JP3289146B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Industrial Application Field] The present invention relates to a novel and useful resin composition.
More specifically, the present invention comprises the use of unique cross-linked particles of cross-linked urethane-urea particles as a specific compounding component. In particular, it is possible to control sagging and to make the film thicker. The present invention relates to a resin composition that can provide a resin composition. [Prior art] From the viewpoint of environmental protection, it has become necessary to regulate the amount of solvent discharged, and in response to this, the coatings industry has been working to reduce the amount of solvent discharged by using high-emission liquids with low solvent content. Started to use solid type resin. However, the paint using the high solid type resin has a problem that it is easy to sag when painted on a vertical surface. For this reason, the coating film thickness is limited, and it is difficult to increase the film thickness. Further, there is a drawback that the appearance of the coating film is inferior to the horizontal plane because of the difficulty in increasing the film thickness. [Problems to be solved by the invention] As described above, as long as the conventional technology is followed,
In fact, it was impossible to avoid sagging, and it was extremely difficult to control sagging. To this end, the present inventors have somehow sought, as much as possible, a highly useful resin composition that can control sagging,
Research has begun. Therefore, the problem to be solved by the present invention is to provide a highly useful resin composition which can control the generation of such sagging as much as possible and make the film as thick as possible. It is. That is, an object of the present invention is to provide a new and useful resin composition in which the above-mentioned disadvantages have been successfully solved. [Means for Solving the Problems] Thus, the present inventors focused on the problems to be solved by the invention as described above, and as a result of earnest and intensive studies, they were obtained by a reaction in an aqueous medium. When using a resin composition containing a specific amount of specific particles such as specific cross-linked urethane-urea particles, the present invention is completed by finding that even if the film thickness is increased, the occurrence of sagging can be suppressed. Reached. That is, the present invention relates to a resin composition containing (A) a coating film-forming component composed of a resin capable of forming a coating film and (B) crosslinked urethane-urea particles as essential components. (A) 99.5 to 80% by weight and crosslinked urethane-urea particles (B) 0.5 to less than 20% by weight, and the crosslinked urethane-urea particles (B) contain two isocyanates in one molecule. Isocyanate prepolymer (B1) having at least two isocyanate groups in one molecule obtained by reacting a diisocyanate having a group with a polyol having at least two hydroxyl groups in one molecule (provided that "C18 Isocyanate prepolymer obtained by using a polyester polyol containing a carboxylic acid of from .about.60, the same applies hereinafter.) And at least two amino groups in one molecule. Resin composition, characterized in that is obtained by reaction in an aqueous medium with Riamin compound (B2), crosslinked urethane - urea particles (B)
However, a polyol having a carboxylic acid group or a polyol having a carboxylic acid group and a sulfonic acid group is used as at least one of the polyols having at least two hydroxyl groups in one molecule, and these acid groups are converted to amines. It is obtained by reacting an isocyanate prepolymer with a polyamine compound after forming a salt or a metal salt, and preferably a crosslinked urethane-urea particle (B) is a polyol having at least two hydroxyl groups in one molecule. At least one of which is obtained by using a polyol having a polyoxyethylene chain, preferably the crosslinked urethane-urea particles (B)
At least one of polyols having at least two hydroxyl groups in the molecule is obtained by using a monoglyceride of a fatty acid. Preferably, the film-forming component (A) comprises a hydroxyl-containing resin and a melamine resin. And a resin composition comprising a combination of a hydroxyl group-containing resin and a polyisocyanate. Here, first, the above-mentioned coating film forming component (A)
As a matter of course, as long as it is a resin capable of forming a coating film, it is not particularly limited, and includes an acrylic lacquer and a thermoplastic emulsion resin, and further, a combination of a hydroxyl group-containing resin and a melamine resin, or As represented by a combination of a hydroxyl group-containing resin and a polyisocyanate, a combination of resins having functional groups that can react with each other,
Alternatively, a thermosetting resin represented by an alkyd resin or the like may be used. Next, the above-mentioned crosslinked urethane-urea particles (B)
It is obtained by a reaction of an isocyanate prepolymer having at least two isocyanate groups in one molecule with a polyamine compound having at least two amino groups in one molecule in an aqueous medium. Examples of the isocyanate prepolymer include a diisocyanate having two isocyanate groups in one molecule and a polyol having at least two hydroxyl groups in one molecule (provided that “polyester containing a carboxylic acid having 18 to 60 carbon atoms”). Polyols "), and only those typical examples of such diisocyanates include 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, and 1,4′-diphenylmethane diisocyanate. 6-hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-
And methylene bis (cyclohexyl isocyanate). On the other hand, if only typical examples of the above-mentioned polyols are given, ethylene glycol, 1,3-
Aliphatic hydrocarbon diols having 2 to 10 carbon atoms, such as propanediol, 1,4-butanediol, 1,5-pentanediol or neopentyl glycol; represented by aliphatic monoglycerides derived from animal and vegetable oils Carboxyl group-containing diols such as dimethylolpropionic acid; diols such as compounds having both sulfonic acid groups and hydroxyl groups such as dimethylolpropanesulfonic acid; polyoxyethylene glycol, polyoxyethylene glycol An equimolar reaction product of monomethyl ether, polyoxyethylene tetramethylene glycol or polyoxyethylene tetramethylene glycol monomethyl ether with the above diisocyanates has one amine hydrogen and two hydroxyl groups such as diethanolamine. Such as glycerin, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol or sorbitol; phthalic acid, maleic acid, adipic acid or hexahydrogen. Polyester polyols obtained by an esterification reaction of at least one dicarboxylic acid selected from phthalic acid or anhydrides thereof with a diol as described above; or as described in US Pat. No. 3,919,351. As well as adducts of the above polyol compounds with cyclic caprolactones such as ε-caprolactone (however,
Excludes "polyester polyols containing a carboxylic acid having 18 to 60 carbon atoms". ). The reaction between the diisocyanate and the polyol,
The reaction should be carried out in a molar ratio such that two isocyanate groups are present in one molecule of the resulting isocyanate prepolymer. As a solvent used in the reaction, any solvent having no active hydrogen may be used. If necessary, a metallic, basic or acidic urethanization catalyst represented by di-n-butyltin dioctoate, 1,4-diazabicyclo [2.2.2] octane or boron trifluoride may be used in a conventional manner. Can be used. Furthermore, if only typical examples of the polyamine compound having at least two amino groups in one molecule described above are exemplified, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (2-aminoethyl ) Amine, 4-
Aminomethyl-1,8-diaminooctane, hydrazine,
And polyoxyalkyleneamines represented by “Jeffamine” (trademark of Texaco, USA). The reaction between the isocyanate prepolymer and the polyamine compound is performed in an aqueous medium. Such an aqueous medium means water or an aqueous solution of a solvent comprising water and a solvent soluble in water. When reacting in such a medium, a mixed solution of a polyamine compound and an aqueous medium is mixed with an isocyanate pre- There is a method of dropping a polymer solution into an aqueous dispersion, or a method of mixing an aqueous medium with an isocyanate prepolymer solution to form an aqueous dispersion and then dropping a polyamine compound. When the isocyanate prepolymer has a carboxylic acid group or a sulfonic acid group, it must be neutralized with a tertiary amine compound. When an aqueous medium is dropped into the isocyanate prepolymer solution to form an aqueous dispersion, a resin having an aqueous dispersing ability may be used. Examples of such a resin having an aqueous dispersing ability include a polycarboxylic acid amine-neutralized resin and a resin having a polyoxyethylene chain. An appropriate mixing ratio of the isocyanate prepolymer and the polyamine compound is such that the ratio of isocyanate group / amino group is 0.8 or more. By doing so, a favorable result is obtained in appearance. The urethane-urea particle dispersion synthesized by the above-described method may be subjected to azeotropic dehydration with an organic solvent that is not completely soluble in water, such as toluene, xylene, methyl isobutyl ketone or methyl amyl ketone, if necessary. ,
It may be used in such a form that it is mixed with the film-forming component and then azeotropically dehydrated with the organic solvent as described above. Urethane-urea particles (B) to the film-forming component (A)
The compounding amount of the film-forming component (A) is from 0.5 to 40 parts by weight based on 100 parts by weight of the solid content of the film-forming component (A). % Is less than 80% to 99.5% by weight of the urethane-urea particles (B), from the viewpoint of anti-sagging effect and appearance of the coating film. The resin composition of the present invention thus obtained contains, as necessary, a colorant such as an organic pigment or an inorganic pigment, a known and commonly used color separation inhibitor, an ultraviolet absorber, and various additives such as an antioxidant. Fibrous derivatives such as nitrocellulose and cellulose acetate butyrate (CAB); various resins such as chlorinated polyethylene, chlorinated polypropylene, petroleum resin or chlorinated rubber; [Examples] Next, the present invention by reference examples, examples and comparative examples,
Although described more specifically, the present invention is not limited to only these examples. In the following examples, “%” and “parts” are all based on weight unless otherwise specified. Reference Example 1 (Preparation example of vinyl resin having water dispersibility) A mixed liquid composed of 200 parts of styrene, 176 parts of methyl methacrylate, 24 parts of methacrylic acid, and 8 parts of tert-butyl peroxyoctoate was prepared. . A stirring device, a condenser, a nitrogen atmosphere flask equipped with a nitrogen inlet tube and a dropping device, charged 60 parts of the above mixed solution and 400 parts of methyl ethyl ketone, 30 minutes after maintaining at 75 ℃,
The remaining mixture was added dropwise over 5 hours, and the mixture was further reacted at the same temperature for 8 hours to obtain a target resin having a nonvolatile content of 50%, an acid value of 20, and a Gardner viscosity at 25 ° C of W. Was. Reference Example 2 (Preparation Example of Urethane-Urea Particles) The same compound as in Reference Example 1 was charged with the following compound. "Placcel 212-JI-1" [polycaprolactone diol; Mn = 1,250 manufactured by Daicel Chemical Industries, Ltd.]
178 parts, 108 parts of safflower oil-modified diol, and 186 parts of isophorone diisocyanate 120 with stirring
After the temperature was raised to ° C. and maintained for 30 minutes, 0.05 parts of di-butyltin dioctate was added, and the temperature was further maintained for 1 hour. After cooling to 80 ° C, add 500 parts of methyl ethyl ketone, 28 parts of dimethylolpropionic acid, and heat and stir at 75 ° C for 7 hours to obtain a nonvolatile content of 51%.
Thus, an isocyanate prepolymer having an acid value of 12, an isocyanate content of 1.3%, and a Gardner viscosity at 25 ° C of Z2 was obtained. Next, the mixture was stirred and mixed at a mixing ratio of 200 parts of isocyanate prepolymer and 100 parts of methyl ethyl ketone, and an aqueous solution consisting of 4.5 parts of triethylamine and 400 parts of water and an aqueous solution consisting of 1.67 parts of diethylenetriamine and 20 parts of water were gradually added dropwise. Thereafter, the mixture was stirred at 70 ° C. for 1 hour and the solvent was removed under reduced pressure to obtain a urethane-urea particle dispersion having a nonvolatile content of 26% and a particle size of 1 μm or less. This is abbreviated as A-1. Reference Example 3 (same as above) In the same apparatus as Reference Example 1, “Macromonomer HS-6” [Toa Gosei Chemical Industry Co., Ltd.
Diol having a polystyrene chain; Mn = 6,000] 117 parts Methyl ethyl ketone 370 parts Isophorone diisocyanate 88 parts Tin octenoate 0.01 parts were mixed and stirred at 80 ° C. for 2 hours.
Next, 150 parts of “Placcel 212-JI-1” were added and 3
Stirred for hours. After that, dimethylolpropionic acid
Add 20 parts and hold for 5 hours, non-volatile content 40%, acid value
An isocyanate prepolymer having a content of 10 and an isocyanate content of 0.9% was obtained. Then, the mixture was stirred and mixed at a mixing ratio of 200 parts of isocyanate prepolymer and 100 parts of ethyl ethyl ketone, and an aqueous solution consisting of 3.6 parts of triethylamine and 400 parts of water and an aqueous solution consisting of 1.67 parts of diethylenetriamine and 20 parts of water were gradually added dropwise. Next, after stirring at 70 ° C. for 1 hour, the solvent was removed under reduced pressure to obtain a urethane-urea particle dispersion having a nonvolatile content of 20% and a particle size of 1 μm or less. This is abbreviated as A-2. REFERENCE EXAMPLE 4 (same as above) In a reactor similar to Reference Example 1, 200 parts of a vinyl resin having water dispersibility and
After stirring and mixing 20 parts of "DN-950" (isocyanate prepolymer manufactured by Dainippon Ink and Chemicals, Inc.) and 80 parts of methyl ethyl ketone, an aqueous solution consisting of 4 parts of triethylamine and 400 parts of water is gradually added thereto. Then, an aqueous solution comprising 2 parts of diethylenetriamine and 20 parts of water was gradually added dropwise, and the mixture was heated to 70 ° C. and reacted for 1 hour. Thereafter, the organic solvent was removed under reduced pressure to obtain a urethane-urea particle dispersion having a nonvolatile content of 30% and a particle system of 1 μm or less. This is abbreviated as A-3. Examples 1 to 5 and Comparative Examples 1 to 3 Using each of the resin solutions obtained in Reference Examples 2 to 4, coating materials were prepared at the compounding composition ratios shown in Table 1 and spray-coated separately. The results of the sagging limit film thickness and the appearance of each coating film are shown in the same table.

[Table 1] [Effects of the Invention] As described above, the resin composition of the present invention can achieve, in particular, a thick film, and can control sagging.
From a place where it is extremely useful, for general baking such as for home appliances, for exteriors such as buildings, tiles or coil coatings such as PCM, or for automobiles, in particular, as enamel paint or clear paint for automobiles ,
Further, it can be used for surface protection of porous materials such as glass, ceramic products, foamed concrete and woodwork products.

Claims (5)

(57) [Claims] 1. A resin composition comprising (A) a film-forming component comprising a resin capable of forming a coating film and (B) crosslinked urethane-urea particles as essential components. The cross-linked urethane-urea particles (B) comprise 99.5 to 80% by weight of the water-soluble component (A) and 0.5 to less than 20% by weight of the cross-linked urethane-urea particles (B). A diisocyanate having a group,
An isocyanate prepolymer (B1) having at least two isocyanate groups in one molecule obtained by reacting a polyol having at least two hydroxyl groups in one molecule (B1) (provided that a carboxylic acid having 18 to 60 carbon atoms is used. The same applies to the following.) And a polyamine compound (B2) having at least two amino groups in one molecule in an aqueous medium. A resin composition characterized by being obtained. 2. A crosslinked urethane-urea particle (B) comprising a polyol having a carboxylic acid group or a carboxylic acid group and a sulfonic acid group in at least one of polyols having at least two hydroxyl groups in one molecule. 2. The resin composition according to claim 1, wherein the resin composition is obtained by using a polyol having an amine salt or a metal salt and then reacting an isocyanate prepolymer with a polyamine compound. object. 3. A crosslinked urethane-urea particle (B) obtained by using a polyol having a polyoxyethylene chain as at least one of polyols having at least two hydroxyl groups in one molecule. The resin composition according to claim 1, wherein: 4. The crosslinked urethane-urea particles (B) are obtained by using a resin acid monoglyceride as at least one of polyols having at least two hydroxyl groups in one molecule. The resin composition according to claim 1, wherein 5. A film-forming component (A) comprising a combination of a hydroxyl group-containing resin and a melamine resin or a combination of a hydroxyl group-containing resin and a polyisocyanate. 5. The resin composition according to any one of the above items 4.