JPS59138276A - 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 second 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 first-stage emulsion polymerization at zero or relatively low level compared with that of the second-stage polymerization. The weight ratio of A/B is 99/1-16/86 (solid basis).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based paint composition useful as a top coat, and will be described in detail. This relates to the 7J aqueous coating composition with particularly improved coating performance.

As a resin vehicle for water-based paint compositions, water-based resins are used as a resin vehicle (an attempt has recently been made to overcome the incurable properties of aqueous resins by combining them with silk).
It's attracting attention. For example, special
J, No. 51-25224, etc., resin particles 10-70W
It is also known in Japanese Patent No. 1911-1271 that 095-30 wt % of water-dilutable resin based on the resin particles is added to a slurry consisting of 90-30 wt parts of water to stabilize the storage of the composition.
No. 51 also describes adding water flakes f14 or a water-dispersible resin corresponding to 5 to 50% of the powder resin to a slurry consisting of powder resin and water. However, with these slurry-type paints, it is common to increase the concentration of non-volatile matter in foreign countries, and it is not possible to apply a +9 coat, and the paint film after painting (=1) is prone to cracking due to insufficient adhesion, making it difficult to work with the paint. , practical application in terms of storage stability, coating film performance, etc. (this has not yet been achieved.
No. 262, Special Publication No. 55-4149, etc. contain powder m %'
A water-dispersible paint product containing water-soluble resin as a main component, in which the water-soluble resin is blended in an amount of about 10 to 20% of the powder resin, is described. 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. 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 has proposed a combination of a water-soluble or water-dispersible resin and a water-insoluble resin (including a resin vehicle). Developed the composition and applied for a patent (Patent application 11468/1986)
No. 6) was done. [This invention is based on the invention in which 5 g of a water-based varnish with a viscosity range commonly used in paints is weighed into a 100 m1 beaker, diluted with deionized water, and poured into a No. 1 type (26-boin) through the beaker. The surface tension of a solution obtained by diluting an aqueous varnish with deionized water to a solid content of 1% W/W is expressed as the water dilution ratio at which the water-based resin (printed on page 1) becomes unreadable. The selection parameters for water-dispersible resin (the same shall apply hereinafter) are at least one type of water-based resin that satisfies the requirements of water tolerance of 4 or more and surface tension of 51 dyne/cm or less.'J et al.
4. Water-insoluble resin fine powder with solid content j [Early ratio - (
98:2 to 45: Wide range of formulations as in 55, +1 life C, viscosity of mouth B series, 119 people were not seen, 111
Is it possible to increase the resin content of water-based paints? '−
JIS＞If a coating composition with excellent performance is provided, J
It was Rushino. lcl [Water-based coating II according to the above application]
The eye and mouth composition is the same as the various proposals that have been made so far, with intermediate coating, i”
1ff) Painting was developed in 1981 (
-1 In particular, it did not meet the coating film performance as a top coat, which requires a high gloss and flat surface. However, the water-based coating composition did not meet the coating properties such as workability and storage stability. Not only does it have scratches, but it also has durability and gloss, 7M
A composition of Mizutake coating, which has excellent coating film performance of 7 to 10 degrees and is useful as a top coat, is urgently required in various painting fields including the automobile industry. .

The present applicant has an average particle size of 0.3 to 6μ and a maximum particle size of 10μ obtained by polymerizing an aqueous resin (made from an alkyd resin or a polyester resin) and an ethylenically unsaturated compound.
The following resin particles have a solid content ratio of 99:1 to 40:
Water-based coating composition containing 60% of resin particles with an average particle diameter of 0.01 to 0.1μ obtained by polymerizing an aqueous resin selected from acrylic resin, alkyd resin, and polyester resin and an ethylenically unsaturated compound. 9 in weight ratio
9:1 to 15: An aqueous coating composition containing ε35 or so, an aqueous paint composition selected from +5 acrylic modified alkyd resins and acrylic modified polyester resins (average particles obtained by polymerization of a resin and an ethylenically unsaturated compound) Diameter 0.01
~6μ resin fine particles at a solid weight ratio of 99:1 to 15:
It was discovered that a water-based paint composition containing a ratio of 85% to 85% not only has excellent storage stability and durability, but also provides a high gloss and smooth painted surface, making it useful as a two-coat paint. , respectively, patent application No. 174890/1989, and 174/174/1989.
Patent applications were filed as No. 4.891 and No. 5/-174892.

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

However, the above defense is based on the combination of a specific water-based resin and a specific water-insoluble resin, and the combination of C, average diameter of resin particles of 41'1, or 4Fj constant; Ze(1st history [If you say it, there is no special system Δron-1st f
Sexual old 'Jj IJJul□No increase in number of people [this resin portion) 1
The two-coat paint should meet the requirements of -C. The water-based paint composition was supposed to be 1 q (-), but the present inventors further investigated the particle structure and particle surface structure from the IC particle size of 4 forces and 1 fat particle. Particles are made by a stage emulsion polymerization method of α, β-ethylenically unsaturated monomers, and at this time, the concentration of the chain transfer agent in the first stage and the second stage is controlled. By partially or entirely coating the polymer with a relatively soft, low molecular weight polymer (-1), which has a relatively large number average molecular weight and is optionally three-dimensional. However, since the particle as a whole is relatively hard and can provide a durable topcoat composition that is suitable for combination with an aqueous resin, the outside of the particle is relatively soft. 1] The temporary properties of paints have changed, workability has been improved significantly in terms of coating performance, and we have also learned that a wider range of combinations of water-based and water-insoluble resins can be used. The purpose of the present invention is to provide a top coat composition that has excellent coating properties such as thick coating, storage stability, and durability, and can provide a high-gloss coating surface. In terms of workability, the present invention aims to provide a water-based paint composition that can exhibit particularly excellent effects in terms of paint film performance for snow removal.

The object of the present invention is to provide an aqueous coating composition which contains an aqueous resin, water-insoluble resin fine particles, and a binder component consisting of 7. j5, the aqueous resin is at least one selected from the group consisting of polyester resin, alkyd resin, acrylic resin, acrylic modified polynisder resin, and acrylic modified alkyd resin, and water-insoluble resin fine particles or α,β-ethylenically inert resin are used. Saturated monomer two-stage emulsion polymerization method, however, 1μ of chain transfer creation during the second stage emulsion polymerization is 0.3μ to the total amount of monomer using a 1-J disylmercazotane model.
~ 7 layers are set to 6, and the concentration of the transfer agent during the first stage emulsion polymerization is 1 fj. The average particle diameter obtained by the method of using σ is 0゜3-, ・(5
This can be achieved by using an aqueous coating composition in which the solid content of the aqueous resin and the water-insoluble 11 resin is in the range of 99:1 to 15:85riJg.

The water-based resin (Water 7d/14 resin or water-dispersible resin, hereinafter the same) used in the present invention is commonly used in the paint field.
11 Polyester, alkyd, acrylic, acrylic modified polyester or acrylic modified alkyd resin used.

However, the polyester resin used in the present invention is a general polynisder resin obtained by a polycondensation reaction of a polybasic acid and a polyhydric alcohol. Acid, linear dichloride such as azelaic acid, sebacic acid, etc. 1j9: Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 1 ~ Aromatic fatty acids such as limelittic acid, 1 ~ limelittic anhydride ~ acid, pyromellitic anhydride, biromellitic anhydride, etc.: Unsaturated 2 J+ such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc.
%'+ 4J W etc., and examples of polyhydric alcohols include ethylene glycol, pyrene glycol, 1
．． 3-butylene diol, 1,6-hexane diol,
Diethylene glycol, neopentyl glycol, 1
- Glycols such as lyethylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimedylol di[tan], trimethylolpropane, pentaerythritol, etc. are used as appropriate. However, the above-mentioned polyhydric M acids and polyhydric alcohols are not limited to these, and any materials that can be used as ordinary polyester resin raw materials can be used. It is also possible to use basic acids or monohydric alcohols.

Alkyd resin is made by combining the above polyester with drying oil, fat M
／、Do C esterification modified chichino, oil and fat components include C, 7 Niura, tung oil, tung oil, ) j11 water castor oil, Any known alkyd resin can be used, such as , 1-l oil fatty acid, human omega-cured acid, or Δ-cutylic acid, and epoxy-modified, rosin-modified, or phenol resin-modified alkyd resins may be used.

The manufacturing methods for these resins are well known to those of skill in the art and there is no need to go into details.

Acrylic resins can also be suitably used in the present invention.

This acrylic resin has one or more polymerizable ethylenically unsaturated bonds in its molecule and can be obtained by polymerizing any combination of monomers listed below (121).

1) Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, chlorine,
2) Hydroxyl group-containing monomers such as itaconic acid, maleic acid, fumaric acid, etc.
J-xypropyl acrylate, 2-hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methalyl alcohol, etc. 3) Nitrogen-containing alkyl acrylate-1- or methacrylate such as dimethylaminoethyl acrylate-1 ~, dimethylaminoethyl methacrylate, etc. 4) Polymerizable amides such as acrylamide, methacrylic acid amide, etc. 5) Polymerizable nitriles such as acrylonitrile, methacrylateril, etc. 6) Alkyl acrylate or methacrylate-1 ~ For example, methyl acrylate, methyl methacrylate, ethyl acrylate , ethyl methacrylate, n-ethyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate-1, etc. 7) Polymerizable aromatic compounds such as styrene, α-methylstyrene, vinyl 1-helene, butylstyrene, etc. ε3) α- A Refine Examples include ethylene, propylene, etc. 9) Vinyl compounds such as acid-resistant vinyl, vinyl propionate, etc. 10) Diene compounds such as butadiene, inbrene, etc. Saturated monomers for these α, β-ethylenically inert compounds Light, heat,
It can be prepared by any known polymerization method in the presence of a radical initiator such as a polyhydric peroxide, an inorganic peroxide, or an azo compound.

Yet another group of aqueous resins which are preferably used in the present invention are acrylic modified polyester or alkyd resins, i.e. resins in which acrylic polymer segments are incorporated into the polyester resin or alkyd resin. can be given. Such acrylic modified resins can be obtained, for example, by the following methods.

1) Synthesis of acrylic resin in the presence of polyester or alkyd resin having unsaturated groups.

When producing borini[methyl] by polycondensation reaction of polybasic acid and polyhydric alcohol, unsaturated acids such as maleic acid, maleic anhydride, fumaric acid, silica to laconic acid, itaconic acid, and dimer are used as the polybasic acid. When an acid is used, a polyester having unsaturated groups can be obtained, and when such an unsaturated polyester or saturated polyester is subjected to esterification modification by acting with a drying oil, a fatty acid, etc., an alkyd resin having unsaturated groups can be obtained. . In the presence of polyester or alkyd resins containing such unsaturated groups, customary free radical catalysts such as azohisisobutyronitrile, hexyl peroxide, di-t-butyl peroxide, cumene hydro Acrylic modified polyester or alkyd resins used in the present invention can be obtained by polymerizing acrylic monomers with peroxides, etc., or alternatively with chain transfer agents such as ethyl mercaptan, butyl mercaptan, dodecyl mercaptan, carbon tetrabromide, carbon tetrachloride, etc. is obtained. In this case, the acrylic hinomer is a polymeric ul fiti having one or more units in the molecule, which is usually used in the production of acrylic resins.
41: The above-mentioned various compounds having an unsaturated bond can be used.

(2) Polymerization of an acrylic monomer group containing an oxirane group-containing unsaturated monomer in the presence of a covering polyester or alkyd resin containing a carboxylic acid group is carried out.

Poly1 stell resin or alkyd resin has manufacturing ratio
A carboxylic acid group based on the polybasic nature of 1 is usually included. Therefore, ethylenically unsaturated monomers containing oxirane groups such as glycidyl acrylate and glycidyl methacrylate 1
An acrylic modified polyester or alkyd resin can be obtained by polymerizing the above-mentioned acrylic monomer group containing the polyester as one component in the presence of such a carboxylic acid group-containing polyester or alkyd resin.

(3) Containing carboxylic acid group in the presence of polyester or alkyd resin containing oxirane group M 7w L
A chassis of an acrylic monomer group containing lj-M isomers as one component is produced.

When producing a polyester or alkyd resin, for example, a polyhydric alcohol component having two or more oxirane groups and a polybasic acid component yield 1↓t of a polyester or alkyd resin that contains oxirane groups, so in the presence of these resins, , the aforementioned acrylic monomer containing as one component α,β-ethylenically unsaturated monoω substance having a carboxylic acid group, such as acrylic acid, methacrylic acid, crotonic acid, isonic acid, maleic acid, fumaric acid, etc. By reacting the bodies, the acrylic modified polyester or alkyd resin used in the present invention can be obtained.

(4) A method of reacting a polyester or alkyd resin (or acrylic resin) containing a carboxylic acid group with an acrylic resin (or polyester or alkyd resin) containing an oxirane group.

If a polyester or alkyd resin and an acrylic resin are supported with a carboxylic acid group on the one side and an oxirane group on the other side, and both resins are reacted, the acrylic modified polyester or alkyd resin will be formed by the reaction between the carvone RW and the oxirane group. ? It will be done.

(5) An acrylic monomer is polymerized in the presence of a polynysdel or an alkyl resin.

Polyester or Norkito resin is obtained using polybasic acid or polyhydric alcohol,
This is utilized in a chain transfer reaction to polymerize the aforementioned acrylic monomer.

The above t is a typical manufacturing method example of the acrylic modified polynisdel or alkyd resin of the present invention, but does not limit the present invention. Or alkyd resin is 1! It should be understood that any method can be used as long as it is suitable for the purposes of the present invention. Now, such a resin can be made water-soluble by conventional methods, such as replacing acidic groups such as carboxyl groups with basic substances (e.g., dimethylamine, dimethylamine, trimethylamine, monoethylamine, triethylamine, monoethanolamine, diisopropylamine, diethylenetriamine, etc.).
1-ethylene 1-ethylamine, monoethanolamine,
Jetanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, dimethylethanolamine, morpholine, methylmorboline, piperazine, ammonia, helium hydroxide, potassium hydroxide, lithium hydroxide, etc.) By neutralizing it, water solubility or water dispersibility is imparted and it can be conveniently used for the purpose of the present invention. The aqueous resin may be selected from one or more of the various resins mentioned above, and may be either a thermoplastic type or a thermosetting type. That is, they may or may not carry a functional group that can react with other aqueous fats and/or functional groups of the powdered resin when heated. Examples of such functional groups to be supported include carboxylic acid group, sulfone 1g, phosphorus M
W, hydroxyl group, oxirane group, active methylol group, amino group, reactive carbon-carbon unsaturated bond, isocyanate group,
Block sardine ana-1 to 1 groups, halogens, etc. are included, and these can be selected by selecting a single unit during resin production, if desired.
General methods such as controlling the polymerization reaction ("Silk can be easily incorporated into seasoned fat.

In the present invention, a small amount of water-insoluble resin powder is used together with the above-mentioned aqueous aI fat.
- Acrylic or vinyl polymers or copolymers obtained by polymerizing α, β unsaturated compounds. The ethylenically unsaturated compound in this case is also the same as the acrylic water-based resin mentioned above, and is any compound that has one or more polymerizable ethylenically unsaturated bonds in the molecule. I. They may be used alone or in combination.

However, in the present invention, Jυ is also an important feature, in addition to the fact that the fine particles of the acrylic or vinyl polymer or copolymer are water-insoluble and microscopic particles. Constructed as fine particles with a special structure obtained by a two-stage emulsion polymerization method: a first stage reaction in which the chain transfer agent concentration is relatively small, and a second stage reaction in which the chain transfer agent concentration is increased relative to 4 fl. It is.

When preparing polymer particles from α,β-ethylenically unsaturated monopolymers by emulsion polymerization, chain transfer agents, such as one or more alkyl mercaptans (ethyl mercaptan, butyl mercaptan, dodecyl mercaptan carbon 8), are used. If it is used in an amount of 0.3 to 7% by weight (in terms of dodecyl mercapkun) per 1 volume of monomer, relatively soft polymer particles with a number average molecular weight of approximately 2,500 to 50,000 may be removed. Are known.

It is known that by increasing or decreasing the amount of the chain transfer agent Fuchimaro, the molecular weight of the resulting polymer can be made smaller or smaller. The present inventors carried out this emulsion polymerization in two stages, and in the first stage, the chain transfer agent concentration was zero or dodecyl mercaptan was added to the monomer weight in a relatively small amount compared to the amount used in the second stage. Converted To 0.3-7% heavy forging, unvortexed, preferably within the range of 0.3-5% by weight, 83 in the second stage
relatively large amount, preferably 0.3 to 7
When a chain transfer agent with a heavy cliff% is used, a relatively hard core is first made of a polymer of ethylenically unsaturated compounds, and then (
A relatively soft small aggregate with a relatively small molecular weight relative to the co)no here is obtained, and fine particles with a 4'l IA. When fine particles are combined with an aqueous resin, the interaction between the two is
, 14. To provide a top coat 1 which has unique fluidity properties, is superior in terms of workability and film performance such as pins, and has a high gloss and smooth coating ml, and further J. It was discovered that these fine resin particles could be combined with a wide range of aqueous resins, and based on this knowledge, the present invention was completed.

When performing emulsion polymerization in the second stage by roughly adding single φ bodies to the core particles produced in the first stage, the polymer produced in the second stage (the polymer produced is not necessarily completely = 1 However, in order to make it easier to understand the present invention, it is assumed below that the inner shell is formed in the first step, and the outer shell that completely covers it is formed in the second step. The present invention will be explained.

In general, in emulsion polymerization, extremely fine particles can be easily formed; molecular weight control is also relatively easy; therefore, it is particularly preferable to use emulsion polymerization for both the inner shell part J5 and the outer shell part 7t'. : This two-stage emulsification method is adopted in the invention. That is, in the present invention, first, in an aqueous medium containing a surfactant or an emulsifier, and in the presence of a polymerization initiator, a single piece of the inner shell component is polymerized using a 11V emulsion polymerization method.

At this time, the chain transfer agent concentration is zero or the amount of dodecyl mercaptan relative to the monomer weight is adjusted to be relatively smaller than the amount used in the second stage. As the emulsifier, any one commonly used in emulsion polymerization, or instead of or together with it, for example, Japanese Patent Application No. 54-110865: 55-5
6048; 55-1 1 6293; 53-1
23899: 55-4 7652: 56-71
86/l: 57-13053 etc. can be used, and the polymerization initiator can also be a common one, for example, an organic peroxide such as benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide. ; Azobiscyanovaleric acid, azobisin butyronitrile, azobis-(
Organic azo compounds such as 2,4-dimethyl)valeronitrile, azobis(2-amidinopropane)hydride [chloride 1]; potassium persulfate, ammonium persulfate, sodium persulfate M9, hydrogen peroxide, etc.) shallow water soluble Radical initiator: A radical initiator can be used. In addition, the particle size is preferably 0.3 to 6μ.
J
00 or more, 1!1 minutes")', !+; will be done later.

Next, Ii]l- or another monomer (?i\) is added, if desired, along with an additional lubricant, and polymerization is carried out by emulsion polymerization using the polymer fine particles constituting the inner shell as seeds. However, the concentration of the chain transfer agent is lower than the above.
i1m body l dodecyl mercaptan replacement cylinder O2°3~
By setting it within the range of 7%, the average molecular weight is relatively smaller and softer than that of the inner shell part molecules. 4j°C, and has double-structured fine particles with a total particle size of 0.3 to 6μ, preferably 0.4 to 5μ. The number average molecular weight of the outer shell polymer is typically 2,500 to 50,000. The particles can also be prepared using the CN A 0 method using non-aqueous solvents.

A relatively rigid inner shell polymer can also be achieved by forming a crosslinked polymer by three-dimensionalization in a preferred embodiment. This platform contains two or more of the aforementioned ethylenically unsaturated monomers (with mutually reactive groups such as epoxy and small xyl; amine and carboxyl) forming the inner shell copolymer. Phoxyl epoxy and carboxylic acid anhydride; amine and acid chloride; alkylene imine and carbonyl; organoalkoxysilane and carboxyl cyanate, etc.; A compound containing two or more ethylenically unsaturated radically polymerizable groups (hereinafter referred to as a Kurihashi monomer) is used to copolymerize them. Examples include polymerizable unsaturated monocarboxylic acid esters of alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and aromatic compounds substituted with J5 and 2 or more vinyl groups. Acrylate, ethylene glycol dimethacrylate 1-, triethylene glycol dimethacrylate 1-, ethylene glycol dimethacrylate-1-1, 1,3-butylene glycol dimethacrylate-1, trimethylolpropane 1- ~React Relay 1-
, 1~Rimechi 1]-Lube L]Bread 1~Rimeku Relay 1
~, 1,4-butanediol diacrylate [・, neobentyl glycol diacrylate-1 ~,], 6-hegizandiol diacrylate-1, pentaerythri 1-1 diacrylate-1 ~, pentaerythri 1 Hale 1 Reacrylic Relay 1~, Pentaerythritol vl□Lacrylic Relay 1
-, pentaerythritol dimethacrylate, pentaerythritol (Hale 1-remethacrylate, pentaerythritol 1
, 1 slitol tetramethacrylate (・, to glycerol cymethacrylate 1, glycerol diacrylate, glycerol aryloxy methacrylate 1 to 1,1
．． 1-t-tris hydroxymethylethane diacrylate, 1.1 trishydroxymethylethane triacrylate, 1.

1,1-1-trishydroxymethylethane dimethacrylate, 1,1.1-trishydroxymethyl"-tansimekryle-i~, 1,'l,1-1-1 noshidoosugishimethylethane 1-remethacrylate-1~,1 .

1,1-1~lishydroxymethylbronobencyacryle-1~,1,1,'tt~to lis hydroxymethylbronobenthylacrylate-I, 1,1.1-1-1noshydroxy Methylpropane dimecryle-1-,1.

1,1-1-Lishydroxymethyl bronopene 1-1 methacrylate-1~, I. Realylcyamelate 1) Allyl isocyanurate-1~, triallyl trime 1 note 1
-, diallyl terephthalate, diallyl phthalate-1, schichnirhenzen, etc. By copolymerizing these monomers in an aqueous or aqueous medium using a conventional method, it is possible to obtain a three-dimensional copolymer with a high molecular weight.

As already mentioned, the relative number average molecular weight (double structure of the hard inner shell made of a large polymer force and the soft outer shell made of a number average molecular m force < IJX ψ I * D ~) By using a polymer of an ethylenically unsaturated compound having a microorganism, not only the permissible range of the aqueous resin combined with it is greatly expanded, but also the average particle diameter of the white of the fine particles is 1i. It can be expanded to a wide range of things. However, when fine particles with a double structure such as those mentioned above are processed using a two-stage emulsification method,
When trying to produce ultra-fine particles, it is uneconomical to obtain ultra-fine particles, and the effect of 1 T f stage is only a fill C, so the average particle size of the fine particles is the most practical Q0.3~ 6
It is selected within the range of μ.

In the double-structured fine particles, the ratio of the monomers of dilenically unsaturated compounds constituting the inner shell and the outer shell can be varied over a wide range, but preferably the outer shell is 3 to 3. 60/97 to 40% by weight of the inner shell. The number average molecular weight of the polymer constituting the IC outer shell is usually 2,500 to 50,0.
Preferably it is 00. However, these are not absolute, and can be changed as appropriate depending on desired effects and other factors.

It is possible to use one type or a combination of two or more types of MA resin fine particles having the above-mentioned specific 114 structure and specified particle size. It is possible to carry a reactive functional group or not to carry such a functional group.

Ultimately, the resin composition used in the present invention is -C1
It may be thermoplastic or thermosetting. In the coating composition of the present invention, the aqueous resin and water-insoluble resin fine particles have a solid molecular m ratio C' of 99 to 15% for the former.
, the latter 1-85%, preferably +iiij 98-40%
, the latter needs to be roughly combined within a range of 2 to 60%. This is because the water-based resin content is too low [rubbing will compromise the dispersion stability of the resin particles and impair the smoothness of the coating film, and if the resin particles are less than 1%, the purpose of the present invention as a top coat will not be achieved. This is because it is not done.

Water is used as the medium, but a hydrophilic polar organic solvent can also be co-present if desired.

Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, ethanol, impropyl alcohol, n-butanol, 5ec-butanol, 1-ethanol, dimedilne. However, in the composition of the present invention, J3 is quite fluid in terms of the proportion of the resin component in the water medium.

This is because the solid content is usually around 10-80% for spray painting, 5-90% for dipping, and 1-60% for dipping.
However, the composition of the present invention has a 1% improvement in the dispersion stability of powdered resin due to its long-lasting fluidity.
It is cloudy and can be stored for a long time even in a relatively solid state, and when used, it can be diluted with water to the desired level.

In the present invention, the above-mentioned water-based resin, water-insoluble resin fine particles with a specific structure, and water are essential ingredients, and by using such a water-based resin composition as it is as a CRIT7-paint, it is possible to create a high-gloss, smooth coating, especially pins, etc. It is possible to obtain a topcoat surface with excellent coating film performance. In addition, by adding pigments, crosslinking agents, and other additives to this resin composition according to ordinary paint manufacturing techniques and uniformly dispersing and mixing it, it has a particularly high level of workability, high gloss, smoothness, and smoothness. A water-based paint composition for top coating of bottles etc. is obtained which has poor coating film performance.

As the pigment, any pigment commonly used in top coatings can be used and can be well dispersed.

When blending pigments, make a pigment paste in advance using a part of the water-based resin, add the remaining amount of the water-based resin, (1) fine particles, and the same amount of additives, and mix with a known gate mixer.
It is particularly preferable to use a dispersion machine such as a high-speed disperser to uniformly mix and disperse. However, of course, it is also possible to form a paint by mixing and dispersing each component using a dispersion machine from the beginning.

If desired, a crosslinking agent can also be added to the coating composition of the present invention, such as melamine formaldehyde (
Any known material such as aminoblast, isocyanate, isocyanate, polyisocyanate, block isocyanate, etc., phenol resin, etc. crosslinking agents are preferably used. Furthermore, if desired, other conventional additives may be added, such as anti-sagging agents, anti-settling agents, anti-color separation agents, anti-repellent agents, surface agents, etc. It is also possible to add additives, etc. The amounts of these additives, cross-linking agents, and other additives, blending methods, etc. can be selected and used as appropriate in accordance with the production of the top coating in (1) above.

The 4 Jul iI] product of the present invention is applied as it is or roughly diluted with water, applied by a conventional coating method such as spraying, dipping, or brushing, and then dried or baked by heating.
This process produces a 1':I topcoat surface that is highly glossy, smooth, durable, and has excellent coating properties, especially pins. In addition, the storage stability of the paint is also good.
It is extremely useful as a water-based paint composition for top coating.

The present invention will be explained below with reference to production examples, practical examples, and comparative examples.

Note that unless otherwise specified, "parts" means "parts by weight."

Production Example 1 Production of Resin Fine Particles-1 Weigh out 1100 parts of skin ionized water into a 2-liter glass reaction vessel equipped with a stirrer, temperature controller, and cooling tube, and bring the temperature to 80°C. . In this water, with stirring, an aqueous solution consisting of 100 parts of deionized water, 6 parts of ammonium persulfate, 210 parts of methyl methacrylate, 75 parts of 2-ethylhexyl acrylate, and 15 parts of dodecyl mercaptan were added.
Add 5 parts of a monomer mixture consisting of 5 parts and continue stirring for 5 minutes. Thereafter, 295 parts of the monomer mixture was dropped into the reaction solution over 1 hour. After continuing stirring for 15 minutes after the dropwise addition, an aqueous solution consisting of 10 parts of ionized water and 1 part of ammonium persulfate was added, stirring was continued for 1 hour to complete the reaction, and a sheet emulsion with a non-volatile content of 20% was obtained. get.

215 parts of deionized water and 25 parts of seed emulsion are weighed into a reaction vessel similar to that used for seed emulsion synthesis, and the temperature is brought to 80°C. An aqueous solution consisting of 20 parts of stirred lower layer ionized water and 0.1 part of ammonium persulfate was added to the reaction vessel, followed by 295 parts of methyl methacrylate,
100 parts of 2-ethylhexyl acrylate, 1 to 34 parts of 2-hydroxyethyl acrylate, 1 it) Ionized water 2
00 parts, sodium dodecylhenzenesulfonate 0.4
A pre-emulsion consisting of 0.9 parts of ammonium is added dropwise for 2 hours.After 1 hour and 30 minutes have passed from the start of dropping the pre-emulsion, 1 to 45 parts of methyl methacrylate, 2 parts of methyl methacrylate are added. -15 parts of ethylhexyl acrylate-1, 1-5 parts of 2-hydroxyethyl acrylate, 30 parts of deionized water, 0.06 parts of sodium dodecylbenzenesulfonate, 0.14 parts of ammonium persulfate, n-dodecyl A second pre-emulsion consisting of 6 parts of mercaptan was added dropwise for 30 minutes at the same time as the pre-emulsion. After stirring was continued for 30 minutes after the addition, II+>
An aqueous solution consisting of 20 parts of ionized water and 0.2 parts of ammonium persulfate was added, and stirring was continued for 1 hour to complete the reaction and the mixture was covered. 1q emulsion (J non-volatile content 50.0
%, the average particle diameter of the contained resin fine particles is 1.6μ,
The maximum particle size was 2.5μ. J3,) The cryodiameter was measured using a transmission electron microscope.

Production Example 2 Production of Resin Fine Particles-2 In a reaction vessel similar to that used in Production Example 1, 25 liters of deionized water was added.
Weigh out 0 part and 25 parts of sheet emulsion, and bring the temperature to 80.
℃. In this reaction vessel, 17 parts of stirred lower layer ionized water and 0.0 parts of ammonium persulfate were added. Add an aqueous solution consisting of 1 part to 195 parts of methyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 200 parts of deionized water, 0.4 parts of dodecylbenzenesulfonic acid,
Two parts of a pre-emulsion consisting of 0.9 parts of ammonium persulfate are added dropwise. Stirring was continued for 10 minutes after the completion of the dropping, at which point (after the inner shell was formed) a monomer mixture of 135 parts of methyl methacrylate, 65 parts of 2-ethylhexyl acrylate, and 6 parts of n-dodecyl mercaptan was added. τ・drop story for 15 minutes. After stirring was continued for 30 minutes after the dropwise addition was completed, an aqueous solution consisting of 20 parts of di-ionized water and 0.2 parts of ammonium persulfate was added, and the reaction was completed by continuing to stir roughly for 1 hour.The resulting emulsion The average particle diameter of the fine resin particles containing 50.0% non-volatile content was 2.83 μm, and the maximum particle diameter was 4.0 μm.

Production Example 3 Preparation of Resin Fine Particles-3 Weigh out 48551 deionized water into a reaction vessel similar to that used in Production Example 1, set the temperature to 80'C, and add 3 to this water (with stirring). 100 parts of water, an aqueous solution of 15 parts of ammonium persulfate, 1.385 parts of methyl methacrylate, 1 to 110 parts of 2-ethylhexyl acrylate, and ethylene glycol. Add 201 Hayabusa, a monomer 112 mixture consisting of 1 to 5 parts of -dimethacrylate, and continue stirring for 5 minutes.After that, for 1 hour (480 parts of the monomer mixture of D-C is added to the reaction bath) in 1 hour. Stirring was continued for 15 minutes after the addition was completed, and then 48 parts of methyl methacrylate, 48 parts of 2-ethylhexyl acrylate, 12 parts of methacrylic acid, 12 parts of 2-hydroxyethyl acrylate, and 2 parts of 1]-dodecyl mercaptan were added. A single mother mixture consisting of ?1 is applied 20e and dripped.Continued l)2
An aqueous solution consisting of 40 parts of ionized water and 0.2 parts of ammonium persulfate is added, and stirring is continued for 1 hour to complete the reaction.

The nonvolatile content of the obtained emulsion was 50.0%, and the average particle size of the fine resin particles was 0.42 μm, and the maximum particle size was 1.2 μm.

Reference Example Manufacture of Comparative Resin Fine Particles In a reaction vessel similar to that used in the production of Resin Fine Particles-1, 900 parts of deionized water and 1° of Me1~Rose'60SH-50 (manufactured by I-Ogoe Chemical Co., Ltd., methylcellulose) were added. 5δl(, 1 to 210 parts of methyl methacrylate, 63 parts of 2-ethylhexyl acrylate, 2-hydroxy'delacryle-1-
21 parts of methacrylic acid, 6 parts of 1-dodecyl mercury, and 6 parts of azobisisobutyronitrile were weighed out, and the temperature was kept at 65° for 7 hours while stirring at a rotation speed of 25 Orpm.
Continue to step C to complete the reaction. The resulting suspension was
0 mesh gold particles are filtered out to obtain burr particles with a particle size of 20μ to 600μ. 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 resin was 7,600.

Production example 4 Water/l! 1. Production of Inl fat-1 1-2 tanks equipped with a stirrer, temperature controller, and decanter 1-
In a reaction vessel containing 273 parts of 1-helical oil fatty acid, 197 parts of 1 to 1 to 1-limethylolbroban, and 78 parts of neopentyl glycol.
91 parts of hydrogenated bisphenol A, 204 parts of isophthalic acid
parts, trimellitic anhydride 157 parts, xylene 20 ro
Charge i(S) and cover with lf1 without stirring.The reaction temperature was maintained at 180°C to 210°C, and the reaction was continued for 51,j without removing the produced water. acid 1i11
i 65, Ol-1 value 100. number average molecular end 1500,
Obtain an alkyd resin with an oil length of 30.

Continued-C ethylene glycol monobutyl ether 183
After adding 3 parts and 9 parts of dimethylethanolamine, l1
Dilute with 11-in water (powder) to obtain an aqueous varnish with a non-volatile content of 5096.

Production Example 5 Production of Water-Based Resin-2 In a reaction vessel similar to that used in the production of Water-Based Resin-1, 69 parts of trimedium [1-lube], 297 parts of neopendel glycol, 91 parts of hydrogenated bisphenol 8, and isophthalic acid were added. 201 parts of acid, 186 parts of tetrahydrophthalic acid, 155 parts of trimellitic anhydride, and 10 parts of xylene were charged, stirred, and then heated.

The reaction temperature was maintained at 180°C to 210°C, and the reaction was continued for 5 hours while removing the produced water to reach an acid value of 55 and an O
HHI300. A polyester coffin with an average molecular weight of up to 1500 can hold 1 fat.

Subsequently, after adding 183 parts of ethylene glycol butyl ether and 82 parts of dimethylethanolamine, IB)
Dilute with ionized water to obtain an aqueous varnish with a non-volatile content of 50%.

Production Example 6 4 <・i raw material 11 taste - 3 Pre-stirring) 76 parts of ethylene glycol monobutyl ether was charged into a 1 liter reaction vessel equipped with a temperature controller and a cooling tube, and roughly mixed with styrene. 45 parts, 63 parts of methyl methacrylate, 2-
Added 61 parts of a mono-l solution consisting of 1 to 48 parts of hydroxyethyl methacrylate, 11 parts of n-butyl acrylate, 27 parts of methacrylic acid, 3 parts of lauryl mercaptan, and 3 parts of azopisisobutyronitrile. C stirring lower reservoir 11
The temperature was set to 120°C. After dropping 245 parts of the monomer solution mentioned above at 311 degrees, stirring was continued for 1 u.

Furthermore, 28 parts of dimethylethanolamine and 200 parts of 11-Ion water were added to obtain an acrylic resin varnish with a non-volatile content of 50% and a (i) number of fats having an equivalent molecular weight of t136,000.

Production Example 7 Production of water/11 resin-4 Stirrer, temperature controller, cold comb [11 in a 1 liter/1 her reaction vessel equipped with 1 tube] 1 water, 117 parts of castor oil, 17 parts of soybean oil
After weighing out 3 parts of glycerin, 17 parts of glycerin, 1 to 61 parts of pentaerythritol, and 132 parts of phthalic anhydride, and adding 7.5 parts of xylene, the stirring temperature was maintained at 180°C to 220°C to polyesterify. The reaction was continued for 3 hours while water produced by the reaction was removed azeotropically to obtain an algide resin having an oil length of 57%, an acid value of 10, and an Mn of 1800. This resin was diluted with xylene to make an alkyd resin varnish with a non-volatile content of 60%.

Into a reaction vessel similar to that used for resin synthesis, 200 parts of the above alkyd resin varnish and 104 parts of ethylene gsocol hetanobudel ether were charged, and the stirring temperature was set to 130°C. To this, 1260 parts of Ste, 1102 parts of methyl methacrylate
parts, 65 parts of 2-hydroxyethyl methacrylate, 31 parts of acrylic acid, 143 parts of n-butyl acrylate, di-t
-6 parts of butyl peroxide, 8 parts of lauryl mercaptan
Department, consisting of seven summers? 8 liquid was added dropwise over 3 hours, and stirring was continued for another 1 hour to complete the reaction. The obtained acrylic modified alkyd resin had an acid value of 5o and a molecular weight of 7,300. 100% the above reaction solution with dimethylethanolamine
After neutralization, dilute with 1 liter water to 50% non-volatile content.
It was made into a water-based varnish.

Production Example 8 Production of Aqueous Resin-5 In a reaction vessel similar to that used in the synthesis of Aqueous Resin-1, 169 parts of neopentyl glycol and 1926 parts of trimethylol were added.
parts, hydrogenated bisphenol A 46 parts, isophthalic acid 17 parts
4 parts, adipic acid 65 parts, maleic anhydride M 407:l
! was charged, 10 parts of xylene was added, and the temperature was maintained at 190 to 210'C under stirring once, and the water produced by the polyvarnish-fluorization reaction was azeotropically removed from /f to 4 [1,'
Continuing the reaction for 7 days -c1 acid value 48, number 1) homogeneous molecular weight 1
200 polyester resin was obtained.

This 4'sl Ili was diluted with ethylene glycol heptanobutyl ether-C4 to make polynisdel lf5'l fat alligator with a non-volatile content of 5.780%.

In the latter stage of Production Example 7, d-3 [Instead of using 200 parts of alkyd resin varnish and 104 parts of ethylene glycol monoethyl needle in the production of acrylic modified alkyd resin, 150 parts of the above polynisder resin, etc., and ethylene glycol] An acrylic modified polyester resin having an acid value of 50 and a molecular weight of 6,500 was obtained in the same manner using 15/1 part of nityl (monobutyl).

This was 100% neutralized with dimethylethanolamine, and 1
1) Diluted with water to obtain an aqueous varnish with a non-volatile content of 50%.

Examples 1 and -6 and Comparative Examples 1 and 2 Adjustment of Facial Resin-1 and 320 parts of Water-Based Resin-1 and 320 parts (7 )'
;I Weighed out Iheku R-820 (manufactured by 6 Hara Sangyo Co., Ltd., Rujiru type oxidized ditashi pigment) and 78 parts of Rui 1st water, added 500 cc of glass pieces, premixed with stirring,
Pigment Paste 1 was mixed and dispersed for 2 hours in a paint 1 conditioner. Using the same method, 'pf4 utilization pace spaces 1, 3, 4, and 5 were obtained.

Weigh out the ingredients in a stainless steel container according to the recipe listed in Table 1 below, mix them with a stirrer at the lowest temperature, and make 1q of the paint composition.
Noko.

Examples 1-6 Each of the coating compositions of Ayopi Comparative Examples 1-2 was diluted with deionized water and adjusted to a viscosity of 30 seconds in a foot cup #4. Spray paint on the steel plate according to the full method, 15
After cerading for 5 minutes, dry the film with a baking tray at 150°C for 15 minutes. For each composition, the B+ bottle, sag limit film thickness, and gloss value are listed in the same table.

1]! 1 to 1 j limit thin bribe) thickness limit sauce gloss 111j 60° gloss 1111◎
50μL] 2 ◎ 50μL, /, top
◎ 90 or more○ liOμ or more 040μ or more Q 85 or more/＼ 30-・110μ
△ 30~40μ △ 80~85×30/no more ×30μ or less ×80 or less (Meto ζ white)

Claims (5)

[Claims] (1) In a water-based paint composition containing C as an essential component and a binder consisting of a water-based resin and water-insoluble resin fine particles, d3 and C1 water-based resins are added to polyester resin, alkyl [~(Δ1 fat, acrylic (Go1 fat, acrylic modified polyester resin) and at least one selected from the group consisting of acrylic-modified alkyd resins, water-insoluble resins or α,β-ethylenically inert saturated monomer physical strength two-stage emulsion polymerization method, provided that
The chain transfer agent concentration during the second stage emulsion polymerization is set at 0.3 to 7% by weight based on the total monomer set in terms of dotesyl mercaptan, and the chain transfer agent concentration during the first stage emulsification is set at zero or at the second stage. Stage I
These are fine particles with an average particle diameter of 0.3 to 6μ, which can be obtained by using a relatively small amount of the water-insoluble resin (19), and the solid content heavy chain ratio of the water-insoluble resin is 99: 1-1
5:85-(Aqueous thread characterized by certain, E composition) Of course. (2) The average particle diameter of water-soluble (p) fat particles is 0.4-5
The composition according to 11th pi, wherein μ is 91δ^. (3) The composition according to claim 1 or 2, which contains a crosslinkable monomer having a functional or higher functionality than an α,β-ethylenically unsaturated saturated monomer during the first stage emulsion polymerization. (4) The chain transfer agent is argyl mercaptan or
] Any one of claims 1 to 3, which is a genified carbon (composition according to this statement). (5) First stage emulsion polymerization [Claims 1 to 41] The concentration of the chain transfer agent in step 11 is 0.3 to 5% in terms of dodecyl mercapkun based on the total monomer. The composition according to any one of.