JP4984859B2 - Laminate manufacturing method and water-based paint used therefor - Google Patents

Description

  The present invention relates to a method for producing a laminate including a polyolefin-based resin molded body and a water-based paint used therefor.

  Polyolefins typified by polypropylene and polyethylene are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are widely used in building materials, home appliances such as mobile phones and personal computers, and automobiles. Used in the field. However, since polyolefins have no polar groups in their molecules, they are generally low in polarity and difficult to paint or bond. Conventionally, coating properties and adhesion can be achieved by applying a primer such as a modified polyolefin (adhesive primer for polyolefins). It was common to apply a paint on the surface. When applying a design such as painting to a polyolefin molded body, first apply a primer, and then laminate a base coat, clear coat, etc., and the appearance is beautiful and the physical properties of the coating such as adhesion, moisture resistance, chemical resistance, etc. In addition, an excellent laminate was obtained.

The primer is usually in a form in which a modified polyolefin or the like is dissolved in an organic solvent or dispersed in water. In recent years, an aqueous dispersion is preferably used from the viewpoint of safety and health and reduction of environmental pollution. For example, Patent Document 1 describes a laminate in which a modified polyolefin aqueous dispersion containing a surfactant as a primer is applied to a polyolefin substrate.
By the way, since the cost of the laminated body increases as the number of layers increases, there is a demand in recent years to reduce the number of layers to reduce the cost. In order to respond to this, for example, one-coat coating in which only one paint having the performance of a primer is applied to a polyolefin base material is performed (Patent Document 2), but it is limited to organic solvent-based paints.
JP 2004-107538 A JP 2005-239852 A

However, as mentioned above, there is a great demand for health and safety and environmental pollution reduction, and water-based paints that are excellent in these are demanded, and paints that can be applied in one coat with both the performance of the primer and the performance of the surface layer. It was.
Also, if chlorine-based polyolefin is used, the resin can be easily hydrophilized, but chlorine is also undesirable because it can be a source of dioxins generation, and a substantially non-chlorine water-based paint has also been required.

  That is, an object of the present invention is to provide an excellent water-based paint and a method for producing a laminate, which can produce a polyolefin resin laminate excellent in appearance, adhesion, moisture resistance, and chemical resistance.

As a result of intensive studies to achieve the above object, the present inventors apply an aqueous paint containing an aqueous dispersion having specific properties on a polyolefin resin molded body, and heat to form an outermost surface layer. Thus, the inventors have found that the above problems can be solved, and have reached the present invention.
That is, the present invention is a method for producing a laminate in which a water-based paint is applied to a polyolefin resin molded body and heated to form an outermost surface layer, and the water-based paint comprises an aqueous dispersion of non-chlorine-modified polyolefin. (1) The solid content of the aqueous medium is 50% by weight or less and 5% by weight or more, and (2) no surfactant is contained in the aqueous dispersion, or an alkyl group having 4 to 30 carbon atoms. A surfactant having a hydrophobic group selected from the group consisting of an alkenyl group, an alkylaryl group, and an alkenylaryl group, in an amount of less than 0.5 part by weight based on 100 parts by weight of the non-chlorine-modified polyolefin, (3) the non-chlorine The modified polyolefin is a polymer (C) formed by bonding a hydrophilic polymer (B) or an acidic group to a polyolefin (A) having a weight average molecular weight Mw of 10,000 or more, and the non-chlorine modified The present invention relates to a method for producing a laminate, wherein an extract obtained by extracting a dry coating film of a polyolefin aqueous dispersion with water at 40 ° C. is 10% by weight or less of the weight of the dry coating film.

The present invention also relates to a method for producing a laminate in which a polyolefin resin molded product and an outermost surface layer are in direct contact.
Moreover, this invention relates to the manufacturing method of the laminated body whose solid content of this non-chlorine modified polyolefin aqueous dispersion is 10 to 100 weight% with respect to the solid content of this aqueous coating material .

Moreover, this invention relates to the manufacturing method of the laminated body whose polyolefin (A) is a propylene-type polymer whose content rate of propylene is 50 mol% or more.
Furthermore, the present invention provides an aqueous dispersion of non-chlorine-modified polyolefin in which the extract obtained by extracting the dry coating film of the non-chlorine-modified polyolefin aqueous dispersion with water at 40 ° C. is 10% by weight or less of the weight of the dry coating film. (1) The solid content of the aqueous medium is 50% by weight or less and 5% by weight or more, and (2) the aqueous dispersion does not contain a surfactant or has 4 to 30 carbon atoms. A surfactant having a hydrophobic group selected from the group consisting of an alkyl group, an alkenyl group, an alkylaryl group, and an alkenylaryl group in an amount of less than 0.5 parts by weight based on 100 parts by weight of the non-chlorine-modified polyolefin; ) The non-chlorine modified polyolefin contains the aqueous dispersion which is a polymer (C) in which a hydrophilic polymer (B) or an acidic group is bonded to a polyolefin (A) having a weight average molecular weight Mw of 10,000 or more. In particular, the present invention relates to an aqueous dispersion of non-chlorine-modified polyolefin for forming an aqueous coating that forms the outermost surface layer of a laminate including a polyolefin resin molded body.
The present invention also relates to an aqueous paint containing the aqueous dispersion.

The present invention also relates to a water-based paint for forming an outermost surface layer of a laminate in which the polyolefin resin molded body and the outermost surface layer are in direct contact.
Moreover, this invention relates to the aqueous coating material whose solid content of this non-chlorine modified polyolefin aqueous dispersion is 10 to 100 weight% with respect to the solid content of an aqueous coating material .
Or the invention, the polyolefin (A) is, the content of propylene is an aqueous coating composition is a propylene-based polymer of 50 mol% or more.

According to the present invention, there is an advantage that a polyolefin-based resin laminate having high adhesion, no surface layer peeling, no bleed-out, excellent appearance, no stickiness, and high moisture resistance and chemical resistance can be produced.
Therefore, water-based paints can be used for applications that conventionally used organic solvent-based paints, which is preferable from the viewpoint of safety and hygiene. In addition, since the water-based paint according to the present invention is not an organic solvent solution, VOC (volatile organic chemical substances) emission can be reduced, which is preferable in terms of environment. Moreover, since it does not substantially contain chlorine, there are no problems such as dioxins and toxicity, and this is also very preferable from the viewpoint of the environment.

In addition, since the water-based paint of the present invention is excellent in adhesion to a polyolefin resin molded article which is usually difficult to apply or adhere to, the outermost surface layer can be formed by directly applying this to the polyolefin resin molded article and heating. There is also an advantage that so-called one-coat coating can be performed. Since the painting process only needs to be performed once, the manufacturing cost of the laminate can be reduced.
Therefore, the water-based paint of the present invention is particularly suitable for automobile interior coating laminates that are finished by a single coating.

Furthermore, by adding other resins to the water-based paint, the improvement of physical property values derived from other resins, specifically, the strength of the coating film, water resistance, weather resistance, abrasion resistance, solvent resistance, etc. A more improved laminate can be produced.
In the present invention, it is not always essential to exhibit all the effects, and it is only necessary to have one or more of the effects described above.

The aqueous paint of the present invention is an aqueous paint for forming the outermost surface layer of a laminate comprising a polyolefin resin molded article, the aqueous paint comprising an aqueous dispersion of non-chlorine-modified polyolefin, and the non-chlorine-modified The extract obtained by extracting the dry coating film of the aqueous polyolefin dispersion with water at 40 ° C. is 10% by weight or less of the weight of the dry coating film.
The layer formed using such a paint is excellent in adhesion to the polyolefin resin molded product and has an excellent appearance, so that the polyolefin resin laminate excellent in all appearance, adhesion, and environmental resistance. Can be provided. Moreover, the coating material of the present invention is water-based and substantially free of chlorine, so that it is excellent in both safety and health and environmental pollution reduction.
[1] Modified polyolefin aqueous dispersion In the modified polyolefin aqueous dispersion of the present invention, the amount of the extract of the dried coating film into water at 40 ° C is 10% by weight or less of the weight of the dried coating film.

The amount of extract in 40 ° C. water can be measured as follows.
First, the modified polyolefin aqueous dispersion is put in a 5 cm × 5 cm box made of release paper and dried at normal pressure and 90 ° C. for 3 hours or more to obtain a film-like modified polyolefin dry coating film having a thickness of about 400 μm. After cutting this to about 5 mm × 5 mm, take 1 g and put it in a glass bottle, and add 19 g of distilled water to make a sample.

  Next, the lid of the glass bottle is closed and left in a constant temperature apparatus at 40 ° C. for 10 days. Thereafter, the sample taken out is filtered through a 400-mesh wire mesh, divided into a solid and water, the filtered water is dried at 100 ° C. for 3 hours or more, and the weight of the remaining solid [W gram] is measured. This is substituted into the following equation (1).

[Amount of extraction into water at 40 ° C. (% by weight)] = [Solid weight remaining after drying water after extraction (W grams)] / [Weight of modified polyolefin dry coating film used (1 gram)] × 100 ... (1)
When the amount of extraction is more than 10% by weight, the moisture resistance, water resistance and chemical resistance are poor and stickiness tends to occur. Since there are many water-soluble and hydrophilic low molecular weight components, it has high affinity with humidity, moisture, etc., and it is estimated that these components are likely to cause bleed-out. Therefore, the extraction amount is 10% by weight or less. It is preferably 5% by weight or less, more preferably 3% by weight or less, particularly preferably 2% by weight or less, and most preferably 1% by weight or less. The lower the extraction amount, the better. However, it is difficult to achieve 0%, and it is usually 0.01% by weight or more.

The modified polyolefin aqueous dispersion of the present invention is substantially free of chlorine. Specifically, the chlorination degree of polyolefin is less than 5% by weight. The chlorinated modified polyolefin more than this has a high polymer polarity, and the affinity with the polyolefin substrate is lowered and the adhesion is lowered. In addition, for the purpose of reducing the environmental burden, chlorine is not substantially contained.
The modified polyolefin is not particularly limited as long as it can achieve the object of the present invention. Preferably, the modified polyolefin is a polymer obtained by bonding a hydrophilic polymer (B) or an acidic group to a polyolefin (A). (C). Since such a polymer (C) is extremely excellent in water dispersibility, the dispersion particle size is fine by using only a very small amount of a low molecular weight, water-soluble and highly hydrophilic surfactant. In addition, an aqueous dispersion in which the particle size distribution is narrow and the particles are stably dispersed can be obtained.

In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved.
Hereinafter, the polymer (C) formed by bonding the hydrophilic polymer (B) or the acidic group to the polyolefin (A) will be described in detail.

[1-1] Polyolefin (A)
The polyolefin (A) is not limited to various known polyolefins. Examples thereof include ethylene or propylene homopolymers, copolymers of ethylene and propylene, and copolymers of ethylene or / and propylene and other comonomers. Can be mentioned. Examples of the comonomer include an α-olefin comonomer having 2 or more carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, and norbornene. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 8 carbon atoms, and more preferably an α-olefin comonomer having 2 to 6 carbon atoms. Alternatively, two or more kinds of these α-olefin comonomers can also be used.

In addition, if the polyolefin part is included, it may contain a monomer other than olefin, a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester or methacrylic acid ester, an aromatic vinyl monomer and a conjugated diene monomer. A hydrogenated product of a copolymer of two or more monomers selected from the above can also be used.
When the polyolefin (A) is a copolymer of two or more α-olefins, it may be a random copolymer or a block copolymer, but is preferably a random copolymer. The melting point of the copolymer can be lowered more effectively. The polyolefin (A) may be linear or branched.

Polyolefin (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the polyolefin (A) include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, propylene-ethylene-butene copolymer, chlorinated polyethylene, chlorinated polypropylene, Chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SBS) (SEBS), styrene-isoprene- A hydrogenated product (SEPS) of a styrene block copolymer (SIS). A propylene homopolymer or a copolymer of propylene and another α-olefin is preferred. More preferred are propylene homopolymer, ethylene-propylene copolymer, propylene-butene copolymer, propylene-ethylene-butene copolymer, and more preferred are propylene homopolymer and propylene-butene copolymer.

  A propylene-based polymer having a propylene content of the polyolefin (A) of 50 mol% or more is preferable. In particular, homopolypropylene or propylene-α-olefin copolymer is preferable. More preferably, the propylene content is 70 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.

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

  The molecular weight distribution Mw / Mn represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the polyolefin (A) is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. This means that the molecular weight distribution is narrow and the molecular weight of the polyolefin is uniform. By using such a polyolefin (A), it is easy to control the particle size when dispersed in water, and the dispersed particles There is an advantage that an aqueous dispersion having a small diameter, a narrow particle size distribution, and a stable dispersion can be obtained. Preferably Mw / Mn is 3.0 or less. However, it is usually 1.0 or more.

  The polyolefin (A) preferably has a melting point Tm of 100 ° C. or lower. More preferably, it is 90 degrees C or less. It is preferable that the melting point Tm is lower than 100 ° C. because the crystallinity is low and the solubility in a solvent is improved, and the emulsification and dispersion operations are easily performed at a low temperature. The melting point Tm of the polyolefin (A) is usually 25 ° C. or higher, preferably 35 ° C. or higher. It is advantageous in terms of high heat resistance, high hardness, and non-stickiness.

  When the polyolefin (A) is a polymer composed of an α-olefin having 3 or more carbon atoms, it is preferable that the stereoregularity has an isotactic structure in whole or in part. For example, not only ordinary isotactic polypropylene but also isotactic block polypropylene as described in JP-A-2003-231714 (US2004-162403) and US4,522,982, A stereoblock polypropylene having a tactic block and an atactic block, a propylene polymer copolymerized with an α-olefin comonomer, and the like can also be preferably used.

  When the polyolefin (A) is a polymer composed of an α-olefin having 3 or more carbon atoms, the [mmmm] pentad exhibiting isotactic stereoregularity is preferably in the range of 10% to 100%. A preferable value of the lower limit is 20%, more preferably 30%, and still more preferably 40%. A preferable value of the upper limit value is 95%, more preferably 90%, still more preferably 80%. As a method for measuring the pentad ratio, the method described in JP-A-2003-231714 (US2004-162403) can be used. There is a tendency that the degree of stickiness becomes smaller as the value is lower than the lower limit, and the degree of crystallinity becomes lower and the appearance of the coating layer of the laminate tends to be better as the value is lower than the upper limit.

When combining 2 or more types of polyolefin (A), values, such as a propylene content, molecular weight distribution, a chlorination degree, take the weight average value of the value of each polymer.
In summary, the polyolefin (A) is preferably a stereoblock polypropylene polymer having a propylene content of 50 mol% or more and having an isotactic block and an atactic block, and a propylene-α-olefin. It is a copolymer or a combination thereof.

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

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

[1-2] Polymer (C1) formed by bonding an acidic group to polyolefin (A)
The acidic group in the present invention refers to an electron pair accepting group, and is not particularly limited. For example, a carboxylic acid group (—COOH), a sulfo group (—SO ₃ H), a sulfino group (—SO ₂ H), and a phosphono group. (-PO ₂ H), and the like. Of these, a carboxyl group is preferred. The carboxylic acid group may be in a dicarboxylic anhydride group (—CO—O—OC—) before being dispersed in water. Examples of the carboxylic acid group include a (meth) acrylic acid group, a fumaric acid group, a maleic acid group or an anhydride group thereof, an itaconic acid group or an anhydride group thereof, and a crotonic acid group.

  The binding amount of the acidic group is preferably in the range of 0.4 to 5 mmol, that is, 0.4 to 5 mmol / g per 1 g of the polyolefin (A). A more preferred lower limit is 0.6 mmol / g, and a more preferred lower limit is 0.8 mmol / g. A more preferred upper limit is 3 mmol / g, a still more preferred upper limit is 1.6 mmol / g, and a further preferred upper limit is 1.2 mmol / g. The higher the lower limit value, the greater the polarity of the polymer (C1) and the greater the hydrophilicity, so the dispersed particle size tends to decrease. The lower the upper limit value, the greater the adhesion to the crystalline polyolefin as the substrate. . In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

  About the manufacturing method of a polymer (C1), the method similar to the manufacturing method of polyolefin (A2) which a reactive group couple | bonds with polyolefin (A) mentioned later in [1-3-1] can be used.

[1-3] Polymer (C2) obtained by bonding hydrophilic polymer (B) to polyolefin (A)
The ratio of the polyolefin (A) to the hydrophilic polymer (B) is preferably (A) :( B) = 100: 1 to 100: 500 (parts by weight). By setting (B) to 1 part by weight or more, the dispersibility of the polymer (C) in water can be improved, and the dispersed particle size can be reduced without causing aggregation or separation. By making (B) 500 parts by weight or less, it is possible to improve the adhesion to the polyolefin substrate. More preferably, (A) :( B) = 100: 5 to 100: 500 (parts by weight).

  As a method for producing a polymer (C2) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) and bonded to the polyolefin (A). Examples include the method (R1) for forming the hydrophilic polymer (B), or the method (R2) for bonding the prepolymerized hydrophilic polymer (B) to the polyolefin (A). The combination may be appropriately selected according to the characteristics of the target polymer (C2). Further, the hydrophilic polymer (B) may be directly bonded to the polyolefin (A), or the polymer (A2) in which a reactive group is bonded to the polyolefin (A) described below is used, and the hydrophilic polymer (B) is used. The polymer (B) may be bound.

[1-3-1] Polyolefin (A2) in which a reactive group is bonded to polyolefin (A)
Examples of the polyolefin (A2) having a reactive group include a copolymer (A2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization, or reactive. A polymer (A2b) obtained by graft polymerization of a radically polymerizable unsaturated compound having a group to a polyolefin (A), and a propylene-α-olefin copolymer having an unsaturated end group is converted into an element group of Groups 13 to 17 The polymer (A2c) obtained can be used.

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

  The polymer (A2b) is obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin, and the unsaturated compound having a reactive group is grafted to the main chain. For example, polyolefins such as polyethylene and polypropylene, (meth) acrylic acid, fumaric acid, maleic acid or anhydride thereof, itaconic acid or anhydride thereof, crotonic acid, 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid It is a polymer grafted with 2-hydroxypropyl, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid (2-isocyanato) ethyl, or the like. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and others are based on this.

As polyolefin of this reaction, the above-mentioned polyolefin (A) can be used.
Specific examples of the polymer (A2b) include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified propylene-ethylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include a modified propylene-ethylene copolymer and a chlorinated product thereof, and an acrylic acid-modified propylene-butene copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type.

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

The use ratio of the radical polymerization initiator and the graft copolymer unit is usually in the range of radical polymerization initiator: graft copolymer unit = 1: 100 to 2: 1 (molar ratio). Preferably it is the range of 1: 20-1: 1.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 200 ° C. The reaction time is usually about 2 to 20 hours.

  About the manufacturing method of a polymer (A2b), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

  As the polymer (A2c), for example, as described in JP-A-2001-288372, the double bond portion of a polyolefin having a terminal double bond is converted into a group 13 element group such as a boron group or an aluminum group. Polyolefin (A2c1), a polyolefin (A2c2) obtained by converting a double bond portion of a polyolefin having a terminal double bond to a halogen element as described in JP-A-2005-48172, and JP-A-2001-98140 As described in (1), a polyolefin (A2c3) obtained by converting a double bond portion of a propylene-based polymer having a terminal double bond into a mercapto group can be used.

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

As a method for converting the double bond portion into a mercapto group, for example, there is a method in which thioacetic acid is reacted in the presence of a radical initiator and then treated with a base.
The production method of the polymer (A2c) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced. Any production method may be used, but a method of heating and stirring in a solution is preferably used. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

In addition, regarding the polymer (A2a), the polymer (A2a) is regarded as the polyolefin (A), and the propylene content and the molecular weight distribution Mw / Mn are measured.
Regarding the polymer (A2b), the propylene content and the molecular weight distribution Mw / Mn are measured with respect to the polyolefin (A) before graft polymerization of the radically polymerizable unsaturated compound having a reactive group.

Regarding the polymer (A2c), the propylene content and the molecular weight distribution Mw / Mn are measured for the polyolefin (A) before the terminal double bond is converted.
The content of the reactive group in the polymers (A2a) and (A2b) formed by bonding reactive groups may be in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g per 1 g of polyolefin. preferable. A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, and particularly preferably 0.5 mmol / g.

  The content of the reactive group in the polymer (A2c) formed by bonding the reactive group is usually 1 reactive group or less per polymer molecule from the production method, and is 1 / number average molecular weight Mn (mol / g) or less. And tends to be lower than those of the copolymers (A2a) and (A2b). Accordingly, it is preferably in the range of 0.004 to 2 mmol / g per gram of polyolefin. A more preferred lower limit is 0.005 mmol / g. A more preferred upper limit is 0.2 mmol / g.

  The higher the lower limit value, the more the hydrophilic polymer (B) is bound and the higher the hydrophilicity of the polymer (C). Therefore, the dispersed particle size tends to decrease. The lower the upper limit value, the lower the crystallinity of the base material. There is a tendency for adhesion to polyolefin to increase. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

The polyolefin (A2) may be linear or branched. Polyolefin (A2) may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, both the polyolefin (A) itself and the polyolefin (A2) formed by bonding a reactive group are used in combination with the hydrophilic polymer (B) and the properties of the target polymer (C). It can be used as appropriate. However, it is preferable to include at least a polyolefin (A2) formed by bonding a reactive group. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B) and various reactions that can be used for binding. Only the polyolefin (A2) formed by bonding a reactive group may be used.

Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, mercapto groups, and halogen groups. More preferably, it is at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group. These carboxylic acid groups and the like are not only highly reactive and easy to bond with hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.
Any of the polymers (A2a), (A2b), and (A2c) can be used, but the polymer (A2b) is usually preferred. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).

[1-3-2] Hydrophilic polymer (B)
In the following, only the polyolefin (A) will be described for simplification of explanation, but the same applies to the polyolefin (A2).
In the present invention, the hydrophilic polymer means a polymer having an insoluble content of 1% by weight or less when dissolved in water at 25 ° C. at a concentration of 10% by weight. The hydrophilic polymer (B) is not particularly limited as long as the effects of the present invention are not significantly impaired, and any of synthetic polymers, semi-synthetic polymers, and natural polymers can be used. It may have a reactive group.

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

  Among these, a synthetic polymer that can easily control the degree of hydrophilicity and has stable characteristics is preferable. More preferred are acrylic resins such as poly (meth) acrylic resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, and polyether resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Highly hydrophilic polyether resins are most preferred.

  The acrylic resin used in the present invention is usually obtained by polymerizing an unsaturated carboxylic acid or its ester or anhydride by radical polymerization, anionic polymerization, or cationic polymerization. The bonding method with the polyolefin (A) is not limited. For example, radical polymerization in the presence of propylene-α-olefin copolymer, reaction of hydroxyl group, amino group, glycidyl group, (anhydrous) carboxylic acid group, etc. And a method of reacting an acrylic resin having a reactive group with a propylene-α-olefin copolymer having a reactive group.

Preferably, the unsaturated carboxylic acid or its ester or anhydride exhibiting hydrophilicity is preferably (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (dimethyl) ethyl dimethylaminoethyl (meth) acrylate. And (meth) acrylamide.
Moreover, a hydrophobic radically polymerizable compound can be copolymerized within a range showing hydrophilicity. Examples of the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.

  Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and the like.

Examples of the (meth) acrylic acid ester monomer having an aryl group or arylalkyl group having 1 to 12 carbon atoms include phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, and the like. It is done.
Examples of the polymerizable vinyl monomer having a hydrocarbon group having 1 to 12 carbon atoms include vinyl acetate and styrene monomer.

Preferably, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate are used.
Alternatively, there is a method in which a radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then modified to obtain a hydrophilic polymer (B). Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. Examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, as the polyolefin (A), a polyolefin (A2) obtained by bonding a reactive group can be used, but usually a polyolefin (A) having no reactive group is used.

The polyvinyl alcohol resin is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.
The polyvinyl pyrrolidone resin is usually obtained by polymerizing vinyl pyrrolidone.
The polyether resin is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with the polyolefin (A) is not limited, but for example, a method of ring-opening polymerization of a cyclic alkylene oxide in a propylene-α-olefin copolymer having a reactive group, a polymer obtained by ring-opening polymerization or the like. Examples thereof include a method of reacting a hydrophilic polymer having a reactive group such as ether polyol or polyether amine with a propylene-α-olefin copolymer having a reactive group.

Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.
Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.

Or as a polyetheramine, you may use Huntsman's Jeffamine M series, D series, ED series, etc.
The hydrophilic polymer (B) used in the present invention preferably has at least one reactive group capable of reacting with the polyolefin (A) before bonding with the polyolefin (A). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and preferably have at least an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, a glycidyl group, and an isocyanate group, it is easy to bond a polyolefin and a hydrophilic polymer. The amino group may be primary, secondary, or tertiary, but more preferably is a primary amino group.

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

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

  If the hydrophilic polymer (B) does not dissolve in THF, use a column that is soluble in a solvent such as water, methanol, ethanol, acetonitrile, dimethylformamide, acetone, chloroform, dimethyl sulfoxide, and that matches the polarity of the solvent. GPC can be measured with the same solvent. Further, by adding an ionic substance such as sodium nitrate, an ionic substance can be measured particularly well. In addition, a calibration curve prepared with a standard substance suitable for the polarity of the solvent can be used. For example, polyethylene oxide is preferably used.

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

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

The hydrophilic polymer (B) can be bonded to the polyolefin (A) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.
Reactions using reactive groups are those in which both polyolefin (A) and hydrophilic polymer (B) have reactive groups that are reacted to form covalent bonds or ionic bonds. Is done. Examples of this reaction include esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. The term “carboxylic acid group” as used herein includes dibasic acids or anhydrides such as maleic acid and maleic anhydride. In that case, 1 mol of the dibasic acid or its anhydride can be calculated as 2 equivalents, and the counterpart group may be reacted with one equivalent or with two equivalents.
[1-3-3] Method for Producing Polymer (C2) The method for producing the polymer (C2) by combining the polyolefin (A) and the hydrophilic polymer (B) is usually hydrophilic in the presence of polyolefin. (R1) for forming a hydrophilic polymer (B) obtained by polymerizing a polymerizable radical polymerizable unsaturated compound and bonded to a polyolefin, or for bonding a prepolymerized hydrophilic polymer (B) to a polyolefin (R2) There is.

[1-3-3-1] Production method (R1) of polymer (C2)
In this method, a hydrophilic polymer (B) bonded to polyolefin is obtained by polymerizing a hydrophilic radically polymerizable unsaturated compound (hydrophilic monomer) in the presence of polyolefin. As a polymerization method of the hydrophilic radically polymerizable unsaturated compound, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic radical polymerizable unsaturated compound may be copolymerized as long as a hydrophilic polymer can be formed after polymerization. In either case, the polyolefin (A) having no reactive group or the polyolefin (A2) formed by bonding a reactive group can be used as the polyolefin.

  Specifically, for example, there is a method in which a hydrophilic radical-polymerizable unsaturated compound is graft-polymerized into a polyolefin-polyacrylic graft copolymer in the presence of a polyolefin (A) and a radical polymerization initiator such as a peroxide or an azo compound. is there. Further, as described in JP-A No. 2001-288372, a hydrophilic radical-polymerizable unsaturated compound is prepared in the presence of polyolefin (A2c1) having a group 13 element group such as a boron group or an aluminum group at its terminal and oxygen. There is a method of polymerizing into a block copolymer of polyolefin and polyacryl. Further, as described in JP-A No. 2004-131620 and JP-A No. 2005-48172, a polyolefin (A2c2) having a halogen atom at the terminal, copper halide, ruthenium halide, etc. are used, and an atom transfer living radical method is used. There is a method of using a block copolymer of a propylene polymer and polyacryl. Also, as described in JP-A-2001-98140, a polyolefin / polyacryl block copolymer is obtained by polymerizing a radical initiator and a hydrophilic radical-polymerizable unsaturated compound in the presence of a polyolefin having a mercapto group at its terminal. There is a method.

The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples include methacrylic acid dimethylaminoethyl quaternized compounds, vinyl pyrrolidone and the like.
Examples of the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.

  Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and the like.

Examples of the (meth) acrylic acid ester monomer having an aryl group or arylalkyl group having 1 to 12 carbon atoms include phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, and the like. It is done.
Examples of the polymerizable vinyl monomer having a hydrocarbon group having 1 to 12 carbon atoms include vinyl acetate and styrene monomer.

Preferably, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate are used.
Reactive surfactants and reactive emulsifiers can also be used as the aqueous radical polymerizable unsaturated compound. Examples thereof include alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts and salts of sulfates thereof described in JP-A-4-53802 and JP-A-4-50204. Among them, alkyl propenyl phenol ethylene oxide 20 mol adduct, 30 mol adduct, 50 mol adduct (Daiichi Kogyo Seiyaku, Aqualon RN-20, RN-30, RN-50) and alkyl propenyl phenol polyethylene oxide 10 mol. Adduct sulfate ammonium salt and 20 mol adduct sulfate ammonium salt (Daiichi Kogyo Seiyaku, Aqualon HS-10, HS-20) are used.

  Alternatively, there is a method in which a radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then modified to obtain a hydrophilic polymer (B). Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. Examples of the copolymerizable hydrophobic radical polymerizable unsaturated compound include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, as the propylene-α-olefin copolymer, a polyolefin (A2) having a reactive group can be used, but usually a polyolefin (A) having no reactive group is used.

Alternatively, there is a method in which a hydrophilic polymer (B) is obtained by polymerizing a hydrophilic ring-opening polymerization monomer or the like using a polyolefin (A2) having a reactive group and using this reactive group as an initiation terminal.
Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

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

[1-3-3-2] Method for producing polymer (C2) (R2)
In this method, the previously polymerized hydrophilic polymer (B) is bonded to the polyolefin (A). In this case, as the hydrophilic polymer (B), those mentioned in [1-3-2] can be used.

  Specifically, for example, when a hydrophilic monomer is first polymerized to form a hydrophilic polymer, an unsaturated double bond is left in the molecule, and then graft polymerization is performed on the polyolefin using a radical polymerizable initiator. There is a way. In this case, the polyolefin (A2) having a reactive group can be used as the polyolefin, but the polyolefin (A) having no reactive group is usually used.

  There is also a method in which a hydrophilic polymer having a reactive group at the terminal is first polymerized, and then this is bonded to a polyolefin (A2) formed by bonding a reactive group. The hydrophilic polymer having a reactive group at the terminal can be obtained by polymerizing a hydrophilic monomer using a compound having a reactive group as an initiator or a chain transfer agent. Alternatively, it can also be obtained by ring-opening polymerization of a hydrophilic ring-opening polymerization monomer such as an epoxy compound.

As the hydrophilic monomer that can be used at this time, various hydrophilic monomers listed in [1-3-3-1] 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 in [1-1] can be used similarly.
By the technique as described above, the polymer (C) formed by bonding the hydrophilic polymer (B) or the acidic group to the polyolefin (A) can be obtained.

[1-4] Method for Producing Modified Polyolefin Aqueous Dispersion A method for producing an aqueous dispersion containing a modified polyolefin according to the present invention is not particularly limited. For example, a modified polyolefin, water, and a mixture of solvents other than water are used. Examples thereof include a method of preparing an aqueous dispersion by removing the solvent from the mixture after the preparation, a method of adding water after melting at a temperature higher than the temperature at which the modified polyolefin melts, and the like. The former is preferred. According to the former method, an aqueous dispersion having a fine particle diameter is easily obtained.

When preparing a mixture, you may heat as needed. The temperature is usually 30 to 150 ° C. The ratio of the solvent other than water in the aqueous dispersion is usually 50% or less. It is preferably 20% or less, more preferably 10% or less, and particularly preferably 1% or less.
Among these, a method of adding a solvent other than water to the modified polyolefin and adding water after heating and dissolving as necessary is more preferable because an aqueous dispersion having a finer particle size can be easily produced. The temperature at the time of dissolution in a solvent or at the time of addition of water is usually 30 to 150 ° C. Moreover, when dissolving once in solvents other than water, after adding water, you may distill a solvent off. The ratio of the solvent other than water in the aqueous dispersion is as described above.

Alternatively, an aqueous dispersion having a small particle size can be obtained by adding water and another solvent other than water to a solution in which the modified polyolefin is dissolved in a solvent, heating and dissolving the solution as necessary, and then distilling off the solvent. Easy to make. The temperature at the time of addition of water is usually 30 to 150 ° C. The ratio of the solvent other than water in the aqueous dispersion is as described above.
Examples of the solvent other than water used in the present method include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic systems such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrocarbons, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol and other alcohols, dipropyl alcohol Organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, etc. , Polar solvents such as dimethylformamide and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

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

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

[1-5] Aqueous Dispersion Since the aqueous dispersion of the modified polyolefin of the present invention has a fine dispersed particle diameter and the resin is stably dispersed, a coated product having an excellent appearance can be obtained by using this.
The dispersed particle diameter of the modified polyolefin in the aqueous dispersion is usually when a cumulative 50% particle diameter (referred to as 50% particle diameter or 50% average particle diameter) is calculated from the smaller particle diameter in terms of volume. The 50% particle size is 10 μm or less, preferably 1 μm or less. According to the present invention, the 50% particle size can be 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the 90% particle diameter is determined, the 90% particle diameter can be more preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. Further, a reduction in the ratio of the 90% particle diameter to the 50% particle diameter means that the particle size distribution becomes narrow, and as a result, the dispersion stability is improved. There is no restriction | limiting in particular about the lower limit of a dispersed particle diameter.

  The aqueous dispersion of 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. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The smaller the amount of solid content, the lower the viscosity, the easier it can be applied to various application methods and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  In the present invention, in view of the purpose, the aqueous dispersion preferably contains only a small amount or substantially no surfactant. This is because the surfactant is a low molecular weight having a high hydrophilicity and thus easily becomes the above-mentioned water extract. Specifically, the surfactant content is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 2 parts by weight or less with respect to 100 parts by weight of the modified polyolefin. Most preferably, it is substantially free of surfactant. “Substantially no surfactant” means less than 0.5 part by weight per 100 parts by weight of the modified polyolefin.

  Thereby, when this aqueous dispersion is used as a coating material, there is an advantage that a bleed-out can be suppressed and a coated product having an excellent appearance can be obtained, and this aqueous dispersion can be used as a coating material on the outermost surface of coating. In addition, it can improve the water resistance and oil resistance (gasohol resistance) of the coating, and the resulting aqueous dispersion has excellent adhesion, water resistance, moisture resistance, oil resistance, and chemical resistance. Become.

  As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. As the surfactant, those having an alkyl group, alkenyl group, alkylaryl group or alkenylaryl group having 4 or more carbon atoms as a hydrophobic group are usually used. Preferably it is C8 or more, More preferably, it is C12 or more. However, it usually has 30 or less carbon atoms.

  Examples of the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, and sodium polyoxyethylene lauryl sulfate. Examples of the cationic surfactant include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and the like. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.

Moreover, what is called a reactive surfactant etc. in which said surfactant has a radically polymerizable functional group can also be used. When a reactive surfactant is used, the water resistance of the film formed using this aqueous dispersion can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).
In addition, since nonionic surfactant is hard to reduce water resistance compared with other surfactant, nonionic surfactant may be included a little more. For example, when the surfactant other than the nonionic surfactant should be 5 parts by weight or less with respect to 100 parts by weight of the modified polyolefin, the nonionic surfactant may be 10 parts by weight or less.

  As long as the effect of this invention is not impaired remarkably, an acidic substance and a basic substance can be added to the aqueous dispersion of this invention as needed. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of the basic substance include inorganic bases such as sodium hydroxide and potassium hydroxide, triethylamine, diethylamine, diethylethanolamine, 2-methyl-2-amino-propanol, and morpholine. Moreover, the high molecular compound containing an acidic group and a basic group may be sufficient.

In the modified polyolefin aqueous dispersion of the present invention, the amount of the extract of the dry coating film into water at 40 ° C. is 10% by weight or less of the weight of the dry coating film.
Examples of the modified polyolefin aqueous dispersion satisfying this and the conditions for obtaining it are as follows.
For example, since polyolefin having a low molecular weight can be extracted into water, a polyolefin having a weight average molecular weight Mw of 3,000 or more is preferably used, preferably 10,000 or more. In terms of the production of polyolefins, production conditions are preferred such that the molecular weight is not too small and low molecular weight components are reduced.

In the modified polyolefin, if the amount of modification is very high, the possibility of extraction into water increases. In the polymer (C), the hydrophilic polymer (B) is preferably 500 (parts by weight) or less, more preferably 300 parts by weight or less, and 100 parts by weight or less with respect to 100 parts by weight of the polyolefin (A). Further preferred. Further, when the hydrophilic polymer (B) used for modification is contained in a free state in the aqueous dispersion, there is a high possibility that it is extracted into water. Therefore, it is desirable to increase the reaction rate of the hydrophilic polymer (B) and reduce the residual amount of the free hydrophilic polymer.

  For example, a highly reactive combination is selected as the reactive species. Since the reactivity of a carboxylic acid group such as maleic acid and a primary amine is extremely high, for example, a polyolefin (A) having a carboxylic acid group (a carboxylic acid anhydride group or a carboxylic acid ester group) as a reactive group, A combination with a hydrophilic polymer (B) having a primary amine as a reactive group is a preferred example. Alternatively, ring-opening amidation by reaction of a carboxylic anhydride group such as a maleic anhydride group with an amine is a combination with a high reaction rate.

Alternatively, it is also preferable to reduce the amount of hydrophilic polymer or acid used for polyolefin as much as possible.
Further, as the kind of the hydrophilic polymer, nonionic ones are more difficult to be extracted into water than ionic ones. For example, it has a structure such as polyethylene oxide.

Furthermore, it is preferable that purification is sufficiently performed in the production of the modified polyolefin to remove free hydrophilic polymers and acids as much as possible. For example, in the case of maleic anhydride, the residual free maleic anhydride is preferably 1 g or less per 100 g of the modified polyolefin, more preferably 0.5 g or less, and even more preferably 0.3 g or less.
In the present invention, it is desirable that a surfactant is not substantially used in the step of forming an aqueous dispersion. However, if used, a nonionic surfactant is preferable because it is relatively difficult to extract into water. Among them, those having as high a hydrophobicity as possible are preferable. In addition, when adding an acidic substance or a basic substance to the aqueous dispersion, it is desirable to reduce the amount used as much as possible.

  Further, when an organic solvent other than water, particularly a hydrophilic / amphiphilic solvent having a high boiling point, is contained in the aqueous dispersion, the aqueous dispersion may remain in the dried coating film and increase the amount of extraction into water. For example, solvents such as ethylene glycol and cellosolve. For this reason, the amount of the hydrophilic or amphiphilic solvent in the aqueous dispersion is preferably 5% by weight or less, more preferably 1% by weight or less. Further, in the production process of the aqueous dispersion, it is preferable not to use a hydrophilic or amphiphilic solvent having a boiling point of 100 ° C. or higher, more preferably not to use a hydrophilic or amphiphilic solvent having a boiling point of 100 ° C. or higher. It is.

  Furthermore, when the aqueous dispersion of the present invention is stored, it is desirable that the environment is such that decomposition does not occur. It is desirable to avoid placing it in an environment of 80 ° C. or more for over a week or in a place exposed to light. A small amount of a stabilizer such as a radical scavenger or an ultraviolet absorber may be added. When a chlorinated polyolefin is used as the polyolefin, it is desirable to add a hydrochloric acid scavenger such as an epoxy compound or hydrotalcite because it tends to decompose and cause dehydrochlorination.

[2] Water-based paint The water-based paint of the present invention is characterized by containing the above-mentioned aqueous dispersion of modified polyolefin. The water-based paint refers to a paint obtained by dispersing or dissolving a resin or pigment in a solvent containing water as a main component (water is 80% by weight or more). Preferably, the amount of water in the solvent is 90% by weight or more, more preferably 95% by weight or more.
As the water-based paint of the present invention, the above-mentioned aqueous dispersion may be used as it is in the case of a clear coat or the like that does not require the addition of a pigment, but depending on the purpose, other resins and pigments, various additions An agent or the like can be added. However, the solid content of the modified polyolefin aqueous dispersion with respect to the solid content of the aqueous coating material of the present invention is preferably 10% by weight or more. This is to obtain high adhesion to the polyolefin resin molded body. More preferably, it is 15 weight% or more. The solid content of the modified polyolefin aqueous dispersion with respect to the solid content of the water-based paint may be 100% by weight, but is usually 80% by weight or less, preferably 50% by weight or less. This is because the properties of the resulting coating film, specifically the strength, water resistance, weather resistance, abrasion resistance, solvent resistance, etc. of the coating film are sufficient. The solid content of the modified polyolefin aqueous dispersion relative to the solid content of the aqueous paint is the weight of the modified polyolefin in the total solid content contained in the aqueous paint.

[2-1] Combined use of other resins In the water-based paint of the present invention, a water-soluble resin or a resin that can be dispersed in water may be mixed and used as necessary within a range that does not significantly impair the effects of the present invention. it can. For example, it is effective for improving the appearance of the coating (glossing or matting) and reducing tackiness. A resin that can be dispersed by using a small amount of a surfactant may be used, but the effect of the present invention is limited to a range that is not significantly impaired. As the water-soluble resin, for example, resins such as those listed as the hydrophilic polymer (B) can be used. For example, an aqueous solution obtained by dissolving these resins in water can be mixed with the aqueous dispersion of the present invention to obtain an aqueous paint. it can.

Examples of the resin that can be dispersed in water include acrylic resin, polyepoxy resin, polyester resin, polyurethane resin, melamine resin, and alkyd resin. For example, an aqueous dispersion obtained by emulsifying and dispersing these resins and a modified polyolefin aqueous dispersion may be mixed.
The total resin content in the water-based paint is preferably such that the weight ratio of the modified polyolefin, the total amount of the other resins, and water is 5:95 to 60:40. That is, the total amount of the modified polyolefin and the other resin is preferably 5 parts by weight or more with the total amount of the modified polyolefin, the other resin and water being 100 parts by weight. This is to improve workability such as coating and heat curing. More preferably, it is 10 parts by weight or more, and further preferably 15 parts by weight or more. However, the total amount is preferably 60 parts by weight or less. This is to make the viscosity moderate, to improve the coating property, and to improve the coating property to gold. More preferably, it is 55 weight part or less, More preferably, it is 50 weight part or less.

Even when these resins are emulsified into a dispersion to obtain a dispersion, a surfactant may be used as necessary within a range not significantly impairing the effects of the present invention. As the surfactant, for example, those described in [1-5] can be used.
In this case, the surfactant content of the water-based paint is preferably 10 parts by weight or less with respect to 100 parts by weight of the total resin amount (the total amount of the modified polyolefin and the other resin). More preferably, it is 5 parts weight or less, More preferably, it is 2 parts weight or less. Most preferably, it is substantially free of surfactant. “Substantially free of surfactant” means less than 0.5 parts by weight per 100 parts by weight of the modified polyolefin.
The other resin used in combination with the aqueous paint is preferably at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, and epoxy resin.

[2-1-1] Acrylic resin The acrylic resin of the present invention is not particularly limited as long as it is a (meth) acrylic polymer, but is a homopolymer or copolymer of acrylic acid and / or its ester, methacrylic acid. And / or a homopolymer or copolymer of an ester thereof. In addition, (meth) acryl refers to acryl and / or methacryl.

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

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

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

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

Although it does not specifically limit as a polymerization method for manufacturing the above acrylic resins, For example, methods, such as solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, can be used.
In order to emulsify the acrylic resin obtained by solution polymerization and bulk polymerization into an aqueous emulsion, it is necessary to emulsify and disperse in the presence or absence of the solution with mechanical force such as a colloid mill. The residual solvent may be distilled off under reduced pressure or atmospheric pressure. If emulsion polymerization or suspension polymerization is used, the polymer can be obtained directly as an aqueous emulsion.

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

[2-1-2] Polyurethane resin The urethane resin of the present invention is not particularly limited. For example, (i) a component containing an average of two or more active hydrogens in one molecule and (ii) many A urethane polymer obtained by reacting a polyvalent isocyanate component, or an isocyanate group-containing prepolymer obtained by reacting the above components (i) and (ii) under an excess of isocyanate groups and a chain extender such as a diol And a urethane polymer obtained by the reaction. These urethane polymers may contain an acid component (acid residue).

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

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

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

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

(4) Polyether ester diol: (anhydrous) dicarboxylic acid as exemplified in the above (3), an ether group-containing diol (polyether diol or diethylene glycol of (2) above) or a mixture of this with another glycol And a product obtained by reacting an alkylene oxide in addition to, for example, a polytetramethylene glycol-adipic acid condensate.
(5) Polycarbonate diol: General formula HO-R- (OC (O) -O-R) x-OH (wherein R is a saturated fatty acid diol residue having 1 to 12 carbon atoms, x is a molecular The compound etc. which show the number of repeating units, and are the integers of 5-50 normally.). These include a transesterification method in which a saturated aliphatic diol and a substituted carbonate (diethyl carbonate, diphenyl carbonate, etc.) are reacted under the condition that the hydroxyl group is excessive, the saturated aliphatic diol and phosgene are reacted, or as necessary. Then, it can be obtained by a method of further reacting with a saturated aliphatic diol.

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

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

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

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

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

[2-1-3] Polyester Resin The polyester resin of the present invention is not particularly limited. Acids and / or anhydrides thereof and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol, or ether group-containing diols ( And polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like).

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

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

[2-1-4] Epoxy Resin The epoxy resin of the present invention is not particularly limited as long as it is a polymer having one or more epoxy groups in one molecule. For example, polyhydric phenol is reacted with epichlorohydrin in the presence of alkali. Examples thereof include polyhydric glycidyl ethers of phenol that can be produced by the above, and epoxy group-containing polymers obtained by reacting such polyhydric glycidyl ethers of phenol with the above polyhydric phenols.

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

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

An aqueous dispersion of an epoxy resin can be obtained by emulsifying these in the presence or absence of a surfactant. Although the manufacturing method is not specifically limited, it can manufacture according to the manufacturing method of the aqueous dispersion of the above-mentioned acrylic resin.
As a typical product available as a commercial product, a de novolak type epoxy resin obtained by adding epichlorohydrin to a phenol novolac resin and forcibly emulsified with a surfactant (emulsifier) is a denar EM150 manufactured by Nagase Chemtech Co., Ltd. Epiretz 6006W70, 5003W55 manufactured by Japan Epoxy Resin Co., Ltd., WEX-5100 manufactured by Toto Kasei Co., Ltd., and the like.

Similarly, bisphenol type epoxy resin obtained by adding epichlorohydrin to bisphenol was forcibly emulsified with an emulsifier, Nagase Chemtech Co., Ltd. DECONAL EM101, EM103, Japan Epoxy Resin Co., Ltd. Epiletts 3510W60, 3515W6, 3522W60, 3540WY55 etc. are mentioned.
Further, as an alkyl type epoxy resin in which epichlorohydrin is added to a polyol such as sorbitol, pentaerythritol, glycerin, etc., Denars EX-611, EX-614, EX-411, EX-313 manufactured by Nagase Chemtech Co., Ltd. and the like can be mentioned.

[2-2] Addition of pigment A pigment can be added to the aqueous paint of the present invention.
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 water-based paint is preferably 10 parts by weight or more with respect to 100 parts by weight of the resin (total amount of modified polyolefin and other resin). More preferably, it is 50 parts by weight or more. However, it is preferably 400 parts by weight or less, and more preferably 200 parts by weight or less. As the addition amount is larger than the lower limit value, the color developability and the hiding property tend to be higher, and as the addition amount is smaller than the upper limit value, the adhesion, moisture resistance and oil resistance tend to be higher.

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

[2-3] Other Additives The water-based paint of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; colorants such as titanium oxide and organic pigments; conductivity imparting agents such as carbon black and ferrite, dyes and leveling agents Various additives such as an antifoaming agent, a thickener, an antiseptic, a fungicide, a rust inhibitor, and a wetting agent may be blended and used.

Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
To further improve the performance of various coatings such as water resistance and solvent resistance. The crosslinking agent can be added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin in the aqueous paint. 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.

  A hydrophilic organic solvent other than water can be added to the water-based paint of the present invention for the purpose of increasing the drying speed or obtaining a surface with a good finish. Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, and ethers thereof. In addition, organic or inorganic compounds other than those described above can be added to the aqueous paint as long as the stability of the aqueous paint is not impaired.

  The water-based paint of the present invention can be used as a paint for forming the outermost surface layer of a polyolefin resin molded body to be described later. In particular, it is effective as a paint for so-called one-coat coating, in which the outermost surface layer is in direct contact with the molded body. For example, it can be used for paints for automobiles such as automobile interiors and exteriors, paints for home appliances such as mobile phones and personal computers, and paints for building materials.

[3] Laminate In the present invention, the outermost surface layer is formed by applying the above-mentioned water-based paint onto the polyolefin resin molded body and heating. Arbitrary layers such as a primer layer and an underlayer may be formed between the molded body and the outermost surface layer, but the present invention is most effective when applied to a laminate in which the outermost surface layer is in direct contact with the molded body. Is expensive.
The outermost surface layer substantially forms the outermost surface layer over a long period of time. For example, even if a wax layer coated with wax or a layer that can be easily peeled is formed on the coating layer, these wax layers are not the outermost surface layer, but the outermost surface layer is a coating layer. It is.

[3-1] Method for Producing Laminate The method for forming the outermost surface layer by applying a water-based paint on a polyolefin resin molded body and heating is not particularly limited, and known methods can be used. For example, a method of applying a water-based paint by a spray, a method of applying by a roller, a method of applying by a brush, and the like can be mentioned.

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

The thickness of the resin layer to be laminated (after curing) can be appropriately selected depending on the material and shape of the substrate, the composition of the paint used, etc., but is usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm. That's it. However, it is usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less.
The laminate obtained in this manner can be used for various applications such as for automobiles, home appliances, and building materials. The substrate may be in any shape, such as a film, sheet, or plate.

  The water-based paint of the present invention can be applied to a crystalline olefin polymer molded body (base material) to form a coating film. Examples of the olefin polymer as a base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene, and other olefin polymers, ethylene / propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, propylene-based polymers are preferably used. Also, molded articles made of polypropylene and synthetic rubber, molded articles made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded articles such as bumpers for automobiles, and for steel plates and electrodeposition treatment It can also be used for surface treatment of steel plates and the like.

The molded article to which the water-based paint of the present invention is applied is obtained by molding the above-mentioned various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be.
A coating film with good adhesion can also be formed when these molded bodies are blended with inorganic fillers such as talc, zinc white, glass fiber, titanium white, and magnesium sulfate, and pigments.

[3-2] Polyolefin-based resin molded body The polyolefin-based resin molded body used in the present invention is usually a molded body of crystalline polyolefin, and various known polyolefins can be used. Although not particularly limited, for example, ethylene or A homopolymer of propylene, a copolymer of ethylene and propylene, ethylene or / and propylene and other comonomers such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, and A copolymer with an α-olefin comonomer having 2 or more carbon atoms such as norbornene, or two or more kinds of copolymers of these comonomers can be used.

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

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

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

Here, the propylene / ethylene block copolymer is composed of a crystalline polypropylene part (a unit part) and an ethylene / propylene random copolymer part (b unit part).
The a unit is usually obtained by homopolymerization of propylene, and in some cases, by copolymerizing a small amount of other α-olefin with propylene.
The MFR of the polypropylene homopolymer of a unit part is preferably 10 g / 10 min or more, more preferably 15 g / 10 min or more, still more preferably 20 g / 10 min or more, particularly preferably 40 g / 10 min or more. . However, it is preferably 500 g / 10 min or less, more preferably 400 g / 10 min or less, still more preferably 300 g / 10 min or less.

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

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

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

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

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

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

[3-3] Inorganic filler component The polyolefin resin molded product used in the present invention may contain an inorganic filler component. In particular, mechanical properties such as bending elastic modulus and rigidity of the molded body can be improved by blending the crystalline polyolefin with an inorganic filler component.

  Specifically, plate fillers such as talc, mica and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber and zonolite; potassium titanate, magnesium Needle-shaped fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Granular fillers; balun fillers such as glass balloons; Inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate can also be used. Of these, talc, mica, glass fiber, and whisker are preferable from the balance between physical properties and cost, and talc, mica, and glass fiber are more preferable.

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

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

An inorganic filler component may be used individually by 1 type, and may be used in combination of 2 or more type.
Hereinafter, preferred fillers will be described in detail.

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

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

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

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

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

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

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

[3-4] Elastomer component When the polyolefin-based resin molded body used in the present invention is a crystalline polyolefin molded body, an elastomer component can be further contained. Thereby, the impact strength of the molded product can be improved.
Examples of the elastomer component include ethylene-α-olefin random copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene-α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Polymer rubber; ethylene-α-olefin-nonconjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM); hydrogenated product of styrene-butadiene-styrene triblock (SEBS), styrene -Styrene-containing thermoplastic elastomer such as hydrogenated product (SEPS) of isoprene-styrene triblock body can be exemplified.

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

[3-5] Other components In addition to the above, the polyolefin-based resin molded product can contain any additive or compounding component as long as the effects of the present invention are not significantly impaired. Specifically, pigments for coloring, antioxidants such as phenols, sulfurs and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, dispersion Agents, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, and other resins such as polyethylene resins.

[3-6] Method for Producing Polyolefin-Based Resin Molded Body Various components are blended in the above-described resin as necessary, and mixed and melt-kneaded. The kneading method is not particularly limited, and the polyolefin of the present invention is obtained by kneading and granulating using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader. A thermoplastic resin composition constituting the resin-based molded article is obtained. In order to improve the dispersion of each component, a twin screw extruder is preferably used.

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

[3-7] Use of Laminate The laminate of the present invention is excellent in coating film adhesion and further has a physical property balance excellent in rigidity and impact resistance. Moreover, since the coating layer which comprises the outermost surface layer of a laminated body does not produce bleeding out easily, it is excellent also in an external appearance.
Therefore, the laminate of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, has sufficient performance for practical use as thinned, highly functional, and enlarged parts / materials. .
For example, automobile parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tanks, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat lids, water tanks and other toiletry parts, It can be used as a molding material for various industrial parts such as parts around the bathroom such as a bathtub, bathroom wall, ceiling, and drain pan.

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

(2) Propylene content The propylene content [P] in the propylene-butene copolymer was measured by a 13C-NMR spectrum measurement method using an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a pulse angle of 90 °, a pulse interval of 10 seconds, and an integration count of 6000.
The chemical shift and content of propylene and butene are described in J. Org. C. Randall, Macromolecules, 11, 592 (1978) was used for calculation.

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

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

(3) -2 Method for measuring molecular weight in terms of polystyrene First, 5 mg of a sample is collected in a 10 ml vial, 5 g of tetrahydrofuran containing 250 ppm of BHT is added as a stabilizer, and completely dissolved at 50 ° C. After cooling to room temperature, the mixture was filtered through a filter having a pore diameter of 0.45 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed using Tosoh Corp. GPC HLC-8020 equipped with a guard column TSK guard column H _XL- H to TSK gel GMH _XL- L (30 cm × 2) as a column. Measurement conditions were as follows: injection volume of sample solution: 50 μl, column temperature: 40 ° C., solvent: tetrahydrofuran, flow rate: 1.0 ml / min.
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.

(4) Graft rate 200 mg of polymer and 4800 mg of chloroform are 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).

(5) Dispersion particle diameter It measured using Microtrack UPA (model 9340 batch type dynamic light scattering method / laser Doppler method) by Nikkiso Co., Ltd. Measured with a dispersion time of 0.9 kg / m ³ , a particle shape of a true sphere, a particle refractive index of 1.50, a dispersion medium of water, and a dispersion medium of 1.33, with a measurement time of 120 seconds. Then, as a volume conversion, 50% particle diameter and 90% particle diameter were obtained from the smaller particle diameter.

(6) Measurement of extraction amount with water at 40 ° C. The modified polyolefin aqueous dispersion is placed in a 5 cm × 5 cm box made of release paper, dried at 90 ° C. under normal pressure for 3 hours or more, and a film having a thickness of about 400 μm. A modified polyolefin dried coating film was obtained. After cutting this to about 5 mm × 5 mm, 1 g was taken and placed in a glass bottle, and 19 g of distilled water was added to prepare a sample.

The lid of the glass bottle was closed and left in a constant temperature apparatus at 40 ° C. for 10 days. Then, the taken-out sample was filtered with the 400 mesh metal-mesh, and it isolate | separated into solid and water. The water after filtration was dried at 100 ° C. for 3 hours or longer, and the weight [W grams] of the remaining solid content was measured.
The amount extracted into water at 40 ° C. was obtained from the following equation.
[Amount of extraction into water at 40 ° C. (% by weight)] = [Solid weight remaining after drying water after extraction (W grams)] / [Weight of modified polyolefin dry coating film used (1 gram)] × 100

(7) Bleed-out The prepared laminate is allowed to stand for 24 hours or more at 25 ° C., then left in a constant temperature room at 40 ° C. for 4 days, and the appearance is visually and ablated to bleed the surfactant onto the surface of the coating film. The presence or absence and the state of out were determined according to the following criteria.
○: No bleed-out of surfactant △: Slightly bleed-out of surfactant ×: Surfactant is bleed-out and sticky when touched with a finger

(8) Adhesiveness After the prepared laminate was allowed to stand at 25 ° C. for 24 hours or longer, a test piece with a grid pattern was prepared from the laminate according to the grid pattern test method described in JIS K 5400. After the cellophane tape (Nichiban Co., Ltd. product) was applied to the coating film, it was peeled in the direction of 90 degrees. The number of grids that were not peeled out of the grid 25 was evaluated.

(9) Moisture resistance The prepared laminate was allowed to stand at 25 ° C. for 24 hours or more, and then left for 4 days under conditions of 50 ° C. and 95% RH. The number of grids that were not peeled was evaluated.

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

To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd.) was collected, 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- 1-Azulenyl) hafnium 131 mg (57 μmol) in toluene was added, and the mixture was stirred at room temperature for 10 minutes to obtain a catalyst slurry (see JP-A 2004-002310 for the method for producing the catalyst).

  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 L. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 67 ° C., and the stirring was continued at the same temperature for 2 hours while keeping the total pressure at the time of polymerization constant at 0.65 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, 11 kg (1.5 kg propylene polymer) of a 13.5 wt% propylene polymer toluene solution was obtained. The weight average molecular weight Mw of the obtained polypropylene was 191,000 (in terms of polypropylene), and the stereoregularity [mmmm] was 45.8%.

(1-2) Production of maleic anhydride-modified polypropylene In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 650 g of toluene and 350 g of polypropylene obtained in (1-1) were placed, and the inside of the container was filled with nitrogen gas The temperature was raised to 110 ° C. After heating, 21 g of maleic anhydride was added, 7 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) 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 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 as maleic anhydride groups, 0.3 mmol as reactive groups). / G). Moreover, the weight average molecular weight Mw was 170,000 (polystyrene conversion).

(1-3) Production method of modified polyolefin aqueous dispersion 30 g of maleic anhydride-modified polypropylene synthesized in (1-2) (content of maleic anhydride groups) in a glass flask equipped with a reflux condenser, a thermometer and a stirrer 4.5 mmol) and 60 g of toluene were added, and the temperature was raised to 110 ° C. to complete dissolution. Next, 4.5 g (4.5 mmol, 100 parts by weight of polyolefin (A) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) Solution corresponding to 15 parts by weight of the hydrophilic polymer (B) was dissolved in 10 g of toluene and reacted at 70 ° C. for 1 hour.

Further, 0.4 g (4.5 mmol) of morpholine was added and reacted at 70 ° C. for 1 hour.
Next, after cooling the reaction liquid temperature (internal temperature) to 60 ° C., a solution in which 108 g of isopropanol and 27 g of water were mixed was added dropwise over 1 hour with stirring. A pale yellow, hazy liquid was obtained. Further, a mixed solution of 30 g of isopropanol and 160 g of water was dropped over 1 hour while maintaining the internal temperature of 60 ° C., and a translucent yellow liquid was obtained.

  Subsequently, the internal temperature was cooled to 40 ° C., and the distillation was started at a pressure of 0.02 MPa. Further, the pressure was gradually reduced from 0.02 MPa to 0.004 MPa, and toluene, isopropanol and water were distilled off until the solid content became 30% by weight to obtain a pale yellow translucent aqueous dispersion. As a result of measuring the dispersed particle size, the 50% particle size was 68 nm, and the 90% particle size was 102 nm.

[Production Example 2]
(Melt modification process)
Super mixer of 200 kg of propylene-butene copolymer (Mitsui Chemicals, Tuffmer XM7070, weight average molecular weight 240,000 (polypropylene equivalent), Mw / Mn = 2.2, propylene content 74 mol%) and maleic anhydride 5 kg After dry blending, perbutyl I was fed by a liquid-feed pump halfway using a twin screw extruder (TEX54αII manufactured by Nippon Steel Co., Ltd.) to 1 part by weight with respect to 100 parts by weight of propylene-butene copolymer. The mixture was kneaded under the conditions of a cylinder temperature of the kneading section of 200 ° C., a screw rotation speed of 125 rpm, and a discharge amount of 80 kg / hour to obtain a pellet-shaped product.

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

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

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

(Emulsification process)
Next, 129 g of toluene was added to the solution for dilution, and then tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Irganox 1010 manufactured by Ciba Specialty Chemicals) ) 0.075 g was added. The jacket temperature (external temperature) was lowered to 75 ° C., 15 g of isopropanol was further added and stirred for 1 hour, and then 600 g of hot water at 70 ° C. was added and stirred. After stirring for 15 minutes, the mixture was allowed to stand to separate into a toluene solution phase at the top and a hot water phase at the bottom and two phases, so warm water was extracted from the bottom extraction valve. After the washing operation with warm water was repeated once more, a solution of 15 g (15 mmol) of Jeffamine M-1000 in 390 g of isopropanol was added dropwise to the toluene solution over 1 hour. Further, an aqueous solution in which 1.5 g (15 mmol) of 90% aqueous solution of 2-amino-2-methyl-1-propanol (AMP90) was dissolved in 90 g of water was added.

  A process of adding a Dean-Stark tube between the reflux condenser and the flask, depressurizing the obtained liquid, distilling 90 g of the solvent, and adding 90 g of water was repeated 5 times. Thereafter, 60 g of water was further added, and toluene, isopropanol and water were distilled off under reduced pressure until the solid content became 30% by weight to obtain a white aqueous dispersion. As a result of measuring the dispersed particle size, the 50% particle size was 42 nm, and the 90% particle size was 80 nm.

[Production Example 3]
Melt modification was performed in the same manner as in Production Example 2 to obtain a maleic anhydride-modified propylene-butene copolymer having a maleic anhydride group content of 0.8% by weight and a weight average molecular weight of 156,000.
Next, after a reflux condenser, a thermometer, a nitrogen gas blowing tube, and a stirrer were installed in a 1 L glass flask, 200 g of the maleic anhydride-modified propylene-butene copolymer and 200 g of toluene were charged and 110 g of nitrogen gas was blown. The mixture was heated and stirred until the temperature reached 0 ° C.
After raising the temperature, 10 g of maleic anhydride and 3.0 g of perbutyl I were added, and thereafter this operation was repeated 3 times every 30 minutes (4 times in total), and then the reaction was continued by stirring at the same temperature for 7 hours.

After completion of the reaction, the internal temperature was cooled to 50 ° C., and 600 g of acetone was added dropwise over about 1 hour to obtain a pale red suspension. After removing the liquid with a suction filter, the remaining white solid was suspended in 500 g of acetone and stirred for 30 minutes. After removing the liquid again with a suction filter, it was placed in a vat coated with Teflon (registered trademark) and dried in a vacuum dryer at 60 ° C. to obtain a modified polymer.
The content (graft ratio) of maleic anhydride groups of this modified polymer is 5.8% by weight (0.58 mmol / g as maleic anhydride groups and 1.16 mmol / g as carboxylic acid groups), and the weight average molecular weight is 89 The number average molecular weight was 44,000 (both in terms of polystyrene).

150 g of this maleic anhydride-modified propylene-butene copolymer and 500 g of THF were charged into a 2 L glass flask equipped with a reflux condenser, a thermometer, and a stirrer, heated, and completely dissolved at 65 ° C. To the obtained solution, 33 g (0.37 mol) of morpholine was added and stirred at the same temperature for 30 minutes. Next, 500 g of water was added over 2 hours to obtain a pale yellow solution.
The obtained liquid was decompressed at a jacket temperature (outside temperature) of 60 ° C., and THF and a part of water were distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 30% by weight. As a result of measuring the dispersed particle size, the 50% particle size was 41 nm, and the 90% particle size was 63 nm.

<Example>
[Example 1]
A substrate obtained by injection molding of automobile grade grade polypropylene into 70 mm × 150 mm × 3 mm was prepared, and the substrate surface was wiped with isopropyl alcohol. Here, as the water-based paint, the modified polyolefin aqueous dispersion obtained in Production Example 1 was spray-coated so that the coating amount was about 30 g / m ² . The coated substrate was dried in a safe ben dryer at 80 ° C. for 30 minutes to produce a laminate.
Adhesion, bleed out, and moisture resistance were evaluated. The results are shown in Table-1.

[Examples 2 and 3]
A laminate was produced in the same manner as in Example 1 except that the aqueous dispersions of Production Examples 2 and 3 were used as the aqueous paint. The evaluation results are shown in Table-1.

[Comparative Example 1]
A laminate was produced in the same manner as in Example 1 except that chlorinated PP emulsion Super Clone E-673 (manufactured by Nippon Paper Industries Co., Ltd., solid content: 30% by weight) was used as the aqueous paint. The evaluation results are shown in Table-1.

[Comparative Example 2]
A laminate was produced in the same manner as in Example 1 except that chlorinated PP emulsion hardene EH-801 (manufactured by Toyo Kasei Co., Ltd., solid content: 30% by weight) was used as the aqueous paint. The evaluation results are shown in Table-1.

[Example 4]
As an aqueous paint, the modified polyolefin aqueous dispersion of Production Example 1 and the aqueous acrylic resin dispersion Rikabond ES-20 (manufactured by Chuo Rika Kogyo Co., Ltd., solid content concentration: 44%, resin Tg: 47 ° C., average particle diameter: 0.10 μm) A laminate was produced in the same manner as in Example 1 except that the 1: 1 mixture (weight ratio) was used.
The solid content of the modified polyolefin aqueous dispersion is 50% by weight with respect to the solid content of the aqueous paint.
Adhesion, bleed out, and moisture resistance were evaluated. The evaluation results are shown in Table-2.

[Examples 5 and 6]
A laminate was produced in the same manner as in Example 4 except that the aqueous dispersions of Production Examples 2 and 3 were used in place of the aqueous dispersion of Production Example 1. The evaluation results are shown in Table-2.

[Comparative Example 3]
A laminate was produced in the same manner as in Example 4 except that chlorinated PP emulsion Supercron E-673 (manufactured by Nippon Paper Industries Co., Ltd., solid content: 30% by weight) was used instead of the aqueous dispersion of Production Example 1. . The evaluation results are shown in Table-2.

[Comparative Example 4]
A laminate was produced in the same manner as in Example 4 except that chlorinated PP emulsion hardene EH-801 (manufactured by Toyo Kasei Co., Ltd., solid content 30% by weight) was used instead of the aqueous dispersion of Production Example 1. . The evaluation results are shown in Table-2.

Claims (9)

A method for producing a laminate in which a water-based paint is applied to a polyolefin resin molded body and heated to form an outermost surface layer, wherein the water-based paint contains an aqueous dispersion of non-chlorine-modified polyolefin, (1) The solid content of the aqueous dispersion is 50% by weight or less and 5% by weight or more, (2) no surfactant is contained in the aqueous dispersion, or an alkyl group, alkenyl group having 4 to 30 carbon atoms, A surfactant having a group selected from the group consisting of an alkylaryl group and an alkenylaryl group as a hydrophobic group is contained in an amount of less than 0.5 part by weight based on 100 parts by weight of the non-chlorine-modified polyolefin; (3) It is a polymer (C) formed by bonding a hydrophilic polymer (B) or an acidic group to a polyolefin (A) having an average molecular weight Mw of 10,000 or more, and the non-chlorine modified polyolefin A method for producing a laminate, wherein an extract obtained by extracting a dry coating film of an aqueous dispersion with water at 40 ° C. is 10% by weight or less of the weight of the dry coating film. The manufacturing method of the laminated body of Claim 1 with which this polyolefin resin molding and this outermost surface layer are directly contacting. The manufacturing method of the laminated body of Claim 1 or 2 whose solid content of this non-chlorine modified polyolefin aqueous dispersion is 10 to 100 weight% with respect to the solid content of this aqueous coating material. The method for producing a laminate according to any one of claims 1 to 3, wherein the polyolefin (A) is a propylene-based polymer having a propylene content of 50 mol% or more. The extract obtained by extracting the dry coating film of the non-chlorine-modified polyolefin aqueous dispersion with water at 40 ° C. is an aqueous dispersion of non-chlorine-modified polyolefin that is 10% by weight or less of the weight of the dry coating film, (1) The solid content of the aqueous medium is 50% by weight or less and 5% by weight or more, (2) the aqueous dispersion does not contain a surfactant, or an alkyl group or alkenyl having 4 to 30 carbon atoms A surfactant comprising a group selected from the group consisting of a group, an alkylaryl group, and an alkenylaryl group as a hydrophobic group, containing less than 0.5 parts by weight with respect to 100 parts by weight of the non-chlorine-modified polyolefin, (3) the non-chlorine-modified polyolefin Includes the aqueous dispersion which is a polymer (C) formed by bonding a hydrophilic polymer (B) or an acidic group to a polyolefin (A) having a weight average molecular weight Mw of 10,000 or more , An aqueous dispersion of non-chlorine-modified polyolefin for forming an aqueous coating that forms the outermost surface layer of a laminate including a resin-based molded product. Including water nature Chikarada according to claim 5, water-based paints. The water-based paint according to claim 6 , wherein the polyolefin resin molded product and the outermost surface layer are in direct contact. The water-based paint according to claim 6 or 7 , wherein the solid content of the non-chlorine-modified polyolefin aqueous dispersion is 10 to 100% by weight with respect to the solid content of the water-based paint. The water-based paint according to any one of claims 6 to 8, wherein the polyolefin (A) is a propylene-based polymer having a propylene content of 50 mol% or more.