JP2003053260A - Plating-like film forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plating-like film forming method capable of shortening a coating process for coating an article to be coated such as a car part or the like and capable of forming a plating-like film having high design effect and excellent coating film capacity. SOLUTION: The cured coating film of the color base paint formed on the article to be coated is coated with an active energy beam curable paint containing a pigment having a plating feeling and the coated article is irradiated with active energy beam to form a cured coating film with a crosslinked molecular weight of 200-1,500 having the plating feeling. The cured coating film having the plating feeling is coated with a clear paint capable of being cured by heating or irradiation with active energy beam and the clear coating film is cured by heating or irradiation with active energy beam to form the plating-like film.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to the production of automobile parts and the like.
The present invention relates to a method for forming a plating-like coating on a substrate. [0002] 2. Description of the Related Art
The formation of a plating-like coating on automotive parts is generally achieved by coloring
Base paint, paint containing pigment with plating feeling, clear
Paint each paint using thermosetting paint
After baking three times painting three times baking method
Was. Therefore, a long baking furnace is required, and a large space is required.
However, the process time required for curing is long, and
In short, there were problems such as low productivity. Sa
Furthermore, according to this method, the orientation of the pigment having a plating feeling is
Is likely to be disturbed, the sharpness is low, and the design is poor.
There was a problem. [0003] The object of the present invention is to address these problems mentioned above.
And has high designability on substrates such as automobile parts.
To form a plating-like coating with excellent coating performance
It is to provide. [0004] Means for Solving the Problems The present inventors have made intensive studies.
As a result of having a plating feeling on the colored base coating film
Apply active energy ray-curable paint containing pigment to activate
After irradiating with energy rays to a certain degree of crosslinking,
That the above purpose can be achieved by applying
And completed the present invention. [0005] Thus, according to the present invention, a shape is formed on an object to be coated.
Has a feeling of plating on the cured coating film of the colored base paint
With active energy ray curable paint containing pigment
And irradiating an active energy ray to make the molecular weight between crosslinks 200
Cured coating film having a plating feeling in the range of ~ 1500
Formed and then heated on the cured coating film having the plating feeling.
Or clear that can be cured by irradiation with active energy rays
-Apply paint and heat or irradiate with active energy rays.
Plating-like film formation method characterized by hardening
Provided. Hereinafter, the method of the present invention will be described in detail.
You. [0006] BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention,
Has a cured coating with a colored base paint, has a plating feeling
Curing coating with active energy ray curable paint containing pigment
A film and a cured coating with clear paint are sequentially formed.
You. [0007] The colored base paint and the clear paint are
Active energy ray-curable
Of active energy ray-curable coatings containing escaping pigments
In the case of these paints,
Radiation polymerization or cation
Contains a binder component that can be cured by
Cured by irradiation with energy rays. [0008] Bis curable by the above radical polymerization
The radical component is a radical polymerizable unsaturated group in one molecule.
A polymerizable unsaturated group-containing resin having at least one
Examples of the monomer include a saturated group-containing monomer. Examples of the above polymerizable unsaturated group-containing resin include:
For example, hydroxyl-containing polyester and acrylic acid or
Resin esterified with lylic acid, polyurethane containing unsaturated groups
Resin, unsaturated group-containing epoxy resin, unsaturated group-containing
Phosphorous epoxy resin, unsaturated group-containing acrylic resin, unsaturated
Group-containing silicone resin, unsaturated group-containing melamine resin, etc.
Is mentioned. As the polymerizable unsaturated group-containing monomer, the following
A monofunctional polymerizable monomer, a difunctional polymerizable monomer and
Examples include trifunctional or higher polymerizable monomers. The monofunctional polymerizable monomer includes, for example,
For example, styrene, methyl (meth) acrylate, ethyl
(Meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, lauryl
(Meth) acrylate, cyclohexyl (meth) acryl
Rate, cyclohexenyl (meth) acrylate, 2-
Hydroxylethyl (meth) acrylate, hydroxy
Propyl (meth) acrylate, tetrahydrofurfurfur
(Meth) acrylate, ε-caprolactone-modified tet
Lahydrofurfuryl (meth) acrylate, phenoxy
Ethyl (meth) acrylate, phenoxy polyethylene
Glycol (meth) acrylate, dicyclopentenyl
(Meth) acrylate, dicyclopentenyloxyethyl
(Meth) acrylate, isobornyl (meth) acryl
, Benzyl (meth) acrylate, hydroxye
Addition of tyl (meth) acrylate and ε-caprolactone
Additive, polyethylene glycol mono (meth) aclay
G, polypropylene glycol mono (meth) aclayer
G, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, 2-hydroxy-3-butoxypropyl
(Meth) acrylate, monohydroxyethyl phthalate
(Meth) acrylate, Aronix M110 (Toa Go
N-Methylol (meth) acrylamide
, N-methylol (meth) acrylamide butyl acrylate
Ter, acryloyl morpholine, dimethylaminoethyl
(Meth) acrylate, N-vinyl-2-pyrrolidone
And so on. As the above-mentioned bifunctional polymerizable monomer, for example,
For example, ethylene glycol di (meth) acrylate, die
Tylene glycol di (meth) acrylate, polyethylene
Glycol di (meth) acrylate, propylene glycol
Cold di (meth) acrylate, dipropylene glycol
Luji (meth) acrylate, polypropylene glycol
Di (meth) acrylate, neopentyl glycol di
(Meth) acrylate, 1,4-butanediol di (meth)
Acrylate), 1,6-hexanediol di (meth)
T) Acrylate, bisphenol A ethylene oxide
Modified di (meth) acrylate, bisphenol A pro
Pyrene oxide-modified di (meth) acrylate, 2-h
Droxy 1-acryloxy 3-methacryloxypropa
, Tricyclodecane dimethanol di (meth) acryle
And di (meth) acryloyloxyethyl acid acid
Osphate; Kayarad HX-220, Kayarad H
X-620, Kayarad R-604, MANDA (or more
Both are Nippon Kayaku Co., Ltd. bifunctional polymerizable unsaturated monomers
ー). As the above trifunctional or higher functional polymerizable monomer,
Is, for example, trimethylolpropane tri (meth)
Relate, trimethylolpropane ethylene oxide
Modified tri (meth) acrylate, trimethylolpropa
Propylene oxide modified tri (meth) acrylate
G, glycerin tri (meth) acrylate, glycerin
Ethylene oxide-modified tri (meth) acrylate,
Lysine propylene oxide modified tri (meth) acryl
Rate, pentaerythritol tri (meth) aclay
G, pentaerythritol tetra (meth) aclay
G, isocyanuric acid ethylene oxide modified triacrylate
Rate, dipentaerythritol hexa (meth) acryl
Rates and the like. Binder curable by radical polymerization
As the components, the polymerizable unsaturated group-containing resin, polymerizable unsaturated
The sum-group-containing monomer may be used alone or in combination of two or more.
Can be used. In this specification, "(meth) acrelay"
"G" means "acrylate or methacrylate"
I do. The active energy rays to be irradiated are ultraviolet rays.
In some cases, paints curable by radical polymerization
Usually, it contains a photo-radical polymerization initiator. Photo radical polymerization
Benzoin, benzoin methyl ether
Benzoin ethyl ether, benzoin isobutyl
Ether, diethoxyacetophenone, 2-hydroxy
-2-methyl-1-phenylpropan-1-one, ben
Jil dimethyl ketal, 1-hydroxycyclohexyl
-Phenyl ketone, 2-methyl-2-morpholino (4
-Thiomethylphenyl) propan-1-one, 2-ben
Jil-2-dimethylamino-1- (4-morpholinofe
Nyl) -butanone, 2,4,6-trimethylbenzoyl
Phenylphosphine oxide, 2,4,6-trime
Tylbenzoylphenylethoxyphosphine oxide
De, benzophenone, o-benzoyl methyl benzoate,
Hydroxybenzophenone, 2-isopropylthioxa
2,4-dimethylthioxanthone, 2,4-di
Ethylthioxanthone, 2,4-dichlorothioxanth
2,4,6-tris (trichloromethyl) -S-to
Liazine, 2-methyl-4,6-bis (trichloro)-
S-triazine, 2- (4-methoxyphenyl) -4,
6-bis (trichloromethyl) -S-triazine and the like
No. These photopolymerization initiators may be used alone or in combination.
These can be used in combination, and the compounding amount is suitable for radical polymerization.
Therefore, 0.1 to 1 based on the curable binder component
A range of 0% by weight is preferred. Further, the light generated by the above radical photopolymerization initiator
Start photopolymerization with photosensitizer to promote polymerization reaction
You may use together with an agent. As a photosensitizer that can be used in combination
Is, for example, triethylamine, triethanolamine
, Methyldiethanolamine, 4-dimethylamino
Methyl benzoate, ethyl 4-dimethylaminobenzoate, 4
Isoamyl dimethylaminobenzoate, benzoic acid (2-
Dimethylamino) ethyl, Michler's ketone, 4,4_-
Tertiary amines such as diethylaminobenzophenone
Alkylphosphines such as phenylphosphine, β-
And thioethers such as thiodiglycol.
You. These photosensitizers may be used alone or in combination.
The above can be used in combination, and the compounding amount is the above radical
0.1 based on the binder component curable by polymerization.
A range of 1 to 20% by weight is preferred. [0018] The binder curable by the cationic polymerization described above.
The active ingredient is activated
Any binder component that can be cured by polymerization can be used.
As an example, an epoxy having one or more epoxy groups in one molecule
Xy group-containing compound or resin, and oxetani in one molecule
Oxetanyl group-containing compound or tree having at least one
And the like. The epoxy group-containing compound may be a jig
Lysidyl ether, 2-glycidyl phenyl glycidyl
Ether, 2,6-diglycidylphenyl glycidyl ester
Glycidyl ether compounds such as
Glyci such as xendioxide and lemonenedioxide
Compound containing a jyl group and an alicyclic epoxy group;
Lopentadienedioxide, bis (2,3-epoxy
Cyclopentyl) ether, epoxycyclohexeneca
Rubonic acid ethylene glycol diester, bis (3,4
-Epoxycyclohexyl) adipate, 3,4-epo
Xycyclohexymethyl-3,4-epoxycyclo
Xancarboxylate, 3,4-epoxy-6-methyl
Alicyclic epoxy such as rucyclohexanecarboxylate
It contains a group-containing compound and the like. Specific examples of the epoxy group-containing resin include:
For example, bisphenol A type epoxy resin, bisphenol
F-type epoxy resin, Cresol novolak type epoxy
Resin, phenol novolak type epoxy resin;
(Meth) acrylate, methylglycidyl (meth) a
Acrylate, allyl glycidyl ether, 3,4-epo
D. Such as xycyclohexylmethyl (meth) acrylate
Poxyl group-containing ethylenically unsaturated monomer, if necessary
And copolymers with other ethylenically unsaturated monomers.
And so on. The copolymer capable of forming the above copolymer
Other ethylenically unsaturated monomers include, for example, methyl
(Meth) acrylate, ethyl (meth) acrylate
G, butyl (meth) acrylate, 2-ethylhexyl
(Meth) acrylate, cyclohexyl (meth) acryl
C of (meth) acrylic acid such as rate₁~ C₂₄Alkyl
Or cycloalkyl esters; 2-hydroxypro
Pill (meth) acrylate, caprolactone-modified
(T) (meth) acryl such as hydroxyethyl acrylate
Acid C₂~ C₈Hydroxyalkyl esters;
T) Carboxyl group-containing ethylenically unsaturated such as acrylic acid
Sum monomers: styrene, α-methylstyrene, vinyl
Aromatic vinyl compounds such as toluene; perfluorobutyl
Ethyl (meth) acrylate, perfluoroisononyl
Fluorine-containing unsaturated monomers such as ethyl (meth) acrylate
-Polymerizable amides such as (meth) acrylamide;
Polymerizable nitriles such as (meth) acrylonitrile
Can be mentioned. As the oxetanyl group-containing compound, for example,
For example, 3-ethyl-3-methoxymethyloxetane, 3-
Ethyl-3-ethoxymethyloxetane, 3-ethyl-
3-butoxymethyloxetane, 3-ethyl-3-hexyl
Siloxymethyloxetane, 3-methyl-3-hydro
Xymethyloxetane, 3-ethyl-3-hydroxyme
Tiloxetane, 3-ethyl-3-hydroxyethylo
Xetane, 3-ethyl-3-allyloxymethyloxe
Tan, 3-ethyl-3- (2'-hydroxyethyl) o
Xymethyloxetane, 3-ethyl-3- (2'-hydrido)
Roxy-3'-phenoxypropyl) oxymethyloxy
Cetane, 3-ethyl-3- (2'-hydroxy-3'-
Butoxypropyl) oxymethyloxetane, 3-ethyl
R-3- (2'-butoxyethyl) oxymethyloxe
Tan, 3-ethyl-3-benzyloxymethyloxeta
3-ethyl-3- (p-tert-butylbenzyloxy)
Cimethyl) oxetane, the following formula (1) [0023] Embedded image (In the above formula, two R¹Are the same or different
Has the same meaning as above,²Is a group having 1 to 6 carbon atoms.
Alkylene group, cycloalkylene group, phenylene group, xy
Rylene group, polyalkyleneoxy having 4 to 30 carbon atoms
Which represents a group).
You. As the oxetanyl group-containing resin, for example,
For example, 3- (acryloyloxymethyl) 3-methyloxy
Cetane, 3- (methacryloyloxymethyl) 3-methyl
Luoxetane, 3- (acryloyloxymethyl) 3-
Ethyl oxetane, 3- (methacryloyloxymethyl)
L) 3-ethyloxetane, 3- (acryloyloxy)
Methyl) 3-butyloxetane, 3- (methacryloyl)
Oxymethyl) 3-butyloxetane, 3- (acryloyl)
Yloxymethyl) 3-hexyloxetane and 3-
(Methacryloyloxymethyl) 3-hexyloxeta
Oxetanyl-containing ethylenically unsaturated monomers such as
And, if necessary, other ethylenically unsaturated monomers
And copolymers thereof. Shape this copolymer
Other ethylenically unsaturated monomers that can be formed
Is a copolymer which is one of the epoxy group-containing resins.
Other ethylenically unsaturated monomers that can form
The ones exemplified as nomers can be used as well.
You. Binder curable by cationic polymerization
As a component, the cationically polymerizable epoxy group-containing compound
Or a resin, and a cationic polymerizable oxetanyl group-containing compound
Products or resins may be used alone or in combination of two or more.
Can be Cationic polymerization by irradiation with active energy rays
Active energy ray-curable coatings that can be cured by
In addition to the binder component curable by the cationic polymerization,
To generate an acid by irradiation with active energy rays
It is preferable to contain an on-polymerization initiator. As a representative example of the above cationic photopolymerization initiator,
Sulfonium salts and iodonium salts that generate acids
I can do it. For example, as a commercial product, Cyracure UVI
-6970, UVI-6974, UVI-699
0, same UVI-6995 (both are union cars)
Adeka Aptomer SP-150, SP)
-170 (all manufactured by Asahi Denka Co., Ltd.); CI-285
5 (Nippon Soda Co., Ltd.), BBI-102 (Midori Chemical Co., Ltd.)
Manufactured). These are two or more
It can be used in combination, and the compounding amount is based on the above binder component.
The range is preferably 0.1 to 20% by weight. In the method of the present invention, a colored base paint and
All clear paints can be heat-curable
You. In the case of heat-curing type, color base paint and paint
In any of the rear coatings, the binder component is
For example, hydroxyl-containing acrylic resin, hydroxyl-containing polyester
Teramine, base resin such as epoxy resin, melamine resin,
Can be used in combination with crosslinking agents such as isocyanate compounds
Wear. Further, a carboxyl group-containing resin or compound and
Combinations with oxy group-containing resins or compounds may also be mentioned.
it can. In the method of the present invention, the colored base paint is
Active energy ray-curable or heat-curable
Also contain a coloring pigment. As this color pigment
Is a coloring pigment commonly used in paints, such as titanium
White pigments such as white and zinc white; cyanine blue, indane
Blue pigments such as Slen Blue; cyanine green, patina
Green pigments such as azo and quinacridone organic red
Red pigments such as color pigments and red bengara; benzimidazoline
System, isoindolinone system, isoindoline system and quinoff
Organic yellow pigments such as taron, titanium yellow,
Any yellow pigment; use black pigments such as carbon black.
Can be used. Further, an activity containing a pigment having a plating feeling can be obtained.
Has a feeling of plating in reactive energy ray-curable paint
As pigments, for example, aluminum powder, surface coated
Glittering mica powder, glittering glass flakes, etc.
Fees can be used. Active energy containing pigment having plating feeling
In the case of lug-ray curable coatings, the molecules between crosslinks in the cured film
The amount is between 200 and 1500, preferably between 300 and 1000
Must be within range. 200 molecular weight between crosslinks
If less, the cured film has a large shrinkage, and the face has a plating feeling.
The orientation of the material is disturbed, resulting in poor design. On the other hand, 15
If it exceeds 00, cross-linking is insufficient, and when coating clear paint
The plating feeling by the penetration of the solvent etc. in the clear paint
Swelling and dissolution of the coating film that has a feeling of plating
The material moves and the orientation is disturbed, resulting in poor design.
You. In the method of the present invention, the colored base coating
Energy rays containing pigments with coloring and plating feeling
Curable paint and clear paint, if necessary,
Fillers, antiblocking agents, UV absorbers, UV
Stabilizers, surface conditioners, anti-bake agents, etc. inhibit curability
It can be contained within the range not present. An active energy ray-curable colored base
Base paint and clear paint and face with plating feeling
Active-energy radiation-curable coatings containing
Acrylic resin, polyester resin, urethane as required
Resin, epoxy resin, melamine resin, silicone resin,
Curing of polyisocyanate compound, amino resin, etc.
It can be contained within a range not to inhibit. Also, for example
For example, a resin having a hydroxyl group and a polyisocyanate compound
And amino resin in combination,
To provide thermosetting properties in addition to reactive energy ray curing type
Can be. In the method of the present invention, the colored base paint is
For example, spray coating on substrates such as automotive parts materials
Coating method, roll coating method, screen printing, rotary printing
It can be applied by a coating printing method such as [0036] The colored base paint is an active energy ray curable type
, The active energy beam irradiation conditions are
Can be appropriately changed depending on the type of the composition, the film thickness, etc.
You. When irradiating ultraviolet light, the wavelength of the ultraviolet light
Usually, the range of 200 to 450 nm is appropriate,
Depending on the type of initiator, select an irradiation source with a wavelength with high sensitivity.
It can be appropriately selected and used. UV irradiation source and
For example, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon
Lamp, carbon arc, metal halide lamp, sun
Light and the like can be given. UV irradiation conditions on the coating film
Is usually 100 to 2000 mJ / cm², Preferred
Or 500 to 1500 mJ / cm²Suitable range
ing. When irradiating an electron beam,
For example, scanning type, curtain beam type, etc.
An electron beam accelerator can be mentioned. Electron beam irradiation on coating film
The irradiation condition is usually an electron beam with a dose of 50 to 300 KeV.
It is preferable to irradiate 1 to 20 Mrad. When the colored base paint is a heat-curable type,
Heating means is not particularly limited, for example, heat
Drying equipment such as wind furnaces, electric furnaces, and infrared induction heating can be applied.
Wear. The heating temperature is usually about 50 to 200 ° C., preferably.
Or in the range of about 70 to 150 ° C.
You. The heating time is not particularly limited.
Usually, a range of 15 to 45 minutes is suitable. [0038] The cured film thickness of the colored base paint depends on the hiding power and the flatness.
Generally, the range of 10 to 30 μm is preferable from the viewpoint of lubricity. Active energy containing pigment having plating feeling
The rugged wire-curable paint is a coating that has been cured as described above.
Painted on cured coating of color base paint. Paint the sp
Lay coating method, roll coating method, screen printing, wheel
It can be performed by a coating printing method such as transfer printing.
Can be. Active energy containing pigment with plating feeling
The coating film thickness of the rugged wire-curable paint is
From the orientation, the cured film thickness is usually 0.1 to 10 μm,
It is preferable that the thickness be in the range of 0.1 to 5 μm. Me
Active energy ray-curing type containing pigment with sticky feeling
As for the paint, the colored base paint is an active energy ray-curable type.
Can be cured by the same method as if
You. In the method of the present invention, the clear paint is
Active energy ray-curing type containing pigment with sticky feeling
For example, spray coating, roll coating
Paint printing methods such as sheet coating, screen printing, and rotary printing
Can be applied. Coating film of clear paint
The thickness is usually a cured film thickness of 10 to 50 μm, especially 20 to
Preferably, it is in the range of 30 μm. In the method of the present invention, the clear paint
Energy-curable or heat-curable
Depending on its cured form, the colored base paint
Curing by the same curing method as in curing
Can be. In the method of the present invention, the clear paint is heated
A curable type is preferable from the viewpoint of weather resistance and the like. [0042] The present invention will be described below with reference to production examples and examples.
This will be described more specifically. The present invention is not limited to these.
Not. Hereinafter, “parts” and “%” are weights.
It is based on standards. [0043]Manufacture of resin Production Example 1 Thermometer, thermostat, stirrer, reflux cooler and dripping
733 parts of isobutyl acetate was added to a reaction vessel equipped with an apparatus.
And heated to 110 ° C while blowing nitrogen gas
After that, mix the following monomer and initiator from the dropping device
The solution was added dropwise over 3 hours. [0044]       Styrene 200 parts       Methyl methacrylate 300 parts       200 parts of n-butyl methacrylate       100 parts of 2-hydroxyethyl acrylate       Glycidyl methacrylate 200 parts       2,2'-azobis (2-methylbutyronitrile) 50 parts After dropping, the mixture was aged at 110 ° C for 7 hours to obtain a copolymer.
Was. After that, stop blowing nitrogen gas and
0.5 parts of monomethyl ether, tetraethylammonium
Add 5 parts of mubromide and 100 parts of acrylic acid and empty.
The mixture was reacted at 110 ° C. for 5 hours while blowing air, and added.
Confirm that acrylic acid has substantially reacted and cool
And a radical polymerizable unsaturated resin solution having a resin solid content of 60%
Got. GPC (gel permeation chromatography) of the obtained resin
F) The number average molecular weight measured is 6000, the unsaturated group concentration
1.25 equivalents / kg and a hydroxyl value of 104. Production Example 2 Thermometer, thermostat, stirrer, reflux cooler and dripping
Add 667 parts of isobutyl acetate to a reaction vessel equipped with an apparatus.
And heated to 110 ° C while blowing nitrogen gas
After that, mix the following monomer and initiator with a dropping device.
The solution was added dropwise over 3 hours. [0046]       Styrene 200 parts       Methyl methacrylate 300 parts       180 parts of n-butyl methacrylate       100 parts of n-butyl acrylate       200 parts of 2-hydroxyethyl acrylate       Acrylic acid 20 parts       2,2'-azobis (2-methylbutyronitrile) 40 parts After the completion of the dropwise addition, the mixture was aged at 110 ° C. for 7 hours to obtain a resin solid content of 60%.
% Acrylic resin was obtained. For GPC measurement of the obtained resin
As a result, the number average molecular weight was 6000, and the hydroxyl value was 90. Production Example 3 Thermometer, thermostat, stirrer, reflux condenser and moisture
296 parts of phthalic anhydride were added to a reaction vessel equipped with a separator.
292 parts of adipic acid, 124 parts of ethylene glycol,
Charge 312 parts of pentyl glycol and pass through a water separator.
2 hours after heating to 160 ° C while dewatering
And heat to 210 ° C. Keep at 210 ° C and add toluene
Azeotropic dehydration with, confirming that substantially all of the acid has reacted
To remove the toluene from the container while cooling,
A polyester with a shape fraction of 100% was obtained. G of the obtained resin
Number average molecular weight by PC measurement is 880, hydroxyl value is 127.
Met. Production Example 4 Equipped with thermometer, thermostat, stirrer, reflux condenser
The reaction vessel is charged with isophorone diisocyanate 444.
Parts, 232 parts of 2-hydroxyethyl acrylate, high
Charge 0.5 parts of droquinone monomethyl ether, air
While reacting at 80 ° C. for 5 hours while blowing.
Verify that substantially all of the xyl ethyl acrylate has reacted.
Then, 880 parts of the polyester obtained in Production Example 3 was added.
Then, the reaction was carried out at 80 ° C. for 7 hours. Isocyanate is substantial
After confirming the complete reaction, isobutyl acetate was added to 1
Add 037 parts and cool, radical polymerization of resin solid content 60%
An unsaturated resin was obtained. According to GPC measurement of the obtained resin
The number average molecular weight is 1500, and the unsaturated group concentration is 1.28 equivalent /
kg. Production Example 5 Thermometer, thermostat, stirrer, reflux cooler and dripping
Add 677 parts of isobutyl acetate to a reaction vessel equipped with an apparatus.
And heated to 110 ° C while blowing nitrogen gas
After that, mix the following monomer and initiator from the dropping device
The solution was added dropwise over 3 hours. [0050]       Styrene 200 parts       Methyl methacrylate 300 parts       200 parts of n-butyl methacrylate       100 parts of 2-hydroxyethyl acrylate       3,4-epoxycyclohexylmethyl acrylate 200 parts       2,2'-azobis (2-methylbutyronitrile) 40 parts After completion of the dropping, the mixture was aged at 110 ° C for 2 hours, cooled, and solidified.
60% of cationic polymerizable epoxy group-containing resin
Was. The number average molecular weight of the obtained resin measured by GPC was 6
000, epoxy group concentration 1.10 equivalent / kg, hydroxyl value
45. [0051]Preparation of paint Preparation Example 1 Carbon brass was added to 100 parts of the unsaturated resin solution obtained in Production Example 4.
Was added and dispersed in a roll mill.
Later, Irgacure 819 (Ciba Specialty Chemicals)
Addition of 3 parts of a radical photopolymerization initiator manufactured by
Then, dilute with isobutyl acetate and adjust the paint viscosity
No. 4. Adjust to 20 seconds with UV curable black paint
Created. Preparation Example 2 100 parts of the unsaturated resin solution obtained in Production Example 4 and
60 parts of titanium white and a mixture of
And 1 part of carbon black.
After sprinkling, trimethylolpropane triacrylate 1
0 parts, 4 parts Irgacure 819, Sumidur N75
(Sumitomo Bayer Urethane, polyisocyanate compound
Product), dissolve by adding 10 parts, and dilute with isobutyl acetate
And the paint viscosity was set to Ford Cup No. 4 for 20 seconds
Then, an ultraviolet curable gray paint was prepared. Preparation Example 3 Cationic polymerizable epoxy group-containing resin 10 obtained in Production Example 5
0 parts with 30 parts of titanium white and 0.5 parts of carbon black
After adding and dispersing the pigment with a roll mill, Silacure UV
I-6990 (manufactured by Union Carbide, cationic photopolymerization)
(Initiator) Add 2 parts and dissolve, then dilute with isobutyl acetate
And adjust the paint viscosity to 20 seconds with Ford Cup No.4
Then, an ultraviolet curable gray paint was prepared. Preparation Example 4 Titanium white 60 was added to 120 parts of the polyester obtained in Production Example 3.
Parts, 1 part of carbon black and 120 parts of isobutyl acetate
After adding and dispersing the pigment in a roll mill, Sumidur N
Add 20 parts of 75 and dissolve, then dilute with isobutyl acetate
And adjust the paint viscosity to 20 seconds with Ford Cup No.4
Then, a heat-curable gray paint was prepared. Preparation Example 5 100 parts of the unsaturated resin solution obtained in Production Example 1
Slurry KM100 ”(produced by Toyo Aluminum Co., Ltd.)
180 parts (aluminum pigment solid)
18 parts as a fraction) and dispersed with a disper
Thereafter, 4 parts of Irgacure 819 was added and dissolved, and
Diluted with sodium butyl and adjusted to 50% by weight of paint solids,
An ultraviolet-curing paint having a plating feeling was prepared. Preparation Example 6 100 parts of the unsaturated resin solution obtained in Production Example 1, obtained in Production Example 2.
50 parts of acrylic resin solution
100 "to 240 parts (2 as aluminum pigment solids)
4 parts) and dispersed with a disper.
A 819, 4 copies of Cymel 236 (Mitsui Cytec Co., Ltd.)
10 parts of melamine resin) was added and dissolved.
Dilute with butyl, adjust to 50% by weight of paint solids, add
UV-curable coating with thermosetting properties
It was created. Preparation Example 7 100 parts of the unsaturated resin solution obtained in Production Example 5
Slurry KM100 ”(produced by Toyo Aluminum Co., Ltd.)
180 parts (aluminum pigment solid)
18 parts as a fraction) and dispersed with a disper
Then, add 4 parts of Cyracure UVI-6990 and dissolve
After that, it is diluted with isobutyl acetate, and the solid content of the paint is 50% by weight.
To create a paint with a UV curable plating feeling
did. Preparation Example 8 Sumiju was added to 100 parts of the acrylic resin solution obtained in Production Example 2.
After adding 20 parts of N75, dilute with isobutyl acetate
And the paint viscosity was set to Ford Cup No. 4 for 20 seconds
Then, a heat-curable clear paint was prepared. Preparation Example 9 Cymer 2 was added to 100 parts of the acrylic resin solution obtained in Production Example 2.
36, and diluted with isobutyl acetate.
Ford cup No. 4 Adjust to 20 seconds,
A thermosetting clear coating was prepared. Preparation Example 10 100 parts of the unsaturated resin solution obtained in Production Example 1, Irgacure
184 (made by Ciba Specialty Chemicals), 2 copies
Nubin 400 (made by Ciba Specialty Chemicals)
1.2 parts, Tinuvin 144 (Ciba Specialty Chemicals)
After dissolving by adding 0.6 parts), isobutyl acetate was added.
Dilute and adjust paint viscosity to 20 seconds with Ford Cup No.4
Knot was prepared to produce a UV-curable clear coating. Preparation Example 11 (for comparison) In 100 parts of the polyester obtained in Production Example 3, "Metascene
Slurry KM100 ”(400 parts)
40 parts) and 100 parts of isobutyl acetate
After stirring, add 20 parts of “Sumidur N75”
After dissolution, dilute with isobutyl acetate and paint
The coating composition was adjusted to the weight% to give a plating feeling. Preparation Example 12 (for comparison) In 100 parts of the acrylic resin solution of Production Example 2, "Metascene
180 parts of slurry KM100 (aluminum pigment
18 parts as a fraction) was added and stirred.
36 parts, and diluted with isobutyl acetate
And adjusted to 3% by weight of paint solids, giving a feeling of plating
Paint was created. Examples 1 to 8 and Comparative Examples 1 and 2 Colored rear injection mirror cover made of ABS resin
After spray coating base paint, with conveyor conveyor
UV irradiator (80W / cm metal halide run)
), Depending on the curing system of the paint, 1000-2000m
J / cm²Irradiation or baking in hot air dryer
To obtain a cured film. On top of that, a feeling of plating
After spray coating with paint, with conveyor conveyor
UV irradiation equipment (80W / cm metal halide
500mJ / cm²(0.25 minutes) or 100
0mJ / cm²(0.5 min) to obtain a cured film. Sa
Spray a clear paint on it and apply UV light
Cured by irradiation or heating in a hot air dryer
Then, a plating tone film was formed. Forming a Plating Film in Examples and Comparative Examples
Time required for curing the coating film and irradiation equipment or drying
The length of the equipment, the mounting of the cured coating film with a coating with a feeling of plating
Molecular weight between bridges, appearance of coating film of plating tone (plating design,
60 ° mirror gloss) are shown in Table 1 below. Obtained in the example
All of the plated coatings have good coating properties.
Was. Plating of a cured coating film with a paint having a plating feeling
Molecular weight between bridges, plating design of plating-like coating and 60 degree mirror
The surface glossiness was determined by the following method. [0066]Plating of cured coating film with paint with plating feeling
Bridge molecular weight: Active energy containing pigment with plating feeling
Lug wire curable paint is applied on a glass plate with a cured film thickness of 5 μm.
And dried at 80 ° C for 10 minutes to remove the solvent.
After removal, apply the same amount of UV light as in each example.
Line irradiation equipment (80W / cm metal halide lamp)
Irradiated (contains pigment with plating feeling of Comparative Example)
For thermosetting paint, the same conditions as in each comparative example
Baked in). Peel the coating film to 5cm square and measure the weight
(Wf). 24 hours in xylene at 20 ° C
Immersed for a while, lifted up, wiped off solvent on surface and wiped with paper
The weight taken is measured (Ws). 1 hour at 100 ° C
Dry and weigh (Wd). Of these weight measurements
The value is introduced into the following equation to determine the molecular weight between crosslinks. Υ = 1 / [1 + ρ_R/ ｛Ρ_S* (Ws-W
d) / Wd｝] υ: Volume fraction of polymer in swollen film ρ_R: Density of cured coating ρ_S: Density of immersion solvent μ-μs = RT [ln (1-υ) + υ + χυ²+ VN
(Υ^1/3-Υ / 2)] μ: Chemical function of the solvent inside the crosslinked chain μs: Chemical function of the solvent outside the bridge χ: Interaction constant between cured coating and solvent N: Crosslink density Molecular weight between crosslinks Mc = ρ_R/ NPlating design : Judgment of brilliancy of plating-like coating visually
You. [0068]60 degree mirror gloss: JIS K5400
7.6 (1990) according to the 60 degree specular gloss
Measure the gloss of the coating. [0069] [Table 1][0070] [Table 2] [0071] According to the present invention, there is provided a method for forming a plating tone film.
Can shorten the coating process for coating objects such as automobile parts.
You. In the method for forming a plating tone film of the present invention, the plating
Irradiation of paint containing pigments
And cured in a short time to have a molecular weight between crosslinks of 200 to 15
00 to form a cured coating within the range of
Can suppress orientation disturbance due to heat flow and hardening stress of
You. Plating coating obtained by the method of the present invention
The film is excellent in plating design and coating film gloss.

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Claims (1)

Claims: 1. An active energy ray-curable paint containing a pigment having a plating feeling is applied on a cured coating film of a colored base paint formed on an object to be coated, and an active energy ray is applied. Irradiation to form a cured coating film having a plating feeling having a molecular weight between crosslinks in the range of 200 to 1500, and then a clear paint curable on the cured coating film having the plating feeling by heating or irradiation with active energy rays. Coating method and curing by heating or irradiation with active energy rays.