JP2002179953A - Actinic-radiation-curable resin composition for coating plastic, and coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a very useful resin composition which is curable by actinic radiation and can give a coating film excellent in wear resistance and adherence to a polycarbonate based resin molding, and a coated material made by using it. SOLUTION: The resin composition contains as the essential constituents (A) a urethane acrylate having a carbonate bond and (B) a polyfunctional (meth) acrylate compound. It can give a coating film excellent particularly in wear resistance and adherence to a polycarbonate based resin molding by applying it to a base material and curing it by actinic radiation. The coated material is obtained by using it.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful energy ray-curable resin composition for plastic coating,
And painted objects. More specifically, an energy ray-curable resin composition for plastic coating, comprising a carbonate bond-containing urethane acrylate (A) and a polyfunctional (meth) acrylate compound (B) as essential components, and The present invention can provide a coating film having excellent abrasion resistance, adhesion to a polycarbonate resin molded product, and surface hardness, particularly for a painted product of a polycarbonate resin molded product.

[0002]

2. Description of the Related Art In recent years, plastic materials such as engineering plastics are lightweight, and have excellent moldability and toughness.
It is used as a base material in general industry and daily necessities. However, plastics are inferior in surface hardness and abrasion resistance, so that the surface of the base material is often coated with a surface protective layer.

An energy ray-curing type coating agent which is cured by irradiation with ultraviolet rays, electron beams, etc.
Plastic surface protection layers have been put into practical use with added value such as energy saving, workability improvement, and productivity improvement.However, depending on the type of plastic base material, adhesion to the base material and surface hardness, In many cases, it is difficult to balance with abrasion.

When the number of functional groups of the polyfunctional acrylate compound is increased or the content of the compound is increased in order to satisfy abrasion resistance, the shrinkage due to the curing reaction in the polymerization reaction at the time of energy ray irradiation causes Distortion was generated at the interface of the coating film, and the coating film tended to peel or warp. In particular, transparency, strength, dimensional stability, electrical insulation,
Polycarbonate having excellent characteristics in terms of heat resistance and the like is a substrate whose adhesion is difficult to satisfy, and has a problem that it is difficult to balance adhesion, surface hardness, and abrasion resistance.

Therefore, a two-component reaction type polyurethane resin paint comprising a polyol compound and a polyisocyanate compound, as disclosed in Japanese Patent Application Laid-Open No. 05-007833, is used to prepare a molar ratio of isocyanate groups (NCO) to hydroxyl groups (OH). Improvement of adhesion and the like has been studied by a method of applying as a primer on polycarbonate at a ratio of (NCO / OH) of 1.3 to 5, and then applying an ultraviolet-curable paint thereon. However, since the two-component polyurethane resin paint has a pot life, its handling is complicated. In addition, the two-component polyurethane resin paint is reacted with the ultraviolet-curable paint after reacting the two-component polyurethane resin paint. Due to the coat method, productivity and work efficiency are deteriorated.

JP-A-56-28213 discloses a polyurethane acrylate comprising a polycarbonate diol, a diisocyanate compound and an acrylate monomer having a hydroxyl group. However, this publication discloses that a coating film obtained by radiation curing has a large tensile strength. It states the superiority of having strength, adherence to plastic substrates, especially polycarbonate resin moldings,
There was a problem that the surface hardness and the wear resistance were not improved.

[0007] JP-A-60-108477 and JP-A-62-215665 disclose polyurethane acrylate, acrylic acid, and monoethylenic unsaturated monomers comprising a polycarbonate diol, a diisocyanate compound and an acrylate monomer having a hydroxyl group. A UV-curable resin composition comprising a monomer and a photopolymerization initiator as essential components is disclosed, and if necessary, a polyfunctional acrylate monomer can be used in an amount of 25% by weight or less of the total amount of the composition. It is described. The composition disclosed in this publication requires a PC that requires post-processing because the coating film has toughness due to the polycarbonate component as a constituent component.
It states that it is effective for use as an overcoating agent for optical fibers where flexibility is required for paints and constructions or coatings. However, there is a problem in that there is no description about the adhesion to the plastic substrate, and no improvement has been made. Further, the amount of the polyfunctional acrylate monomer used is 25% of the total amount of the composition.
The use of more than 10 wt% is not preferred because the use of more than 10 wt% lowers the flexibility of the obtained coating film, and was not designed for the purpose of the surface hardness and abrasion resistance of the coating film.

[0008]

The problem to be solved by the present invention is to provide a coating film for plastic coating which can provide a coating film having excellent abrasion resistance, surface hardness and excellent adhesion to polycarbonate resin moldings among plastics. An object of the present invention is to provide an energy ray-curable resin composition and a coated product.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while aiming at the above-mentioned problems, and as a result, have found that urethane acrylate (A) containing a carbonate bond and polyfunctional (meth) acrylate Very useful for obtaining a coating film excellent in abrasion resistance, surface hardness, and especially adhesion to a polycarbonate resin molded product among plastics, characterized by containing the compound (B) as an essential component. A novel energy ray-curable resin composition and a coated product obtained by applying the composition to a plastic were found.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention relates to a plastic characterized by comprising [1] a urethane acrylate (A) containing a carbonate bond and a polyfunctional (meth) acrylate compound (B) as essential components. An object of the present invention is to provide an energy ray-curable resin composition for coating, and [2] a polycarbonate bond-containing urethane acrylate (A) comprising a polycarbonate polyol (a1).
And a urethane acrylate obtained by reacting a polyisocyanate compound (a2) with a hydroxyl group-containing (meth) acrylate compound (a3), which provides the energy ray-curable resin composition for plastic coating according to [1]. The present invention also provides an energy ray-curable resin composition for plastic coating according to [2], wherein the carbonate polyol (a1) is a diol. 4] The polyisocyanate compound (a2) is an aliphatic diisocyanate compound,
Alternatively, the present invention provides the energy ray-curable resin composition for plastic coating according to [2] or [3], which is a trimer of the aliphatic diisocyanate compound, and the present invention provides [5] a hydroxyl group-containing resin composition. The present invention provides the energy ray-curable resin composition for plastic coating according to any one of [2] to [4], wherein the (meth) acrylate compound (a3) is pentaerythritol triacrylate. The invention provides the energy ray for plastic coating according to any one of [1] to [5], wherein the [6] polyfunctional (meth) acrylate compound (B) is a 3 to 6-functional (meth) acrylate compound. Another object of the present invention is to provide a curable resin composition, wherein the polyfunctional (meth) acrylate compound (B) is dipentaerythritol pentaacrylate Which is a mixture of preparative and dipentaerythritol hexaacrylate are those provides [1] to [5] any one plastic coating for radiation-curable resin composition according to, present invention also
[8] The weight ratio (A) / (B) of the carbonate bond-containing urethane acrylate (A) to the polyfunctional (meth) acrylate compound (B) is 20/80 to 65/35, [1] to [7]. ] The present invention provides an energy ray-curable resin composition for plastic coating according to any one of [1] to [9], which is [9] an energy ray-curable resin composition for polycarbonate resin coating. 1] ~
[8] The invention provides an energy ray-curable resin composition for plastic coating according to any one of [8], and the present invention provides the plastic according to any one of [10] [1] to [9]. An object of the present invention is to provide a coated article characterized in that an energy ray-curable resin composition for coating is applied to a polycarbonate resin molded article.

The urethane acrylate (A) used in the present invention may be any urethane acrylate having a carbonate bond, and is not particularly limited. For example, a polycarbonate polyol (a1), a polyisocyanate compound (a2), and a hydroxyl group-containing (A) Examples thereof include those obtained by reacting with a (meth) acrylate compound (a3).

The polycarbonate polyol (a1) is
The polyol is not particularly limited as long as it has a carbonate bond in the molecule and has two or more hydroxyl groups. Among them, to prevent the polycarbonate polyol (a1) from reacting with the polyisocyanate compound (a2) to form a three-dimensional network structure and cause gelation,
Diols are preferred, and polycarbonate diol (a'1) represented by the following formula (1) is particularly preferred.

[0013]

Embedded image (Wherein R represents 2 to 20, preferably 2 to 8 carbon atoms)
Represents an alkylene group. X represents an integer of 1 to 40. )

The polycarbonate diol (a′1) is
It is a reaction product of a polyol and an organic carbonate compound or phosgene. As the polyol, for example, an alkylene glycol or a polyoxyalkylene glycol is used. Preferably, the molecular weight is between 300 and 3000.

R in the formula (1) preferably does not contain an aromatic group, particularly preferably an alkylene group, in order to prevent the urethane acrylate from having a high viscosity. Examples of the alkylene group include an ethylene group, a propylene group, a butylene group, and a hexamethylene group.

Examples of the polycarbonate diol (a'1) include 1,4-butanediol, 1,6-hexanediol ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 2-ethyl-1,
3 hexanediol, 1,5-pentanediol, 1,
Examples include 4-cyclohexanediol and polycarbonate diols made from polyoxyethylene glycol. These may be used alone or in combination of two or more having different molecular weights and compositions.

The polyisocyanate compound (a2) comprises 1
Compounds containing two or more isocyanate groups in the molecule, such as aliphatic diisocyanate compounds and aromatic diisocyanate compounds. The aliphatic diisocyanate compound referred to herein means a diisocyanate compound in which an isocyanate group is bonded to a chain carbon atom, a diisocyanate compound in which an isocyanate group is bonded to a carbon atom of a cyclic saturated hydrocarbon, and an aromatic diisocyanate compound. An isocyanate compound in which an isocyanate group is bonded to a carbon atom of an aromatic ring.

Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3- or 1,4- Diisocyanate cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, m- or p-tetramethylxylene diisocyanate, 1,
4-tetramethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, lysine Diisocyanate, norbornane diisocyanate and the like.

Examples of the aromatic diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate,
1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate,
Examples include diisocyanate monomers such as 1,4- or 1,6-phenylene diisocyanate.

Of these, an aliphatic diisocyanate compound and a trimer of the aliphatic diisocyanate compound are preferred for improving the weather resistance of the coating film. Examples of the trimer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanate, and specific examples thereof include hexamethylene diisocyanate and isophorone diisocyanate. These may be used alone or in a mixture.

The hydroxyl group-containing (meth) acrylate compound (a3) is a compound having at least one hydroxyl group and one (meth) acrylate in one molecule. Specifically, ethylene glycol mono (meth) acrylate , Propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tri Ethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Mono (meth) acrylates of dihydric alcohols such as polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ;

Trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris-2-hydroxyethyl isocyanurate mono (meth) acrylate, glycerin mono ( (Meth) acrylate, trimethylolpropanedi (meth) acrylate, ethoxylated trimethylolpropanedi (meth) acrylate, propoxylated trimethylolpropanedi (meth) acrylate, Tris 2
-Mono- and di- (meth) acrylates of trihydric alcohols such as hydroxyethyl isocyanurate di (meth) acrylate and glycerin di (meth) acrylate, and some of the hydroxyl groups of these alcohols have been modified with alkyl groups and ε-caprolactone. Mono and di (meth) acrylates;

Pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate,
Dipentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) ) Polyfunctional (meth) acrylates of tetravalent or higher alcohols having a hydroxyl group, such as acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanehexa (meth) acrylate, etc. And a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying a part of the hydroxyl group of these alcohols with an alkyl group or ε-caprolactone.

Among the above-mentioned hydroxyl group-containing (meth) acrylate compounds (a3), pentaerythritol triacrylate is particularly preferred because of its low viscosity and excellent curability due to having many polymerizable unsaturated double bonds.

The carbonate bond-containing urethane acrylate (A) used in the present invention is obtained by subjecting a polycarbonate polyol (a1), a polyisocyanate compound (a2) and a hydroxyl group-containing (meth) acrylate compound (a3) to the usual reaction conditions for urethanization reaction, That is, 20 ° C to 100 ° C,
Preferably, it can be obtained by reacting at 40 ° C to 80 ° C. The reaction can be performed under a nitrogen atmosphere,
The reaction is preferably carried out in a dry air atmosphere containing oxygen so that the acrylate groups do not undergo polymerization.

The ratio (OH / NCO) of the total number of moles of hydroxyl groups contained in the polycarbonate polyol (a2) and the hydroxyl group-containing (meth) acrylate compound (a3) to the number of moles of isocyanate groups contained in the polyisocyanate compound (a1) ) Is preferably 100/100 to 100/90. By making the total number of moles of hydroxyl groups larger than the number of moles of isocyanate groups, the remaining unreacted isocyanate groups can be reduced, and the storage stability can be improved.

When the total number of moles of hydroxyl groups is smaller than the number of moles of isocyanate groups, monoalcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol can be added to eliminate unreacted isocyanate groups.

In the urethanization reaction, a normal organic tin catalyst represented by dibutyltin diacetate or dibutyltin dilaurate, or a tertiary amine compound such as triethylamine may be used to promote the reaction. Further, in order to prevent polymerization of the acrylate group from occurring during the reaction, a polymerization inhibitor such as methoquinone or hydroquinone or an antioxidant may be used.

In the urethanization reaction, an organic solvent having no active hydrogen group that reacts with an isocyanate group can be used alone or in combination of two or more. Specific examples include ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and aromatic solvents such as toluene and xylene.

The polyfunctional (meth) acrylate compound (B) contained as an essential component in the energy ray-curable resin composition for plastic coating of the present invention is not particularly limited as long as it has two or more (meth) acrylate groups. Although not limited, 3 to 6 (meth) acrylate groups are contained in one molecule.
Are preferred.

(Meth) acrylate groups in one molecule
Examples of the (meth) acrylate compound having six compounds include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris-2-hydroxyethyl isocyanate. Tri (meth) acrylates such as nurate tri (meth) acrylate and glycerin tri (meth) acrylate;

Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra Polyfunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropanepenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ditrimethylolpropanehexa (meth) acrylate; Examples thereof include polyfunctional (meth) acrylates in which a part of these (meth) acrylates is substituted with an alkyl group or ε-caprolactone.

Among them, a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as the main components is particularly preferable since it has excellent curability and the resulting coating film has good abrasion resistance.

In the present invention, the mixing ratio of the urethane acrylate containing a carbonate bond (A) and the polyfunctional (meth) acrylate compound (B) is such that the adhesion to the plastic as the base material is good, and the coating film is hardly peeled off. Further, the weight ratio [(A) / (B)] is preferably 20/80 to 65/35 in order to sufficiently obtain the abrasion resistance of the obtained coating film.

Further, a polyfunctional (meth) acrylate compound (C) other than the polyfunctional (meth) acrylate compound (B)
And / or a monofunctional (meth) acrylate compound can be used in combination.

Polyfunctional (meth) acrylate compound (B)
Other polyfunctional (meth) acrylate compounds (C) include, for example, butanediol di (meth) acrylate,
Hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Di (meth) acrylates, such as neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, and hydroxypivalate neopentyl glycol di (meth) acrylate; other urethane acrylate resins, epoxy acrylate resins, Various types of energy ray curing such as resins containing unsaturated double bonds, represented by vinyl urethane resins, vinyl ester resins, unsaturated polyester resins, etc. Resins and the like.

Monofunctional (meth) acrylate compound (D)
For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-
Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloyl morpholine,
N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2- Ethoxyethyl (meth) acrylate, 3
-Methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide-modified phenoxy (meth) acrylate, propylene oxide Modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (Meth) acrylate, 2- (meth) acryloyloxyethyl-2-
Hydroxypropyl phthalate, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl Tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) Ada having monovalent mono (meth) acrylate derived from acrylate, 2-adamantane and adamantanediol Adamantane derivative mono (meth) acrylate, such as emissions chill acrylate.

Polyfunctional (meth) acrylate compound (C)
As the monofunctional (meth) acrylate compound (D), the above compounds may be used alone, or two or more kinds may be used in combination. , (A) and (B) is preferably 100 parts by weight or less, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the total amount.

The energy ray-curable resin composition for plastic coating used in the present invention may further contain an organic solvent (E), a photopolymerization initiator (F), a pigment (G), a natural or synthetic resin. Polymeric substances (H) and other compounding agents (I) can be used.

The composition of the present invention can use an organic solvent (E) for adjusting the viscosity. When an organic solvent is used, it is preferable to remove the organic solvent with a hot air drier after coating, and the amount used is not particularly limited, but is usually in a range where the solid content concentration of the coating material is 5 to 40% by weight. .

The organic solvent (E) usually has a boiling point of 5
Those having a temperature of 0 to 180 ° C are preferable from the viewpoint of workability during coating and drying before and after curing. For example, alcohol solvents such as methanol, isopropyl alcohol, n-butanol, and isobutanol; methyl acetate, ethyl acetate, Ester solvents such as butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; And mixtures thereof.

As the photopolymerization initiator (F), any of various types can be used, but if only typical ones are exemplified, benzophenone, benzyl, Michler's ketone, thioxanthone or anthraquinone can be used. Compounds that generate radicals by hydrogen abstraction are exemplified. These compounds are generally used in combination with tertiary amines such as methylamine, diethanolamine, N-methyldiethanolamine, and tributylamine.

As another type of photopolymerization initiator (F), for example, a compound of a type that generates a radical by intramolecular splitting can be mentioned. Specific examples include benzoin, dialkoxyacetophenone, acyl oxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like.

If necessary, a polymerization inhibitor such as hydroquinone, benzoquinone, tolhydrinoquinone or para-tert-butylcatechol may be added in combination with the photopolymerization initiator (F).

The pigment (G) is not particularly limited, and may be, for example, an extender, a white pigment, a black pigment, a gray pigment, and a pigment described in Handbook of Coating Materials, 1970 Edition (edited by the Japan Paint Manufacturers Association). Organic pigments and inorganic pigments such as a red pigment, a brown pigment, a green pigment, a blue pigment, a violet pigment, a metal powder pigment, a luminescent pigment, and a pearlescent pigment, and further, a plastic pigment. Various examples of these colorants (G) include various pigments. Examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc .; Lake C, Carmine 6B, Bordeaux Soluble azo pigments such as 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine-dyed lakes such as rhodamine lake and methyl violet lake;
Various mordant dye pigments such as quinoline lake and fast sky blue; various vat dye pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments; Quinacridone pigments; various oxazine pigments such as oxazine violet; various condensed azo pigments such as chromophtal; and aniline black.

Examples of the inorganic pigments include various chromates such as graphite, zinc chromate, molybdate orange and the like; various ferrocyan compounds such as navy blue and the like;
Various metal oxides such as titanium oxide, zinc oxide, mapico yellow, iron oxide, red iron oxide, chrome green, etc .; various sulfides or selenides such as cadmium yellow, cadmium red, mercury sulfide, etc .; barium sulfate, sulfuric acid Various sulfates such as lead; various silicates such as calcium silicate and ultramarine blue; calcium carbonate;
Various carbonates such as magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; Metallic pigments and pearl pigments, such as metal flake pigments, mica flake pigments, mica flake pigments coated with metal oxides, mica-like iron oxide pigments, and the like; graphite, carbon black, and the like.

Examples of the extender pigments include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, dolomite, alumina white, silica, hydrous finely divided silica (white carbon), ultrafine anhydrous silica (Aerosil),
Examples include silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess and the like.

Further, a plastic pigment [for example, Grandol PP-100 manufactured by Dainippon Ink and Chemicals, Inc.]
0, PP-2000S] can also be used.

The proportion of the pigment (G) used depends on the type of the pigment, the desired hue, the photopolymerization initiator (F) to be used, etc., and is not particularly limited. Since a large amount of ultraviolet light necessary for curing is absorbed, a range in which sufficient ultraviolet light for curing can be supplied to the unsaturated double bond produced by radical polymerization is preferable. Usually, the solid content is 100 parts by weight based on the solid content of the resin composition. The range of the pigment (G) is preferably 30 parts by weight or less.

The natural or synthetic high molecular substances (H) include various vinyl ester resins, polyisocyanate compounds, polyepoxides, acrylic resins, alkyd resins, urea resins, melamine resins, Polyvinyl acetate, vinyl acetate copolymers, polybutadiene elastomers, saturated polyesters or saturated polyethers, nitrocellulose or cellulose derivatives such as cellulose acetate butyrate; linseed oil, tung oil, soybean oil, castor oil or Fats and oils such as epoxidized oils are exemplified.

The other compounding agents (I) include antioxidants, ultraviolet absorbers, leveling agents, surfactants, slip agents, defoamers and the like.

The composition of the present invention as described above comprises
If necessary, it is adjusted to an appropriate coating viscosity with an organic solvent (E) or the like, and is applied to a plastic molding material as a base material, and ultraviolet, visible, laser, electron, X-ray, γ-ray, plasma, microwave Irradiation with such energy rays as above can be cured to produce a coating film.

Examples of the substrate include an ABS resin, a polymethyl methacrylate resin, a polycarbonate resin, and a synthetic resin molded product produced from such a polymer alloy resin. On the other hand, the energy ray-curable resin composition of the present invention has excellent adhesion.

[0054]

The present invention will be described in more detail with reference to the following examples. In the following, all parts and percentages are by weight unless otherwise specified. The isocyanate content is a numerical value representing the content of isocyanate groups contained in the sample on a weight basis.

Synthesis Example 1 (Urethane acrylate A1) In a 1 liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, 157.9 parts of isophorone diisocyanate, 0.1 part of dibutyltin diacetate, Sumilizer BHT 1.8 parts (manufactured by Sumitomo Chemical Co., Ltd .: antioxidant), Methoquinone (manufactured by Seiko Chemical Co., Ltd.):
(Polymerization inhibitor) 0.4 part was added, and the temperature was gradually increased while uniformly mixing.
After adding 279.0 parts of 8 (manufactured by Daicel Chemical Industries, Ltd .: polycarbonate diol, hydroxyl value 142.3),
The reaction was performed at 80 ° C. for 3 hours. In addition, Aronix M-
363.2 parts of 305 (manufactured by Toa Gosei Co., Ltd .: pentaerythritol triacrylate, hydroxyl value: 123) was added, and the mixture was further reacted at 80 ° C. for 5 hours.
9.1 parts and 99.1 parts of butyl acetate were added, and a carbonate bond-containing urethane acrylate (A1) (non-volatile content;
9.4%, Gardner viscosity; Z ₁ -Z ₂ ² (25 ° C.), Gardner color; 1 or less, isocyanate content: 0
%) Was obtained.

Synthesis Example 2 (Urethane acrylate A2) In the same reactor as in Synthesis Example 1, 184.8 parts of isophorone diisocyanate, 0.1 part of dibutyltin diacetate,
1.8 parts of Sumilyzer BHT and 0.4 part of methoquinone were added, and the temperature was gradually increased while uniformly mixing. When the temperature reached 60 ° C, Praxel CD205PL (manufactured by Daicel Chemical Industries, Ltd .: polycarbonate diol, hydroxyl value 22)
3.3) After adding 208.2 parts, the mixture was reacted at 80 ° C. for 3 hours. Further, Aronix M-3054066.2 parts was added, and the mixture was further reacted at 80 ° C. for 5 hours. Then, 100.0 parts of ethyl acetate and 100.0 parts of butyl acetate were added, and a urethane acrylate (A2) containing a carbonate bond (nonvolatile content) was added. ; 79.5%, Gardner viscosity; Z-Z ₁ ³ (25
C), Gardner color; 1 or less, isocyanate content: 0%).

Synthesis Example 3 (Urethane acrylate A3) In the same reactor as in Synthesis Example 1, Vernock DN-980 was used.
S (manufactured by Dainippon Ink and Chemicals, Inc .: isocyanurate type polyisocyanate, isocyanate content;
0%) 252.0 parts, dibutyltin diacetate 0.1
, 1.6 parts of Sumilyzer BHT and 0.3 part of methoquinone, and the temperature was gradually increased with uniform mixing. When the temperature reached 60 ° C, 165.5 parts of Praxel CD208 was added, followed by reaction at 80 ° C for 3 hours. I let it. Further, 383.0 parts of Aronix M-305 was added, and the mixture was further reacted at 80 ° C. for 5 hours. Then, 100.0 parts of ethyl acetate and 100.0 parts of butyl acetate were added, and a urethane acrylate containing a carbonate bond (A4) (non-volatile Min; 80.5%, Gardner viscosity; Z ₆ -Z ₇ (25 ° C.), Gardner color;
1 or less, isocyanate content: 0%).

Synthesis Example 4 (Urethane Acrylate A4) In the same reactor as in Synthesis Example 1, Vernock DN-980 was used.
S 391.2 parts, dibutyltin diacetate 0.1 part,
1.6 parts of Sumilyzer BHT and 0.3 parts of methquinone were added, and the temperature was gradually increased while uniformly mixing. When the temperature reached 60 ° C, 256.9 parts of Praxel CD208 was added, and the mixture was reacted at 80 ° C for 3 hours. . Further, 151.3 parts of 2-hydroxyethyl acrylate was added, and the mixture was further reacted at 80 ° C. for 5 hours. Then, 101.1 parts of ethyl acetate and 101.1 parts of butyl acetate were added, and a urethane acrylate containing a carbonate bond (A4 and ( Nonvolatile content: 80.8%,
Gardner viscosity; Z ₇ -Z ₈ (25 ° C.), Gardner color; 1 or less, isocyanate content;
I got a copy.

Comparative Synthesis Example (Urethane Acrylate A ')
1) In the same reactor as in Reference Example 1, Vernock DN-901 was used.
S (manufactured by Dainippon Ink and Chemicals, Inc .: isocyanurate type polyisocyanate, isocyanate content; 23.
38.6) 448.6 parts, dibutyltin diacetate 0.1
, 1.4 parts of Sumilyzer BHT and 0.3 part of methquinone were added, and the temperature was gradually increased while uniformly mixing. 80 ° C
For 3 hours. Further, 202.1 parts of 2-hydroxyethyl acrylate was added, and the mixture was further reacted at 80 ° C. for 5 hours.
50.0 parts were added, and urethane acrylate (A'1)
(Non-volatile content; 68.9%, Gardner viscosity; XY
³ (25 ° C.), 1000 parts of Gardner color; 1 or less, isocyanate content: 0%).

Examples and Comparative Examples Compositions (X1 to 4, RX1) were prepared by using the urethane acrylates (A1 to 4, A'1) obtained in the synthesis examples and the comparative synthesis examples according to the formulations shown in Table 1. did.

Examples 1 to 8, Comparative Examples 1 and 2 Polycarbonate, polycarbonate / AB as base material
Compositions (X1 to 4, RX1) prepared on each substrate using S alloy and polymethyl methacrylate plastic
Was applied using a bar coater so that the dry film thickness became 10 μm, and then dried at 70 ° C. for 10 minutes using a hot air drier to volatilize and remove the organic solvent. Next, using an ultraviolet irradiation device, a 5 m / cm.
The film was passed twice at a speed of min to form a cured coating film, and the obtained cured coating film was evaluated by the following method. The evaluation results are shown in Table 2 (1) and Table 2 (2).

<Evaluation method> (1) Primary adhesion: 1 mm × 1 on the coated surface with a cutter knife
100 mm grids were created, and Nichiban Co., Ltd. cellophane tape was attached thereto, followed by peeling. At this time, the number of grids in which the coating film adhered without peeling was evaluated. (2) Pencil hardness: A scratch test was carried out with a 1 kg load using a Mitsubishi Pencil Uni, and the hardness was indicated as one rank lower than the lowest hardness at which scratches were made. (3) Wear resistance: 1 using steel wool # 0000
After a 200 reciprocating abrasion test was carried out under a load of kg, those having no scratches on the appearance of the coating film were indicated by ○, and those having scratches were indicated by x. (4) Hot water adhesion test: After immersing the coated substrate in 50 ° C. hot water for 24 hours, the coated surface was 1 mm × 1 m with a cutter knife.
After 100 cross-cuts of m were created, and cellophane tape manufactured by Nichiban Co., Ltd. was attached, peeling was performed. At this time, the number of grids in which the coating film adhered without peeling was evaluated.

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[Table 1]

<Footnotes to Table 1> Kayarat DPHA: (mixture of dipentaerythritol hexaacrylate / dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.)

[0065]

[Table 2]

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[Table 3]

<Footnotes to Tables 2 (1) and 2 (2)> PC (abbreviation of polycarbonate): PC / ABS (abbreviation of polycarbonate / ABS alloy) manufactured by Testpiece Co., Ltd .: Uberoy CX55A (Ube (Sycon Corporation)
Injection molded product of PMMA (abbreviation of polymethyl methacrylate): Sumipec E (manufactured by Sumitomo Chemical Co., Ltd.)

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EFFECT OF THE INVENTION The energy ray-curable resin composition of the present invention and a coated article applied to a plastic using the same,
It comprises a carbonate bond-containing urethane acrylate (A) and a polyfunctional (meth) acrylate compound (B) as essential components. Among them, in particular, abrasion resistance, surface hardness, and plastics. An extremely useful energy ray-curable resin composition capable of obtaining a coating film having excellent adhesion, and a coated article using the same.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08F 290/06 C08F 290/06 F term (Reference) 4F100 AH02 AH08 AK25B AK25J AK45A AK51B AK51J AK74 AL01B AL05 BA02 BA07 CA06 EH46 EJ54 GB48 GB51 GB71 JK09 JK12 JL11 YY00B 4J027 AG03 BA24 BA26 BA27 CC03 CD08 4J034 BA08 CA02 CA04 CB01 CC02 DF02 DP18 HA07 HC01 RA07 4J038 DG121 DG261 FA112 FA281 GA03 PA17 PC08 PC08

Claims (10)

[Claims] 1. A carbonate bond-containing urethane acrylate (A) and a polyfunctional (meth) acrylate compound (B)
And an energy ray-curable resin composition for plastic coating, comprising: 2. The urethane acrylate (A) containing a carbonate bond is a polycarbonate polyol (a1).
The energy ray-curable resin composition for plastic coating according to claim 1, which is a urethane acrylate obtained by reacting a polyisocyanate compound (a2) with a hydroxyl group-containing (meth) acrylate compound (a3). 3. The energy ray-curable resin composition for plastic coating according to claim 2, wherein the carbonate polyol (a1) is a diol. 4. The polyisocyanate compound (a2) is
The energy ray-curable resin composition for plastic coating according to claim 2 or 3, which is an aliphatic diisocyanate compound or a trimer of the aliphatic diisocyanate compound. 5. The energy ray-curable resin composition for plastic coating according to claim 2, wherein the hydroxyl group-containing (meth) acrylate compound (a3) is pentaerythritol triacrylate. 6. The energy ray-curable resin for plastic coating according to claim 1, wherein the polyfunctional (meth) acrylate compound (B) is a tri- to hexa-functional (meth) acrylate compound. Composition. 7. The energy beam for plastic coating according to claim 1, wherein the polyfunctional (meth) acrylate compound (B) is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Curable resin composition. 8. A urethane acrylate containing a carbonate bond (A) and a polyfunctional (meth) acrylate compound (B)
The energy ray-curable resin composition for plastic coating according to any one of claims 1 to 7, wherein the weight ratio (A) / (B) is 20/80 to 65/35. 9. The energy ray-curable resin composition for plastic coating according to claim 1, which is an energy ray-curable resin composition for polycarbonate resin coating. 10. A coated article, characterized in that the energy ray-curable resin composition for plastic coating according to any one of claims 1 to 9 is applied to a polycarbonate resin molded article.