, the glass transition temperature (Tg) of said polymer (B1) can be determined by a well-known method. For example, from the method of measuring with a differential scanning calorimeter (DSC) according to JIS K7121, or the glass transition temperature of a homopolymer formed by each monomer component of a radical polymerizable monomer (B) other than olefin, For example, a method of calculating by a formula.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
However, Tg: Glass transition temperature (absolute temperature) of polymer (B1), W _{1 to} W _n : Weight fraction of components _{1 to n of} monomer (B), Tg _{1 to} Tg _n : Monomer ( B) Glass transition temperature (absolute temperature) of the homopolymer of components 1 to n

  Here, an example of Tg of a homopolymer is as follows. Methyl acrylate: 8 ° C, ethyl acrylate: -22 ° C, butyl acrylate: -52 ° C, 2-ethylhexyl acrylate: -70 ° C, 2-methoxyethyl acrylate: -45 ° C, 2-ethoxyethyl acrylate : -50 ° C, methyl methacrylate: 105 ° C, styrene: 100 ° C, vinyl acetate: 30 ° C, acrylonitrile: 105 ° C, acrylic acid: 106 ° C, 185 ° C methacrylic acid.

  By the way, in general, when an aqueous dispersion (emulsion) is used as a coating agent such as a paint or an adhesive, the formation of a coating film is often inferior to that of a solution-based coating agent. Does not form a film.

  In the solution system, since the resin component is dissolved in the solvent, the film is formed in such a manner that the molecules of the resin approach each other and become entangled as the solvent volatilizes and the drying proceeds. Accordingly, if the solvent is volatilized, the film formation proceeds automatically. Therefore, the temperature does not affect the possibility of film formation even though the temperature may affect the volatilization rate of the solvent, that is, the film formation rate.

  On the other hand, in the aqueous dispersion, the resin has a particle structure, and in order to form a film, the particles need to be fused and integrated. For this purpose, flexibility is required so that the particles can be fused together, and the relationship between the glass transition point (Tg) and melting point of the resin and the temperature conditions for forming the coating film is important. That is, in an aqueous dispersion, whether or not a film can be formed is determined by the heating temperature. The “temperature above a certain level” necessary for forming a film from this aqueous dispersion is the minimum film-forming temperature (MFT). In order to lower the MFT, methods such as adjustment of Tg by copolymerization or the like, addition of plasticizer components such as texanol isobutyrate and DBE (mixed ester such as dibutyl adipate) are used.

  As can be seen from the examples described later, the MFT of the emulsion can be lowered by combining with acrylic. This indicates that the film can be formed at a low temperature by combining. Moreover, generally in the case of an acrylic emulsion, MFT becomes higher than the glass transition point (Tg) (comparative example 1). However, in Examples 5-8, the MTF is lower than the Tg of the acrylic component, and in Examples 6-8, the MFT (38 ° C, 1 ° C., 1 ° C.). Therefore, by combining, the MFT can be lowered than that of each single emulsion, and the feature that enables film formation at a lower temperature can be exhibited.

  Thus, in order to make MFT lower than the glass transition point (Tg) of the acrylic component, by distributing a component having a high affinity with the dispersion medium or a component having a low Tg on the surface layer of the resin particles in the dispersion, It is effective to design the particles so that the particles tend to fuse with each other.

[Polyolefin-based composite resin aqueous dispersion (composite resin dispersion)]
As described above, the composite resin dispersion according to the present invention is obtained by dispersing composite resin particles in water.

  The mixing ratio of the resin (A) and the polymer (B1) in the composite resin particles is 95: 5 to 5:95 by weight. That is, the total amount of the polyolefin resin component and the monomer other than polyolefin is 100 parts by weight, and the amount of the resin (A) is 5 parts by weight or more and 95 parts by weight or less. When the amount of the resin (A) is less than 5 parts by weight, the adhesion to the polyolefin-based substrate tends to be insufficient. Preferably it is 20 weight part or more, More preferably, it is 30 weight part or more. On the other hand, when the amount of the resin (A) is larger than 95 parts by weight, the physical properties of the coating film obtained from such a composite resin dispersion, specifically, the strength of the coating film, water resistance, weather resistance, abrasion resistance, Solvent resistance will be insufficient. Preferably it is 80 weight part or less, More preferably, it is 70 weight part or less.

  The solid content of the composite resin dispersion of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more based on the whole. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. The smaller the amount of solid content, the lower the viscosity, the easier it can be applied to various application methods and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  The dispersed particle diameter of the polymer (resin) in the composite resin dispersion is usually 3 μm or less, preferably 1 μm or less as an average particle diameter. According to the present invention, the average particle size can be 0.5 μm or less, and more preferably 0.3 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. The dispersed particle diameter can be measured by a dynamic light scattering method or the like.

  According to the present invention, it is one of the advantages that a composite resin dispersion can be obtained without using a surfactant, and therefore bleed-out conventionally caused by a surfactant can be suppressed. 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.

  When a surfactant is used as required according to other purposes and applications, the composite resin particles are 100 parts by weight, or when other resins are included, the interface with respect to the composite resin particles and the other resins in total 100 parts by weight The ratio of the activator is usually 10 parts by weight or less, preferably 5 parts by weight or less. It can also be substantially free of surfactant. The surfactant is essentially free of 100 parts by weight of composite resin particles, or when other resins are included, the amount used is less than 1 part by weight with respect to 100 parts by weight of the total of composite resin particles and other resins. This is the case.

[Production method of composite resin particles and composite resin dispersion]
Although there is no restriction | limiting in particular in the manufacturing method of the said composite resin particle and composite resin dispersion, For example, the aqueous dispersion of resin (A) (A self-emulsifiable polymer (E), such as a copolymer (D)) is included. Among them, a radical polymerizable monomer (B) other than the olefin is emulsion-polymerized using a radical polymerization initiator, a radical polymerizable monomer (B) other than the olefin previously emulsified in the aqueous dispersion. ) In a lump, divided or continuously, and emulsion polymerization using a radical polymerization initiator, or a resin (A) and a radical polymerizable monomer (B) other than an olefin were mixed and emulsified in advance. Examples thereof include a method in which the dispersion is added all at once, divided or continuously, added to an aqueous medium, and emulsion polymerization is performed using a radical polymerization initiator.

  In this method, since a part of the (meth) acrylic acid ester is graft-polymerized to the resin (A), composite resin particles that are more preferable than simply mixing the resin (A) and the (meth) acrylic polymer are obtained. Can do. As the radical polymerization initiator that can be used for the polymerization, those mentioned for the polymer (A12) can be used similarly.

[Structure of composite resin dispersion]
The composite resin dispersion can have various particle structures depending on its composition and production method. In general, in the presence of a highly hydrophilic self-emulsifying polymer (E), a radical polymerizable monomer ( When a hydrophobic monomer is polymerized as B), particles having a core-shell structure in which a highly hydrophilic polymer is in the shell (outside) and a hydrophobic polymer is in the core (inside) are obtained. These structures can be confirmed by observing the particle cross section with an electron microscope. For this reason, in this invention, the composite resin particle which is the objective of this invention can be obtained by making radically polymerizable monomer (B) higher hydrophobicity than a copolymer (D).

[Other compounded resins]
The composite resin dispersion of the present invention may contain other types of resins depending on the purpose. For example, a resin made of a (meth) acrylic polymer formed during polymerization of a (meth) acrylic acid ester may be included. In addition, as other resins used in combination, at least one resin selected from acrylic resins, polyurethane resins, polyester resins, vinyl acetate resins, epoxy resins, polyolefin resins, etc. An aqueous dispersion can be used in combination. In particular, acrylic resins, polyurethane resins, and polyester resins are preferable for reasons of weather resistance, wear resistance, and economy. There is no restriction | limiting in particular in the method of obtaining the aqueous dispersion of these resin, A well-known method can be used. For example, a method of emulsion polymerization in the presence of a surfactant, a method of mechanically forcibly emulsifying a previously obtained resin using a surfactant, a hydrophilic group such as a carboxylic acid group contained in the resin as a base There is a method of neutralizing and dispersing in an aqueous medium.

[Other additives]
In the composite resin dispersion of the present invention, various additives can be contained as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; conductivity imparting agents such as carbon black and ferrite, dyes, pigment dispersants, leveling agents, antifoaming agents, Various additives such as a sticking agent, an antiseptic, a fungicide, a rust inhibitor, and a wetting agent may be used in combination.

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

  When the composite resin dispersion of the present invention is used for applications such as primers, paints and inks, a hydrophilic organic solvent other than water is blended for the purpose of increasing the drying speed or obtaining a surface with a good finish. Can do. Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, glycols such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether and propylene glycol monomethyl ether, and ethers thereof. .

[Pigment]
If necessary, a pigment can be added to the composite resin dispersion of the present invention. A composite 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 composite resin dispersion of the present invention is preferably 10 parts by weight or more with respect to 100 parts by weight (solid content) of the resin. 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 .; an acidic block copolymer such as BYK-190 manufactured by Big Chemie; a styrene-maleic acid copolymer; manufactured by Air Products (Air Products) 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. Moreover, you may add an antifoamer to the resin composition of this invention. Examples include Surfynol 104PA and Surfynol 440 manufactured by Air Products.

[Usage]
The composite resin dispersion of the present invention can be used for primers, paints, adhesives, ink binders, compatibilizers of different materials from polyolefins, and particularly useful for paints, inks and adhesives. As applications, it can be used for automobile paints for automobile interiors and exteriors, paints for home appliances such as mobile phones and personal computers, paints for building materials, heat sealants and the like.

[paint]
The paint in the present invention is a liquid that contains a pigment or dye, and is a material that is applied to the surface for the purpose of protecting and beautifying the object, or for imparting unique functions such as rust prevention and water repellency. In particular, the type of paint is not limited. Specific examples include automotive interior paints, exterior primers, electrodeposition paints, intermediate paints, base paints, automotive paints such as clear paints, paints for home appliances such as mobile phones and personal computers, and paints for building materials. It can be used for anti-rust paints, anti-corrosion paints and the like.

[ink]
The ink (ink) in the present invention is a liquid containing a pigment or dye, and is used for writing letters or coloring the surface, and the type of ink is not particularly limited. Specific examples include gravure printing ink, flexographic printing ink, screen printing ink, offset printing ink, inkjet ink, and the like.

[adhesive]
The adhesive in the present invention is a substance that can bind the adherends to each other by the cohesiveness of the inside and the interface, and the type of the adhesive is not particularly limited. It can be used for various adhesives for automobiles, home appliances, building materials, food packaging materials, adhesives for lamination such as dry lamination, extrusion lamination (EC lamination), and heat sealing agents.

[Laminate]
The composite resin dispersion of the present invention or a coating material using the composite resin dispersion is applied to the thermoplastic resin molded body (F) and heated to form a resin layer, which can be used as a laminate. Thereby, the laminated body in which the layer which consists of a composite resin dispersion was formed on the thermoplastic resin molding (F) is obtained. The lamination method is not particularly limited, and a known method can be used, and examples thereof include a method of applying a composite resin dispersion or paint by spray, a method of applying by a roller, and a method of applying by a brush. It is done.

  The thickness of the layer made of the composite resin dispersion to be laminated can be appropriately selected depending on the material and shape of the molded product, the composition of the paint used, etc., but is usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm or more. However, it is usually 500 μm or less, preferably 300 μm or less, more preferably 100 μm or less.

[Thermoplastic resin molding (F)]
Although it does not specifically limit as said 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.

  The polyolefin resin molded body is a molded body of crystalline polyolefin resin, and is a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, Random or block copolymers with 2 or more, preferably 2 to 6 α-olefin comonomers, such as octene-1, cyclopentene, cyclohexene, norbornene, or two or more types of copolymers of these comonomers, or A copolymer with a comonomer such as vinyl acetate or (meth) acrylate, an aromatic vinyl monomer / conjugated diene block copolymer, or a hydrogenated product thereof is used. These can be used alone or as a mixture depending on the application.

[Inorganic filler component]
The thermoplastic resin molded product (F) used in the present invention can contain an inorganic filler component. By blending an inorganic filler component with crystalline polypropylene, mechanical properties such as flexural modulus and rigidity of the molded product can be improved. Specifically, plate fillers such as talc, mica and montmorillonite, short fiber glass fibers, long fiber glass fibers, carbon fiber, aramid fiber, alumina fiber and other fibrous fillers, potassium titanate, magnesium oxysulfate, silicon nitride , Basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, acicular filler such as silicon carbide, precipitated calcium carbonate, heavy calcium carbonate, granular filler such as magnesium carbonate, zinc white, titanium white, Inorganic fillers and pigments such as magnesium sulfate can also be used. Among these, talc, mica, glass fiber, and whisker are preferable from the balance of physical properties and cost.

[Elastomer component]
Furthermore, when the thermoplastic resin molding (F) used in the present invention is crystalline propylene (F-1), an elastomer component can be contained. By blending an elastomer component with crystalline polypropylene, 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-olefins such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Copolymer rubber, ethylene-α-olefin / non-conjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM), hydrogenated product of styrene-butadiene-styrene triblock (SEBS) And styrene-containing thermoplastic elastomers such as hydrogenated styrene-isoprene-styrene triblock (SEPS).

[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, Examples of the additives include dispersants, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, and various resins other than the propylene-based block copolymer, such as polyethylene resins.

[Manufacturing method of polyolefin resin molding]
The manufacturing method of the composition which comprises the polyolefin resin molding which comprises the thermoplastic resin molding (F) in this invention is not specifically limited, It is a conventionally well-known method, The said compounding component is propylene as needed. It can manufacture by mix | blending with a system resin, mixing and melt-kneading. In the present invention, the above-described essential components, that is, the polyolefin resin and optional components used as necessary are blended in the above blending ratio, and a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, By kneading and granulating using a normal kneader such as a lavender plastograph or kneader, the thermoplastic resin composition constituting the thermoplastic resin molded article (F) of the present invention is obtained.

[Production of thermoplastic resin molded product (F) and its use]
The thermoplastic resin molded body (F) which is the base material of the present invention can be obtained by molding by various known methods using the thermoplastic resin molded body (F). 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. Various molded bodies can be obtained by molding. Among these, in consideration of productivity, purpose of use, and the like, a molded body by injection molding, compression molding, injection compression molding, and stretched film molding is preferable.

  The propylene-based resin-coated molded article of the present invention is various industrial parts field, particularly various molded products that are thin, highly functional, and large in size, such as automobile parts such as bumpers, instrument panels, trims, garnishes, TV cases, Household appliance parts such as washing machine tub, refrigerator parts, air conditioner parts, vacuum cleaner parts, toilet seats, toilet seat covers, toilet tank parts such as water tanks, bathtubs, bathroom walls, ceiling parts, etc. As a molding material for various industrial parts such as these parts, food packaging containers, various sheets, films, synthetic papers, etc., it has sufficient performance for practical use.

  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 is collected in a 30 ml vial and contains 0.04% by weight of BHT (3,5-dibutyl-4-hydroxytoluene) as a stabilizer. 20 g of orthodichlorobenzene was added. 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 average molecular weight, a commercially available monodisperse polystyrene is used as a standard sample, and a calibration curve relating to the retention time and average molecular weight is prepared from the polystyrene standard sample and the viscosity formula of polypropylene, and propylene-α-olefin copolymer The molecular weight of the coalesced 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 of 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 BHT 250 ppm is added as a stabilizer, and completely dissolved at 50 ° C. After cooling to room temperature, the mixture was filtered through a filter having a pore diameter of 0.45 μm to prepare a sample solution having a polymer concentration of 0.1% by weight.

Next, GPC measurement was performed using Tosoh Corp. GPC HLC-8020 equipped with a guard column TSK guard column H _XL- H to TSK gel GMH _XL- L (30 cm × 2) as a column. 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) Stereoregularity The stereoregularity [mmmm] of polypropylene was measured by a ¹³ C-NMR spectrum measurement method using an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a flip angle of 90 ° and a pulse interval of 5T1 or more (T1 is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, since the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition. Measurement was carried out by integrating over 20 hours.

(4) Glass transition temperature (Tg) of polymer (B1)
The glass transition temperature (Tg) of the polymer (B1) was calculated from the following equation from the glass transition temperature of the homopolymer formed by the monomer components of the radical polymerizable monomer (B) other than olefin.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
However, Tg: Glass transition temperature (absolute temperature) of polymer (B1), W _{1 to} W _n : Weight fraction of components _{1 to n of} monomer (B), Tg _{1 to} Tg _n : Monomer ( B) Glass transition temperature (absolute temperature) of the homopolymer of components 1 to n
The Tg of the homopolymer of butyl acrylate (BA) is −52 ° C., and the Tg of the homopolymer of methyl methacrylate (MMA) is 105 ° C.

(5-1) Dispersion Particle Diameter of Polyolefin Resin (A) Aqueous Dispersion Measured using Microtrac UPA (model 9340 batch type dynamic light scattering method / laser Doppler method) manufactured by Nikkiso Co., Ltd. The density of the dispersion is 0.87 kg / m ³ , the shape is spherical, the dispersion medium is water and the measurement time is 180 seconds, and the volume is converted from the finer particle to the 50% particle diameter and 90% particle diameter. Asked.

(5-2) Dispersion Particle Diameter of Aqueous Polyolefin Composite Resin Dispersion Measured using ELS-8000 (dynamic light scattering method) manufactured by Otsuka Electronics Co., Ltd. Measurement was made at a liquid temperature of 25 ° C. with a filter value of 25%, and the calculated average particle size was determined.

<Evaluation as primer for paint>
(6) Adhesion (adhesive strength)
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 polyolefin-based composite 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 is blended as a base coat from the top of the coating, blended with a predetermined curing agent, further adjusted for viscosity with a special thinner, and spray-coated so that the dry coating amount is 200 to 300 g / m ^2. And baked at 90 ° C. for 30 minutes to obtain a coated plate.

  The obtained coated plate was held at 23 ° C. and 65% RH for one day, and then a gummed tape was applied over the coating to reinforce. After that, the coating film was cut into a width of 10 mm, the peel strength when measured in a 180 degree direction at a pulling speed of 50 mm / min was measured using a FUDO rheometer, and the peel strength was converted to 1 cm. The peel strength was calculated.

(7) Minimum film forming temperature (MFT)
Using a thermal gradient testing apparatus (ASTM D2354-65T manufactured by Nikkei Shoji Co., Ltd.), a polyolefin composite resin aqueous dispersion coated with a 0.2 mm applicator was measured according to JIS K6828-2.

(8) Elongation and strength of film A 15 cm square glass plate was placed on a hot plate at 70 ° C, and 7.5 g of a polymer having a solid content adjusted to 30% was poured uniformly to form a film. The prepared film was returned to room temperature, cut into strips having a length of 60 mm and a width of 5 mm, and cured at 23 ° C. and 50% RH for 16 hours or more to obtain test pieces. This was subjected to a tensile test using an Autocom C-type universal machine (manufactured by KeySE Co., Ltd.) in a measurement atmosphere of 23 ° C. and 50% RH, with a crosshead speed of 200 mm / min and a chuck interval of 20 mm The maximum strength (MPa) and the maximum elongation (%) were measured.

<Raw materials>
[Resin (A) related]
Propylene-α olefin copolymer: polymerized by metallocene catalyst, melting point 75 ° C., weight average molecular weight (Mw) 240,000 (polypropylene equivalent), molecular weight distribution (Mw / Mn) 2.2
-Maleic anhydride-manufactured by Mitsubishi Chemical Corporation-t-butyl peroxyisopropyl monocarbonate-manufactured by NOF Corporation: Perbutyl I, hereinafter referred to as "Perbutyl I".
-Toluene-Sanwa Chemical Industry Co., Ltd.-Methoxypoly (oxyethylene / oxypropylene) -2-propylamine (number average molecular weight 1,000)-Huntsman's product: Jeffamine M-100 (10 in 25 ° C water) (Insoluble content is 1 wt% or less when dissolved at a concentration of wt%.)
Isopropanol: manufactured by Sanwa Chemical Industry Co., Ltd., hereinafter referred to as “IPA”.

[Related to radically polymerizable monomer (B)]
・ Butyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as “BA”.
-Methyl methacrylate: Mitsubishi Rayon Co., Ltd., hereinafter referred to as "MMA".
· Α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -ammonium salt of poly (oxy-1,2-ethanediyl) ... manufactured by Adeka Co., Ltd .: trade name Adekaria Soap SR-10
Emulsifier: polyoxyethylene alkyl ether, manufactured by Kao Corporation: Trade name Emulgen 1118S-70
T-Butyl hydroperoxide: Kayaku Akzo Co., Ltd .: Trade name Kayabutyl H-70
-Thiourea disulfide ... Made by Adeka Co., Ltd .: Trade name Techlite

[Production Example 1: Production of maleic anhydride-modified propylene copolymer]
After 200 kg of propylene-α olefin copolymer and 5 kg of maleic anhydride were dry blended with a super mixer, a biaxial extruder (TEX54αII manufactured by Nippon Steel Co., Ltd.) was used, and 1 per 100 parts by weight of propylene-α olefin copolymer. While feeding perbutyl I in the middle with a liquid pump so as to be in parts by weight, the kneaded part was kneaded under the conditions of a cylinder temperature of 200 ° C., a screw rotation speed of 125 rpm, and a discharge rate of 80 kg / hour to produce a pellet-like product (anhydrous A maleic acid-modified propylene-α-olefin copolymer) was obtained.
The maleic anhydride group content (grafting ratio) of the maleic anhydride-modified propylene-α-olefin copolymer thus obtained was 0.8% by weight (0.08 mmol / g as maleic anhydride group, carboxylic acid group As 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).

[Production Example 2: Production of aqueous dispersion of maleic anhydride and polyalkylene glycol-modified propylene copolymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 g of the maleic anhydride-modified propylene-α-olefin 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 110 ° C. to dissolve the copolymer. After the copolymer was dissolved, 1.5 g of maleic anhydride 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 by washing, and then 15 g (15 mmol; component (C) methoxypoly (oxyethylene / oxypropylene) -2-propylamine; A solution in which 280 g of IPA was dissolved in 100 parts by weight of the polymer) was added dropwise and reacted at 70 ° C. for 1 hour. Further, 1.4 g (15.6 mmol) of aminomethylpropanol 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, so that a milky white resin having a resin solid concentration of 30% by weight was used without using a surfactant. An aqueous dispersion (component (A)) was obtained.
As a result of measuring the dispersed particle size by the measurement method described in (5-1) above, the 50% particle size was 0.106 μm, and the 90% particle size was 0.200 μm.

  In addition, acetone was added to the modified propylene copolymer before the reaction with methoxypoly (oxyethylene / oxypropylene) -2-propylamine, the precipitated polymer was filtered off, and the obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.5% by weight (0.15 mmol / g).

[Production Example 3: Production of maleic anhydride-modified polypropylene]
In a 1,000 ml round bottom flask, 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved with stirring. In this solution, 16.7 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.

  To 4.4 g of the chemically treated montmorillonite obtained, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration: 99 mg clay / ml).

  In another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd.) was collected, 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- A toluene diluted solution of 131 mg (57 μmol) of 5,6,7,8-tetrahydro-1-azulenyl) hafnium was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry (for the catalyst production method, see JP2004-002310A). No. gazette).

  Next, 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 72 ° C., and stirring was continued for 2 hours at the same temperature while keeping the total pressure during polymerization constant at 0.7 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 1 kg (0.73 kg propylene polymer) of a 7.3% by weight propylene polymer toluene solution was obtained. The weight average molecular weight Mw of the obtained polypropylene was 39,000 (polypropylene conversion), and the stereoregularity [mmmm] was 37.6%. The melting point was measured by DSC but did not show a clear melting point.

  Into a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 350 g of the polypropylene obtained above and 650 g of toluene were placed, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After heating, 17.5 g of maleic anhydride was added, 8.75 g of t-butyl peroxyisopropyl monocarbonate (Nippon Yushi Co., Ltd., Perbutyl I) was added, and the reaction was continued for 7 hours at the same temperature. . After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain white powdery maleic anhydride-modified polypropylene. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.5% by weight (0.15 mmol / g). Moreover, the weight average molecular weight was 35,000 (polystyrene conversion).

[Production Example 4: Production of aqueous dispersion of polyalkylene glycol-modified polypropylene]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 g of maleic anhydride-modified polypropylene synthesized in Production Example 3 and 150 g of toluene were added, and the temperature was raised to 110 ° C. and completely dissolved. Next, methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) 15 g (7.5 mmol, maleic anhydride modified polypropylene 100 parts by weight) (Corresponding to 15 parts by weight) was dissolved in 280 g of IPA and reacted at 70 ° C. for 1 hour. Thereafter, in the same manner as in Production Example 2, a milky white aqueous dispersion (component (A)) having a resin solid content concentration of 26.8% was obtained.
As a result of measuring the dispersed particle size by the measurement method described in (5-1) above, the 50% particle size was 0.118 μm, and the 90% particle size was 0.240 μm.

[Reference Example 1]
Using the modified propylene copolymer aqueous dispersion (component (A)) obtained in Production Example 2, the dispersion particle size was measured by the measurement method described in (5-2) above. It was 106 μm. Table 1 shows the evaluation results of the aqueous dispersion obtained in Production Example 2.

[Reference Example 2]
Using the modified polypropylene aqueous dispersion (component (A)) obtained in Production Example 4, the dispersion particle size was measured by the measurement method described in (5-2) above, and as a result, it was 0.118 μm. It was. The evaluation results of the aqueous dispersion obtained in Production Example 4 are shown in Table 1.

[Example 1] Production of aqueous composite resin dispersion of polyalkylene glycol-modified propylene copolymer and (meth) acrylic ester 70 parts by weight of aqueous dispersion of modified propylene copolymer obtained in advance in Production Example 2 (solid Min), ammonium salt of α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) in 12 parts by weight of BA and 18 g of MMA. A mixed solution in which 45 g was dissolved was added to a flask having a propeller-type stirring blade while stirring to prepare a mixed dispersion. In a glass flask equipped with a reflux condenser, dropping funnel, thermometer, and stirrer, 18 g of water, 0.32 g of emulsifier, and 26.37 g of the previously prepared mixed dispersion were added, and the temperature was adjusted to 65 ° C. did. Thereto was added 0.13 g of t-butyl hydroperoxide, and 2.30 g of a 2% aqueous thiourea disulfide solution was added to initiate emulsion polymerization of the (meth) acrylic acid ester. Ten minutes later, the remaining mixed dispersion was continuously added at 70 ° C. over 2.5 hours, and then an aging reaction was carried out at 70 ° C. for 2 hours to obtain a composite resin dispersion.
It was 0.134 micrometer as a result of measuring a dispersed particle diameter by the measuring method as described in said (5-2). The evaluation results of the obtained composite resin dispersion are shown in Table 1.

[Examples 2 to 6]
As described in Example 1, except that the amount of the modified propylene copolymer aqueous dispersion (component (A)) obtained in Production Example 2 and the amounts of MMA and BA used are those shown in Table 1. According to the method, a composite resin dispersion was obtained.
Table 1 shows the results of measuring the dispersed particle size by the measurement method described in (5-2) above. The evaluation results of the obtained composite resin dispersion are shown in Table 1.

[Examples 7 and 8]
Instead of the aqueous dispersion of the modified propylene copolymer obtained in Production Example 2, the aqueous dispersion of the modified polypropylene obtained in Production Example 4 was used, and the amount used and the amounts of MMA and BA used are shown in Table 1. A composite resin dispersion was obtained according to the method described in Example 1 except that the amount described was used.
Table 1 shows the results of measuring the dispersed particle size by the measurement method described in (5-2) above. Table 1 shows the evaluation results of the obtained composite resin dispersion.

[Comparative Example 1] Production of aqueous dispersion of (meth) acrylic resin A mixed dispersion was prepared using 18 g of water without using the aqueous dispersion of the modified propylene copolymer of Example 1. Others were carried out according to Example 1.
It was 0.135 micrometer as a result of measuring the dispersed particle diameter by the measuring method as described in said (5-2). Table 1 shows the evaluation results of the obtained resin aqueous dispersion.

[Example 6-2]
The composite resin dispersion obtained in Example 6 was dried under reduced pressure at room temperature to prepare a film, and the film was embedded with an epoxy resin. Furthermore, the film was stained with RuO4 to prepare an ultrathin section having a thickness of 80 nm.
The obtained ultrathin slice was observed at an acceleration voltage of 120 KV using a transmission electron microscope JEM1230 (manufactured by JEOL Ltd.).
The observation results are shown in FIG. As shown in FIG. 1, the composite resin particle has a core / shell structure in which the inside (core) contains an acrylic component that is not dyed with RuO4 as a main component and the outer side (shell) of the particle contains a polypropylene component that is dyed as a main component. You can see that

Claims (12)

A polyolefin-based composite resin aqueous dispersion in which composite resin particles having a core / shell structure are dispersed in water,
A polymer (B1) in which the shell (outer side) of the composite resin particle contains a polyolefin resin (A) as a main component and the core (inner side) is polymerized with a radical polymerizable monomer (B) other than olefin. A polyolefin-based composite resin aqueous dispersion, comprising as a main component and having a core: shell weight ratio of 95: 5 to 5:95 in the composite resin particles.   The polyolefin resin (A) binds the hydrophilic polymer (C) to the olefin polymer (A1) at a ratio of (A1) :( C) = 100: 1 to 100: 300 (weight ratio). The aqueous polyolefin-based composite resin dispersion according to claim 1, which is an olefin polymer-hydrophilic polymer copolymer (D). A polyolefin-based composite resin aqueous dispersion in which composite resin particles containing a polymer (B1) obtained by polymerizing a polyolefin-based resin (A) and a radical polymerizable monomer (B) other than an olefin are dispersed in water. There,
A self-emulsifiable olefin polymer (E) is used as the polyolefin resin (A), and in the aqueous dispersion of the self-emulsifiable olefin polymer (E), a radical polymerizable monomer (B) other than olefin. The aqueous dispersion of a polyolefin-based composite resin, wherein the composite resin particles obtained by emulsion polymerization are dispersed in water.   The self-emulsifiable olefin polymer (E) is a ratio of (A1) :( C) = 100: 1 to 100: 300 (weight ratio) of the hydrophilic polymer (C) to the olefin polymer (A1). The aqueous polyolefin-based composite resin dispersion according to claim 3, which is an olefin polymer-hydrophilic polymer copolymer (D) formed by bonding with a polymer.   The polyolefin-based composite resin aqueous dispersion according to any one of claims 1 to 4, wherein the radical polymerizable monomer (B) is a monomer containing a (meth) acrylic acid ester. The olefin polymer (A1) constituting the polyolefin resin (A) is a propylene polymer having all the characteristics of (1) to (3) below. 2. A polyolefin-based composite resin aqueous dispersion according to item 1.
(1) Propylene content is 50 mol% or more (2) Molecular weight distribution [Mw / Mn] is 4.0 or less (3) Melting point [Tm] is 125 ° C. or less   The olefin polymer-hydrophilic polymer copolymer (D) is a graft copolymer obtained by grafting a hydrophilic polymer (C) to an olefin polymer (A1). 7. The polyolefin-based composite resin aqueous dispersion according to any one of 6 above.   The aqueous polyolefin-based composite resin dispersion according to any one of claims 2, 4 to 7, wherein the hydrophilic polymer (C) is a polyether resin.   The aqueous polyolefin-based composite resin dispersion according to any one of claims 1 to 8, wherein the composite resin particles are dispersed in water with a dispersed particle diameter of 0.5 µm or less.   The polyolefin-based composite resin aqueous dispersion according to any one of claims 1 to 9, which is used as one selected from a paint, a primer, an ink, and an adhesive.   A radically polymerizable monomer (B) other than olefin is mixed and dispersed in a solvent to obtain a mixed liquid, and then the mixed liquid is weighted to the polyolefin resin (A) and the radically polymerizable monomer (B). Is added to the aqueous dispersion of the polyolefin resin (A) comprising the self-emulsifiable olefin polymer (E) so that the ratio becomes 95: 5 to 5:95, and then the radical polymerizable monomer (B) A method for producing an aqueous dispersion of a polyolefin-based composite resin, characterized by emulsion polymerization.   The laminated body which has a resin layer formed using the polyolefin-type composite resin aqueous dispersion of any one of Claims 1 thru | or 10 on a thermoplastic resin molded object (F).