JPH06279562A - Urethane oil composition - Google Patents

Abstract

(57) [Summary] [Structure] Dry or semi-dry oils and / or their fatty acids (A), oxycarboxylic acids such as dimethylolpropionic acid (B), other hydroxyl compounds (C), and organic isocyanate compounds ( A urethanized oil composition containing a urethanized oil obtained by reacting D) with a chain extender (E) as a main component. [Effect] The urethanized oil composition of the present invention is water-based, environmentally friendly, and nonflammable at room temperature, so there is little risk of fire, the coating film has good dryness and a long-lasting feeling, and is coated. It has excellent workability when brushing and sagging, and has excellent storage stability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful urethanized oil composition having excellent hydrolysis stability. More specifically, a drying oil and / or a fatty acid thereof, an oxycarboxylic acid, and an organic isocyanate compound in excess of the hydroxyl groups of this carboxylic acid are reacted with each other, and then dispersed in water to form a residual isocyanate group. The present invention relates to a urethanized oil composition which is obtained by reacting with an extender and has extremely excellent hydrolysis stability.

[0002]

2. Description of the Related Art In recent years, conversion from organic solvent-based paints to water-based paints has been urgently required due to ignition and explosion of organic solvents in paints, air pollution, occupational safety and hygiene problems.

Diglyceride obtained by transesterifying a drying oil,
The so-called urethane oil obtained by addition reaction of monoglyceride with isocyanate is required to have air-curing property, drying property, coating workability, smoothness of coated surface and feeling of flesh.
For this purpose, a drying oil and / or a semi-drying oil modified medium-long oil urethane-forming oil is mainly used as the urethane-forming oil.

However, when this urethane oil is used,
The ester bond is hydrolyzed by water, resulting in poor drying properties and storage stability. In particular, urethane oil is used for indoor and outdoor buildings,
Since it is widely used in various fields, it is often stored at the site of use and temperature control is difficult. Particularly in the summer, the storage location is often high in temperature, which easily causes significant hydrolysis, resulting in difficulty in water-solubilization, and improvement thereof has been demanded.

Therefore, various methods have been proposed. For example, the method disclosed in Japanese Examined Patent Publication No. 59-41664 is a method having a remarkable effect on improving the hydrolysis stability.

However, although this method can produce a urethanized oil having a relatively low molecular weight, it is difficult to produce a urethanized oil having a high molecular weight. That is, unless the urethanization reaction is carried out at a relatively low temperature, the allophanate reaction causes gelation or marked coloring. For this reason 100 ° C
It is necessary to carry out in the range of 60 to 80 ° C. more preferably below, but it is difficult to stir if the reaction is carried out with an increased molecular weight, so that the molecular weight could not be increased. Further, according to the above method, there is a drawback that a wrinkle pattern is likely to be formed on the coating film due to the dryness.

[0007]

In view of the present situation, the present inventors have found that the present invention is a urethane-based resin which is air-curable, has good coating workability, smoothness of the coated surface, good feeling of flesh, and excellent hydrolysis stability. Intensive research was started to develop an oil composition.

Therefore, the problem to be solved by the present invention is
Like mid-long oil alkyd resin modified with drying oil and / or semi-drying oil, it is air-curable, has good coating workability, has excellent smoothness of the coated surface, has a feeling of flesh, and can be dried by drying on the coating film. It is an object of the present invention to provide a urethanized oil composition that hardly causes wrinkle patterns and has extremely excellent hydrolysis stability.

[0009]

Therefore, as a result of intensive studies conducted by the inventors of the present invention, the drying oil or the semi-drying oil and / or their fatty acids, oxycarboxylic acids, and Other hydroxy compounds, a terminal isocyanate prepolymer obtained by reacting with an organic isocyanate is dispersed in water, and by reacting the isocyanate group of the remaining organic isocyanate compound with a chain extender, extremely hydrolytic stability is achieved. It was found that an excellent urethanized oil composition can be obtained, and the present invention has been completed.

That is, the present invention comprises a drying oil and / or a fatty acid (A) thereof, an oxycarboxylic acid (B), another hydroxyl compound (C), an organic isocyanate compound (D) and a chain extender (E). The present invention relates to a urethanized oil composition containing a urethanized oil obtained by the reaction as a main component.

The polyurethane oil of the present invention is mainly composed of a urethane bond which is difficult to be hydrolyzed, and the ester bond of a portion which is easily hydrolyzed is a carboxyl group of a drying oil and / or a semi-drying oil and a polyhydric alcohol. Only the connecting part with. It is well known that the hydrolysis of this ester bond in water is apt to undergo hydrolysis by the acid or alkali catalyst due to the antimeric effect due to the ester bond adjacent to the carboxyl group. The urethanized oil of the present invention is particularly excellent in hydrolysis stability because the bond adjacent to the carboxyl group is a urethane bond and there is no ester bond adjacent to the carboxyl group. In addition, since the polymer has a high molecular weight after being dispersed in water by the chain extender, the high molecular weight can be easily achieved, the drying property is fast, and it is possible to obtain a coating film which is free from wrinkles due to top drying.

The amount of the drying oil of the present invention and / or the fatty acid (A) thereof used is not particularly limited, but it is preferably used in the range of 10 to 70% by weight. If the amount used is 10% by weight or less, the air-curable double bond for ensuring the necessary air-curability cannot be secured, and if it is 70% by weight or more, a resin design that secures the carboxyl groups and the like necessary for water solubilization Is difficult to do, which is not preferable. More preferably 20-60
It is better to use it in the range of wt%.

The fats and oils of the present invention undergo a transesterification reaction with a polyhydric alcohol. For example, the drying oil and / or the semi-drying oil is 200 to 250 ° C., 10 to 10 ° C. under a nitrogen gas reflux while being well stirred with at least one or more polyhydric alcohol.
Hold for 100 minutes. If necessary, a low molecular weight alkyd resin obtained by subsequently adding a polybasic acid, a polyhydric alcohol and the like and then reacting at 200 to 250 ° C. may be used. At this time, a catalyst may be added in an extremely small amount to react. Examples of the catalyst include basic catalysts such as sodium hydroxide, potassium hydroxide, sodium acetate, lithium acetate and lithium hydroxide. The hydroxyl value of the obtained resin solution is preferably 30 to 250.

It can also be obtained by the so-called fatty acid method, which is produced by keeping the fatty acid of the oil and fat and the polyhydric alcohol at 180 to 250 ° C. for 2 to 6 hours with good stirring. In this case, if necessary, it can be produced under reflux of an organic solvent such as xylene or toluene.

Fats and oils that can be used in the present invention are drying oil and semi-drying oil. As the drying oil and / or the fatty acid (A) thereof, a drying oil such as flaxseed oil, tung oil, dehydrated castor oil, soybean oil, rice oil, safflower oil, sunflower oil, and sardine seed oil,
Semi-drying oils and polymerized oils thereof, and fatty acids thereof are included.

Polyhydric alcohols that can be used include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol having a number average molecular weight of 150 to 6000, polypropylene glycol, neopentyl glycol, diethyl propane diol, ethyl butyl. Propane diol, cyclohexane dimethanol, butylene glycol, pentane diol, hexane diol, hydrogenated bisphenol A, ethylene glycol adduct of bisphenol A, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol and other polyhydric alcohols. .

Further, usable fatty acids include phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, succinic acid, adipic acid, sebacic acid, benzoic acid, alkylbenzoic acid, maleic anhydride, It is possible to use one kind or several kinds of monovalent and polyvalent carboxylic acids such as itaconic anhydride and fumaric acid, and to use them in an arbitrary ratio.

The oxycarboxylic acid (B) used as an essential component in the present invention is not particularly limited, but for example, 1,2-hydroxystearic acid, ricinoleic acid, dimethylolpropionic acid, hydroxybivalic acid, lactic acid, Examples include apple acid, tartaric acid, and the like. The amount of the oxycarboxylic acid used is not particularly limited, but it is preferable to use 3 to 25% by weight in order to secure the carboxyl group necessary for making the aqueous solution. It is necessary to secure an amount of 5 to 70 in terms of acid value. When the acid value is 5 or less, it is often difficult to secure the water dispersion stability even if other hydrophilic groups are introduced, and when the acid value is 70 or more, the dryness and water resistance of the resulting coating film are not good. Is more likely to occur, and it is more preferable to use the acid value in the range of 15 to 50 in terms of acid value.

The other hydroxy compound (C) having reactivity with an isocyanate group which can be used in the present invention is not particularly limited, and examples thereof include epoxy resin, phenol resin, polyester resin, alkyd resin and acryl. Resin, polyether resin, amino resin,
High molecular weight compounds such as polybutadiene resin, polyamide resin and ethanol, butanol, amyl alcohol,
Octanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, number average molecular weight 150 to 6
000 polyethylene glycol, polypropylene glycol, neopentyl glycol, diethyl propane diol, ethyl butyl propane diol, cyclohexane dimethanol, butylene glycol, pentane diol, hexane diol, hydrogenated bisphenol A, ethylene glycol adduct of bisphenol A, tri Examples include monohydric and polyhydric alcohols such as methylolpropane, trimethylolethane, glycerin, and pentaerythritol. The amount used is not particularly limited, but 50% by weight or less is preferably used.

The organic isocyanate compound (D) which can be used as the other essential component in the present invention is
Although not particularly limited, for example, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, dimethylbiphenylene diisocyanate, dimethoxybiphenylene diisocyanate, dichlorobiphenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexylene diisocyanate, xylylene diisocyanate,
Tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate,
Examples thereof include isophorone diisocyanate and dimethyldicyclohexylmethane diisocyanate. With respect to the amount used, a stoichiometric amount of 0.5 to 3.0 is preferable with respect to 1 equivalent of the hydroxyl group contained. A stoichiometric amount of 0.
When it is 5 or less, there is a problem that the added isocyanate group for binding each raw material is insufficient and the molecular weight is not increased, or each added raw material is not completely homogenized. When the stoichiometric amount of 3.0 or more is added to the contained hydroxyl groups, the crosslinking density becomes high, and instantaneous gelation occurs during chain extension, and the hardness of the coating film tends to be hard and brittle, which is not preferable. More preferably stoichiometric amount of 0.7 to 2.5
Is.

The chain extender (E) used as an essential component in the present invention is not particularly limited,
Known ones can be used. For example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 25-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-.
Diamines such as dicyclohexylmethanediamine and 1,4-cyclohexanediamine; diethylenetriamine,
Examples include polyamines such as dipropylenetriamine and triethylenetetramine; hydrazines; acid hydrazides, and these may be used alone or in combination.

The chain extender is used in an amount of 1: 1 in terms of an equivalent ratio with the residual isocyanate group.
Isocyanate group Cont
You can know by measuring. The amount of residual isocyanate groups is not particularly limited, but usually the urethanization reaction is often completed within the range of 0.3 to 5.0% by weight. If it is 0.3% by weight or less, the amount of the chain extender is small and the effect is reduced, and if it is 5.0% by weight or more, the urethanization reaction is insufficient and free hydroxylcarboxylic acid compounds tend to remain, which is not preferable. Therefore,
The chain extender is used in the range of 0.3 to 5.0% by weight.
More preferably, it is in the range of 0.5 to 4.0% by weight.

The method for producing the urethanized oil composition of the present invention is as follows. For example, a composition containing a drying oil or a semi-drying oil and / or a fatty acid thereof as an essential component, an oxycarboxylic acid, an organic isocyanate, and another hydroxyl compound having reactivity with an isocyanate group are reacted at 50 to 80 ° C. with good stirring. The isocyanate prepolymer thus obtained can be produced by dispersing it in water, adding a chain extender, and stirring the mixture well.

After reacting an oxycarboxylic acid, another hydroxy compound having reactivity with an isocyanate group, and an organic isocyanate compound at 50 to 80 ° C., a drying oil or a semi-drying oil and / or a fatty acid thereof is used as an essential component. It can also be produced by adding the composition described above and subsequently reacting it to obtain a terminal isocyanate prepolymer dispersed in water, and then adding a chain extender and stirring well.

Furthermore, after reacting an oxycarboxylic acid and an organic isocyanate at 50 to 80 ° C., another hydroxyl compound, a drying oil or a semi-drying oil and / or a fatty acid thereof having reactivity with an isocyanate group is used as an essential component. It can also be produced by dispersing the terminal isocyanate prepolymer obtained by adding the above composition and continuing the reaction in water, adding a chain extender and stirring well.

The organic isocyanate compound has a hydroxyl group of 1.
During the production of a terminal isocyanate prepolymer obtained by reacting 0.5 to 3.0 equivalents of isocyanate groups with respect to 0 equivalents, the reaction is carried out at a relatively low temperature because the reaction is carried out in the excess of hydroxyl groups, and the reduction rate of the isocyanate compound is decreased. Need to be controlled and reacted.

When the urethane resin is dispersed in water, residual isocyanate groups are reacted with a blocking agent and then dispersed in water, and the blocking agent is removed by a method such as heating in water to remove the isocyanate and the chain extender. The reaction of may be performed.

The blocking agent that can be used is not particularly limited, and already known blocking agents such as alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, and i-butanol, phenol, cresol, nitrophenol, chloro. Phenols such as resorcinol, thiochols such as benzenethiol, caprolactams such as epsilon caprolactam, carbamates such as ethylcarbamate, ketoenols such as acetylacetone, ketooximes such as MEK oxime, and sodium bisulfite. it can.

Using these blocking agents, already known isocyanate compounds or their prepolymers are reacted at 30 to 100 ° C. without catalyst or in the presence of a catalyst such as dibutyltin dilaurylate to block the isocyanate groups. Can be used.

When producing the terminal isocyanate prepolymer, the reaction may be carried out in an organic solvent, if necessary. The organic solvent that can be used is not particularly limited, but methyl ethyl ketone having no reactivity with isocyanate,
Ketones such as methyl butyl ketone and methyl isobutyl ketone, aromatics such as toluene and xylene, alicyclic compounds such as cyclohexane and methylcyclohexane, and ethers such as ethyl ether and butyl ether are preferably used. If necessary, these organic solvents may be dispersed in water,
Alternatively, the solvent may be removed by vacuum distillation after dispersion.

Further, as a medium of urethanized oil and water, in order to facilitate dispersion in water, a hydrophilic organic solvent may be added before or after dispersion in water and dispersed in water. The organic solvent that can be used in that case is not particularly limited, and examples thereof include alcohols such as ethanol, isopropyl alcohol, n-butanol, isobutanol, amyl acol, 3methoxybutanol, ethylene glycol, diethylene glycol, propylene glycol, and methyl. Ethylene glycol derivatives such as cellosolve, cellosolve, butyl cellosolve, hexyl cellosolve, ethyl carbitol, and butyl carbitol, and aprotic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide. .

When the urethanized oil is dispersed in water, a part or all of the carboxyl groups are neutralized with a basic substance, or dispersed in water while being neutralized in water. A volatile amine is preferable as the basic substance used here, and an inorganic base is not preferable because it tends to remain in the coating film and deteriorate water resistance. Examples of the amine include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, dimethyl n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine. , N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N
Examples thereof include amines such as N-dimethylpropanolamine, and one or more of these can be used.

As a method for dispersing the urethanized oil in water, water may be dropped while stirring the urethanized oil to perform phase inversion emulsification, or the reaction product may be dropped into well-stirred water. You may let me. Alternatively, a method of dispersing in water while applying mechanical shearing force using a homogenizer, colloid mill, static mixer, manton gory, microfluidizer, or the like is also preferable. A method of using ultrasonic waves when dispersing in water is also a preferable method.

The urethanized oil composition of the present invention may be used in combination with a curing agent for improving solvent resistance and alkali resistance. The urethanized oil composition of the present invention can be directly kneaded with various curing agents, various pigments and the like, and in this case, the coating film has a fast drying property and is extremely excellent in the storage stability of the coating material. Have.

Examples of curing agents that can be used include amino resins, blocked isocyanates, desiccants, epoxy compounds, aziridine compounds and the like. There is no particular limitation on these types, but among these, the water-soluble urethane oil and the amino resin having good storage stability, blocked isocyanate,
A desiccant or the like is generally used. Examples of amino resins include Super Beckamine J-820-60 and G-821-6.
0, L-128-60 and other butyl etherified melamine resins, G-1850, P-196-60 and other butyl etherified urea resins (all manufactured by Dainippon Ink and Chemicals), Cymel 300, Cymel 303, Cymel 325, etc. A commercially available product such as methyl etherified melamine resin (manufactured by Mitsui Cyanamide) may be used as it is.

As the blocked isocyanate, when a non-aqueous block isocyanate is used, unless the block isocyanate is added to the paint immediately before use and the mixture is forcibly stirred, the stability is poor and sedimentation occurs. The use of an aqueous block isocyanate is preferred because it may occur.

As the desiccant, a metal such as a cobalt salt, a manganese salt, a zirconium salt, a calcium salt, a lead salt or the like using an aliphatic carboxylic acid such as oleic acid or an alicyclic carboxylic acid such as naphthenic acid as a carrier. There are soaps and compounds obtained by adding anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers, etc. to make them water-soluble, and tertiary amines such as dimethylaniline, diethylaniline, and dimethylparatoluidine. These are used alone or in combination. The above can be used together. If the addition amount is 0.003% by weight (metal content) or less, the effect is not recognized, and if it is 0.5% by weight (metal content) or more, there are drawbacks such as poor water resistance. The preferred amount used is in the range of 0.05 to 0.4% by weight (metal content).

The urethanized oil composition of the present invention comprises a plasticizer,
Emulsion, styrene-butadiene latex, acrylic resin, alkyd resin, polyester resin, maleated oil phenol resin, other water-based resin, etc. can be added and used.

The coating composition using the urethanized oil composition obtained by the present invention is dip coating, shower coating,
It can be applied by any method such as electrodeposition coating, brush coating, spray coating, roll coating, etc. It is excellent by pre-coating on metal surface such as iron, aluminum, copper, nickel, stainless steel, surface rust-prevented steel plate, etc. It is possible to impart excellent performance. Also, it can be directly applied to a substrate such as wood, synthetic resin, glass, and ceramics.

[0040]

The present invention will be described in more detail based on the following examples, but the invention is not limited to the technical idea thereof.
The present invention is not limited to these examples. Unless otherwise specified, the ratio of each component is based on weight.

[Production Example 1] 500 parts of flaxseed oil, 500 parts of soybean oil, 66 parts of pentaerythritol, and 0.15 parts of lithium hydroxide were placed in a clean container in which nitrogen gas was refluxed, and the temperature was raised to 250 ° C with stirring. It was warmed, held for 2 hours and then cooled. Resin solution a was obtained.

[Production Example 2] 1000 parts of safflower oil, 150 parts of pentaerythritol and 0.1 part of lithium hydroxide were placed in a clean container in which nitrogen gas was refluxed, and the mixture was stirred and heated to 250 ° C for 2 hours. It was held and then cooled. Resin liquid b
Got

Example 1 730 parts of resin solution a, 30 parts of PPG 400 (polypropylene glycol molecular weight 400), 48 parts of dimethylol propionic acid, 192 parts of tolylene diisocyanate and 700 parts of methyl ethyl ketone were added to a clean container in which nitrogen gas was refluxed. While stirring well,
Hold at 70 ° C. for 3 hours. When the NCO% was measured, it was 1.5% (solid content). The mixture was cooled to 30 ° C. or lower, 37 parts of triethylamine was added, and immediately, 15 parts of piperazine was added to a solution prepared by dissolving 2000 parts of water, and the mixture was further stirred.

Thereafter, the methyl ethyl ketone was desolvated and removed by distillation under reduced pressure at 40 to 50 ° C. Semi-transparent nonvolatile content 3
Resin solution A of 5% was obtained. Example 2 60 parts of 12-hydroxystearic acid, 50 parts of polyoxyethylene monomethyl ether (molecular weight 4000), 100 parts of butylethyl propanediol, 270 parts of hexamethylene diisocyanate, 667 parts of methyl ethyl ketone were placed in a clean container in which nitrogen gas was refluxed. Was added and kept at 60 ° C. for 3 hours with good stirring.
After adding 600 parts, the mixture was heated to 70 ° C. and kept for 5 hours. NC
When the O% was measured, it was 2.0% (solid content).

A solution prepared by dissolving 14.4 parts of hydrated hydrazine and 20 parts of dimethylethanolamine in 2000 parts of water was placed in another container, and the contents were immediately added to the solution while stirring and then depressurized at 40 to 55 ° C. The solvent of methyl ethyl ketone was removed by distillation to obtain a semi-transparent 35% non-volatile resin liquid B.

Example 3 100 parts of dimethylolpropionic acid, 300 parts of tolylene diisocyanate, 200 parts of Epicoat 1001 (epoxy resin manufactured by Yuka Shell Co., Ltd.) and 700 parts of methyl ethyl ketone were added to a clean container in which nitrogen gas was refluxed. After maintaining at 60 ° C. for 2 hours while stirring well, 400 parts of resin solution a was added and the mixture was further maintained for 5 hours. When the NCO% was measured, it was 4.0% (solid content).

Cooled to 30 ° C. or below, 40 parts of piperazine,
85 parts of triethylamine was added to a solution prepared by dissolving 2000 parts of water, and the mixture was further stirred. The solvent of methyl ethyl ketone was removed by distillation under reduced pressure at 40 to 55 ° C to obtain a semi-transparent 35% non-volatile resin liquid C.

[Comparative Example 1] In a clean container in which nitrogen gas was refluxed, 690 parts of resin solution b, 55 parts of PPG 400 (polypropylene glycol molecular weight 400), 60 parts of dimethylol propionic acid, 195 parts of tolylene diisocyanate,
After 700 parts of methyl ethyl ketone was added and well stirred, the mixture was maintained at 70 ° C. for 6 hours, cooled to 30 ° C. or lower, added with 65 parts of triethylamine, and further added with 2000 parts of water to carry out phase inversion emulsification. The solvent of methyl ethyl ketone was removed by distillation under reduced pressure at 40 to 55 ° C. to obtain a semi-transparent 35% non-volatile resin liquid D.

Comparative Example 2 200 parts of flaxseed oil, 150 parts of soybean oil, 83 parts of pentaerythritol and 0.05 part of lithium hydroxide were charged into a clean container in which nitrogen gas was refluxed, and the temperature was raised to 250 ° C. with stirring. After holding for 2 hours,
After cooling to 0 ° C., 52 parts of pentaerythritol, 170 parts of neopentyl glycol and 440 parts of isophthalic acid were charged, the temperature was raised to 230 ° C., the reaction was carried out to an acid value of 30 for 4 to 5 hours, and then the mixture was cooled to 150 ° C. After adding 27 parts and stirring for 2 hours, 465 parts of n-butyl cellosolve and 75 parts of triethylamine were added and well stirred to obtain a viscous resin liquid E having a nonvolatile content of 65%.

Comparative Example 3 340 parts of butyl cellosolve, 50 parts of n-butanol, and styrene 225 were placed in a clean container.
Part, 2-ethylhexyl methacrylate 225 parts, acrylic acid 20 parts, methacrylic acid 25 parts, ethyl acrylate 200 parts, perbutyl O (manufactured by NOF Corporation) 14 parts, perbutyl Z (manufactured by NOF CORPORATION), 20 parts, lauryl mercaptan 5 parts were added. While stirring, the temperature is gradually raised to 80 ° C. and kept for 3 hours, then raised to 100 ° C. and kept for 8 hours, and then cooled. 25 parts of triethylamine was added and stirred well. A viscous resin liquid F having an acid value of 40 and a nonvolatile content of 65% was obtained.

Tables 1 and 2 below show formulation examples and the performance of the clear coating film. <Test Method and Criteria> Dryability: 6 after each coating on a glass plate with a 6 mil applicator
It was forcedly dried at 0 ° C. for 20 minutes and judged by the strength of the surface tack.

⊚: No tack. ◯: Slightly tacked. Δ: Slightly tacked. X: Tacked. Wrinkle property of coating film surface: After drying at room temperature for 3 days, the coating film surface was visually judged.

⊚: Good surface smoothness ×: Wrinkles on the surface Feeling of flesh; After coating with a 6 mil applicator on a paper-bonded plywood,
After forced drying at 60 ° C for 20 minutes and room temperature drying for 3 days, the coating film surface was visually judged.

⊚: There is a feeling of fleshness ◯: There is a slight lack of feeling of fleshness Δ: There is a lack of feeling of fleshness Painting workability: It was judged by air spray coating by spraying workability and dripping property of the paint.

⊚: Both spray coating workability and paint dripping are good ◯: Paint dripping is good Δ: Spray coating workability is good

[0056]

[Table 1] In the table, Decknate 3111 represents a desiccant (dispersed with an emulsifier manufactured by Dainippon Ink and Chemicals, Inc.).

[0057]

[Table 2]

[0058]

EFFECT OF THE INVENTION The urethanized oil composition obtained according to the present invention is water-based and environmentally friendly, and has no flammability at room temperature, so there is little risk of fire, and the coating film has a dryness and a long-lasting feeling. It has excellent workability such as brushing and sagging during painting, and has excellent storage stability.

The composition of the present invention is particularly useful as a coating agent for undercoating and topcoating various substrates such as aluminum, iron plates, tin-plated steel plates, various pretreated steel plates, steel, alkali substrates, various woods.

In addition, it can be used in a wide variety of applications such as various emulsifiers, surfactants, printing inks, textile chemicals, paper chemicals, adhesives, adhesives, synthetic leathers, and the like.

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[Procedure amendment]

[Submission date] April 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

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[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

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[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 4

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[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful aqueous urethanated oil composition having excellent hydrolysis stability. More specifically, after reacting with an organic isocyanate in excess with respect to the hydroxyl group of oxycarboxylic acid, and further with a resin having a hydroxyl value of 30 to 250 containing a drying oil and / or fatty acid thereof as an essential component. The present invention relates to an aqueous urethanized oil composition which is dispersed in water and reacts with a residual isocyanate group and a chain extender, which is extremely excellent in hydrolysis stability.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

Therefore, as a result of intensive studies conducted by the inventors of the present invention, the drying oil or the semi-drying oil and / or their fatty acids were reacted as essential components. Hydroxyl value obtained from 30 to 2
50 resins, oxycarboxylic acid, and other hydroxy compounds are reacted with an organic isocyanate to disperse a terminal isocyanate prepolymer,
It was found that a urethane-ized oil composition having extremely excellent hydrolysis stability can be obtained by reacting the isocyanate group of the remaining organic isocyanate compound with a chain extender, and completed the present invention.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

That is, according to the present invention, a resin (A) having a hydroxyl value of 30 to 250 and an oxycarboxylic acid (B) obtained by reacting a drying oil and / or a fatty acid thereof as an essential component.
And a hydroxylated compound (C), an organic isocyanate compound (D), and a chain extender (E).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

Hydroxyl value of 30 to 25 obtained by reacting the oil and fat of the present invention and / or fatty acid thereof as an essential component
Although the amount of the resin (A) of 0 used is not particularly limited,
It is preferably used in the range of 70% by weight. If the amount used is 10% by weight or less, the air-curable double bond for ensuring the necessary air-curability cannot be secured, and if it is 70% by weight or more, a resin design that secures the carboxyl groups and the like necessary for water solubilization Is difficult to do, which is not preferable. More preferably 2
It is preferably used in the range of 0 to 60% by weight.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

The chain extender is used in a stoichiometric amount with respect to the residual isocyanate groups, that is, in an equivalent ratio of 1: 1.
Used to be. The amount of residual isocyanate groups is
It can be known by measuring the isocyanate group Cont. The amount of the residual isocyanate group is not particularly limited, but usually the urethanization reaction is often completed within the range of 0.3 to 5.0%. If it is less than 0.3%, the amount of the chain extender is small and the effect is small.
The above is not preferable because the urethanization reaction is insufficient and free hydroxylcarboxylic acid compounds tend to remain. Therefore, the chain extender is used in the range of 0.3 to 5.0%. The range is more preferably 0.5 to 4.0%.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

The method for producing the urethanized oil composition of the present invention is as follows. For example, a resin having a hydroxyl value of 30 to 250 reacted with a drying oil or a semi-drying oil and / or a fatty acid thereof as an essential component, an oxycarboxylic acid, an organic isocyanate, and another hydroxyl compound having reactivity with an isocyanate group are well stirred. While 50-8
The isocyanate prepolymer obtained by reacting at 0 ° C. can be produced by dispersing it in water, adding a chain extender and stirring well.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

The organic isocyanate compound has a hydroxyl group of 1.
During the production of a terminal isocyanate prepolymer obtained by reacting 0.5 to 1.0 equivalent of an isocyanate group with respect to 0 equivalent, the reaction is carried out at a relatively low temperature because the reaction is carried out in the excess of hydroxyl groups, and the reduction rate of the isocyanate compound is reduced. It is necessary to react while controlling.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Examples of curing agents that can be used include amino resins, blocked isocyanates, desiccants, epoxy compounds, aziridine compounds and the like. There is no particular limitation on these types, but among these, the aqueous urethane-modified oil and an amino resin having good storage stability, a blocked isocyanate,
A desiccant or the like is generally used. Examples of amino resins include Super Beckamine J-820-60 and G-821-6.
0, L-128-60 and other butyl etherified melamine resins, G-1850, P-196-60 and other butyl etherified urea resins (all manufactured by Dainippon Ink and Chemicals), Cymel 300, Cymel 303, Cymel 325, etc. A commercially available product such as methyl etherified melamine resin (manufactured by Mitsui Cyanamide) may be used as it is.

Claims (4)

[Claims] 1. A drying oil and / or a fatty acid (A) thereof, an oxycarboxylic acid (B), another hydroxyl compound (C), an organic isocyanate compound (D) and a chain extender (E) are reacted. The urethane-ized oil composition which has the obtained urethane-ized oil as a main component. 2. Drying oil and / or fatty acid (A) thereof, oxycarboxylic acid (B) and other hydroxyl compound (C) in a weight ratio of 10 to 70/3 to 25/0 to 50.
The urethanized oil composition according to claim 1, which is used. 3. The organic isocyanate compound (D) is added in an equivalent ratio of hydroxyl group / isocyanate group = 1 / 0.5 to 1/3.
The urethanized oil composition according to claim 1 or 2, which is used in the range of 0. 4. A chain extender (E) in an amount of 0.3 to 5.0% by weight.
The urethanized oil composition according to any one of claims 1 to 3, which is used.