JP3348389B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin which is low in toxicity, excellent in workability and weatherability, and which is composed of a polyisocyanate having an isocyanurate ring and which is extremely useful in the industrial fields such as paints, adhesives and molding materials. It relates to a composition.

[0002]

2. Description of the Related Art Alkylene diisocyanates, which are known as non-yellowing diisocyanates, and polyisocyanates derived from cycloalkylene diisocyanates, which are curing agents for polyurethane resins having excellent mechanical properties such as abrasion resistance and chemical resistance, are known. Good weather resistance and durability,
In particular, the polyisocyanate having an isocyanurate ring, which is a polyisocyanate having a high chemical stability of the isocyanurate ring, is known to be a curing agent particularly excellent in weather resistance and durability.

However, isocyanurate-type polyisocyanates generally have a strong odor due to the high polarity of the isocyanurate ring, and are used after being dissolved in an organic solvent such as ethyl acetate, toluene, or xylene, which is a polar solvent having a strong dissolving power. And there were practical problems in terms of working environment, pollution, performance, and the like.

In other words, when referring to a more specific application, for example, a paint, the polyisocyanate used in the conventional two-pack type urethane paint must use a highly polar solvent. In addition to being subject to strong odor pollution, there is always a risk of lifting of the old coating film in repair painting or the like, which has caused a great problem in practical use.

Therefore, as a method for solving problems in terms of working environment, pollution, performance, and the like, Japanese Patent Publication No. Sho 62-5196 has been proposed.
As proposed by the present inventors in Japanese Patent Publication No. 8, polyisocyanates having low odor, low dissolving power, and low solubility in non-polar solvents such as mineral terpen having low toxicity have been developed.

As a typical method proposed in the above publication, an alkylene diisocyanate is converted to isocyanurate in the presence of an alkylene diol having a long-chain hydrocarbon group to obtain a long-chain hydrocarbon group. By incorporating an alkylene diol into an isocyanurate-type polyisocyanate, the polarity of the polyisocyanate is reduced, and a polyisocyanate having solubility in a nonpolar solvent is produced.

However, the non-polar solvent-soluble polyisocyanate obtained by such a method is linked by a diol residue having a long-chain hydrocarbon group in the main chain.
Because the skeleton of the resin is soft and the softening point is low, preparing a coating film by combining such a polyisocyanate with the polyol of the base material generally causes slow drying, and adhesion of dust and the like to the coating film surface during the drying of the coating film. In addition to being easily caused, the cured coating film is also soft and has a tendency to cause stains. In particular, when the softening point of the polyol used as the main agent is low, this tendency becomes more remarkable.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the above-mentioned drawbacks, solve problems in working environment, pollution, performance, etc., and provide a non-polar material which is excellent in drying property and hardly causes lifting. An object of the present invention is to provide a solvent-soluble isocyanurate ring-containing polyisocyanate resin composition.

[0009]

Accordingly, the present inventors aimed at the above-mentioned problems and introduced a structure having a long-chain hydrocarbon group in the side chain to the isocyanurate ring-containing polyisocyanate, thereby obtaining a non-isocyanate. The present invention was completed by obtaining an isocyanurate ring-containing polyisocyanate resin composition having excellent solubility in a polar solvent and excellent drying properties.

That is, the present invention relates to an isocyanurate type polyisocyanate (A) derived from a non-yellowing type organic diisocyanate (a) having 6 to 15 carbon atoms, and a polyol in which a fatty acid is linked to a polyhydric alcohol by an ester bond. The present invention relates to a resin composition comprising an isocyanurate ring-containing polyisocyanate (C) obtained by using (B) as an essential component, and a nonpolar organic solvent.

Hereinafter, the present invention will be described in more detail. As the non-yellowing organic diisocyanate having 6 to 15 carbon atoms (a) used in the present invention, any alkylene diisocyanate having 6 to 15 carbon atoms and any cycloalkylene diisocyanate can be used, C6-C15 cycloalkylene diisocyanate is more preferred.

Representative examples of cycloalkylene diisocyanate include isophorone diisocyanate,
Hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Examples thereof include 1,3- or 1,4-diisoanatocyclohexane, and among them, isophorone diisocyanate is particularly preferable because it is easily available and easily manufactured.

Further, as the alkylene diisocyanate which is a kind of non-yellowing type organic diisocyanate, for example, 1,6-hexamethylene diisocyanate, 1,1
Examples thereof include 2-dodecamethylene diisocyanate and 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate. In addition, xylylene diisocyanate, m-
Alternatively, a diisocyanate such as p-tetramethylxylene diisocyanate can be used.

The above-mentioned alkylene diisocyanate and araliphatic diisocyanate may be used in combination with cycloalkylene diisocyanate which is a more preferable non-yellowing type organic diisocyanate in the present invention.

The term "isocyanurate-type polyisocyanate" as used in the present invention means an isocyanate prepolymer having an isocyanurate ring and having an isocyanate group at the terminal. It is intended to mean an isocyanate prepolymer obtained by isocyanurating a compound.

The polyol (B), which is one of the constituent elements of the present invention and in which a fatty acid is linked to a polyhydric alcohol by an ester bond, refers to glycerin, trimethylolethane, trimethylolpropane, pentaerythrol and the like. It means a bifunctional or higher functional polyol having a structure in which a fatty acid is bonded to a polyhydric alcohol by an ester bond.

More specifically, for example, a condensation reaction between a fatty acid having 12 or more carbon atoms and the above-mentioned polyhydric alcohol having a short carbon number in the main chain, or a transesterification reaction between animal and vegetable oils and a polyhydric alcohol, etc. What you can get. As used herein, animal and vegetable oils include beef tallow, lard, cottonseed oil, rapeseed oil, castor oil, coconut oil, linseed oil, palm kernel oil, safflower oil, soybean oil, tung oil, dehydrated castor oil, and the like.

The fatty acids referred to herein are caprylic acid,
Long-chain organic fatty acids having 12 or more carbon atoms such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, and eleostearic acid, and an unsaturated double bond in the molecule May be a fatty acid having

However, if the number of unsaturated double bonds in the molecule is too large, oxidative polymerization is liable to occur and the storage stability of the polyisocyanate of the present invention is unpreferably deteriorated. Therefore, stearic acid composed of a saturated hydrocarbon and oleic acid having one unsaturated double bond in the molecule are particularly preferably used. For animal and vegetable oils, monoglyceride obtained from soybean oil containing a large amount of oleic acid is particularly preferably used.

The monoglyceride (B) used in the present invention has a molecular weight of 150 to 2,000, preferably 300.
~ 1,000. Monoglycerides of high purity obtained by distilling and purifying these are particularly preferable because the isocyanurate ring-containing polyisocyanate (C) of the present invention is easily dissolved in a nonpolar organic solvent.

The method for producing the isocyanurate ring-containing polyisocyanate (C) of the present invention includes the following two methods.

The first method is a method of subjecting an isocyanurate type polyisocyanate (A) derived from a diisocyanate compound and a polyol (B) to urethanation reaction to obtain a desired isocyanurate ring-containing polyisocyanate (C). It is.

In the second method, the diisocyanate compound (a) and the polyol (B) are reacted in the presence of an isocyanurate-forming catalyst such as quaternary ammonium carboxylate, and the desired isocyanurate ring-containing polyisocyanate (C ).

Further, the non-polar organic solvent which is one of the components of the present invention refers to an aniline point containing an aliphatic and / or naphthenic organic solvent having a aniline point of 10 to 70 ° C, preferably 12 to 65 ° C. It is a non-toxic organic solvent with low toxicity and low solubility.

Representative examples of such non-polar organic solvents include the following. : House (manufactured by Shell Chemical Co., Ltd., aniline point 15 ° C.), Swazole 310
(Manufactured by Maruzen Oil Co., Ltd., aniline point 16 ° C.) 6 (manufactured by Exxon Chemical Co., Ltd., aniline point 4
3 ° C),

Loose (manufactured by Shell Chemical Co., Ltd., aniline point: 44 ° C.), Essonafusa No. 5 (manufactured by Exxon Chemical Co., Ltd., aniline point 55 ° C), petroleum hydrocarbon organic solvents such as Vegasol (manufactured by Mobil Oil Co., Ltd., aniline point 55 ° C), and methylcyclohexane (aniline point 40 ° C), ethyl Cyclohexane (aniline point: 44 ° C.) and the like can also be mentioned.

The resin composition of the present invention is prepared by mixing the isocyanurate ring-containing polyisocyanate (C) obtained by the above-mentioned method and a non-polar organic solvent as constituents. It is obtained by mixing the ring-containing polyisocyanate (C) and the non-polar organic solvent in an arbitrary ratio of 10/90 to 90/10.

The resin composition of the present invention means a resin composition comprising the above-mentioned isocyanurate ring-containing polyisocyanate and a non-polar organic solvent as essential components,
It not only includes the isocyanurate ring-containing polyisocyanate and the non-polar organic solvent as components, but also includes a composition containing a polyol (solution) as a main component of a polyurethane resin, further, a filler, an additive, and the like as further components. .

The main polyol of the urethane resin described above is a polyol having two or more hydroxyl groups in one molecule. The present invention is a polyol having compatibility with the resin composition. For example, alkyl polyols, alkyd polyols, acrylic polyols, polybutadiene polyols and the like can be mentioned as examples.

In practical use, the present invention also includes a composition which is put to practical use in the form of a composition comprising the above-mentioned isocyanurate ring-containing polyisocyanate (C) and a non-polar organic solvent to which a polar organic solvent is added. . Further, as a special case, the isocyanurate ring-containing polyisocyanate (C) of the present invention is dissolved in a polar organic solvent, and the polyol is dissolved in a non-polar organic solvent.
Resin compositions in the case of mixing and using immediately before practical use are also included in the present invention.

In this case, the content of the polar organic solvent contained in the resin composition of the present invention is preferably 35% or less, preferably 20% or less, more preferably 10% or less of the total organic solvent. Necessary in order not to impair the effect.

Examples of the polar organic solvent include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as butyl cellosolve acetate, and low molecular weight aromatics such as xylene. It is an organic solvent that is generally called a polar organic solvent, including a system solvent.

When the resin of the present invention is put to practical use, the working environment is remarkably improved, the pollution is reduced, and the performance is reduced as compared with the case where a conventional highly toxic polar organic solvent is used. Significant improvement is also possible. That is, for example, in the case of applying a coating that is easily attacked by a polar organic solvent to a formed material, or when repairing the coating, the coating made of the resin composition of the present invention is seen when a coating containing a polar organic solvent is applied. Gives a smooth, good commercial value coating film with no lifting.

[0034]

Next, the present invention will be described more specifically with reference to examples. In the following, all parts and percentages are by weight unless otherwise specified.

Example 1 A three-liter glass four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, an air cooling tube, and a thermometer was placed under a nitrogen gas atmosphere in a VESTANAT-T.
1890/100 (manufactured by Daicel Huels Co., Ltd .: IP
1530.0 g of DI isocyanurate-type polyisocyanate, isocyanate content = 17.0%). 66.0 (Exxon Chemical Co., Ltd., petroleum hydrocarbon solvent aniline point 43 ° C.) was charged in an amount of 966.0 g, and the temperature was raised to 50 ° C. with stirring.

In this solution, Sunsoft 8000 (manufactured by Taiyo Chemical Co., Ltd .: monoglyceride palmitate / monoglyceride stearate = 1/1, purity of 90% or more) 2
70.3 g was added, and the temperature was gradually raised to 130 ° C. while stirring. After maintaining at 130 ° C. for 3 hours, the temperature was lowered to room temperature to terminate the reaction, and 2766.0 g of a transparent polyisocyanate solution as a target resin composition was obtained.

The resulting polyisocyanate solution had a nonvolatile content of 65.5%, Gardner viscosity Z4-Z5 ^3, Gardner color number of 1 or less, a 7.0% content of isocyanate group, a diluting solvent Essonafusa No. The dilution ratio for 6 is 1
000% or more.

This polyisocyanate solution and Veccosol J-557 (manufactured by Dainippon Ink and Chemicals, Inc .: safflower oil-modified medium-oil alkyd resin, catalog specification properties;
Non-volatile content = 50 ± 1%, Solvent = Swazole 310, Phthalic acid content = 30%, Oil = Safflower oil, Oil length 51%,
Viscosity = V to X, number of colors = 7 or less, acid value = 8 or less, measured hydroxyl value = 60), NCO / OH = 1/1, and equivalent amounts of Esonaphtha No. 6 was added thereto, and a resin varnish adjusted to have a nonvolatile content of 50% was applied on a glass plate. Further, when the coated film was touched, the dry time to touch, which is the time until fingerprints did not adhere to the coated film, was measured and found to be 40 minutes.

(Example 2) Using the same reactor as in Example 1, VESTANAT-T1890M (manufactured by Daicel Huls Co., Ltd .: IPDI isocyanurate type polyisocyanate, isocyanate content = 12.0%, nonvolatile content = 70) %, Solvent = mineral spirit)
0.0 g, Essonafusa No. 6 (manufactured by Exxon Chemical Co., Ltd., petroleum hydrocarbon solvent aniline point 43 ° C).
When 3 g was charged and the temperature was raised to 50 ° C. while stirring, the contents of the flask became a homogeneous liquid.

150.0 g of Exel O-95R (manufactured by Kao Corporation: monoglyceride oleate, purity: 93% or more) was added to the solution, and the temperature was gradually raised to 130 ° C. with stirring. After maintaining at 130 ° C. for 3 hours, the temperature was lowered to room temperature to terminate the reaction, and 1644.3 g of a transparent polyisocyanate solution as a target resin composition was obtained.

The obtained polyisocyanate solution had a nonvolatile content of 70.1%, a Gardner viscosity of Z ₅ -Z ₆ , a Gardner color number of 1 or less, and an isocyanate group content of 7.5%.
Diluent solvent Esonaphtha No. The dilution ratio for 6 is 100
It was confirmed that it was 0% or more.

The polyisocyanate solution and Veccosol J-557 were blended in equal amounts so that NCO / OH = 1/1. 6 was added thereto, and a resin varnish adjusted to have a nonvolatile content of 50% was applied on a glass plate. The dry time to touch of the coated film was measured and found to be 3
5 minutes.

(Comparative Example 1) Using the same reactor as in Example 1, Burnock DN-980S (manufactured by Dainippon Ink and Chemicals, Inc .: isocyanurate type polyisocyanate)
Isocyanate content = 21.0%) to 1500.0
g, Essonafusa No. 6 (manufactured by Exxon Chemical Co., Ltd.
857.1 g of petroleum hydrocarbon solvent (aniline point 43 ° C.)
When the temperature was raised to 50 ° C. while charging and stirring, the contents of the flask became a homogeneous liquid.

To this solution, 501.0 g of Sobamol J-900 (manufactured by Henkel Co., Ltd .: hydrogenated oleyl alcohol dimer, hydroxyl value = 210) was charged, and the temperature was gradually raised to 130 ° C. with stirring. After maintaining at 130 ° C. for 3 hours, the temperature was lowered to room temperature to complete the reaction. In this way, 2857.1 g of a transparent polyisocyanate solution as the target resin composition of the present invention was obtained.

The resulting polyisocyanate solution had a nonvolatile content of 70.1%, a Gardner viscosity of ZZ ₁ , a Gardner color number of 1 or less, and an isocyanate group content of 8.3%.
Diluent solvent Esonaphtha No. The dilution ratio for 6 is 100
It was confirmed that it was 0% or more.

This polyisocyanate solution and Veccosol J-557 were blended in equal amounts so that NCO / OH = 1/1. 6 was added thereto, and a resin varnish adjusted to have a nonvolatile content of 50% was applied on a glass plate.
The touch drying time of the coated film after application was measured and was 5 hours.

According to the present invention, the working environment is remarkably improved as compared with the case where a conventional highly toxic polar organic solvent is used.
A resin that gives a smooth, high-commercial coating without lifting when it is applied to a material that has low pollution and is easily eroded by polar organic solvents. A composition can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-209124 (JP, A) JP-A-2-250872 (JP, A) JP-A-2-105812 (JP, A) (58) Field (Int. Cl. ⁷ , DB name) C08G 18/00-18/87

Claims (7)

(57) [Claims] 1. An isocyanurate-type polyisocyanate (A) derived from a non-yellowing organic diisocyanate (a) having 6 to 15 carbon atoms, and a polyol (B) in which a fatty acid is linked to a polyhydric alcohol by an ester bond. A resin composition comprising an isocyanurate ring-containing polyisocyanate (C) obtained as an essential component and a non-polar organic solvent. 2. The resin composition according to claim 1, wherein the non-yellowing organic diisocyanate having 6 to 15 carbon atoms (a) is a cycloalkylene diisocyanate having 6 to 15 carbon atoms. 3. The resin composition according to claim 1, wherein the non-yellowing organic diisocyanate having 6 to 15 carbon atoms (a) is isophorone diisocyanate having 6 to 15 carbon atoms. 4. The resin composition according to claim 1, wherein the polyol (B) in which a fatty acid is linked to a polyhydric alcohol by an ester bond is a monoglyceride obtained by addition-condensing a fatty acid to glycerin. 5. The polyol (B) in which a fatty acid is linked to a polyhydric alcohol by an ester bond is a monoglyceride in which a long-chain fatty acid having 12 or more carbon atoms is added and condensed to glycerin. The resin composition as described in the above. 6. The resin composition according to claim 1, wherein the polyol (B) in which a fatty acid is linked to a polyhydric alcohol by an ester bond is monoglyceride of stearic acid. 7. The resin composition according to claim 1, wherein the polyol (B) in which a fatty acid is linked to a polyhydric alcohol by an ester bond is oleic acid monoglyceride.