JPH02273574A - Painting finish method - Google Patents

Abstract

PURPOSE:To improve the gloss and weather resistance of a composite film by applying base coat paint composed of a curable resin containing metallic pigment and applying top coat clear paint having a specific composition to the coated surface to perform curing. CONSTITUTION:Base coat paint containing a curable resin compounded with metallic pigment and/or colored pigment as an essential component for forming a film is applied to a surface to be coated. Top coat clear paint containing a curable resin as an essential film forming component is applied to the obtained coated surface and, thereafter, curing treatment is performed to perform two- coat/one-bake painting finish. In this case, either one of water-soluble and water- dispersible resin compositions is selected and resin compositions of a different kind are always respectively used in the base coat paint and top coat clear paint.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel and useful coating process. More specifically, 9, the present invention is a base coat paint and a top coat clear paint by selecting and combining a specific curable resin composition or a water-based curable resin composition. Formation of a composite cured coating film consisting of both resin compositions provides a composite cured coating film with excellent gloss, finish appearance, and excellent weather resistance. This invention relates to a novel 2-coat/1-beam painting finishing method that meets the demand for low pollution because a water-based resin composition is used.

[Traditional technique/Minami]

In recent years, in automotive top coating finishing methods, not only metallic paint finishing methods are applied in which paints containing metallic powder are applied, but also so-called solid color finishing methods in which paints containing colored pigments are applied. , After applying the base coat paint, Tosobny!・The effectiveness of the 2-coat, 1-bake method that allows the paint to be applied! ? It has been 24 years.

That is, such a two-coat, one-bake paint finish 1".

The paint film obtained by this process has an excellent finished appearance and texture.In particular, solid color paints whose main component is vinyl polymers have the disadvantage of extremely poor weather resistance. Although there is C, it takes 2 coats/L
The fact that the application of this type of solid color paint to the bake finish method still brings about various advantages such as the ability to obtain a coating film with excellent weather resistance, means that such a two-coat/one-bake finish method still provides various advantages. This is the ultimate proof of the effectiveness of the painting finishing method.

On the other hand, in the paint industry, from the standpoint of pollution-free and resource saving,
Coating compositions that use Mu1-7 filtrate as a diluent rather than organic abrasions have attracted attention, and in fact, water-soluble or water-soluble Dispersible paints 2, so-called water-based paints, are being studied or some are being adopted.

2 or 1°, so the appearance and coating of the paint film! l! The current situation is that water-based paints that are comparable in physical properties to 4-solvent soluble paints (solution-type paints) have not yet been developed.

[Problem to be solved by the invention]

To this end, the present invention utilizes the conventional technology as described above! ? To provide a useful coating finishing method that eliminates all the various disadvantages of coating, in other words, to provide a coating film that is particularly excellent in gloss and finished appearance, and also has excellent coating film performance such as weather resistance. like? ! The main focus is on providing a 1-bake paint finishing method, and at the same time, in addition, the gloss and finish are superior to those of organic solvent-soluble paints (solution-type paints). Comparable in terms of appearance and weather resistance,
- Layer 7, a novel 21 that meets the demands of low pollution -
The main focus of the A11fiJ is to provide a 1-bake paint finish method.

L7, this is what the present invention attempts to solve! 1! The problem is that by using a water-based resin paint, which is a water-soluble or water-dispersible paint, as either the base coat paint or the clear paint for Top 1-1, it is possible to further reduce the pollution of the entire paint system. This is an extremely useful two-coat coating that provides a composite cured coating with excellent gloss, color tone, finished appearance, and weather resistance.
One example is Kiyoko, which provides a one-bake painting method and a second-bake method.

[Means to solve the problem]

Therefore, as a result of intensive studies by the present inventors in order to solve each of the above-mentioned problems one by one, the present inventors have found that the combination of a specific curable resin composition and a water-based resin composition.
By applying either one to each of the base coat paint and the top coat clear paint, 1, that is, the base coat paint,
7. If the specific curable resin composition in 2 is used, it will inevitably be top coated, and conversely, if the base coat paint is a water-based resin composition, it will inevitably be coated with a clear top coat. Depending on the application method in which this particular curable resin composition is used as a paint,
1.7, which has excellent properties such as 1 hit, 1 property ("no blur, gloss, color tone, and finish appearance, etc.")
The present invention has been completed and completed by discovering an extremely practical two-coat, one-base painting method that achieves water-based coating on a portion of the coating system. reached.

In other words, the present invention provides a curable (base comprising M fat as an essential component of the film-forming phase) in which metallic pigments and/or colored pigments are distributed. Next, 9. The thus obtained painted surface (I.'J-1. Layer 1.) j-0: A coating comprising a curable resin, an essential skin-forming component, and 7. :1-i
It consists of applying a clear paint for 1 and then curing it.2''-!・・'1 for the 1-beta paint finishing method? C1, respectively, the paint for base coat and the clear paint for 1-1 and L5,
- The force expressed by the tiger formula - Bonnet =) 0.2 = 90% by weight of the polymerizable monomer (al) containing carboxyl group, 0.2 = 90% by weight of the polymerizable monomer (a-2L) containing carboxyl group. 01-・30 overlapping part,
.

In addition, other vinyl φ-mers (a-
3), the total concentration is 100% t (a carbonate group-containing copolymer (A) obtained by copolymerizing a filter monomer mixture, and a polyamine compound () 3) are further required. According to 2, a curable resin composition (1) comprising a phosphorus-containing compound (C) and/or a nitrogen-containing purple compound (D) without any essential components, or a water-soluble or water-dispersible resin composition.・Choose one of these 7, paint for the base (1) and clear for the top (7).
As the paint 2, there is also a painting finishing method that consists of using different types of resin compositions together and forming a composite cured coating film according to Section 21-7. It is an attempt to capture and provide information.

The configuration of the present invention will now be described in detail.

The carbonate to group-containing polymerizable #φ polymer (,1-1) used in the present invention includes 2,3-carbonate propyl (meth)acrylate, 3.4 carbonate dobutyl (meth) ) Acrylate...-1., 4.5-carbonate pentyl (meth)acrylate, 5.6-carbonate hexyl (meth)acrylate [-, or 6.
Particularly representative examples include 7-carbonate hexyl(meth)a'pI.-. The amount used for these is 0.2
-90% by weight, preferably 2-45% by weight.

Next, a carboxyl group-containing polymerizable monomer (J-
To mention only the representative examples of 2), 1.
ri) Acrylic acid, crotonic acid, itaconic acid, maleic acid 5, fumaric acid, itaconic acid monoalkyl ester, 71
/ monoalkyl inic acid or monoalkyl fumaric acid esters, hydroxyl group-containing vinyl monomers such as 4- or β-hydroxyethyl (meth)acrylate, and succinic anhydride or trimellitic anhydride. There are monomers having a carboxyl group, such as additions of E with acid anhydrides such as: The amount of the carboxyl group-containing polymerizable monomer (a-2) used is 1, boriamini/
Compatibility with compound (B) and polyamine compound (B)
) from the point of view of viscosity during mixing, o, oi ~ 30% by weight,
A suitable range is preferably 0.1 to 10% by weight.

Furthermore, the component (a-1), which is (a-3), and (
a-2) Component, Jl: Other vinyl monomer rods that can be copolymerized Firstly, all those that can be copolymerized with components (a-1) and (a-2) can be used, and ), but to name only the most representative ones, (I) methyl acrylate, (meth) acrylic acid, (meth) acrylate
': J building, butyl (meth)acrylate, (Iri)? 2-ethyl-7xyl acrylate, (meth)'lauryl acrylate; styrene.

Vinyltoluene, α-methylstyrene, dimethylstyrene, (meth)acrylamide, tri-methylol(meth)acrylamide, butyl-xy(meth)acrylamide; (meth)acrylonitrile, vinyl acetate, °-,l, diethyl maleisoate , dibutyl maleate, dibutyl fumarate, diethyl itaconate, dibutyl itaconate; 2-
Hydroxyethyl (meth)acrylate -)-12-hydroxypropyl (meth)acrylate (., 3-Hydroxybutyl (meth)!acrylate, 4-hydroxybutyl (meth)acrylate...-1., 3-Chloro-2-hydroxypropyl (meth)acrylate 5. Di-2-hydroxyethyl fumarate (or mono-2-hydroxyethyl-monobutyl fumarate +/-) or polypropylene glycol, 1-ol or polyethylene glycol Seven (meth)acrylide-1, [Plaxel FM, < is FA'l,) °7-] [caprolactone addition monomer manufactured by Daiyaru Kagaku ■], and diethylaminoethyl (meth)acrylate b i...
< is diethylaminoethyl (meth)acrylic -1, 1).

The copolymer is prepared from the various monomers that constitute the carbonate group-containing copolymer (A) component described above! ! 11° (This can be done by any known and commonly used force, but the most convenient method is 1) Solution radical polymerization υk. In this case, aromatic polymers such as toluene or Hydrocarbon; hexane, pentane Moshi 7
(Cyclic) aliphatic hydrogenation such as cyclo-xane I; Ester solvents such as acetic acid, butyl acetate, or ethylene glycol monomethyl ether acetate;・N, methyl-1so
- such as butyl getone or cyclohexanone -
Tone-based solvents; isopropanol, n-butanol (
The polymerization may be carried out by a conventional method using a solvent such as an alcoholic solvent such as 1 or isobutanol, and 5 a known and commonly used polymerization initiator such as an azo or peroxide type polymerization initiator.

Then, in carrying out the polymerization reaction, at 1, t
, ev t-dodecyl mercaptan, lauryl mercaptan or thioglycolic acid alkyl esters or β-mercap [The polymerization reaction can also be carried out using mercaptans such as propionic acid or a molecular weight regulator such as α-methylstyrene dimer.

Next, in C1, the polyamine compound and component (B) constituting the resin composition for paint of the present invention will be explained.

Carbonate group-containing copolymer (A) prepared as follows: 7ff1, min: 1. This polyamine compound is mixed with component (B) as a curing agent.

Here, the polyamine compounds (B) and 1 are selected from a few known and commonly used polyamines such as aliphatic polyamines, aromatic polyamines, composite polyamines, modified aliphatic polyamines, and heterocyclic polyamines.
is selected as appropriate.

・As a specific example, Echi 1. Non-diamine, 1.2
-diaminopropane, ll3-diaminopropane, 1.
4-diaminobutane, 1,5-diaminopentane, 1.
6-sia5minohebyusan, 1.7-dia, minohebbutane, 1,8-diaminooctane, 1.9-diaminononane, 1.10-diaminodecane, 1.2-diaminocyclohexane, 1゜4 Bis(3-remi, nofu'rovir)bibeudin, 3,9-bis(3-aminopropyl)
-2,4,B,10-tel-laoxasbimouth (5++'
, 1) undecane, 8 diethylenetriamine 5, triethyl 1. / Ntetrami, /, Tej Laech 1.・Nbentamine, bertaethylene\xamine, N,N'-bis(2-71minomethyl)ethylenediamine, N,N"
-bis(2-aminoethyl)ethylenediamine, N,N
'-bis(3-aminopropyl)ethyl1,...diamine,,N,N'-bis(2-aminomethyl)-L3
-Propanediamine, N, N'-bis(2-aminoethyl)-1,3-propanediamine, N,N''-bis(3-aminopropyl) -1,3-propanediamine, N,N'-bis (2-aminomethyl)-1,4-butanediamine, NN'-bis(2-aminoethyl)-i
, 4- Pig],,! Diamine, N, N"-bis(3-
aminopropyl) -1,4=butanediamine 1, bis(4-aminosylhexyl)methane also j, 7, <(
, :yo, 1,3-bis(aminomethyl) Schiff IJ^ Kizan or [Jeffamine D-230 or D-4
Various difunctional primary 1:mine compounds such as 40J (Mitsui Texaco Chemical 0@product); 1' Ginifermin T-403
Various trifunctional primary amine compounds such as J (product of the same company); Particularly representative examples include ethylene oxide adducts 1 and oligoester (meth)acrylate 1/- adducts with various polyamines such as those listed in 1. Polyamide resins are also used. As a specific example, any known and commonly used one can be used, but
E'Rackamite'' [Dainippon Ink Kagaku Gyokugyo special product]
There are polyamide amine resins such as ``Zanmide'' [Special product of Sansho Kagaku Kogyo].

Such a polyamine compound (B) and 1. The blending ratio with the carbonate group-containing copolymer (A) is carbonate group equivalent/primary amino actual weight -2-0.5, preferably 1.2-0. A ratio of 78 is suitable and gives good coating performance. In the case of , 7, if the compounding ratio exceeds 24, the curing will be insufficient and the coating performance will be poor, while if the compounding ratio is less than 0.5, the compatibility will deteriorate and eventually Since it will self-extinguish, either case is preferable (2 (no).

Next, the above-mentioned phosphorus-containing compound (C) and/or nitrogen-containing compound is used together with the ten polyamine compounds (B) to become a curing (co)catalyst component of the curable resin composition (ff). (D) and 1. Now, if I were to limit myself to illustrating some typical examples of samurai, they would be as follows.

First, such phosphorus-containing compounds (D) include triethylphosphine, tributylphosphine, butylphosphine,
Tripentylphosphine, trihexylphosphine, triheptylphosphine, trioctylphosphine, trinonylphosphine, /, tridecylphosphine; silicyclohexy! Lefosphini/; dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, dibutylphenylphosphine, dicyclohexylf), nylphosphine, methylshifj, nilphosphine, ethyldiphenylbosphine, 7buU bildife::, ruphosphine , butyldiph, a, nilbosphine, dichlorohexyldiphenylphosphine; bis(
2,j1,2bis(diphenylphosphino)ethane, 1,2-(-'; phenylphosphino)ethylene, 1,4-bis(diphenylphosphino)butane; triphenylphosphine, i −
Li-o-tolylbosphine, 7 tolylphosphine 5. Tri p-tolylphostuin, diphenyl (0
-tolyl)phosphine, dichloro, nyl(m-tolyl)phosphine, or diphenyl(p-t-syl)sulfone, etc.5; Of course, both can be used.

Also, tetrabutylphosphonium bu IJ mite 1, tetrabutylphosphonium chloride, tetrabutylphosphonium hydride 1'3 oxide, methyltriphenyl bromide, methyltriphenylchloride, methyltriphenyliodidemomethyltriphenylbosubonium n'-phyto, chloromethyltriphenylphosphonium chloride, vinyltriphenylphosphonium chloride, ethyl j.riphenylphosphonium bromide F, Hydroxymethyl triphenyl chloride, phosphonium chloride, methoxymethyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, propazil!・Riphenylphosphonium bromide, brobanzyltriphenylphosphonium chloride, carbomethoxymethyltriphenylphosphonium 12mite, carbomethoxymethyl (・lyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, allyl)・Rifronylphosphonium chloride, cyclopropyltriphenylphosphonium bromide, cyclobrobyltriphenylphosphonium chloride, acetonyltriphenylphosphonium bromide, acetonyltriphenylphosphonium chloride, probyltriphenylphosphonium bromide, propyl Triphenylphosphonium chloride, (carbethoxymethyl) tri-rifninylbosphonium bromide, 7 (carbethoxymethyl)
Triphenylphosphonium chloride, 1,3-dioxolan-2-ylmethyltriphenylphosphonium bromide, 13-dioxolan-2-ylmethyltriphenylphosphonium chloride, butyl triphenyl phosphonium fluoride, butyl triphenyl phosphonium bromide D, nylphosphonium bromide, 2-dimethylamino)triphenylphosphonyl 11lide,
(4-carbutyl)triphenylphosphonium bromide, 8 (4-carbutyl)triphenylphosphonium bromide, [2..(1.3-.dioxolan-2-yl)ethyl] triphenylphosphonium bromide, (2-(1. 3-dioxolan-2-yl)ethyl]triphnynylphosbonium chloride, 2
-Hydroxybenzyltriphenylphosponium bromide, 2~human l::r -'H~cybenzyltriphenylphosphonium chlorine 1', benzyl(・riphenylphosponium bromide, benzyl(・liphenylbosphonium) chlora, i1', phenacyltriphenylbosboniumbutomide, phenacyltriphenylphosbonium chloride.

(4-ethylbenzyl)triphenylphosphonium bromide, (4-ethylbenzyl)triphenylphosphonium chloride, p-xylylene bis(triphenylbosbo,nium fluoride) or p-xylylene bis(triphenylposbonium chloride) ) are exemplified as typical examples, but it goes without saying that in addition to these, any four-coordinated organic phosphorus compound can be used.

Next, the nitrogen-containing compounds (f)) are particularly representative, such as 42-hydroF dipyridine, 115-diazabicyclo[3.4.0]nonene-5
, l+5-diazabicyclo(5.4.0)undecene-
5 or 1.4-diazabiscif 1] [2.2.2] cyclic basic compounds such as octane.

The amount of the phosphorus-containing compound (C) and/or nitrogen-containing compound (11) used is as follows:
The equivalent ratio with respect to the group is preferably 1 equivalent or less; if it exceeds 1 equivalent, undesirable problems such as yellowing of the coating film inevitably occur, so it is preferable. 2<No.

On the other hand, when carrying out the painting finishing method of the present invention, the curable resin composition (+) as described above is used together with a paint for Baseco-1 or: Ni or Tonobuni 1-, respectively. 1. The water-soluble or water-dispersible water-soluble or water-dispersible paint used for either one of the following:
As the curable resin & I composition (II), ie, the so-called water-based curable resin composition, any known and commonly used water-soluble or water-dispersible curable resin composition can be used as is.

First, the water-soluble curable composition is a water-soluble polyester resin or a water-soluble vinyl copolymer that contains a carboxyl group in the resin and is neutralized with an organic or inorganic base to become water-soluble; Using various basic nitrogen compounds such as aminoalkyl esters of (meth)acrylic acid or N-aminoalkylamides as essential raw materials, l'? The base resin component is various water-soluble resins such as water-soluble vinyl copolymers having 1 or 2 amino groups, which can be made water-soluble by being neutralized with organic or inorganic acids,
On the other hand, those containing various crosslinking agents as listed below as curing agent components are particularly representative. ,=1.
,,,.

can be mentioned.

Next, as a water-dispersible curable resin composition, for example, an anionic surfactant, a cationic tetrasurfactant, an amphoteric surfactant, or a nonionic surfactant is used as an emulsifier. to prepare the carbonate group-containing copolymer (A) constituting the curable resin composition (I).
1.7 From the various polymerizable monomers and polymers listed above, excluding the carbonate group-containing polymerizable monomer (a-1), and water-soluble polymerizable monomers Dispersing the vinyl qi-mer in a form in which the monomer is also removed in an aqueous phase 1,
Water-dispersible vinyl copolymers obtained by polymerization in the presence of various water-soluble radical polymerization initiators such as potassium persulfate, hydrogen peroxide, or cumene hydroperoxide;
Alternatively, various organic solvent-soluble resins such as polyester resins, vinyl copolymers, epoxy resins, or urethane resins obtained using the various organic solvents listed above may be used. Add the surfactants, and then add the solvent component (dispersion medium component) to 9. There is no so-called post-emulsification method, which involves phase inversion from an organic solvent to water.
2 is a water-dispersible polyester resin obtained by phase inversion emulsification method, water-dispersible vinyl copolymer 1. Various water-dispersible resins such as water-dispersible epoxy resins and water-dispersible polyester resins; and (4. Various resins such as copolymers, epoxy resins, or urethane resins are reacted with surface-active components, that is, reaction f': emulsifiers, to impart self-emulsifying properties, and then post-emulsification (phase inversion emulsification) is performed. Various water-dispersible resins such as various water-dispersible resins such as water-dispersible polyester resins, water-dispersible vinyl copolymers, water-dispersible epoxy resins, or water-dispersible urethane resins in the form obtained by component and 12, while next (,:.

Various crosslinking agents such as those mentioned above are combined with the curing agent component in 1. Particularly representative examples include those that include
Up! Of course, the method for preparing each resin is not limited to the above.

The water-soluble or water-dispersible curable resin composition is prepared by mixing each base resin with a cross-linking agent that is reactive with the functional groups present in the base resin. The second is as described above, but only the most representative examples of such crosslinking agents (#1,5) are listed below.When the base resin contains hydroxyl groups For example, block polyisocyanates or amino resins are preferable, and when the base resin contains an epoxy group, 1 is preferably a 7-carboxyl group-containing resin or polycarboxylic M group. When the base resin contains a carboxyl group, a compound having at least two epoxy groups in the molecule is preferable. , the curable resin composition (+) and the water-soluble or water-dispersible curable resin composition (II) are the coating film composition 1-. of the present invention. To carry out this method, it is best to use base coat paint or top coat paint.
Used for one side of the clear paint for i.

In other words, in carrying out the method of the present invention, 1. A curable resin composition ( 1) and the water-soluble or water-dispersible curable resin composition (11), that is, the resin composition (1) or the resin composition (I) is used as the base coat paint.
If one of I) is used, and the other resin composition is used as a clear paint for toru 2, 21, these One of the ambidextrous resin compositions must be applied to the paint for BASENIA-1 and the clear paint for TO/BUF-1.

Furthermore, when each of the curable resin compositions is used as a 1-7 coat paint, it can be used as a clear paint as is.
-2, the transparency is impaired 41. Colored pigments or dyes can also be used, to the extent that they are not included.

On the other hand, each curable resin composition A: -Base 1-
When used as a coating material (2), such a curable composition is mixed with known and commonly used aluminum mini-uno, powder, copper $5),
J, ゛mori, < is various metallic powders such as M mother powder, 2, or titanium oxide or charcoal! By blending various 41n materials such as calcium, or various in-house rn materials such as futa v' cyanine brutriidine red or benzidine yellow 1:2. , metallic paint or solid color paint.

In order to improve the ``Miroku-1 painting house'' - Genori (view),
Base coat I paint and 1. It goes without saying that various additives, resin types, or resin compositions capable of imparting thixotropy to the curable resin composition used for pseudoplasticity can be added as appropriate. be.

Furthermore 1. 1. Addition of known and commonly used agents such as leveling agents, ultraviolet absorbers, or pigment dispersants, etc., to the top coating and base coat coating, respectively, as necessary. Of course, it is also possible to distribute medicines.

And 1, the book 2''～・[・l Baking painting finishing method 4'', respectively, base coat ・-1・
Air and top] -1-
Spray painting and electrostatic spraying are suitable for painting, and in this case, the dry film thickness of the paint for Tonobu is 10-100 microns, preferably 10-100 microns.
The suitable dry film thickness of the base coat paint is within the range of 60 microns, and the appropriate dry film thickness of the base coat paint is within the range of 5 to 50 microns, preferably 8 to 20 microns.

Furthermore, the interval time (interval) between the base coat paint and the Totsubuko paint is 5, about 1-45 minutes at about 20°C, preferably 1o7< is 2-
・A time of 20 minutes is appropriate, but by forcing the base coat to dry (tighten), you can shorten the time between coatings, thereby shortening the time.
□1. It goes without saying that it is also possible to have a ′: point.

In this case, under the drying conditions described in 1 and 5 above, that is, at room temperature or in a relatively low-temperature region around it, the base coat film was brought to a touch-dry or semi-cured dry state. , 1...'' It is sufficient to apply Bucoat paint.

Next, the paint films of the base coat and the base coat applied in this way are baked at a predetermined temperature and time after the top coat paint is applied.
It is sufficient to harden it by performing a baking process (King), and in such baking hardening, 1O-
It is desirable to perform so-called forced drying for about 60 minutes in terms of curing performance and productivity, but of course, it is preferable to perform forced drying for about 60 minutes.
) and the different types and characteristics of each type of paint.

Or painting 4 to 4 forest or material (subject to be painted) aX
"Appropriate depending on the situation" 1. Changing the drying and curing conditions does not make any difference.

Above 5. runi, ii1 curable resin composition (1
) and a water-soluble or water-dispersible curable resin composition (IN)
The 2J-1 base coating finish of the invention was carried out by using one of each of the curable resin compositions as a base coat paint and a top coat paint. The drying method is to dry at room temperature or heat dry in a relatively warm area to improve weather resistance, gloss, and color tone. It is also possible to form composite cured coatings with excellent coating performance for various types of coatings such as coatings and finishing (4) reeds, etc.
Moreover, compared to conventional thermosetting acrylic resin paints and amino alkyd resin paints, it is 1. [EFFECTS OF THE INVENTION] The coating finishing method of the present invention can be used for both methods. 6. The curable resin composition (1) comprises an ethylene carbonate l-group-containing copolymer (2) constituting the resin composition.
A strong coating film is formed by the bridging reaction between the air carbonate groups in A) and the primary amine groups in the polyamine compound (B), while water-soluble or water-dispersible The curable resin composition forms a coating film with excellent transparency due to the crosslinking reaction between the resin and the crosslinking agent, which is included in the compositions 1 and 2 of the curable resin composition.

Among these, curable resin compositions (when used in combination with Totsubukoto coatings, coatings with excellent gloss, color tone, and appearance) are obtained.
In addition, when this resin composition (1) is used as a base coat paint, if it is a metallic paint, a paint film with excellent brightness and metal coordination can be obtained.
If it is a solid color paint, there are many advantages such as the ability to obtain a coating film with excellent color development.

In particular, the method of the present invention further uses a water-based curable resin composition (11) to produce a hair coat paint or a tombuni 1-!・Since it is a coating film finishing method by combining λU with paint, a part of the water-soluble or water-dispersible curable resin composition is always used. Compared to conventional organic solvent-soluble paints (solution-type paints), the layer 5 exhibits low-pollution curing7, and the resulting composite cured film has excellent physical properties, gloss, and finish. -1- It has an additional and mutual effect of being excellent in various properties of the coating film, such as appearance and appearance.

[Example] Next, the present invention will be specifically explained using reference examples and examples.
: Unless otherwise specified, all are assumed to be the overlapping group it.

Te? Example 1 [Preparation example of copolymer (A) containing dilene carbonate groups] 700 parts of toluene was added to a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a cooling tube, and a gas introduction tube. The temperature was raised to 110°C under nitrogen gas atmosphere, and 300 parts of styrene, 1 and 200 parts of methyl methacrylate were added.
95 parts of acrylic acid, 5 parts of acrylic acid, 400 parts of 1.2° 3-carbonate methacrylate 1:1, abbis isobutylene 1:1
-IJ71. (A I BN) io part, t, erL
-Butyo-Ruba・-Oxyoctoate・L (TBPO)
10 parts of
A mixture consisting of 5 parts of Zoet (TB 1) F3) and 300 parts of l.ruene was added dropwise over 3 hours, and after the dropwise addition was completed, the temperature was maintained for 15 hours to carry out the polymerization reaction. Continuing, the nonvolatile content (NV> is 50.2% and 1, number average molecular [1 (Mn) is 137.000 5
, Ethi 1/Tsuka-bonate group-containing vinyl copolymer (A
) was obtained. Hereinafter, this will be referred to as vinyl copolymer (A-1
).

Reference Examples 2 to 4 (Same as above) Various Ethi! A solution of the vinyl copolymer (A) containing carbonate groups was obtained.

Reference Example 5 [Preparation of water-soluble or water-dispersible resin! Example] Warm)
800 parts of butyl cellosolve and 5 parts of '1'' BPH were charged into a reaction vessel equipped with a y-meter, a stirrer, a reflux condenser, and a nitrogen gas III inlet tube, and the temperature was raised to 120°. To, dienalene glycol monomethacrylate--
49 parts of 1,2-hydroxyethyl methacrylate -
490 parts of 1, 20 parts of acrylic acid, 200 parts of butyl cellosolve and 10 parts of benzo ylva-oxide.
A mixture consisting of 3 parts was added dropwise at 1-i, .
'r Polymerization was carried out in 2 lines, 1, then 5 parts of glycybasil, methacrylate, 0.5 part of dimethyl laurylamine and 0.5 part of hydrodonone were added. The mixture was further maintained at the same temperature for 5 hours L2 to obtain a solution of a water-soluble vinyl copolymer. Hereinafter, this will be used as a dispersion stabilizer (D
It is abbreviated as S-1).

2. Then, 600 parts of this dispersion stabilizer (1) S-1) was added to 9.-1. Pour into a reaction vessel similar to that described above, raise the temperature to 80°C, and then \1. 200 copies of Stishin'n, 7n-
43 parts of butyl acrylate 1, 2-hydroxyethyl methacrylate! A mixture of 7 parts of ・, 200 parts of water, and 7 parts of ammonium persulfate was added dropwise over a period of 5-2 hours, and even after the addition was completed, the temperature was kept at the same temperature for 8 hours.
Meanwhile, the polymerization reaction was continued by adding a total of 3 parts of ram with persulfuric acid.
In addition, a 1''-like dispersion having a Pluck Field viscosity of about 4.5 voids at 825° C. was obtained. Hereinafter, this will be abbreviated as water-dispersible resin (1''-1).

Reference Example 6 (Same 14) In a reaction vessel similar to Reference Example 5, 1. For U, ', g Roux = 270 parts of 1 solv and 30 parts of water are charged, and then 35 parts of the parent 5 aqueous 1,000 tour shown by the following formula are added to it until 1.130'c. ? I boiled it.

Then here are 476 copies of 1,000 copies, -n, 210 copies of n.
A mixture of 1.-butyl acrylic acid, 14 parts of meccrylic acid, and 14 parts of tert-glycanhydride II peroxide was added dropwise over a period of 3 hours, and the same temperature was maintained for 622 hours after the dropwise addition was completed. 18.Continue the polymerization reaction"L
After that, cool to 7.80℃ and remove any UIII.
Add 615 parts of water dropwise over 2 hours to the T, cool to 625 t; An aqueous dispersion of copolymer resin was obtained.

Next, this resin dispersion was made alkaline with 5% aqueous ammonia to neutralize the carboxyl groups in the resin.

The aqueous dispersion of the vinyl copolymer resin thus obtained is abbreviated as water-dispersible resin (F-2), and the NV of 77- is 45.2%, and the viscosity is 5 and L8 voids. .

Reference Example 7 (Same”-) In the same reaction vessel as Reference Example 5, add 1 and 3 of isopropanol.
8 parts by adding 00 parts and 300 parts of gutil cellosolve.
Raise the temperature to 01; and add 200 parts of sujishin, 313
1 part of methyl methacrylate, 270 parts of n-butyl acrylate, 117 parts of 2-hydroxy/'r-methyl methacrylate, 200 parts of methacrylic acid, Tl3P
A mixture consisting of 20 parts of O, 200 parts of isopropanol, and 200 parts of butyl cellosolve was added dropwise over a period of 4 hours, and after 1 drop was finished, the temperature was kept at the same temperature for 8 hours to determine the degree of polymerization. ki ki 1 line see 19. Me5, NV is 494
A clear solution of a 9% copolymer resin was obtained.

Next, 404 parts of a 25% dimethyl ethane/nolamine aqueous solution was added to this resin solution, and the mixture was stirred for 30 minutes with
A clear water-soluble tree with a V of 45.7% was obtained. Hereinafter, 1, τ is abbreviated as water-soluble resin (E-1).
, "Item No. 4 did not become cloudy even when diluted with water (No. 2), and showed complete water solubility. It was confirmed that it was a so-called water-soluble vinyl copolymer resin and ZC.

1st J-Person Examples 1 to B Paints for Tonobuko-1 and
・-Squaw] After preparing the paint, dilute it with thinner to a viscosity that can be sprayed, and apply 1 rhi phosphate paint and 1 tbuni 1 to the facing plate treated with lead phosphate.
The dry film thickness of the paint for -1 is 183. t'1 and 3
The coating was applied by air spraying so that the coating film had a thickness of 0 microns, and then cured by heating or heating under the curing conditions 6 shown in the same table: A cured coating film was obtained.

The physical properties evaluated for each coating film obtained with "Kakushi" are summarized in the same table.

Note 1. The evaluation of each of these physical properties was carried out immediately after baking at room temperature for 3 days.

, /・' As is clear from the results in Table 2, the coating film obtained by the coating finishing method of the present invention has excellent gloss, color tone, and finished appearance, and has excellent brightness and metallic coordination. It is known that it does not come loose and has excellent chemical resistance.

In this way, the method of the present invention is extremely useful.
It can be said that it is a baking finish method.

1゜ Procedures (heavy industry, writing) 1999 Ritsu/? Day Display of incidents 1999 Patent Application No. 9 No. 1902

Claims (1)

[Scope of Claims] 1. A base coat paint comprising a curable resin containing metallic pigments and/or colored pigments as an essential component for forming a paint film is applied, and then, on the thus obtained painted surface, A two-coat/one-bake painting finishing method comprising applying a top coat clear paint containing a curable resin as an essential film-forming component and then curing the base coat paint and the top coat paint, respectively. As a clear paint for coating, (I) (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [However, R in the formula represents a hydrogen atom or a methyl group, and n is 1 to 4. Let it be an integer. ] Carbonate group-containing polymerizable monomer (a-1) represented by
0.2 to 90% by weight of the carboxyl group-containing polymerizable monomer (a-2), and each of the above-mentioned polymerizable monomers (a-1) and (a- 2)
consisting of another vinyl monomer (a-3) copolymerizable with
A carbonate group-containing copolymer obtained by copolymerizing a monomer mixture having a total amount of 100% by weight and (B) a polyamine compound are essential components, and if necessary, (C
) a curable resin composition also containing a phosphorus-containing compound and/or (D) a nitrogen-containing compound; or (II) a water-soluble or water-dispersible resin composition; A painting finishing method characterized in that a base coat paint and a top coat clear paint are used as a combination of the above-mentioned different resin compositions, thereby forming a composite cured paint film.