JPH0670103B2 - Method for producing polyisocyanate compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyisocyanate compound, more specifically, a polyisocyanate compound composed of a polyisocyanate and a vinyl polymer, which is particularly suitable for paints. The present invention relates to a manufacturing method of.

[Conventional technology]

Since the initial drying property of the polyurethane-based paint is slow depending on the application, improvement has been demanded and various studies have been made. For example, the method of adding a catalyst to the polyisocyanate compound can improve the drying property, but is not practical because the storage stability is lowered. Further, a method of introducing an isocyanurate group into a polyisocyanate compound is widely used, but improvement in initial drying property is not sufficient.

[Problems to be solved by the invention]

The present inventor has conducted various studies on organic polyisocyanates in order to improve the initial drying property. As a result, a vinyl monomer is polymerized into a reaction product of the organic polyisocyanate and a compound having a hydroxyl group and an unsaturated group in one molecule. The inventors have found that the method for producing the obtained polyisocyanate compound has excellent initial drying property, and have reached the present invention.

[Means for solving problems]

That is, in the present invention, an organic polyisocyanate and a compound having a hydroxyl group and an unsaturated group in one molecule are used in an NCO group / active hydrogen equivalent ratio of 3/1 to 20/1.
Then, 10 parts by weight to 200 parts by weight of the vinyl monomer (B) is added to 100 parts by weight of the reaction product (A) obtained by reacting at 60 ° C. to 150 ° C. for 1 to 6 hours at 60 ° C. to 150 ° C. in 30 minutes~
A method for producing a polyisocyanate compound, which comprises polymerizing for 5 hours. The polyisocyanate compound according to the present invention is characterized in that it has improved initial drying properties, good compatibility with other components such as acrylic polyols, and excellent storage stability.

As the organic polyisocyanate used in the present invention, all the isocyanates used for polyurethane coatings can be used. For example, an adduct of tolylene diisocyanate and trimethylol propane, a trimer of tolylene diisocyanate, an adduct of hexamethylene diisocyanate and trimethylol propane, a trimer of hexamethylene diisocyanate, an NCO group-terminated prepolymer with polyisocyanate and a polyol. and so on.

The compound having a hydroxyl group and an unsaturated group in one molecule used in the present invention (hereinafter abbreviated as a hydroxyl group-containing unsaturated compound) is
For example, 2-hydroxyethyl methacrylate, allyl alcohol, oleyl alcohol, ethylene glycol maleate and the like. These are compounds having one or more hydroxyl groups and one or more unsaturated groups in one molecule.

The reaction between the organic polyisocyanate of the present invention and the hydroxyl group-containing unsaturated compound is carried out at an NCO group / active hydrogen equivalent ratio of 3/1 to 20/1,
The reaction can be performed under the conditions of a reaction temperature of 30 to 120 ° C. and a reaction time of 1 to 6 hours. The equivalence ratio can be selected according to the molecular weight of the both and the number of functional groups. In this case, the equivalence ratio is 3 /
If it is less than 1, the toughness is insufficient when formed into a coating film, which is not preferable. On the other hand, when it exceeds 20/1, the vinyl polymer in the obtained polyisocyanate compound is more likely to be separated, which is not preferable.

The vinyl monomer used in the present invention is, for example, methyl methacrylate, methyl acrylate, butyl methacrylate, acrylonitrile, styrene, maleic anhydride, N-vinyl-2-pyrrolidone or the like. These can be used alone or as a mixture of two or more kinds.

The blending ratio of the reaction product (A) of the organic polyisocyanate of the present invention and the hydroxyl group-containing unsaturated compound and the vinyl monomer (B) is 10 to 200 parts by weight of (B) with respect to 100 parts by weight of (A). The polymerization of these A and B can be carried out in the same manner as the ordinary vinyl polymerization reaction. In the polymerization, commonly used solvents can be used. As a solvent,
For example, butyl acetate, toluene, xylene and the like can be used. This reaction condition can be carried out at a reaction temperature of 60 to 150 ° C. and a reaction time of 30 minutes to 5 hours. In this case, 10 parts by weight of the reaction product (A) was used to add 10 parts of vinyl monomer.
When the amount is less than the amount by weight, the proportion of the vinyl polymer in the polyisocyanate composition is too small to improve the initial drying property of the coating film. Also, vinyl monomer
If it exceeds 200 parts by weight, the viscosity of the polyisocyanate compound becomes high, the workability is deteriorated, and the proportion of polyurethane in the coating film becomes low, so that the characteristics of polyurethane are not exhibited, which is not preferable.

The method for producing the polyisocyanate compound of the present invention is preferably a method in which the polyisocyanate compound and a hydroxyl group-containing unsaturated compound are subjected to a urethanization reaction, and then a vinyl monomer is added to carry out polymerization. As another method, a vinyl monomer may be added to a mixture of an organic polyisocyanate and a hydroxyl group-containing unsaturated compound to carry out the urethanization reaction and the vinyl polymerization at the same time. It is also possible to add a vinyl monomer to the hydroxyl group-containing unsaturated compound to carry out vinyl polymerization first, and then add an organic polyisocyanate to carry out the urethanization reaction. All the commonly used additives can be mixed with the polyisocyanate compound of the present invention. For example, antioxidants,
Examples include UV absorbers, pigments, fillers, plasticizers, antifungal agents, and modifiers.

The resin of the present invention can be used not only for paints but also for adhesives, ink binders and the like.

〔Example〕

Next, the present invention will be described in more detail with reference to examples. In the examples, "parts" and "%" represent "parts by weight" and "% by weight" unless otherwise specified.

Example 1. In a 500 ml four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, hexamethylene diisocyanate trimer (Nippon Polyurethane Industry Co., Ltd., Coronate EH) NCO
The content of 21.3%, 111.7 g, 1.4 g of 2-hydroxyethyl methacrylate and 59.8 g of butyl acetate are weighed and mixed by heating while flowing nitrogen gas. Reaction was carried out at 80 ° C. for 1 hour to obtain a reaction product (A). To this, 26.5 g of methyl methacrylate and Percure O as vinyl monomer (B) components
(Nippon Oil and Fats Co., Ltd., aliphatic peroxide catalyst, dimethyl phthalate 50% solution) A mixture of 0.6 g is added dropwise at 90 ° C. over 15 minutes. After completion of dropping, the reaction was completed by heating at 110 ° C. for 1 hour and 30 minutes. This polyisocyanate compound has an NCO content of 12.0.
%, Nonvolatile content 69.4%, viscosity 3100 cP / 25 ° C. 4.6 g of this polyisocyanate resin Acrydec A-801 (acrylic polyol manufactured by Dainippon Ink and Chemicals, hydroxyl value 50 mg
KOH / g, non-volatile content 50 g) 13.5 g, and butyl acetate 1.8 g were weighed in a beaker and mixed to obtain a coating composition liquid. This compounded solution was applied on a glass plate in an atmosphere of 25 ° C. to a thickness of 70 μm. As a result of measuring the finger catalyst drying time, it was 12 minutes.

Comparative Example 1. A coating solution was prepared using a trimer of hexamethylene diisocyanate (same as in Example 1). Acrydeck A
-801 14.4g, Coronate EH 2.8g and Butyl acetate 2.8g
Were weighed into a beaker and mixed. This compounded solution was applied on a glass plate in an atmosphere of 25 ° C. to a thickness of 70 μm. As a result of measuring the touch dry time, it was 16 minutes.

Example 2. In a flask equipped with the same equipment as in Example 1, hexamethylene diisocyanate trimer (same as Example 1) 111.7
g, 1.4 g of 2-hydroxyethyl methacrylate and 59.8 g of butyl acetate are weighed and mixed by heating while flowing a nitrogen gas. Reaction was carried out at 80 ° C. for 1 hour to obtain a reaction product (A). To this, a mixture of 26.5 g of styrene and 0.6 g of Percure O was added dropwise at 90 ° C over 15 minutes. 110 ° C for 1 hour after completion of dropping 3
The reaction was completed by heating for 0 minutes. The reaction product was filtered using a 200-mesh wire net, NCO content 12.1%, non-volatile content 68.9
%, A polyisocyanate compound having a viscosity of 1700 cP / 25 ° C. was obtained. 4.6 g of this polyisocyanate compound, 13.5 g of Acrydec A-801 and 1.8 g of butyl acetate were weighed in a beaker and mixed to obtain a coating composition liquid. This compounded solution was applied onto a glass plate at a thickness of 7 μm in an atmosphere of 25 ° C., and the touch-drying time was measured, and the result was 13 minutes.

Example 3. A trimethylolpropane adduct of tolylene diisocyanate (Nippon Polyurethane Industry Co., Ltd., Coronate L) with an NCO content of 13.0 was placed in a flask equipped with the same equipment as in Example 1.
%, 119.7 g, 2-hydroxyethyl methacrylate 1.
Weigh 5 g and 49.8 g of butyl acetate, and mix with heating while flowing nitrogen gas. The reaction product (A) was obtained by reacting at 60 ° C. for 1 hour and 30 minutes. 28.4g of methyl methacrylate
And 0.6 g of Vercure O are added dropwise at 80 ° C. over 30 minutes. After completion of the dropping, the reaction was completed by heating at 90 ° C. for 1 hour. This polyisocyanate compound has an NCO content of 8.0% and a nonvolatile content.
The viscosity was 55.8% and the viscosity was 45 cP / 25 ° C. 6.7 g of this polyisocyanate compound and 13.5 g of Acrydeck A-801 were weighed in a beaker and mixed to obtain a coating composition liquid. This compounded solution was applied onto a glass plate at a thickness of 70 μm in an atmosphere of 25 ° C., and the touch-drying time was measured, and the result was 6 minutes.

Comparative Example 2. A trimethylolpropane adduct of tolylene diisocyanate (same as in Example 3) was used to prepare a coating composition liquid. Acrydec A-801 13.6g, Coronate L4.3g
And 2.1 g of butyl acetate were weighed in a beaker and mixed.
This compounded solution was applied onto a glass plate at a thickness of 70 μm in an atmosphere of 25 ° C., and the touch-drying time was measured, and it was 10 minutes.

〔The invention's effect〕

The polyisocyanate compound of the present invention can improve the initial drying property when used as a raw material for a moisture-curable coating material, a two-component mixed coating material, etc., and can be used for coating materials in various fields. For example, it can be used as a paint for woodwork, a paint for plastics, a paint for metals, and the like.

Claims (1)

[Claims] 1. An organic polyisocyanate and a compound having a hydroxyl group and an unsaturated group in one molecule at an NCO group / active hydrogen equivalent ratio of 3/1 to 20/1 at 60 ° C. to 150 ° C. for 1 hour to 6 hours. 100 parts by weight of the reaction product (A) obtained by the reaction, 10 parts by weight to 200 parts by weight of the vinyl monomer (B) at 60 ° C to 150 ° C
A method for producing a poisocyanate compound, comprising polymerizing for 30 minutes to 5 hours.