JPS59138275A - Water-based paint composition - Google Patents

Abstract

PURPOSE:To provide a water-based paint composition containing a specific water-soluble resin and water-insoluble resin particles as a film forming component, and giving a film having especially improved gloss. CONSTITUTION:The objective composition is composed of fine particles having an average particle diameter of 0.3-6mu and obtained by the two-step emulsion polymerization of (A) a water-soluble resin composed of (acryl-modified) polyester resin, an (acryl-modified) alkyd resin and/or an acrylic resin and (B) an alpha, beta-ethylenic unsaturated monomer adjusting the concentration of the chain- transfer agent in the first emulsion polymerization to 0.3-7wt% based on whole monomer in terms of dodecylmercaptan, and keeping the concentration of the chain transfer agent in the second-stage emulsion polymerization at zero or relatively low level compared with that of the first-stage polymerization. The weight ratio of A/B is 99/1-15/85 (solid basis).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based paint composition useful as a top coat, and more particularly to a water-based paint composition with particularly improved gloss, which contains a water-based resin and water-insoluble resin fine particles as film-forming components, and contains C. It concerns things.

Recently, attempts have been made to use a combination of an aqueous resin and a water-insoluble resin powder as a resin vehicle for an aqueous coating composition. For example, the patent application 51-31 (53 U (5 yen, 51
In No. 25224, etc., 0.5 to 30 wt % of water-dilutable resin of resin particles is added to a slurry consisting of 10 to 70 wt parts of fat particles and 7 i < 90 to 30 w [parts] for the purpose of storage stability of the composition. 'Adding it is also a patent! rl 1li(4
No. 9127151 also describes adding a water-soluble or water-dispersible resin corresponding to 5 to 50% of the powder resin to a slurry consisting of the powder resin and water. However, these slurry-type paints (generally increase the non-volatile element content or rotate), cannot be applied thickly, and are prone to cracking due to insufficient coating activity after painting, resulting in poor painting workability.
It has not been put into practical use due to storage stability, coating performance, etc. Also, Japanese Patent Application No. 54-74606, No. 54-170
No. 262, Japanese Patent Publication No. 55-4149, etc. are water-dispersible coating i4 compositions containing powder coatings and water-soluble EL fat as main components, and water-soluble resins are blended in an amount of about 10 to 20% of the powder resin. is listed. However, when these are dispersed in water, they become a water-powder resin slurry, and the water-soluble resin is expected to play the role of a dispersion stabilizer. stay in the drug,
In the end, it is no different from a slurry-type paint, and it does not essentially improve its inherent drawbacks. Under such circumstances, the present applicant developed a very remarkable water-based paint composition containing a resin vehicle that is a combination of a water-soluble or water-dispersible resin and water-insoluble resin particles, and filed a patent application (Japanese Patent Application No. 1983). -114686). The invention according to the application involves weighing 5 q of water-based varnish with a viscosity range commonly used in paints into a 100 ml beaker, diluting it with deionized water, and straining it through a beaker to make the No. 1 type (26 point type) unreadable. The surface tension of the solution obtained by diluting the water-based varnish with deionized water to a solid content of 1%'lV/W is calculated as the water-based resin (water-soluble resin or water-dispersible resin, hereinafter referred to as water-based resin). same), the water tolerance is 4 or more, and the surface tension is 51.
If at least one type of aqueous resin that satisfies the requirements of dyne/cl'n or less is used, the solid content weight ratio of the aqueous resin and water-insoluble resin fine powder is 98:2 to 45: 5
Wide range 0) n+', case:; Even if J and C are added, an increase in the viscosity of the system is observed, and the resin content of the C/l resistant coating film is increased. It is possible to improve workability (
It has excellent footing, and has 1 in 'j;, V'r performance.
The coating composition provided in this article was ◇.

However, the above-mentioned water/H coating film') 1 silk composition (similar to various previous proposals, intermediate coating, and G'8 coating) was developed, However, the water-based coating '31 composition did not meet the requirements for topcoat ('), which requires a high gloss and flat coating surface, and the film performance of C. A water-based coating 3'1 composition that not only has excellent paint performance but also excellent performance such as durability, gloss, and smoothness, and is useful for top coating. J5 is in urgent demand in various UH fields including the automobile industry.

The applicant previously described the average particle diameter of 0.3 to 6μ and the maximum particle diameter of 10μ obtained by polymerizing an ethylenically unsaturated compound with an aqueous resin selected from alkyd resins and polyeustyrene resins.
The following resin particles were mixed at a solid content weight ratio (99:'1 to 40).
: The average particle size obtained by polymerizing an ethylenically unsaturated compound with an aqueous resin selected from acrylic resins, alkyd resins, and polynisder resins, containing 60 parts of water and 1 part of water. An aqueous paint composition containing resin particles of 1μ in a solid content weight ratio of 99:1 to 15:85, an aqueous resin selected from d3, an acrylic-modified alkyd resin, and an acrylic-modified polyester resin, and an ethylenically unsaturated Average particle size of 1C produced by compound polymerization: 0
．． 01~6μ 1fil fat fine particles with a solid content weight ratio of 99
A water-based paint composition containing a ratio of 1 to 15:85 has excellent workability, storage stability, and durability.
It was discovered that it provides a high gloss and smooth painted surface and is useful as a top coat, and patent applications No. 57174890, 11jl 57-174891, and 57-1748 were filed, respectively.
A patent application was filed as No. 92.

The present invention is a further development of the above invention.

In other words, the above invention is a combination of a specific water-based resin and a specific water-insoluble resin, and the average diameter of the resin particles is 1.
If you use a combination of substances within a certain range at a certain mixing ratio, due to the special rheological properties of the system, it will be possible to give a person a fat content of 1 fat without increasing the amount of fat. It is assumed that a water-based paint composition is to be used as a topcoat paint, which is flexible, can produce a high-gloss, smooth coating surface, and fully satisfies the requirements of -C. However, the present inventors have further researched the particle structure and surface structure of the four fat particles, and have developed these particles into α, β, and
- Eglenic inert saturated monomers are produced by stage emulsion polymerization, and by controlling the degree of opening (chain transfer agent) in the first stage and second stage, polymers with relatively large number average molecular weights are produced. By configuring the coalescence as fine particles that are attached to the outer shell, the gloss of the coating film can be further improved, and the combination of water-based resin and water-insoluble resin can be made wider. reached.

Therefore, the object of the present invention is to provide a water-based paint composition that has excellent workability, storage stability, and durability, and is capable of providing a high-gloss, flat painted surface, and which exhibits little effect (particularly on painted glossy surfaces). There is a vine composition provided.

The object of the present invention is to contain a binder component consisting of an aqueous resin and water-unbathable (i) fat particles as essential constituents, and optionally contain pigments, crosslinking agents, and other paint additives.
In the water-based coating composition C, the water-based resin is at least one selected from polyester resins, alkyd resins, acrylic resins, acrylic-modified polyester resins, and acrylic-modified alkyd resins; Insoluble 14 resin fine particles are α, β-ethylenically inert saturated monomer two-stage emulsion market method, but the temperature of the chain transfer agent at the first stage emulsion polymerization port is the total amount of one monomer per article. 0.3 to 7% by weight, and the chain transfer agent wetness of the second stage emulsion polymerization I Samurai is adjusted to 9 or a) relative to the degree of accent in the first stage. or 0
This can be achieved by a water-based coating composition characterized in that the particles are fine particles with a diameter of 3 to 6 microns, and the solid content weight ratio of the water-based resin to the water-insoluble resin is 99:1 to 15:85.

4. The water-based resin (water-soluble resin or water-dispersible resin, hereinafter the same) used in the invention is polyester, alkyd, acrylic, acrylic modified (polyester or acrylic modified alkyl) commonly used in the paint field. ~Resin (there is.

J4 Lele et al., polynisfur tree 1 finger is a lot of j fukuki acid dota (
General polyvinyl resin C' obtained by the polycondensation reaction of polybasic acids such as sulfuric acid, monosuccinic acid, succinic anhydride, adipic acid, and aliphatic acid. Straight-chain dibasic acids such as gelaic acid and sebacic acid; phthalic acid, phthalic anhydride, isophthalic acid, telenotalic acid, tetrahydrophthalic anhydride, hexyhydrophthalic anhydride, tetrabromno-11, (water) Aromatic fatty acids such as phthalic acid, trimelin l-1ffl, trimelin anhydride, pyromelli 1-he acid, pyromelli 1-he acid anhydride; unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. However, examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,
3-butylene A-ru, 1,6-hex4nanediol,
Diethylene glycol, neopendel glycol, 1-
Glycols such as ethylene glycol, aqueous hisphenol A, bisphenol dihydroxyprobyl -
Dell, glycerin, 1- to 1-rimethylolethane, trimethylolpropane, pentaerythritol, etc. can be used as appropriate. If the polyhydric alcohol is not limited to 111J, it may be any alcohol that can be used as a raw material for a normal polyester resin, and the molecular weight can be adjusted by a conventional method. It is possible to use base acids or alcohols for this purpose.

Alkyd resin is obtained by esterifying and modifying polyester with drying oil and fatty acids, and uses it as an oil and fat component.
Any known oil can be used, such as C linseed oil, linseed oil, perilla oil, watered castor oil, coconut oil, hydrogenated coconut oil, rice sugar fatty acid, 1 to 1-l oil and fat, soybean oil, octylic acid, etc. Further, the alkyd resin may be modified with Ebogishi, L1 gin, or phenol resin. The methods for producing these resins are well known to those skilled in the art and need not be detailed.

Acrylic resins are also preferably used in the present invention. This acrylic fat has 1 or more polymers in the molecule + iJ f
It: As shown below with an ethylenically unsaturated bond! 1
i Handle early 1 ho alone or in any combination ze C1
It is something that can be beaten.

1) Carbohydrates containing small xyl groups such as (,15)'acrylic acid, methacrylic acid, chloric acid, itaconic acid, maleic acid, fumaric acid, etc. 2) H[-
(1-i-mer such as 2-hydroxyethyl acrylate, hydroxyprohylacrylate-1~
, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate-1 to hydroxybutyl acrylate-1
~, human 13-xybutyl methacrylate-], allylnonol, methalyl alcohol, etc.; 3) Nitrogen-containing alkyl acrylate-1~ or methacrylate-1~ For example, dimedylamine ethyl acrylate, dimethylamino''nidyl methacrylate (3) Alkyl acrylate-1 ~ or methacrylates such as medyl acrylate-1 ~, medyl acrylate,
Ethyl acrylate-1~, Ethyl methacrylate-1~, Kanobutyl acrylate-1-11)-Butyl methacrylate-1-1
2-1 Derhexyl acrylate etc. 7) Polymerization 14″15
Aromatic compounds such as styrene, α-methylstyrene, vinyl 1-toluene, t-butylstyrene, etc. 8) α-olefins i.e. ethylene, propylene, etc. 9) Vinyl compounds such as vinyl acetate, vinyl propionate, etc. 10) Dienes In the presence of compounds such as butadiene, isoprene, etc., these α,β-ethylenically unsaturated monomers, light, heat, radical initiators such as orange peroxides or inorganic peroxides, and azo compounds, Any public 9/11 agreement can be combined.

Furthermore, another -81 aqueous 6A fat, which is preferably used in the present invention, is an acrylic-modified ILC.
Liesdel Ori ['', alkyd resin, Rinawachi Poly 1
Examples include resins in which 11 acrylic polymer segments are incorporated into 11 resins or alkyd resins.

Such acrylic modified resins can be obtained, for example, by the following methods.

(1) An acrylic resin is synthesized in the presence of a polyester or alkyd resin containing unsaturated groups.

Polycondensation reactions such as polycondensation reactions (in the production of polyester, unsaturated acids such as maleic acid, maleic anhydride, fluoric acid,
When citraconic acid, itaconic acid, dimer acid, etc. are used, a polyester with unsaturated groups is produced (1), and when such unsaturated polynisdales or saturated polyesters are modified to become Nissdales by acting with a drying oil, fatty acid, etc., unsaturated groups are formed. In the presence of a polyester or alkyd resin containing such unsaturated groups, a free radical catalyst such as azobis is used as an initiator. Isobutyronyl l-lyl, henzoyl peroxide, cy[-butyl peroxide, cumenehydrobel 71- = l-cytoside, or chain transfer agents such as edylmer butane, butyl mercarbutane, dodecyl merbutane, etc. J-butane, carbon tetrabromide, carbon tetrachloride, etc. are used to superimpose an acrylic monomer and the acrylic modified polyester or alkyl resin used in the present invention is (54).In this case, As the acrylic monomer, various small compounds having one or more polymerizable ethylenically unsaturated bonds in the molecule, which are usually used in the production of acrylic resins, are used.

(2) In the presence of a polyester or alkyd resin containing a carboxylic acid group, polymerization is carried out of a covering acrylic monomer group containing a covering ethylenically unsaturated monomer containing an oxirane group as one component.

Polyester resin or alkylene 1 to resin is made of 3
1j 'A'il] λ11 A carboxylic acid group is usually included in the group 11. So C゛Glycidyl acrylate-I
~, containing an ethylenically unsaturated jti-mer having an oxirane group such as glycidyl methacrylate-1 as one component; c1 a carboxylic acid group-containing polynisdel or alkyd containing an acrylic intermediate group as described above; If polymerization is avoided in the presence of a resin, acrylic modified polyester or (L
A resin is obtained for Alki 1.

(3) In the presence of a polyester or alkyd resin containing an oxirane group, polymerization of an acrylic monomer (1) containing carboxyl 11 is carried out.

In the production of polyester or alkyd resins, for example, polynisder or alkyd resins containing oxirane groups are mixed with a polyalkydyl component having two or more oxirane groups and a polybasic acid component. α, β with carvone q22j4 in the presence
- ethylenically unsaturated 11j monobase, e.g.) 7acrylic acid,
If the above-mentioned acrylic resins containing methacrylic acid, chloro-chloric acid, itaconic acid, maleic acid, fumaric acid, etc. as one component are reacted, acrylic modified polyester or alkyd resin used in O\Komyo can be obtained. is obtained.

(4) A method in which a polyester or alkyd (or acrylic resin) containing a carboxylic acid group is reacted with an acrylic resin (or polynisder or alkyd resin) containing an oxirane group.

If a polyester or alkyd resin and an acrylic resin are supported with acid groups on one side and oxirane groups on the other, and both resins are reacted, an acrylic modified polyester is produced by the reaction between the acid groups and the oxirane groups. Alternatively, alkyd resins can be obtained.

(5) Polymerizing an acrylic monomer in the presence of a mercapto group-containing polyester or alkyd resin.

Polybasic acids or polyhydric alniol containing mercapto groups
to obtain polyester or (J Alki 1) resin using
This is utilized in a chain transfer reaction to polymerize the aforementioned acrylic monomer.

The above is a typical example of the production method of the acrylic modified polyester or fl alkyd resin of the present invention.
)! 'iL Rirushi's (゛ is very important, polyester or al-1-de (during degreasing) acrylic modified polyester or alkitoy in which acrylic polymer segments are incorporated is one finger per finger. Any Ij method as far as possible)
However, it should be understood that any of them may be suitably used in accordance with the present invention. Now it takes 8
The Δglucification of 1-fatty acids is carried out according to the textile method, for example, by converting acidic groups such as carboxylic groups into 1-basic substances (for example, monomethyl-7mine, dimebylamine, trimedelamine, monoethylamine, 1-liezylamine, monoisobutyl-1). ” biruamine, diisopropylamine, diethylene 1-helamine, triethylenetetramine, 7] supratanolamine, jetanolamine, i-liethanolamine, monoisobut-1]panolamine, diisopropanolnonomine,
Dimethylethanolonomine, morpholine, methylmorpholone, piperazine, ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.) to impart water bathing property or water dispersibility f4, and for the purpose of the present invention. The water-based resin can be selected from one or more of the various resins listed in 112 (as appropriate), and may be either a thermoplastic type or a thermosetting type. . That is, these may or may not be supported with a functional group capable of reacting with the other aqueous resin J3 and/or the functional group of the powdered resin upon heating. Examples of such functional groups to be supported include carbonic acid groups, sulfonic acid L↓, phosphoric acid groups, hydroxyl groups, oxirane groups, active methyl groups, amino groups, reactive carbon-carbon unsaturated bonds, Examples include sardine-l-group, blocked isocyanate group, halogen, etc. These can be easily incorporated into the resin by selecting monomers during resin production, controlling the molecularization reaction, etc., if desired. I can do it.

A: In the invention, is a fine water-insoluble resin powder used together with the above-mentioned aqueous resin? The fine water-insoluble resin powder is an acrylic or vinyl polymer obtained by polymerizing an ethylenically α, β-unsaturated compound, or It is a copolymer. The ethylenically unsaturated compound in this case can be any compound C' that has one or more polymerizable ethylenically unsaturated bonds in its molecule, as described above for the acrylic water-based resin. Can be used alone or in combination.

However, in the present invention, the most important '4:
One of the features of the process - C1 In addition to the fact that the fine particles of this acrylic or hinyl polymer or copolymer are water-insoluble and fine particles, there is also a special TA method (no chain transfer agent). It is composed of fine particles with a special structure obtained by a two-stage emulsion polymerization method: a first stage reaction in which the Fuchimaro is relatively large, and a second stage reaction in which the Fuchimaro is relatively small. .

When manufacturing fine polymer particles by emulsion polymerization of α, β-ethylenically unsaturated monomers, chain transfer agents such as alkyl mercaptans (ethyl mercaptan, butyl mercaptan, dodecyl mercaptan, etc.), halogenated carbon (
Carbon Sixin, Carbon Tetrachloride, etc.) 0.3 to 7 per monomer
It is known that relatively soft polymer particles having a number average molecular weight of about 2,500 to 50,000 can be obtained when about % by weight (in terms of dodecyl mercaptan) is used.

It is also known that the molecular weight of the resulting polymer can be made smaller or larger by increasing or decreasing the concentration of the chain transfer agent. The present inventors carried out this emulsion polymerization in two stages, and the first stage (Koi'C chain transfer agent) was used at a concentration of 0.3 to 7% of the heavy chain of dodecyl mercaptan based on the weight of the monomer. In the second stage, if the chain transfer agent is used in the range of 0.3 to 5% by weight relative to the opening degree (0 or 1st stage), First, a relatively soft core is made of a polymer of an ethylenically unsaturated compound, and then this core is partially or completely coated with a relatively hard polymer having a relatively larger molecular weight. When these fine particles are combined with a water-based resin, the interaction between the two gives them unique flow characteristics, which not only provides excellent workability but also creates a high-gloss, smooth coating. It has now been found that a top coat can be obtained which is able to provide a smooth surface and exhibits a further improved effect, especially in terms of gloss. In addition, these fine resin particles can be combined with a wide range of aqueous resins, and the present invention was completed based on this knowledge.

[■ (As mentioned above, when a monomer, etc. is further added to the core particles made in one stage and a second stage of emulsion polymerization is carried out, the polymer produced in the second stage does not necessarily completely contain the core particles. However, in order to facilitate the J(P solution), an outer shell 8 [1 that completely covers a part of the core is formed in the second emulsification process. The present invention will be briefly explained.

In general, emulsion polymerization is easy to produce extremely fine particles (because they can be produced and the molecular weight is relatively easy to control), the inner shell d3
It is particularly preferable that both the polymers of the outer shell portion are formed by emulsion polymerization, and in the present invention, this two-stage emulsion polymerization method is adopted. In other words, in the present invention: J: 1',
In a Mizutake effect containing a surfactant or an emulsifier, monomers to form the inner shell are polymerized by a conventional emulsion polymerization method in the presence of a polymerization initiator.

In this case, the chain transfer agent is used in an amount of 0.3 to 7% by weight based on the monomer weight in terms of dodecyl mercaptan. The emulsifier may be one of those normally used in emulsion polymerization, or in place of, or in conjunction with, for example, Japanese Patent Application No. 1983.
-110865:55-56048: 55-116
293: 53-123899: 55-4765
2; 56-71864: 57-13053, etc. can be used, and the polymerization initiator can also be a common one, such as benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, etc. Leading peroxides; azobiscyanovaleric acid, azobisisobutyronitrile, azobis(2,4-dimethyl)haleronitosol,
Organic azo compounds such as azobis(2-amidinopropane)hydrochloride; inorganic water-soluble radical initiators such as potassium persulfate, ammonium persulfate, sodium peroxide, and hydrogen peroxide; redox initiators can be used. . In addition, the particle size is preferably 0.3 to 6μ
The number average molecular weight of the polymer is usually 2.500 to 50,000 depending on the chain
Controlled within the range of 0. However, depending on the molecular weight of the outer shell assembly, the number average molecular weight of the inner shell polymer may be greater than the above range. The same or different monomer(s) are then added, optionally with additional monomers.
In addition, the fine polymer particles constituting the inner shell are seeded and Φ polymerization is carried out by emulsion polymerization, but by reducing the chain transfer agent concentration to zero or lower than the above, the number average molecular weight is lower than that of the inner shell. (1 q of double-structured fine particles larger than a book's edge and having a total particle size of 0.3 to 6 μm, preferably 0.4 to 5 μm.) Furthermore, in the present invention, ,
It is also possible to use the NAD method using a non-aqueous solvent.

The relatively hard polymer of the outer shell, which has a relatively large average molecular weight compared to the inner shell, is also suitable for three-dimensionalization (such as the polymer described in Section 4) in a preferred embodiment. There are also things to do.

In this case, mutually reactive groups on the two or more ethylenically unsaturated monomers to be formed into the outer shell copolymer;
For example, epoxy and carboxyl; amine and carboxyl; epoxy and carboxylic acid anhydride; amine and acid chloride; alkyleneimine and carbonyl; organoalkoxysilane and carboxyl; In addition to this, compounds having an ethylenically unsaturated group capable of containing two or more radicals Φ in the molecule (hereinafter referred to as crosslinkable simplex)
) and copolymerize them. Examples of such crosslinking monomers include polymerizable unsaturated monocarboxylic esters of polyhydric alcohols, polymerizable unsaturated alcohols of polybasic acids, and aromatic compounds substituted with two or more vinyl groups. There are compounds such as (Yo, ethylene glycol cyacrylate-1, ethylene glycol dimethacrylate 1-, 1-lyethylene glycol dimethacrylate, tetra-ethylene glycol dimethacrylate, 1, 3
-butylene glycol dimethacrylate-1, 1 herimedylolb L1 pantriacrylate-i~, trimethylolpropane trimethacrylate-1, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate-1~, pentaerythritol de-1~
laacryle-i~, pentaerythritol dimethacrylate, penta-trime 1) 1~-ru 1-rimethacrylate, penta] mawari suri 1~-rute 1 hera methafrylate, chrycerol cymethacrylate 1, glycerol diacryle -(′・, glycerol allyloxydimethacryle-1-, 1,1.1-trishydroxymethylethanethacryle-1, 1,1.1-1-lishydroxymethyl”nitane 1-rif7 acrylate ;-, 1, 1.1-1~
Suhi l<' ugishimethylconitane dimethacrylate
1-, 1.

1, 1-1 ~ Lis 1-1" oxymethylethanesimethacryl 1 ~, 1, I, 1-1 ~ Lis hydroxymethyl"
Tan-i-rimethacrylate, 1,1.1-1-lischt 1] to dimethylbrobane diacrylate-1, 1.

1,1-1-lishydroxymethylpropane 1-reacrylate, 1,1.1-1-lishydroxymethylpropane
1 pancymethacrylate-1, 1,1.1-1-lishydroxymethylpropane trimethacrylate-+-, 1 helylyl cyanurate, triallyl isocyanurate-1~, (
Heliaryl I ~ Limeritate, Sialyl Terephthalate I
~, diallylphthale-1~, divinyl l\ren, and the like. By copolymerizing these monomers in an aqueous or organic medium according to a conventional method, a three-dimensional, high-molecular-weight copolymer can be obtained.

As already mentioned, the hard outer shell portion is made of a polymer with a relatively large number average molecular weight and the polymer D1 has a small number average molecular weight.
By using fine particles of a polymer of an ethylenically unsaturated compound having a double structure with a soft inner shell consisting of The average particle size distribution of the fine particles themselves can be expanded over a wide range. However, when attempting to produce fine particles having a double tM m such as small by, for example, a two-stage emulsion polymerization method, it is uneconomical to obtain ultrafine particles, and no particular effect can be expected. The average particle diameter is selected within the most practical range of 0.3 to 6μ.

In the double-structured fine particles, the ratio of the polymer of the ethylenically unsaturated compound constituting the inner shell and the outer shell can be varied over a wide range, but preferably the outer shell has a ratio of 3 to 60%. /Inner shell part 9
7-40% (selected. Inner shell 7' + VS
Number-average molecules of polymers that cover the composition! li jJ Tsutomi 2,5
00 to 50,000 or 91' is preferable. However, starting from 4g, these are absolute (but can be changed as appropriate depending on the desired effect etc.).

9 above. 'J constant (14 size, resin fine I with defined particle size: 1 weigh, :i2/J should be used in combination of two or more types. Alternatively, it is also possible to support functional It which reacts with Ti during heating between resin fine particles, or not to support LJ-like groups.

Conclusion) i5 The present invention has been used for a long time - it has been destroyed (tsu) Fatty silk composition (J
, complete binding ζ, thermoplastic C or thermosetting. In the coating composition of the present invention, the above-mentioned aqueous resin and water-insoluble resin fine particles have a solid content C1 of 99 to 85% of the former, 1 to 85% of the latter, preferably 9% of the former.
It is necessary that the latter be combined within a range of 8-40% and 2-60% of the latter. (If the resin content is too low, the dispersion stability of the resin particles will deteriorate (the smoothness of the crotch will be impaired, and the resin particles will have a high content of 1!lTi %). This is because the purpose of the present invention as a paint coating cannot be achieved.

Water is used as the medium, but if desired, it can be used with a hydrophilic solvent.

With such Arisawa solvents (for example, ethylene glycol methyl ether, ethylene glycol hinoethyl ether, ethylene glycol monobutyl, methanol, butanol, isobutyl alcohol, n
-butanol, 5ec-butanol, 5ec-butanol,
Shimedil formamide and the like are included. However, in the composition of the present invention, J3 has a water medium and a resin content of 'j';
Regarding 1 cup, it is quite fluid.

Which one usually has a solid content of 10-80% for spray painting, 5-90% for brushing, and 1-60% for dipping.
Due to its unique fluidity, the composition of the present invention has a 1.
This is because it can be stored for a long time even in a relatively solid state, and can be divided into single servings and diluted with water to a desired concentration.

Akira Obi 1 is the above-mentioned aqueous HH, 4 fat, 1,
+ I'J Jjn's Water Hand (γi resin fine particles, water is bound as an essential component, and the water-based oily silk composition is directly transferred to chestnuts 7)
- To be used as a paint (gloss,
The top coat 947 surface with excellent smoothness is coated with 15 h < tesaru 6, and this resin composition is also used;
・] (Follow, order O'31, crosslinking agent, part 0) (I!!
By adding the additives and uniformly dispersing and mixing, work 1
1st place (cloudy) <, glossy, smooth, 1!
An aqueous overcoat composition capable of providing a unique coating surface at point C of I can be prepared in 11-7.

An arbitrary face N used for the top coat of paint from ship 2'to and C1.
'il /] 8 and well mixed (1 (contained.
Using a part of individual fat (make face 1 11 base 1 ~, add the remaining amount of water-based resin, % jli effect fine particles, and other additives, It is especially preferable to use a dispersion machine such as a dispersion machine to evenly distribute the mixture in a range of 1 to 9.7'. However, it is of course possible to mix and disperse each component from the beginning with a dispersion machine to form λ'4.

The coating composition of the present invention may also include the addition of a crosslinking agent as desired, such as (J melamine formaldehyde resin, methyl-oxy-modified resin, methyl-oxy-modified melamine formaldehyde resin, urea resin, Aminoplus 1 such as thiourea resin, guanamine resin, ace 1 and guanamine resin, etc.
Any known crosslinking agent such as a compound for isocyanate 1 such as . Furthermore, other additives may be added as desired, such as anti-sagging agents, anti-settling agents, anti-color separation agents, anti-cissing agents, surface tension control agents, etc. It is also possible to add an agent, an oxidizing rainproofing agent, a light stabilizer, and an ultraviolet absorber as appropriate. - these pigments,
The amount of the crosslinking agent and other additives used, the blending method, etc. are selected from q to q to manufacture the topcoat of all six types.

Coating) 1 of the present invention is diluted with D6 or water as it is, applied by a conventional coating method such as spraying, dipping, brushing, etc., and then dried or baked by heating to improve gloss and smoothness. It is particularly excellent in terms of durability, and provides a top-coated surface with excellent durability.

;i: /,: ! It is useful for the stability and workability of iγ゛1, and the coating composition for topcoating.

The present invention will now be explained with reference to Minazuke 191, Examples, and Comparisons 1 and 11. In addition, unless otherwise specified, "part" means "l-jJj hanging part".

Production Example 1 Production of Fat Fine Particles-1 A sample of J1 (Pi(, paste, 1 Yakusho υ1) ([j, seepage 1)] was provided, and 1. 1 in container b
Add 100 parts of deionized water to a 11x scale and warm to 80°C. In this water, with stirring, an aqueous solution consisting of 100 parts of deionized water and 6 parts of ammonium persulfate, 210 parts of methylmethacryle-h, 2-]]]nidylhexyl acrylate 1-755, and 15-dodecylmercaptan were added. Add part and l) s + Ronaru Jl h 3-body mixture b blue fl and continue stirring for 5 minutes. After 1 hour, drop 295 parts of the monomer mixture into the reaction solution. After the addition is complete, stir for 15 minutes and add 10 parts of deionized water. An aqueous solution consisting of 1 part of ammonium persulfate was added, and the reaction was continued for 1 hour at 112 strokes to complete the reaction, yielding a sheet emulsion with a non-volatile content of 20%.

Weigh 300 parts of deionized water and 25 parts of Sea 1-emulsion into a reaction vessel similar to that used for seed emulsion synthesis and bring the wet volume to 80'C. Into this reaction B vessel, 1 o rs of deionized water + 0 ammonium persulfate was added under stirring.
．． Add an aqueous solution consisting of 1 part to 295 parts of C-methyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 1 to 34 parts of 2-ethylhexyl acrylate, and 247 η of T-silmercaptan to 11 parts; , deionized water 180 i++, dodecylbenzenesulfonic acid 1~
Silium, 35 parts, per 1iJtj mD ammonium 0
．． A pre-emulsion consisting of 7 parts was added dropwise for 211) minutes. Start of dropping pre-emulsion 1 hour 3
After 0 minutes, 45 parts of methyl methacrylate, 2
A monomer mixture consisting of 5818 and 15 parts of 2-hydroxyethyl acrylate (15 parts of 2-ethylhexyl) 7-acrylate was added dropwise for 30 minutes (at the same time as the pre-emulsion).

When stirring was continued for 30 minutes after the dropwise addition was completed, an aqueous solution consisting of 20 parts of deionized water and 0.2 parts of ammonium persulfate was added, and 1 bone 1'1' was added to 111'J RI Il.
1. Finish the reaction. The obtained J-solution was 50.0% containing 111i.
The average particle diameter of the fat particles is 1.6 μ, the maximum particle diameter f,
1: 4,5μ(-').The particle size was measured using a transmission microscope with a transmission of 3μ and 2μ.

1 Tokuzo 1 Siri 2 ISI 1 finger (Kin-o Tateryo-2's (everyone) blue production example 1 and [111-like reaction vessel (Kon + a ∆ water 2G5
Weigh out 25 parts of sheet emulsion and 8 parts of 11 parts of water.
Spelled out to 0'C. Into this reaction vessel (while stirring 1j1), a water-cooled solution I consisting of 10 parts of ionized water and 0.1 part of ammonium persulfate was added, and then methyl methacrylate-1-203
Parts, 2-” Nidylhexyl acrylate 1 to 69 parts, 2-
An ILI emulsion consisting of 23 parts of ethyl acrylate 1, 16 parts of n-1-decyl mercaptan, 200 parts of deionized water, 3 parts of dodecylbenzenesulfonated sodium, and 0.6 parts of ammonium persulfate was prepared. Drop and cover over 2 hours.

After 10 minutes of instillation, stirring was continued for 10 minutes (after the formation of the inner shell), and 1 to 137 parts of Melmekkuryel and 2-Sochiru were added.
\1~/'17 parts of xyl acrylate and 2-hi 1 [1 monomer mixture consisting of 16 parts of xyl acrylate]
It drips in 5 minutes. ) 1:1 After stirring for 30 minutes,
At one point in time (20 parts of deionized water and 0.2 parts of ammonium persulfate) was added, stirring was continued for 1 hour and 1741 hours to complete the reaction. The average particle size 1 of the fine resin particles contained at .0% is 2.6μ, the maximum particle diameter +, j3.
It was 8μ.

Production Example 3 Production of Antilipid Fine Particles-3 520 parts of deionized water was placed in the same reaction vessel (J) used in Production Example 1, and the temperature was brought to 80°C.

While stirring this water, Ili! Ion water 10 Suito 0
An aqueous solution consisting of 15 parts of 0 parts n-diammonium sulfur, 1 to 384 parts of methyl methacrylate, 96 parts of 2-ethylhexyl acrylate, and 40 β of 1)-do-T silmercarbutane.
Add 20 parts of the monomer mixture consisting of [3] and continue stirring for 5 minutes. After that, over 1 hour, 50% of the monomer mixture was added.
0 part was added dropwise into the reaction solution. After the completion of extraction 1] () minutes of stirring, 1-48 parts of methyl methacrylate, 2 parts of methyl methacrylate, 1 to 16 parts of methacrylic acid, and 2 parts of methacrylic acid were added. Hydroxyethyl acrylate′
A monomer mixture consisting of 12 parts of ethylene glycol cymec acrylate and 12 parts of ethylene glycol cymec acrylate was added dropwise over a period of 20 minutes. Subsequently, 40 parts of deionized water and 10 parts of per-Tl1lj acid ammorum were added.
．． An aqueous solution consisting of 2i'4β is added and stirring is continued for one period to complete the reaction.

(Non-volatile content of Maruji 4 is 50.0%)
The average particle diameter of the resin fine particles contained in is 0. /1.0μ
, the maximum particle diameter was 1.2μ 4. Resin fine particles for comparison example! ! 1 In a reaction vessel similar to that used for producing resin fine particles-1,
j (1 ion water 900 parts, Metrose 60 S +-1
-50 (manufactured by Shin-Etsu Chemical Co., Ltd., methylcellulose) 1°5 parts,
210 parts of methyl methacrylate, 1 to 63 parts of 2-■derhexyl acrylate, 21 parts of 2-hydroxyethyl 7-acrylate, 6 parts of methacrylic acid, 6 parts of 1)-dodecylmerno-J butane, 6 parts of azobisinbutylene nitrile The reaction was completed by keeping the temperature at 65°C for 7 hours while stirring at 250 rpm. I was raped
Filter the lazy Shu liquid through a 200-mesh wire mesh to remove 20μ to 60%
Obtain pearl particles with a particle size of 0μ. This was ground in a ball mill for 24 hours to obtain fine resin particles with an average particle size of 18 μm and a maximum particle size of 45 μm. The molecular weight of this 4-mu]fat was 7,600.

Production Example 4 Production of Aqueous Resin-1 In a 2-liter reaction vessel equipped with a stirrer, a temperature controller, and a decanter, 273 parts of 1-liter fatty acid, 197 parts of trimedylolbroban, and 78 parts of neopentyl glycol were added. Department,
91 parts of hydrogenated bisphenol A, 204 parts of isophthalic acid,
1 to 157 parts of anhydrous trimeriso and 20 parts of xylene were charged, and the temperature was raised while stirring. The reaction temperature was maintained at 180'C to 210°C and the reaction was continued for 5 hours while removing the water produced to obtain an alkyd resin with an acid value of 65, an OHI West of 100, a number average molecular weight of 1500, and an oil length of 30. .

Subsequently, 183 parts of ethylene glycol monobutyl ether and 96 parts of dimethyl ethanolamine were added, and the mixture was diluted with 1 liter water to obtain an aqueous varnish with a non-volatile content of 50%.

Kej4 example 5 water 1! Production of I Resin-2 Into a reaction vessel similar to that used in the production of aqueous resin-1 were added 69 parts of trimethyl-1'-propane, 297 parts of neopentyl glycol, 891 parts of hydrogenated bisphenol, and 201 parts of isophthalic acid. , Te1~rabide E] 186 parts of phthalic acid, j
155 parts of water trimellitic acid and 10 parts of xylene were added and heated while stirring.

The reaction temperature was maintained at 180°C to 210°C, and the reaction was continued for 5 hours while removing the beef filtrate, resulting in an acid value of 55 and an OH
A polyester resin having a value of 100 and a number average molecular weight of 1,500 is obtained.

Subsequently, 183 parts of ethylene glycol monobutyl ether and 82 parts of dimethyl diF-tanolamine were added, and 11 parts of ethylene glycol monobutyl ether were added.
) Dilute with ionized water to obtain an aqueous varnish with a non-volatile content of 50%.

Production Example 6 Preparation of Aqueous 4-1 Fat-3 Into a 1-liter reaction vessel equipped with a stirrer, a temperature controller, and a cooling color, 76 parts of ethylene glycol heptanobutyl needle were charged, and 45 parts of styrene and methyl methacrylate were added. Ray
1 to 63 parts, 2-hydroxyethyl meccrylate 48
parts, n-butyl acrylate 117 parts, methacrylic acid 2 parts
7 parts of lauryl mercaptan, 3 parts of azobisisobutyroni, and 61 parts of a mono-l solution consisting of 1 part of azobisisobutyronitrile were added (IY! The temperature was brought to 120°C with stirring. 245 parts of the above seven-mer solution. was added dropwise over 3 hours, and stirring was continued for 1 hour.

Further, 28 parts of dimethylethanolamine and 200 parts of deionized water were added to obtain an acrylic resin varnish with a non-volatile content of 50% and a number average molecular weight of the resin of 6000.

Example 7 Production of Water-Based Resin-4 In a 1-liter reaction vessel equipped with a stirrer, a temperature controller, and a cooling tube, 117 parts of dehydrated castor oil, 173 parts of soybean oil, 17 parts of glycerin, and 1-liter of pentaerythrin were added. Part 61, Teru 7j (
Weigh out 32 parts of Nokur n's 1,' and add 7 parts of xylene.
, 57Sl(), and then warmed to 180° with stirring.
The reaction was carried out for 301 minutes while maintaining the temperature between 0 and 220'C and azeotropically removing the water produced by the polynisderlation reaction.
Subsequently, oil (57%, acid value 10, Mn 1800)'
Le 1-1 mii'll IjEI. Dilute this 4A'1 month with xylene and alkali I with a non-volatile content of 60%.
lfl fat I nonis doshino.

(6 parts) The above alkyd varnish (200 parts of fat varnish, 104 parts of ethylene glycol monoethyl ether) was placed in a reaction vessel similar to that used for fat synthesis, and stirred at 130'C.
I made it. To this, 60 parts of styrene, 102 parts of meblu methacrylate-1, 165 parts of 2-hydroxygodel methacrylate, 31 parts of acrylic compound, 143 parts of former-1 tylacrylate, 6 parts of di-t-butylper A oxide, and lauryl A monomer solution consisting of 8 parts of mercaptan was added dropwise over 3 hours, and stirring was continued for an additional hour to complete the reaction. The obtained acrylic modified alkyd resin had an acid value of 50 and a molecular weight of 7,300. The reaction solution was 100% neutralized with dimethyl phenolamine, and then diluted with 1151 ion water to obtain an aqueous varnish with a nonvolatile content of 50%.

Production Example 8 Production of Aqueous Resin = 5 In a reaction vessel similar to that used in the synthesis of aqueous tJ resin-1, 169 parts of neopentyl glycol, 6 parts of 1-rimethyl 1''-ruethane, 46 parts of hydrogenated bisphenol A, and isophthalic acid were added. 174 parts, 65 parts of Adipine, anhydrous! 40 parts of leic acid was charged, 10 δ15 of xylene was added, and the reaction was carried out for 1 hour by IP et al., keeping the temperature at 190 to 210 C and removing the water produced by the polyesterification reaction azeotropically. Continuing, acid value 48, number average molecular ffl 1200
Polyconistyl resin was obtained.

This No. 4 fat was diluted with ethylene glycol monobutyl ether to prepare a polyester (stock varnish) with a -C nonvolatile content of 80%.

In the production of acrylic modified alkyd resin in the latter stage of production VA7, d-3, 150 parts of the above polyester resin and 154 parts of ethylene glycol monoethyl ether were used instead of 200 parts of alkyd resin varnish and 104 parts of ethylene glycol monoethyl ether. I 17; I ball c, WiIlIr50, acrylic modified poly with molecular weight 6500, stell resin 1! I was.

Is this dimethylated nolamine? '100% neutralized,
rj;

Examples 1 to G and Comparative Examples 1 to 2 Preparation of facial paste 1.5 liters was placed in a sealed stainless steel container with a capacity of 16 liters.
0 parts of aqueous resin-1 obtained in Production Example 4 and 320 parts (1)
Weigh out Taibake R-820 (manufactured by Gohara Sangyo, Rujiru type titanium oxide liquid) and 78 parts of deionized water, add 500 cc of glass peas, stir (premix with a certain person, and then use paint conditioner for 2 hours). Pigment paste-1 was obtained by dispersing the five mixtures.Also, in place of water-based resin-1, Production Example 5~
Similarly, using the aqueous resins 2, 3, 4, and 5 obtained in step 8,
Pigment paste 2, 3, 4, 5 to 1
Noboru.

Add each Q4 to a stainless steel container according to the recipe listed in Table 1 below.
Weigh out %'A and at room temperature (mix with a stirrer and apply composition)
Of course I got it.

Each coating composition of Examples 1 to 6 and Company Comparative Examples 1 to 2 (!:
l) It was diluted with 1 liter of water and adjusted to a viscosity of 30 seconds in a cup of powder. h: Spray coating on a steel plate according to the method, setting for 15 minutes, and baking at 150° C. for 15 minutes to obtain a dry coating. The film thickness and gloss value for each composition are listed on the back of the Jffi1 table.

However, film thickness limit pin Film thickness limit sag Gloss value At 60° gloss value ◎ 50 parts or more ◎ 5
oμ or more ◎ 9 copies or more 0 40 copies or more
040 copies or more 085 or more△ 30~40μ
△ 30~40μ △ 8o~85×30μ
Less than × 30 μ or more × 80 or less (margin below)

Claims (1)

[Scope of Claims] (1) Water-based method 1 composition containing C as an essential component and a binder consisting of a fat and a water-insoluble resin fine particle at δ3! A I fingers are at least one type selected from the group consisting of polyester (δ11 fingers, alkyd resins, acrylic resins, acrylic modified polyester resins, and acrylic modified 11 alkyd resins), and are water-insoluble resin fine particles or α , β-ethylenically unsaturated monomer two-stage emulsion polymerization method (゛, IL! The chain transfer agent of the first emulsion monomer was made resistant to monomer by using door silmer J butane) 0.3 to 7% binding, chain transfer agent at the second stage of emulsification) zero agricultural degree or jtia ICLJ at the first stage,
Average particle diameter of 0.3 obtained by a method in which the amount is relatively small.
~6μ fine particles, the water = l'l 4i Solid content weight ratio of fat and water-insoluble resin is 99:1 ~ 15:85 C8
Aqueous method) '31 composition characterized by vines. <2) The composition according to claim 1, wherein yj<insoluble, and the average particle diameter of the resin particles is 1iR/)Xo, 4 to 5μ. (3) Second-stage emulsion polymerization Special E'l containing a crosslinking monomer greater than the α,β-1-thyrenic unsaturated monomer of 1
The composition according to item 2 of the scope of crystallization, item 1 or item 2. (4) Chain transfer agent or alkyl mercaptan or halogen
] A composition of 2 in any one of the ranges 1 to 3 of ``J'', which is gunified carbon. (5) Second-stage emulsification-type congruent chain transfer creation Converted to dodecyl mercaptan (0, 3 to 5%)
The composition according to any one of claims 1 to 4.