JP2008019314A - Ultraviolet curable coating agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet curable coating agent composition excellent in adhesion for a metal and a plastic and in designing properties. <P>SOLUTION: This ultraviolet curable coating agent composition comprises: 5 to 50 parts by mass of a thermoplastic polyurethane resin (A1) and/or a (meth)acrylate polymer (A2) having a specific recurring unit; 5 to 50 parts by mass of a monomer (B) having one or more carboxyl group(s) and one or more (meth)acryloyloxy group(s) in one molecule thereof; 5 to 70 parts by mass of a monomer (C) having one or more (meth)acryloyloxy group(s) in one molecule thereof; and 2 to 10 parts by mass of an optical polymerization initiator (D), relative to 100 parts by mass of all solid contents. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ultraviolet curable coating composition.

Plastics such as acrylic resin, polycarbonate resin, polystyrene resin, and ABS resin are used in various fields because they are lightweight, have excellent impact resistance and molding processability, and are inexpensive.
In general, plastic molded articles are coated with a coating film for the purpose of protecting the surface from damage.

  For example, in Patent Document 1, it is possible to sufficiently prevent deterioration of a molded product even when used outdoors for a long period of time, and it can be cured by ultraviolet irradiation having excellent scratch resistance, coating adhesion, crack resistance, and the like. For the purpose of providing a resin composition for coating, “(a) 1 to 2 functional monomer 10 having an ether bond and 1 to 2 acryloyloxy groups in one molecule and having a molecular weight of 130 to 700” Containing at least a film-forming component comprising: -70% by weight, (b) 5-60% by weight of an aliphatic urethane acrylate oligomer, and (c) 10-30% by weight of a methyl methacrylate polymer having a molecular weight of 10,000-200000, and An ultraviolet curable coating tree comprising, as essential components, (e) 2 to 10 parts by weight of a photopolymerization initiator and (f) 2 to 20 parts by weight of an ultraviolet absorber for 100 parts by weight of a coating film component. Composition. "Is described.

  Patent Document 2 discloses a photocurable resin composition for modifying a polyolefin surface, which is used for forming a cured coating film having excellent friction resistance and adhesion on the surface of polyolefin. Component: In the side chain of the methyl methacrylate homocopolymer, the methyl methacrylate copolymer having a methyl methacrylate content of 80% by weight or more, and the methyl methacrylate copolymer having a methyl methacrylate content of 80% by weight or more ( At least one polymer selected from a modified product having a meth) acryloyl group introduced therein, (B) component: polyfunctional acrylate containing 50% by weight or more of dipentaerythritol hexaacrylate, (C) component: solvent, and ( Component D): A photopolymerization initiator is contained, and the weight ratio of component (A) / component (B) is in the range of 0.1 to 10. The photocurable resin composition for polyolefin surface modification is described.

  Patent Document 3 discloses a molded product in which a hard coat layer having excellent adhesion, wear resistance, chemical resistance, heat resistance, appearance, and the like is provided on the surface of a molded product made of a thermoplastic norbornene resin, and For the purpose of providing the production method, “(A) 20 to 100% by weight of a polyfunctional monomer (a-1) having three or more (meth) acryloyloxy groups in one molecule; 10 to 90 parts by weight of a monomer mixture consisting of 80 to 0% by weight of 1 to 2 functional monomer (a-2) having 1 to 2 (meth) acryloyloxy groups in the molecule, (B) 5-80 parts by weight of a coating resin comprising a homopolymer or copolymer of a vinyl monomer containing at least 10% by weight of at least one monomer selected from (meth) acrylic acid esters, and (C) UV curing comprising 0.1 to 15 parts by weight of photopolymerization initiator The thermoplastic norbornene-based resin molded article having a hard coat layer formed by curing the sexual composition. "Is described.

Patent Document 4 contains a photopolymerizable compound in which an ester bond is not easily hydrolyzed even in an acidic high temperature etching solution, and forms an etching pattern by corroding a metal plate like a high quality shadow mask or lead frame. Photopolymerization represented by the chemical formula 1 [CH ₂ = CR′COO (CH ₂ CHR ″ COO) _n H] for the purpose of providing an ultraviolet curable resin composition suitably used as a cured film used in An ultraviolet curable resin composition containing at least a functional compound, a polyfunctional monomer, and a polymerization initiator (wherein n is 0 to 3, R ′ and R ″ are H or a methyl group) Is).

  In Patent Document 5, there is superior corrosion resistance to acid etching solutions and uniform coating film formation without coating unevenness compared to conventional water-soluble resin type or UV curable anticorrosive backing agents. For the purpose of providing an ultraviolet curable composition for corrosion protection of metal etching, in which part of the coating film constituent material does not elute into the etching solution, has high fine processing accuracy, and can be easily peeled off with an alkaline solution. A (meth) acrylate compound (component A) having at least one carboxyl group and at least one (meth) acryloyl group at the terminal, and a polyfunctional (meth) acrylate and / or a monofunctional (meth) acrylate other than the component A (B component) and a photopolymerization initiator (C component) containing a compound having a specific structure, which is an acid-resistant and alkali-soluble metal etch UV-curable composition for grayed corrosion is described.

JP 2000-281935 A Japanese Patent Publication No. 7-91489 Japanese Patent No. 3377301 JP 2001-354730 A JP 2002-20411 A

However, the inventor has found that the composition described in Patent Document 1 is inferior in adhesion to metal.
Moreover, this inventor discovered that the composition containing the (meth) acrylate type polymer as described in patent document 2 or 3 was inferior to adhesiveness with a plastics.
It has been found that when a composition as described in Patent Documents 1 to 5 is applied to a substrate by spin coating, the resulting laminate is inferior in design.
Then, an object of this invention is to provide the ultraviolet curable coating agent composition which is excellent in the adhesiveness with respect to a metal and a plastic, and designability.

  As a result of intensive studies to solve the above problems, the present inventor has found that a composition containing a specific resin and / or (meth) acrylate polymer and a specific monomer in a specific quantitative ratio is a metal and The present invention has been completed by finding that it can be an ultraviolet curable coating agent composition excellent in adhesiveness and design to plastics.

That is, the present invention provides the following (1) to (9).
(1) In 100 parts by mass of the total solid content,
5 to 50 parts by mass of the thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2) having a repeating unit represented by the following formula (1),
5 to 50 parts by mass of a monomer (B) having one or more carboxy groups and one or more (meth) acryloyloxy groups in one molecule;
5 to 70 parts by mass of the monomer (C) having one or more (meth) acryloyloxy groups in one molecule;
The ultraviolet curable coating agent composition containing 2-10 mass parts of photoinitiators (D).

(式中、Ｒは、水素原子またはメチル基である。)

(In the formula, R is a hydrogen atom or a methyl group.)

(2) The ultraviolet curable coating agent composition according to the above (1), wherein the thermoplastic polyurethane resin (A1) has a molecular weight of 3,000 to 100,000.
(3) The ultraviolet curable coating composition according to the above (1) or (2), wherein the (meth) acrylate polymer (A2) has a molecular weight of 10,000 to 300,000.
(4) The ultraviolet curable coating agent composition according to any one of (1) to (3), wherein the monomer (B) is a compound represented by the following formula (2).

（式中、ｎは、０〜１の整数である。）

(In the formula, n is an integer of 0 to 1.)

(5) The ultraviolet curable coating agent composition according to any one of (1) to (4), wherein the monomer (C) is a compound represented by the following formula (3).

(6) The ultraviolet curable coating composition according to any one of (1) to (5), further comprising a methyl methacrylate polymer (A3).
(7) The ultraviolet curable coating composition according to (6), wherein the methyl methacrylate polymer (A3) has a molecular weight of 10,000 to 300,000.
(8) The ultraviolet curable coating composition according to any one of (1) to (7), further comprising a urethane (meth) acrylate compound (E).
(9) The ultraviolet curable coating composition according to (8), wherein the amount of the urethane (meth) acrylate compound (E) is 5 to 50 parts by mass in 100 parts by mass of the total solid content.

  The ultraviolet curable coating agent composition of the present invention is excellent in adhesion and design to metals and plastics.

The present invention will be described in detail below.
The present invention
In 100 parts by mass of the total solid content,
5 to 50 parts by mass of the thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2) having a repeating unit represented by the following formula (1),
5 to 50 parts by mass of a monomer (B) having one or more carboxy groups and one or more (meth) acryloyloxy groups in one molecule;
5 to 70 parts by mass of the monomer (C) having one or more (meth) acryloyloxy groups in one molecule;
It is an ultraviolet curable coating agent composition containing 2-10 mass parts of photoinitiators (D).

  In the formula, R is a hydrogen atom or a methyl group.

The ultraviolet curable coating agent composition of the present invention contains a thermoplastic polyurethane resin (A1) and / or a (meth) acrylate polymer (A2) as a film-forming component.
The thermoplastic polyurethane resin (A1) will be described below.
The thermoplastic polyurethane resin is a mixture of an active hydrogen-containing compound containing a polyol compound and a polyisocyanate compound, so that the molar ratio of isocyanate group (NCO group) to active hydrogen is about 1/1, and reacting. It is a linear polymer obtained.
When the ultraviolet curable coating agent composition of the present invention contains the thermoplastic polyurethane resin (A1), the viscosity is high and the film-forming property is excellent.

The polyisocyanate compound used when producing the thermoplastic polyurethane resin (A1) is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule.
Specific examples include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'- MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1, Aromatic polyisocyanates such as 5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI) What aliphatic polyisocyanate; trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), _{H 12} MDI (hydrogenated MDI), fat such as H ₆ TDI (hydrogenated TDI) Cyclic polyisocyanates; polyisocyanate compounds such as polymethylene polyphenylene polyisocyanates; carbodiimide-modified polyisocyanates of these isocyanate compounds; isocyanurate-modified polyisocyanates of these isocyanate compounds.

Of these, isophorone diisocyanate and tolylene diisocyanate are preferred from the viewpoints of excellent film forming properties and excellent design properties.
A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.
A monoisocyanate compound having only one NCO group in the molecule can also be used by mixing with a diisocyanate compound or the like.

If the polyol compound used when manufacturing a thermoplastic polyurethane resin (A1) is a compound which has 2 or more of hydroxyl groups (OH group), the molecular weight, frame | skeleton, etc. will not be specifically limited.
Examples thereof include low-molecular polyhydric alcohols, polycarbonate polyols, polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  The low molecular weight polyhydric alcohol as the polyol compound is not particularly limited. For example, ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, pentanediol, neopentylglycol, hexanediol, cyclohexanedimethanol, glycerin, Low molecular polyols such as 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol; and saccharides such as sorbitol.

The polycarbonate polyol as the polyol compound is not particularly limited.
For example, transesterification of alcohols such as 1,6-hexanediol, 1,4-butanediol, and 1,5-pentanediol with dialkyl carbonates such as dimethyl carbonate and diethyl carbonate is carried out in the presence of a catalyst. Can be obtained.

Examples of the polyether polyol and polyester polyol as the polyol compound usually include those derived from low-molecular polyhydric alcohols. Low molecular weight polyhydric alcohols can be mentioned as one of preferred embodiments derived from aromatic diols.
Examples of aromatic diols include xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; bisphenol A structure (4,4′-dihydroxyphenylpropane) shown below. ), A bisphenol F structure (4,4'-dihydroxyphenylmethane), a brominated bisphenol A structure, a hydrogenated bisphenol A structure, a bisphenol S structure, and a bisphenol AF structure.

As the polyether polyol, for example, at least one selected from low molecular weight polyhydric alcohols and / or aromatic diols, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide (tetramethylene oxide), styrene oxide, and the like. The polyol obtained by adding is mentioned.
Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol.
Specific examples of polyether polyols having a bisphenol skeleton include polyether polyols obtained by adding ethylene oxide and / or propylene oxide to bisphenol A (4,4'-dihydroxyphenylpropane). .

Examples of the polyester polyol as the polyol compound include condensates of low-molecular polyhydric alcohols and / or aromatic diols and polybasic carboxylic acids (condensation polyester polyols); lactone polyols; polycarbonate polyols. .
Examples of the polybasic carboxylic acid used in the production of the condensed polyester polyol include glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and others. And low molecular carboxylic acids, oligomeric acids, castor oil, and hydroxycarboxylic acids such as a reaction product of castor oil and ethylene glycol.
Examples of the lactone-based polyol include ring-opening polymers such as propionlactone and valerolactone.
In addition, examples of the polyester polyol having a bisphenol skeleton include condensed polyester polyols obtained by using a diol having a bisphenol skeleton instead of or together with a low molecular polyhydric alcohol. Specific examples include polyester polyols obtained from bisphenol A and castor oil, polyester polyols obtained from bisphenol A, castor oil, ethylene glycol, and propylene glycol.

  Examples of other polyol compounds include polymer polyols having a carbon-carbon bond in the main chain skeleton such as acrylic polyols; polybutadiene polyols; and hydrogenated polybutadiene polyols.

The polyol compound is preferably a polyester polyol from the viewpoint of excellent film-forming properties and excellent design properties.
A polyol compound can be used individually or in combination of 2 types or more, respectively.

As the active hydrogen-containing compound to be reacted with the polyisocyanate compound, an amine compound can be used in combination with the polyol compound.
Examples of the amine compound include amines and alkanolamines.
Examples of amines include xylylenediamine, ethylenediamine, and trimethylenediamine.
Examples of alkanolamines include ethanolamine and propanolamine.

  The thermoplastic polyurethane resin (A1) is preferably obtained by reacting a polyester polyol and isophorone diisocyanate from the viewpoints of excellent film-forming properties, increasing the viscosity of the composition, and improving design properties.

In the present invention, the thermoplastic polyurethane resin (A1) has a number average molecular weight of 3,000 to 100,000 from the viewpoints of excellent film-forming properties, high viscosity of the composition, and excellent design properties. Is preferable, and it is more preferable that it is 10,000-40,000.
In addition, the thermoplastic polyurethane (A1) has excellent film-forming properties, increases the viscosity of the composition, and is superior in design properties. In this specification, the viscosity measured by an E-type viscometer (in this specification, The viscosity is measured in the same manner below.) Is preferably 5 to 100 mPa · s, more preferably 10 to 50 mPa · s.

  A commercially available product can be used as the thermoplastic polyurethane resin (A1). Examples of commercially available products of the thermoplastic polyurethane resin (A1) include SBU lacquer 0866 manufactured by Sumitomo Bayer Urethane Co., Ltd., Desmocol 400, Desmocol 500, and Pandex T5205 manufactured by Dainippon Ink.

  The amount of the thermoplastic polyurethane resin (A1) is 5 to 30 parts by mass in 100 parts by mass of the total solid content in the composition from the viewpoint of excellent film forming properties, increasing the viscosity of the composition, and being excellent in design. It is preferable that it is 10-20 mass parts.

The (meth) acrylate polymer (A2) will be described below.
The (meth) acrylate polymer (A2) contained in the ultraviolet curable coating agent composition of the present invention has a repeating unit represented by the following formula (1).

  In the formula, R is a hydrogen atom or a methyl group.

In the present specification, (meth) acrylate means acrylate or methacrylate.
In the present specification, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group. When two or more (meth) acryloyloxy groups are contained in one molecule, the (meth) acryloyloxy groups may be the same or different.
In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

The (meth) acrylate polymer (A2) is not particularly limited as long as it has a repeating unit represented by the formula (1).
Further, the (meth) acrylate polymer (A2) is not limited for its production. For example, by polymerizing 2-hydroxy-3-phenoxypropyl (meth) acrylate and (meth) acrylic acid alkyl ester represented by the following formula (4) in a solvent using a polymerization initiator and a chain transfer agent. Obtainable.
When the 2-hydroxy-3-phenoxypropyl (meth) acrylate represented by the formula (4) is polymerized, the repeating unit represented by the formula (1) is obtained.

  In the formula, R is a hydrogen atom or a methyl group.

Examples of the (meth) acrylic acid alkyl ester that can be used in producing the (meth) acrylate polymer (A2) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl Examples include methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, and octyl methacrylate.
Of these, methyl methacrylate, butyl acrylate, and butyl methacrylate are preferable, and methyl methacrylate and butyl methacrylate are more preferable from the viewpoint of increasing the viscosity of the composition and improving the design and adhesiveness.

Mole ratio of 2-hydroxy-3-phenoxypropyl (meth) acrylate and (meth) acrylic acid alkyl ester represented by formula (4) (2-hydroxy-3-phenoxypropyl (meth) acrylate / (meth) acrylic) The acid alkyl ester) is preferably from 10/1 to 1/10, more preferably from 5/1 to 1/5, from the viewpoint of increasing the viscosity of the composition and being superior in design and adhesion. preferable.
When methyl methacrylate and butyl acrylate are used as the (meth) acrylic acid alkyl ester, the molar ratio of 2-hydroxy-3-phenoxypropyl (meth) acrylate represented by formula (4) to methyl methacrylate and butyl acrylate [2-hydroxy-3-phenoxypropyl (meth) acrylate / (methyl methacrylate + butyl acrylate)] is represented by the formula (4): 2-hydroxy-3-phenoxypropyl (meth) acrylate and (meth) acrylic acid It is the same as the molar ratio with the alkyl ester, and the molar ratio of butyl acrylate to methyl methacrylate (butyl acrylate / methyl methacrylate) is 10/1 from the viewpoint of increasing the viscosity of the composition and being superior in design and adhesion. ~ 1/10 Is preferably that, and more preferably 5 / 1-1 / 5.

A polymerization initiator will not be restrict | limited especially if it can be used when manufacturing a (meth) acrylate polymer. For example, α, α′-azobisisobutyronitrile and di-t-butyl peroxide are exemplified.
The amount of the polymerization initiator is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used when the (meth) acrylate polymer (A2) is produced, and 0.5 to 3 More preferred is part by mass.

A chain transfer agent will not be restrict | limited especially if it can be used when manufacturing a (meth) acrylate polymer. Examples thereof include n-octyl mercaptan and n-dodecyl mercaptan.
The amount of the chain transfer agent is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used when the (meth) acrylate polymer (A2) is produced, and 0.5 to 3 More preferred is part by mass.

A solvent will not be restrict | limited especially if it can be used when manufacturing a (meth) acrylate polymer. Examples thereof include methyl ethyl ketone (MEK), ethyl acetate, and butyl acetate.
The amount of the solvent is preferably 100 to 500 parts by mass, and 200 to 400 parts by mass with respect to 100 parts by mass of the total amount of monomers used when the (meth) acrylate polymer (A2) is produced. More preferred.

The reaction temperature for producing the (meth) acrylate polymer (A2) is preferably 50 to 100 ° C, more preferably 60 to 80 ° C.
The (meth) acrylate polymer (A2) is preferably prepared, for example, in an inert gas atmosphere such as nitrogen gas or argon.

  In the present invention, the (meth) acrylate polymer (A2) has a repeating unit represented by the formula (1) in one molecule from the viewpoint of increasing the viscosity of the composition and being excellent in design properties and adhesiveness. It is preferable to have 5 to 30 mol%, more preferably 10 to 20 mol%, in 100 parts by mass of the total amount of the (meth) acrylate monomer used.

  When the (meth) acrylate polymer (A2) has a repeating unit other than the repeating unit represented by the formula (1), a repeating unit other than the repeating unit represented by the formula (1) is used. It is preferable to have 5 to 30 mol%, and more preferably 10 to 20 mol%, in 100 parts by mass of the total amount of the monomer.

  In addition, the (meth) acrylate polymer (A2) preferably has a number average molecular weight of 10,000 to 300,000 from the viewpoint of increasing the viscosity of the composition and being superior in design and adhesiveness. More preferably, it is 20,000-100,000.

  The amount of the (meth) acrylate polymer (A2) is preferably 5 to 50 parts by mass in 100 parts by mass of the total solid content from the viewpoint of increasing the viscosity of the composition and being excellent in design and adhesiveness. 10 to 40 parts by mass is more preferable.

  When the thermoplastic polyurethane resin (A1) and the (meth) acrylate polymer (A2) are used in combination as a film-forming component, the viscosity of the composition is increased, the composition does not easily sag, and the design properties and adhesiveness Excellent.

In the present invention, the amount of the thermoplastic polyurethane resin (A1) and / or the (meth) acrylate polymer (A2) is 5 to 50 parts by mass in 100 parts by mass of the total solid content in the composition.
Among them, the amount of the thermoplastic polyurethane resin (A1) and / or the (meth) acrylate polymer (A2) is increased from the viewpoint of increasing the viscosity of the composition and being excellent in design properties and adhesiveness. It is preferable that it is 5-50 mass parts in 100 mass parts of solid content, and it is more preferable that it is 10-40 mass parts.

  When the thermoplastic polyurethane resin (A1) and the (meth) acrylate polymer (A2) are used in combination as a film-forming component, the viscosity of the composition is increased, the composition does not easily sag, and the design properties and adhesiveness From the viewpoint of superiority, the mass ratio of the thermoplastic polypolyurethane resin (A1) and the (meth) acrylate polymer (A2) (thermoplastic polypolyurethane resin (A1) / (meth) acrylate polymer (A2)) is 1 It is preferably / 10 to 1/1, and more preferably 1/5 to 1/2.

  The ultraviolet curable coating agent composition of the present invention can further contain a methyl methacrylate polymer (A3) as a film-forming component. In such a case, the scratch resistance is excellent and the adhesiveness is excellent.

The methyl methacrylate polymer (A3) will be described below.
The methyl methacrylate polymer (A3) that the ultraviolet curable coating composition of the present invention can further contain is not particularly limited as long as it is a homopolymer of methacrylic acid methyl ester.

Especially, it is preferable that the number average molecular weight of a methyl methacrylate polymer (A3) is 10,000 or more from a viewpoint that it is excellent in film forming property and can become a composition which is hard to sag when apply | coated.
Moreover, it is preferable that the number average molecular weight of a methylmethacrylate polymer (A3) is 300,000 or less from a viewpoint that the composition obtained is easy to apply | coat with a spray and is excellent in design property.
In addition, the number average molecular weight of the methyl methacrylate polymer (A3) is 10,000 to 300, from the viewpoint that it is excellent in film-forming property, becomes a composition that hardly sags when applied and is easily applied by spray, and is superior in design properties. 000 is preferable, and 50,000 to 150,000 is more preferable.

The methyl methacrylate polymer (A3) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
Moreover, a commercial item can be used for the methyl methacrylate polymer (A3). As a commercial item of the methyl methacrylate polymer (A3), for example, trade names Delpet 60N and Delpet 80N (both manufactured by Asahi Kasei Chemicals) may be mentioned.
In this invention, since a commercial item can be used as a methyl methacrylate polymer (A3), it is not necessary to superpose | polymerize a methyl methacrylate polymer, and manufacture of a composition can be performed simply.

  In the present invention, the amount of the methyl methacrylate polymer (A3) is 5 to 100 parts by mass in total solid content from the viewpoint of excellent adhesiveness and design properties, low viscosity and excellent spray coating properties, and difficult to sagging the paint. It is preferably 20 parts by mass, more preferably 10 to 15 parts by mass.

The monomer (B) will be described below.
The monomer (B) contained in the ultraviolet curable coating agent composition of the present invention has one or more carboxy groups and one or more (meth) acryloyloxy groups in one molecule. .

The monomer (B) contains one or more carboxy groups (—COOH) and one or more (meth) acryloyloxy groups (CH ₂ ═CR—COO—, R: H or —CH ₃ in one molecule. ) And is not particularly limited.

A monomer (B) is mentioned as one of the aspects with preferable having a carboxy group at the terminal.
The number of carboxy groups is preferably 1 to 3 in the monomer (B) from the viewpoint of excellent adhesiveness and excellent compatibility with the resin.

The number of (meth) acryloyloxy groups in one molecule of the monomer (B) is one or more.
The number of (meth) acryloyloxy groups in one molecule of the monomer (B) is preferably 1 to 2 from the viewpoint of being excellent in adhesiveness and design properties. Hereinafter, a monomer having one or more carboxy groups and one or two (meth) acryloyloxy groups in one molecule may be referred to as “monomer (B-1)”.
Further, the number of (meth) acryloyloxy groups in one molecule of the monomer (B) is preferably 3 to 6 from the viewpoints of adhesiveness and coating film hardness. Hereinafter, a monomer having one or more carboxy groups and three or more (meth) acryloyloxy groups in one molecule may be referred to as “monomer (B-2)”.

  In this invention, it is preferable that a monomer (B) is a monomer (B-1) and / or a monomer (B-2) from a viewpoint that it is excellent with adhesiveness and designability.

  Examples of the monomer (B-1) include a reaction product of hydroxy (meth) acrylate and a polybasic acid and / or an acid anhydride thereof, ω-carboxypolycaprolactone mono (meth) acrylate, (meth) acrylic. An acid dimer is mentioned.

The reaction of hydroxy (meth) acrylate with a polybasic acid and / or acid anhydride thereof is not particularly limited, and examples thereof include conventionally known methods.
Examples of the polybasic acid and anhydride used in the reaction of hydroxy (meth) acrylate with the polybasic acid and / or acid anhydride thereof include succinic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid. Acid, sebacic acid, adipic acid, azelaic acid, glutaric acid, suberic acid, malonic acid, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, methylhexahydrophthalic acid, methyltetrahydro Phthalic acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like, and mixtures thereof.

  Examples of the hydroxy (meth) acrylate used in the reaction of the hydroxy (meth) acrylate with a polybasic acid and / or its anhydride include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and the like, and mixtures thereof.

  As the monomer (B-1) obtained by reacting a polybasic acid and / or acid anhydride thereof with hydroxy (meth) acrylate, for example, synthesized from 2-hydroxypropyl (meth) acrylate and tetrahydrophthalic anhydride 2- (meth) acryloyloxypropyl monotetrahydrophthalate and the like.

  The ω-carboxypolycaprolactone mono (meth) acrylate as the monomer (B-1) can be obtained as a commercial product. An example of such a commercial product is M-5400 manufactured by Toagosei Co., Ltd.

  Moreover, as a monomer (B-1), the compound represented by following formula (2) and Formula (5) is mentioned, for example.

In formula (2), n is an integer of 0-10.
In such a range, since the carboxylic acid value becomes large, the adhesiveness is more excellent.
n is preferably 0 to 1 from the viewpoint of further excellent adhesiveness.
In addition, when n in Formula (2) is 0, the compound represented by Formula (2) is acrylic acid. Since acrylic acid has one carboxy group and one acryloyloxy group in one molecule, acrylic acid is included in the compound represented by the formula (2) in this specification.

The monomer (B-1) is preferably a compound represented by the formula (2) or the formula (5) from the viewpoint of adhesiveness and ease of procurement of raw materials, and is represented by the formula (2). More preferably, it is a compound.
A mixture of a compound (acrylic acid) represented by the formula (2) and n is 0 and a compound represented by the formula (2) and n is 1 can be obtained as a commercial product. An example of such a commercial product is M-5600 manufactured by Toagosei Co., Ltd.
The compound represented by Formula (5) can be obtained as a commercial item. Examples of such commercially available products include M-5400 manufactured by Toagosei Co., Ltd. and HOA-MPL manufactured by Kyoeisha Chemical Co., Ltd.
A monomer (B-1) can be used individually or in combination of 2 types or more, respectively.

Examples of the combination of two or more monomers (B-1) include a combination of acrylic acid and a compound represented by the formula (2) and n is 1.
The combination of two or more monomers (B-1) is a compound (acrylic acid) in which n is 0 and the formula (2) represented by the formula (2) from the viewpoint of adhesiveness and ease of raw material procurement. In combination with a compound in which n is 1.

  As a monomer (B-2), the reaction product of a hydroxy (meth) acrylate, a polybasic acid, and / or its acid anhydride is mentioned, for example.

The reaction of hydroxy (meth) acrylate with a polybasic acid and / or acid anhydride thereof is not particularly limited, and examples thereof include conventionally known methods.
The polybasic acid and its anhydride used in the reaction of hydroxy (meth) acrylate with the polybasic acid and / or its anhydride are as defined above.

  The hydroxy (meth) acrylate used in the reaction of the hydroxy (meth) acrylate with the polybasic acid and / or its anhydride is as defined above.

  As a monomer (B-2), the compound represented by following formula (6) is mentioned, for example.

  A commercial item can be used for a monomer (B-2). As a commercial item of a monomer (B-2), brand name: NK ester CBX-1 (made by Shin-Nakamura Chemical Co., Ltd.) is mentioned, for example.

The monomer (B-2) is preferably a compound represented by the formula (6) and a hydrogenated product thereof from the viewpoints of adhesiveness, compatibility with the resin, and ease of raw material procurement.
A monomer (B) can be used individually or in combination of 2 types or more, respectively.

In this invention, the quantity of a monomer (B) is 5-50 mass parts in 100 mass parts of total solid.
Especially, it is preferable that it is 5-50 mass parts in 100 mass parts of total solids from a viewpoint that the quantity of a monomer (B) is excellent by adhesiveness and designability, and is 10-30 mass parts. Is more preferable.

The monomer (C) will be described below.
The monomer (C) contained in the ultraviolet curable coating agent composition of the present invention has one or more (meth) acryloyloxy groups in one molecule.

  The monomer (C) is not particularly limited as long as it has one or more (meth) acryloyloxy groups in one molecule. For example, a monomer (C-1) having 1 to 2 (meth) acryloyloxy groups in one molecule, a monomer (C-2) having 3 (meth) acryloyloxy groups, 4 Monomer (C-3) having (meth) acryloyloxy group, and monomer (C-4) having 5 or more (meth) acryloyloxy groups.

The monomer (C-1) is not particularly limited as long as it is a compound having one or two (meth) acryloyloxy groups in one molecule.
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isoamyl acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, tricyclodecanyl (meth) Acrylate, hydrogenated product, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl acrylate, phenoxyethyl ( (Meth) acrylate, phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acryloyl Monofunctional (meth) acrylate monomers such as morpholine; ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate 1,4-heptanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 2 -Butyne-1,4-di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, 1,5-pentanedi (meth) acrylate, trimethylolethane ( (Meth) acrylate, tricyclodecanyl di (meth) acrylate, hydrogenated product thereof, trimethylolpropane di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate 2,2-bis- (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxy (2-hydroxypropoxy) phenyl) propane, bis- (2-methacryloyl) And bifunctional (meth) acrylate monomers such as oxyethyl) phthalate.

From the viewpoint of low viscosity and curability, long chain aliphatic 1-2 functional monomers and alicyclic 1-2 functional monomers are preferred.
Examples of the long-chain aliphatic monofunctional monomer include lauryl acrylate, stearyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, and 2-ethylhexyl acrylate.
Examples of the long-chain aliphatic bifunctional monomer include 1,6-hexanediol di (meth) acrylate represented by the following formula (7).

  Examples of the alicyclic monofunctional monomer include tricyclodecanyl acrylate, a hydrogenated product thereof, cyclohexyl acrylate, isobornyl acrylate represented by the following formula (8), dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-dicyclopentenoxyethyl acrylate is mentioned.

  Examples of the alicyclic bifunctional monomer include tricyclodecanyl diacrylate, a hydrogenated product thereof, dicyclopentanyl diacrylate represented by the following formula (3), isobornyl diacrylate, and hydrogenated bisphenol A diester. Examples include acrylate and cyclohexane-1,4-dimethanol diacrylate.

  Among these, from the viewpoint of low viscosity, adhesion to a substrate, and solvent resistance, dicyclopentanyl diacrylate represented by formula (3), 1,6-hexanediol di represented by formula (7) (Meth) acrylate and isobornyl acrylate represented by formula (8) are preferred, and dicyclopentanyl diacrylate represented by formula (3) is more preferred.

As a commercial item of the compound represented by Formula (3), for example, NK ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd., light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), Ebecryl IRR214-K (Daicel Cytec Co., Ltd.) Manufactured).
As a commercial item of the compound represented by Formula (7), for example, NK ester A-HD-N manufactured by Shin-Nakamura Chemical Co., Ltd., light acrylate 1.6HX-A (manufactured by Kyoeisha Chemical Co., Ltd.), Ebecryl HDODA (Daicel) Cytec Co., Ltd.).
As a commercial item of the compound represented by Formula (8), NK ester A-IB by Shin-Nakamura Chemical Co., Ltd. is mentioned, for example.

  As a monomer (C-2) having three (meth) acryloyloxy groups in one molecule, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri ( And (meth) acrylate.

  Examples of the monomer (C-3) having four (meth) acryloyloxy groups in one molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and tripentaerythritol tetra ( And (meth) acrylate.

  As the monomer (C-4) having 5 or more (meth) acryloyloxy groups in one molecule, for example, a compound represented by the following formula (7), dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate.

  Among these, from the viewpoint of fast curability, coating film hardness, water resistance, solvent resistance, and chemical resistance, trimethylolpropane triacrylate represented by the following formula (9), represented by the following formula (10) Pentaerythritol tetraacrylate, a compound represented by the following formula (11), and dipentaerythritol tetra (meth) acrylate are preferable.

As a commercial item of the trimethylol propane triacrylate represented by Formula (9), M-309 (made by Toagosei Co., Ltd.), light acrylate TMP-A (made by Kyoeisha Chemical Co., Ltd.), Ebecryl TEMPT (made by Daicel Cytec Co., Ltd.), for example. ), NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.).
Examples of the pentaerythritol tetraacrylate represented by the formula (10) include M-450 (manufactured by Toagosei Co., Ltd.), light acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Ebecryl PETAK (manufactured by Daicel Cytec Co., Ltd.), and NK ester. ATMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
As a commercial item containing the dipentaerythritol hexaacrylate represented by Formula (11), for example, M-402 (made by Toagosei Co., Ltd.), light acrylate DPE-6A (made by Kyoeisha Chemical Co., Ltd.), Ebecryl DDHA (Daicel Cytec Co., Ltd.) And NK ester A-PPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).

A monomer (C) can be used individually or in combination of 2 types or more, respectively.
Among these, from the viewpoint of compatibility with the resin, the monomer (C-1), the monomer (C-2), the monomer (C-3), the monomer (C-4), and the monomer A combination with at least one selected from the group consisting of a monomer (C-5) is preferred.

  Examples of such combinations include dicyclopentanyl diacrylate represented by formula (3), 1,6-hexanediol di (meth) acrylate represented by formula (7), and formula (8). And at least one selected from the group consisting of isobornyl acrylate, trimethylolpropane triacrylate represented by formula (9), pentaerythritol tetraacrylate represented by formula (10), and formula (11) And a combination with at least one selected from the group consisting of dipentaerythritol tetra (meth) acrylates.

In this invention, the quantity of a monomer (C) is 5-70 mass parts in 100 mass parts of total solid content.
Among these, the amount of the monomer (C) is 10 to 50 parts by mass in 100 parts by mass of the total solid content from the viewpoints of curability, coating film hardness, water resistance, solvent resistance, and chemical resistance. It is preferable that it is 20 to 40 parts by mass.

The photopolymerization initiator (D) will be described below.
The photopolymerization initiator (D) contained in the ultraviolet curable coating agent composition of the present invention is not particularly limited as long as it can be used for the ultraviolet curable coating agent composition.
Examples thereof include carbonyl compounds such as acetophenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, represented by the following formula (12) Carbonyl compounds such as 1-hydroxycyclohexyl phenyl ketone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis-2,4- Azo compounds such as Mechirubarero; benzoyl peroxide, include peroxide compounds such as di-tertiary butyl peroxide.

Among these, from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility with resin, low volatility, and low odor, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
Examples of commercially available 1-hydroxycyclohexyl phenyl ketone include Irgacure 184 (manufactured by Ciba Specialty Chemicals).
A photoinitiator (D) can be used individually or in combination of 2 types or more, respectively.

In this invention, the quantity of a photoinitiator (D) is 2-10 mass parts in 100 mass parts of total solids.
Especially, it is preferable that the quantity of a photoinitiator (D) is 3-7 mass parts in 100 mass parts of total solid content from a viewpoint of a cure rate and the hardness of a coating film.

  The ultraviolet curable coating agent composition of the present invention preferably further contains a urethane (meth) acrylate compound (E) from the viewpoint that the viscosity of the composition is increased and the resulting cured product is excellent in flexibility. .

  The urethane (meth) acrylate compound (E) is not particularly limited as long as it has a urethane bond and a (meth) acryloyloxy group. For example, those having a (meth) acryloyloxy group at the terminal and a urethane bond in the skeleton can be mentioned.

  The urethane (meth) acrylate compound (E) is not particularly limited in its production, and is produced, for example, by reacting a polyisocyanate compound with a hydroxy group-containing compound having a hydroxy group and a (meth) acryloyloxy group. be able to.

The polyisocyanate compound used when producing the urethane (meth) acrylate compound (E) is not particularly limited. For example, the same thing as the above is mentioned.
Especially, an aliphatic polyisocyanate compound is mentioned as one of the preferable aspects from a compatible viewpoint with resin.
Examples of the aliphatic polyisocyanate compound used for producing the urethane (meth) acrylate compound (E) include isophorone diisocyanate, hexamethylene diisocyanate, and 4,4′-dicyclohexyl diisocyanate.
A urethane prepolymer can be used as the polyisocyanate compound. The urethane prepolymer is not particularly limited. For example, a conventionally well-known thing is mentioned.

  Examples of the hydroxy group-containing compound used in producing the urethane (meth) acrylate compound (E) include trimethylolpropane di (meth) acrylate, pentaglycerol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

  The reaction between the polyisocyanate compound and the hydroxy group-containing compound is not particularly limited. For example, a conventionally well-known thing is mentioned.

The urethane (meth) acrylate compound (E) is obtained by reacting a difunctional or higher isocyanate with an acrylate having a hydroxy group from the viewpoint of increasing the flexibility of the coating film and increasing the viscosity of the composition. Those are preferred.
The urethane (meth) acrylate compound (E) preferably has 5 to 10 (meth) acryloyloxy groups from the viewpoint of increasing the flexibility of the coating film and increasing the viscosity of the composition.

The number average molecular weight of the urethane (meth) acrylate compound (E) is preferably 1,000 to 5,000 from the viewpoint of increasing the flexibility of the coating film and increasing the viscosity of the composition. More preferably, it is 2,000 to 3,000.
The urethane (meth) acrylate compound (E) and the viscosity thereof are preferably 1,000 to 100,000 mPa · s, and more preferably 10,000 to 50,000 mPa · s.

  The amount of the urethane (meth) acrylate compound (E) is 5 to 50 parts by mass in 100 parts by mass of the total solid content from the viewpoint of increasing the flexibility of the coating film and increasing the viscosity of the composition. Preferably, it is 10-20 mass parts.

  A commercial item can be used for a urethane (meth) acrylate compound (E). As a commercial item of a urethane (meth) acrylate compound, NK oligo UA-1100 (made by Shin-Nakamura Chemical Co., Ltd.) is mentioned, for example.

  In addition to the above-mentioned components, the ultraviolet curable coating composition of the present invention is within the range not impairing the object of the present invention, and various additives such as fillers, anti-aging agents, antistatic agents, A flame retardant, an adhesion imparting agent, a dispersant, an antioxidant, an antifoaming agent, a leveling agent, a matting agent, a light stabilizer (for example, a hindered amine compound), a dye, a pigment, and a solvent can be contained.

  Examples of the filler include wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, oxidized Magnesium; calcium carbonate, magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.

The ultraviolet curable coating composition of the present invention is superior in coating workability, more excellent design properties (smoothness, uniformity) of the coated film, and better adhesion to the substrate of the cured film. Can be used to adjust the viscosity of the composition.
Examples of the solvent include ethanol, isopropanol, butanol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, and butyl acetate.

  The ultraviolet curable coating agent composition of the present invention is not particularly limited for its production. For example, thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2), monomer (B), monomer (C), and methyl which can be used as necessary By mixing the methacrylate polymer (A3), the urethane (meth) acrylate compound (E), and the additive so as to be uniform, and adding the photopolymerization initiator (D), and further stirring and mixing. It can be made uniform.

  The ultraviolet curable coating agent composition of the present invention has a viscosity of preferably 5 to 100 mPa · s, and more preferably 10 to 50 mPa · s, from the viewpoint that it is more excellent in design.

  Examples of the method of using the ultraviolet curable coating agent composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) include an application step of applying the composition of the present invention to plastic. The composition of the present invention applied to the plastic is cured by ultraviolet rays, and a curing step using the composition of the present invention as an undercoat, and metal deposition or coating containing a metal is applied on the undercoat, What comprises a metal layer arrangement | positioning process is mentioned.

First, in the coating step, the composition of the present invention is applied to plastic.
The composition of the present invention can be applied to various plastic substrates regardless of whether it is a thermoplastic plastic or a thermosetting plastic. Specific examples include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin.

The method for applying the composition of the present invention to the plastic is not particularly limited, and known application methods such as brush coating, flow coating, dip coating, spray coating, and spin coating can be employed.
Since the composition of the present invention has an appropriate viscosity and excellent film forming properties, it is preferable to apply the composition by spin coating.

  The coating amount of the composition of the present invention on the plastic is preferably such that the thickness of the coating film upon curing is 1 to 30 μm. When the film thickness of the cured coating film is 1 μm or more, it is particularly excellent in the effect of preventing the surface deterioration of the plastic as the base material.

After the coating process, in the curing process, the composition of the present invention applied to the plastic is cured by ultraviolet rays to form an undercoat in which the composition of the present invention is adhered onto the plastic.
The irradiation amount of the ultraviolet rays used when the composition of the present invention is cured is preferably 500 to 3000 mJ / cm ² from the viewpoint of fast curability and workability.
The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, Nippon Battery Co., Ltd. GS UV SYSTEM is mentioned.
The temperature at which the composition of the present invention is cured by ultraviolet irradiation is preferably 20 to 80 ° C.
Moreover, before hardening by ultraviolet irradiation, it is mentioned as one of the preferable aspects that the composition of this invention apply | coated to the plastic on 30-80 degreeC conditions is previously dried with hot air.
One of the preferred embodiments is that hot air drying is performed at 50 ° C. for about 3 minutes.

After the curing step, in the metal layer arranging step, metal deposition or coating containing metal is performed on the undercoat.
The metal used in metal vapor deposition is not particularly limited. An example is Sn.
The method for metal deposition is not particularly limited. For example, a conventionally well-known thing is mentioned.

  The coating material that can be used in the metal placement step is not particularly limited as long as it contains a metal. For example, a conventionally well-known thing is mentioned. Moreover, the coating material which does not contain a metal can also be used.

After the metal placement step, a laminate having an undercoat on the plastic and a metal layer on the undercoat can be obtained.
After the metal step, a top coat agent can be further applied on the metal layer.
The top coat agent is not particularly limited. The method of applying the topcoat agent is as defined above.

  Laminates having an undercoat on plastic, a metal layer on the undercoat, and a topcoat on the metal layer include, for example, various electric / electronic devices and communication devices (for example, cellular phones) ) Etc., and can be used as an electromagnetic wave shield.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Preparation of (meth) acrylate polymer 10 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate (M-5700, manufactured by Toagosei Co., Ltd.) and 5 parts by mass of butyl methacrylate (trade name Light Ester NB, manufactured by Kyoeisha Chemical Co., Ltd.) , 5 parts by mass of methyl methacrylate (trade name Light Ester M, manufactured by Kyoeisha Chemical Co., Ltd.) and 46.6 parts by mass of MEK as a solvent (manufactured by Kanto Chemical Co., Ltd.) are put in a container, where α, α are used as polymerization initiators. 0.2 parts by mass of '-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Inc.) was added to form a mixture, and the mixture was polymerized under stirring at 80 ° C for 12 hours to give 2-hydroxy-3-phenoxypropyl. An acrylate polymer having a repeating unit composed of acrylate was obtained.
The obtained acrylate polymer has a solid content of 30% by mass, a number average molecular weight measured by GPC of about 70,000, and the content of 2-hydroxy-3-phenoxypropyl acrylate is in the total solid content. 50%.
The obtained acrylate polymer was used as (meth) acrylate polymer A2 in the Examples.

2. Evaluation method The adhesiveness and designability of the composition were evaluated by the following methods. The results are shown in Table 1.
(1) Adhesiveness The adhesiveness was evaluated by a cross-cut tape peeling test.
Specifically, first, each composition obtained was sprayed on the center of a 10 cm long and 10 cm wide ABS resin (Psycolac, manufactured by UMG ABS, the same applies hereinafter). Apply (spray coating amount: 1.0 g / second, spray coating time: 2.0 seconds), and rotate the ABS resin coated with the composition for 10 seconds at a rotation speed of 200 times per minute using a spin coater. By spin-coating the composition, the spin-coated ABS resin was dried with hot air at 50 ° C. for 3 minutes, and then the spin-coated ABS resin was integrated with GS UV SYSTEM manufactured by Nihon Battery Co., Ltd. The composition was cured by irradiating it with ultraviolet rays so as to be 1200 mJ, and a test specimen for evaluating adhesiveness was obtained.
Next, 100 bases of 1 mm (10 × 10) are made on the obtained specimen, and cellophane adhesive tape (width 18 mm) is completely attached on the base, and immediately one end of the tape is attached to the ABS resin. While keeping at a right angle, they were pulled apart instantaneously, and the number of bases that remained without being completely removed was examined.
As the evaluation standard for adhesiveness, the number of remaining bases that are not completely peeled off is 100, that is, those that have not peeled off at all, and are most practical if they are 90 or more.

(2) Designability Each composition obtained by spraying the center part of ABS resin 10 cm long and 10 cm wide by spraying (spray coating amount: 1.0 g / second, spray coating time: 2.0 seconds), A sample was obtained by spin-coating the composition by rotating the ABS resin coated with the composition at a rotational speed of 200 revolutions per minute for 10 seconds using a spin coater.
The rotation was stopped and the sample was observed with the naked eye from an angle of 45 ° with respect to the spin-coated surface.
The evaluation criteria for the design properties were “◯” when the coated surface was smooth, “Δ” when slightly uneven, and “x” when wrinkles were conspicuous on the coated surface.

3. Preparation of compositions (Examples 1-13, Comparative Examples 1-6)
The components shown in Table 1 were blended in the component ratio (parts by mass) shown in Table 1 to prepare each composition.
The film forming properties of the compositions of Examples 1 to 13 were all good.
Further, slight unevenness was observed on the coated surface of the composition of Comparative Example 6.
In contrast, in Examples 1 and 3 to 13, the coating film uniformly and continuously covered the surface of the substrate as compared with Comparative Example 6 in which only the methyl methacrylate polymer was used as the film forming component.

Each component shown in Table 1 is as follows.
Thermoplastic polyurethane resin A1: SBU lacquer 0866, manufactured by Sumika Bayer Urethane Co., Ltd., solid content 30% by mass, number average molecular weight about 30,000
-(Meth) acrylate polymer A2: prepared as described above-Methyl methacrylate polymer A3: Methyl methacrylate polymer, trade name Delpet 60N, manufactured by Asahi Kasei Chemicals Corporation, solid content 30% by mass, number average molecular weight approx. 100,000
Monomer B1: Carboxy group-containing acrylate monomer, trade name M-5600, manufactured by Toagosei Co., Ltd.Monomer B2: Carboxy group-containing acrylate monomer, trade name M-5400, manufactured by Toagosei Co., Ltd. Monomer B3: carboxy group-containing acrylate monomer, trade name NK ester CBX-1, made by Shin-Nakamura Chemical Co., Ltd., monomer C1: trifunctional acrylate, trade name M-309, made by Toagosei Co., Ltd. C2: 4-functional acrylate, trade name M-450, manufactured by Toagosei Co., Ltd./Monomer C3: 5-6 functional acrylate, trade name M-402, manufactured by Toagosei Co., Ltd./monomer C4: 2-functional acrylate, trade name NK Ester A-DCP, Shin-Nakamura Chemical Co., Ltd., monomer C5: bifunctional acrylate, trade name NK Ester A-HD-N, Shin-Nakamura Chemical Co., Ltd., monomer C6: 1 functional acrylate, trade name N Ester A-IB, Shin-Nakamura Chemical Co., Ltd. Photopolymerization initiator D: Irgacure 184, Ciba Specialty Chemicals Urethane acrylate E: NK Oligo UA-100, Shin-Nakamura Chemical Co., Ltd. Leveling agent: Polyflow 450, Kyoeisha Chemical Co., Ltd. Solvent: Butyl acetate

As is apparent from the results shown in Table 1, Comparative Example 1 containing no thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2) was inferior in adhesiveness and design to plastic.
Comparative Example 2 containing more than 50 parts by mass of the thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2) was inferior in design.
The comparative example 3 which does not contain the monomer (B) which has 1 or more carboxy groups and 1 or more (meth) acryloyloxy groups was inferior in the adhesiveness with respect to a plastic.
Comparative Example 4 containing more than 70 parts by mass of monomer (C) was inferior in adhesiveness to plastic.
The comparative example 5 which does not contain a photoinitiator (D) was inferior to the adhesiveness with respect to a plastic.
Comparative Example 6 containing the methyl methacrylate polymer (A3) but not containing the thermoplastic polyurethane resin and / or (meth) acrylate polymer is a circle centered on the rotation axis when the plastic is rotated after spin coating. Wrinkles were generated and the design was inferior.
Such wrinkles are due to the low viscosity of the composition, and the centrifugal force generated during spin coating causes the composition to be biased toward the edge of the film, resulting in a circularly thick edge at the end of the film, and the solvent The inventor has inferred that it is generated by volatilization and contraction of the coating film toward the center of the coating film.
On the other hand, the composition of Examples 1-13 became the laminated body which was excellent in the adhesiveness with respect to a plastic, the surface of the coating film became smooth, and was excellent in the designability.
This is because the ultraviolet curable coating composition of the present invention has a high viscosity, so that the entire coating film has a uniform thickness without any unevenness in film thickness due to centrifugal force generated during spin coating. Inferred.

Claims (9)

In 100 parts by mass of the total solid content,
5 to 50 parts by mass of the thermoplastic polyurethane resin (A1) and / or (meth) acrylate polymer (A2) having a repeating unit represented by the following formula (1),
5 to 50 parts by mass of a monomer (B) having one or more carboxy groups and one or more (meth) acryloyloxy groups in one molecule;
5 to 70 parts by mass of the monomer (C) having one or more (meth) acryloyloxy groups in one molecule;
The ultraviolet curable coating agent composition containing 2-10 mass parts of photoinitiators (D).

(In the formula, R is a hydrogen atom or a methyl group.)   The ultraviolet curable coating composition according to claim 1, wherein the thermoplastic polyurethane resin (A1) has a molecular weight of 3,000 to 100,000.   The ultraviolet curable coating composition according to claim 1 or 2, wherein the (meth) acrylate polymer (A2) has a molecular weight of 10,000 to 300,000. The ultraviolet curable coating composition according to any one of claims 1 to 3, wherein the monomer (B) is a compound represented by the following formula (2).

(In the formula, n is an integer of 0 to 1.) The said monomer (C) is a compound represented by following formula (3), The ultraviolet curable coating agent composition in any one of Claims 1-4.

  Furthermore, the ultraviolet curable coating agent composition in any one of Claims 1-5 containing a methylmethacrylate polymer (A3).   The ultraviolet curable coating composition according to claim 6, wherein the methyl methacrylate polymer (A3) has a molecular weight of 10,000 to 300,000.   Furthermore, the ultraviolet curable coating agent composition in any one of Claims 1-7 containing a urethane (meth) acrylate compound (E).   The amount of the said urethane (meth) acrylate compound (E) is 5-50 mass parts in 100 mass parts of total solid, The ultraviolet curable coating agent composition of Claim 8.