JP2003183590A - Active energy ray-curable primer composition for polyolefin resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable primer composition for a polyolefin resin, which is excellent in adhesion to the polyolefin resin and adhesion to a coating applied to the primer-coated surface and that is no problems on discoloration and malodor of the cured product. <P>SOLUTION: The active energy ray-curable primer composition for the polyolefin resin comprises a copolymer having a maleimide group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable primer composition for a polyolefin resin, wherein the composition of the present invention has excellent adhesion to a polyolefin resin and is coated on the primer surface. It is excellent in adhesion to the paints, inks, adhesives, etc. to be manufactured and can be used in these technical fields.

[0002]

2. Description of the Related Art In the fields of automobile interior parts, home electric appliances and office supplies, plastic has been used in place of conventional metal for the purpose of weight reduction, rust prevention and other purposes. Among them, polyolefin-based resins such as polyethylene and polypropylene have excellent useability such as moldability, light weight, low cost, and recyclability, and thus the amount of use is expanding.

However, since polyolefin resins generally have high crystallinity and small polarity, when coating, printing or adhering to polyolefin resins, paints, inks and adhesives (hereinafter These are collectively referred to as paints, etc.) and have a drawback that they are difficult to adhere to.

As a method for improving the adhesion of a paint or the like to a polyolefin resin, there is a method of surface-treating the surface of the polyolefin resin. Specifically, there are physical treatments such as polishing, chemical treatments with a chromic acid mixed solution and a solvent, and other treatments with plasma or corona discharge, but these pretreatment steps require large-scale equipment. However, there is a problem that the treatment cannot be performed uniformly depending on the shape of the resin.

As a method other than the above-mentioned surface treatment, there is known a method of applying various kinds of primers having excellent adhesion to a polyolefin resin. However, the conventional primer has a problem of poor practicality because of insufficient film performance such as interlayer adhesion to the top coat and weather resistance. As a primer excellent in coating film performance such as adhesion to polyolefin resin, solvent resistance and hardness,
A composition comprising a chlorinated polyolefin and an acrylic polymer is known. However, since the primer has a problem that the compatibility between the chlorinated polyolefin and the acrylic polymer is insufficient and the adhesion with the resin is insufficient, the chlorinated polyolefin to be used contains a specific chlorine. Although a composition having a high ratio and a composition containing a grafted resin are known, the storage stability and the adhesiveness are still unsatisfactory. In order to solve these problems, various improvements have been attempted on the chlorinated polyolefin graft resin, but when an acrylic paint is used as the top coat on the primer surface, the problem that the adhesiveness decreases It was something that had. Furthermore, in recent years, the use of chlorine-based compounds has tended to be avoided due to environmental issues, and there is a demand for a method of improving adhesion to polyolefin-based resins without using chlorinated polyolefins.

[0006]

An active energy ray-curable composition containing (meth) acrylate is known as a primer for solving the above problems. However, the photopolymerization initiator such as benzophenone used in the composition has a strong hydrogen abstraction ability, and radically abstracts hydrogen from the substrate to form a chemical bond to improve the adhesiveness. . However, this method also
A low molecular weight photopolymerization initiator such as benzophenone remains in the cured product after curing of the composition, deteriorating the weather resistance of the resulting cured product, and coloring or fading, peeling or cracking of the coating film. Therefore, it was insufficient for applications requiring weather resistance. In addition, a low molecular decomposition product such as benzophenone present in the cured product after curing may cause an odor of the cured product.

The present inventors have found that the active energy for a polyolefin resin is excellent in the adhesion with the polyolefin resin and the adhesion with a paint or the like coated on the surface thereof, and the cured product has no problems of coloring and odor. The inventors have earnestly studied to find a line-curable primer composition.

[0008]

Means for Solving the Problems As a result of various investigations for solving the above problems, the present inventors have found that a composition containing a polymer having a maleimide group is a cured product obtained by a polyolefin resin resin. It has excellent adhesiveness with, and with coatings etc. applied on the surface thereof, and the composition is not blended with a photopolymerization initiator, or is blended in a small amount and easily cured by irradiation with active energy rays. Therefore, the inventors have found that the obtained cured product has no problems such as coloring and odor, and completed the present invention. In the present specification, acrylate and /
Alternatively, methacrylate is (meth) acrylate, acrylic acid and / or methacrylic acid is (meth) acrylic acid,
(Meth) acryloyl group and / or methacryloyl group
Collectively referred to as an acryloyl group. The unit of acid value is mg
KOH / g, and the description thereof is omitted below.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an active energy ray-curable primer composition for polyolefin resin containing a polymer (A) having a maleimide group. Hereinafter, the polymer having a maleimide group will be described.

1. Polymer (A) having a maleimide group It contains the polymer (A) having a maleimide group of the present invention (hereinafter referred to as “component (A)”). Since the component (A) has a maleimide group, the maleimide groups are dimerized by irradiation of an active energy ray to easily crosslink, and the coating has excellent adhesion, hardness, water resistance and chemical resistance. Becomes Further, even in the case of crosslinking by ultraviolet rays, there is no problem of coloring or odor because no photopolymerization initiator is blended at all or a small amount of a photopolymerization initiator is blended to have excellent crosslinkability. In the component (A), various maleimide groups can be used, and those represented by the following formula (1) are preferable.

[0011]

[Chemical 1]

[In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkenyl group or an aryl group, or R ¹ and R ² represent a saturated hydrocarbon group which together form a 5-membered ring or a 6-membered ring. ]

Examples of the aryl group include a phenyl group and the like. As a saturated hydrocarbon group which forms a 5-membered ring or 6-membered ring as one, a group —CH ₂ CH ₂ CH
_{2 -, - CH 2 CH 2} CH 2 CH 2 - and the like.

R¹And R²As for, one is a hydrogen atom and the other is
One is an alkyl group having 4 or less carbon atoms, R ¹And R²Both are charcoal
Alkyl groups with a prime number of 4 or less, and each becomes one
Saturated hydrocarbon group forming a carbocycle facilitates polymer
A composition that can be produced, has excellent solubility and storage stability, and is obtained
It is preferable in that the crosslinked coating film (1) has excellent water resistance. Furthermore, this
Among these, each forms a carbocycle.
Saturated hydrocarbon group is more preferable, and a particularly preferable group-
CH₂CH₂CH₂CH₂− Specific examples of maleimide group
Are shown in the following equations (2) to (7). Among these, dissolution
It is represented by formula (2) or formula (3) in terms of excellent stability and storage stability.
Maleimide groups are preferred.

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

As the component (A) of the present invention, those produced by various methods can be used. As the component (A), a homopolymer of an ethylenically unsaturated monomer having a maleimide group (hereinafter referred to as a maleimide monomer), or a maleimide monomer and a copolymerizable with the same, can be easily produced. Preferred are copolymers of ethylenically unsaturated monomers (hereinafter simply referred to as unsaturated monomers). Hereinafter, the maleimide monomer and the unsaturated monomer will be described.

1-1-1. Maleimide Monomer The maleimide monomer is preferably a compound having an ethylenically unsaturated group and a maleimide group represented by the above formula (1).

Examples of the ethylenically unsaturated group in the maleimide monomer include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

The maleimide monomer has the following general formula:
The compound represented by (8) [hereinafter referred to as imide (meth) acrylate] is preferable.

[0022]

[Chemical 5]

However, in the formula (8), R ¹ and R ² are the same groups as described above. R ³ is an alkylene group, R ⁴ is hydrogen or a methyl group, and n is an integer of 1 to 6.

Among formulas (8), those in which n is 1 to 2 are preferable, and those in which n is 1 are more preferable. R ³ preferably has 1 to 6 carbon atoms, and more preferably an ethylene group or a propylene group.

1-1-2. Unsaturated Monomer As the component (A) in the present invention, a copolymer of a maleimide monomer and an unsaturated monomer is prepared by curing the resulting composition upon irradiation with ultraviolet rays. It is preferable because of its excellent speed. Examples of the unsaturated monomer include styrene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, and (meth) acrylate. Specific examples of the (meth) acrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, cyclohexyl. Alicyclic alkyl (meth) acrylates such as (meth) acrylate, substituted aryl (meth) acrylates such as benzyl (meth) acrylate, alkoxy (such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate). Examples thereof include (meth) acrylate, isobornyl (meth) acrylate, and alkoxysilyl group-containing (meth) acrylate. In addition to these monomers, macromonomer type monomers can be used. As a result, the component (A)
It becomes a graft copolymer or a block copolymer. Examples of the macromonomer type monomer include those having a polysiloxane and those having a fluorine-based polymer chain. Two or more kinds of these monomers may be used in combination.

1-1-3. Method for producing component (A) As a method for producing the component (A), the above-mentioned monomers are polymerized by a conventional method such as a solution polymerization method, an emulsion polymerization method and a high temperature continuous polymerization method. Can be manufactured. In the case of synthesizing by a solution polymerization method, it can be obtained by dissolving a raw material monomer to be used in an organic solvent, adding a thermal polymerization initiator, and stirring with heating. In the case of synthesizing by radical polymerization by the solution polymerization method, it can be obtained by dissolving the raw material monomer to be used in an organic solvent, adding a thermal radical polymerization initiator, and stirring with heating. Further, if necessary, a chain transfer agent can be used to control the molecular weight of the polymer. Examples of the thermal polymerization initiator used include peroxides, which generate radical species by heat, azo compounds, and redox initiators. Examples of peroxides include benzoyl peroxide, lauroyl peroxide,
Cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and the like can be mentioned. Examples of azo compounds include azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile.
Examples of redox initiators include hydrogen peroxide-iron (II)
Examples thereof include salts, peroxodisulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salt and the like. Examples of the organic solvent used include benzene, toluene, ethyl acetate, methanol and dimethylformamide. Examples of the chain transfer agent include dodecyl mercaptan, xanthate disulfide, diazothioether, 2-propanol and the like.

The component (A) can also be produced by high temperature continuous polymerization, if necessary. According to the high temperature continuous polymerization method, a prepolymer having a low molecular weight and low viscosity can be obtained, and further, the polymerization method does not require the use of a thermal polymerization initiator, or even when a thermal polymerization initiator is used, a small amount of Since a prepolymer having a desired molecular weight is obtained by use, the copolymer is preferable because it has a high purity and contains almost no impurities that generate radical species by heat or light, and stable physical properties can be obtained. As a high temperature continuous polymerization method,
JP-A-57-502171, 59-6207, and 6
The known method disclosed in, for example, 0-215007 may be followed. For example, a reactor capable of pressurization is filled with a solvent, and a predetermined temperature is set under pressure, and then a monomer mixture consisting of a monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate. Then, a method of extracting an amount of the reaction solution commensurate with the supply amount of the monomer mixture can be mentioned. Also, in the monomer mixture,
If necessary, a thermal polymerization initiator can be added. The reaction temperature is preferably 150 to 350 ° C. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and the solvent used, and does not affect the reaction, but may be any pressure at which the reaction temperature can be maintained. The residence time of the monomer mixture is
It is preferably 2 to 60 minutes.

The proportion of the maleimide group in the component (A) is preferably 0.04 to 4 mmol / g, more preferably 0.2 to 4 mmol / g. This ratio is 0.
If it is less than 04 mmol / g, weather resistance may be insufficient, or curing or crosslinking (hereinafter simply referred to as curing) may be insufficient, resulting in insufficient hardness, while 4 mmol
If it exceeds / g, when a thick film is cured, the cured film may proceed only on the surface, resulting in poor adhesion. (A)
The number average molecular weight of the component is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000.
If this value is less than 1000, the weather resistance may be insufficient or the adhesion may be insufficient, while if it exceeds 1 million, the stability of the solution may be impaired. still,
In the present invention, the number average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent based on the molecular weight of polystyrene.

The composition of the present invention essentially comprises the component (A), and its forms include a solution of the component (A) in an organic solvent, an aqueous dispersion of the component (A) and a component (A). Examples thereof include a composition comprising the component (B) described below. In this case, the proportion of the component (A) is preferably 5 to 95% by weight in the case of an organic solvent solution, and 10 to 70% by weight in the case of an aqueous dispersion.
Is preferable, more preferably 20 to 60% by weight,
When used in combination with the component (B), it is as described below.

1-2. Maleimide group and ethylenically unsaturated group
As the component (A) in the present invention , a polymer having an ethylenically unsaturated group in the maleimide group (hereinafter referred to as an unsaturated polymer) is preferable because it has excellent curability by active energy rays. As the unsaturated polymer, polymers obtained by various methods can be used. As the production method, there are various methods, and a method of reacting a compound having a functional group capable of reacting with the functional group with a prepolymer having a functional group and a maleimide group shown below is produced. It is preferable to prepare a prepolymer having a functional group and to react a compound having a maleimide group with a functional group capable of reacting with the functional group, which is shown in (1) and (2) below.

A compound having an ethylenically unsaturated group and an isocyanate group in the maleimide group- and hydroxyl group-containing prepolymer (hereinafter referred to as isocyanate-based unsaturated compound)
How to add. A method of adding a compound having an ethylenically unsaturated group and an epoxy group (hereinafter referred to as an epoxy-based unsaturated compound) to a maleimide group- and acidic group-containing prepolymer. A method of adding a compound having an ethylenically unsaturated group and an acidic group (hereinafter referred to as an acidic unsaturated compound) to a maleimide group- and epoxy group-containing prepolymer. A method of adding a compound having an ethylenically unsaturated group and a hydroxyl group (hereinafter referred to as a hydroxyl-based unsaturated compound) to a maleimide group- and isocyanate group-containing prepolymer. A method of adding a hydroxyl-based unsaturated compound to a prepolymer containing a maleimide group and an acid anhydride group. A method of adding a compound having a maleimide group and a hydroxyl group (hereinafter referred to as maleimide alcohol) and a hydroxyl-based unsaturated compound to an acid anhydride group-containing prepolymer. A method of adding a compound having a maleimide group and a carboxyl group and an acidic unsaturated compound to an epoxy group-containing prepolymer. Hereinafter, each manufacturing method will be described.

1-2-1. Method for Producing Prepolymer As a method for producing the prepolymer having a maleimide group in any one of the above methods (1) to (5), a maleimide monomer and a hydroxy unsaturated compound [the above method] , An acidic unsaturated compound [the above method], an epoxy unsaturated compound [the above method], an isocyanate unsaturated compound [the above method] and a compound having an ethylenically unsaturated group and an acid anhydride group (hereinafter referred to as acid anhydride (Referred to as a physical compound) [the above method] to obtain a prepolymer.

As the maleimide monomer, the same ones as those mentioned in the section 1-1-1 can be used.

Hydroxy unsaturated compounds include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Examples thereof include acrylates and hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether.

In the acidic unsaturated compound, examples of the acidic group include a carboxyl group, a sulfonyl group and a phosphoric acid group. Examples of the ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group.

Of these, unsaturated compounds having a carboxyl group are preferable in that the obtained composition is excellent in stability and the cured film is excellent in water resistance. Examples of the compound include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, cinnamic acid, and (meth) acrylic acid.
Examples thereof include oligomers in the form of monomers or more, ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, and monohydroxyethyl (meth) acrylate succinate.

Examples of the epoxy-based unsaturated compound include glycidyl (meth) acrylate and epoxy group-containing (meth) acrylates such as cyclohexene oxide group-containing (meth) acrylate represented by the following formula (9).

[0038]

[Chemical 6]

As the isocyanate-based unsaturated compound,
Examples thereof include (meth) acryloyloxyethyl isocyanate and dimethyl-m-isopropenylbenzyl isocyanate represented by the following formula (10).

[0040]

[Chemical 7]

Examples of the acid anhydride unsaturated compound include maleic anhydride and itaconic acid.

Further, in the above method, a prepolymer can be obtained by polymerizing an acid anhydride unsaturated compound, and in the above method, polymerizing an epoxy unsaturated compound.

If desired, the prepolymer may be copolymerized with a monomer copolymerizable with these compounds. As the monomer, the same one as the unsaturated monomer can be used.

The prepolymer can be produced by polymerizing the above-mentioned monomers by a conventional method such as a solution polymerization method, an emulsion polymerization method and a high temperature continuous polymerization method. Specific methods include the same methods as those mentioned in Section 1-1-3.

1-2-2. Method for Producing Unsaturated Polymer In the above methods (1) to (3), an isocyanate-based unsaturated compound [the above method] and an epoxy-based unsaturated polymer are added to the maleimide group-containing prepolymer having various functional groups, respectively. A polymer can be obtained by adding a saturated compound [the above method], an acidic unsaturated compound [the above method] and a hydroxyl-based unsaturated compound [the above method]. Further, in the above method, a compound having a maleimide group and a hydroxyl group and a hydroxyl-based unsaturated compound are added to the acid anhydride group-containing prepolymer, and in the above method, the epoxy group-containing prepolymer has a maleimide group and A polymer can be obtained by adding a compound having a carboxyl group and an acidic unsaturated compound.

As the compound having an isocyanate unsaturated compound, an epoxy unsaturated compound, an acidic unsaturated compound and a hydroxyl unsaturated compound, the same compounds as mentioned above can be mentioned.

Examples of the maleimide alcohol in the method (1) include compounds represented by the following formula (11).

[0048]

[Chemical 8]

[However, in the formula (11), R ¹ and R ² have the same meanings as described above. R ⁵ represents a linear or branched alkylene group having 1 to 6 carbon atoms. ]

Examples of the carboxyl group-containing compound having a maleimide group used in the method (1) include compounds represented by the following formula (12).

[0051]

[Chemical 9]

[However, in the formula (12), R ¹ and R ² have the same meanings as described above. R ⁵ represents a linear or branched alkylene group having 1 to 6 carbon atoms. ]

In any case, it can be produced by adding each compound to the prepolymer in an organic solvent, in an aqueous medium or without a solvent. As conditions for each addition reaction, the reaction temperature, reaction time and catalyst may be selected according to each reaction.

The ratio of the maleimide group in the unsaturated polymer is 0.04 to 4 mmol / g for the same reason as above.
Is preferable, and more preferably 0.2 to 4 mmol / g. The proportion of ethylenically unsaturated groups in the unsaturated polymer is preferably 0.1 to 4 mmol / g. If this ratio is less than 0.1 mmol / g,
If the weather resistance is insufficient or the curing is insufficient, the hardness becomes insufficient. On the other hand, if it exceeds 4 mmol / g, the adhesion may be poor. The number average molecular weight of the unsaturated polymer is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000 for the same reason as above.

1-3. Heavy containing maleimide group and acidic group
When the composition in the present invention is used as an aqueous composition, a polymer containing a maleimide group and an acidic group (hereinafter referred to as an acidic polymer) or a salt thereof (hereinafter referred to as an acidic compound) is used as the component (A). It is preferable to use a combination (referred to as a salt). Acidic Polymer (Salt) It is a polymer that dissolves or self-disperses in an aqueous medium depending on the hydrophilicity of the acidic group or its salt.

The maleimide group and ethylenically unsaturated group in the acidic polymer are preferably the same as those mentioned above.

As the acidic polymer, various polymers can be used, and examples thereof include the polymers listed in (1) to (6) below. (1) a polymer obtained by polymerizing a maleimide monomer and an acidic unsaturated compound (2) a polymer having a carboxyl group or an acid anhydride group and an esterified product of maleimide alcohol (3) a polymer having a carboxyl group Amidation product of compound having maleimide group and amino group (hereinafter referred to as maleimidoamine) (4) Polymer having carboxyl group and adduct of compound having maleimide group and epoxy group (5) Polymer having isocyanate group, and maleimide Alcohol or maleimidoamine adduct (6) Epoxy group-containing polymer and maleimide group and carboxyl group-containing compound adduct (7) Maleimide group and hydroxyl group-containing polymer and acid anhydride, etc. To be

Among these acidic polymers, from the viewpoint of easy production, the polymer obtained by the production method (1), that is, the maleimide monomer and the acidic unsaturated compound are used as constituent monomer units. A copolymer [hereinafter referred to as a copolymer (1)] is preferable because it can be produced in one step. The following (1)
The manufacturing method of will be described.

As the maleimide monomer, the same as those listed in the above 1-1-1 can be used, and as the acidic unsaturated compound, the same as those listed in the above 1-2-1. Things can be used.

The copolymerization ratio of the acidic unsaturated compound is as follows:
The ratio of the acid value of the obtained copolymer to a value satisfying the preferable acid value described later is preferable.

The copolymer (1) comprises, in addition to the maleimide monomer and the acidic unsaturated compound, an ethylenically unsaturated group-containing monomer copolymerizable with these monomers (hereinafter referred to as other monomer). It is also possible to use a copolymer.

As the other monomer, various monomers other than the maleimide monomer and the acidic unsaturated compound can be used, and the same ones as described above can be used.

Among these monomers, the hydrophobic monomer is preferable because the copolymer (1) exhibits excellent performance as an emulsifier. In the present invention, the hydrophobic monomer is 20 ° C.
Means a monomer having a solubility in water of 2% by weight or less. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth).
Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate,
Lauryl (meth) acrylate, isobornyl (meth)
Examples thereof include methacrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate, acrylates having 2 to 22 carbon atoms, perfluoroalkyl (meth) acrylate, vinyl propionate, styrene, and α-methylstyrene. The proportion of the hydrophobic monomer unit in the copolymer (1) is preferably 20% by weight or more, more preferably 40% by weight or more, based on all the monomers.

In addition to these monomers, macromonomer type monomers can be used. As a result, the copolymer (1) becomes a graft copolymer, and becomes a copolymer in which a polysiloxane chain and a fluorine-based polymer chain are grafted depending on the kind of macromonomer.

The copolymer (1) may be any of those obtained by polymerizing the above-mentioned monomers by a conventional method, and examples thereof include solution polymerization, emulsion polymerization and suspension polymerization. These polymerization methods may be adopted depending on the purpose. When economic efficiency is required, the emulsion polymerization method is preferable, and when the acidic unsaturated compound has high water solubility, the solution polymerization method is preferable.

When the solution polymerization method is adopted, a conventional method may be used, but a semi-batch method in which the raw material monomers are successively charged into the reactor is preferable in order to narrow the composition distribution. As the solvent, known solvents can be used, but those capable of dissolving the resulting copolymer are preferred. Examples of the polymerization initiator include peroxides that generate radical species by heat, azo compounds, and redox polymerization initiators, and the same ones as described above can be used. Further, if necessary, a chain transfer agent can be used to adjust the molecular weight of the polymer. As the chain transfer agent, the same ones as described above can be used. The water-solubilization or water-dispersion of the copolymer obtained by solution polymerization may be performed according to a conventional method. For example, a method of adding the copolymer to the aqueous medium with stirring, a method of neutralizing the copolymer with an alkaline compound to form a salt of the copolymer, and then adding this to the aqueous medium with stirring. Is mentioned. As the copolymer, the organic solvent solution after the copolymerization may be used as it is, or the organic solvent solution of the copolymer may be a solid or liquid copolymer obtained by removing the organic solvent by a distillation or reprecipitation method in advance. A polymer may be used. When an organic solvent solution of the copolymer is used, it is preferable to disperse this in an aqueous medium and then distill off the organic solvent under reduced pressure. In the present invention,
It is preferable to use a copolymer excluding the organic solvent, since there is almost no problem such as odor and coloring of the aqueous composition finally obtained in the present invention. The copolymer (1) can also be produced by an emulsion polymerization method. However, in emulsion polymerization, when a highly water-soluble acidic unsaturated compound is used, the polymerization may become unstable, or the acidic unsaturated compound may be polymerized mainly in the aqueous phase without being incorporated into the polymer particles. is there. Therefore, when the emulsion polymerization method is adopted, the acidic unsaturated compound used is preferably one having lipophilicity as high as methacrylic acid.

In the production of the copolymer (1) in the emulsion polymerization, the amount of the polymerization initiator can be increased or a chain transfer agent can be used in order to adjust the molecular weight to be described later. Examples of the polymerization initiator include those mentioned in the polymerization described below, and examples of the chain transfer agent include the same ones as described above.

Although various emulsifiers can be used, in applications where water resistance is required, in order to prevent a decrease in water resistance due to the emulsifier, a method using a reactive emulsifier or a method using no emulsifier is used. An emulsifier-free polymerization method in which particles are emulsified with a polymerization initiator segment to carry out polymerization is preferred.

In the emulsion polymerization method, an alkaline compound may be added directly after the completion of the polymerization to make the salt of the copolymer water-soluble or water-dispersible.

The weight average molecular weight of the acidic polymer is 1,00.
0 to 500,000 is preferable, and more preferably 2,0
00 to 100,000. When this value is less than 1000, the strength, water resistance and adhesion to the polyolefin resin of the cured film may be insufficient. On the other hand, when this value exceeds 500,000, the acidic weight The polymerization reaction carried out in the presence of the coalescence (salt) may become unstable, causing problems such as aggregation.

The ratio of the maleimide group in the acidic polymer is preferably 0.04 to 4 mmol / g, more preferably 0.2 to 4 mmol / g. This ratio is 0.0
If it is less than 4 mmol / g, the cross-linking property may be deteriorated and satisfactory physical properties of the cured film may not be obtained.
When it exceeds g, the production becomes difficult, and when a compound having a (meth) acryloyl group, which will be described later, is added, the cured film may become cloudy.

The acid value of the acidic polymer is preferably 20 to 400, more preferably 40 to 200. If the acid value is less than 20, the polymerization stability may be lowered in the polymerization of the monomer in the presence of the acidic polymer (salt). If the acid value exceeds 400, the water resistance of the cured film and the The alkali resistance and the wettability with the polyolefin resin may decrease. As a monomer that constitutes the copolymer,
When a highly hydrophobic monomer such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and styrene is used, the acid value is preferably 100 to 400.

When the acidic group of the acidic polymer is a carboxyl group, it is preferable to neutralize a part or all of the carboxyl group in the copolymer with an alkaline compound to form a salt of the copolymer. The resulting aqueous composition has excellent stability. Examples of alkaline compounds include ammonia, organic amines, and inorganic bases such as sodium hydroxide and potassium hydroxide. Among these, ammonia or low molecular weight organic amines are preferable because they evaporate and scatter from the cured film during drying and the finally obtained cured film has excellent water resistance. Examples of low molecular weight organic amines include trialkylamines such as trimethylamine, triethylamine and tributylamine, and hydroxyalkylamines such as N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine.

When a compound having a (meth) acryloyl group, which will be described later, is added to the composition, it is preferable to use a tertiary amine which does not add to the (meth) acryloyl group among the above amines.

The neutralization ratio of the acidic polymer is 10 to 100 mol% based on the total amount of carboxyl groups in the polymer.
Are preferably neutralized, more preferably 30
~ 100 mol%. If this ratio is less than 10 mol%, the copolymer may be difficult to dissolve or disperse in the aqueous medium. As the addition ratio of the alkaline compound, similarly to the total amount of carboxyl groups in the polymer,
10-100 mol% is preferable, and more preferably 30-
It is 100 mol%. If this ratio is less than 10 mol%, the polymer may be difficult to dissolve or disperse in an aqueous medium as described above. On the other hand, if it exceeds 100 mol%, ammonia or amine may be used as an alkaline compound. When used, odor may remain in the resulting aqueous composition.

1-4. Maleimide group, ethylenically unsaturated group and
And a polymer containing an acidic group or a salt thereof , as the acidic polymer of the present invention, a polymer having an ethylenically unsaturated group in addition to a maleimide group and an acidic group (hereinafter referred to as an acidic unsaturated polymer) or a salt thereof [Hereinafter referred to as an acidic unsaturated polymer (salt)] is preferable because it has excellent curability. Examples of the maleimide group, ethylenically unsaturated group and acidic group include the same ones as described above, and the same ones as described above are preferable.

As the acidic unsaturated polymer in the present invention, those produced by various methods can be used.
Those produced by the methods shown in (1) 'to (6)' are preferable. (1) 'prepolymer having a maleimide group and an acidic group,
A method of adding an epoxy unsaturated compound. (2) ′ A method in which an acidic unsaturated compound is added to a prepolymer having a maleimide group and an epoxy group, and an acid anhydride is added to the hydroxyl group generated by this reaction. (3) 'A method of adding an isocyanate unsaturated compound to a prepolymer having a maleimide group, a hydroxyl group and an acidic group. (4) 'A method of adding a hydroxyl-based unsaturated compound to a prepolymer having a maleimide group, an isocyanate group and an acidic group. (5) 'A method of adding a hydroxyl-based unsaturated compound to a prepolymer having a maleimide group and an acid anhydride group. (6) A method of adding a maleimide alcohol and a hydroxyl-based unsaturated compound to a prepolymer having an acid anhydride group.

1-4-1. Method for Producing Prepolymer As a method for producing the prepolymer having a maleimide group in the above methods (1) ′ to (5) ′, a maleimide monomer and an acidic non-reactive monomer are used. Saturated compound [method of (1) 'above],
Epoxy unsaturated compound [the method of (2) '], hydroxy unsaturated compound and acidic unsaturated compound [the method of (3)'], isocyanate unsaturated compound and acidic unsaturated compound [the above The prepolymer can be obtained by copolymerizing the method (4) ′] and the acid anhydride unsaturated compound [the method (5) ′]. Examples of these unsaturated compounds are the same as those mentioned above.

If necessary, the prepolymer may be copolymerized with other monomers. Examples of the other monomer include the same ones as described above.

The prepolymer can be produced by polymerizing raw material monomers according to a conventional method such as a solution polymerization method, an emulsion polymerization method and a high temperature continuous polymerization method. In the production of the prepolymer, an isocyanate-based unsaturated compound and an acid anhydride-based unsaturated compound which are subject to decomposition by water are not used, and in the production method (1) 'and (2)', a solution polymerization method is used. Any of the emulsion polymerization method and the high temperature continuous polymerization method can be adopted, and in the production method of the above (3) 'to (6)' using an isocyanate unsaturated compound, a solution polymerization method and a high temperature continuous polymerization method. Is preferably adopted. However, in emulsion polymerization, when an acidic unsaturated compound having high water solubility is used, the polymerization becomes unstable, or the acidic unsaturated compound is not incorporated into the polymer particles and is mainly polymerized in the aqueous phase. Sometimes. Therefore, when the emulsion polymerization method is adopted, the acidic unsaturated compound used is preferably one having lipophilicity as high as methacrylic acid.

As the solution polymerization method, the high temperature continuous polymerization method and the emulsion polymerization method, the same methods as mentioned above can be mentioned.

In the present invention, in order to further improve the polymerization stability, other emulsifiers can be used in combination with the composition as long as the physical properties such as water resistance and chemical resistance are not impaired. Examples of other emulsifiers include the same as those mentioned above.

1-4-2. Method for Producing Acidic Unsaturated Polymer In the methods (1) ′ to (5) ′, the epoxy-unsaturated compound is added to the maleimide group-containing prepolymer having various functional groups. [Method (1) '], acidic unsaturated compound and acid anhydride [method (2)'], isocyanate unsaturated compound [method (3) '], hydroxy unsaturated compound [ An acidic unsaturated polymer can be obtained by adding the above method (4) 'or (5)'. Further, in the method (6) ′, an acid polymer can be obtained by adding maleimide alcohol to the acid anhydride group-containing prepolymer. Examples of these unsaturated compounds are the same as those mentioned above.

In the production of the prepolymer or the addition reaction of the unsaturated compound, the above-mentioned (1) 'and ((a) are used without using an isocyanate unsaturated compound and an acid anhydride unsaturated compound which are decomposed by water. 2) ′ In the production method, an acidic polymer can be produced by adding each unsaturated compound to the prepolymer in an organic solvent, an aqueous medium or a solvent-free manner. Further, the isocyanate-based unsaturated compound and the acid anhydride-based unsaturated compound (3) '~
In the manufacturing method of (6) ', in an organic solvent or without a solvent,
It is preferred to add each unsaturated compound to the prepolymer. As conditions for each addition reaction, the reaction temperature, reaction time and catalyst may be selected according to each reaction.

The ratio of the maleimide group in the acidic unsaturated polymer is 0.04 to 4 mmol / for the same reason as above.
g is preferable, and more preferably 0.2 to 4 mmol / g
Is. The ratio of the ethylenically unsaturated group in the acidic unsaturated polymer is 0.1 to 4 mmo for the same reason as above.
It is preferably 1 / g. The weight average molecular weight of the acidic unsaturated polymer is 1,000 to 50 for the same reason as above.
50,000 is preferable, and 2,000 to 1 is more preferable.
It is 0,000. The acid value of the acidic unsaturated polymer is preferably 20 to 400, more preferably 40 to 200 for the same reason as above.

In the composition of the present invention, a part or all of the acidic groups in the acidic unsaturated polymer are neutralized with an alkaline compound and dissolved or dispersed in an aqueous medium as a salt of the acidic unsaturated polymer. Preferably, it is used as an aqueous composition. The aqueous composition obtained from this has excellent stability. Examples of the method for forming the salt of the acidic unsaturated polymer include the same methods as described above.

The neutralization ratio of the acidic unsaturated polymer is preferably 10 to 100 mol% with respect to the total amount of acidic groups in the polymer for the same reason as above. More preferably, it is 30 to 100 mol%.

2. Other components 2-1. Compound having ethylenically unsaturated group (B) The composition of the present invention, the strength of the coating film, for the purpose of adjusting the flexibility and productivity, if necessary (A The compound (B) having an ethylenically unsaturated group other than the component (B) [hereinafter referred to as the component (B)] can be blended. As the component (B), various components other than the component (A) can be used, and both monomers and oligomers can be used.

2-1-1. Monomer Examples of the monomer include (meth) acrylate and vinyl ether. Examples of the (meth) acrylate include 2-hydroxyethyl (meth) acrylate and 2
-Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate; Acrylates of alkylene oxide adducts of phenol such as phenoxyethyl (meth) acrylate and halogen nucleus substitution products thereof; Mono or di (meth) acrylate of ethylene glycol Mono- or di (meth) acrylates of glycols such as mono (meth) acrylate of methoxyethylene glycol, mono- or di (meth) acrylate of tetraethylene glycol and mono- or di (meth) acrylate of tripropylene glycol; trimethylolpropane tri (Meth) acrylate, trihydroxyethyl isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ac Rate and (meth) acrylates of polyols such as dipentaerythritol hexaacrylate, and alkylene oxide adducts of these polyols (meth) acrylate.

Examples of vinyl ethers include triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether and hydroxyethyl vinyl ether.

Examples of the monomers other than the above include N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, N-vinylformamide and N-vinylacetamide.

2-1-2. Oligomer As the oligomer, urethane (meth) acrylate,
Examples thereof include polyester (meth) acrylate and epoxy (meth) acrylate. Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a polyol and an organic polyisocyanate reaction product with a hydroxyl group-containing (meth) acrylate. Here, as the polyol, there are low molecular weight polyol, polyethylene glycol, polyester polyol and the like. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol and 3-methyl-1,5-pentanediol, and examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Are reaction products of these low molecular weight polyols and / or polyether polyols with diacids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or acid components such as anhydrides thereof. . As the organic polyisocyanate, tolylene diisocyanate, 4,4'-
Examples thereof include diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Examples of the polyester (meth) acrylate oligomer include dehydration condensation products of polyester polyol and (meth) acrylic acid. As the polyester polyol, ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-
Low molecular weight polyols such as 1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, and polyols such as alkylene oxide adducts thereof, adipic acid, succinic acid, phthalic acid, Examples thereof include a reaction product with a dibasic acid such as hexahydrophthalic acid and terephthalic acid, or an acid component such as an anhydride thereof.

Epoxy acrylate is obtained by addition-reacting (meth) acrylic acid with epoxy resin, and includes (meth) acrylate of bisphenol A type epoxy resin, (meth) acrylate of phenol or cresol novolac type epoxy resin and polyether. Examples thereof include (meth) acrylic acid addition products of diglycidyl ether.

As the component (B), those having two or more (meth) acryloyl groups in one molecule are preferable because the obtained cured product is excellent in hardness and abrasion resistance. Further, as the component (B), it is preferable to use an aliphatic or alicyclic compound because it is excellent in weather resistance and curability as compared with a compound having an aromatic ring.

The component (B) preferably has a compatibility parameter (hereinafter abbreviated as SP value) in the range of 7.5 to 9.5, and more preferably in the range of 8.0 to 9.3. There is something. When the SP value of the component (B) is less than 7.5, the adhesion with the coating material or the like applied on the cured film may be reduced, and when it is greater than 9.5, the polyolefin resin of the composition is The wettability with respect to may decrease.
The SP value in the present invention refers to Michael M. Coleman et al .; Specific Interactions and the misc.
Compatibility of Polymer Blends); Technomic Publisher (T
echomic Publishing Co., Inc.) (Pennsylvania), published in 1991.

When the component (B) is blended, the proportion of the component (B) in the composition is 95 to 0 mass of the component (B) based on the total amount of the component (A) and the component (B). %, More preferably 90 to 20% by mass. If the ratio of the component (B) exceeds 95% by weight, the curability may be deteriorated, and the interfacial tension of the composition may be 45 dyn / c.
m or less, more preferably 41 dy
It is n / cm or less.

2-2. Photopolymerization Initiator The composition of the present invention is cured by irradiation with active energy rays, and even when cured by ultraviolet rays, it can be cured without the addition of a photopolymerization initiator. For the purpose of further improving the curability, a photopolymerization initiator can be blended within a range that does not impair the weather resistance.

As the photopolymerization initiator, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and its alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone and 2-methyl-
Acetophenones such as 1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone Such as anthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,
Examples include thioxanthone such as 4-diisopyrthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone such as benzophenone, and xanthone. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator. A preferred mixing ratio of these photopolymerization initiators is 5 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the composition.

2-3. Weather resistance improver The composition of the present invention contains one or more weather resistance improvers selected from ultraviolet absorbers, light stabilizers and antioxidants for the purpose of further improving weather resistance. Agents can also be included.

As the ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2
Examples thereof include benzotriazole-based ultraviolet absorbers such as-(3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole.

Examples of the light stabilizer include hindered amine type and benzoate type light stabilizers. Hindered amine-based light stabilizers include bis (1,2,2,2)
6,6-Pentamethyl-4-piperidinyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) and the like. As the benzoate-based light stabilizer, 2,4-di-
Examples thereof include t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

As the antioxidant, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-methyltriene glycol
Hydroxylphenyl) propionate] and 1,6-
Hexanediol-bis [3,5-di-t-butyl-4
-Hydroxyphenyl) propionate] and the like.

The preferred blending ratio of the weather resistance improver is 0.01 to 5 parts by mass with respect to 100 parts by mass of the composition. If this ratio is less than 0.01 parts by mass, the effect of blending the weather resistance improver component cannot be obtained, while if it exceeds 5 parts by mass, the curability of the composition is reduced or the composition obtained is The wear resistance of the cured product may decrease.

3. Active energy for polyolefin resin
Wire-curable primer composition The composition of the present invention is used as a primer for a polyolefin resin. It can be used as a primer for polyolefin resins in the fields of automobile interior parts, home appliances and office supplies. The polyolefin resin to which the composition of the present invention is applicable is applicable to various resins such as polyethylene resin, polypropylene resin, polybutadiene resin, cycloolefin resin,
Examples thereof include TPO resin, EPDM rubber and the like, and alloys and composite resins of these and other materials.

The composition may be used according to a conventional method. Specifically, for example, a method of irradiating active energy rays such as ultraviolet rays and electron beams to a desired polyolefin resin after applying it by a general coating method such as spray coating, roll coating and brush coating, etc. Can be mentioned.

On the surface of the obtained cured film, depending on the purpose,
Paints, inks, adhesives, etc. are painted, printed and adhered according to the usual methods. As the resin constituting the paint, ink, adhesive, etc., urethane type resin, silicon type resin and the like are preferable.

[0108]

EXAMPLES The present invention will be described more concretely with reference to the following examples. In the following,% means mass% and part means mass part. The abbreviations used are shown below. MMA: methyl methacrylate BA: butyl acrylate CHMA: cyclohexyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate HEA: hydroxyethyl acrylate MOI: methacryloxyethyl isocyanate THPI-A: 3,4,5,6-tetrahydrophthalimidoethyl acrylate, the following formula Compound represented by

[0109]

[Chemical 10]

DMI-M: dimethylmaleimidoethyl methacrylate, a compound represented by the following formula

[0111]

[Chemical 11]

PGM: Propylene glycol monomethyl ether AMBN: 2,2'-azobis (2-methylbutyronitrile) M-350: Aronix M-35 manufactured by Toagosei Co., Ltd.
0, trimethylolpropane ethylene oxide 3 mol modified triacrylate M-320: Aronix M-32 manufactured by Toagosei Co., Ltd.
0, trimethylolpropane propylene oxide 6 mol modified triacrylate M-305: Aronix M-30 manufactured by Toagosei Co., Ltd.
5, pentaerythritol triacrylate irgacure 184: photopolymerization initiator, manufactured by Ciba Geigy Ltd., hydroxycyclohexyl acetophenone

Production Example 1 (Production of Polymer A-1) In a flask equipped with a stirrer, a thermometer and a cooling tube, 30 g of THPI-A, 15 g of MMA and 10 g of BA were added at room temperature.
g, CHMA 20 g, MAA 15 g and PGM 1
Charge 00 g, stir to dissolve, then add AMBN
3 g was charged and uniformly dissolved. 85 ° C under nitrogen stream
The mixture was stirred for 2 hours at 100 ° C. for 1 hour to obtain a solution containing the polymer A-1. This is called polymer solution A-1. Regarding the obtained polymer solution A-1, the number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter Mw) of the polymer A-1.
Table 1 shows non-volatile components (hereinafter abbreviated as Nv).

Production Example 2 (Production of Unsaturated Polymer A-2) 1 part of GMA was added to the solution of the polymer A-1 obtained in Production Example 1.
0 g, triethylamine 0.5 g and hydroquinone 0.1 g were added and dissolved with stirring. Further, the mixture was heated and stirred at 100 ° C. for 5 hours to obtain a solution containing the unsaturated polymer A-2. This is called polymer solution A-2. Table 1 shows Mn, Mw, and Nv of the polymer A-2 of the obtained polymer solution A-2.

Production Example 3 (Production of Unsaturated Polymer A-3) In Production Example 1, 30 g of THPI-A and 26 g of MMA were used.
g, BA 20 g, MAA 14 g, PGM 100 g
A polymer was obtained in the same manner as in Production Example 1 except that 3 g of AMBN and AMBN were used. GMA was added to the obtained polymer solution.
10 g, triethylamine 0.5 g and hydroquinone 0.1 g were added and dissolved by stirring. 100 more
The solution was heated and stirred at 5 ° C. for 5 hours to obtain a solution containing the unsaturated polymer A-3. This is called polymer solution A-3. Table 1 shows Mn, Mw, and Nv of the polymer A-3 of the obtained polymer solution A-3.

Production Example 4 (Production of Unsaturated Polymer A-4) In Production Example 1, 40 g of DMI-M and 20 of MMA were used.
g, BA 14 g, HEA 11 g, butyl acetate 10
A polymer was obtained in the same manner as in Production Example 1, except that 0 g and 3 g of AMBN were used. The obtained polymer solution was added with M
15 g of OI, 0.1 g of dibutyltin laurate and 0.1 g of hydroquinone were added and dissolved with stirring. Further, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a solution containing the unsaturated polymer A-4. This is called polymer solution A-4. Regarding the obtained polymer solution A-4, Mn and M of the polymer A-4
Table 1 shows w and Nv.

[0117]

[Table 1]

Production Example 5 (Production of Acidic Polymer Salt A-5) A flask equipped with a stirrer, a thermometer and a condenser was charged with 145 g of ion-exchanged water, set in a water bath and blown with nitrogen to obtain an internal temperature. Was set to 80 ° C. Next, 1 g of ammonium persulfate as a polymerization initiator and 3 g of ion-exchanged water
Was dissolved in and added. Five minutes after the addition, 30 g of THPI-A, 15 g of MMA, 10 g of BA and 2 of CHMA were added.
100 parts of a mixture containing a monomer and a chain transfer agent, in which 5 g, 15 g of MAA and 5 g of OTG were mixed, was added dropwise over 2 hours for polymerization. After the dropping of the monomer mixture, it was aged for 1.5 hours. The reaction temperature was controlled within the range of 80 ° C ± 1 ° C. The polymerization was very stable with no formation of aggregates. As a result, an emulsion containing an acidic polymer A-5 having an acid value of 98 and Mw of 10,400 was obtained. The emulsion of this polymer had a solid content of 40.1% (a non-volatile content remaining after removing the volatile content by heating at 155 ° C. for 30 minutes, the same applies hereinafter). Further, 17.6 parts of triethylamine (hereinafter abbreviated as TEA) was added to this emulsion, and ion-exchanged water was further added so that the solid content was 30%, and the mixture was stirred, so that the salt of the acidic polymer A-5 was added to water. A dispersed liquid was obtained. This is called polymer aqueous solution A-5. Regarding the obtained polymer aqueous solution A-5, M of the polymer A-5
Table 2 shows w, acid value and Nv.

Production Example 6 (Production of Acidic Polymer Salt A-6) 30 g of THPI-A, 23 g of MMA, and 20 of BA
g, MAA (14 g) and OTG (3 g) were mixed, and an acidic polymer A-6 was produced in the same manner as in Production Example 5, except that the composition of the monomer and the chain transfer agent was changed. The emulsion of the obtained acidic polymer 2 had a solid content of 40.3%. Further, in the same manner as in Production Example 5, 9.9 g of TEA was added to this emulsion, ion-exchanged water was added so that the solid content was 30%, and the mixture was stirred to give a salt of the acidic polymer A-6.
A liquid dispersed in water was obtained. This is called polymer aqueous solution A-6. About the obtained polymer aqueous solution A-6, the polymer A
Table 2 shows Mw, acid value and Nv of -6.

Production Example 7 (Production of Acidically Unsaturated Polymer A-7) To the polymer aqueous solution A-6 of Production Example 6, 9.2 g of GMA and 0.1 g of hydroquinone were added and dissolved with stirring. Further, the mixture was heated and stirred at 100 ° C. for 5 hours to obtain a liquid in which the salt of the acidic unsaturated polymer A-7 was dispersed in water. This is called polymer aqueous solution A-7. Table 2 shows the Mw, acid value, and Nv of the polymer A-7 of the obtained polymer aqueous solution A-7.

[0121]

[Table 2]

Comparative Production Example 1 (Production of Polymer C-1) Polymerization C was performed in the same manner as in Production Example 1 except that the components and compositions shown in Table 3 below were used. A solution containing -1 was obtained. This is called polymer solution C-1. Regarding the obtained polymer solution C-1, the polymer C-
The Mn, Mw and Nv of 1 are shown in Table 3.

[0123]

[Table 3]

Comparative Production Example 2 Polymerization was carried out in the same manner as in Production Example 5 except that the components and compositions shown in Table 4 below were used, and the salt of polymer C-2 was dispersed in water. A liquid was obtained. This is called polymer aqueous solution C-2. Table 4 shows Mw, acid value and Nv of the obtained polymer aqueous solution C-2.

[0125]

[Table 4]

Example 1 50 parts of the polymer solution A-1 obtained in Production Example 1 (however, the number of parts in terms of solid content), M-350 (SP value: 9.
24 parts of 50) and 3 parts of Irgacure 184 were mixed with 100 parts of the solid content of the composition by an ordinary method to produce an active energy ray-curable composition. The obtained composition was evaluated for surface tension, curability and adhesion according to the following methods. The results are shown in Table 5.

○ Interfacial tension of evaluated composition Automatic interfacial tension meter [CBVP-Z type, Kyowa Interface Science Co., Ltd.
Manufactured by the company) was used, and the value 10 minutes after the start of measurement was taken as the interfacial tension of the composition.

An EPDM rubber substrate was used as a curable substrate, the obtained composition was applied to the substrate at a film thickness of 10 μ, dried under the following conditions, and then 120 W / cm condensing type high pressure mercury lamp. (1 light) Below 5m
It was passed at a conveyor speed of / min and evaluated by the number of passes until the surface was tack-free by touching with hands.

<Drying Conditions> Examples 1 to 12 and Comparative Examples 1 to 4: 50 ° C. × 15 min
Dry Examples 13 to 20 and Comparative Examples 5 to 8: 90 ° C. × 15 mi
n dry

Adhesion with a polyolefin resin A sample after the curability test was used and JISK-5400 was used.
According to the test method of 1., the cellophane tape was peeled off, and the squares remaining in 100 squares were used to evaluate the following four grades. ⊚: 100, ∘: 90 or more, Δ: 10 to 90, x: 10
Less than

Adhesion with Topcoat Paint A topcoat paint was applied onto the obtained cured film, and the adhesion with the topcoat paint was evaluated. An ultraviolet curable composition having the following composition was used as the top coat paint. <Coating composition used> A composition comprising pentaerythritol hexaacrylate (80 parts), a polymer (20 parts, the following monomer composition) and 3 parts of Irg184 ⁴ (photopolymerization initiator). -Polymer composition Methyl methacrylate (50 parts), isobornyl methacrylate (10 parts), styrene (40 parts) copolymer, Mw 45000 polymer. <Adhesion test> The coating composition was applied so as to have a film thickness of 10 μm, and the coating was applied under a 120 W / cm concentrating high pressure mercury lamp (1 lamp).
After passing and curing three times at a conveyor speed of 5 m / min, the cellophane tape was peeled off according to the test method of JISK-5400, and the squares in 100 squares were used for evaluation in the following four stages. ⊚: 100, ∘: 90 or more, Δ: 10 to 90, x: 10
Less than

Examples 2 to 12 Compositions for a primer were prepared in the same manner as in Example 1 except that the polymer solution and the component (B) shown in Table 5 below were used. In all the compositions, 3 parts of Irgacure 184 was added to 100 parts of the solid content of the composition.
Then, the description is omitted. The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 5.

[0133]

[Table 5]

Comparative Example 1 A primer composition was prepared in the same manner as in Example 1 except that the polymer solution and the component (B) shown in Table 6 below were used. In all the compositions, 3 parts of Irgacure 184 was added to 100 parts of the solid content of the composition.
Then, the description is omitted. The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 6.

[0135]

[Table 6]

Example 14 With respect to 50 parts of the acidic polymer A-5 obtained in Production Example 5 (however, the number converted to solid content), 50 parts of M-350 and 100 parts of the solid content of the composition. Irgacure 184 of 3
The parts were mixed according to a conventional method to prepare a primer composition. The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 7.

Examples 15 to 21 A primer composition was prepared in the same manner as in Example 13 except that the polymer solution and the component (B) shown in Table 7 below were used. All compositions had a solid content of 100%.
Although 3 parts of Irgacure 184 was blended to the parts, the description thereof is omitted in Table 7. The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 7.

[0138]

[Table 7]

Comparative Example 2 A primer composition was prepared in the same manner as in Example 13 except that the polymer aqueous solution and the component (B) shown in Table 8 below were used. The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0140]

[Table 8]

[0141]

EFFECT OF THE INVENTION The active energy ray-curable primer composition for polyolefin resin of the present invention has excellent adhesion to the polyolefin resin and further has excellent adhesion to the coating material or the like coated on the top of the automobile interior parts. It is useful as a primer for polyolefin resin used in various fields such as home electric appliances and office supplies, and has an extremely large industrial value.

Claims (7)

[Claims] 1. An active energy ray-curable primer composition for a polyolefin resin, which comprises a polymer (A) having a maleimide group. 2. The active energy ray-curable primer composition for polyolefin resin according to claim 1, wherein the component (A) is a polymer having a maleimide group and an ethylenically unsaturated group. 3. The active energy for a polyolefin resin according to claim 1 or 2, wherein the component (A) is a polymer containing a maleimide group and an acidic group or a salt thereof, and further contains an aqueous medium. Ray-curable primer composition. 4. The active energy ray-curable primer composition for polyolefin resin according to claim 3, wherein the component (A) is a polymer containing a maleimide group, an ethylenically unsaturated group and an acidic group or a salt thereof. . 5. The compound according to claim 1, which further comprises a compound (B) having an ethylenically unsaturated group other than the component (A).
An active energy ray-curable primer composition for polyolefin resin according to any one of 1. 6. The component (B) has a solubility parameter of 7.5.
The active energy ray-curable primer composition for a polyolefin-based resin according to claim 5, which is in a range of to 9.5. 7. The active energy ray-curable primer composition for a polyolefin resin according to claim 1, wherein the composition has an interfacial tension of 45 dyn / cm or less.