JP2808661B2 - Room temperature drying type high solid paint composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel and useful cold-drying high-solid paint composition. More specifically, the composition comprises an air-curable low-molecular-weight specific alkyd resin and a vinyl copolymer containing N-alkoxy (meth) acrylamide as an essential monomer component. A resin containing the resin, the vinyl copolymer, a specific metal-based crosslinking agent, and a metal soap compound. Particularly, it is a high solid (high solid content concentration), and has good drying properties, durability, coating film properties, and appearance. The present invention relates to a one-part, room temperature, dry-type coating composition having excellent properties.

[Conventional technology]

Until now, this kind of room temperature drying type alkyd resin has been
From the viewpoints of coating film performance, price, ease of use, and the like, they are frequently used in vehicles, machinery, steel constructions, and the like, and are mainly used in organic solvent solutions.

By the way, conventional alkyd resins often have a relatively high molecular weight region such as a weight average molecular weight ( _W ) of 100,000 to 300,000, and the organic solvent solution of such a high molecular weight alkyd resin generally has a high viscosity, and therefore, the The non-volatile content (solid content) of paint at the time is 35
As low as ~ 60% by weight. That is, the content of the organic solvent is high.

However, in recent years, organic solvents volatilized from paint have become a major social problem, and regulations such as air pollution prevention, poisoning prevention, and occupational health have been strengthened. An alkyd resin paint having a low solvent content has been eagerly desired.

Therefore, in order to achieve high solidification by lowering the viscosity of the paint, generally, a low molecular weight of the resin itself is an effective means, but in the case of an alkyd resin paint, as long as such means is followed, In any case, it is not preferable because the drying property and the curing property are greatly reduced.

[Problems to be solved by the invention]

In view of the above-mentioned various drawbacks or problems in the prior art, the present inventors have made intensive studies, aiming at various unsolved problems in the prior art, and found that the air-curing Or a specific vinyl copolymer having N-alkoxy (meth) acrylamide as an essential monomer component, or each of these alkyd resins and vinyl copolymer By using a cold-drying high solid paint composition in the form of a polymer and further comprising a specific metal-based cross-linking agent and a metal soap compound, for the first time, the alkyd resin generally becomes compatible with the alkyd resin. It also succeeded in improving the compatibility with the insoluble acrylic copolymer, and as a result, it was difficult to solve the problem or made a high solid as long as the conventional technology was followed. The resulting play, moreover, the drying property and excellent in curability, moreover, extends the finding that the coating material having excellent cold-curing was obtained led to the completion of the present invention.

Therefore, the problem to be solved by the present invention is to overcome the existing concept or idea that the alkyd resin and the acrylic resin are not compatible with each other, and to improve the compatibility of these two, Accordingly, it is an object of the present invention to provide a coating composition for a room temperature drying composition which has a high solidity which is difficult to solve and has excellent drying properties and curability.

[Means for solving the problem]

It is the present invention that has the following means to reach the area of completion along the line of such a solution.

That is, the present invention has an iodine value of 100 as an essential component.
The oil length obtained by using the above fatty acids is 20-70%,
And _W of alkyd resin (A) of 3,000-100,000
40-95% by weight, general formula N-alkoxy (meth) acrylamide (b)
-1) and the N-alkoxy (meth)
A vinyl copolymer (B) having a _W of 5,000 to 40,000 obtained by polymerizing 70 to 97% by weight of another vinyl monomer (b-2) copolymerizable with acrylamide (b-1) A cold-drying high solid paint composition comprising 5 to 60% by weight;
As an essential component, it is obtained by using a fatty acid having an iodine value of 100 or more. The oil length is 20-70%, and _W is 3,000-1.
40-95% by weight of the alkyd resin (A) of the general formula N-alkoxy (meth) acrylamide (b)
-1) and the N-alkoxy (meth)
A vinyl copolymer (B) having a _W of 5,000 to 40,000 obtained by polymerizing 70 to 97% by weight of another vinyl monomer (b-2) copolymerizable with acrylamide (b-1) 5 to 60% by weight, and 0.1 to 10 parts by weight of the alkyd resin (A) and the vinyl copolymer (B) constituting the binder component, respectively, with respect to 100 parts by weight of the total non-volatile content. Room temperature drying comprising a metal-based crosslinking agent (C) containing at least one metal selected from the group consisting of aluminum, titanium and zirconium in a proportion by weight and a suitable amount of a metal soap compound (D). It is an object of the present invention to provide a composition for a high-solid type paint.

By the way, although the addition and blending of a metal-based crosslinking agent into an alkyd resin coating is already well known, when the molecular weight of such an alkyd resin is high, the viscosity of the alkyd resin is significantly increased in the course of its application. from treatment tends to be, on the use of the metal-based crosslinking agent, there were many restrictions, we brilliantly this, _W is 3,000～10
By using the alkyd resin (A) having a specific molecular weight range of 0.000, there is no appreciable increase in viscosity, and at the same time, the addition and blending of the crosslinking agent can be achieved without practically impairing the storage stability of the paint. Finding something that can be done,
Furthermore, by using a specific copolymer resin of an acrylic copolymer that is compatible with the alkyd resin, it has also been found that a room temperature drying coating composition having significantly improved drying properties and curability can be obtained. All the unsolved problems of the prior art have been solved.

In other words, the present invention is a highly solid, yet, conventional, 100,000-300,000, having a drying property and curability comparable to a coating composition in the form of using a so-called high molecular weight alkyd resin, very useful It is an object of the present invention to provide a coating composition.

Here, the alkyd resin (A) is obtained by using a fatty acid having an iodine value of 100 or more, and has an oil length of 20 to 70% and a _W of 3,000 to 1,
No. 00,000, other than these limitations, there is no remarkable reduction, therefore, not only alkyd resin, but also styrenated alkyd resin, acrylated alkyd resin, urethane alkyd resin, phenol-modified alkyd resin, polyamide Various modified alkyd resins such as a modified alkyd resin, a silicon-modified alkyd resin, a rosin-modified alkyd resin, and an epoxy-modified alkyd resin can also be applied, and the type thereof is not limited, and is obtained according to a conventional method.

The above-mentioned iodine value is one of the coefficients indicating the abundance or content of unsaturated double bonds serving as cross-linking points by oxygen in the air of the alkyd resin (A). Inevitably, the drying property and the curing property are not preferable because they are apt to be remarkably reduced. Therefore, in the present invention, in order to achieve the room temperature drying property, 100 or more,
Preferably, 120 or more are appropriate.

If the oil length is more than 70%, the coating film tends to be too soft and the drying property tends to be insufficient, and furthermore, the vinyl copolymer (B) With 20%
If it is less than 1, the crosslink density of the cured coating film tends to be low, and the curability, solvent resistance, physical properties of the coating film, etc. are deteriorated.

Therefore, in the present invention, it is appropriate to use an alkyd resin having an oil length of 20 to 70%, preferably 30 to 60%.

Further, with respect to _W of the alkyd resin (A),
If it exceeds 100,000, the viscosity when formed into a coating is likely to be high, and therefore, it is unsuitable for high solidification as one of the objects of the present invention. If the ratio is less than 10%, both the drying property and the curing property are deteriorated.

Therefore, the alkyd resin (A) in the present invention
_W is suitably in the range of 3,000 to 100,000, preferably in the range of 5,000 to 50,000.

Thus, if only typical examples of the above-mentioned fatty acids having an iodine value of 100 or more are given, examples thereof include unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid and eleostearic acid, as well as "pamorin". 200 or 300 "(synthetic drying oil fatty acid manufactured by Hercules, USA), Chinese nagiri oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid) or cottonseed oil (fatty acid), soybean oil (fatty acid) ), Safflower oil (fatty acids), sunflower oil (fatty acids) or various fish oils (fatty acids)
And so on.

In addition, if only typical examples are given as polyhydric alcohols (polyols) used for preparing the alkyd resin (A), ethylene glycol, propylene glycol, 1,3-butylene glycol, 6-hexanediol, diethylene glycol,
Examples include dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and cyclohexadimethanol.

Further, the acid component used in preparing the alkyd resin (A) is mainly an aromatic carboxylic acid, an alicyclic carboxylic acid and an aliphatic carboxylic acid,
First, typical examples of aromatic carboxylic acids include (phthalic anhydride), isophthalic acid, and terephthalic acid, and benzoic acid and p-
Methylbenzoic acid or p-tert-butylbenzoic acid can also be used effectively.

Also, any polybasic acid of trimellitic anhydride or pyromellitic anhydride can be used as needed.

Next, typical alicyclic carboxylic acids include 1,1
-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydro (phthalic anhydride) phthalic acid, methylhexahydro (phthalic anhydride) phthalic acid and the like. Cyclohexane monocarboxylic acid, hexahydrobenzoic acid and the like can also be used.

Representative examples of the aliphatic carboxylic acid include adipic acid, azelaic acid, and sebacic acid.

In addition to the various acids as described above, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, heptic anhydride, hymic anhydride, maleic anhydride, fumaric acid, itaconic acid, and the like can also be used.

In addition, some of these various components can be replaced with various isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and phenyl isocyanate.

In order to prepare the alkyd resin (A) using the various raw material components listed above, any of a conventional method, a melting method or a solvent method may be used.

Next, as the vinyl copolymer (B) as another essential component constituting the composition of the present invention, 3 to 30% by weight of the N-alkoxy (meth) acrylamide monomer (b-1)
And another vinyl monomer (b-2) copolymerizable with the N-alkoxy (meth) acrylamide monomer (b-1).
By polymerizing a 70-97 wt% of the obtained, _W 5,000
Those within the range of ~ 40,000 are used.

Among them, the N-alkoxy (meth) acrylamide monomer (b-1) is used in order to ensure compatibility with the alkyd resin (A) described above.
When the amount of -1) is less than 3% by weight, the compatibility with the alkyd resin (A) tends to be insufficient. On the other hand, when the amount exceeds 30% by weight, it is inevitably obtained. The viscosity of the vinyl copolymer (B) solution is
Eventually, the viscosity of the obtained resin composition is also increased, and therefore, it is difficult to achieve high solidification, and the water resistance and weather resistance of the obtained coating film are reduced, and of course, However, this also leads to a rise in price, so neither is preferable.

Therefore, in the present invention, the amount of the N-alkoxy (meth) acrylamide monomer (b-1) used is in the range of 3 to 30% by weight, preferably in the range of 5 to 20% by weight. Is appropriate.

As for _W of the vinyl copolymer (B),
In order to achieve such a high solidification, a lower value is desirable, but if it is less than 5,000, the drying property is insufficient, and it is extremely difficult to obtain by a usual polymerization method. On the other hand, if it exceeds 40,000, it is inevitably difficult to meet the purpose of high solidification.

Therefore, _W is preferably in the range of 5,000 to 40,000, and more preferably, in the range of 7,000 to 25,000.

If only typical representative examples of the N-alkoxy (meth) acrylamide monomer (b-1) are given, N-methylol (meth) acrylamide, N-
Ethoxymethyl (meth) acrylamide, Nn-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide or N -Tert-butoxymethyl (meth) acrylamide and the like.

On the other hand, if only the typical vinyl monomer (b-2) copolymerizable with the N-alkoxy (meth) acrylamide monomer (b-1) described above is used, only typical examples are given below. It looks like this:

(A): Aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, and vinyltoluene; (B): Methyl (meth) acrylate, ethyl (meth)
Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth)
Acrylate, isobutyl (meth) acrylate, tert
-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl ( (Meth) acrylates such as meth) acrylate or alkoxyalkyl (meth) acrylate; diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols; vinyl acetate, vinyl benzoate, "Veoba" (C) Vinyl carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Α, β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as citraconic acid, and monoesters of these dicarboxylic acids with monohydric alcohols; 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3
-Chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-
Α, such as hydroxyethyl-monobutyl fumarate or polyethylene glycol mono (meth) acrylate
β-unsaturated carboxylic acid hydroalkyl esters and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid,
Examples include tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Hymic acid" (a product of Hitachi Chemical Co., Ltd.), and adducts of polycarboxylic acids with anhydrides such as tetrachlorophthalic acid or dodecinylsuccinic acid. (D): Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxy Propyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polypropylene glycol or polyethylene glycol mono (meth) acrylate, "Placcel FM, FA monomer" [Daicel Chemical ( Co., Ltd., caprolactone-added monomer] such as α, β-ethylenically unsaturated carboxylic acids or adducts thereof with ε-caprolactone; (meth) acrylic acid, crotonic acid, maleic acid Α, β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as formic acid, fumaric acid, itaconic acid or citraconic acid, and monoesters of these dicarboxylic acids with monohydric alcohols, or The α, β-unsaturated carboxylic acid hydroxyalkyl esters and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, “Hymic acid” [Hitachi Chemical Industry ( Products), various unsaturated carboxylic acids such as adducts of polycarboxylic acids with anhydrides such as tetrachlorophthalic acid or dodecinylsuccinic acid, and "Kajura E" (a branched synthetic fatty acid produced by Shell, Netherlands). Glycidyl ester), coconut oil fatty acid glycidyl ester or octane Monoglycidyl ester of a monovalent carboxylic acid such as glycidyl luate or an adduct thereof with a monoepoxy compound such as butyl glycidyl ether, ethylene oxide or propylene oxide; or an adduct thereof with ε-caprolactone; hydroxyethyl vinyl ether; (E): dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphites or (meth) acryloyl Roxyalkyl acid phosphites, and the like. Further, the above (meth) acryloyloxyalkyl acid phosphates, or alkylene oxide adducts of acid phosphites, Ester compounds of an epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate or methyl glycidyl (meth) acrylate with phosphoric acid or phosphorous acid or acidic esters thereof, 3-chloro-2-acidphosphoxypropyl (meth) Phosphorus atom-containing vinyl monomers such as acrylate; (f): dimethylaminoethyl (meth) acrylate;
Dialkylaminoalkyl (meth) acrylates such as diethylaminomethyl (meth) acrylate; (g): epoxy group-containing monomers such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) acrylicidyl ether; Or (h): vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate, “KR-215, X-22-5002”
[Products of Shin-Etsu Chemical Co., Ltd.].

The vinyl copolymer (B) can be prepared by making use of a known and commonly used copolymerization reaction method or a graft copolymerization reaction method, in which case azobisisobutyronitrile ( AIBN), benzoyl peroxide (BPO), tert-butyl perbenzoate (TBPB), ter
t-butyl hydroperoxide, di-tert-butyl peroxide (DTBPO), cumene hydroperoxide (C
HP) or other radical-generating polymerization catalysts alone or in combination of several types.

The ratio of the non-volatile components of the alkyd resin (A) and the vinyl copolymer (B), which are essential film-forming components of the composition of the present invention, is as follows. The solid content weight ratio of the polymer (B) = 40: 60 to 95: 5 is appropriate, and preferably, the range of 50:50 to 90:10 is appropriate.

When the amount of the vinyl copolymer (B) used is less than 5% by weight, the effect of the drying property can hardly be expected. Increases, and the coating film becomes brittle,
Neither is preferred.

The metal-based cross-linking agent (C), which is one of the essential components constituting the other room-temperature-dried high-solid coating composition of the present invention, is a metal compound selected from aluminum, titanium and zirconium. In addition, it refers to one having such a cross-linking effect, and the amount of the metal-based cross-linking agent (C) used is determined by the amount of the two essential components of the alkyd resin and the vinyl copolymer (B). A suitable range is 0.1 to 10 parts by weight based on 100 parts by weight of the nonvolatile components.

The curability, particularly the internal curability of the coating film is remarkably promoted by using the crosslinking agent (C) in combination with the known and commonly used metal soap compound (D).

If the amount of the crosslinking agent (C) is less than 0.1 part by weight, sufficient curability cannot be achieved by all means. Neither of them is preferable because the viscosity increases and the stability of the paint tends to be adversely affected.

If only typical examples of the cross-linking agent (C) are given as examples, alkoxides of aliphatic alcohols having 1 to 8 carbon atoms of aluminum, titanium or zirconium may be added to alkoxides of acetylacetone, methyl acetoacetate, acetoacetate, etc. So-called keto-acids such as ethyl acetate, malonic diester or diacetylacetate
Enol tautomeric compound; 1,3-propanediol, 1,
Diols such as 3-butanediol or 2,4-pentanediol; and compounds obtained by reacting salicyloyl derivatives such as salicylic acid esters and salicylaldehyde.

Specifically, aluminum diisopropoxide monoacetylacetonate, aluminum diisopropoxide monomethylacetoacetate, aluminum diisopropoxide monoethylacetoacetate, aluminum di-sec-butoxide monoacetylacetonate, aluminum Di-sec-butoxide monomethyl acetoacetate, aluminum di-sec-butoxide monoethyl acetoacetate, aluminum di-n-
Butoxide monomethyl acetoacetonate, aluminum di-n-butoxide monomethyl acetoacetate,
Aluminum di-n-butoxide monoethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (methylacetoacetate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (methylacetoacetate) Acetate) or aluminum monoacetylacetonate bis (ethylacetoacetate); titanium diisopropoxide bis (acetylacetonate), titanium diisopropoxide
Bis (methyl acetoacetate), titanium diisopropoxide bis (ethyl acetoacetate), titanium di-n-butoxide bis (acetylacetonate), titanium di-n-butoxide bis (methyl acetoacetate) , Titanium di-n-butoxide bis (ethylacetoacetate); zirconium
Tri-n-butoxymonoacetylacetonate, zirconium tri-n-butoxymonomethylacetate, zirconium tri-n-butoxymonoethylacetoacetate, zirconium tetraacetylacetonate,
Zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate; aluminum di-n-butoxide-1,3-propane dioxide, aluminum di-n-butoxide-1,3-butaneoxide; titanium diisopropoxide Bis (1,3-propane oxide); zirconium tri-n-butoxide-1,3-phthalane dioxide; aluminum diisopropoxide methyl salicylate or titanium diisopropoxide bis (ethyl silicylate) Are typical.

Particularly, it is preferable to use a compound obtained by reacting an alkoxide compound with a keto-enol tautomeric compound, and particularly preferably, a reaction product of an alkoxide compound and acetoacetate, or a reaction product of an alkoxide compound and acetylacetone. Is the use of

On the other hand, as the above-mentioned metal soap compound (D), of course, any of those generally used for room temperature drying type alkoxide resin paints can be used, and among them, particularly typical ones are listed. If you stop at
Various saturated aliphatic monocarboxylates such as octylate, isooctylate, neodecanoate, nonanoate or heptanoate of various metals such as cobalt, manganese, zirconium, lead, calcium and zinc, or naphthenic acid It is a cyclic saturated fatty acid salt such as a salt.

The metal soap compound (D) is added in an amount of 100 parts by weight of a nonvolatile content of both essential components of the alkyd resin (A) and the vinyl copolymer (B).
It can be said that a metal content of about 0.005 to 0.2 parts by weight is sufficient.

The thus-obtained room-temperature-dried high-solid coating composition of the present invention further includes, if necessary, a pigment dispersant, a leveling agent, an ultraviolet absorber, and various other coatings that are generally known in the art. It goes without saying that the additives can be used in a conventional amount, and if the additives are compatible with and soluble in the coating composition of the present invention, for the purpose of improving the performance, a plasticizer, another resin, for example, Acrylic copolymers, cellulose-based compounds, acrylated alkyd resins, alkyd resins, silicone resins, fluororesins, ketone resins, epoxy resins, etc., can also be used in combination as appropriate, or as a mixture of pigments as an enamel paint, Can be used as clear paint without mixing.

The coating may be performed by a known method such as a spray or a roller.

The room temperature drying type high solid paint composition of the present invention is used for repairing automobiles, for large vehicles, for building exteriors, for building materials, for bridges,
It can be applied to general metals, floors, plastics, aluminum sashes, paper, tiles, cement tiles, inorganic materials, woodwork or plants.

〔The invention's effect〕

Using the coating composition of the present invention, 65% by weight or more,
In addition, depending on the proper formulation, a non-volatile content of 70% by weight or more can be secured, and on the other hand, excellent in dryness and curability, and also excellent in durability, physical properties of the coating film, appearance, etc., at room temperature. It can be a dry type high solid paint.

〔Example〕

Next, the present invention by reference examples, examples and comparative examples,
More specifically, in the following, parts and%
All are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Alkyd Resin (A)] In a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube, a nitrogen gas introducing tube, and a heating device, 350 safflower oil was added.
Parts, 119 parts of pentaerythritol and 93 parts of trimethylolethane and 0.07 part of lithium hydroxide were charged, reacted at 250 ° C. for 1 hour, and then cooled to 150 ° C.
Add 203 parts of p-tert-butylbenzoic acid, 10 parts of neopentyl glycol and 277 parts of phthalic anhydride,
The temperature was raised to 240 ° C. in 2 hours, and the temperature was maintained for 8 hours to continue the dehydration condensation reaction. Thereafter, the temperature was lowered to 125 parts of methyl ethyl ketone and 125 parts of xylene.
Parts.

The solution of the target resin (A) thus obtained has a nonvolatile content of 80% and a Gardner viscosity at 25 ° C. (the same applies hereinafter).
In Z _1, an acid value of the resin solution (the same applies hereinafter) is 5.5, _W; at [Japan Analytical Industry Co., Ltd. GPC (model "LC-08") values were measured using the same manner] 14,000 And the oil length is 35
%. Hereinafter, this is abbreviated as resin (A-1).

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 438 safflower oil was added.
Parts, 119 parts of pentaerythritol and 0.0 parts of zinc acetate
Eight parts were charged and reacted at 250 ° C. for 1 hour. After the temperature was lowered to 150 ° C., 166 parts of benzoic acid and 250 parts of phthalic anhydride were added.

Then, the temperature was raised to 240 ° C. over 2 hours, the temperature was maintained for 7 hours to continue the dehydration condensation reaction, and then the temperature was lowered and 175 parts of methyl-n-propyl ketone was added.

The resin solution obtained here has a nonvolatile content of 85% and a viscosity of 85%.
Z ₂ , acid value was 5.0, _W was 9,200, and oil length was 44%. Hereinafter, the resin (A)
-2).

REFERENCE EXAMPLE 3 (Same as above) In a reaction vessel similar to Reference Example 1, 272 parts of soybean oil, 272 parts of linseed oil, 139 parts of pentaerythritol and 0.1 part of lithium hydroxide were charged and reacted at 250 ° C. for 1 hour. After reacting for a while, the temperature was lowered to 150 ° C and p-ter
59 parts of t-butylbenzoic acid, 2 parts of dipropylene glycol
0 parts and 275 parts of phthalic anhydride were added, the temperature was raised to 240 ° C. over 2 hours, and the mixture was subjected to a dehydration condensation reaction at the same temperature for 10 hours, and then the temperature was lowered to obtain methyl-n-propyl ketone. Was added.

The resin solution obtained here had a nonvolatile content of 75%, a viscosity of V, an acid value of 7.4, a _W of 74,000, and an oil length of 54%.
Had various characteristic values. Hereinafter, this is abbreviated as resin (A-3).

Reference Example 4 (same as above) First, 650 of soybean oil were placed in the same reaction vessel as in Reference Example 1.
, 136 parts of pentaerythritol and 0.15 part of lithium hydroxide, and the mixture was reacted at 250 ° C. for 1 hour, and then cooled to 150 ° C., and further reacted with 241 parts of phthalic anhydride.
Parts and 30 parts of xylene, 25
After performing a dehydration condensation reaction at 0 ° C. for 6 hours, the temperature was lowered and 216 parts of “Swazol # 310” (an aromatic hydrocarbon solvent manufactured by Maruzen Oil Co., Ltd.) was added.

The solution of the target resin (A) thus obtained has a nonvolatile content of 80%, a viscosity of Z, an oxidation of 6.3 and a _W of 20,300.
And had various characteristic values such that the oil length was 65%. Hereinafter, this is abbreviated as resin (A-4).

Reference Example 5 [Preparation Example of Vinyl Copolymer (B)] A four-mouth equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube, a monomer and catalyst dropping device, and a heating oil bath. In a flask, first add 334 of xylene
Parts, 133 parts of n-butanol and 2 parts of di-tert-butyl peroxide (BTBPO) were charged and heated to 120 ° C.
1,000 parts of a monomer mixture (hereinafter referred to as monomer premix) consisting of 600 parts of styrene, 300 parts of tert-butyl methacrylate and 100 parts of Nn-butoxymethylacrylamide; 200 parts of xylene, 256 parts of a mixture with a catalyst premix consisting of 6 parts of bisisobutyronitrile (AIBN), 45 parts of tert-butyl hydroperoxide (TBHPO) and 5 parts of tert-butyl perbenzoate (TBPB); It takes a long time to drop and reach 120 ° C
After maintaining for 16 hours, the temperature was lowered, and 73 parts of xylene and 18 parts of n-butanol were added.

The solution of the target copolymer (B) obtained here had various properties such as a nonvolatile content of 60%, a viscosity of U and a _W of 11,400. Hereinafter, this is referred to as a copolymer (B-
Abbreviated as 1).

Reference Example 6 (same as above) In a reaction vessel similar to Reference Example 5, methylamyl ketone was added.
250 parts, 200 parts of n-butanol and 2 parts of DTBPO were charged and heated to 120 ° C., and 300 parts of styrene, 200 parts of methyl methacrylate, and 300 parts of tert-butyl methacrylate were added.
Part and 200 of Nn-butoxymethylacrylamide
Parts of a monomer premix consisting of 1,000 parts; 256 parts of a mixture of the same catalyst premix as in Reference Example 5 and 200 parts of xylene; added dropwise over 6 hours and kept at 120 ° C. for 16 hours Then, the temperature was lowered, and 85 parts of methyl amyl ketone was charged.

The thus-obtained solution of the target copolymer (B) had various characteristics such that the nonvolatile content was 60%, the viscosity was VW, and _W was 14,700. Hereinafter, this is referred to as a copolymer (B-
Abbreviated as 2).

Reference Example 7 (Preparation Example of Control Vinyl Copolymer) In this example, the use ratio of N-alkoxy (meth) acrylamide was 2.5%.

Except that the monomer premix was changed to use 500 parts of styrene, 250 parts of methyl methacrylate, 225 parts of n-butyl methacrylate and 25 parts of Nn-butoxymethylacrylamide,
As in Reference Example 5, the nonvolatile content was 60% and the viscosity was P
And a solution of a control vinyl copolymer having _W of 8,560 was obtained. Hereinafter, this is abbreviated as copolymer (B'-1), which is referred to as resin (A-1), (A-2), or (A-
It was not compatible with any of the alkyd resins of (3) and (A-4).

Reference Example 8 (same as above) First, xylene 650 was placed in the same reaction vessel as in Reference Example 5.
And 150 parts of n-butanol and heated to 105 ° C., and 1,000 parts of a monomer premix consisting of 400 parts of styrene, 250 parts of methyl methacrylate and 350 parts of Nn-butoxymethylacrylamide; of 2
00 parts and 224 parts of a mixture of 24 parts of a catalyst premix consisting of 20 parts of TBHPO and 4 parts of AIBN; allowed to drip over 4 hours, and after completion of the addition, the temperature was raised to 110 ° C. And keep it for 16 hours before cooling down,
I put in 20 copies.

The solution of the control vinyl copolymer obtained here had a nonvolatile content of 50%, a viscosity of W, and _W of 51,100. Hereinafter, this is referred to as a copolymer (B ').
This example is abbreviated as -2), but this example is for the case where the usage rate of N-alkoxy (meth) acrylamide is 35%. Reference Example 9 (Preparation example of alkyd resin for control) In the same reaction vessel as in Reference Example 1, 300 parts of soybean oil, 133 parts of pentaerythritol, and 0.06 part of lithium hydroxide are charged into a reaction vessel same as that in Reference Example 1 at 250 ° C. for 1 hour. 150 ℃ after reacting during
Then, 143 parts of benzoic acid, 125 parts of trimethylolpropane, 10 parts of pentaerythritol and 348 parts of phthalic anhydride were charged and 240 hours over 2 hours.
The temperature was raised to 5 ° C., the temperature was maintained for 5 hours to cause a dehydration condensation reaction, and then the temperature was lowered and 530 parts of methyl-n-propyl ketone was added.

The resin solution obtained here has a nonvolatile content of 65% and a viscosity of V
With acid value of 8.0, _W of 126,300 and oil length of 30%
It was something. This is abbreviated as resin (A'-1).

Reference Example 10 (same as above) In the same reaction vessel as in Reference Example 1, dehydrated castor oil fatty acid
558 parts, pentaerythritol 203 parts, neopentyl glycol 11 parts, benzoic acid 198 parts and phthalic anhydride 1
06 parts were charged, the temperature was raised to 240 ° C. over 4 hours, the temperature was maintained for 8 hours to perform a dehydration condensation reaction, and then the temperature was lowered, and 51 parts of methyl amyl ketone was added.

Thus, the non-volatile content is 95%, the viscosity is Z ₁ -Z ₂ and the acid value is
At 6.2, a solution of the control resin with _W of 2,540 and various property values with an oil length of 58% was obtained. Hereinafter, this is abbreviated as resin (A'-2), but this example is also a case where the molecular weight is out of the range of the alkyd resin in the present invention.

Reference Example 11 (same as above) This example is an example of the alkyd resin of the present invention that deviates from the oil length range.

In the same reaction vessel as in Reference Example 1, 370 parts of linseed oil, 155 parts of pentaerythritol and 0.0 part of lithium hydroxide were added.
After charging 8 parts, the mixture was reacted at 250 ° C. for 1 hour, and then cooled. Further, 354 parts of soybean oil fatty acid, 19 parts of maleic anhydride, 148 parts of phthalic anhydride and 30 parts of xylene were charged. After performing a dehydration condensation reaction at 240 ° C. for 5 hours by a solvent method, 80 parts of a mineral terpene was charged.

Resin solution obtained here is a nonvolatile content of 90%, a viscosity of Z _{4, W} is at 41,400 an acid value of 7.7, and an oil length of 74
%. Hereinafter, this is abbreviated as resin (A'-3), which is referred to as resin (B-1) or (B-
It was not compatible with any of the vinyl copolymers of 2).

Examples 1 to 13 and Comparative Examples 1 to 12 Using various alkyd resins and vinyl copolymers obtained in the above Reference Examples, and further using a metal-based crosslinking agent and a metal soap compound, Table 1 Each paint was separately prepared according to the composition shown in (1) and (2) and according to the paint preparation method described below.

That is, 80 parts of "Taipec R-820" (rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) was added to 100 parts of the total resin solid content of the nonvolatile content of each alkyd resin and the nonvolatile content of the vinyl copolymer, 20 parts of xylene and then kneaded with a sand mill for 30 minutes, and then a predetermined amount of a metal-based crosslinking agent and a metal soap compound, and further, 0.5% of methyl ethyl ketoxime as an anti-skinning agent.
And finally with xylene, Ford Cup # 4
And the viscosity was adjusted to 35 seconds to obtain a paint.

The metal-based cross-linking agent and the metal soap compound used are as follows, and the blending amount of the metal-based cross-linking agent is, as described above, expressed as a number with respect to 100 parts of the resin solid content, On the other hand, the compounding amount of the metal soap compound is
It is displayed as the amount of metal (parts) per 100 parts of resin solids.

First, as a metal-based cross-linking agent, “Alsec 591” was purchased from Dainippon Ink and Chemicals, Inc.
Aluminum diisopropoxide monoethyl acetoacetate solution having an aluminum content of 6% manufactured by Jinsei Co., Ltd., and in Table 1 (1) and (2), "Al59
1 ".

“ALCH-TR” is aluminum trisethyl acetoacetate manufactured by Kawaken Fine Chemical Co., Ltd. In Table 1 (1), it is abbreviated as “Al · TR”.

"Titabond 50" is a titanium di-iso-propoxide bis (acetylacetonate) isopropanol solution containing 74% of an active ingredient manufactured by Nippon Soda Co., Ltd. , "Ti50".

Next, as the metal soap compound, 6% cobalt naphthenate; an organic solvent solution of cobalt naphthenate having a metal cobalt content of 6%. (1) in Table 1
In (2) and above, it is abbreviated as Co.

6% manganese naphthenate; an organic solvent solution of manganese naphthenate having a metal manganese content of 6%. (1) in Table 1
In (2), it is abbreviated as Mn.

6% zirconium naphthenate; an organic solvent solution of zirconium naphthenate having a metal zirconium content of 6%. First
In Tables (1) and (2), it is abbreviated as “Zr”.

24% lead naphthenate; an organic solvent solution of lead naphthenate having a metal lead content of 24%. In Table 1 (1) and (2), it is abbreviated as “Pb”.

For each paint obtained as above,
Comparative examination of the coating film performance was performed in the following manner. The results are collectively shown in Table 1 (1) and (2).

(1) Dryness 40 ± 3μ dry film on glass plate using applicator
The coating was performed so that the temperature was 23. +-. 2.degree. C. and the relative humidity was 70. +-. 5%.

(2) Self-recoating property Undercoat is applied under the same conditions and atmosphere as in the case of dryness, and after 4, 8, 24, 48 and 96 hours, respectively, with an applicator, the same as the undercoating The paint was applied, and a judgment was made based on the state of “lifting” that occurred.

；: Lifting did not occur △: Partial lifting occurred ×: Lifting occurred over the entire surface (3) Masking tape properties Painted under the same conditions and atmosphere as in the case of dryness, for 8, 24 and 48 hours, respectively Later, a masking tape was applied, and after 30 minutes, it was peeled off and left for another 24 hours, and then the state of the masking tape mark was visually evaluated.

○: No trace of masking tape △: Trace of masking tape remains, but condition is not bad ×: Mark of masking tape remains remarkably (4) Coating film performance Coated on Bonderite # 144 treated steel plate (manufactured by Nippon Test Panel Co., Ltd.) to a thickness of ~ 35μ, and dried for 7 days in an atmosphere at a temperature of 23 ± 2 ° C and a relative humidity of 70 ± 5%. Thereafter, the gloss and the Erichsen value were measured. However, the pencil hardness was also measured after drying for 1 day and 3 days.

(5) Paint stability The viscosity of the paint whose viscosity was adjusted to 35 seconds with a Ford cup # 4 was left at 20 ° C for one month, and the viscosity was measured.
The evaluation was as follows.

；: When the paint viscosity is less than 50 seconds △; when the paint viscosity is 50 to 120 seconds ×; when the paint viscosity exceeds 120 seconds XX; within one day and night after adding the metal-based crosslinking agent (C) Is gelled As is clear from Tables (1) and (2), the room-temperature-drying high-solid coating composition of the present invention can secure a solid content of 65% or more, and has another property such as drying and curing. The coating composition of the present invention is known to be excellent in properties and also excellent in coating film performance and coating stability, so that the coating composition of the present invention is well-balanced.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-72785 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 167/06 C09D 133/06-133 / 12 C09D 133/26

Claims (2)

(57) [Claims] An oil having a length of 20 to 70% and a weight average molecular weight of 3,5 obtained by using a fatty acid having an iodine value of 100 or more.
40 to 95% by weight of the alkyd resin (A) of 000 to 100,000
And the general formula N-alkoxy (meth) acrylamide (b)
-1) and the N-alkoxy (meth)
A vinyl copolymer (B) having a weight average molecular weight of 5,000 to 40,000 obtained by polymerizing 70 to 97% by weight of another vinyl monomer (b-2) copolymerizable with acrylamide (b-1) ) Of 5 to 60% by weight of a cold-drying type high solid paint composition. 2. An oil obtained by using a fatty acid having an iodine value of 100 or more, having an oil length of 20 to 70% and a weight average molecular weight of 3,000.
40 to 95% by weight of the alkyd resin (A) of 0 to 100,000;
General formula N-alkoxy (meth) acrylamide (b)
-1) and the N-alkoxy (meth)
A vinyl copolymer having a weight average molecular weight of 5,000 to 40,000 (B) obtained by polymerizing 70 to 97% by weight of another vinyl monomer (b-2) copolymerizable with acrylamide (b-1) A) a binder component consisting of 5 to 60% by weight of
From the aluminum, titanium and zirconium in a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the total non-volatile content of the alkyd resin (A) and the vinyl copolymer (B) constituting the binder component. A metal-based crosslinking agent (C) containing at least one metal selected from the group consisting of
And a room temperature drying type high solid coating composition, comprising: a metal soap compound (D);