JP2010270223A - Active energy ray-curable aqueous resin composition, paint, ink and laminate containing the same - Google Patents

Abstract

The present invention provides an active energy ray-curable aqueous dispersion, paint, and ink that have excellent adhesion to an olefin polymer and are useful as a paint.
[MEANS FOR SOLVING PROBLEMS] 1) A polymer (C) in which a hydrophilic polymer (B) is bonded to a polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio). ), 2) a compound (D) having 2 or more active energy ray-curable unsaturated bonds in one molecule, 3) water, and a weight ratio of the polymer (C) to the compound (D) of 95: The active energy ray-curable aqueous resin composition, wherein the weight ratio of the total amount of the polymer (C) and the compound (D) to water is 5:95 to 90:10. object.
[Selection figure] None

Description

  The present invention relates to an active energy ray-curable aqueous resin composition containing a polymer obtained by modifying a polyolefin, a coating material and ink containing the same, and a laminate obtained therefrom.

  Polyolefins such as propylene polymers and propylene / α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so automobiles, home appliances, food packaging, etc. Is used in a wide range of fields. However, such polyolefins generally have a low polarity because they do not have a polar group in the molecule, and it is difficult to paint or bond them.

For this reason, various methods have been tried, such as chemically treating the surface of a molded product of polyolefin with a chemical or the like, and oxidizing the surface of the molded product by a method such as corona discharge treatment, plasma treatment, or flame treatment. Yes. However, these methods require not only a special apparatus but also an effect of improving paintability and adhesiveness.
Therefore, so-called chlorinated polypropylene, acid-modified propylene / α-olefin copolymers, and acid-modified chlorinated polypropylene have been developed as a device for imparting good paintability and adhesion to polyolefin by a relatively simple method. It was. Such a modified polyolefin is applied as a surface treatment agent, an adhesive, a paint or the like to the surface of the polyolefin molded body.

The modified polyolefin is usually applied in the form of a solution of an organic solvent or a dispersion in water. In recent years, an aqueous dispersion is preferably used from the viewpoint of health and safety and environmental pollution.
For example, an aqueous resin composition in which acid-modified chlorinated polyolefin is made aqueous using a surfactant and a basic substance (Patent Document 1), or acid-modified polyolefin is made aqueous using a surfactant and a basic substance Water-based resin composition (Patent Document 2).

On the other hand, in order to improve the water resistance, solvent resistance, and scratch resistance of the coating film, there is a method of improving the strength of the coating film by crosslinking the components of the paint or ink with energy rays such as ultraviolet rays or electron beams.
For example, an aqueous composition containing a compound having an unsaturated double bond and an active energy ray-curable aqueous composition containing a wax component having a melting point of 125 ° C. or higher (Patent Document 3), an unsaturated carboxylic acid, and (meth) An ultraviolet curable coating composition containing an acrylic ester-modified polypropylene copolymer and a photocurable compound (Patent Document 4), a modification having a reaction product of a functionalized polyolefin and an ethylenically unsaturated compound There is a polyolefin composition (Patent Document 5).

JP-A-3-182534 Japanese Patent Laid-Open No. 6-256592 JP 2002-121247 A JP2003-23885A Special table 2004-520474

  However, in the aqueous resin compositions described in Patent Documents 1 and 2, it is necessary to add a large amount of a surfactant in order to reduce the dispersed particle diameter of the polyolefin. As a result, such an aqueous resin composition There is a problem that paints using materials have poor water resistance and solvent resistance. Further, the surfactant may bleed out to the painted surface after coating, resulting in poor appearance, and further improvements are desired. In addition, the compositions described in Patent Documents 3 to 5 contain a large amount of an organic solvent or a large amount of a surfactant even when it is made aqueous. There is a need for improvement.

The present invention is intended to solve the above-mentioned problems, and is excellent in adhesion to an olefin polymer, excellent in water resistance, oil resistance, solvent resistance, and scratch resistance when used as a cured film. An object of the present invention is to provide an active energy ray-curable aqueous resin composition that is useful as an energy ray-curable paint or ink.
In addition, it aims at providing the coating body and ink which contain such an active energy ray curable aqueous resin composition, and the laminated body obtained by hardening this.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polymer obtained by binding a hydrophilic polymer to a polyolefin at a predetermined ratio, a specific compound, and water, an active energy ray curable composition containing a specific ratio. It has been found that the aqueous resin composition has excellent adhesion to a polyolefin substrate, and that the resulting cured film has water resistance, oil resistance and solvent resistance, and has led to the present invention.

  That is, the gist of the present invention is that a polymer obtained by bonding a hydrophilic polymer (B) to a polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio) ( C) The compound (D) having two or more active energy ray-curable unsaturated bonds in one molecule and water are contained, and the weight ratio of the polymer (C) to the compound (D) is 95: 5 to 5 : 95, and the weight ratio of the total amount of the polymer (C) and the compound (D) to water is 5:95 to 90:10. .

The gist of the present invention is that the active energy ray-curable aqueous solution further contains 0.01 to 10 parts by weight of the photoinitiator (E) with respect to 100 parts by weight of the total of the polymer (C) and the compound (D). Resists in resin composition.
Further, the gist of the present invention is that the at least one resin (F) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin is added to the total of the polymer (C) and the compound (D). The active energy ray-curable aqueous resin composition contains 10 to 400 parts by weight with respect to 100 parts by weight.

The gist of the present invention resides in the active energy ray-curable aqueous resin composition in which the polymer (C) has a 50% average particle size of 5.0 μm or less and is dispersed in water.
The present invention also resides in the active energy ray-curable aqueous resin composition, wherein the polymer (C) is a graft copolymer obtained by grafting a hydrophilic polymer (B) to a polyolefin (A).

The gist of the present invention is that the polyolefin (A) is polymerized by a metallocene catalyst, has a melting point of 125 ° C. or less, and is a polypropylene polymer containing a propylene component in an amount of 50 mol% to 100 mol%. It exists in a linear curable aqueous resin composition.
Moreover, this invention exists in the said active energy ray curable aqueous resin composition whose hydrophilic polymer (B) is polyether resin.

The gist of the present invention is that the pigment (G) is further added to the polymer (C) and the compound (D) in total 10.
The active energy ray-curable aqueous resin composition contains 10 to 400 parts by weight with respect to 0 part by weight.
Another gist of the present invention is the active energy ray-curable aqueous resin composition in which the polymer (C) is dispersed in water to obtain a dispersion, and then the compound (D) is dissolved or dispersed in the dispersion. It exists in the manufacturing method of a thing.

Another gist of the present invention resides in an active energy ray curable coating or an active energy ray curable ink comprising the active energy ray curable aqueous resin composition.
Further, another gist of the present invention is that the active energy ray-curable aqueous resin composition, the active energy ray-curable paint, or the previous active energy ray-curable ink is applied onto the thermoplastic resin molded body (H). It exists in the laminated body by which the resin layer is formed by drying and irradiating an active energy ray.

  Since the polymer (C) used in the present invention is excellent in water dispersibility, it has excellent stability with fine dispersed particle size with little addition of surfactant or substantially no addition of surfactant. An aqueous resin composition is obtained. Therefore, the active energy ray-curable aqueous resin composition containing the polymer (C) and the compound (D) having two or more active energy ray-curable unsaturated bonds in one molecule is an interface that has been a problem in the past. There is an advantage that bleeding out due to the active agent can be suppressed, and as a result, a coated product having an excellent appearance can be obtained.

Moreover, the cured film obtained by applying and curing this is excellent in scratch resistance, water resistance, moisture resistance, oil resistance, and chemical resistance. The resulting cured film exhibits good adhesion to polyolefin materials or plastic materials containing polyolefin, etc., and is also formed on difficult-to-adhere substrates such as untreated polypropylene, which are usually difficult to paint or bond. obtain.
Further, when the active energy ray-curable aqueous resin composition of the present invention contains at least one resin (F) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin, The properties of the resin (F) can be improved, specifically, the strength, water resistance, weather resistance, abrasion resistance, solvent resistance, etc. of the cured film can be improved.

  Therefore, the active energy ray-curable aqueous resin composition of the present invention is extremely useful as a paint, ink, surface treatment agent, coating agent, primer, etc. for olefin polymers such as polypropylene. Further, the present invention includes a case where only the specific effect is particularly excellent among the effects.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, (meth) acryl is a general term for acrylic and methacrylic. The same applies to (meth) acryloxy and (meth) acrylate.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.

  In the active energy ray-curable aqueous resin composition of the present invention, the hydrophilic polymer (B) is added to the polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio). A polymer (C) formed by bonding, a compound (D) having two or more active energy ray-curable unsaturated bonds in one molecule, and water, and the weight ratio of the polymer (C) to the compound (D) Is 95: 5 to 5:95, and the weight ratio of the total amount of the polymer (C) and the compound (D) to water is 5:95 to 90:10. It is an aqueous resin composition.

The active energy ray-curable aqueous resin composition of the present invention is not particularly limited in form as long as it contains the polymer (C), the compound (D) and water in the above composition range, but specifically, the polymer (C C) is dispersed in water, and the compound (D) is preferably dispersed in water or dissolved in water.
When the polymer (C) and the compound (D) are both dispersed in water, they may be dispersed by forming separate particles, or they may be dispersed by forming composite particles including both. You may do it.

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. In particular, the compound (D) may be a water-soluble compound.
In the present invention, the production method is not particularly limited as long as the polymer (C) and the compound (D) are dispersed or dissolved in water. For example, there is a method in which the polymer (C) and the compound (D) are each dispersed or dissolved in water and then mixed. In this case, the particles made of the polymer (C) and the particles made of the compound (D) are formed separately and dispersed in water, or the particles made of the polymer (C) are formed and dispersed in water. In addition, an aqueous resin composition in which the compound (D) is dissolved in water is obtained.

Specifically, the polymer (C) is first dispersed in water to obtain a dispersion, and then the compound (D) is dissolved or dispersed in the dispersion to produce an active energy ray-curable aqueous resin composition. It is preferable to do.
Alternatively, there is a method in which the polymer (C) and the compound (D) are mixed by dissolution, kneading or the like and then emulsified and dispersed in water. In this case, an aqueous resin composition in which particles in which the polymer (C) and the compound (D) are combined is dispersed in water is obtained. For example, by allowing the compound (D) to coexist during the production of the polymer (C), particles containing the polymer (C) and the compound (D) can be formed in one particle.

  In the polymer (C) used in the present invention, the hydrophilic polymer (B) is added to the polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio) (that is, the polyolefin (A) A polymer obtained by bonding the hydrophilic polymer (B) with 1 part by weight or more and 300 parts by weight or less) with respect to 100 parts by weight. If the ratio of the hydrophilic polymer (B) is smaller than this range, the polymer (C) does not disperse well in water, and the dispersed particle size tends to agglomerate or separate. On the other hand, when the ratio of the hydrophilic polymer (B) is larger than this range, the adhesion to the polyolefin substrate and the water resistance of the coating film tend to deteriorate.

  Preferably (A) :( B) = 100: 3 or more, more preferably (A) :( B) = 100: 5 or more, more preferably (A) :( B) = 100: 10 or more, Preferably (A) :( B) = 100: 100 or less, more preferably (A) :( B) = 100: 50 or less, and still more preferably (A) :( B) = 100: 30 or less. That is, the hydrophilic polymer (B) is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, still more preferably 10 parts by weight or more, and preferably 100 parts by weight with respect to 100 parts by weight of the polyolefin (A). Part or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less.

The weight ratio of the polymer (C) and the compound (D) contained in the active energy ray-curable aqueous resin composition of the present invention is 95: 5 to 5:95. That is, when the total amount of the polymer (C) and the compound (D) is 100 parts by weight, the amount of the polymer (C) is 5 parts by weight or more and 95 parts by weight or less. When the amount of the polymer (C) is less than 5 parts by weight, the adhesion to the polyolefin-based substrate tends to be insufficient. Preferably it is 10 weight part or more, More preferably, it is 20 weight part or more. When the amount of the polymer (C) is larger than 95 parts by weight, the physical properties of the cured film obtained from such an active energy ray-curable aqueous resin composition, specifically the strength of the cured film, water resistance, weather resistance, There is a tendency that rubbing resistance, solvent resistance and the like are insufficient. Preferably it is 80 weight part or less, More preferably, it is 70 weight part or less.

  The weight ratio of the total amount of the polymer (C) and the compound (D) to water is 5:95 to 90:10. That is, when the total amount of the polymer (C), the compound (D) and water is 100 parts by weight, the total amount of the polymer (C) and the compound (D) is 5 parts by weight or more and 90 parts by weight or less. . When the total amount of the polymer (C) and the compound (D) is less than 5 parts by weight, workability such as coating and heat curing is poor and impractical. Preferably it is 10 weight part or more, More preferably, it is 15 weight part or more. On the other hand, when it is larger than 90 parts by weight, the viscosity of the resulting active energy ray-curable aqueous resin composition becomes too high, the applicability is deteriorated, and it is difficult to form a uniform coating film. Preferably it is 80 weight part or less, More preferably, it is 60 weight part or less.

Each component contained in the active energy ray-curable aqueous resin composition of the present invention will be described in detail below.
As a method for producing a polymer (C) obtained by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) to form a polyolefin (A). These methods include the method (R1) for forming the bonded hydrophilic polymer (B), or the method (R2) for bonding the hydrophilic polymer (B) previously formed by polymerization to the polyolefin (A). Can be appropriately selected according to the type and combination of polyolefin and hydrophilic polymer, the characteristics of the intended polymer (C), and the like. Moreover, as polyolefin (A), polyolefin (A1) which does not have a reactive group, or polyolefin (A2) which has a reactive group can be used.

Hereinafter, each case will be described separately.
(A) Polyolefin The polyolefin (A) used in the present invention includes a polyolefin (A1) having no reactive group or a polyolefin (A2) having a reactive group.
(A1) Polyolefin not having a reactive group As the polyolefin (A1), various known polyolefins and modified polyolefins can be used, and are not particularly limited. For example, ethylene or propylene homopolymer, ethylene and propylene copolymer Polymers, ethylene or / and propylene and other comonomers such as α-olefin comonomers having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, And a copolymer with an alicyclic unsaturated hydrocarbon comonomer such as norbornene, or a copolymer of two or more of these comonomers. These comonomers are preferably comonomers having 2 to 6 carbon atoms. Also, a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, a copolymer of a comonomer such as an aromatic vinyl monomer, a hydrogenated product thereof, a conjugated diene block copolymer, or The hydrogenated product can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 50% by weight or less, preferably 30% by weight or less.

Specific examples of the polyolefin (A1) include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, and chlorinated ethylene-propylene copolymer. Polymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS). Preferably, it is a propylene homopolymer or a copolymer of propylene and another α-olefin, and these may be chlorinated. More preferred are a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer that are substantially free of chlorine. These may be used individually by 1 type and may be used in combination of 2 or more type.

The polyolefin (A1) is preferably polymerized with a metallocene catalyst.
The melting point of the polyolefin (A1) is preferably 125 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 90 ° C. or lower. When the melting point of polyolefin is lower, there is a tendency that high adhesion can be obtained even if the coating film made of the active energy ray-curable aqueous resin composition is dried at a low temperature.

  The polyolefin (A1) is preferably a polypropylene polymer containing a propylene component in an amount of 50 mol% to 100 mol%. The propylene content is more preferably 60 mol% or more, and even more preferably 70 mol% or more. Usually, there exists a tendency for the adhesiveness to the polypropylene base material in the active energy ray-curable aqueous resin composition obtained, so that the content of propylene is high.

  When the polyolefin (A1) is a propylene homopolymer or a polypropylene copolymer, the stereoregularity thereof preferably has an isotactic structure in whole or in part. For example, not only normal isotactic polypropylene but also isotactic block polypropylene, stereo block polypropylene, etc. as described in JP-A-2003-231714 and US Pat. No. 4,522,982 should be used. Can do.

  One preferable form of polypropylene is a homopolymer or copolymer of a stereoblock polypropylene having an isotactic block and an atactic block. Preferably, [mmmm] pentads exhibiting isotactic stereoregularity are in the range of 20% to 90%. A preferable value of the lower limit is 30%, more preferably 35%. A preferable value of the upper limit is 80%, more preferably 70%, and more preferably 60%. As a method for measuring the pentad ratio, the method described in JP-A-2003-231714 can be used. The higher the lower limit value, the lower the stickiness of the coating film and cured film obtained from the active energy ray-curable aqueous resin composition of the present invention, and the lower the upper limit value, the lower the crystallinity and the polymer ( There is a tendency that the preparation of the aqueous dispersion of C) becomes easy.

In addition, examples of generally available polypropylene polymers include “Wintech” and “Wellnex” manufactured by Nippon Polypro, “Toughmer XM” manufactured by Mitsui Chemicals, and “Ricosen PP” manufactured by Clariant. . These are all polypropylene copolymers polymerized with a metallocene catalyst.
The polyolefin (A1) in the present invention preferably has a weight average molecular weight [Mw] of 5,000 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 is 10,000, more preferably 30,000. A more preferable value of the upper limit value is 300,000, and more preferably 200,000. As Mw is higher than the lower limit, the degree of stickiness of the coating film or cured film obtained from the active energy ray-curable aqueous resin composition of the present invention tends to decrease and the adhesion to the substrate tends to increase, and is lower than the upper limit. As the viscosity decreases, the preparation of an aqueous dispersion of the polymer (C) tends to be easy. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

About the manufacturing method of polyolefin (A1) of this invention, if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.
In the case of coordination polymerization, for example, a polymerization method using a Ziegler-Natta catalyst or a polymerization method using a single site catalyst or a Kaminsky catalyst can be used. A preferable production method includes a production method using a single site catalyst. This is because the molecular weight distribution and stereoregularity distribution of single-site catalysts are generally sharp due to the ligand design. Moreover, as a single site catalyst, a metallocene catalyst and a Brookhart type catalyst can be used, for example. 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, and alicyclic aliphatic carbonization such as cyclohexane and methylcyclohexane. Hydrogen, halogenated hydrocarbons such as chloroform and chlorobenzene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as methanol, ethanol, 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 aliphatic hydrocarbons are preferable, and toluene, xylene, hexane, heptane, cyclopentane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type. The polyolefin (A1) may be linear or branched.

(A2) Polyolefin having a reactive group As the polyolefin (A2) having a reactive group, for example, a copolymer obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization. A polymer (A2b) obtained by graft polymerization of a polymer (A2a) or a radically polymerizable unsaturated compound having a reactive group onto a polyolefin can be used.

  The copolymer (A2a) is obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is inserted into the main chain. Copolymer. For example, it can be obtained by copolymerizing an α-olefin such as ethylene, propylene, or butene with an α, β-unsaturated carboxylic acid such as acrylic acid or maleic anhydride or an anhydride thereof. Specific examples of the copolymer (A2a) include an ethylene-acrylic acid copolymer and an ethylene-acrylic acid ester-maleic anhydride copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type. As the manufacturing method, the method described in (A1) can be similarly used.

The polymer (A2b) is a polymer 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. It is. 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.

As polyolefin of this reaction for obtaining a polymer (A2b), the polyolefin (A1) which does not have the above-mentioned reactive group can be used.
Specific examples of the polymer (A2b) include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include modified polypropylene and chlorinated products thereof, acrylic acid-modified ethylene-propylene copolymers and chlorinated products thereof, and acrylic acid-modified propylene-butene copolymers. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used for the graft polymerization can be appropriately selected from ordinary radical initiators, and examples thereof include organic peroxides and azonitriles. Examples of organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. Diacyl peroxides such as oxide, 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 ratio of the radical polymerization initiator and the radical polymerizable unsaturated compound having a reactive group (graft copolymerization unit) is usually radical polymerization initiator: graft copolymerization unit = 1: 100 to 2: 1 (molar ratio). Range. 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 250 ° C. The reaction time is usually about 1 to 20 hours.

  The polyolefin (A2) having a reactive group preferably has a weight average molecular weight [Mw] of 5,000 to 300,000 as measured by GPC and converted by a polystyrene calibration curve. A more preferable value of the lower limit is 10,000, more preferably 30,000. A more preferable value of the upper limit value is 250,000, more preferably 200,000. As Mw is higher than the lower limit value, the stickiness of the coating film or cured film obtained from the active energy ray-curable aqueous resin composition of the present invention tends to decrease, and the adhesion to the substrate tends to increase. The lower the viscosity, the lower the viscosity and the easier the preparation of the aqueous dispersion of the polymer (C). The GPC is measured by a conventionally known method using a commercially available apparatus using tetrahydrofuran (THF) or the like as a solvent.

  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 as a solvent used by manufacture of polyolefin (A1) can be used similarly.

The content of the reactive group in the polyolefin (A2) having a reactive group is preferably in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g per 1 g of polyolefin. A more preferred lower limit is 0.03 mmol / g, particularly preferably 0.05 mmol / g. A more preferred upper limit is 1 mmol / g, and even more preferably 0.5 mmol / g. When the polymer (C) is higher than the lower limit, the amount of the hydrophilic polymer (B) bonded through the reactive group is increased and the hydrophilicity of the polymer (C) is increased. It tends to be smaller, and the lower the upper limit value, the more the adhesiveness to the crystalline polyolefin that is the substrate in the obtained active energy ray-curable aqueous resin composition tends to increase.

  In the present invention, both the polyolefin (A1) having no reactive group and the polyolefin (A2) having a reactive group are combined with the hydrophilic polymer (B), the characteristics of the target polymer (C), etc. The polyolefin (A2) having a reactive group is preferable. 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.

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

As the polyolefin (A2) having a reactive group, either the polymer (A2a) or the polymer (A2b) can be used, but the polymer (A2b) is usually preferable. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).
(B) Hydrophilic polymer In the present invention, the hydrophilic polymer refers to a polymer having an insoluble content of 1% by weight or less when dissolved in water at 25 ° C. at a concentration of 10% by weight. The hydrophilic polymer (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. Usually, it is a compound having a number average molecular weight [Mn] of 300 or more. Moreover, you may have a reactive group.

Specific polymers include, but are not limited to, for example, poly (meth) acrylic resin, polyvinyl alcohol resin, polyether resin, polyvinylpyrrolidone resin, gum arabic, casein, gelatin, dextrin, carboxyl starch, cationized starch, cationized Cellulose, hydroxyethyl cellulose and the like can be used.
Of these, synthetic polymers such as poly (meth) acrylic resin, polyvinyl alcohol resin, polyether resin, and polyvinylpyrrolidone resin, which can easily control the degree of hydrophilicity and have stable characteristics, are preferable. More preferred are acrylic resins such as poly (meth) acrylic resins, polyvinyl alcohol resins, polyether resins, and polyvinylpyrrolidone resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Of these, polyether resins having high hydrophilicity are most preferable.

  The acrylic resin that can be used in the present invention as the hydrophilic polymer (B) 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, a method of radical graft polymerization directly on a polyolefin, an acrylic resin having a reactive group such as a hydroxyl group, an amino group, a glycidyl group, or an (anhydrous) carboxylic acid group, And a method of reacting with a polyolefin having a reactive group.

Preferably, the unsaturated carboxylic acid or its ester or anhydride exhibiting hydrophilicity is preferably (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (dimethyl) ethyl dimethylaminoethyl (meth) acrylate. And (meth) acrylamide.
The polyvinyl alcohol resin used in the present invention is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.

  The polyether resin that can be used in the present invention as the hydrophilic polymer (B) is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with the polyolefin (A) is not limited. For example, a method of ring-opening polymerization of cyclic alkylene oxide in a polyolefin having a reactive group, a polyether polyol or a polyether amine obtained by ring-opening polymerization, etc. And a method of reacting a hydrophilic polymer having a reactive group with a polyolefin having a reactive group.

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

  Further, as the polyetheramine, Jeffamine M series, D series, ED series, Surfonamin L series, etc. manufactured by Huntsman may be used. The hydrophilic polymer (B) used in the present invention preferably has one or more reactive groups capable of reacting with the polyolefin (A) before bonding with the polyolefin (A). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, a dicarboxylic acid monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and it is preferable to 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 hydrophilic polymer (B) may have at least one reactive group, but more preferably 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 (B) 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 preferably has a weight average molecular weight [Mw] of 200 to 200,000 as measured by GPC and converted by a polystyrene calibration curve. A more preferable value of the lower limit value is 300, and more preferably 500. A more preferable value of the upper limit value is 100,000, more preferably 10,000, and particularly preferably 3,000. 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. The lower the upper limit, the lower the viscosity and the aqueous dispersion of the polymer (C). It tends to be easy to prepare. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using THF or the like as a solvent.

The amount of the hydrophilic polymer (B) bonded to the polyolefin (A) is preferably in the range of 0.01 to 5 mmol, ie 0.01 to 5 mmol / g, per 1 g of polyolefin. A more preferred lower limit is 0.03 mmol / g, particularly preferably 0.05 mmol / g. A more preferred upper limit is 1 mmol / g, and even more preferably 0.5 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. The lower the upper limit value, the more the active energy ray-curable aqueous resin composition has a substrate. There is a tendency for adhesion to certain crystalline polyolefins to increase.

  Examples of the polymer (C) obtained by bonding the hydrophilic polymer (B) to the polyolefin (A) include a graft copolymer in which the hydrophilic polymer (B) is graft-bonded to the polyolefin (A), or a polyolefin (A ) And a block copolymer of the hydrophilic polymer (B) containing a state in which the hydrophilic polymer (B) is bonded to one end or both ends of the hydrophilic polymer (B). It is a graft copolymer. The graft copolymer has an advantage that the content of the hydrophilic polymer (B) can be easily controlled, and the content of the hydrophilic polymer (B) can be easily increased as compared with the block copolymer.

The hydrophilic polymer (B) can be bonded to the polyolefin (A) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.
Reactions using reactive groups are those in which both polyolefin (A) and hydrophilic polymer (B) have reactive groups that are reacted to form covalent bonds or ionic bonds. Is done. Examples of this reaction include esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned.

The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted with respect to one equivalent of the dibasic acid or anhydride.
(C) Polymer As a method for producing a polymer (C) by bonding a polyolefin (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the polyolefin (A) to obtain a polyolefin ( There is a method (R1) for forming the hydrophilic polymer (B) bonded to A) or a method (R2) for bonding the previously polymerized hydrophilic polymer (B) to the polyolefin (A). In any case, the polyolefin (A) can be used together with a polyolefin (A1) having no reactive group or a polyolefin (A2) having a reactive group.

(C-1) Production method (R1) of polymer (C)
In this method, the hydrophilic polymer (B) bonded to the polyolefin (A) is obtained by polymerizing the hydrophilic monomer in the presence of the polyolefin (A). As a method for polymerizing the hydrophilic monomer, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic monomer may be copolymerized as long as a hydrophilic polymer can be formed after polymerization.

  Specifically, for example, a hydrophilic radical polymerizable unsaturated compound that is a hydrophilic monomer is polymerized in the presence of a radical polymerization initiator to form a hydrophilic polymer (B) and bonded to the polyolefin (A). There is a way. In this case, polyolefin (A2) having a reactive group may be used as polyolefin (A), but polyolefin (A1) having no reactive group is usually used.

The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples include methacrylic acid dimethylaminoethyl quaternized compounds, vinyl pyrrolidone and the like. Examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate.

  Alternatively, there is a method in which a radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the polyolefin (A), and then modified to obtain a hydrophilic polymer (B). Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. Examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, polyolefin (A2) having a reactive group can be used as polyolefin (A), but polyolefin (A1) having no reactive group is usually used.

  Alternatively, a polyolefin (A2) having a reactive group is used, and the hydrophilic group is obtained by polymerizing a hydrophilic radical polymerizable unsaturated compound or a hydrophilic ring-opening polymerization monomer, which is a hydrophilic monomer, with this reactive group as a starting end. There is a method for obtaining the polymer (B). As the hydrophilic radical-polymerizable unsaturated compound, those described above can be used similarly. Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent mentioned in (A1) can be used similarly.

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

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

As the hydrophilic monomer that can be used at this time, various hydrophilic monomers listed in (C-1) can be used in the same manner. Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted as a solvent used by manufacture of polyolefin (A1) can be used similarly.

(C-3) Aqueous dispersion of polymer (C) In producing the active energy ray-curable aqueous resin composition of the present invention, when producing an aqueous dispersion of polymer (C), the production method is particularly Although it is not limited, for example, a method of adding a solvent other than water to the aforementioned polymer (C), heating and dissolving as necessary, and then adding water to form a dispersion, polymer (C) melts Examples of the method include a method of adding water after melting at a temperature or higher to obtain a dispersion. The former is preferred.

In the method of adding a solvent other than water and adding water after heating and dissolving as necessary, an aqueous dispersion having a small 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 solvents other than water to the entire solvent including water in the aqueous dispersion is usually 5% by weight or less. It is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 1% by weight or less.

  Examples of the solvent other than water used in the present method include aromatic hydrocarbons such as toluene, xylene, and t-butylbenzene, aliphatic hydrocarbons such as hexane, octane, and decane, and fats such as cyclohexane and methylcyclohexane. Cycloaliphatic hydrocarbons, halogenated hydrocarbons such as 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 Ketones, ketones such as cyclohexanone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol , Ethers such as dipropyl ether, dibutyl ether and tetrahydrofuran, two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol And organic solvents having a polar nature such as dimethylformamide and dimethyl sulfoxide.

  Among them, a solvent that dissolves 1% by weight or more in water at normal temperature is preferable, and more preferably 5% by weight or more. For example, methyl ethyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol, Butanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, and 2-ethoxypropanol are preferred.

  An apparatus for producing a water dispersion by adding water after dissolving the polymer (C) in a solvent or in a molten state is not particularly limited. For example, a reactor equipped with a stirrer, uniaxial or biaxial Can be used. The stirring speed at that time varies depending on the selection of the apparatus, but is usually in the range of 10 to 1000 rpm. Since the polymer (C) used in the present invention is very excellent in water dispersibility, the aqueous dispersion of the polymer (C) has an advantage that the dispersed particle size is small and the resin is stably dispersed. . Therefore, when this is used, a coated product having an excellent appearance can be obtained.

The dispersed particle size of the polymer (resin) in the aqueous dispersion is usually 5.0 μm with a 50% average particle size.
m or less, preferably 1.0 μm or less. According to the present invention, the 50% average particle size can be 0.5 μm or less, more preferably 0.3 μm or less. More preferably, the 90% average particle size can be 1.0 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.

Here, the dispersed particle diameter can be measured by a known method, and for example, it can be measured by using Microtrack UPA (model 9340 batch type dynamic light scattering method / laser Doppler method) manufactured by Nikkiso Co., Ltd.
In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved. Accordingly, there is no particular limitation on the lower limit value of the dispersed particle size.

  The aqueous dispersion of the polymer (C) 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, and still more preferably 50% by weight or less. The smaller the amount of solid content, the lower the viscosity of the obtained active energy ray-curable aqueous resin composition, which can be applied to various coating methods and easy to use, and the stability as a dispersion tends to be high. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  As described above, in the polymer (C) used in the present invention, an aqueous dispersion can be obtained substantially without using a surfactant. Therefore, the active energy ray-curable aqueous resin obtained by using this can be obtained. One of the advantages of the composition is that it can suppress bleed-out conventionally caused by surfactants. However, a surfactant may be included as necessary according to other purposes and applications. As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. Specific examples of the surfactant that can be used here will be described later as the surfactant that can be included in the active energy ray-curable aqueous resin composition of the present invention.

In the aqueous dispersion of the polymer (C), the ratio of the surfactant to 100 parts by weight of the polymer (C) is usually 20 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. is there. Most preferably, it is substantially free of surfactant.
An acidic substance or a basic substance can be added to the aqueous dispersion of the polymer (C) as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of the basic substance include inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, triethylamine, diethylamine, dimethylethanolamine, 2-methyl-2-amino-propanol, and triethanolamine.

(D) Compound having two or more active energy ray-curable unsaturated bonds in one molecule As the active energy ray-curable unsaturated bond in the present invention, (meth) acryloyl group, (meth) acrylamide group, allyl group, A vinyl group etc. are mentioned. Specific examples of the compound (D) include polyalkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylamide, ethylene oxide modified bisphenol A (meth) acrylate, propylene oxide modified bisphenol A (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, caprolactone modified tris ((meta ) Acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene Koxide modified pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl modified dipenta Erythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyisocyanate and hydroxyl group-containing polyfunctional (meth) having a (meth) acryloyl group in the molecule ) Urethane (meth) acrylate obtained by reacting acrylate, tetracarboxylic dianhydride and a hydroxyl group in the molecule and 3 or more Carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting with a hydroxyl group-containing polyfunctional (meth) acrylate having a (meth) acryloyl group, 1,3,5-tri (meth) acryloylhexahydro-1,3,5 -Polyfunctional (meth) acrylamides, such as triazine, and a mixture of two or more thereof.

  Examples of generally available compounds (D) include New Frontier PE-400 (Daiichi Kogyo Seiyaku Co., Ltd.), GX-8854N (Daiichi Kogyo Seiyaku Co., Ltd.), and urethane (meta). As acrylates, the “New Frontier R-1000” series manufactured by Daiichi Pharmaceutical Industry Co., Ltd. “Shikko UV” series manufactured by Nippon Synthetic Chemical Co., Ltd. Series.

  The active energy ray-curable aqueous resin composition of the present invention may contain a compound having one active energy ray-curable unsaturated bond in the molecule as necessary as a diluting monomer separately from the compound (D). I can do it. For example, alkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, (meth) acrylate having a polyalkyleneoxy group, hydroxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylamide, dimethylaminoalkyl (meth) acrylate Dimethylaminoalkyl (meth) acrylamide, acryloylmorpholine and the like.

  These compounds having an active energy ray-curable unsaturated bond can be blended by dissolving or dispersing in water as they are if they are water-soluble or self-emulsifiable compounds. Other compounds may be emulsified using a surfactant and dispersed in water and mixed, or may be simultaneously emulsified in the course of producing an aqueous dispersion of polymer (C) and dispersed in water. I can do it. As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used. Specific examples of the surfactant that can be used here will be described later as the surfactant that can be included in the active energy ray-curable aqueous resin composition of the present invention.

The active energy ray-curable aqueous resin composition of the present invention only needs to contain water as a dispersion medium and / or a solvent, and may contain a dispersion medium and / or a solvent other than water.
The dispersion medium and / or solvent other than water is not particularly limited, and the solvents mentioned as solvents other than water in the production of the dispersion of the polymer (C) can be used. Among them, a solvent that dissolves 5% by weight or more in water at normal temperature is preferable, and more preferably 10% by weight or more. For example, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol , Tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, and the like are preferable.

The ratio of the dispersion medium and / or the solvent other than water in the dispersion medium and / or the solvent containing water is usually 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less.
The active energy ray-curable aqueous resin composition of the present invention preferably has a low surfactant content in terms of foam suppression and bleed-out suppression, but may be necessary depending on other purposes and applications. A surfactant may be contained.

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.
Examples of the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like, Examples of cationic surfactants such as sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate ether, and amphoteric surfactants such as stearyltrimethylammonium chloride and cetyltrimethylammonium bromide Examples thereof include lauryldimethylaminoacetic acid betaine.

In addition, a so-called reactive surfactant having a radical polymerizable functional group can be used as the above surfactant, and when a reactive surfactant is used, the water resistance of the film can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).
The surfactant content of the active energy ray-curable aqueous resin composition of the present invention is the total amount of the polymer (C) and the resin (F) when the polymer (C) or the resin (F) described later is included. The amount is usually preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less with respect to 100 parts by weight. Most preferably, it is substantially free of surfactant.

(E) Photoinitiator The active energy ray-curable aqueous resin composition of the present invention can contain a photoinitiator (E) as necessary.
Examples of the photoinitiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, manufactured by Ciba Specialty Chemicals) Darocur 1173), benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone (for example, Irgacure 184 manufactured by Ciba Specialty Chemicals), 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (eg, Irgacure 2959 manufactured by Ciba Specialty Chemicals), 2-methyl-2-morpholino (4-thiomethylphenyl) propane- Acetophenones such as 1-one (for example, Irgacure 907 manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin ethers such as ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate (for example, BYCURE 55 manufactured by Stower), 1,7-bisacridinylheptane, 9-phenyl Examples include acridine. Among these, a photoinitiator that is easily dissolved or dispersed in water is preferable. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  The addition amount of the photoinitiator is preferably 0.01 to 10% by weight, more preferably 0 with respect to 100 parts by weight in total of the polymer (C) and the compound (D) of the active energy ray-curable aqueous resin composition. .1-7% by weight, more preferably 1-5% by weight. If the addition amount of the photoinitiator is too small, the photocurability is extremely lowered depending on the type of active energy ray, which is substantially unsuitable for industrial production. On the other hand, if the amount is too large, odor may remain in the cured film when the amount of irradiation light is small. In addition, when using an electron beam as an active energy ray, it is usually preferable not to add the photoinitiator. Moreover, when using infrared rays, visible rays, or ultraviolet rays, it is usually preferable to add the photoinitiator.

  Moreover, a well-known photosensitizer can also be added to the active energy ray-curable aqueous resin composition according to the present invention as necessary. Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethyl. Examples include aminoacetophenone. These photosensitizers may also be used alone or in combination of two or more.

Moreover, as the active energy ray used when the coating film of the active energy ray-curable aqueous resin composition of the present invention is cured to produce a cured film, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, etc. can be used. From the viewpoint of the cost and productivity of the apparatus, it is preferable to use an electron beam or an ultraviolet ray, and as a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar laser, He—Cd laser, solid laser, xenon lamp, high frequency induction mercury lamp, sunlight, etc. are suitable. As the ultraviolet light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, or the like is used. The irradiation intensity of the active energy ray varies depending on the active energy ray to be used. For example, in the case of curing by electron beam irradiation, the irradiation intensity is preferably 1 to 20 Mrad, more preferably 3 to 10 Mrad. In the case of ultraviolet irradiation, the irradiation intensity is preferably from 50~1500mJ / cm ^2, more preferably 300~1000mJ / cm ^2.

(F) At least one resin selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin. The active energy ray-curable aqueous resin composition of the present invention includes an acrylic resin, depending on the purpose and application, It is preferable to include at least one resin (F) selected from the group consisting of a polyester resin, a polyurethane resin, and an epoxy resin. Each of these resins (F) is preferably dispersed in water. The dispersion form is not particularly limited, and each resin may independently form particles, or may form composite particles with the polymer (C) or the compound (D).

The content of the resin (F) contained in the active energy ray-curable aqueous resin composition of the present invention is 10 to 400 parts by weight with respect to 100 parts by weight of the total of the polymer (C) and the compound (D). Is preferred. More preferably, it is 20 weight part or more, More preferably, it is 50 weight part or more, More preferably, it is 200 weight part or less, More preferably, it is 100 weight part or less.
(F-1) Acrylic resin The acrylic resin used in 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.

Specific examples of (meth) acrylate esters include (meth) acrylate monomers having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Propyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, etc., or an aryl group or aralkyl group having 6 to 12 carbon atoms ( And (meth) acrylate esters such as phenyl (meth) acrylate and benzyl (meth) acrylate That.

  Alternatively, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meta ) Hydroxybutyl acrylate, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, adducts of (meth) acrylic acid and polyethylene oxide, etc. containing 1 fluorine atom (Meth) acrylic acid esters having 20 to 20 alkyl groups such as trifluoromethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, etc. , (Meth) acrylamide monomers such as (meth) acrylamide, ( Data) acrylic dimethyl amide, and the like, respectively.

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

  As the acrylic resin used in the present invention, the number average molecular weight is preferably 1,000 or more, and more preferably 10,000 or more. However, it is preferably 3,000,000 or less, more preferably 1,000,000 or less. The particle diameter of the acrylic resin particles in the aqueous resin composition of the acrylic resin is preferably 0.01 μm to 0.5 μm. In the case of an aqueous emulsion, the resin solid content is preferably 15 to 70% by weight, and the liquid viscosity is preferably 1 to 50,000 mPa · s.

(F-2) Polyurethane resin The urethane resin used in the present invention is not particularly limited. For example, (a) a component containing an average of two or more active hydrogens in one molecule and (b) many A urethane polymer obtained by reacting a polyvalent isocyanate component, or a chain extender such as a diol and an isocyanate group-containing prepolymer obtained by reacting the component (b) and the component (b) under an excess of isocyanate groups. 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 two or more active hydrogens in average in one molecule of the component (a) 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, etc.

  (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, etc.

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

  (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 In addition to the reaction of alkylene oxide, for example, polytetramethylene glycol-adipic acid condensate, etc.

(5) Polycarbonate diol:
General formula HO-R- (OC (O) -O-R) x-OH
(Wherein R represents a saturated fatty acid diol residue having 1 to 12 carbon atoms, x represents the number of repeating units of the molecule, and is usually an integer of 5 to 50). 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 (b) polyvalent isocyanate component to be reacted with the component (a), 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 20 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 20, water dispersibility tends to be insufficient, and it is often necessary to use a surfactant. On the other hand, if the acid value is greater than 150, the water resistance of the coating tends to be inferior.

  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 used in the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less. When manufacturing the water dispersion of this urethane resin, the manufacturing method is not specifically limited, It can manufacture according to the manufacturing method of the water dispersion of the above-mentioned acrylic resin.

The particle diameter of the urethane resin particles in the active energy ray-curable aqueous resin composition of the urethane 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.
(F-3) Polyester resin The polyester resin used in the present invention is not particularly limited. For example, dicarboxylic acids such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, and phthalic acid are used. 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).

Specifically, ethylene glycol-adipic acid condensate, butanediol-adipic acid condensate, hexamethylene glycol-succinic acid condensate, ethylene glycol-propylene glycol-phthalic acid condensate, polyethylene glycol-adipic acid condensate, etc. is there.
An aqueous dispersion of the 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 used in 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. As for the particle size of the urethane resin particle in the aqueous resin composition 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.

(F-4) Epoxy resin The epoxy resin used in 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-tert-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 is 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 representative commercially available product, a de novolak type epoxy resin obtained by adding epichlorohydrin to a phenol novolac resin and forcibly emulsified with a surfactant (emulsifier), Denar EM150 manufactured by Nagase Chemtech Co., Ltd. Examples include Epiretz 6006W70 and 5003W55 manufactured by Japan Epoxy Resin Co., Ltd., WEX-5100 manufactured by Tohto Kasei Co., Ltd. and the like.

Similarly, Denars EM101 and EM103 manufactured by Nagase Chemtech Co., Ltd., Epiletts 3510W60, 3515W6, 3522W60, and 3540WY55 manufactured by Japan Epoxy Resin Co., Ltd., which are obtained by forcibly emulsifying a bisphenol type epoxy resin obtained by adding epichlorohydrin to bisphenol in the same manner, are listed. It is done.
Further, as an alkyl type epoxy resin in which epichlorohydrin is added to a polyol such as sorbitol, pentaerythritol and glycerin, Denars EX-611, EX-614, EX-411 and EX-313 manufactured by Nagase Chemtech Co., Ltd. may be mentioned.

As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
The content of the surfactant in the aqueous dispersion of the resin (F) is usually 20 parts by weight or less with respect to 100 parts by weight in total of the acrylic resin, polyurethane resin, polyester resin, and epoxy resin. The amount 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. The smaller the content of the surfactant, the more preferable it is because the bleed-out of the surfactant is less likely to occur in the coating film or cured film obtained from the active energy ray-curable aqueous resin composition of the present invention.

<Other additives>
The active energy ray-curable aqueous resin composition of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention.
For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; conductivity imparting agents such as carbon black and ferrite, dyes, pigment dispersants, leveling agents, antifoaming agents, Various additives such as a sticking agent, an antiseptic, a fungicide, a rust inhibitor, and a wetting agent may be used in combination.

  In order to further improve various coating performances such as water resistance, solvent resistance, and chemical resistance. A cross-linking agent can be added. As the crosslinking agent, there can be used a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, etc. Among them, an isocyanate compound, Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

  When the active energy ray-curable aqueous resin composition of the present invention is used for primer, paint, ink, etc., hydrophilic organics other than water are used for the purpose of increasing the drying speed or obtaining a surface with a good finish. A solvent can be blended. Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, and ethers thereof. In addition, organic or inorganic compounds other than those described above can be added to the resin dispersion as long as the stability of the active energy ray-curable aqueous resin composition is not impaired.

(G) Pigment
A pigment (G) can be added to the active energy ray-curable aqueous resin composition of the present invention. A pigment is a powdered solid that does not dissolve in water, oil, solvent, etc., and itself has a color, and mainly forms the color of paint and ink. The aqueous resin composition containing the pigment (G) is used as a paint and ink. Is preferred.

  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 (G) added to the active energy ray-curable aqueous resin composition is preferably 10 parts by weight or more with respect to 100 parts by weight as a total of the polymer (C) and the compound (D). More preferably, it is 50 parts by weight or more. And 400 weight part or less is preferable, More preferably, it is 200 weight part 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.

An antifoaming agent may be added to the aqueous resin composition of the present invention. Examples include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
<Paint>
The active energy ray-curable aqueous resin composition of the present invention can be suitably used as a paint.

  The coating material containing the active energy ray-curable aqueous resin composition of the present invention includes and / or has the purpose of protecting and beautifying the object, or has unique functions such as rust prevention and water repellency. In order to impart, it is applied to the surface, and the type of paint is not particularly limited. Specific examples include automotive interior paints, exterior primers, electrodeposition paints, intermediate paints, base paints, automotive paints such as clear paints, paints for home appliances such as mobile phones and personal computers, and paints for building materials. It can be used for anti-rust paints, anti-corrosion paints and the like.

<Ink>
The active energy ray-curable aqueous resin composition of the present invention can be suitably used as an ink.
The ink (ink) containing the active energy ray-curable aqueous resin composition of the present invention includes and / or is used for writing letters or coloring the surface, The type is not limited. Specific examples include gravure printing ink, flexographic printing ink, screen printing ink, offset printing ink, inkjet ink, and the like.

<Laminated body>
On the thermoplastic resin molded body (H), the active energy ray curable aqueous resin composition of the present invention, the active energy ray curable paint of the present invention, or the active energy ray curable ink of the present invention is applied and dried. By irradiating active energy rays, a resin layer is formed and a laminate can be obtained. The laminate is a laminate in which a resin layer containing at least the polymer (C) and the compound (D) is formed on the thermoplastic resin molded body (H).

The lamination method is not particularly limited, and a known method can be used. For example, an active energy ray curable aqueous resin composition, an active energy ray curable paint, or an active energy ray curable ink can be sprayed. Examples thereof include a coating method, a roller coating method, a brush coating method, gravure printing, screen printing, and inkjet printing.
After applying the active energy ray curable aqueous resin composition, the active energy ray curable paint, or the active energy ray curable ink, the coating film is dried according to a normal method of heating with nichrome wire, infrared rays, etc. Can be irradiated and cured to obtain a molded product having a desired cured film on the surface. The drying conditions of the coating film are appropriately selected depending on the material and shape of the molded product, 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 film thickness of the resin layer containing the polymer (C) and the compound (D) to be laminated can be appropriately selected depending on the material and shape of the molded product, the composition of the paint used, etc., but is usually 0.1 μm or more, preferably Is 1 μm or more, more preferably 3 μm or more. However, it is usually 500 μm or less, preferably 100 μm or less, more preferably 50 μm or less.
(H) Thermoplastic resin molded body The thermoplastic resin molded body (H) is not particularly limited. For example, it is molded from a polyolefin resin, a polyamide resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, or the like. Is the body. Especially, when this invention is applied to the thermoplastic resin molding (H) which consists of polyolefin moldings, it is excellent in adhesiveness etc., and preferable.

The polyolefin molded body is a crystalline polyolefin molded body, which is a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, octene-1. Random copolymers or block copolymers with α-olefin comonomers having 2 or more carbon atoms such as, and cycloaliphatic unsaturated hydrocarbon comonomers such as cyclopentene, cyclohexene, and norbornene, particularly preferably 4-6 α-olefin comonomers. A polymer or a copolymer of two or more of these comonomers, a copolymer with a comonomer such as vinyl acetate or (meth) acrylate, an aromatic vinyl monomer / conjugated diene block copolymer, or a hydrogenated product thereof Is used. These can be used alone or as a mixture depending on the application.

  The polyolefin constituting the polyolefin molded body preferably has a melt flow rate (MFR) of 2 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and particularly preferably 25 g / 10 minutes. 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 polyolefin can be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide during or after polymerization.

  The thermoplastic resin molded body (H) is preferably a crystalline polypropylene molded body. Crystalline polypropylene is a molded product having a propylene homopolymer and / or a propylene homopolymer portion and a propylene / ethylene copolymer portion. Here, the propylene / ethylene copolymer portion is a propylene / ethylene random copolymer and / or a propylene / ethylene block copolymer, preferably a propylene / ethylene block copolymer. The propylene / ethylene block copolymer is a propylene / ethylene block copolymer containing 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 propylene with a small amount of other α-olefin.

  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, further preferably 20 g / 10 min or more, particularly preferably 40 g / 10 min or more. It is. 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. When the MFR of the propylene homopolymer part (a unit part) of the propylene / ethylene block copolymer is higher than the lower limit value, the flowability tends to increase. Conversely, if the MFR is lower than the upper limit value, the mechanical properties tend to increase.

  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 copolymer part (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 of the copolymer part is in the above range, the dispersibility and the glass transition temperature are in an appropriate range, and the impact characteristics tend to be good.

The propylene content of the propylene / ethylene copolymer part can be adjusted by controlling the concentration ratio of propylene and ethylene during the polymerization of the propylene / ethylene copolymer part.
The molecular weight of the propylene / ethylene copolymer 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, it is 300,000-2,500,000, More preferably, it is 400,000-2,000,000.

  Although there is no restriction | limiting in particular about the quantity of a unit part and b unit part, Generally a unit part becomes like this. Preferably it is 95 weight% or less of total polymerization amount, More preferably, it is 50-95 weight%, More preferably, it is 60-90 weight % And b unit parts are preferably adjusted to be 5% by weight or more of the total polymerization amount, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight. When the amount of the b unit part is equal to or higher than the lower limit value, the impact resistance tends to increase, and when it is equal to or lower than the upper limit value, rigidity, strength and heat resistance tend to increase.

<Inorganic filler component>
The thermoplastic resin molded body (H) used in the present invention can contain an inorganic filler component. By blending an inorganic filler component with crystalline polypropylene, mechanical properties such as flexural modulus and rigidity of the molded product can be improved. Specifically, plate fillers such as talc, mica and montmorillonite, short fiber glass fibers, long fiber glass fibers, carbon fibers, aramid fibers, alumina fibers, boron fibers, zonorites and other fibrous fillers, potassium titanate, magnesium Oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide and other needle-shaped (whisker) fillers, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. A granular filler, a balun filler such as a glass balloon. Inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate can also be used. Among these, talc, mica, glass fiber, and whisker are preferable from the balance of physical properties and cost.

<Elastomer component>
Furthermore, when the thermoplastic resin molding (H) used in the present invention is crystalline polypropylene, an elastomer component can be contained. By adding an elastomer component to crystalline polypropylene, the impact strength of the molded article can be improved.
Examples of the elastomer component include ethylene / α-olefin random copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene / α-olefins such as ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-hexene copolymer rubber, and ethylene / 1-octene copolymer rubber. Copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber such as ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM), hydrogenated product of styrene-butadiene-styrene triblock (SEBS) Examples thereof include styrene-containing thermoplastic elastomers such as hydrogenated styrene-isoprene-styrene triblock (SEPS).

<Other ingredients>
In addition to the above, the thermoplastic resin molded body (H) 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 Examples thereof include additives such as an agent, a neutralizing agent, a foaming agent, a copper damage inhibitor, a lubricant, a flame retardant, and various resins other than the propylene block copolymer, such as a polyethylene resin.

<Manufacture of laminated body and its use>
The thermoplastic resin molded body (H) which is the base material of the laminate of the present invention can be obtained by molding by various known methods. For example, injection molding (including gas injection molding), compression molding, injection compression molding (press injection), extrusion molding, hollow molding, rotational molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. Various molded bodies can be obtained by molding. Among these, a molded body by injection molding, compression molding, injection compression molding, uniaxially stretched film molding, or biaxially stretched film molding is preferable.

  The laminate of the present invention has excellent cured film adhesion, and further has a physical property balance excellent in rigidity and impact resistance. The laminate of the present invention is various industrial parts field, in particular, various molded products that are thin, highly functional, and large, such as automobile parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tanks, Home appliance parts such as refrigerator parts, air conditioner parts, vacuum cleaner parts, toiletry parts such as toilet seats, toilet seat covers, water tanks, parts such as bathtubs, bathroom walls and ceilings, parts around the bathroom such as drain pans, etc. It has sufficient performance for practical use as molding materials for various industrial parts, food packaging materials such as trays and packages, and synthetic paper.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.
<Physical property measurement method and evaluation method>
(1) Weight average molecular weight [Mw] and molecular weight distribution [Mw / Mn]
(1) -1 Method for measuring molecular weight in terms of polypropylene First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by weight of butylhydroxytoluene (BHT) was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a polytetrafluoroethylene (PTFE) filter having a pore size of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, gel permeation chromatography (GPC) measurement was performed using Waters GPC150CV equipped with TSKgel GMH-HT (30 cm × 4) and RI detector as columns. 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.

When calculating the molecular weight, a commercially available monodispersed polystyrene was used as a standard sample, a calibration curve relating to the retention time and molecular weight was created from the viscosity formula of the polystyrene standard sample and polypropylene, and the molecular weight of the polymer 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 number average molecular weight [Mn].
(1) -2 Measuring method of molecular weight in terms of polystyrene First, 5 mg of a sample was collected in a 10 ml vial, 5 g of tetrahydrofuran containing 250 ppm of BHT was added as a stabilizer, and completely dissolved at 50 ° C. After cooling to room temperature, the solution was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a sample solution having a polymer concentration of 0.1% by weight. Next, GPC measurement was performed using Tosoh Corp. GPC HLC-8020 equipped with a guard column TSK guard column H _XL- H to TSK gel GMH _XL- L (30 cm × 2) as a column. As measurement conditions, an injection amount of the sample solution: 50 μl, a column temperature: 40 ° C., a solvent: tetrahydrofuran, and a flow rate of 1.0 ml / min were employed.

In calculating the weight average molecular weight [Mw] and the number average molecular weight [Mn], a commercially available monodisperse polystyrene standard sample was measured as a standard sample, and a calibration curve was prepared from the retention time and molecular weight of the standard sample. .
(2) Graft rate 200 mg of the polymer and 4800 mg of chloroform were placed in a 10 ml sample bottle and heated at 50 ° C. for 30 minutes to completely dissolve.

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

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

(4) Antifoaming property 10 g of the active energy ray-curable aqueous resin composition was collected in a 30 ml sample bottle and vigorously stirred for 1 minute in a paint shaker. The sample bottle was allowed to stand, and the state of bubbles was visually confirmed after 3 minutes.
○: No bubbling is observed or slight.
×: Strong foaming

(5) Initial adhesion A substrate obtained by injection molding of automotive exterior grade polypropylene (Exxon 8224) was prepared, and the substrate surface was wiped with isopropyl alcohol. Here, the active energy ray-curable aqueous resin composition was applied with an applicator so that the dry weight after application was about 10 g / m ² . Next, the coated test piece was baked at 100 ° C. for 20 minutes in a safe ben dryer, and then UV light was applied at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp having an irradiance of 400 mW / cm 2 at a wavelength of 254 nm. Irradiation formed a cured film to obtain a laminate.

  After the obtained laminate was allowed to stand at 23 ° C. for 24 hours, a test piece with 25 squares (5 × 5) grids was prepared at 2 mm intervals according to the grid pattern test method described in JIS K 5400 Then, after attaching cellophane tape (Nichiban Co., Ltd.), it was peeled off in the direction of 90 degrees, and this was repeated 5 times. Evaluation was made based on the number of grids that were not peeled out of the 25 grids.

(6) Bleed-out The laminate prepared in the same manner as in the initial adhesion test was allowed to stand at 40 ° C. for 3 days, and the appearance of the surfactant that bleeded out to the cured film surface visually and by touch was determined. did.
○: No bleed-out of surfactant X: Surfactant is bleed-out and sticky when touched with a finger

(7) The laminate prepared in the same manner as in the initial touch tack test was left at 23 ° C. for 1 hour, and the appearance of the cured film was determined by touching the appearance of the coating.
○: No tack ×: There is tack when touched with a finger.
[Production Example 1: Production of maleic anhydride-modified propylene copolymer]
Taphmer XM-7070 (Mitsui Chemicals, melting point 75 ° C., propylene content 74 mol%, weight average molecular weight [Mw] 240,000 (polymerized by a metallocene catalyst as polyolefin (A)) (Polypropylene equivalent), molecular weight distribution [Mw / Mn] 2.2) 200 kg and maleic anhydride 5 kg were dry blended with a super mixer, and then propylene-butene copolymer using a twin screw extruder (TEX54αII manufactured by Nippon Steel Works) While feeding Perbutyl I (manufactured by Nippon Oil & Fats Co., Ltd.) in the middle of the pump so that it becomes 1 part by weight with respect to 100 parts by weight of the coalescence, the cylinder temperature of the kneading part is 200 ° C., the screw rotation speed is 125 rpm, and the discharge amount is 80 kg / hour. Kneaded under the conditions, and the maleic anhydride modified propylene-butene To obtain a copolymer.

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). Moreover, the weight average molecular weight (polystyrene conversion) [Mw] was 156,000, and the number average molecular weight [Mn] was 84,000.
[Production Example 2: Production of aqueous resin dispersion of maleic anhydride and polyalkylene glycol-modified propylene copolymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 g of the maleic anhydride-modified propylene-butene copolymer obtained in Production Example 1 and 150 g of toluene were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to 110 ° C. to dissolve the polymer. After the polymer was dissolved, 1.5 g of maleic anhydride and 1.0 g of perbutyl I were added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the by-product derived from maleic anhydride is removed by washing, and then the hydrophilic polymer (B) is methoxypoly (oxyethylene / oxypropylene) -2-propylamine (number average) which is a polyether resin. Molecular weight [Mn] 1,000) 15 g (15 mmol; equivalent to 15 parts by weight with respect to 100 parts by weight of maleic anhydride-modified propylene-butene copolymer obtained in Production Example 1) in 280 g of isopropanol (IPA) Was added dropwise and reacted at 70 ° C. for 1 hour.

  Further, 1.4 g (15.6 mmol) of aminomethylpropanol was added. Thereafter, while maintaining the temperature at 70 ° C., 280 g of water was added dropwise with stirring, and toluene and IPA were removed under reduced pressure to give a milky white aqueous resin dispersion having a solid content concentration of 30% by weight. Got. As a result of measuring the dispersed particle size, the 50% particle size was 0.10 μm, and the 90% particle size was 0.2 μm.

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

The polymer (C) obtained in Production Example 2 is polyolefin (A): hydrophilic polymer (B) = 99.2: 15 (weight ratio).
Methoxypoly (oxyethylene / oxypropylene) -2-propylamine is a hydrophilic 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.

[Example 1]
<Preparation of active energy ray-curable resin composition>
333 parts by weight of an aqueous resin dispersion containing the polymer (C) obtained in Production Example 2 and 100 parts by weight of New Frontier PE-400 (Daiichi Kogyo Seiyaku Co., Ltd.) as a compound (D) were mixed. An aqueous dispersion containing 200 parts by weight of solid content was prepared by adding 214 parts by weight of distilled water.
1.6 parts by weight of Darocur 1173 and 0.4 parts by weight of Irgacure 2659 (all manufactured by Ciba Specialty Chemicals) as a photoinitiator (E) with respect to 200 parts by weight of the solid content of the aqueous dispersion, Furthermore, 20 parts by weight of n-butyl cellosolve was added as a diluent solvent to prepare an active energy curable aqueous resin composition. The resulting active energy curable aqueous resin composition was evaluated for foam suppression properties, and the results are shown in Table 1.

<Creation of laminate>
A substrate obtained by injection molding of automotive exterior grade polypropylene (Exxon 8224) was prepared, and the substrate surface was wiped with isopropyl alcohol. The active energy ray-curable aqueous resin composition obtained above was applied by an applicator so that the dry weight after coating was about 10 g / m ² .

Next, the coated test piece was baked at 100 ° C. for 20 minutes in a safe ben dryer, and then UV light was applied at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp having an irradiance of 400 mW / cm 2 at a wavelength of 254 nm. Irradiation formed a cured film to obtain a laminate. The resulting laminate was evaluated for initial adhesion, bleed out, and finger tack, and the results are shown in Table 1.
[Examples 2 to 4, Comparative Examples 1 to 5]
An active energy curable aqueous resin composition was prepared in the same manner as in Example 1 so as to obtain the composition shown in Table 1. The resulting active energy curable aqueous resin composition was evaluated for foam suppression properties, and the results are shown in Table 1.

Next, a laminate was prepared in the same manner as in Example 1, and the initial adhesion, bleed out, and finger touch tack were evaluated. The results are shown in Table 1.
In addition, the polymer (C) and the compound (D) used in the Examples and Comparative Examples are as follows.
<Polymer (C)>
EH-801 (Hardylene EH-801 manufactured by Toyo Kasei Co., Ltd.): aqueous chlorinated polyolefin resin dispersion, solid content concentration of 30% by weight, 20 parts by weight of surfactant per 100 parts by weight of chlorinated polyolefin resin

<Compound (D)>
New Frontier PE-400 (Daiichi Kogyo Seiyaku Co., Ltd.): Polyethylene glycol 400 diacrylate (functional group number 2), solid content concentration 100% by weight
New Frontier R-1220 (Daiichi Kogyo Seiyaku Co., Ltd.): urethane acrylate oligomer (functional group number 2), solid content concentration 100% by weight
GX-8854N (Daiichi Kogyo Seiyaku Co., Ltd.): Emulsion containing polyfunctional acrylate (functional group number 2 or more), solid content concentration 36% by weight, urethane resin / polyfunctional acrylate = 1/1 (weight ratio)

According to the present invention, it is possible to prepare a stable active energy ray-curable aqueous resin composition without substantially using an ordinary surfactant. Further, the cured film has good adhesion to the polyolefin substrate, and can form a good cured film without surface tack after curing or bleed-out of the surfactant.
Therefore, the active energy ray-curable aqueous resin composition of the present invention is useful as a paint, primer, ink, adhesive or the like.

Claims (12)

1) Polymer (C) obtained by bonding hydrophilic polymer (B) to polyolefin (A) at a ratio of (A) :( B) = 100: 1 to 100: 300 (weight ratio)
2) Compound (D) having two or more active energy ray-curable unsaturated bonds in one molecule
3) Water is contained, the weight ratio of the polymer (C) to the compound (D) is 95: 5 to 5:95, and the total amount of the polymer (C) and the compound (D) and the weight of water An active energy ray-curable aqueous resin composition having a ratio of 5:95 to 90:10.   Furthermore, 0.01-10 weight part of photoinitiators (E) are contained with respect to a total of 100 weight part of a polymer (C) and a compound (D), Active energy ray-curable aqueous resin of Claim 1 Composition.   Further, at least one resin (F) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin is added to 10 parts by weight with respect to a total of 100 parts by weight of the polymer (C) and the compound (D). The active energy ray-curable aqueous resin composition according to claim 1, which comprises ˜400 parts by weight.   The active energy ray-curable aqueous resin composition according to claim 1, wherein the polymer (C) is dispersed in water with a 50% average particle diameter of 5.0 μm or less.   The active energy ray-curable aqueous resin according to any one of claims 1 to 4, wherein the polymer (C) is a graft copolymer obtained by graft-bonding a hydrophilic polymer (B) to the polyolefin (A). Composition.   The polyolefin (A) is a polypropylene polymer that is polymerized by a metallocene catalyst, has a melting point of 125 ° C. or less, and contains 50 to 100 mol% of a propylene component. The active energy ray-curable aqueous resin composition according to Item.   The active energy ray-curable aqueous resin composition according to any one of claims 1 to 6, wherein the hydrophilic polymer (B) is a polyether resin.   Furthermore, the active energy ray hardening of any one of Claims 1-7 which contains 10-400 weight part of pigment (G) with respect to a total of 100 weight part of a polymer (C) and a compound (D). Water-based resin composition.   The active energy ray-curable property according to any one of claims 1 to 8, wherein the polymer (C) is dispersed in water to obtain a dispersion, and then the compound (D) is dissolved or dispersed in the dispersion. A method for producing an aqueous resin composition.   An active energy ray-curable coating material comprising the active energy ray-curable aqueous resin composition according to any one of claims 1 to 8.   An active energy ray-curable ink comprising the active energy ray-curable aqueous resin composition according to any one of claims 1 to 8. The active energy ray-curable aqueous resin composition according to any one of claims 1 to 8, the active energy ray-curable paint according to claim 10, or the claim, on the thermoplastic resin molded body (H). 11. A laminate comprising a resin layer formed by applying and drying the active energy ray-curable ink according to 11, and irradiating the active energy ray.